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

Abstract

To provide a curable resin composition that can be applied as a single layer coating, exhibits sufficient adherence to a cycloolefin-based copolymer substrate, and is excellent in moisture resistance.SOLUTION: A curable resin composition of the present disclosure is a curable resin composition for coating a cycloolefin-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. The curable resin composition of the present disclosure preferably has a viscosity of 15 mPa s or less at 25°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a curable resin composition, a coating layer, 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 PCs, resin-based substrates have been used. Resin-based substrates are lightweight and have excellent processability. However, they are known to have lower chemical resistance than inorganic materials such as glass, and their optical properties are impaired by whitening and surface roughness. In addition, resin-based substrates have low surface hardness, are prone to scratches, and tend to have reduced transparency. Therefore, when using such resin substrates, a technique of using a coating liquid for protecting the resin substrate and coating the substrate surface has been 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 rate, and high water vapor barrier properties. However, cycloolefin-based polymers have high resistance to acids, alkalis, and polar solvents, and have a problem that even when a coating liquid is applied, the adhesion is poor and it is difficult to laminate a coating film.

[0004] As a technique related to coating a resin substrate containing a cycloolefin-based polymer, Patent Document 1 discloses an invention using a photocurable resin composition containing an acrylic resin. Further, Patent Document 2 discloses an invention using an ultraviolet curable resin containing inorganic fine particles as an easy adhesion layer.

Prior Art Documents

Patent Documents

[0005]

Patent Document

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the invention described in Patent Document 1, it is necessary to use an acrylic resin. Since the acrylic resin needs to be polymerized in a nitrogen atmosphere for sufficient curing, there are problems in handleability. In addition, the cycloolefin copolymer has high chemical resistance and there is also a problem that it is difficult to obtain sufficient adhesion.

[0007] In the invention described in Patent Document 2, it is necessary to laminate another layer as an adhesive layer between the base material and the coating layer. When laminating multiple layers in this way, there is a problem that the uniformity of the film thickness decreases and optical properties and the like are easily impaired.

[0008] In addition, the coating layer itself was also required to have excellent moisture resistance similar to that of the cycloolefin copolymer base material.

[0009] Therefore, an object of the present disclosure is to provide a curable resin composition that can be coated in a single layer, has sufficient adhesion to a cycloolefin copolymer base material, and is excellent in moisture resistance.

Means for Solving the Problems

[0010] As a result of intensive efforts to solve the above problems, the present inventors have found that a 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 can be coated in a single layer, has sufficient adhesion to a cycloolefin copolymer base material, and is excellent in moisture resistance. The present disclosure has been completed based on these findings.

[0011] That is, the present disclosure provides a curable resin composition for coating a cycloolefin 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.

[0012] The curable resin composition preferably has a viscosity at 25 °C of 15 mPa·s or less. By having the viscosity within the above range, it becomes easy to exhibit film thickness uniformity.

[0013] In the curable resin composition, the alicyclic ketone compound is preferably cyclohexanone or cyclopentanone, and the alicyclic ether compound is preferably cyclopentyl methyl ether.

[0014] In the curable resin composition, the cationically polymerizable functional group of the cationically polymerizable silsesquioxane preferably has a cyclic ether structure.

[0015] The present disclosure also provides a coating layer which is a cured product of the curable resin composition.

[0016] The present disclosure also provides a laminate in which the coating layer is laminated on at least one of cycloolefin copolymer substrates.

[0017] In the laminate, it is preferable that 100 meshes are formed in a lattice pattern at 1 mm intervals in the coating layer, an adhesive tape is attached, and when peeled off in the 90 °C direction, 90 or more meshes remain. By having the above configuration, it becomes easy to exhibit adhesion.

[0018] In the laminate, the arithmetic mean height (Sa) of the coating layer is preferably 30 μm or less.

[0019] In the laminate, the cycloolefin copolymer substrate is preferably a substrate for a lens.

[0020] Furthermore, the present disclosure provides a plastic lens including the above laminate.

[0021] Furthermore, the present disclosure provides an image display device including the above laminate.

Effects of the Invention

[0022] The curable resin composition of the present disclosure can be coated in a single layer, has sufficient adhesion to a cycloolefin copolymer substrate, and is excellent in moisture resistance. Therefore, it can be suitably used as a coating for a cycloolefin copolymer substrate.

Modes for Carrying Out the Invention

[0023] [Curable Resin Composition] The curable resin composition of the present disclosure is a curable resin composition for coating a cycloolefin 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 alicyclic ketone compound or the alicyclic ether compound, the surface of the cycloolefin copolymer substrate can be moderately attacked, and even when the curable resin composition is cured in a single layer, it can adhere firmly. Further, by including a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane, sufficient surface hardness and moisture resistance can be exhibited when a coating layer is formed.

[0024] (Cationically Polymerizable Silsesquioxane and / or Cationically Polymerizable Cyclic Siloxane) The curable resin composition includes a cationically polymerizable silsesquioxane and / or a cationically polymerizable cyclic siloxane. As the cationically polymerizable silsesquioxane and / or the cationically polymerizable cyclic siloxane, only one kind of either one may be used, or two or more kinds of either one may be used. Further, one kind of each of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane may be used, or two or more kinds may be used.

[0025] The above cationic polymerizable silsesquioxane is a compound having a cationic polymerizable functional group in the molecule. Examples of the above cationic polymerizable functional group include an epoxy group, an oxetane group, a vinyl ether group, a vinylphenyl group, and the like. Among them, from the viewpoint of further increasing the surface hardness of the coating layer and exhibiting moisture resistance, it is preferable that the above cationic polymerizable functional group has a cyclic ether structure, and an epoxy group is particularly preferable.

[0026] Examples of the group containing the above epoxy group include known or commonly used groups having an oxirane ring, and are not particularly limited. However, from the viewpoints of the curability of the curable resin composition and the heat resistance of the coating layer, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferable, more preferably the group represented by the following formula (1a) and the group represented by the following formula (1c), and even more preferably the group represented by the following formula (1a). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0027] 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 a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group. Among them, R 1aFrom 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 preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0028] In the above formula (1b), R 1b represents a linear or branched alkylene group, and groups similar to R 1a are 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 preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0029] In the above formula (1c), R 1c represents a linear or branched alkylene group, and groups similar to R 1a are exemplified. Among them, as R 1c 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 preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0030] In the above formula (1d), R 1d represents a linear or branched alkylene group, and groups similar to R 1a are 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 preferable, more preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0031] As the group containing an epoxy group, particularly, the group represented by the above formula (1a) in which R 1a is an ethylene group [among them, a 2-(3,4-epoxycyclohexyl)ethyl group] is preferable.

