Curable resin composition, coating laminate, plastic lens, and image display device

Abstract

The purpose of the present invention is to provide a curable resin composition which can be applied in a single layer, has sufficient adhesion to a cycloolefin copolymer base material, and has excellent moisture resistance. [Solution] A curable resin composition according to the present disclosure is a curable resin composition for coating a cycloolefin copolymer substrate, the curable resin composition being characterized by containing an alicyclic ketone compound and / or an alicyclic ether compound, and a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane. Furthermore, it is preferable that the viscosity of the curable resin composition according to the present disclosure is 15 mPa * s or less at 25 DEG C.

Description

Technical Field

[0001] The present disclosure relates to a curable resin composition, a coating, a laminate, a plastic lens, and an image display device. Background Art

[0002] In recent years, with the development of mobile devices such as smartphones and tablet computers, resin substrates have been used. It is known that resin substrates are lightweight and have excellent processability. On the other hand, compared with inorganic materials such as glass, they have low chemical resistance and damage optical properties due to whitening and surface roughness. In addition, the surface hardness of resin substrates is low, and there is a tendency for them to be easily damaged and for their transparency to be easily reduced. Therefore, when using such resin substrates, a coating liquid for protecting the resin substrate and a method of coating the substrate surface are generally known.

[0003] In particular, cycloolefin-based polymers have excellent characteristics such as high transparency, low photoelasticity, good dielectric properties, high softening temperature, low water absorption, and high water vapor barrier properties. However, it is known that cycloolefin-based polymers have high resistance to acids, alkalis, and polar solvents, and have problems such as poor adhesion even when coated with a coating liquid and difficulty in laminating coating films.

[0004] As a technique related to coating on a resin substrate containing a cycloolefin-based polymer, the invention of a photocurable resin composition using an acrylic resin is disclosed in Patent Document 1. In addition, the invention of using an ultraviolet curable resin containing inorganic fine particles as an easy-bonding layer is disclosed in Patent Document 2.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2016-196653

[0008] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2023-92527 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] However, in the invention described in Patent Document 1, it is necessary to use an acrylic resin, and in order to perform sufficient curing, polymerization needs to be carried out in a nitrogen atmosphere, so there are problems in terms of operability. In addition, the cycloolefin-based copolymer has high chemical resistance, and there is also a problem that sufficient adhesion is difficult to obtain.

[0011] In the invention described in Patent Document 2, it is necessary to laminate another layer as an adhesive layer between the substrate and the coating. In the case of laminating multiple layers in this way, there are problems such as a decrease in film thickness uniformity and easy damage to optical properties.

[0012] In addition, the coating itself is also required to have moisture resistance as excellent as that of the norbornene copolymer substrate.

[0013] Therefore, an object of the present disclosure is to provide a curable resin composition that can be applied in a single layer, has sufficient adhesion to a norbornene copolymer substrate, and has excellent moisture resistance.

[0014] Technical Solution

[0015] In order to solve the above problems, the present inventors conducted in-depth research and found that as long as it is a curable resin composition containing an alicyclic ketone compound and / or an alicyclic ether compound and a cationically polymerizable sesquisiloxane and / or a cationically polymerizable cyclic siloxane, it can be applied in a single layer, has sufficient adhesion to a norbornene copolymer substrate, and has excellent moisture resistance. The present disclosure was completed based on these insights.

[0016] That is, the present disclosure provides a curable resin composition for coating a norbornene copolymer substrate, which contains an alicyclic ketone compound and / or an alicyclic ether compound and a cationically polymerizable sesquisiloxane and / or a cationically polymerizable cyclic siloxane.

[0017] Preferably, the viscosity of the above curable resin composition at 25 °C is 15 mPa·s or less. By having the viscosity within the above range, it is easy to achieve uniform film thickness.

[0018] Preferably, the alicyclic ketone compound in the above curable resin composition is cyclohexanone or cyclopentanone, and the alicyclic ether compound is cyclopentyl methyl ether.

[0019] Preferably, the cationically polymerizable functional group of the cationically polymerizable sesquisiloxane in the above curable resin composition has a cyclic ether structure.

[0020] In addition, the present disclosure provides a coating as a cured product of the above curable resin composition.

[0021] In addition, the present disclosure provides a laminate in which the above coating is laminated on at least one side of a norbornene copolymer substrate.

[0022] Preferably, in the above laminate, 100 squares are made in a lattice pattern at an interval of 1 mm in the above coating, a tape is pasted, and when peeled off along the 90° direction, 90 or more squares remain. By having the above configuration, it is easy to exhibit adhesion.

[0023] Preferably, the arithmetic mean height (Sa) of the above coating of the above laminate is 30 μm or less.

[0024] Preferably, the norbornene copolymer substrate of the above laminate is a substrate for a lens.

[0025] In addition, the present disclosure provides a plastic lens including the above-described laminate.

[0026] In addition, the present disclosure provides an image display device including the above-described laminate.

[0027] Advantageous Effects of the Invention

[0028] The curable resin composition of the present disclosure can be coated in a single layer, has sufficient adhesion to a norbornene-based copolymer substrate, and is excellent in moisture resistance. Therefore, it can be suitably used as a coating for a norbornene-based copolymer substrate. Detailed Description of Embodiments

[0029] [Curable Resin Composition]

[0030] The curable resin composition of the present disclosure is a curable resin composition for coating a norbornene-based copolymer substrate, and includes an alicyclic ketone compound and / or an alicyclic ether compound, and a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane. By including the above alicyclic ketone compound or the above alicyclic ether compound, the surface of the norbornene-based copolymer substrate can be appropriately etched, and even when coated in a single layer, the curable resin composition can be firmly adhered when cured. In addition, by including a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane, sufficient surface hardness and moisture resistance can be exhibited when forming a coating.

[0031] (Cationically Polymerizable Silsesquioxane and / or Cationically Polymerizable Cyclic Siloxane)

[0032] The above curable resin composition includes a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane. As the above cationically polymerizable silsesquioxane and / or the above cationically polymerizable cyclic siloxane, any one of them can be used alone, or two or more of them can be used. In addition, one kind of the above cationically polymerizable silsesquioxane and the above cationically polymerizable cyclic siloxane can be used respectively, or two or more kinds can be used.

[0033] The above cationically polymerizable silsesquioxane is a compound having a cationically polymerizable functional group in the molecule. As the above cationically polymerizable functional group, for example, an epoxy group, an oxetanyl group, a vinyl ether group, a vinylphenyl group, etc. can be cited. Among them, from the viewpoint of making the surface hardness of the coating higher and exhibiting moisture resistance, it is preferable that the above cationically polymerizable functional group has a cyclic ether structure, and an epoxy group is particularly preferable.

[0034] Examples of the epoxy group-containing group include known or commonly used groups having an ethylene oxide ring, and there is no particular limitation. From the viewpoints of the curability of the curable resin composition and the heat resistance of the coating, the groups represented by the following formula (1a), the groups represented by the following formula (1b), the groups represented by the following formula (1c), and the groups represented by the following formula (1d) are preferred, the groups represented by the following formula (1a) and the groups represented by the following formula (1c) are more preferred, and the groups represented by the following formula (1a) are further preferred.

[0035] [Chemical formula 1]

[0036]

[0037] [Chemical formula 2]

[0038]

[0039] [Chemical formula 3]

[0040]

[0041] [Chemical formula 4]

[0042]

[0043] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. Among them, as R 1a , from the viewpoint of the curability of the curable resin composition, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, ethylene, trimethylene, and propylene are more preferred, and ethylene and trimethylene are further preferred.

[0044] In the above formula (1b), R 1b represents a linear or branched alkylene group, and groups similar to R 1a can be exemplified. Among them, as R 1b , from the viewpoint of the curability of the curable resin composition, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, ethylene, trimethylene, and propylene are more preferred, and ethylene and trimethylene are further preferred.

