Non-hard coating film, laminate, multiple laminate, and display device

Abstract

The invention relates to a non-hard coating film, a laminate, a multilayer laminate, and a display device. Provided is a non-hard coating film which is light in weight, excellent in mechanical strength, and excellent in heat resistance even if a PFAS-limiting substance is not included. The non-hard coating film satisfies an elastic-plastic ratio of 70% or more and a glass transition temperature and a melting point of not more than 200 DEG C in a press-in test, and satisfies at least one of a Young's modulus of 1000 MPa or more in a press-in test and a Young's modulus of 1000-5000 MPa in a tensile test.

Description

Technical Field

[0001] The present disclosure relates to a non-hard coating film, a laminate, a multi-layer laminate, and a display device. Specifically, the present disclosure relates to a non-hard coating film, a laminate including the non-hard coating film, a multi-layer laminate, and a display device. Background Art

[0002] In monitors such as liquid crystal displays, organic EL displays, and plasma displays, a protective film is adhered or a hard coat is formed, whereby it is possible to obtain effects of preventing screen damage, making fingerprints less likely to adhere to the screen, and easily wiping off dirt adhering 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 thinning and streamlining of optical substrates such as display substrates. Therefore, for substrates for coating hard coats, thinning and streamlining are also being promoted.

[0004] As the above-mentioned substrate, glass, polyimide, and polyethylene terephthalate (PET) are generally used. However, glass has a large self-weight, which causes an increase in the weight of mobile devices, and there is a problem that it is easily broken by impact. In addition, polyimide mostly contains alkyl fluorine in its structure and is subject to the latest restrictions on organic fluorine compounds (PFAS), and may be restricted in some regions. In addition, PET has a problem of low heat resistance.

[0005] In addition, from the viewpoint of thinning, a single-layer film having excellent surface scratch resistance that does not require a hard coat or a supporting substrate has been proposed. For example, in Patent Document 1, a hard coating film containing a crosslinked polymer of a polyurethane acrylate oligomer is disclosed, and in Patent Document 2, a cover window for a substrate-free flexible display device containing an elastomer and a polysiloxane containing an epoxy group-functional group is disclosed.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-214553

[0009] Patent Document 2: Korean Patent Publication No. 10-2023-0050843 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, the crosslinking density of the film of Patent Document 1 is about 60%, and the mechanical strength is insufficient. In addition, the cover window of Patent Document 2 has insufficient mechanical strength due to the inclusion of an elastomer. Moreover, even when using a single-layer film, heat resistance is sometimes required.

[0012] Therefore, an object of the present disclosure is to provide a non-hard coating film that is lightweight, has excellent mechanical strength, and has excellent heat resistance even in the absence of PFAS-restricted substances. In addition, an object of the present disclosure is to provide a laminate, a multilayer laminate, and a display device including the above non-hard coating film.

[0013] Technical Solution

[0014] The inventors of the present disclosure conducted in-depth research to solve the above technical problems and found that, according to a non-hard coating film having specific physical properties, it is lightweight and has excellent mechanical strength even in the absence of PFAS-restricted substances. The present invention has been completed based on these insights.

[0015] That is, the present disclosure provides a non-hard coating film that satisfies an elastic-plastic ratio of 70% or more in an indentation test, a glass transition temperature and a melting point not below 200 °C, and satisfies at least one of a Young's modulus of 1000 MPa or more in an indentation test and a Young's modulus of 1000 to 5000 MPa in a tensile test.

[0016] Preferably, the thickness of the above non-hard coating film is 1 to 1000 μm, and the indentation hardness in the indentation test is 100 MPa or more.

[0017] Preferably, the above non-hard coating film is formed by a cured product of a curable composition, and the glass transition temperature of the cured product is 300 °C or more.

[0018] Preferably, the above non-hard coating film is formed by a cured product of a curable composition, and the pencil hardness of the cured product is 2H or more.

[0019] Preferably, the above curable composition contains a radical-curable polyorganosiloxane.

[0020] Preferably, the above curable composition contains a cationically polymerizable silsesquioxane.

[0021] Preferably, the above curable composition further contains a curable compound having an energy ray-polymerizable functional group.

[0022] In addition, the present disclosure provides a laminate including the above non-hard coating film and a functional layer laminated on the above non-hard coating film.

[0023] In addition, the present disclosure provides a multilayer laminate formed by laminating a plurality of the above laminates.

[0024] In addition, the present disclosure provides a display device including the above multilayer laminate.

[0025] Advantages of the Invention

[0026] According to the present disclosure, there can be provided a non-hard coating film that is lightweight, has excellent mechanical strength, and has excellent heat resistance even without containing PFAS restricted substances, a laminate including the above non-hard coating film, a multi-layer laminate, and a display device. Detailed Embodiments

[0027] [Non-Hard Coating Film]

[0028] The non-hard coating film of the present disclosure satisfies that the elastic-plastic ratio in the indentation test is 70% or more and the glass transition temperature and melting point are not below 200°C, and satisfies at least one of the Young's modulus in the indentation test being 1000 MPa or more and the Young's modulus in the tensile test being 1000 to 5000 MPa. Among them, it is preferable to satisfy both the Young's modulus in the indentation test being 1000 MPa or more and the Young's modulus in the tensile test being 1000 to 5000 MPa.

[0029] In this specification, a "non-hard coating film" refers to a film (sheet) that does not have a hard coating formed on both sides of the film but has hard coatability in a single film layer. The above non-hard coating film does not require an additional hard coating and can achieve a lighter weight.

[0030] The elastic-plastic ratio of the above non-hard coating film in the indentation test is 70% or more, preferably 75% or more, and more preferably 80% or more. If the elastic-plastic ratio is 70% or more, it is not easily damaged when pressure is applied, and the mechanical strength of the film is excellent. In addition, the elastic-plastic ratio is preferably 95% or less, more preferably 95% or less, and further preferably 90% or less. If the elastic-plastic ratio is 95% or less, the flexibility is excellent and the bending resistance is excellent.

[0031] The Young's modulus of the above non-hard coating film in the indentation test is preferably 1000 MPa or more, more preferably 2000 MPa or more, and further preferably 3000 MPa or more. If the Young's modulus in the indentation test is 1000 MPa or more, it becomes a hardness that is not easily damaged, and the mechanical strength of the film is excellent. In addition, the Young's modulus in the indentation test is preferably 10000 MPa or less, more preferably 9000 MPa or less, and further preferably 8000 MPa or less. If the Young's modulus in the indentation test is 10000 MPa or less, the flexibility is excellent and the bending resistance is excellent.

[0032] The indentation hardness of the above non-hard coating film in the indentation test is preferably 100 MPa or more, more preferably 300 MPa or more, and further preferably 700 MPa or more. If the indentation hardness is 100 MPa or more, the surface hardness becomes high, and it is not easily dented or damaged, and the mechanical strength of the film is excellent. In addition, the indentation hardness is preferably 1000 MPa or less, more preferably 900 MPa or less, and further preferably 800 MPa or less. If the indentation hardness is 1000 MPa or less, the flexibility is excellent and the bending resistance is excellent.

[0033] The indentation hardness described above can be measured, for example, by nanoindentation method or the like. As the indenter, a Berkovich indenter can be used.

[0034] The Young's modulus in the tensile test of the non-hard coating film described above is preferably 1000 to 5000 MPa, more preferably 1200 to 4000 MPa, and still more preferably 1500 to 3000 MPa. If the Young's modulus in the tensile test is 1000 MPa or more, the rigidity required for film formation can be maintained, and the mechanical strength of the film is excellent. If the Young's modulus in the tensile test is 5000 MPa or less, elongation and bend resistance can be taken into account while maintaining rigidity, and the mechanical strength of the film is excellent.

[0035] The above-mentioned tensile test can be carried out using a publicly known or commonly used tensile testing machine. The above-mentioned Young's modulus is a value measured under the conditions of an initial chuck distance of 20 mm, a gauge length of 12 mm, and a tensile speed of 2 mm / min at room temperature, with a non-hard coating film in the shape of a No. 7 dumbbell as the test piece. In addition, the Young's modulus in the tensile test can be obtained as an average value after removing the maximum and minimum values from the measured values of n = 5 or more.

[0036] The glass transition temperature (Tg) and melting point (Tm) of the non-hard coating film described above are not below 200 °C, preferably not below 300 °C. If the above-mentioned glass transition temperature and melting point are not below 200 °C, the heat resistance of the non-hard coating film is excellent. The above-mentioned glass transition temperature and melting point are values measured by DSC (differential scanning calorimeter).