[0032] Examples of the cationic polymerizable silsesquioxane include compounds having a structural unit represented by the following formula (1). [R 1 SiO 3 / 2 (1)

[0033] The structural unit represented by the above formula (1) is generally a silsesquioxane structural unit (so-called T unit) represented by [RSiO 3 / 2 . In the above formula, R represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compound. In this specification, a compound having the structural unit represented by the above formula (1) may be referred to as "silsesquioxane (X)". R in formula (1) 1 represents a group (monovalent group) containing the above cationic polymerizable functional group.

[0034] 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).

[0035] Silsesquioxane (X) may have, as the silsesquioxane structural unit [RSiO 3 / 2 , in addition to the structural unit represented by the above formula (1), a structural unit represented by the following formula (2). [R 2 SiO 3 / 2 (2)

[0036] The structural unit represented by the above formula (2) is generally a silsesquioxane structural unit (T unit) represented by [RSiO 3 / 2 . 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.

[0037] R in the above formula (2) 2represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkyl group. Examples of the above aryl group include a phenyl group, a tolyl group, a naphthyl group, etc. Examples of the above aralkyl group include a benzyl group, a phenethyl group, etc. Examples of the above cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Examples of the above alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, etc.

[0038] Examples of the above substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, and substituted alkyl group include groups in which at least one of the hydrogen atoms or a part or all of the main chain skeleton in each of the above aryl group, aralkyl group, cycloalkyl group, and alkyl group is substituted with an alkyl group (especially a linear or branched alkyl group having 1 to 10 carbon atoms), an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (such as a fluorine atom), a mercapto group, an amino group, and a hydroxy group (hydroxyl group).

[0039] Among them, R 2 is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.

[0040] The ratio of each of the above silsesquioxane structural units (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) for forming these structural units.

[0041] Among the silsesquioxanes (X), in particular, the structural unit represented by the above formula (1) in which R 1 is a group containing an alicyclic epoxy group, and R 2It is preferable to contain at least a structural unit represented by the above formula (2) in which Ar is an aryl group which may have a substituent. In this case, the surface hardness, flexibility, processability, and flame retardancy of the coating layer tend to be more excellent.

[0042] In addition to the structural unit represented by the above formula (1) which is a T unit and the structural unit represented by the above formula (2), the silsesquioxane (X) may further have at least one siloxane 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). Note that R in the above M unit and the above D unit is the same group as R in the structural unit represented by the above formula (1) 1 and R in the structural unit represented by the above formula (2). Examples of the siloxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) include a structural unit represented by the following formula (3). 2 [HSiO 3 / 2 (3)

[0043] The silsesquioxane (X) contains a structural unit (T3 body) represented by the following formula (I). Further, it may contain a structural unit (T2 body) represented by the following formula (II). [R a SiO 3 / 2 (I) [R b SiO 2 / 2 (OR c )] (II)

[0044] ​Incidentally, when the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Also, when the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') is bonded to another silicon atom (a silicon atom not shown in formula (I')). On the other hand, each of the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') is bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, both the above T3 unit and T2 unit are structural units (T units) formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compounds. [Chemical formula] [Chemical formula]

[0045] R in the above formula (I) a (R in formula (I') a is the same) and R in formula (II) b (R in formula (II') b 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. Specific examples of R a and R b are the same as those of R 1 in the above formula (1) and R 2 in the above formula (2). Incidentally, R a in formula (I) and R bEach is a group derived from a group bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of the silsesquioxane (X) (a group other than an alkoxy group and a halogen atom), or, for example, when the cationic polymerizable functional group is an epoxy group, it is a group obtained by epoxidizing a group bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material of the silsesquioxane (X) (a group other than an alkoxy group and a halogen atom).

[0046] R in the above formula (II) c (R in the formula (II')) c is the same) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Among them, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. The alkyl group in R in the formula (II) generally originates from the alkyl group forming the alkoxy group in the hydrolyzable silane compound used as a raw material of the silsesquioxane (X). c

[0047] The molar ratio of the structural unit (T3 unit) represented by the above formula (I) to the structural unit (T2 unit) represented by the above formula (II) in the silsesquioxane (X) [structural unit represented by formula (I) / structural unit represented by formula (II)] (may be described as "T3 unit / T2 unit") is not particularly limited, but is preferably 5 or more, more preferably 5 to 20, still more preferably 5 to 18, still more preferably 6 to 16, still more preferably 7 to 15, and particularly preferably 8 to 14. By setting the above molar ratio [T3 unit / T2 unit] to 5 or more, the surface hardness of the coating layer tends to be further improved.

[0048] The above molar ratio [T3 unit / T2 unit] in the silsesquioxane (X) can be determined, for example, 29 by Si-NMR spectrum measurement. 29 ​In the Si-NMR spectrum, since the silicon atom in the structural unit (T3 form) represented by the above formula (I) and the silicon atom in the structural unit (T2 form) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts), the molar ratio [T3 form / T2 form] can be determined by calculating the integration ratio of these respective peaks. Specifically, for example, when the silsesquioxane (X) has a structural unit in which R 1 is a 2-(3,4-epoxycyclohexyl)ethyl group, the signal of the silicon atom in the structure (T3 form) represented by the above formula (I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 form) represented by the above formula (II) appears at -54 to -60 ppm. Therefore, in this case, the molar ratio [T3 form / T2 form] can be determined by calculating the integration ratio of the signal at -64 to -70 ppm (T3 form) and the signal at -54 to -60 ppm (T2 form).

[0049] The Si-NMR spectrum of the silsesquioxane (X) 29 can be measured, for example, by the following apparatus and conditions. Measuring apparatus: Trade name "JNM-ECA500 NMR" (manufactured by JEOL Ltd.) Solvent: Deuterochloroform Number of integrations: 1800 times Measuring temperature: 25 °C

[0050] The fact that the molar ratio [T3 form / T2 form] of the silsesquioxane (X) is 5 or more means that there is a certain amount or more of the T2 form relative to the T3 form in the silsesquioxane (X). Examples of such T2 forms include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. 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 R in formula (II).c Similarly, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [R 1 SiO 2 / 2 (OR c )] (4) [R 2 SiO 2 / 2 (OR c )] (5) [HSiO 2 / 2 (OR c )] (6)

[0051] The cationically polymerizable silsesquioxane (especially, silsesquioxane (X)) may be a silsesquioxane having a cage-type shape (cage-type silsesquioxane). The cage-type silsesquioxane includes a perfect cage-type silsesquioxane and an imperfect cage-type silsesquioxane, and among them, the imperfect cage-type silsesquioxane is preferable.