[0045] In the above formula (1c), R 1c represents a linear or branched alkylene group, and groups similar to R 1a can be exemplified. Among them, as R1c , from the viewpoint of the curability of the curable resin 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 (1d), R 1d represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1d , from the viewpoint of the curability of the curable resin 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] As the above epoxy group-containing group, a group in which R 1a is vinyl in the group represented by the above formula (1a) is particularly preferred [among them, 2-(3,4-epoxycyclohexyl)ethyl is preferred].

[0048] As the above cationically polymerizable silsesquioxane, for example, a compound having a structural unit represented by the following formula (1) can be cited.

[0049] [R 1 SiO 3 / 2 (1)

[0050] The structural unit represented by the above formula (1) is usually a silsesquioxane structural unit represented by [RSiO 3 / 2 (so-called T unit). 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 cationically polymerizable functional group.

[0051] The 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).

[0052] Alternatively, in the silsesquioxane (X), as the silsesquioxane structural unit [RSiO 3 / 2 , in addition to having the structural unit represented by the above formula (1), it may also have a structural unit represented by the following formula (2).

[0053] [R 2 SiO3 / 2 (2)

[0054] The structural unit represented by the above formula (2) is usually a 3 / 2 silsesquioxane structural unit (T unit) represented by [RSiO

[0055] . 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)

[0056] 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. As the above aryl group, for example, phenyl, tolyl, naphthyl, etc. can be cited. As the above aralkyl group, for example, benzyl, phenethyl, etc. can be cited. As the above cycloalkyl group, for example, cyclobutyl, cyclopentyl, cyclohexyl can be cited. As the above alkyl group, for example, linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, etc. can be cited.

[0057] Among them, as R 2 , it is preferably 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.

[0058] 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.

[0059] 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 aryl group that may have a substituent. In this case, there is a tendency for the surface hardness, flexibility, processability, and flame retardancy of the coating to be more excellent.

[0060] Alternatively, in addition to the structural units represented by the above formula (1) serving as T units and the structural units represented by the above formula (2), the silsesquioxane (X) further has a structural unit selected from the group consisting of a structural unit represented by [R3SiO 1 / 2 (so-called M unit), a structural unit represented by [R2SiO 2 / 2 (so-called D unit), and a structural unit represented by [SiO 4 / 2 (so-called Q unit). It should be noted that R in the above M unit and the above D unit may be the same groups as R 1 in the structural unit represented by the above formula (1) and R 2 in the structural unit represented by the above formula (2). As silsesquioxane structural units other than the structural units represented by the above formula (1) and the structural units represented by the above formula (2), for example, a structural unit represented by the following formula (3) can be cited.

[0061] [HSiO 3 / 2 (3)

[0062] 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).

[0063] [R a SiO 3 / 2 (I)

[0064] [R b SiO 2 / 2 (OR c )](II)

[0065] 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 located 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 T2 body are structural units (T units) formed by hydrolysis and condensation reactions of corresponding hydrolyzable trifunctional silane compounds.

[0066] [Chemical formula 5]

[0067]

[0068] [Chemical formula 6]

[0069]

[0070] R in the above formula (I) a (R in formula (I')) a (which is the same) and R in formula (II) b (R in formula (II')) b (which is the same) each represent a group containing a cationic polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a hydrogen atom. As specific examples of R a and R b , groups the same as R in the above formula (1) 1 and R in the above formula (2) 2 can be exemplified. It should be noted that R in formula (I) a and R in formula (II) b 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 cationic polymerizable functional group is an epoxy group, are 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).

[0071] R in the above formula (II) c (R in formula (II')) c (which is the same) 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 cited. Among them, methyl and ethyl are preferred, and methyl is more preferred. The alkyl group in R c in formula (II) generally originates from the alkyl group of the alkoxy group in the hydrolyzable silane compound used as the raw material of the silsesquioxane (X).

[0072] The molar ratio of the structural unit (T3 body) represented by the above formula (I) to the structural unit (T2 body) represented by the above formula (II) in the silsesquioxane (X) [structural unit represented by formula (I) / structural unit represented by formula (II)] (sometimes referred to as "T3 body / T2 body") is not particularly limited, and is preferably 5 or more, more preferably 5 to 20, further preferably 5 to 18, further preferably 6 to 16, further preferably 7 to 15, and 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 coating to be further improved.

[0073] The above molar ratio [T3 body / T2 body] in the silsesquioxane (X) can be determined, for example, by 29 Si-NMR spectroscopy. In 29 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, by calculating the integral ratio of these respective peaks, the above molar ratio [T3 body / T2 body] is determined. Specifically, for example, in the case where the silsesquioxane (X) has a structural unit represented by the above formula (1) and 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 above molar ratio [T3 body / T2 body] can be determined by calculating the integral ratio of the signal (T3 body) at -64 to -70 ppm to the signal (T2 body) at -54 to -60 ppm.

[0074] The 29 Si-NMR spectrum of the silsesquioxane (X) can be measured, for example, using the following apparatus and conditions.

[0075] Measuring apparatus: Trade name "JNM-ECA500 NMR" (manufactured by JEOL Ltd.).

[0076] Solvent: Deuterochloroform.

[0077] Number of integration times: 1800 times.

[0078] Measurement temperature: 25 °C.

[0079] The above molar ratio [T3 body / T2 body] of the silsesquioxane (X) being 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). Examples of such T2 bodies include 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. 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.

[0080] [R 1 SiO 2 / 2(OR c )](4)

[0081] [R 2 SiO 2 / 2 (OR c )](5)

[0082] [HSiO 2 / 2 (OR c )](6)

[0083] The cationically polymerizable silsesquioxane (especially silsesquioxane (X)) can be a silsesquioxane having a cage shape (cage silsesquioxane). Cage silsesquioxanes include complete cage silsesquioxanes and incomplete cage silsesquioxanes, and incomplete cage silsesquioxanes are preferred.

[0084] Generally, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of T3 units, and there are no T2 units in the molecule. That is, it is implied that: the above molar ratio [T3 unit / T2 unit] is 5 or more, and the silsesquioxane having an intrinsic absorption peak at around 1100 cm -1 as described later has an incomplete cage silsesquioxane structure.

[0085] 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 intrinsic absorption peaks at around 1050 cm -1 and around 1150 cm -1 respectively, and there is an intrinsic absorption peak at around 1100 cm -1 , the silsesquioxane (X) is identified as having a cage (incomplete cage) silsesquioxane structure. In contrast, when there are usually intrinsic absorption peaks at around 1050 cm -1 and around 1150 cm -1 respectively in the FT-IR spectrum, it is 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.

[0086] Measuring apparatus: Trade name "FT-720" (manufactured by Horiba, Ltd.).

[0087] Measuring method: Transmission method.

[0088] Resolution: 4 cm -1 .

[0089] Measurement wavenumber range: 400 - 4000 cm -1 .

[0090] Number of integrations: 16 times.

[0091] The proportion (total amount) of the structural unit having a cationic polymerizable functional group (such as the structural unit shown in the above formula (1), the structural unit shown in the above formula (4), etc.) in the cationic polymerizable silsesquioxane relative to the total amount of siloxane structural units [total siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, and is preferably 50 mol% or more (for example, 50 - 100 mol%), more preferably 55 - 100 mol%, still more preferably 65 - 99.9 mol%, further preferably 80 - 99 mol%, and particularly preferably 90 - 98 mol%. When the above proportion is 50 mol% or more, the curability of the curable resin composition is improved, and the surface hardness of the coating is significantly improved. It should be noted that the proportion of each siloxane structural unit in the cationic polymerizable silsesquioxane can be calculated, for example, from the composition of the raw materials and NMR spectrum measurement.

[0092] The proportion of the structural unit (T3 body) shown in the above formula (I) in the silsesquioxane (X) relative to the total amount of siloxane structural units [total siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, and is preferably 50 mol% or more, more preferably 60 - 99 mol%, still more preferably 70 - 98 mol%, further preferably 80 - 95 mol%, and particularly preferably 85 - 92 mol%. It is speculated that when the proportion of the structural unit of the T3 body is 50 mol% or more, it is easy to form an incomplete cage shape with an appropriate molecular weight, and there is a tendency for the surface hardness of the coating to be further improved.