[0037] The thickness of the non-hard coating film described above is preferably 1 to 1000 μm, more preferably 10 to 600 μm, and still more preferably 30 to 400 μm. If the above-mentioned thickness is 1 μm or more, the mechanical strength and scratch resistance are more excellent. If the above-mentioned thickness is 1000 μm or less, it is lighter in weight and has excellent bend resistance.

[0038] (Curable composition)

[0039] The non-hard coating film described above is preferably a non-hard coating film formed from a cured product of a curable composition. That is, the curable composition preferably contains a curable compound. The curable compound can be used alone or in combination of two or more.

[0040] As the above-mentioned curable compound, a cationically polymerizable silsesquioxane is preferred. By containing the above-mentioned cationically polymerizable silsesquioxane, the curable composition is less likely to shrink during curing, and a relatively thick non-hard coating film can be easily obtained, thereby forming a non-hard coating film with more excellent scratch resistance. The above-mentioned cationically polymerizable silsesquioxane is preferably a photo-cationically polymerizable silsesquioxane.

[0041] The above-mentioned cationically polymerizable silsesquioxane has a cationically polymerizable functional group in the molecule. Examples of the above-mentioned cationically polymerizable functional group include: hydroxyl group, epoxy group, oxetanyl group, vinyl ether group, vinylphenyl group, etc. Among them, from the viewpoint of further improving the surface hardness of the non-hard coating film, the epoxy group is preferred.

[0042] Examples of the above-mentioned group containing an epoxy group include known or conventional groups having an ethylene oxide ring, and there is no particular limitation. From the viewpoints of the curability of the curable composition and the heat resistance of the non-hard coating film, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferred, and the group represented by the following formula (1a) and the group represented by the following formula (1c) are more preferred, and the group represented by the following formula (1a) is further preferred.

[0043]

[0044]

[0045] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene and other linear or branched alkylene groups having 1 to 10 carbon atoms. Among them, as R 1a , from the viewpoint of the curability of the curable composition, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, and ethylene, trimethylene, and propylene are more preferred, and ethylene and trimethylene are further preferred.

[0046] In the above formula (1b), R 1b represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1b , from the viewpoint of the curability of the curable composition, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, and ethylene, trimethylene, and propylene are more preferred, and ethylene and trimethylene are further preferred.

[0047] In the above formula (1c), R 1c represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1c, from the viewpoint of the curability of the curable composition, it is preferably a linear alkylene having 1 to 4 carbon atoms or a branched alkylene having 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and further preferably ethylene or trimethylene.

[0048] In the above formula (1d), R 1d represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a . Among them, as R 1d , from the viewpoint of the curability of the curable composition, it is preferably a linear alkylene having 1 to 4 carbon atoms or a branched alkylene having 3 or 4 carbon atoms, more preferably ethylene, trimethylene, or propylene, and further preferably ethylene or trimethylene.

[0049] As R 1 in the formula (1), a group represented by the above formula (1a), that is, a group in which R 1a is ethylene [wherein, 2-(3,4-epoxycyclohexyl)ethyl] is particularly preferred.

[0050] As the above cationic polymerizable silsesquioxane, for example, a compound having a structural unit represented by the following formula (1) can be cited.

[0051] [R 1 SiO 3 / 2 (1)

[0052] The structural unit represented by the above formula (1) is usually a silsesquioxane structural unit (so-called T unit) represented by [RSiO 3 / 2 . It should be noted that R in the above formula represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound. It should be noted that in this specification, a compound having the structural unit represented by the above formula (1) is sometimes referred to as "silsesquioxane (X)". R 1 in the formula (1) represents a group (monovalent group) containing the above cationic polymerizable functional group.

[0053] Silsesquioxane (X) may have only one kind of the structural unit represented by the above formula (1) or may have two or more kinds of the structural units represented by the above formula (1).

[0054] In addition, silsesquioxane (X) may have a structural unit represented by the following formula (2) as a silsesquioxane structural unit [RSiO 3 / 2 in addition to the structural unit represented by the above formula (1).

[0055] [R 2 SiO3 / 2 (2)

[0056] The structural unit represented by the above formula (2) is usually a 3 / 2 silsesquioxane structural unit (T unit) represented by [RSiO

[0057] . That is, the structural unit represented by the above formula (2) is formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compound. 2 R in the above formula (2)

[0058] represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkyl group. Examples of the above aryl group include phenyl, tolyl, naphthyl, etc. Examples of the above aralkyl group include benzyl, phenethyl, etc. Examples of the above cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl, etc. Examples of the above alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, etc.

[0059] Among them, examples of the above substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, and substituted alkyl group include those in which one or more hydrogen atoms or a part or all of the main chain skeleton of the above aryl group, aralkyl group, cycloalkyl group, and alkyl group are substituted with at least one selected from the group consisting of an alkyl group (especially a linear or branched alkyl group having 1 to 10 carbon atoms), an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (such as a fluorine atom), a mercapto group, an amino group, and a hydroxyl group. 2 Preferably, R is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group.

[0060] The ratio of each silsesquioxane structural unit (the structural unit represented by formula (1) and the structural unit represented by formula (2)) in the silsesquioxane (X) can be appropriately adjusted according to the composition of the raw materials (hydrolyzable trifunctional silane) used to form these structural units.

[0061] Among them, the silsesquioxane (X) preferably contains at least 1 the structural unit represented by the above formula (1) in which R is a group containing an alicyclic epoxy group, and 2 the structural unit represented by the above formula (2) in which R is an optionally substituted aryl group. In this case, there is a tendency for the surface hardness, flexibility, processability, and flame retardancy of the non-hard coating film to be more excellent.

[0062] In addition to having the structural units represented by the above formula (1) as T units and the structural units represented by the above formula (2), the silsesquioxane (X) may also have a structural unit (so-called M unit) selected from the group consisting of 1 / 2 represented by [R3SiO 2 / 2 , a structural unit (so-called D unit) represented by [R2SiO 4 / 2 , and a structural unit (so-called Q unit) represented by [SiO 1 . It should be noted that the R in the above M unit and the above D unit may be the same group as the R 2 in the structural unit represented by the above formula (1) and the R

[0063] in the structural unit represented by the above formula (2). As the silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2), for example, the structural unit represented by the following formula (3) can be cited. 3 / 2 (3)

[0064] The silsesquioxane (X) contains a structural unit (T3 body) represented by the following formula (I). Moreover, it may also contain a structural unit (T2 body) represented by the following formula (II).

[0065] [R a SiO 3 / 2 (I)

[0066] [R b SiO 2 / 2 (OR c )](II)

[0067] It should be noted that if the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). In addition, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). The three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') are respectively bonded to other silicon atoms (silicon atoms not shown in formula (I')). On the other hand, the two oxygen atoms above and below the silicon atom shown in the structure represented by the following formula (II') are respectively bonded to other silicon atoms (silicon atoms not shown in formula (II')). That is, both the above T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

[0068]

[0069] The R a in the above formula (I) (the R a in formula (I') is the same) and the R in formula (II)b (R in formula (II')) b also (similarly for R in formula (II')) represents a group containing a cationically polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a hydrogen atom. As specific examples of R a and R b , groups the same as R 1 in the above formula (1) and R 2 in the above formula (2) can be exemplified. It should be noted that R a in formula (I) and R b in formula (II) are respectively groups derived from the groups bonded to the silicon atom (groups other than alkoxy groups and halogen atoms) in the hydrolyzable trifunctional silane compound used as the raw material of the silsesquioxane (X), or, for example, when the above cationically polymerizable functional group is an epoxy group, groups obtained by epoxidizing the groups bonded to the silicon atom (groups other than alkoxy groups and halogen atoms) in the hydrolyzable trifunctional silane compound used as the raw material of the silsesquioxane (X).

[0070] R c (R c in formula (II') also) in the above formula (II) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, for example, linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl can be mentioned. Among them, methyl and ethyl are preferred, and methyl is more preferred. The alkyl group in R c in formula (II) usually comes from the alkyl group of the alkoxy group in the hydrolyzable silane compound used as the raw material of the silsesquioxane (X).

[0071] The molar ratio of the structural unit (T3 body) shown by the above formula (I) to the structural unit (T2 body) shown by the above formula (II) in the silsesquioxane (X) [structural unit shown by formula (I) / structural unit shown by formula (II) (sometimes referred to as "T3 body / T2 body")] is not particularly limited, preferably 5 or more, more preferably 5 to 20, further preferably 5 to 18, further preferably 6 to 16, further preferably 7 to 15, and particularly preferably 8 to 14. By setting the above molar ratio [T3 body / T2 body] to 5 or more, there is a tendency for the surface hardness of the non-hard coating film to be further improved.