[0052] Generally, the perfect cage-type silsesquioxane is a polyorganosilsesquioxane composed only of T3 units, and there is no T2 unit in the molecule. That is, the above molar ratio [T3 unit / T2 unit] is 5 or more, and as described later, when there is one specific absorption peak near 1100 cm -1 in the FT-IR spectrum, the silsesquioxane is suggested to have an imperfect cage-type silsesquioxane structure.

[0053] Whether the silsesquioxane (X) has a cage-type (imperfect cage-type) silsesquioxane structure can be confirmed by FT-IR spectrum [Reference: R.H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. Specifically, in the FT-IR spectrum, there are no specific absorption peaks near 1050 cm -1 and near 1150 cm -1 , and near 1100 cm -1When there is one specific absorption peak in the vicinity, it can be identified that the silsesquioxane (X) has a cage-type (incomplete cage-type) silsesquioxane structure. In contrast, generally, in the FT-IR spectrum, when there are specific absorption peaks at around 1050 cm -1 and around 1150 cm -1 respectively, it is identified as having a ladder-type silsesquioxane structure. The FT-IR spectrum of the silsesquioxane (X) can be measured, for example, under the following apparatus and conditions. Measuring apparatus: Trade name "FT-720" (manufactured by Horiba, Ltd.) Measuring method: Transmission method Resolution: 4 cm -1 Measuring wavenumber range: 400 - 4000 cm -1 Number of integrations: 16 times

[0054] The ratio (total amount) of the structural unit having a cationic polymerizable functional group (for example, the structural unit represented by the above formula (1), the structural unit represented by the above formula (4), etc.) to the total amount of the siloxane structural units [total siloxane structural units; total amount of M unit, D unit, T unit, and Q unit] (100 mol%) in the cationic polymerizable silsesquioxane is not particularly limited, but 50 mol% or more (for example, 50 - 100 mol%) is preferable, 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 ratio is 50 mol% or more, the curability of the curable resin composition is improved, and the surface hardness of the coating layer becomes extremely high. The ratio 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, etc.

[0055] The ratio of the structural unit (T3 unit) represented by the above formula (I) to the total amount of siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) in the silsesquioxane (X) is not particularly limited, but is preferably 50 mol% or more, more preferably 60 to 99 mol%, still more preferably 70 to 98 mol%, still more preferably 80 to 95 mol%, and particularly preferably 85 to 92 mol%. By setting the ratio of the structural unit of the T3 unit to 50 mol% or more, it is presumed that it becomes easier to form an incomplete cage-type shape having an appropriate molecular weight, and the surface hardness of the coating layer tends to be further improved.

[0056] The ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) to the total amount of siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) in the silsesquioxane (X) is not particularly limited, but is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, still more preferably 0 to 30 mol%, and particularly preferably 1 to 15 mol%. By setting the above ratio to 50 mol% or less, the ratio of the structural unit having a cationic polymerizable functional group can be relatively increased, so that the curability of the curable resin composition is improved and the surface hardness of the coating layer tends to be higher.

[0057] The ratio (total amount), particularly the total ratio of the T3 unit and the T2 unit, of the structural unit represented by the above formula (I) and the structural unit represented by the above formula (II) with respect 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%) in the silsesquioxane (X) is not particularly limited, but is preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. By setting the above ratio to 60 mol% or more, it is presumed that it becomes easier to form an incomplete cage type shape having an appropriate molecular weight, and the surface hardness of the coating layer tends to be further improved. In particular, it is preferable that the ratio (total amount) of the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is within the above range.

[0058] The number average molecular weight (Mn) in terms of standard polystyrene of the silsesquioxane (X) by gel permeation chromatography is not particularly limited, but is preferably 1000 to 3000, more preferably 1000 to 2800, still more preferably 1100 to 2600, and particularly preferably 1500 to 2500. By setting the number average molecular weight to 1000 or more, the surface hardness of the coating layer tends to be further improved. The heat resistance and wear resistance of the coating layer tend 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 the heat resistance of the coating layer tends to be improved.

[0059] The molecular weight distribution (Mw / Mn) in terms of standard polystyrene of the silsesquioxane (X) by gel permeation chromatography is not particularly limited, but is preferably from 1.0 to 3.0, more preferably from 1.1 to 2.0, still more preferably from 1.2 to 1.9, still more preferably from 1.3 to 1.8, and particularly preferably from 1.45 to 1.80. By setting the molecular weight distribution to 3.0 or less, the surface hardness of the coating layer tends to be higher. On the other hand, by setting the molecular weight distribution to 1.0 or more (particularly 1.1 or more), it tends to become liquid and the handleability tends to be improved.

[0060] Incidentally, the number average molecular weight and molecular weight distribution of the silsesquioxane (X) can be measured by the following apparatus and conditions. Measuring apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation) Columns: Shodex KF-801×2, KF-802, and KF-803 (manufactured by Showa Denko K.K.) Measurement temperature: 40 °C Eluent: THF, sample concentration 0.1 to 0.2 mass% Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation) Molecular weight: In terms of standard polystyrene

[0061] The cationically polymerizable silsesquioxane can be produced by a known or commonly used method for producing silsesquioxane, and is not particularly limited. For example, it can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds.

[0062] The above cationically polymerizable cyclic siloxane is a compound having at least a cyclic siloxane skeleton composed of siloxane bonds (Si-O-Si). Further, in addition to the above cyclic siloxane skeleton, it may contain a linear or branched silicone (linear or branched polysiloxane), a siloxane skeleton such as a cage-type or ladder-type polysilsesquioxane, and the like.

[0063] The number of Si-O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) of the above cationically polymerizable cyclic siloxane is preferably from 2 to 12, more preferably from 4 to 8.

[0064] Also, the above cationically polymerizable cyclic siloxane preferably has two or more alicyclic epoxy groups in the molecule. The above alicyclic epoxy group means a cyclic olefin group epoxidized in the molecule. The "epoxidized cyclic olefin group" is a group (monovalent group) formed by removing one hydrogen atom from a structure in which 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) is epoxidized. That is, the epoxidized cyclic olefin group contains an aliphatic hydrocarbon ring structure and an epoxy group, and the epoxy group is a group in which the epoxy group is composed of two adjacent carbon atoms and an oxygen atom constituting the aliphatic hydrocarbon ring.