[0093] The proportion (total amount) of the structural unit shown in the above formula (2) and the structural unit shown in the above formula (5) in the silsesquioxane (X) relative to the total amount of siloxane structural units [total siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, and is preferably 0 - 50 mol%, more preferably 0 - 40 mol%, still more preferably 0 - 30 mol%, and particularly preferably 1 - 15 mol%. By setting the above proportion to 50 mol% or less, the proportion of the structural unit having a cationic polymerizable functional group can be relatively increased, so the curability of the curable resin composition is improved, and there is a tendency for the surface hardness of the coating to become higher.

[0094] The ratio (total amount) of the structural unit represented by the above formula (I) and the structural unit represented by the above formula (II) in the silsesquioxane (X) relative to the total amount of siloxane structural units [total siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) (total amount) (in particular, the total ratio of T3 body and T2 body) is not particularly limited, preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is speculated that by setting the above ratio to 60 mol% or more, it is easy to form an incomplete cage shape with an appropriate molecular weight, and there is a tendency for the surface hardness of the coating to be further improved. Particularly preferably, the ratio (total amount) of the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is within the above range.

[0095] The number average molecular weight (Mn) in terms of standard polystyrene obtained by gel permeation chromatography of the silsesquioxane (X) is not particularly limited, preferably 1000 to 3000, more preferably 1000 to 2800, further preferably 1100 to 2600, and particularly preferably 1500 to 2500. By setting the number average molecular weight to 1000 or more, there is a tendency for the surface hardness of the coating to be further improved. There is a tendency for the heat resistance and abrasion resistance of the coating to be improved. On the other hand, by setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable resin composition is improved, and there is a tendency for the heat resistance of the coating to be improved.

[0096] The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene based on gel permeation chromatography of the silsesquioxane (X) is not particularly limited, preferably 1.0 to 3.0, more preferably 1.1 to 2.0, further preferably 1.2 to 1.9, further preferably 1.3 to 1.8, and particularly preferably 1.45 to 1.80. By setting the molecular weight dispersity to 3.0 or less, there is a tendency for the surface hardness of the coating to become higher. On the other hand, by setting the molecular weight dispersity to 1.0 or more (especially 1.1 or more), there is a tendency for it to be easily in a liquid state and the operability to be improved.

[0097] 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.

[0098] Measuring apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation).

[0099] Chromatographic column: Shodex KF-801×2 pieces, KF-802 and KF-803 (manufactured by Showa Denko K.K.).

[0100] Measured temperature: 40°C.

[0101] Eluent: THF, sample concentration 0.1 - 0.2 mass%.

[0102] Flow rate: 1 mL / min.

[0103] Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation).

[0104] Molecular weight: in terms of standard polystyrene.

[0105] The cationically polymerizable sesquisiloxane can be produced by a known or conventional method for producing sesquisiloxane, and there is no particular limitation. For example, it can be produced by hydrolyzing and condensing one or more hydrolyzable silane compounds.

[0106] The above-mentioned cationically polymerizable cyclic siloxane is a compound having at least a cyclic siloxane skeleton composed of siloxane bonds (Si-O-Si). In addition, in addition to the above-mentioned cyclic siloxane skeleton, it may also contain a linear or branched siloxane (linear or branched polysiloxane), a cage-type or ladder-type polysesquisiloxane, and other siloxane skeletons.

[0107] The number of Si-O units forming the siloxane ring of the above-mentioned cationically polymerizable cyclic siloxane (equal to the number of silicon atoms forming the siloxane ring) is preferably 2 - 12, more preferably 4 - 8.

[0108] In addition, the above-mentioned cationically polymerizable cyclic siloxane preferably has two or more alicyclic epoxy groups in the molecule. The above-mentioned alicyclic epoxy group refers to a cyclic olefin group epoxidized in the molecule. "Epoxidized cyclic olefin group" refers to a group (monovalent group) formed by removing at least one hydrogen atom from an epoxide structure from at least one of the carbon-carbon unsaturated bonds of a cyclic olefin (a cyclic aliphatic hydrocarbon in which at least one of the carbon-carbon bonds forming the ring is a carbon-carbon unsaturated bond). That is, the epoxidized cyclic olefin group contains an aliphatic hydrocarbon ring structure and an epoxy group, and the above-mentioned epoxy group is an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting the above-mentioned aliphatic hydrocarbon ring.

[0109] As the cycloalkenyl group in the above epoxidized cycloalkenyl group (the form before epoxidation), examples thereof include: cycloalkenyl groups such as cyclopropenyl (e.g., 2-cyclopropen-1-yl, etc.), cyclobutenyl (e.g., 2-cyclobuten-1-yl, etc.), cyclopentenyl (e.g., 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, etc.), cyclohexenyl (e.g., 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, etc.); cyclodienyl groups such as 2,4-cyclopentadien-1-yl, 2,4-cyclohexadien-1-yl, 2,5-cyclohexadien-1-yl; polycyclic groups such as dicyclopentenyl, dicyclohexenyl, norbornenyl, etc.

[0110] It should be noted that in the aliphatic hydrocarbon ring forming the cycloalkenyl group in the above epoxidized cycloalkenyl group, one or more substituents may be bonded. As the above substituents, for example, substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms) can be cited. More specifically, examples include: halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; alkoxy groups such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutoxy (preferably C 1-6 alkoxy, more preferably C 1-4 alkoxy); alkenyloxy groups such as allyloxy (preferably C 2-6 alkenyloxy, more preferably C 2-4 alkenyloxy); aryloxy groups optionally having C 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents on the aromatic ring, such as phenoxy, tolyloxy, naphthyloxy (preferably C 6-14 aryloxy); aralkyloxy groups such as benzyloxy, phenoxy (preferably C 7-18 aralkyloxy); acyloxy groups such as acetoxy, propionyloxy, (meth)acryloxy, benzoyloxy (preferably C 1-12 acyloxy); mercapto group; alkylthio groups such as methylthio, ethylthio (preferably C 1-6 alkylthio, more preferably C 1-4 alkylthio); alkenylthio groups such as allylthio (preferably C 2-6 alkylthio, more preferably C 2-4 alkylthio); arylthio groups optionally having C 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents on the aromatic ring, such as phenylthio, methylphenylthio, naphthylthio (preferably C 6-14 arylthio); aralkylthio groups such as biphenylthio, phenylthio (preferably C 7-18 aralkylthio); carboxyl group; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl (preferably C 1-6(alkoxy-carbonyl); aryloxy-carbonyl such as phenoxy-carbonyl, tolyloxy-carbonyl, naphthyloxy-carbonyl (preferably C 6-14 (aryloxy-carbonyl); aralkyloxy-carbonyl such as benzyloxy-carbonyl (preferably C 7-18 (aralkyloxy-carbonyl); amino; mono- or dialkylamino such as methylamino, ethylamino, dimethylamino, diethylamino (preferably mono- or di-C 1-6 alkylamino); acylamino such as acetylamino, propionylamino, benzoylamino (preferably C 1-11 acylamino); a group containing an oxetanyl group such as ethyloxetanyloxy; acyl groups such as acetyl, propionyl, benzoyl; oxy; a group formed by bonding two or more of these via C 1-6 alkylidene bond, etc.

[0111] Among them, as the above cyclic olefin group, a cyclic olefin group having 5 to 12 carbon atoms is preferred, a cycloalkenyl group having 5 to 12 carbon atoms is more preferred, and a cyclohexenyl group is further preferred. That is, as the above epoxidized cyclic olefin group, a group obtained by epoxidizing a cyclic olefin group having 5 to 12 carbon atoms is preferred, a group obtained by epoxidizing a cycloalkenyl group having 5 to 12 carbon atoms is more preferred, and a group obtained by epoxidizing a cyclohexenyl group (cyclohexenyloxy) is further preferred. It should be noted that the above first epoxide may have one kind of epoxidized cyclic olefin group or two or more kinds.