[0072] The above molar ratio [T3 body / T2 body] in the silsesquioxane (X) can be determined, for example, by 29 Si-NMR spectrum measurement. In 29In the Si-NMR spectrum, the silicon atoms in the structural unit (T3 body) represented by the above formula (I) and the silicon atoms in the structural unit (T2 body) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, the molar ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, when the silsesquioxane (X) has a structural unit in which R 1 is 2-(3',4'-epoxycyclohexyl)ethyl, the signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears at -54 to -60 ppm. Therefore, in this case, the molar ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of the signal (T3 body) at -64 to -70 ppm and the signal (T2 body) at -54 to -60 ppm.

[0073] The silsesquioxane (X) 29 Si-NMR spectrum can be measured, for example, by the following apparatus and conditions.

[0074] Measuring apparatus: Trade name “JNM-ECA500 NMR” (manufactured by JEOL Ltd.).

[0075] Solvent: Deuterochloroform.

[0076] Number of accumulations: 1800 times.

[0077] Measuring temperature: 25 °C.

[0078] The fact that the molar ratio [T3 body / T2 body] of the silsesquioxane (X) is 5 or more means that there is a certain amount or more of the T2 body relative to the T3 body in the silsesquioxane (X). As such a T2 body, for example, the structural unit represented by the following formula (4), the structural unit represented by the following formula (5), the structural unit represented by the following formula (6), etc. can be cited. R in the following formula (4) 1 and R in the following formula (5) 2 are the same as R in the above formula (1) 1 and R in the above formula (2) 2 respectively. R in the following formulas (4) to (6) c is the same as R in formula (II) c and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0079] [R 1 SiO 2 / 2 (OR c )](4)

[0080] [R 2SiO 2 / 2 (OR c )](5)

[0081] [HSiO 2 / 2 (OR c )](6)

[0082] The cationically polymerizable silsesquioxane (especially silsesquioxane (X)) can be a silsesquioxane having a cage shape (cage silsesquioxane). Among cage silsesquioxanes, there are complete cage silsesquioxanes and incomplete cage silsesquioxanes, and incomplete cage silsesquioxanes are preferred.

[0083] Generally, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of T3 units, and there are no T2 units in the molecule. That is, the above molar ratio [T3 unit / T2 unit] is 5 or more, and further, as described later, when there is a characteristic absorption peak at around 1100 cm -1 in the FT-IR spectrum, it implies that the silsesquioxane has an incomplete cage silsesquioxane structure.

[0084] Whether the 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, when there are no characteristic absorption peaks at around 1050 cm -1 and around 1150 cm -1 respectively, and there is a characteristic absorption peak at around 1100 cm -1 , the silsesquioxane (X) can be identified as having a cage (incomplete cage) silsesquioxane structure. In contrast, generally, in the FT-IR spectrum, when there are characteristic absorption peaks at around 1050 cm -1 and around 1150 cm -1 respectively, it can be identified as having a ladder silsesquioxane structure. It should be noted that the FT-IR spectrum of the silsesquioxane (X) can be measured, for example, by the following apparatus and conditions.

[0085] Measuring apparatus: Trade name "FT-720" (manufactured by Horiba, Ltd.).

[0086] Measuring method: Transmission method.

[0087] Resolution: 4 cm -1 .

[0088] Measuring wavenumber range: 400 - 4000 cm -1 .

[0089] Cumulative number of times: 16 times.

[0090] With respect to the total amount of siloxane structural units in the cationically polymerizable silsesquioxane [total amount of all siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the proportion (total amount) of the structural units having a cationically polymerizable functional group (for example, the structural units represented by the above formula (1), the structural units represented by the above formula (4), etc.) is not particularly limited, and is preferably 50 mol% or more (for example, 50 to 100 mol%), more preferably 55 to 100 mol%, still more preferably 65 to 99.9 mol%, further preferably 80 to 99 mol%, and particularly preferably 90 to 98 mol%. By setting the above proportion to 50 mol% or more, the curability of the curable composition is improved, and in addition, the surface hardness of the non-hard coating film is significantly increased. It should be noted that the proportion of each siloxane structural unit in the cationically polymerizable silsesquioxane can be calculated, for example, from the composition of the raw materials and NMR spectrum measurement.

[0091] With respect to the total amount of siloxane structural units in the silsesquioxane (X) [total amount of all siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the proportion (total amount) of the structural unit represented by the above formula (I) (T3) is not particularly limited, and is preferably 50 mol% or more, more preferably 60 to 99 mol%, still more preferably 70 to 98 mol%, further preferably 80 to 95 mol%, and particularly preferably 85 to 92 mol%. It is presumed that by making the proportion of the structural units of the T3 form 50 mol% or more, it becomes easy to form an incomplete cage shape having an appropriate molecular weight, but there is a tendency for the surface hardness of the non-hard coating film to be further increased.

[0092] With respect to the total amount of siloxane structural units in the silsesquioxane (X) [total amount of all siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%), the proportion (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) is not particularly limited, and is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, still more preferably 0 to 30 mol%, and particularly preferably 1 to 15 mol%. By setting the above proportion to 50 mol% or less, the proportion of the structural units having a cationically polymerizable functional group can be relatively increased, and thus the curability of the curable composition is improved, and there is a tendency for the surface hardness of the non-hard coating film to be further increased.

[0093] With respect 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%), the ratio (total amount) of the structural units represented by the above formula (I) and the structural units represented by the above formula (II) (in particular, the combined ratio of T3 bodies and T2 bodies) is not particularly limited, and is preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is presumed that by making the above ratio 60 mol% or more, it becomes easier to form an incomplete cage shape with an appropriate molecular weight, but there is a tendency for the surface hardness of the non-hard coating film to be further improved. In particular, the ratio (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) is preferably within the above range.

[0094] The number average molecular weight (Mn) in terms of standard polystyrene obtained by gel permeation chromatography of the silsesquioxane (X) is not particularly limited, and is preferably 1000 to 3000, more preferably 1000 to 2800, still more preferably 1100 to 2600, and particularly preferably 1500 to 2500. By making the number average molecular weight 1000 or more, there is a tendency for the surface hardness of the non-hard coating film to be further improved. In addition, there is a tendency for the heat resistance and abrasion resistance of the non-hard coating film to be improved. On the other hand, by making the number average molecular weight 3000 or less, there is a tendency for the compatibility with other components in the curable composition to be improved and the heat resistance of the non-hard coating film to be improved.

[0095] The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene based on gel permeation chromatography of the silsesquioxane (X) is not particularly limited, and is preferably 1.0 to 3.0, more preferably 1.1 to 2.0, still more preferably 1.2 to 1.9, still more preferably 1.3 to 1.8, and particularly preferably 1.45 to 1.80. By making the molecular weight dispersity 3.0 or less, there is a tendency for the surface hardness of the non-hard coating film to be further increased. On the other hand, by making the molecular weight dispersity 1.0 or more (in particular, 1.1 or more), there is a tendency for it to be easily in a liquid state and the operability to be improved.

[0096] It should be noted that the number average molecular weight and molecular weight dispersity of the silsesquioxane (X) can be measured by the following apparatus and conditions.

[0097] Measuring apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation).

[0098] Chromatographic columns: Shodex KF-801 (2 pieces), KF-802, and KF-803 (manufactured by Showa Denko K.K.).

[0099] Measurement temperature: 40 °C.

[0100] Eluent: THF, sample concentration 0.1 - 0.2 wt%.

[0101] Flow rate: 1 mL / min.

[0102] Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation).

[0103] Molecular weight: in terms of standard polystyrene conversion.

[0104] The cationically polymerizable silsesquioxane can be produced by a known or conventional method for producing silsesquioxane, and there is no particular limitation. For example, it can be produced by hydrolyzing and condensing one or more hydrolyzable silane compounds.

[0105] The content ratio of the cationically polymerizable silsesquioxane in the above curable composition is not particularly limited. Relative to the total amount of the curable compounds (100% by mass), it is preferably more than 50% by mass (for example, more than 50% by mass and 98% by mass or less), more preferably 60 - 95% by mass, further preferably 70 - 93% by mass, and particularly preferably 80 - 90% by mass. If the above content ratio exceeds 50% by mass, there is a tendency for the surface hardness of the non-hard coating film to be further improved. If the above content ratio is 98% by mass or less, other components can be contained, and there is a tendency for the effects obtained to be further improved by containing these components. In addition, the above curable composition can contain a curing catalyst, and thus there is a tendency for the curable composition to be cured more efficiently.