[0065] Examples of the cyclic olefin group (in the form before epoxidation) in the above epoxidized cyclic olefin group include cycloalkenyl groups such as cyclopropenyl group (e.g., 2-cyclopropen-1-yl group, etc.), cyclobutenyl group (e.g., 2-cyclobuten-1-yl group, etc.), cyclopentenyl group (e.g., 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, etc.), cyclohexenyl group (e.g., 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, etc.); cycloalkadienyl groups such as 2,4-cyclopentadien-1-yl group, 2,4-cyclohexadien-1-yl group, 2,5-cyclohexadien-1-yl group, etc.; polycyclic groups such as dicyclopentenyl group, dicyclohexenyl group, norbornenyl group, etc.

[0066] In addition, one or more substituents may be bonded to the aliphatic hydrocarbon ring forming the cyclic olefin group in the epoxidized cyclic olefin group. Examples of the substituent include substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms), and more specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxy group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, and isobutyloxy group (preferably C 1-6 alkoxy group, more preferably C 1-4 alkoxy group); alkenyloxy groups such as allyloxy group (preferably C 2-6 alkenyloxy group, more preferably C 2-4 alkenyloxy group); aryloxy groups such as phenoxy group, tolyloxy group, and naphthyloxy group, which may have substituents such as C 1-4 alkyl group, C 2-4 alkenyl group, halogen atom, and C 1-4 alkoxy group on the aromatic ring (preferably C 6-14 aryloxy group); aralkyloxy groups such as benzyloxy group and phenethyloxy group (preferably C 7-18 aralkyloxy group); acyloxy groups such as acetyloxy group, propionyloxy group, (meth)acryloyloxy group, and benzoyloxy group (preferably C 1-12 acyloxy group); mercapto group; alkylthio groups such as methylthio group and ethylthio group (preferably C 1-6 alkylthio group, more preferably C 1-4 alkylthio group); alkenylthio groups such as allylthio group (preferably C 2-6 alkenylthio group, more preferably C 2-4 alkenylthio group); arylthio groups such as phenylthio group, tolylthio group, and naphthylthio group, which may have substituents such as C 1-4 alkyl group, C 2-4 alkenyl group, halogen atom, and C 1-4 alkoxy group on the aromatic ring (preferably C 6-14 arylthio group); aralkylthio groups such as benzylthio group and phenethyloxy group (preferably C 7-18an aralkylthio group); a carboxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group (preferably a C 1-6 alkoxy-carbonyl group); an aryloxycarbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group, a naphthyloxycarbonyl group (preferably a C 6-14 aryloxy-carbonyl group); an aralkyloxycarbonyl group such as a benzyloxycarbonyl group (preferably a C 7-18 aralkyloxy-carbonyl group); an amino group; a mono- or dialkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group (preferably a mono- or di-C 1-6 alkylamino group); an acylamino group such as an acetylamino group, a propionylamino group, a benzoylamino group (preferably a C 1-11 acylamino group); an oxetanyl group-containing group such as an ethyloxetanyloxy group; an acyl group such as an acetyl group, a propionyl group, a benzoyl group; an oxo group; a group in which two or more of these are bonded via a C 1-6 alkylene group, etc. may be mentioned.

[0067] Among them, as the above cyclic olefin group, a cyclic olefin group having 5 to 12 carbon atoms is preferable, more preferably a cycloalkenyl group having 5 to 12 carbon atoms, and still more preferably a cyclohexenyl group. That is, as the above epoxidized cyclic olefin group, a group in which a cyclic olefin group having 5 to 12 carbon atoms is epoxidized is preferable, more preferably a group in which a cycloalkenyl group having 5 to 12 carbon atoms is epoxidized, and still more preferably a group in which a cyclohexenyl group is epoxidized (cyclohexene oxide group). In addition, the above first epoxy compound may have one kind of epoxidized cyclic olefin group or two or more kinds.

[0068] The number of epoxidized cyclic olefin groups that the above first epoxy compound has in the molecule may be 2 or more and is not particularly limited, but 2 to 6 are preferable, more preferably 3 to 5, and still more preferably 4.

[0069] Examples of the cationically polymerizable cyclic siloxane include 2,4 - di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8,8 - hexamethyl - cyclotetrasiloxane, 4,8 - di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8 - hexamethyl - cyclotetrasiloxane, 2,4 - di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8 - dipropyl - 2,4,6,8 - tetramethyl - cyclotetrasiloxane, 4,8 - di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6 - dipropyl - 2,4,6,8 - tetramethyl - cyclotetrasiloxane, 2,4,8 - tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8 - pentamethyl - cyclotetrasiloxane, 2,4,8 - tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6 - propyl - 2,4,6,8 - tetramethyl - cyclotetrasiloxane, 2,4,6,8 - tetra[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8 - tetramethyl - cyclotetrasiloxane, and the like.

[0070] The contents of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane in the above curable resin composition are not particularly limited, but are 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, based on the total amount (100% by mass) of the curable compounds. When the above content ratio is more than 50% by mass, the surface hardness of the coating layer tends to be further improved and the moisture resistance can be exhibited. When the above content ratio is 99% by mass or less, other components can be contained, and the effects obtained by containing these tend to be further improved. In addition, a curing catalyst can be contained, and thereby the curing of the curable resin composition tends to proceed more efficiently. When the curable resin composition contains only one of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane, it is preferable that the content satisfies the above range.

[0071] Further, the contents of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane are preferably 10 to 90% by mass, more preferably 12 to 80% by mass, and still more preferably 14 to 70% by mass, based on 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 layer when cured. 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 cycloolefin-based copolymer substrate can be exhibited. When the curable resin composition contains only one of the cationically polymerizable silsesquioxane and the cationically polymerizable cyclic siloxane, it is preferable that the content satisfies the above range.

[0072] (alicyclic ketone compound and / or alicyclic ether compound) 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 are used as solvents for the above curable resin composition. By containing the above alicyclic ketone compound or the above alicyclic ether compound, the surface of the cycloolefin copolymer substrate can be moderately invaded, and sufficient adhesion can be exhibited even in a single layer. As the above alicyclic ketone compound and / or the above alicyclic ether compound, only one kind of either one may be used, or two or more kinds of either one may be used. Also, one kind of each of the above alicyclic ketone compound and the above alicyclic ether compound may be used, or two or more kinds may be used.