[0112] The number of epoxidized cyclic olefin groups in the above first epoxide in the molecule only needs to be 2 or more, and there is no particular limitation. It is preferably 2 to 6, more preferably 3 to 5, and further preferably 4.

[0113] Examples of the cationically polymerizable cyclic siloxane include 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetrakis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane, and the like.

[0114] The contents of the cationically polymerizable sesquisiloxane and the cationically polymerizable cyclic siloxane in the above curable resin composition are not particularly limited. Relative to the total amount (100% by mass) of the curable compounds, it is preferably more than 50% by mass (for example, more than 50% by mass to 99% by mass or less), more preferably 60 to 96% by mass, still more preferably 70 to 95% by mass, and particularly preferably 80 to 93% by mass. If the above content ratio exceeds 50% by mass, the surface hardness of the coating is further improved, and there is a tendency to exhibit moisture resistance. If the above content ratio is 99% by mass or less, other components can be contained in the curable resin composition, and there is a tendency for the effects obtained by containing them to be further improved. In addition, a curing catalyst can be contained in the curable resin composition, and thus there is a tendency for the curing of the curable resin composition to proceed more effectively. It should be noted that when the above curable resin composition contains only one of the above cationically polymerizable sesquisiloxane and the above cationically polymerizable cyclic siloxane, its content preferably satisfies the above range.

[0115] In addition, the content of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane is preferably 10 to 90% by mass, more preferably 12 to 80% by mass, and still more preferably 14 to 70% by mass relative to the total amount (100% by mass) of the curable resin composition. When the above content ratio is 10% by mass or more, it becomes easy to use as a coating during curing. When the above content ratio is 90% by mass or less, an alicyclic ketone compound and / or an alicyclic ether compound can be sufficiently contained, and the adhesion to the norbornene copolymer substrate can be exhibited. It should be noted that when the above curable resin composition contains only either the above cationically polymerizable silsesquioxane or the above cationically polymerizable cyclic siloxane, its content preferably satisfies the above range.

[0116] (alicyclic ketone compound and / or alicyclic ether compound)

[0117] The above curable resin composition contains an alicyclic ketone compound and / or an alicyclic ether compound. The above alicyclic ketone compound and the above alicyclic ether compound are preferably liquid at normal temperature (about 25°C) and used as a solvent for the above curable resin composition. By containing the above alicyclic ketone compound or the above alicyclic ether compound, the above curable resin composition can appropriately etch the surface of the norbornene copolymer substrate and can exhibit sufficient adhesion even in a single layer. As the above alicyclic ketone compound and / or the above alicyclic ether compound, either one of them alone or two or more of them can be used. In addition, one kind of each of the above alicyclic ketone compound and the above alicyclic ether compound can be used, or two or more kinds can be used.

[0118] The above alicyclic ketone compound is a compound having at least an alicyclic ring and a ketone group in its structure. It may not have a ketone group on the alicyclic ring, but a compound having a ketone group on the alicyclic ring is preferred. As the above alicyclic ring, a cyclic aliphatic hydrocarbon containing no carbon-carbon unsaturated bond is preferred, and the above alicyclic ring can be a monocyclic or polycyclic ring. As the above monocyclic ring, specifically, cycloalkyl groups having 3 to 10 carbon atoms can be cited, and cycloalkyl groups having 4 to 7 carbon atoms are preferred. In addition, as the above polycyclic ring, a polycyclic cyclic aliphatic hydrocarbon composed of 5- to 7-membered rings and containing no carbon-carbon unsaturated bond can be cited, and the number of rings of the above polycyclic ring is preferably 2 to 10.

[0119] Moreover, in the above alicyclic ring, one or more substituents can be bonded in addition to the ketone group. As the above substituents, for example, substituents having 0 to 20 carbon atoms can be cited, and more specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, and isobutoxy group (preferably C 1-6 alkoxy group); allyloxy group and other allyloxy groups (preferably C 2-6alkenyloxy); phenoxy, tolyloxy, naphthyloxy, etc., which optionally have C on the aromatic ring 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents to form aryloxy (preferably C 6-14 aryloxy); aralkyloxy such as benzyloxy and phenoxy (preferably C 7-18 aralkyloxy); acyloxy such as acetoxy, propionyloxy, (meth)acryloxy, benzoyloxy, etc. (preferably C 1-12 acyloxy); mercapto; alkylthio such as methylthio and ethylthio (preferably C 1-6 alkylthio, more preferably C 1-4 alkylthio); alkenylthio such as allylthio (preferably C 2-6 alkylthio, more preferably C 2-4 alkylthio); phenylthio, methylphenylthio, naphthylthio, etc., which optionally have C on the aromatic ring 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents to form arylthio (preferably C 6-14 arylthio); aralkylthio such as biphenylthio and phenylthio (preferably C 7-18 aralkylthio); carboxyl; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, etc. (preferably C 1-6 alkoxy-carbonyl); aryloxycarbonyl such as phenoxycarbonyl, tolyloxycarbonyl, naphthyloxycarbonyl, etc. (preferably C 6-14 aryloxy-carbonyl); aralkyloxycarbonyl such as benzyloxycarbonyl (preferably C 7-18 aralkyloxy-carbonyl); amino; mono- or dialkylamino such as methylamino, ethylamino, dimethylamino, diethylamino, etc. (preferably mono- or di-C 1-6 alkylamino); acylamino such as acetylamino, propionylamino, benzoylamino, etc. (preferably C 1-11 acylamino); groups containing oxetanyl such as ethyloxetanyloxy; acyl groups such as acetyl, propionyl, benzoyl; oxy; groups formed by bonding two or more of these via C 1-6 alkylene bond, etc.

[0120] As the above alicyclic ketone compound, preferably, an alicyclic ketone compound having a single ring in the form of an alicyclic ring, specifically, cyclopentanone, cyclohexanone, cycloheptanone, 2-methyl-cyclopentanone, etc. can be mentioned. From the viewpoint of the action on the above cycloolefin copolymer base material, cyclohexanone or cyclopentanone is more preferable.

[0121] The above alicyclic ether compound is a compound having at least an alicyclic ring and an ether group in its structure. Preferably, it is a compound in which the alicyclic group is connected to another alicyclic group or a hydrocarbon group other than the alicyclic group through an ether group. More preferably, it is a compound in which the alicyclic group is connected to a hydrocarbon group other than the alicyclic group through an ether group. Specifically, as the above alicyclic ether compound, a compound represented by the following formula (A) is preferred.

[0122] [Chemical formula 7]

[0123]

[0124] (In the above formula, R A represents an alicyclic group, and R B represents an alkyl group having 1 to 6 carbon atoms)

[0125] As the alicyclic ring of the above alicyclic group, the same alicyclic rings as those exemplified in the above alicyclic ketone compound can be cited.

[0126] As the above R B , it is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0127] As the above alicyclic ether compound, specifically, cycloalkyl C 1-6 alkyl ether is preferred. As the above cycloalkyl C 1-6 alkyl ether, cyclopentyl C 1-3 alkyl ether and cyclohexyl C 1-3 alkyl ether are preferred, and among them, cyclopentyl methyl ether is preferred.

[0128] The total content of the above alicyclic ketone compound and the above alicyclic ether compound is preferably 15 to 90% by mass, more preferably 25 to 85% by mass, and further preferably 35 to 80% by mass with respect to the total amount (100% by mass) of the curable resin composition. By the total content of the alicyclic ketone compound and the alicyclic ether compound being 15% by mass or more, the viscosity of the curable resin composition can be sufficiently reduced, and it is easy to uniformly form a thin film. In addition, by the total content being 90% by mass or less, the effect as a coating can be exerted. It should be noted that when the curable resin composition contains only one of the above alicyclic ketone compound or the above alicyclic ether compound, its content preferably satisfies the above range.