[0106] The above curable compound preferably contains a curable compound having a photoenergy ray polymerizable functional group (sometimes referred to as "photoenergy ray curable compound"). In this case, the dispersibility of the radical curable polyorganosiloxane described below in the curable composition and the non-hard coating film can be improved. It should be noted that the above photoenergy ray curable compound is a compound that does not belong to the above cationically polymerizable silsesquioxane.

[0107] Examples of the above photoenergy ray polymerizable functional group include vinyl, propenyl, isopropenyl, (meth)acryloyl (acryloyl, methacryloyl), etc. Among them, methyl (meth)acrylate is preferred.

[0108] The number of the above-mentioned unsaturated bonds in the above-mentioned active energy ray-curable compound is 1 or more, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1.

[0109] The above-mentioned active energy ray-curable compound may also have a cationic polymerizable functional group in the molecule. In this case, the above-mentioned active energy ray-curable compound is reactive with the above-mentioned cationic polymerizable silsesquioxane, and a non-hard coating film with higher mechanical strength and surface hardness can be obtained. As the above-mentioned cationic polymerizable functional

[0110] group that the above-mentioned active energy ray-curable compound can have, the groups exemplified and described as the cationic polymerizable

[0111] functional groups of the above-mentioned cationic polymerizable silsesquioxane can be cited, and among them, an epoxy group is preferred.

[0112] The number of the above-mentioned cationic polymerizable functional groups in the above-mentioned active energy ray-curable compound

[0113] is 1 or more, preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

[0114] The functional group equivalent of the active energy ray-polymerizable functional group of the above-mentioned active energy ray-curable compound is not particularly limited, and is preferably 50 to 500, more preferably 80 to 480, and still more preferably

[0115] 120 to 450. If the above-mentioned functional group equivalent is 50 or more, the bending resistance of the non-hard coating film is more

[0116] excellent. If the above-mentioned functional group equivalent is 500 or less, the surface hardness of the non-hard coating film is further increased.

[0117] It should be noted that the above-mentioned functional group equivalent can be calculated by the following formula.

[0118] [Functional group equivalent of active energy ray-polymerizable functional group] = [Molecular weight of the above-mentioned active energy ray-curable compound] / [Number of active energy ray-polymerizable functional groups possessed by the above-mentioned active energy ray-curable compound]

[0119] [Functional group equivalent of active energy ray-polymerizable functional group] = [Molecular weight of the above-mentioned active energy ray-curable compound] / [Number of active energy ray-polymerizable functional groups possessed by the above-mentioned active energy ray-curable compound]

[0120] The functional group equivalent of the cationic polymerizable functional group of the above-mentioned active energy ray-curable compound

[0121] is not particularly limited, and is preferably 50 to 500, more preferably 80 to 480, and still more preferably 120 to

[0122] 450. When the functional group equivalent is 50 or more, the bending resistance of the non-hard coating film is more excellent. If

[0123] the functional group equivalent is 500 or less, the surface hardness of the non-hard coating film further increases. It should be noted

[0124] that the above functional group equivalent can be calculated by the following formula.

[0125] [Functional group equivalent of cationic polymerizable functional group] = [Molecular weight of the above active energy ray curable compound]

[0126] / [Number of cationic polymerizable functional groups possessed by the above active energy ray curable compound]

[0127] The above active energy ray curable compound preferably has a polyether skeleton such as a polyethylene glycol skeleton, a polypropylene glycol

[0128] skeleton, or a polyglycerol skeleton.

[0129] As the above active energy ray curable compound, specifically, for example, it can be exemplified: 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, dipropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting two epoxy groups of (meth)acrylic acid with dipropylene glycol diglycidyl ether), dipropylene glycol diglycidyl ether semi-(meth)acrylate

[0130]

[0131]

[0132]

[0133] ​​​Esters (compounds obtained by reacting (meth)acrylic acid with one epoxy group of tripropylene glycol diglycidyl ether), bisphenol A epoxy di(meth)acrylate (compounds obtained by reacting (meth)acrylic acid with two epoxy groups of bisphenol A diglycidyl ether), bisphenol A epoxy semi(meth)acrylate (compounds obtained by reacting (meth)acrylic acid or its derivatives with one epoxy group of bisphenol A diglycidyl ether), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy semi(meth)acrylate, bisphenol S epoxy di(meth)acrylate, bisphenol S epoxy semi(meth)acrylate, etc., compounds having an epoxy group and / or a hydroxyl group and a (meth)acryloyl group in one molecule; 3-oxetanylmethyl (meth)acrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 3-butyl-3-oxetanylmethyl (meth)acrylate, 3-hexyl-3-oxetanylmethyl (meth)acrylate, etc., compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 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-dimethylethyl 2-vinyloxyethyl ester, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxycyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenyl (meth)acrylate, m-vinyloxymethylphenyl (meth)acrylate, o-vinyloxymethylphenyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)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-(vinyloxyisopropoxyethoxy)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-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate and other compounds having a vinyl ether group and a (meth)acryloyl group in one molecule, etc.,

[0134] From the viewpoints of the flexibility resistance and surface hardness of the non-hard coating film, as the above-mentioned active energy ray curable compound, a compound having an epoxy group and / or a hydroxyl group as a cationic polymerizable functional group and a (meth)acryloyl group as an active energy ray polymerizable functional group in one molecule is preferred. Specifically, methyl 3,4-epoxycyclohexyl (meth)acrylate, glycidyl (meth)acrylate, dipropylene glycol diglycidyl ether mono(meth)acrylate, bisphenol A epoxy mono(meth)acrylate, bisphenol F epoxy mono(meth)acrylate, bisphenol S epoxy mono(meth)acrylate, etc. are preferred.

[0135] The above-mentioned active energy ray curable compound can be produced by a known method. For example, it can be obtained by a method of reacting a part of the cationic polymerizable functional groups of a compound having two or more cationic polymerizable functional groups (e.g., epoxy group, hydroxyl group) in one molecule with a carboxylic acid (e.g., acrylic acid, methacrylic acid, etc.) or its derivative having an active energy ray polymerizable functional group. In addition, as the above-mentioned compound A, commercially available products such as the trade names "LIGHTESTER G", "EPOXYESTER 200PA", "EPOXYESTER 200PA-E5" (manufactured by Kyoeisha Chemical Co., Ltd.), and the trade name "NK OLIGO EA1010N" (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.

[0136] The content ratio of the above-mentioned active energy ray curable compound in the above-mentioned curable composition is not particularly limited, and is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and further preferably 0.6 to 3% by mass relative to the total amount (100% by mass) of the curable compound. When the content ratio is within the above range, there is a tendency for the dispersibility of the radical curable polyorganosiloxane to be further improved.

[0137] The content of the above-mentioned active energy ray curable compound is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and further preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the above-mentioned cationic polymerizable sesquisiloxane. When the content is within the above range,

[0138] there is a tendency for the dispersibility of the radical curable polyorganosiloxane to be further improved.

[0139] The above-mentioned curable compound preferably contains an aliphatic compound having a cationic polymerizable functional group (cationic curable aliphatic compound). In this case, the non-hard coating film can be imparted with softness.

[0140]

[0141] Properties, further improving flexibility and flex resistance. It should be noted that the above cation-curable aliphatic

[0142] compounds are compounds that do not belong to the above cation-polymerizable sesquisiloxanes and the above active energy ray-curable compounds.

[0143] As the above cation-polymerizable functional group of the above cation-curable aliphatic compound, groups exemplified and described as the cation-polymerizable functional groups of the above cation-polymerizable sesquisiloxanes can be cited, among which an epoxy group is preferred, and a glycerol group is more preferred from the viewpoint of reactivity.

[0144] Considering, a glycerol group is more preferred.

[0145] The number of cation-polymerizable functional groups in one molecule of the above cation-curable aliphatic compound is preferably 2 or more, more preferably 2 to 5, further preferably 2 to 3, and particularly preferably 2.

[0146] The functional group equivalent of the cation-polymerizable functional group of the above cation-curable aliphatic compound is not particularly limited, and is preferably 50 to 500, more preferably 80 to 480, and further preferably 120 to

[0147] 450. If the above functional group equivalent is 50 or more, the flex resistance of the non-hard coating film is more excellent. If the above

[0148] functional group equivalent is 500 or less, the surface hardness of the non-hard coating film is further increased. It should be noted that the above functional group equivalent can be calculated by the following formula.