[0073] The above alicyclic ketone compound is a compound having at least an alicyclic ring and a ketone group in its structure. It does not necessarily have a ketone group on the alicyclic ring, but is preferably a compound having a ketone group on the alicyclic ring. The above alicyclic ring is preferably a cyclic aliphatic hydrocarbon not containing a carbon-carbon unsaturated bond, and the above alicyclic ring may be a monocyclic ring or a polycyclic ring. Specifically, as the above monocyclic ring, a cycloalkyl group having 3 to 10 carbon atoms can be mentioned, and preferably a cycloalkyl group having 4 to 7 carbon atoms. Also, as the above polycyclic ring, a polycyclic cyclic aliphatic hydrocarbon composed of 5 to 7-membered rings and not containing a carbon-carbon unsaturated bond can be mentioned, and the number of rings of the above polycyclic ring is preferably 2 to 10.

[0074] Furthermore, one or more substituents other than the ketone group may be bonded to the above alicyclic ring. Examples of the above substituents include substituents having 0 to 20 carbon atoms, and more specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxy group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group (preferably C 1-6 alkoxy group); alkenyloxy groups such as allyloxy group (preferably C 2-6 alkenyloxy group); phenoxy group, tolyloxy group, naphthyloxy group, etc., with C 1-4Alkyl group, C 2-4 Alkenyl group, halogen atom, C 1-4 An aryloxy group (preferably C) which may have a substituent such as an alkoxy group 6-14 aryloxy group; aralkyloxy group such as benzyloxy group, phenethyloxy group (preferably C 7-18 aralkyloxy groups; acyloxy groups such as acetyloxy groups, propionyloxy groups, (meth)acryloyloxy groups, and benzoyloxy groups (preferably C 1-12 acyloxy group; mercapto group; alkylthio group such as methylthio group or ethylthio group (preferably C 1-6 Alkylthio groups, more preferably C 1-4 Alkylthio group; alkenylthio group such as allylthio group (preferably C 2-6 Alkenylthio groups, more preferably C 2-4 alkenylthio group); phenylthio group, tolylthio group, naphthylthio group, etc., with C in the aromatic ring 1-4 Alkyl group, C 2-4 Alkenyl group, halogen atom, C 1-4 An arylthio group (preferably C) which may have a substituent such as an alkoxy group 6-14 arylthio group; aralkylthio group such as benzylthio group, phenethylthio group (preferably C 7-18 aralkylthio groups; carboxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups, and butoxycarbonyl groups (preferably C 1-6 Alkoxy-carbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group (preferably C 6-14 Aryloxycarbonyl group; aralkyloxycarbonyl group such as benzyloxycarbonyl group (preferably C 7-18 aralkyloxy-carbonyl group; amino group; mono- or di-alkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group (preferably mono- or di-C 1-6an alkylamino group); an acylamino group such as an acetylamino group, a propionylamino group, or a benzoylamino group (preferably C 1-11 an acylamino group); an oxetanyl group-containing group such as an ethyloxetanyloxy group; an acyl group such as an acetyl group, a propionyl group, or a benzoyl group; an oxo group; a group in which two or more of these are bonded via a C 1-6 alkylene group, etc. may be mentioned.

[0075] Among the above alicyclic ketone compounds, those having a monocyclic ring as the alicyclic ring are preferably used. Specifically, cyclopentanone, cyclohexanone, cycloheptanone, 2-methyl-cyclopentanone, etc. may be mentioned, and cyclohexanone or cyclopentanone is more preferable from the viewpoint of the action on the above cycloolefin copolymer base material.

[0076] The above alicyclic ether compound is a compound having at least an alicyclic ring and an ether group in its structure, and preferably a compound in which a group having the above alicyclic ring and a group having the above alicyclic ring or a hydrocarbon group other than the group having the above alicyclic ring are linked by an ether group, and more preferably a compound in which a group having the above alicyclic ring and a hydrocarbon group other than the group having the above alicyclic ring are linked by an ether group. Specifically, the above alicyclic ether compound is preferably represented by the following formula (A).

[0077] [Chemical formula] (In the above formula, R A represents a group having an alicyclic ring, and R B represents an alkyl group having 1 to 6 carbon atoms.)

[0078] Examples of the alicyclic ring of the group having the above alicyclic ring include the same alicyclic rings as those exemplified for the above alicyclic ketone compounds.

[0079] The above R B is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0080] Specifically, as the alicyclic ether compound, cycloalkyl C 1-6 alkyl ether is preferable. As the cycloalkyl C 1-6 alkyl ether, cyclopentyl C 1-3 alkyl ether and cyclohexyl C 1-3 alkyl ether are preferable, and among them, cyclopentyl methyl ether is particularly preferable.

[0081] 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 still more preferably 35 to 80% by mass with respect to the total amount (100% by mass) of the curable resin composition. When the total content of the above alicyclic ketone compound and alicyclic ether compound is 15% by mass or more, the viscosity of the curable resin composition can be sufficiently reduced, and it becomes easy to uniformly form a thin film. Further, when it is 90% by mass or less, the effect as a coating layer can be exhibited. When the curable resin composition contains only one of the above alicyclic ketone compound or the above alicyclic epoxy compound, it is preferable that its content satisfies the above range.

[0082] The curable resin composition may further contain other solvents other than the above alicyclic ketone compound and the above alicyclic ether compound, but from the viewpoint of exhibiting adhesion to the cycloolefin-based copolymer substrate, it is preferable not to contain the above other solvents. The above other solvents are not particularly limited as long as they can dissolve the above cationic polymerizable silsesquioxane and components added as necessary and do not inhibit polymerization. Only one kind of the above other solvents may be used, or two or more kinds may be used.

[0083] The above-mentioned other solvent is preferably a solvent that can impart fluidity suitable for applying the coating layer and can be easily removed by heating at a temperature capable of suppressing the progress of polymerization. It is preferable to use a solvent having a boiling point (at 1 atm) of 170°C or lower (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.).

[0084] When the above-mentioned other solvent is contained, its content is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more with respect to the total amount (100% by mass) of the curable resin composition. The upper limit is not particularly limited, but it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

[0085] 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 still more preferably 90% by mass or more with respect to the total amount (100% by mass) of the solvent. When the content of the alicyclic ketone compound and the alicyclic ether compound in the solvent is 50% by mass or more, it becomes easy to exhibit adhesion to the cycloolefin copolymer substrate. The upper limit is not particularly limited, but it may be 100% by mass.

[0086] The above-mentioned curable resin composition may contain other curable compounds other than the above-mentioned cationic polymerizable silsesquioxane. Examples of the above-mentioned other curable compounds include other cationic polymerizable compounds and radical polymerizable compounds other than the above-mentioned cationic polymerizable silsesquioxane. Only one kind of the above-mentioned other curable compound may be used, or two or more kinds may be used.