[0129] The above-mentioned curable resin composition may further contain other solvents other than the above-mentioned alicyclic ketone compound and the above-mentioned alicyclic ether compound. From the viewpoint of exhibiting adhesion to the norbornene-based copolymer substrate, it is preferably free of the above-mentioned other solvents. As the above-mentioned other solvents, as long as they can dissolve the above-mentioned cationically polymerizable silsesquioxane and the components added as needed and do not hinder the polymerization, there is no particular limitation. The above-mentioned other solvents may be used alone or in combination of two or more.

[0130] The above-mentioned other solvents are preferably solvents that can impart fluidity suitable for coating the coating film and can be easily removed by heating at a temperature capable of suppressing the progress of polymerization. Solvents having a boiling point (under one atmosphere) of 170 °C or lower are preferably used (for example, aromatic solvents such as toluene, xylene, and mesitylene; esters such as butyl acetate; ketones such as methyl isobutyl ketone; ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc.).

[0131] When the above-mentioned other solvents are contained, as the content thereof, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more with respect to the total amount (100% by mass) of the curable resin composition. In addition, there is no particular limitation as the upper limit, and it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

[0132] The content of the above-mentioned alicyclic ketone compound and the above-mentioned alicyclic ether compound is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more with respect to the total amount (100% by mass) of the solvents. By having the content of the alicyclic ketone compound and the alicyclic ether compound in the solvent be 50% by mass or more, it is easy to exhibit adhesion to the norbornene-based copolymer substrate. In addition, there is no particular limitation as the upper limit, and it may be 100% by mass.

[0133] The above-mentioned curable resin composition may also contain other curable compounds other than the above-mentioned cationically polymerizable silsesquioxane. Examples of the above-mentioned other curable compounds include other cationically polymerizable compounds other than the above-mentioned cationically polymerizable silsesquioxane, radical polymerizable compounds, and the like. The above-mentioned other curable compounds may be used alone or in combination of two or more.

[0134] As the above-mentioned other cationically polymerizable compounds, for example, there can be mentioned: compounds having one or more epoxy groups in the molecule, compounds other than the above-mentioned cationically polymerizable sesquisiloxanes (sometimes referred to as "other epoxy compounds"), compounds having one or more oxetanyl groups in the molecule (sometimes referred to as "oxetane compounds"), compounds having one or more vinyl ether groups in the molecule (sometimes referred to as "vinyl ether compounds"), compounds having two or more hydroxyl groups in the molecule (sometimes referred to as "polyol compounds"), and the like.

[0135] As the above-mentioned other epoxy compounds, there can be mentioned compounds having one or more glycidyl ether groups in the molecule. Among the compounds having one or more glycidyl ether groups in the molecule, for example, there are included: aromatic glycidyl ether-based epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol type epoxy compounds, phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, cresol novolak type epoxy compounds of bisphenol A, naphthalene type epoxy compounds, epoxy compounds obtained from triphenol methane, etc.; hydrogenated glycidyl ether-based epoxy compounds; glycidyl ester-based epoxy compounds; glycidyl amine-based epoxy compounds, etc.

[0136] Among the above-mentioned hydrogenated glycidyl ether-based epoxy compounds, for example, there are included: compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane, and their polymers (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, and their polymers (hydrogenated bisphenol F type epoxy compounds); hydrogenated bisphenol type epoxy compounds; hydrogenated phenol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds; hydrogenated cresol novolak type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds obtained from triphenol methane, etc.

[0137] Examples of the above oxetane compounds include: trimethylene oxide, 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy))methyl]benzene, bis{[1-ethyl(3-oxetanyl)]methyl}ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 3-ethyl-3{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, and the like.

[0138] Examples of the above vinyl ether compounds include: 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol mono vinyl ether, 1,4-cyclohexanedimethanol mono vinyl ether, 1,3-cyclohexanedimethanol mono vinyl ether, 1,2-cyclohexanedimethanol mono vinyl ether, p-xylene glycol mono vinyl ether, m-xylene glycol mono vinyl ether, o-xylene glycol mono vinyl ether, diethylene glycol mono vinyl ether, triethylene glycol mono vinyl ether, tetraethylene glycol mono vinyl ether, pentaethylene glycol mono vinyl ether, oligoethylene glycol mono vinyl ether, polyethylene glycol mono vinyl ether, dipropylene glycol mono vinyl ether, tripropylene glycol mono vinyl ether, tetrapropylene glycol mono vinyl ether, pentapropylene glycol mono vinyl ether, oligopropylene glycol mono vinyl ether, polypropylene glycol mono vinyl ether, and their derivatives, and the like.

[0139] Examples of the above polyol compounds include: polyester polyol, polyether polyol, polycarbonate polyol, phenoxy resin, polybutadiene having a hydroxyl group, acrylic polyol, and the like.

[0140] When the above-mentioned curable resin composition contains the above-mentioned other cationically curable compounds, the content of the other cationically curable compounds is not particularly limited. Relative to the total amount (100% by mass) of the curable resin composition, it is preferably 1% by mass or more and less than 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass. If the above content is 1% by mass or more, there is a tendency to more easily obtain the effects obtained by using the other cationically curable compounds. On the other hand, if the above content is less than 50% by mass, a sufficient amount of cationically polymerizable silsesquioxane can be used.

[0141] In addition, when the above-mentioned curable resin composition contains the above-mentioned other cationically curable compounds, the content of the other cationically curable compounds is not particularly limited. Relative to the total amount (100% by mass) of the curable compounds, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass.

[0142] The above-mentioned curable resin composition preferably contains a curing catalyst. The above-mentioned curing catalyst is a compound capable of initiating or promoting the polymerization reaction of the above-mentioned cationically polymerizable silsesquioxane and the above-mentioned other curable compounds. The above-mentioned curing catalyst can be used alone or in combination of two or more.

[0143] As the above-mentioned curing catalyst, it can be selected according to the type of the curable functional group possessed by the above-mentioned curable compound. Among them, a cationic polymerization initiator or a radical polymerization initiator is 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.

[0144] Examples of the above-mentioned cationic polymerization initiator include a photo cationic polymerization initiator (photoacid generator) and a thermal cationic polymerization initiator (thermal acid generator).

[0145] As the above-mentioned photo cationic polymerization initiator, known or commonly used photo cationic polymerization initiators can be used. For example, there can be mentioned: 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.

[0146] 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)phenyl di-(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; trialkylsulfonium salts such as dimethylbenzoylmethylsulfonium salt, benzoylmethyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0147] Examples of the above-mentioned diphenyl[4-(phenylthio)phenyl]sulfonium salt include: diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. In addition, commercially available products such as the trade name "CPI-101A" (manufactured by San-Apro Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate) and 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.

[0148] Examples of the above-mentioned iodonium salts include: the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, 45% alkyl glycidyl ether solution of bis(4-dodecylphenyl)iodonium = hexafluoroantimonate), the trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Roudia Japan Co., Ltd., tetrakis(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodonium), the trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, etc.

[0149] 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.

[0150] As the above ammonium salts, for example, the following can be cited: 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.

[0151] As the above phosphonium salts, for example, the following can be cited: 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.

[0152] As the salts of the above transition metal complex ions, for example, the following can be cited: salts of chromium complex cations such as (η 5 -cyclopentadienyl)(η 6 -toluene)Cr + , (η 5 -cyclopentadienyl)(η 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.

[0153] As the anions constituting the above salts, for example, the following can be cited: SbF6 - , PF6 - , BF4 - , (CF3CF2)3PF3 - , (CF3CF2CF2)3PF3 - , (C6F5)4B - , (C6F5)4Ga -, sulfonic acid anions (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, naphthofluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc.), (CF3SO2)3C - , (CF3SO2)2N - , perhalate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0154] Examples of the above-mentioned 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, examples of the anions constituting the above salts include the same anions as those in the photo cationic polymerization initiators.