[0149] 450. If the above functional group equivalent is 50 or more, the flex resistance of the non-hard coating film is more excellent. If the above

[0150] functional group equivalent is 500 or less, the surface hardness of the non-hard coating film is further increased. It should be noted that the above functional group equivalent can be calculated by the following formula.

[0151] [Functional group equivalent of cation-polymerizable functional group] = [Molecular weight of the above cation-curable aliphatic compound]

[0152] / [Number of cation-polymerizable functional groups possessed by the above cation-curable aliphatic compound]

[0153] The "aliphatic compound" in the above cation-curable aliphatic compound refers to an aliphatic compound that does not have a cyclic structure other than the above cation-polymerizable functional group. As the above cation-curable aliphatic compound, for example, glycidyl ethers of dihydric or higher alcohols without a cyclic structure; glycidyl esters of dicarboxylic acids [such as adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] can be cited. As the above dihydric or higher alcohols without a cyclic structure, for example,

[0154] can be cited.

[0155] Examples include: ethylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,4 - butanediol, neopentyl glycol, 1,6 -

[0156] hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and other diols; glycerol, diglycerol, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and other polyols with three or more hydroxyl groups. In addition, the polyols with two or more hydroxyl groups can be polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, etc.

[0157] As the above - mentioned cation - curable aliphatic compound, a compound having two cation - polymerizable functional groups at both ends of the above - mentioned aliphatic compound is preferably used. Specifically, a compound represented by the following formula (A) is preferably used.

[0158] [Chemical formula 7]

[0159] E 1 -O-M-O-E 2 (A)

[0160] 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: ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene and other linear or branched alkylene groups having 2 to 10 carbon atoms. Among them, from the viewpoints of improving the surface hardness, flexibility, flexural resistance of the non - hard coating film and the stain - proof performance not being easily reduced, 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 further preferably a linear alkylene group having 6 carbon atoms (hexamethylene).

[0161] In the above formula (A), E 1 and E 2 which are the same or different, represent cation - polymerizable functional groups. From the viewpoints of reactivity, improving the surface hardness, flexibility, flexural resistance of the non - hard coating film and the stain - proof performance not being easily reduced, a group represented by the following formula (E) is preferably used.

[0162]

[0163] 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: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc. Among them, as R A, from the viewpoints of improving reactivity, surface hardness, flexibility, and flexural resistance of the non-hard coating film and making it less likely to reduce the antifouling performance, a linear alkylene group having 1 to 4 carbon atoms is preferred, a methylene group or an ethylene group is more preferred, and a methylene group is further preferred. R 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, and more preferably a hydrogen atom.

[0164] Specific examples of the cation-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, 2-methyl-2,4-pentanediol 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, 1,9-nonanediol diglycidyl ether, etc., alkylene glycol diglycidyl ethers (alkanediol diglycidyl ethers) such as diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, etc., (poly)alkylene glycol diglycidyl ethers. Among them, from the viewpoints of improving reactivity, surface hardness, flexibility, and flexural resistance of the non-hard coating film and making it less likely to reduce the antifouling performance, 1,6-hexanediol diglycidyl ether is preferred.

[0165] Examples of commercially available products of the cation-curable aliphatic compound include the product names "EPOLIGHT40E", "EPOLIGHT 100E", "EPOLIGHT 200E", "EPOLIGHT 400E", "EPOLIGHT 1600", "EPOLIGHT 1600N" (manufactured by Kyoeisha Chemical Co., Ltd.), the product name "YH-300" (manufactured by NIPPON STEEL Chemical&Material Co., Ltd.), etc.

[0166] The content ratio of the above-mentioned cation-curable aliphatic compound in the above-mentioned curable composition is not particularly limited, and is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 12% by mass, relative to the total amount (100% by mass) of the curable compounds. If the above content ratio is within the above range, the flexibility and bending resistance of the non-hard coating film are more appropriate.

[0167] The content of the above-mentioned cation-curable aliphatic compound is not particularly limited, and is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, still 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 above-mentioned cation-polymerizable silsesquioxane. If the above content is within the above range, the flexibility and bending resistance of the non-hard coating film are more appropriate.

[0168] The above-mentioned curable composition preferably contains a radical-curable polyorganosiloxane. By using the above-mentioned radical-curable polyorganosiloxane, the smoothness of the surface of the non-hard coating film is improved, the sebum resistance is excellent, and fingerprints are not easily attached to the surface of the non-hard coating film. In addition, the above-mentioned energy ray-curable polyorganosiloxane preferably does not belong to PFAS restricted substances. In this case, although it does not belong to PFAS restricted substances, it exhibits the above effects. Since the above-mentioned radical-curable polyorganosiloxane has radical curability, it also belongs to the above-mentioned curable compounds. The above-mentioned radical-curable polyorganosiloxane may be used alone or in combination of two or more.

[0169] The above-mentioned radical-curable polyorganosiloxane has a radical-polymerizable functional group in the molecule. Examples of the above-mentioned radical-curable functional group include a photo-radical-polymerizable functional group.

[0170] Examples of the above-mentioned photo-radical-polymerizable functional group include: (meth)acryloyl, (meth)acrylamide group, vinyl, vinylthio group, etc. Among them, (meth)acryloyl is preferred.

[0171] As the polyorganosiloxane in the above-mentioned radical-curable polyorganosiloxane, linear polyorganosiloxane is preferred from the viewpoint of further exerting the effect as a leveling agent.

[0172] The content ratio of the above-mentioned radical-curable polyorganosiloxane in the above-mentioned curable composition is not particularly limited, and is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and still more preferably 0.04 to 1% by mass, relative to the total amount (100% by mass) of the curable compounds. If the above content ratio is within the above range, the sebum resistance of the surface of the non-hard coating film is more excellent.

[0173] The content of the above-mentioned free-radical curable polyorganosiloxane is not particularly limited, and is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and further preferably 0.04 to 1 part by mass with respect to 100 parts by mass of the above-mentioned cationically polymerizable silsesquioxane. If the above content is within the above range, the sebum adhesion resistance of the non-hard coating film surface is more excellent.

[0174] The content ratio of the above-mentioned curable compound in the above-mentioned curable composition is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 97% by mass or more with respect to the total amount of non-volatile components (total amount excluding solvents) in the above-mentioned curable composition. If the above content ratio is 90% by mass or more, the mechanical strength of the non-hard coating film is more excellent. It should be noted that in this specification, the ratio of each component in the curable composition to the total amount of non-volatile components is equivalent to the ratio of the component from the component in the above-mentioned non-hard coating film.

[0175] The above-mentioned curable composition preferably contains a curing catalyst. The above-mentioned curing catalyst is a compound that can initiate or promote the polymerization reaction of curable compounds such as the above-mentioned cationically polymerizable silsesquioxane, the above-mentioned active energy ray curable compound, and the above-mentioned cationically polymerizable aliphatic compound. The above-mentioned curing catalyst can be used alone or in combination of two or more.

[0176] As the above-mentioned curing catalyst, it can be selected according to the type of curable functional group possessed by the above-mentioned curable compound. Among them, a cationic polymerization initiator and / or a radical polymerization initiator are preferred. The above-mentioned cationic polymerization initiator is a compound that generates cationic species by heat or active energy ray irradiation and initiates the curing reaction of the curable compound.

[0177] Examples of the above-mentioned cationic polymerization initiator include photo cationic polymerization initiators (photo acid generators) and thermal cationic polymerization initiators (thermal acid generators).

[0178] As the above-mentioned photo cationic polymerization initiator, known or commonly used photo cationic polymerization initiators can be used. For example, sulfonium salts (salts formed by sulfonium ions and anions), iodonium salts (salts formed by iodonium ions and anions), selenonium salts (salts formed by selenonium ions and anions), ammonium salts (salts formed by ammonium ions and anions), phosphonium salts (salts formed by phosphonium ions and anions), salts formed by transition metal complex ions and anions, etc. can be cited.

[0179] Examples of the above-mentioned sulfonium salts include: triarylsulfonium salts such as triphenylsulfonium salt, tris(p-tolyl)sulfonium salt, tris(o-tolyl)sulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tris-1-naphthylsulfonium salt, tris-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, 4-(p-tolylthio)phenylbis(p-phenyl)sulfonium salt; diarylsulfonium salts such as diphenylbenzoylmethylsulfonium salt, diphenyl 4-nitrobenzoylmethylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; dialkylsulfonium salts such as dimethylbenzoylmethylsulfonium salt, benzoylmethyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0180] Examples of the above-mentioned diphenyl[4-(phenylthio)phenyl]sulfonium salt include diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, etc. In addition, commercially available products such as the trade name "CPI-100P" (manufactured by SAN-APRO Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate) can also be used.