[0087] Examples of the above-mentioned other cationically polymerizable compounds include compounds having one or more epoxy groups in the molecule, which are compounds other than the above-mentioned cationically polymerizable silsesquioxane (sometimes referred to as "other epoxy compounds"), compounds having one or more oxetane 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 hydroxy groups in the molecule (sometimes referred to as "polyol compounds"), and the like.

[0088] Examples of the above-mentioned other epoxy compounds include compounds having one or more glycidyl ether groups in the molecule. The compounds having one or more glycidyl ether groups in the molecule include, for example, aromatic glycidyl ether-based epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenol 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, and epoxy compounds obtained from trisphenol methane; hydrogenated glycidyl ether-based epoxy compounds; glycidyl ester-based epoxy compounds; glycidyl amine-based epoxy compounds, and the like.

[0089] Examples of the hydrogenated glycidyl ether-based epoxy compound include 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 multimers (hydrogenated bisphenol A type epoxy compounds); compounds obtained by hydrogenating bisphenol F type epoxy compounds such as 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 multimers (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol 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 of epoxy compounds obtained from trisphenol methane, and the like.

[0090] Examples of the oxetane compound 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.

[0091] Examples of the vinyl ether compound 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 monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and derivatives thereof.

[0092] Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, phenoxy resin, polybutadienes having a hydroxyl group, acrylic polyol, and the like.

[0093] When the above-mentioned curable resin composition contains the above-mentioned other cationic curable compound, the content of the other cationic curable compound is not particularly limited, but 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 with respect to the total amount (100% by mass) of the curable resin composition. When the above content is 1% by mass or more, there is a tendency to more easily obtain the effect of using the other cationic curable compound. On the other hand, when the above content is less than 50% by mass, a sufficient amount of cationically polymerizable silsesquioxane can be used.

[0094] Also, when the above-mentioned curable resin composition contains the above-mentioned other cationic curable compound, the content of the other cationic curable compound is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass with respect to the total amount (100% by mass) of the curable compound.

[0095] 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 compound. Only one type of the above-mentioned curing catalyst may be used, or two or more types may be used.

[0096] The above-mentioned curing catalyst is selected according to the type of the curable functional group of the above-mentioned curable compound. Among them, a cationic polymerization initiator or a radical polymerization initiator is preferable. The above-mentioned cationic polymerization initiator is a compound that generates a cation species by heat or irradiation with active energy rays and initiates the curing reaction of the curable compound.

[0097] 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).

[0098] As the above-mentioned photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, etc. can be mentioned.

[0099] Examples of the above-mentioned sulfonium salts include triarylsulfonium salts such as triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, 4-(p-tolylthio)phenyl di-(p-phenyl)sulfonium salt; diarylsulfonium salts such as diphenylphenacylsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0100] Examples of the 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, etc. Commercially available products such as the product name "CPI-101A" (manufactured by San-Apro Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate) and the product name "CPI-100P" (manufactured by San-Apro Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate) can also be used.

[0101] Examples of the iodonium salt include the product name "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, 45% alkyl glycidyl ether solution of bis(4-dodecylphenyl)iodonium hexafluoroantimonate), the product name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Ltd., [(1-methylethyl)phenyl](methylphenyl)iodonium tetrakis(pentafluorophenyl)borate), the product 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.

[0102] Examples of the selenium salt include triarylselenium salts such as triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, 1-naphthyldiphenylselenium salt; diarylselenium salts such as diphenylphenacylselenium salt, diphenylbenzylselenium salt, diphenylmethylselenium salt; monoarylselenium salts such as phenylmethylbenzylselenium salt; trialkylselenium salts such as dimethylphenacylselenium salt, etc.

[0103] Examples of the ammonium salt include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt; pyrrolidinium salts such as N,N-dimethylpyrrolidinium salt, N-ethyl-N-methylpyrrolidinium 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.

[0104] Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, and tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt, and the like.

[0105] Examples of the salt of the transition metal complex ion include 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 + , and the like.

[0106] Examples of the anion constituting the above salt include SbF6 - , PF6 - , BF4 - , (CF3CF2)3PF3 - , (CF3CF2CF2)3PF3 - , (C6F5)4B - , (C6F5)4Ga - , sulfonic acid anions (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anion, p-toluenesulfonic acid anion, etc.), (CF3SO2)3C - , (CF3SO2)2N -, examples include perhalate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0107] Examples of the above-mentioned thermal cationic polymerization initiators include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc. Also, examples of the anions constituting the above salts are the same as those in the photo cationic polymerization initiators.

[0108] Examples of the above 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 "Sun-Aid SI-60L", "Sun-Aid SI-60S", "Sun-Aid SI-80L", "Sun-Aid SI-100L", "Sun-Aid SI-150L" (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the above aluminum chelates include aluminum diisopropyl ethylacetoacetate, aluminum tris(ethylacetoacetate), etc. Also, examples of the above boron trifluoride amine complexes include boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, etc.

[0109] The above radical polymerization initiator is a compound that generates radicals by heat or irradiation with active energy rays to initiate the curing reaction of the curable compound.

[0110] Examples of the above radical polymerization initiators include photo radical polymerization initiators and thermal radical polymerization initiators. Examples of the above photo radical polymerization initiators include alkylphenone-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.

[0111] Examples of the above alkylphenone-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-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one oligomers, and the like.

[0112]

[0113] Examples of the above oxime ester-based photo radical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyl oxime, and the like.

[0114] ​Examples of the α-hydroxy ketone-based photo radical polymerization initiator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like.

[0115] The content (blending amount) of the curing catalyst in the curable resin composition is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the curable compounds. When the content of the curing catalyst is 0.01 part by mass or more, the curing reaction can proceed efficiently and sufficiently, and the surface hardness of the coating layer tends to be further improved. On the other hand, when the content of the curing catalyst is 10 parts by mass or less, the storage stability of the curable resin composition tends to be improved and the coloring of the cured product tends to be suppressed.