[0155] Examples of the above-mentioned arylsulfonium salts include hexafluoroantimonate salts, etc. In the curable resin composition of the present disclosure, for example, commercially available products such as trade names "SP-66", "SP-77" (manufactured by ADEKA Corporation); trade names "San-Aid SI-60L", "San-Aid SI-60S", "San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of the above-mentioned aluminum chelates include: ethyl acetoacetate aluminum diisopropyl, tris(ethylacetoacetato)aluminum, etc. In addition, examples of the above-mentioned boron trifluoride amine complexes include: boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, etc.

[0156] The above-mentioned radical polymerization initiator is a compound that generates radicals by heat or irradiation with active energy rays and initiates the curing reaction of the curable compound.

[0157] Examples of the above-mentioned radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators. Examples of the above-mentioned photo radical polymerization initiators include: alkylbenzophenone-based photo radical polymerization initiators, acylphosphine oxide-based photo radical polymerization initiators, oxime ester-based photo radical polymerization initiators, α-hydroxyketone-based photo radical polymerization initiators, etc.

[0158] Examples of the above-mentioned alkyl phenyl ketone-based photo radical polymerization initiators include: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-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)phenyl phosphonate, 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.

[0159] Examples of the above-mentioned acylphosphine oxide-based photo radical polymerization initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc.

[0160] Examples of the above-mentioned oxime ester-based photo radical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxy), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyl oxime, etc.

[0161] Examples of the above-mentioned α-hydroxy ketone-based photo radical polymerization initiators include: 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.

[0162] The content (mixing amount) of the above-mentioned curing catalyst in the above-mentioned curable resin composition is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and further preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the curable compound. If the content of the curing catalyst is 0.01 part by mass or more, the curing reaction can proceed effectively and sufficiently, and there is a tendency for the surface hardness of the coating to be further improved. On the other hand, if the content of the curing catalyst is 10 parts by mass or less, there is a tendency for the storage stability of the curable resin composition to be improved or the coloring of the cured product to be suppressed.

[0163] The above curable resin composition may further contain the following conventional additives as other components: curing agents, curing aids, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, aluminum oxide, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, and inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; fillers such as conductive metal powders of silver, copper, etc., curing aids, stabilizers (light stabilizers, heat stabilizers, heavy metal passivators, etc.), ultraviolet absorbers (triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers), 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 (flowability improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (slip agents, etc.), matting agents, defoaming agents, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, etc. The above other components may be used alone or in combination of two or more. The content of the above 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.

[0164] In addition, the content of the antimony compound in the above curable resin composition is preferably 1000 mass ppm or less relative to the total amount (100%) of the curable resin composition. By setting the content of the antimony compound in the curable resin composition to 1000 mass ppm or less, a curable resin composition with more excellent safety can be produced. In addition, there is no particular limitation on the lower limit value, and it may also be 0 mass ppm.

[0165] The above curable resin composition is not particularly limited, and can be prepared by stirring and mixing the above components at room temperature or while heating as needed. It should be noted that the above curable resin composition can directly use a substance obtained by premixing the respective components as a one-component system composition, or can also be used as a multi-component system (for example, a two-component system) composition in which two or more components separately stored are mixed at a specified ratio before use.

[0166] The above curable resin composition is not particularly limited, and is preferably a liquid at normal temperature (about 25°C). More specifically, the viscosity of the above curable resin composition at 25°C is preferably 15 mPa·s or less, more preferably 12 mPa·s or less, and further preferably 10 mPa·s or less. By setting the above viscosity to 15 mPa·s or less, the above curable resin composition can be uniformly coated on a substrate in the form of a thin film (exhibiting film thickness uniformity), and it can easily exhibit optical properties. On the other hand, the lower limit is not particularly limited, and for example, it is preferably 0.5 mPa·s or more.

[0167] [Coating]

[0168] As an embodiment of the present disclosure, a coating containing a cured product of the above curable resin composition can be cited.

[0169] As a method for manufacturing the above coating, it can be manufactured according to a well-known or conventional method for manufacturing a coating. The manufacturing method is not particularly limited. For example, it can be manufactured by coating the above curable resin composition on at least one surface of the above cycloolefin copolymer substrate, and if necessary, removing the solvent by heating and drying, and at the same time curing the above curable resin composition. The coating method of the curable resin composition and the conditions for curing it are not particularly limited, and for example, they can be appropriately selected from the following conditions.

[0170] As a method for coating and curing the above coating, a usual coating method can be used. For example, an immersion method, roll coating, gravure coating, inkjet coating, spin coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spraying, gravure offset printing method, organic vapor deposition method, etc. can be used.

[0171] As a curing method, when a photo-curable catalyst is used in the above curable resin composition, for example, light irradiation using a mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, sunlight, electron beam source, laser light source, LED light source, etc. can be cited. It should be noted that when ultraviolet rays are irradiated during the curing of the above coating, for example, the cumulative irradiation amount is preferably set to about 1 to 5000 mJ / cm 2 or so.

[0172] As specific curing conditions, there is no particular limitation. For example, the above curable resin composition can be first heat-treated (pre-baked) at preferably 60°C or higher, more preferably 120°C or higher, and further preferably 150°C or higher, and preferably for 10 seconds or longer, more preferably 30 seconds or longer, and further preferably 60 seconds or longer. Then, ultraviolet rays are irradiated (irradiation conditions (irradiation amount): preferably 300 mJ / cm 2 or more; irradiation intensity: 100 mW / cm 2Above), finally, heat treatment (aging) is preferably carried out at 120 °C or higher for preferably 0.5 hours or more to cure it.

[0173] In addition, as a curing method, when using a thermosetting catalyst, the specific heating temperature is preferably 100 to 200 °C, more preferably 110 to 170 °C. In addition, the heating time is preferably 30 minutes to 6 hours, more preferably 1 to 4 hours. It should be noted that the above heating temperature and heating time can be appropriately changed. In addition, the curing conditions are not limited to these ranges, and the pre-baking temperature, time, aging temperature, and time can be appropriately selected according to the solvent used. In addition, the ultraviolet irradiation conditions can also be appropriately selected according to the curing catalyst used.

[0174] As described above, the above-mentioned curable resin composition can be coated and cured to achieve high adhesion to a norbornene copolymer substrate in a single layer without using other adhesive layers, and further, a coating having high surface hardness and moisture resistance can be formed.

[0175] The thickness of the above coating is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm. When the thickness of the coating is 0.1 μm or more, the performance as a coating can be exhibited. In addition, when the thickness of the coating is 10 μm or less, it is easy to coat as a film with high smoothness.

[0176] [Laminate]

[0177] In addition, as an embodiment of the present disclosure, a laminate in which the above coating is formed on at least one surface of a norbornene copolymer substrate can be cited. The above laminate can improve the surface hardness by including a coating that is a cured product of the above curable resin composition, and at the same time has sufficient adhesion to the above norbornene copolymer substrate and exhibits moisture resistance. The above coating can be provided only on one surface of the above norbornene copolymer substrate, or can be provided on both surfaces. In addition, when the coating is provided on both surfaces of the norbornene copolymer substrate, coatings with the same composition and thickness can be provided on each surface, or coatings with different compositions and thicknesses can be provided.

[0178] In addition, the above laminate may contain other layers other than the above substrate and the above coating, and from the viewpoint of coating in the form of a film, it may not contain other layers. As the above other layers, for example, a primer layer and an antireflection layer can be cited. The above other layers can be formed only on one surface of the above norbornene copolymer substrate, or can be formed on both surfaces. In addition, when the above other layers are formed on both surfaces of the above norbornene copolymer substrate, the same layers can be laminated respectively, or layers with different thicknesses and compositions can be laminated respectively.