[0181] Examples of the above-mentioned iodonium salts include: the trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Ltd., [(1-methylethyl)phenyl](methylphenyl)iodonium tetrakis(pentafluorophenyl)borate), the trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, etc.

[0182] Examples of the above-mentioned selenonium salts include: triarylselenonium salts such as triphenylselenonium salt, tris(p-tolyl)selenonium salt, tris(o-tolyl)selenonium salt, tris(4-methoxyphenyl)selenonium salt, 1-naphthyldiphenylselenium salt; diarylselenonium salts such as diphenylbenzoylmethylselenonium salt, diphenylbenzylselenonium salt, diphenylmethylselenonium salt; monoarylselenonium salts such as phenylmethylbenzylselenonium salt; trialkylselenonium salts such as dimethylbenzoylmethylselenium salt, etc.

[0183] Examples of the above ammonium salts include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt; pyrrolonium salts such as N,N-dimethylpyrrolonium salt, N-ethyl-N-methylpyrrolonium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt; tetrahydropyrimidinium salts such as N,N'-dimethyltetrahydropyrimidinium salt, N,N'-diethyltetrahydropyrimidinium salt; morpholinium salts such as N,N-dimethylmorpholinium salt, N,N-diethylmorpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt, N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt, N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolinium salts such as N-methylquinolinium salt; isoquinolinium salts such as N-methylisoquinolinium salt; thiazolium salts such as benzylbenzothiazolium salt; acridinium salts such as benzylacridinium salt, etc.

[0184] Examples of the above phosphonium salts include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetrakis(p-tolyl)phosphonium salt, tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylbenzoylmethylphosphonium salt, etc.

[0185] Examples of the above transition metal complex ion salts include salts of chromium complex cations such as (η 5 -cyclopentadienyl)(η 6 -toluene)Cr + , (η 5 -cyclopentadienyl)(η[[ID=

[15] ] 6 -xylene)Cr + ; salts of iron complex cations such as (η 5 -cyclopentadienyl)(η 6 -toluene)Fe + , (η 5 -cyclopentadienyl)(η 6 -xylene)Fe + ), etc.

[0186] Examples of the anions constituting the above salts include PF6 - , BF4 - , (C6F5)4B - , (C6F5)4Ga -, sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), perhalate anions, halosulfonate anions, sulfate anions, carbonate anions, aluminate anions, carboxylate anions, arylborate anions, thiocyanate anions, nitrate anions, etc.

[0187] Examples of the above thermal cationic polymerization initiators include arylsulfonium salts, aryl iodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc. In addition, as the anions constituting the above salts, the same anions as those in the photo cationic polymerization initiators can be mentioned.

[0188] Examples of the above arylsulfonium salts include pentafluorophenyl borate, hexafluorophosphate, etc. In the curable composition of the present invention, for example, commercially available products such as the trade names "SP-66", "SP-77" (manufactured by ADEKA Corporation); 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", "San-Aid SI-B2A" (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the above aluminum chelates include ethyl acetoacetate aluminum diisopropyl, tris(ethylacetoacetato)aluminum, etc. In addition, examples of the above boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, etc.

[0189] The above radical polymerization initiator is a compound that generates radicals by heat or irradiation with active energy rays to initiate the curing reaction of the curable compound.

[0190] Examples of the above radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators. Examples of the above photo radical polymerization initiators include alkyl phenyl ketone-based photo radical polymerization initiators, acylphosphine oxide-based photo radical polymerization initiators, oxime ester-based photo radical polymerization initiators, α-hydroxy ketone-based photo radical polymerization initiators, etc.

[0191] As the above-mentioned alkylbenzene-based photo-free radical polymerization initiators, for example, the following can be cited: 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-morpholino)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphonate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, etc.

[0192] As the above-mentioned acylphosphine oxide-based photo-free radical polymerization initiators, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc. can be cited.

[0193] As the above-mentioned oxime ester-based photo-free radical polymerization initiators, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyl oxime, etc. can be cited.

[0194] As the above-mentioned α-hydroxy ketone-based photo-free radical polymerization initiators, for example, the following can be cited: benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, etc.

[0195] The content (blending amount) of the above-mentioned curing catalyst in the above-mentioned curable composition is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass, still more preferably 0.3 to 2.7 parts by mass, and particularly preferably 0.5 to 2.5 parts by mass, based on 100 parts by mass of the total amount of the curable compound. When the content of the curing catalyst is 0.01 part by mass or more, the curing reaction can proceed efficiently and sufficiently, and there is a tendency for the surface hardness of the cured product to be further improved. On the other hand, by setting the content of the curing catalyst to 10 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved or the coloring of the cured product to be suppressed.

[0196] The content (blending amount) of the above-mentioned cationic polymerization initiator in the above-mentioned curable composition is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass, based on 100 parts by mass of the total amount of the curable compound. When the above content is 0.01 part by mass or more, the curing reaction can proceed efficiently and sufficiently, and there is a tendency for the surface hardness of the cured product to be further improved. When the above content is 10 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved or the coloring of the cured product to be suppressed.

[0197] The content (blending amount) of the above-mentioned radical polymerization initiator in the above-mentioned curable composition is not particularly limited, and is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, still more preferably 0.05 to 2 parts by mass, and particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total amount of the curable compound. When the above content is 0.005 part by mass or more, the curing reaction can proceed efficiently and sufficiently, and there is a tendency for the surface hardness of the cured product to be further improved. When the above content is 5 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved or the coloring of the cured product to be suppressed.

[0198] The above-mentioned curable composition may further contain other components in addition to the above-mentioned respective components. The above-mentioned curable composition may further contain the following conventional additives as other optional components: 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, boron nitride, etc.; 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, copper, etc., curing agents (amine-based curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, etc.), curing aids, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis 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 passivators, etc.), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (fluidity improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (antifoaming agents, etc.), surface modifiers (slip agents, etc.), matting agents, defoaming agents, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, surfactants, etc. The above-mentioned other components may be used alone or in combination of two or more. The content (mixing amount) of the above-mentioned other components is not particularly limited, and is preferably 100 parts by mass or less, more preferably 30 parts by mass or less (for example, 0.01 to 30 parts by mass), and further preferably 10 parts by mass or less (for example, 0.1 to 10 parts by mass) relative to 100 parts by mass of the total amount of the curable compound.

[0199] As the above-mentioned organic solvent, known or conventional organic solvents can be cited. For example, 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.), acetate cellosolves, amides (dimethylformamide, dimethylacetamide, etc.), etc. can be cited.

[0200] The above-mentioned curable composition is not particularly limited and can be prepared by stirring / mixing the above-mentioned various components at room temperature or while heating as needed.

[0201] (Cured product, non-hard coating film)

[0202] The above curable composition can be cured to obtain the above cured product (non-hard coating film). The surface pencil hardness of the above non-hard coating film is not particularly limited, and is preferably H or more (for example, H to 9H), more preferably 2H or more, further preferably 3H or more, further preferably 4H or more, further preferably 5H or more, further preferably 6H or more, further preferably 7H or more, further preferably 8H or more, and particularly preferably 9H. It should be noted that the pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0203] For the purpose of improving the adhesion to other layers, etc., roughening treatment, easy adhesion treatment, antistatic treatment, sandblasting treatment (sand mat treatment), discharge treatment (such as corona discharge treatment, glow discharge treatment, etc.), plasma treatment, chemical etching treatment, water mat treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, etc., which are well-known or commonly used surface treatments, can be performed on a part or all of the surface of the above non-hard coating film.

[0204] The above non-hard coating film is obtained as follows: The above curable composition is coated on the release-treated surface of a temporary substrate such as a separator, the solvent is removed by drying as needed, and then the curable compound in the above curable composition is subjected to a polymerization reaction, whereby the above curable composition is cured to obtain a cured product, and then the cured product is peeled off from the temporary substrate.

[0205] As the coating method of the above curable composition, a well-known or commonly used coating method can be used. As the coating device, for example, roll coater, air knife coater, knife coater, bar coater, reverse coater, rod coater, comma coater, dip / squeeze coater, die coater, gravure coater, microgravure coater, screen coater method, spray coater, etc. can be cited. In addition, as the coating method, in addition to the method using a coating device, dipping method (dip coating), spin coating method, etc. can also be cited. Among them, it is suitable to perform coating (spraying) with a spray coater.