[0116] The above curable resin composition may further contain, as other components, a curing agent, a curing aid, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, inorganic fillers treated with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; fillers such as conductive metal powders of silver, copper, etc., a curing aid, a stabilizer (light stabilizer, heat stabilizer, heavy metal deactivator, etc.), an ultraviolet absorber (triazine-based ultraviolet absorber, benzotriazole-based ultraviolet absorber, benzophenone-based ultraviolet absorber, oxybenzophenone-based ultraviolet absorber, salicylic acid ester-based ultraviolet absorber, cyanoacrylate-based ultraviolet absorber), a flame retardant (phosphorus-based flame retardant, halogen-based flame retardant, inorganic-based flame retardant, etc.), a flame retardant aid, a reinforcing material (other fillers, etc.), a nucleating agent, a coupling agent (silane coupling agent, etc.), a lubricant, a wax, a plasticizer, a release agent, an impact resistance improver, a hue improver, a clarifying agent, a rheology modifier (fluidity improver, etc.), a processability improver, a colorant (dye, pigment, etc.), an antistatic agent, a dispersant, a surface modifier (slip agent, etc.), a matting agent, an antifoaming agent, a foam suppressant, a defoaming agent, an antibacterial agent, a preservative, a viscosity modifier, a thickener, a photosensitizer, a foaming agent and other conventional additives. Only one kind of the above other components may be used, or two or more kinds may be used. The content of the above other components is not particularly limited, but 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 still more preferably 10 parts by mass or less (for example, 0.1 to 10 parts by mass) with respect to 100 parts by mass of the total amount of the curable compounds.

[0117] Further, the curable resin composition preferably has an antimony compound content of 1000 mass ppm or less with respect to the total amount (100% by mass) of the curable resin composition. By having an antimony compound content of 1000 mass ppm or less in the curable resin composition, the safety can be made more excellent. The lower limit is not particularly limited and may be 0 mass ppm.

[0118] The above curable resin composition is not particularly limited, but can be prepared by stirring and mixing the above components at room temperature or while heating as necessary. The curable resin composition can also be used as a one-component composition in which the components are pre-mixed and used as is, or, for example, as a multi-component (e.g., two-component) composition in which two or more components stored separately are mixed at a predetermined ratio before use and then used.

[0119] The above curable resin composition is not particularly limited, but is preferably liquid at normal temperature (about 25°C). More specifically, the viscosity of the curable resin composition at 25°C is preferably 15 mPa·s or less, more preferably 12 mPa·s or less, and even more preferably 10 mPa·s or less. By setting the viscosity to 15 mPa·s or less, it is possible to uniformly coat the substrate with a thin film (exhibiting film thickness uniformity) and it is easier to exhibit optical properties. On the other hand, the lower limit is not particularly limited, but for example, it is preferably 0.5 mPa·s or more.

[0120] [Coating layer] As one embodiment of the present disclosure, a coating layer including a cured product of the above curable resin composition can be mentioned.

[0121] As a method for manufacturing the above coating layer, it can be manufactured according to a known or conventional method for manufacturing a coating layer, and the manufacturing method is not particularly limited. For example, the curable resin composition can be applied to at least one surface of the cycloolefin-based copolymer substrate, and the curable resin composition can be cured while removing the solvent by heating and drying as necessary. The coating method of the curable resin composition and the conditions for curing are not particularly limited and can be appropriately selected from the following conditions, for example.

[0122] As the coating and curing method of the above coating layer, ordinary coating methods can be used. For example, well-known methods such as dipping method, roll coating, gravure coating, inkjet coating, spin coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method, organic vapor deposition method, etc. can be used.

[0123] As the curing method, when a photo-curing 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 mentioned. In addition, when irradiating ultraviolet rays in the curing of the above coating layer, for example, the integrated irradiation amount is preferably 1 to 5000 mJ / cm 2 It is preferably about this.

[0124] Specific curing conditions are not particularly limited. For example, the above curable resin composition is first heat-treated (pre-baked) preferably at 60°C or higher, more preferably at 120°C or higher, still more preferably at 150°C or higher, preferably for 10 seconds or longer, more preferably for 30 seconds or longer, still more preferably for 60 seconds or longer, and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): preferably 300 mJ / cm 2 or more; irradiation intensity: 100 mW / cm 2 or more), and finally, it can be cured by heat treatment (aging) preferably at 120°C or higher and preferably for 0.5 hours or longer.

[0125] Also, as the curing method, when a heat-curing catalyst is used, the specific heating temperature is preferably 100 to 200°C, more preferably 110 to 170°C. Also, the heating time is preferably 30 minutes to 6 hours, more preferably 1 to 4 hours. Note that the above heating temperature and heating time can be appropriately changed. Also, the curing conditions are not limited to these ranges, and the pre-bake temperature, time, and aging temperature, time can be appropriately selected according to the solvent used, and the ultraviolet irradiation conditions can also be appropriately selected according to the curing catalyst used.

[0126] As described above, by coating and curing the above-mentioned curable resin composition, it is possible to exhibit high adhesion to a cycloolefin copolymer substrate with a single layer without using other adhesive layers. Furthermore, it is possible to form a coating layer having high surface hardness and moisture resistance.

[0127] The thickness of the above coating layer is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm. When the thickness of the coating layer is 0.1 μm or more, the performance as a coating layer can be exhibited. Also, when it is 10 μm or less, it becomes easy to apply as a thin film with high smoothness.

[0128] [Laminate] Further, as an embodiment of the present disclosure, a laminate in which the above coating layer is formed on at least one surface of a cycloolefin copolymer substrate can be mentioned. By including a coating layer that is a cured product of the above curable resin composition, the laminate can increase the surface hardness, have sufficient adhesion to the above cycloolefin copolymer substrate, and exhibit moisture resistance. The above coating layer may be provided on only one surface of the above cycloolefin copolymer substrate, or may be provided on both surfaces. Also, when coating layers are provided on both surfaces of the cycloolefin copolymer substrate, coating layers having the same composition and thickness may be provided on each surface, or coating layers having different compositions and thicknesses may be provided.

[0129] In addition, the laminate may contain other layers other than the base material and the coating layer, or may not contain other layers from the perspective of coating with a thin film. Examples of the other layers include an undercoat layer and an antireflection layer. The other layer may be formed on only one surface of the cycloolefin-based copolymer base material, or may be formed on both surfaces. Further, when the other layer is formed on both surfaces of the cycloolefin-based copolymer base material, the same layers may be laminated respectively, or layers having different thicknesses and compositions may be laminated respectively.

[0130] Examples of the cycloolefin-based copolymer used for the cycloolefin-based copolymer base material include cycloolefin polymer (COP) and cycloolefin copolymer (COC). Only one type of the cycloolefin-based copolymer may be used, or two or more types may be used.