[0179] Examples of the cycloolefin copolymer used as the base material of the above cycloolefin copolymer include cycloolefin polymer (COP) and cycloolefin copolymer (COC). The above cycloolefin copolymer may be used alone or in combination of two or more.

[0180] The above cycloolefin polymer (COP) is a polymer having a structural unit derived from a cyclic olefin in one or both of the main chain and the side chain. The above cyclic olefin is not particularly limited and may be a polycyclic cyclic olefin or a monocyclic cyclic olefin. Examples of the above polycyclic cyclic olefin include norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene and other norbornene compounds, dicyclopentadiene, dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene and other dicyclopentadiene compounds, tetracyclododecene, methyltetracyclododecene, dimethyltetracyclododecene, tricyclopentadiene, tetracyclopentadiene and the like. Examples of the above monocyclic cyclic olefin include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatriene and the like.

[0181] The above cycloolefin copolymer (COC) is a polymer having a structural unit derived from a cyclic olefin as described above and a structural unit derived from an acyclic olefin such as ethylene and α-olefin. Examples of the above α-olefin include linear α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; branched α-olefins having 4 to 20 carbon atoms such as 4-methyl-1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene and the like.

[0182] The content of the cycloolefin copolymer in the above cycloolefin copolymer base material is not particularly limited, and is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount (100% by mass) of the above base material. In addition, there is no particular limitation as the upper limit, and it may also be 100% by mass.

[0183] The above cycloolefin copolymer base material may further contain other components such as resins other than those exemplified above, flame retardants, antioxidants, light stabilizers, metal deactivators, plasticizers, nucleating agents, clarifying agents, antistatic agents, lubricants, etc. as required.

[0184] The form of the above-mentioned cycloolefin copolymer base material is not particularly limited, and examples thereof include base materials for films, base materials for lenses, and the like. When the above-mentioned cycloolefin copolymer base material is a base material for films, the thickness of the above-mentioned cycloolefin copolymer base material is preferably 1 to 200 μm, more preferably 3 to 100 μm, and further preferably 5 to 50 μm. In addition, when the above-mentioned cycloolefin copolymer base material is a base material for lenses, the thickness of the above-mentioned cycloolefin copolymer base material is preferably 500 to 5000 μm, more preferably 700 to 4500 μm, and further preferably 1000 to 4000 μm. It should be noted that when the above-mentioned base material is a base material for films, it can be formed and manufactured by a melt extrusion molding method, a solution casting method, or the like. When the above-mentioned base material is a base material for lenses, it can be manufactured by an injection molding method, a compression molding method, a transfer molding method, an injection compression molding method, or the like.

[0185] For the above-mentioned laminate, according to JIS K5600-5-6:1999, scrape with a cutter at intervals of 1 mm from the coating side to make 100 squares in a grid pattern, stick with tape, peel off along the 90° direction, and visually confirm whether the surface of the coating is peeled off from the tape. It is preferably that 70 or more remain, more preferably 90 or more, and particularly preferably 100. By having 70 or more remaining on the base material, it can be confirmed that the coating exhibits sufficient adhesion to the cycloolefin copolymer base material. It should be noted that when coatings are laminated on both sides of the above-mentioned base material, at least one surface needs to satisfy the above range.

[0186] The above-mentioned laminate preferably shows no whitening or cracking after a PCT test (autoclave test) of being stored in a thermo-hygrostat at 120 °C and 100% RH for 8 hours. It should be noted that when coatings are laminated on both sides of the above-mentioned base material, at least one surface needs to satisfy the above description.

[0187] The arithmetic mean height (Sa) of the above-mentioned coating in the above-mentioned laminate is preferably 30 μm or less, more preferably 25 μm or less, and further preferably 20 μm or less. By having the arithmetic mean height of 30 μm or less, it is easy to improve the film thickness uniformity. It should be noted that the lower limit is not particularly limited and is 0.1 μm or more. It should be noted that when coatings are laminated on both sides of the above-mentioned base material, at least one surface needs to satisfy the above range.

[0188] When using a film base material as the above-mentioned cycloolefin copolymer base material, the thickness of the above laminate is preferably 1 to 200 μm, more preferably 3 to 100 μm, and further preferably 5 to 50 μm. In addition, when using a lens base material as the above-mentioned cycloolefin copolymer base material, that is, when the above laminate is a plastic lens, the thickness of the above laminate is preferably 500 to 5000 μm, more preferably 700 to 4500 μm, and further preferably 1000 to 4000 μm.

[0189] In addition, since the above laminate is coated with a highly adherent coating on a cycloolefin copolymer base material having excellent physical properties such as moisture resistance, the surface hardness is improved, so it can be suitably used as a plastic lens or an image display device.

[0190] Each aspect disclosed in this specification can also be combined with any other features disclosed in this specification. In addition, each configuration and the combination of each configuration in each embodiment are examples, and appropriate addition, omission, and other changes of the configuration can be made without departing from the gist of the present disclosure. The present disclosure is not limited by the embodiments but only by the claims.

[0191] Examples

[0192] Hereinafter, an embodiment of the present disclosure will be described in more detail based on examples. It should be noted that unless otherwise specified, the unit of the numerical values described in the table represents parts by mass.

[0193] Production Example 1

[0194] (Production of cationically polymerizable silsesquioxane)

[0195] Into a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50 °C. To the mixture thus obtained, 7.74 g of a 5% potassium carbonate aqueous solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added 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 5 hours under a nitrogen stream.

[0196] Thereafter, while cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% brine were added. The solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again for washing with water. After liquid separation, the aqueous layer was drawn out and washed with water until the lower layer became neutral. After separating the upper layer, the solvent was distilled off from the upper layer under the conditions of 1 mmHg and 50 °C to obtain 75.18 g of a colorless, transparent, and liquid product (low molecular weight polyorganosilsesquioxane containing epoxy groups: silsesquioxane) containing 23% by mass of methyl isobutyl ketone.

[0197] It should be noted that the product was analyzed, and as a result, the number average molecular weight was 2235 and the molecular weight dispersity was 1.54. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the 29 Si-NMR spectrum of the above product was 11.9. It was confirmed by 1H-NMR and 29 Si-NMR of the obtained low molecular weight polyorganosilsesquioxane containing epoxy groups.

[0198] It should be noted that the molecular weight of the product was measured using a pump: Shimadzu LC-20AD, a detector: ShodexRI-504, a chromatographic column: Shodex GPC KF-602, KF-603, a guard column: Shodex GPC KF-G, a solvent: THF, and measurement conditions: 40 °C. In addition, the ratio of T2 body to T3 body [T3 body / T2 body] in the product was measured by Si-NMR spectrum measurement using JEOLECA500 (500 MHz). 29 It was carried out.

[0199] Examples 1 to 13, Comparative Examples 1 to 6

[0200] A mixed solution having the composition ratio shown in Table 1 was prepared and used as the curable resin composition of the examples and comparative examples. In addition, using a wire bar #5, the above curable resin composition was applied to the surfaces of a norbornene-based copolymer substrate (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and (a ring-opening metathesis polymer of norbornene type, thickness 2000 μm, COP substrate) so that the cured thickness was about 1 μm, and then heat-treated in an oven at 100 °C for 2 hours to fabricate the coatings of the examples and comparative examples.

[0201] Comparative Example 7

[0202] Prepare a mixed solution with the composition ratio shown in Table 1 and use it as the curable resin composition of Comparative Example 7. In addition, using a wire bar #5, apply the above curable resin composition onto the surfaces of a cycloolefin copolymer (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and a (norbornene-based ring-opening metathesis polymer, thickness 2000 μm, COP substrate) so that the thickness after curing is about 1 μm, and then perform heat treatment in an oven at 100 °C for 1 hour and heat treatment in an oven at 120 °C for 2 hours to produce the coating of Comparative Example 7.