[0206] The curing method can be appropriately selected from known methods without particular limitation, and is appropriately selected according to the type of curable functional groups possessed by the curable compound. For example, irradiation with active energy rays and heating methods can be cited. As the above-mentioned active energy rays, for example, any one of infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α-rays, β-rays, γ-rays, etc. can be used. Among them, from the viewpoint of excellent operability, ultraviolet rays are preferred. The irradiation of the above-mentioned active energy rays (especially electron beams) is preferably carried out in an inert gas atmosphere such as a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere.

[0207] When removing the above-mentioned solvent after coating the above-mentioned curable composition, heating can be carried out. The temperature for removing the above-mentioned solvent is not particularly limited, and is preferably 40 to 200 °C, more preferably 50 to 170 °C, further preferably 60 to 150 °C, and particularly preferably 80 to 140 °C. In addition, the time for maintaining at the above temperature is not particularly limited, and is preferably about 30 seconds to 5 hours.

[0208] The conditions (such as the irradiation conditions of active energy rays) for curing the above-mentioned curable composition by irradiating active energy rays can be appropriately adjusted according to the type, energy of the irradiated active energy rays, the shape, size, etc. of the above-mentioned non-hard coating film, and there is no particular limitation. In the case of irradiating ultraviolet rays, it is preferably set, for example, to 1 to 10000 mJ / cm 2 (preferably 50 to 5000 mJ / cm 2 , more preferably 70 to 3000 mJ / cm 2 , further preferably 100 to 1000 mJ / cm 2 ). It should be noted that for the irradiation of active energy rays, for example, deep ultraviolet (Deep UV) lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, carbon arcs, metal halide lamps, sunlight, LED lamps, halogen lamps, lasers (such as helium-cadmium lasers, excimer lasers, etc.) can be used. A heat treatment (annealing, aging) can be further carried out after irradiating the active energy rays to further carry out the curing reaction.

[0209] The irradiation dose when curing by irradiating an electron beam is not particularly limited, and is preferably 1 to 200 kGy, more preferably 5 to 150 kGy, further preferably 10 to 100 kGy, and particularly preferably 20 to 80 kGy. The acceleration voltage is not particularly limited, and is preferably 10 to 1000 kV, more preferably 50 to 500 kV, and further preferably 100 to 300 kV.

[0210] In the above-mentioned aging, the heating temperature is not particularly limited, preferably 30 to 200 °C, more preferably 50 to 190 °C, and further preferably 60 to 180 °C. The heating time is not particularly limited, preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours, and further preferably 45 minutes to 3 hours.

[0211] [Laminated body]

[0212] A laminated body is obtained by laminating other layers on the above-mentioned non-hard coating film. As the above-mentioned other layers, functional layers capable of imparting various functions can be cited. The above-mentioned laminated body includes the above-mentioned non-hard coating film and a functional layer laminated on the above-mentioned non-hard coating film. The above-mentioned other layers may be only one layer or two or more layers.

[0213] As the above-mentioned functional layer, for example, a surface protective film for protecting the surface of the non-hard coating film, a hard coat layer, an antireflection layer, an antiglare layer, a fingerprint-resistant layer, an antifouling layer, a scratch-resistant layer, a fingerprint-resistant rubbing layer, an antibacterial layer, a bonding layer, a polarizing layer, an optical substrate, etc. can be cited. In addition, the above-mentioned functional layer is preferably formed from a thermosetting resin composition or a radiation-curable resin composition, and more preferably formed from a radiation-curable resin composition. Furthermore, it can also be used by laminating on a substrate such as glass.

[0214] In the case of having the above-mentioned surface protective film, there is a tendency for the punching processability and operability of the non-hard coating film to be improved. In such a case where the surface protective film is provided, for example, even if the hardness of the non-hard coating film is very high and it is likely to peel off from the support or crack during punching, the punching process using a Thomson knife can be carried out without such problems.

[0215] As the above-mentioned surface protective film, a publicly known or commonly used surface protective film can be used, and there is no particular limitation. For example, a surface protective film having an adhesive layer on the surface of a plastic film can be used. As the above-mentioned plastic film, for example, those formed 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, polyamide, etc. can be cited. As the above-mentioned adhesive layer, for example, an adhesive layer formed of one or more of publicly known or commonly used adhesives such as acrylic adhesives, natural rubber adhesives, synthetic rubber adhesives, ethylene-vinyl acetate copolymer adhesives, ethylene-(meth)acrylate copolymer adhesives, styrene-isoprene block copolymer adhesives, styrene-butadiene block copolymer adhesives, etc. can be cited. In the above-mentioned adhesive layer, various additives (for example, antistatic agents, slip agents, etc.) can be contained. It should be noted that the plastic film and the adhesive layer can each have a single-layer structure or a multi-layer (laminated) structure. In addition, the thickness of the surface protective film is not particularly limited and can be appropriately selected.

[0216] As the surface protective film, for example, commercially available products such as the "Sanitect" series (manufactured by Sun A Kaken 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.), the "Alphan" series (manufactured by Oji F-Tex Corporation), etc. can be purchased from the market.

[0217] As the above-mentioned laminate, specifically, for example, those having layer structures such as [non-hard coating film / adhesive layer / surface protective film], [non-hard coating film / adhesive layer / antireflection layer], [non-hard coating film / antiglare layer / surface protective film], [non-hard coating film / substrate / adhesive layer], [glass / non-hard coating film / surface protective film], [glass / non-hard coating film / adhesive layer], [non-hard coating film / fingerprint-resistant layer / scratch-resistant fingerprint layer], [non-hard coating film / antifouling layer / surface protective film], [non-hard coating film / antiglare layer / antireflection layer], [non-hard coating film / antireflection layer / fingerprint-resistant layer], [non-hard coating film / adhesive layer / glass], [non-hard coating film / adhesive layer / polarizing layer], [glass / non-hard coating film / polarizing layer], [glass / non-hard coating film / adhesive layer / polarizing layer], [glass / non-hard coating film / antireflection layer] can be cited. In addition, by laminating a plurality of the above-mentioned laminates, a multi-layer laminate is obtained.

[0218] The above-mentioned multilayer laminate and other laminate can be used as constituent materials for various products, their components or parts. Examples of the above products include: various household appliances, various electrical / electronic products, various optical devices, etc. For example, display devices such as liquid crystal displays and organic EL displays can be cited; input devices such as touch panels can be cited; solar cells; portable electronic terminals such as game consoles, personal computers, tablet computers, smart phones, and mobile phones; display devices such as displays in automobiles; lenses of glasses; transparent components such as front headlights of automobiles, cameras of FA, surveillance cameras, etc. used in harsh environments such as outdoors, high temperature and high humidity. The above non-hard coating film is preferably a layer that protects the surface of the product.

[0219] Each aspect disclosed in this specification can also be combined with any other features disclosed in this specification. Each structure and the combination of each structure in each embodiment are examples, and appropriate addition, omission, replacement, and other changes of the structure can be made without departing from the gist of the present disclosure. In addition, each invention of the present disclosure is not limited by the embodiments and the following examples, but only by the patent claims.

[0220] Examples

[0221] Hereinafter, an embodiment of the present disclosure will be described in more detail based on examples. It should be noted that the molecular weight of the product was measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), chromatographic column: Tskgel GMH HR -MX2 (manufactured by TOSOH Corporation), guard column: Tskgelguardcolumn H HR L (manufactured by TOSOH Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 °C, molecular weight: in terms of standard polystyrene. In addition, the ratio [T3 body / T2 body] of the T2 body and the T3 body in the product was measured by using JEOL ECA500 (500 MHz) 29 Si-NMR spectrum measurement. The T d5 (temperature at 5% weight loss) of the product can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a heating rate of 5 °C / minute.

[0222] Example 1

[0223] (Preparation of epoxy group-containing polyorganosilsesquioxane)

[0224] Under a nitrogen stream, 161.5 mmol (39.79 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 9 mmol (1.69 g) of phenyltrimethoxysilane, and 165.9 g of acetone were charged into a 300 mL flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube, and the temperature was raised to 50 °C. To the mixture thus obtained, 4.70 g of a 5% aqueous potassium carbonate solution (1.7 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 minutes. It should be noted that no significant temperature rise occurred during the addition. Thereafter, the temperature was maintained at 50 °C, and a polycondensation reaction was carried out for 4 hours under a nitrogen stream.

[0225] The product in the reaction solution after the polycondensation reaction was analyzed. As a result, the number-average molecular weight was 1911, and the molecular weight dispersity was 1.47. The ratio of the T2 body to the T3 body [T3 body / T2 body] calculated from the 29 Si-NMR spectrum of the above product was 10.3.

[0226] Thereafter, the reaction solution was cooled, washed with water until the lower layer became neutral, the upper layer was separated, and then the solvent was distilled off from the upper layer under the conditions of 1 mmHg and 40 °C to obtain a colorless transparent liquid product (epoxy group-containing silsesquioxane, solid content 77% by mass). The T d5 of the above product was 370 °C.

[0227] (Preparation of curable composition 1)

[0228] As the curable compound 1, it can be prepared as follows: 66.8 parts by mass (active ingredient 77%) of the epoxy group-containing silsesquioxane obtained above, 1.5 parts by mass of "EPOXYESTER 200PA-E5" (a compound having an acryloyl group, an epoxy group, and a polyglycerol 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 polyorganosiloxane containing a free-radical curable functional group (trade name "MEGAFAC RS-57", active ingredient 20%, not subject to PFAS restrictions, manufactured by DIC Corporation, active ingredient 20%) are mixed with 0.5 parts by mass of a photo cationic polymerization initiator (a salt of triarylsulfonium and tetrakis(pentafluorophenyl)gallium) as a curing catalyst, 0.2 parts by mass of a photo radical polymerization initiator (trade name "Omnirad127", manufactured by IGM Resins), 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) as a solvent, and 15.8 parts by mass of methyl ethyl ketone (MEK) to prepare a curable composition. It should be noted that the content ratios shown in Table 1 are the compounding ratios of the respective components. The silsesquioxane and RS-57 are values of the solutions, and the other components are values of the active ingredients.

[0229] (Fabrication of non-hard coating film)

[0230] Using a hand-held spray gun (manufactured by Anest-iwata Corporation), the above curable composition 1 was sprayed onto the demolding surface of the diaphragm placed on a Teflon (registered trademark) frame. Then, drying (80 °C, 2 hours) and UV irradiation (300 mJ / cm 2 ) were carried out. After that, the Teflon (registered trademark) frame was removed, and aging was performed at 120 °C for 1 hour to cure it, obtaining a cured product (non-hard coating film) with a thickness of about 0.150 mm.

[0231] Example 2

[0232] (Preparation of curable composition 2)

[0233] Except for changing the content ratios of the respective components as shown in Table 1, the curable composition 2 was prepared in the same manner as the curable composition 1. "EPOLIGHT 400E" shown in Table 1 is the trade name "EPOLIGHT 400E" (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol #400 diglycidyl ether).

[0234] (Fabrication of non-hard coating film)

[0235] In addition to using the above-mentioned curable composition 2, a cured product (thickness: approximately 0.150 mm) (non-hard coating film) of Example 2 was produced in the same manner as in Example 1.

[0236] Example 3

[0237] (Preparation of curable composition 3)

[0238] Except for changing the content ratios of the respective components as shown in Table 1, curable composition 3 was prepared in the same manner as curable composition 1.

[0239] (Production of non-hard coating film)

[0240] In addition to using the above-mentioned curable composition 3, a cured product (thickness: approximately 0.150 mm) (non-hard coating film) of Example 3 was produced in the same manner as in Example 1.

[0241] The cured products (non-hard coating films) obtained in Examples 1 to 3 were evaluated as follows. The results are shown in Table 1.

[0242] (1) Surface hardness (pencil hardness)

[0243] The pencil hardness of the surface of the non-hard coating film obtained above was evaluated according to JIS K5600-5-4.

[0244] (2) Tensile test

[0245] The non-hard coating film obtained above was punched into the shape of a No. 7 dumbbell (JIS K6251) to prepare a test piece. Using a TENSILON universal material testing machine (trade name “RTF-1350”, manufactured by A&D Company, Limited), according to JIS K7161 (1994), a test was conducted at a tensile speed of 2 mm / minute, a distance between chucks of 20 mm, and a distance between gauge marks of 12 mm. A tensile test was performed on n = 8, and the average value of the Young's modulus obtained after removing the two points of the upper and lower limits from the obtained Young's modulus was used as the evaluation result of the Young's modulus.

[0246] (3) Indentation test

[0247] For the non-hard coating film obtained above, using a nanoindentation instrument (trade name “ENT-2100”, manufactured by Elionix Corporation), as a Berkovich indenter, ten points were measured in such a way that the maximum load was 500 μN, and the average values of the indentation hardness and Young's modulus were measured.

[0248] (4) Glass transition temperature, melting point

[0249] For the cured product obtained above, DSC measurement was carried out using a differential scanning calorimeter (trade name "DSC-6220", manufactured by Hitachi High-Tech Corporation) in the temperature range from room temperature to 300 °C. As a result, for any of Examples 1 to 3, no displacement of the baseline from the glass transition temperature and no peak from the melting point were observed in the range below 300 °C.

[0250] [Table 1]

[0251] (Table 1)

[0252]

[0253] As shown in the evaluation results of Table 1, the non-hard coating film of Example 1 was judged to have an appropriate Young's modulus in the tensile test, a sufficient elastic-plastic ratio in the indentation test, and a sufficiently high Young's modulus in the indentation test, and excellent mechanical strength even without using PFAS-restricted substances. In addition, the non-hard coating film of Example 1 is not made of glass but of resin and is lightweight compared to glass. Furthermore, no glass transition temperature and melting point were confirmed below 300 °C, and it was judged to have excellent heat resistance.

[0254] Hereinafter, modifications of the invention of the present disclosure will be described.

[0255] [Supplementary Note 1] A non-hard coating film that satisfies an elastic-plastic ratio in the indentation test of 70% or more, and the glass transition temperature and melting point are not below 200 °C, and satisfies at least one of a Young's modulus in the indentation test of 1000 MPa or more and a Young's modulus in the tensile test of 1000 to 5000 MPa.

[0256] [Supplementary Note 2] The non-hard coating film according to Supplementary Note 1, wherein the thickness is 1 to 1000 μm and the indentation hardness of the indentation test is 100 MPa or more.

[0257] [Supplementary Note 3] The non-hard coating film according to Supplementary Note 1 or 2, wherein the non-hard coating film is formed from a cured product of a curable composition, and the glass transition temperature of the cured product is 300 °C or more.

[0258] [Supplementary Note 4] The non-hard coating film according to any one of Supplementary Notes 1 to 3, wherein the non-hard coating film is formed from a cured product of a curable composition, and the pencil hardness of the cured product is 2H or more.

[0259] [Supplementary Note 5] The non-hard coating film according to Supplementary Note 3 or 4, wherein the curable composition contains a free-radical curable polyorganosiloxane.

[0260] [Supplementary Note 6] The non-hard coating film according to any one of Supplementary Notes 3 to 5, wherein the curable composition contains a cationically polymerizable silsesquioxane.

[0261] [Supplementary Note 7] The non-hard coating film according to any one of Supplementary Notes 3 to 6, wherein the curable composition further contains a curable compound having an energy ray-polymerizable functional group.

[0262] [Supplementary Note 8] A laminate including the non-hard coating film according to any one of Supplementary Notes 1 to 7 and a functional layer laminated on the non-hard coating film.

[0263] [Supplementary Note 9] A multi-layer laminate formed by laminating a plurality of the laminates according to Supplementary Note 8.

[0264] [Supplementary Note 10] A display device including the multi-layer laminate according to Supplementary Note 9.

Claims

1. A non-hard coating film that satisfies an elastic-plastic ratio of 70% or more in an indentation test and a glass transition temperature and a melting point not below 200 °C, and satisfies at least one of a Young's modulus of 1000 MPa or more in the indentation test and a Young's modulus of 1000 to 5000 MPa in a tensile test.

2. The non-hard coating film according to claim 1, wherein, The thickness is 1 to 1000 μm, and the indentation hardness in the indentation test is 100 MPa or more.

3. The non-hard coating film according to claim 1 or 2, wherein The non-hard coating film is formed of a cured product of a curable composition, and the glass transition temperature of the cured product is 300 °C or more.

4. The non-hard coating film according to claim 1 or 2, wherein, The non-hard coating film is formed of a cured product of a curable composition, and the pencil hardness of the cured product is 2H or more.

5. The non-hard coating film according to claim 3, wherein, The curable composition contains a free-radical curable polyorganosiloxane.

6. The non-hard coating film according to claim 3, wherein The curable composition contains a cationically polymerizable silsesquioxane.

7. The non-hard coating film according to claim 6, wherein The curable composition further contains a curable compound having an energy ray-polymerizable functional group.

8. A laminate that includes the non-hard coating film according to claim 1 or 2 and a functional layer laminated on the non-hard coating film.

9. A multi-layer laminate formed by laminating a plurality of the laminates according to claim 8.

10. A display device that includes the multi-layer laminate according to claim 9.

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