[0203] Comparative Example 8

[0204] Prepare a mixed solution with the composition ratio shown in Table 1 and use it as the curable resin composition of Comparative Example 8. In addition, using a wire bar #5, apply the above curable resin composition onto the surfaces of a cycloolefin copolymer (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and a (norbornene-based ring-opening metathesis polymer, thickness 2000 μm, COP substrate) so that the thickness after curing is about 1 μm, and then perform heat treatment in an oven at 120 °C for 2 hours to produce the coating of Comparative Example 8.

[0205] The following details each component listed in Table 1.

[0206] POSS101: Trade name "POS101", manufactured by ConsTrue Chemical Co., Ltd. (glycidyl epoxy organosiloxane).

[0207] OX-SQ: Trade name "OX-SQ", manufactured by Toagosei Co., Ltd. (oxetane organosilsesquioxane).

[0208] KR-470: Trade name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd. (cyclic epoxy organosilicon resin).

[0209] CELLOXIDE 2021P: Trade name "CELLOXIDE 2021P", manufactured by Daicel Corporation (alicyclic epoxy resin).

[0210] YD-128: Trade name "YD-128", manufactured by Nippon Steel Chemical & Material Co., Ltd. (bisphenol A epoxy resin).

[0211] KER-2500A: Manufactured by Shin-Etsu Chemical Co., Ltd. (two-component addition-curable silicone resin).

[0212] KER-2500B: Manufactured by Shin-Etsu Chemical Co., Ltd. (two-component addition-curable silicone resin).

[0213] OE-6630A: Manufactured by Dow TORAY Co., Ltd. (two-component silicone resin).

[0214] OE-6630B: Manufactured by Dow TORAY Co., Ltd. (two-component silicone resin).

[0215] SI-100L: Trade name "SI-100L", manufactured by Sanshin Chemical Co., Ltd. (thermal polymerization initiator).

[0216] [Evaluation]

[0217] The following evaluations were carried out on the curable resin compositions and coatings of the examples and comparative examples, and the results are shown in Table 1.

[0218] (1) Viscosity

[0219] Approximately 1.1 mL of the curable resin compositions of the examples and comparative examples was taken, and the viscosity was measured at a temperature of 25 °C using an E-type viscometer (trade name "TV-25", manufactured by Toki Sangyo Co., Ltd.). The average value of the results of two measurements was taken as the viscosity of each curable resin composition.

[0220] (2) Adhesion test

[0221] On the coating surfaces of the examples and comparative examples, according to JIS K5600-5-6:1999, 100 squares were made in a grid pattern by scraping with a cutter at intervals of 1 mm. A tape was adhered and peeled off in the 90° direction, and it was visually confirmed whether the surface of the coating was peeled off from the tape. When 90 or more were adhered, it was designated as ◎, when 70 or more and less than 90 were adhered, it was designated as ○, and when less than 70 were adhered, it was designated as ×. (3) PCT test (autoclave test)

[0222] Regarding the coatings that received an evaluation of ○ or above in the above adhesion test, they were put into an autoclave test device (trade name "EHS-411M", manufactured by Espec Co., Ltd.) and stored in a constant temperature and humidity chamber at 120 °C and 100% RH for 8 hours. The appearance change after taking out was visually confirmed, and when there was no appearance change, it was designated as ○, and when whitening or wrinkles occurred, it was designated as ×.

[0223] (4) Arithmetic mean height (Sa)

[0224] According to ISO25178, it was placed on the test bench of a laser microscope (trade name "VK-8710", manufactured by Keyence Corporation), and Nikon Corporation's ×10 / 0.30 OFN25 (WP

[0225] 16.5) Measure the arithmetic roughness of the coating surface as a lens. Calculate the arithmetic mean height of the coating in a size of 200 μm × 200 μm, obtain the results 10 times, and take the average of the middle 6 test results as the arithmetic mean height.

[0226] [Table 1]

[0227] Table 1

[0228]

[0229]

[0230] It was confirmed that the curable resin composition of the example, by containing an alicyclic ketone compound and / or an alicyclic ether compound, and a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane, can be coated in a single layer, has sufficient adhesion to the norbornene-based copolymer substrate, and is excellent in moisture resistance. On the other hand, in the case of not using the cationically polymerizable silsesquioxane and / or the cationically polymerizable cyclic siloxane, the moisture resistance is poor, or sufficient adhesion to the norbornene-based copolymer substrate cannot be exhibited (Comparative Examples 1 to 4, Comparative Examples 7, 8). In addition, in the case of not using the alicyclic ketone compound and / or the alicyclic ether compound, the adhesion to the norbornene-based copolymer substrate cannot be exhibited (Comparative Examples 5, 6).

[0231] Hereinafter, modifications of the invention of the present disclosure will be described.

[0232] [Supplementary Note 1]

[0233] A curable resin composition which is a curable resin composition for coating a norbornene-based copolymer substrate, the curable resin composition containing an alicyclic ketone compound and / or an alicyclic ether compound and a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane.

[0234] [Supplementary Note 2]

[0235] The curable resin composition according to Supplementary Note 1, wherein the curable resin composition has a viscosity of 15 mPa·s or less at 25°C.

[0236] [Supplementary Note 3]

[0237] The curable resin composition according to Supplementary Note 1 or 2, wherein the alicyclic ketone compound is cyclohexanone or cyclopentanone, and the alicyclic ether compound is cyclopentyl methyl ether.

[0238] [Supplementary Note 4]

[0239] The curable resin composition according to any one of Supplementary Notes 1 to 3, wherein the cationically polymerizable functional group of the cationically polymerizable silsesquioxane has a cyclic ether structure.

[0240] [Supplementary Note 5]

[0241] A coating which is a cured product of the curable resin composition according to any one of Supplementary Notes 1 to 4.

[0242] [Supplementary Note 6]

[0243] A laminate which is formed by laminating the coating according to Supplementary Note 5 on at least one side of a norbornene-based copolymer substrate.

[0244] [Supplementary Note 7]

[0245] For the laminate according to Supplementary Note 6, 100 squares are made in a lattice pattern at 1 mm intervals on the coating, a tape is adhered, and when peeled off in the 90° direction, 90 or more squares remain.

[0246] [Supplementary Note 8]

[0247] For the laminate according to Supplementary Note 6 or 7, the arithmetic mean height (Sa) of the coating is 30 μm.

[0248] [Supplementary Note 9]

[0249] For the laminate according to any one of Supplementary Notes 6 to 8, the norbornene-based copolymer substrate is a substrate for a lens.

[0250] [Supplementary Note 10]

[0251] A plastic lens which includes the laminate according to Supplementary Note 9.

[0252] [Supplementary Note 11]

[0253] An image display device which includes the laminate according to any one of Supplementary Notes 6 to 9.

Claims

1. A curable resin composition for coating a norbornene-based copolymer substrate, the curable resin composition comprising: an alicyclic ketone compound and / or an alicyclic ether compound, and a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane.

2. The curable resin composition according to claim 1, wherein the curable resin composition has a viscosity of 15 mPa·s or less at 25°C.

3. The curable resin composition according to claim 1 or 2, wherein the alicyclic ketone compound is cyclohexanone or cyclopentanone, and the alicyclic ether compound is cyclopentyl methyl ether.

4. The curable resin composition according to claim 1 or 2, wherein the cationically polymerizable functional group of the cationically polymerizable silsesquioxane has a cyclic ether structure.

5. A coating which is a cured product of the curable resin composition according to claim 1 or 2.

6. A laminate which is formed by laminating the coating according to claim 5 on at least one side of a norbornene-based copolymer substrate.

7. The laminate according to claim 6, wherein 100 squares are formed in a grid pattern at 1 mm intervals on the coating, a tape is adhered, and when peeled off in the 90° direction, 90 or more squares remain.

8. The laminate according to claim 6, wherein the arithmetic mean height Sa of the coating is 30 μm or less.

9. The laminate according to claim 6, wherein the norbornene-based copolymer substrate is a substrate for a lens.

10. A plastic lens comprising the laminate according to claim 9.

11. An image display device comprising the laminate according to claim 6.

Images