[0131] The 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 cyclic olefin is not particularly limited and may be a polycyclic cyclic olefin or a monocyclic cyclic olefin. Examples of the polycyclic cyclic olefin include norbornene compounds such as norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidene norbornene, butylnorbornene; dicyclopentadiene compounds such as dicyclopentadiene, dihydrodicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene; tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene, tetracyclopentadiene, etc. Examples of the monocyclic cyclic olefin include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclododecatriene, etc.

[0132] The above-mentioned 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, and branched α-olefins having 4 to 20 carbon atoms such as 4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene.

[0133] The content of the cycloolefin copolymer in the cycloolefin copolymer base material is not particularly limited, but it is preferably 80% by mass or more, more preferably 90% by mass or more, based on the total amount (100% by mass) of the base material. The upper limit is not particularly limited, but it may be 100% by mass.

[0134] The above-mentioned 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, and lubricants, if necessary.

[0135] The form of the above cycloolefin copolymer base material is not particularly limited, and examples thereof include a base material for films and a base material for lenses. When the cycloolefin copolymer base material is a base material for films, the thickness of the cycloolefin copolymer base material is preferably 1 to 200 μm, more preferably 3 to 100 μm, and even more preferably 5 to 50 μm. When the cycloolefin copolymer base material is a base material for lenses, the thickness of the cycloolefin copolymer base material is preferably 500 to 5000 μm, more preferably 700 to 4500 μm, and even more preferably 1000 to 4000 μm. When the base material is a base material for films, it can be formed and manufactured by a melt extrusion molding method, a solution casting method, etc. When the 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, etc.

[0136] The above laminate is scratched with a cutter blade at intervals of 1 mm from the coating layer side in accordance with JIS K5600-5-6:1999 to create 100 meshes in a grid pattern, pasted with an adhesive tape, peeled off in the 90° direction, and visually confirmed whether the surface of the coating layer adheres to the adhesive tape and then peels off. When visually confirmed, 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 layer exhibits sufficient adhesion to the cycloolefin copolymer base material. When the coating layer is laminated on both sides of the above base material, it is sufficient if at least one surface satisfies the above range.

[0137] The above laminate is preferably one in which no whitening or cracking is confirmed after a PCT test (pressure cooker test) of storing in a thermo-hygrostat at 120 °C and 100% RH for 8 hours. When the coating layer is laminated on both sides of the above base material, it is sufficient if at least one surface satisfies the above description.

[0138] The arithmetic mean height (Sa) of the coating layer in the above laminate is preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less. When the arithmetic mean height is 30 μm or less, it becomes easier to improve the film thickness uniformity. The lower limit is not particularly limited, but it is 0.1 μm or more. When the coating layer is laminated on both sides of the base material, it is sufficient to satisfy the above range on at least one side.

[0139] When using a base material for film as the cycloolefin copolymer base material, the thickness of the above laminate is preferably 1 to 200 μm, more preferably 3 to 100 μm, and even more preferably 5 to 50 μm. When using a base material for lens as the 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 even more preferably 1000 to 4000 μm.

[0140] In addition, since the above laminate is coated with a coating layer having high adhesion to a cycloolefin copolymer base material having excellent physical properties such as moisture resistance, and the surface hardness is improved, it can be suitably used as a plastic lens or an image display device.

[0141] Each aspect disclosed in this specification can be combined with any other features disclosed in this specification. Also, each configuration and their combinations in each embodiment are examples, and within the scope not departing from the gist of the present disclosure, addition, omission, and other changes of the configuration can be made as appropriate. The present disclosure is not limited by the embodiments, but is limited only by the scope of the claims.

Examples

[0142] Hereinafter, an embodiment of the present disclosure will be described in more detail based on examples. Unless otherwise specified, the units of the numerical values described in the table indicate parts by mass.

[0143] Production Example 1 (Production of Cationically Polymerizable Silsesquioxane) In a 1000 milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, 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% aqueous potassium carbonate 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. During the addition, no significant temperature rise occurred. Thereafter, the polycondensation reaction was carried out at 50 °C for 5 hours under a nitrogen stream. Thereafter, while cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% brine were added. This solution was transferred to a 1 L separatory funnel, 137.70 g of methyl isobutyl ketone was added again, and washing with water was carried out. After liquid separation, the aqueous layer was extracted, washing with water was carried out until the lower layer liquid became neutral, the upper layer liquid was separated, and then the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 °C to obtain 75.18 g of a colorless transparent liquid product (epoxy group-containing low molecular weight polyorganosilsesquioxane: silsesquioxane) containing 23% by mass of methyl isobutyl ketone. When the product was analyzed, the number average molecular weight was 2235 and the molecular weight dispersity was 1.54. The ratio of the T2 body to the T3 body [T3 body / T2 body] calculated from the 29 Si-NMR spectrum of the above product was 11.9. The 1H-NMR of the obtained epoxy group-containing low molecular weight polyorganosilsesquioxane, 29 was confirmed by Si-NMR. The molecular weight of the product was measured using a pump: Shimadzu LC-20AD, a detector: Shodex RI-504, columns: Shodex GPC KF-602, KF-603, a guard column: Shodex GPC KF-G, a solvent: THF, and measurement conditions: 40°C. The ratio of T2 form to T3 form [T3 form / T2 form] in the product was measured by 29 Si-NMR spectrum measurement using JEOL ECA500 (500 MHz).

[0144] Examples 1 to 13, Comparative Examples 1 to 6 A mixed solution with the formulation ratios shown in Table 1 was prepared and used as the curable resin composition of the examples and comparative examples. Also, using a wire bar #5 so that the thickness after curing of the above curable resin composition became about 1 μm, it was applied to the surfaces of a cycloolefin copolymer substrate (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and (a ring-opening metathesis polymer of norbornenes, thickness 2000 μm, COP substrate), and then heat-treated in an oven at 100°C for 2 hours to prepare the coating layers of the examples and comparative examples.

[0145] Comparative Example 7 A mixed solution with the formulation ratios shown in Table 1 was prepared and used as the curable resin composition of Comparative Example 7. Also, using a wire bar #5 so that the thickness after curing of the above curable resin composition became about 1 μm, it was applied to the surfaces of a cycloolefin copolymer (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and (a ring-opening metathesis polymer of norbornenes, thickness 2000 μm, COP substrate), and then heat-treated in an oven at 100°C for 1 hour and in an oven at 120°C for 2 hours to prepare the coating layer of Comparative Example 7.

[0146] Comparative Example 8 A mixed solution having the composition ratio shown in Table 1 was prepared and used as the curable resin composition of Comparative Example 8. Further, the curable resin composition was applied onto the surfaces of a cycloolefin copolymer (trade name "TOPAS", manufactured by Polyplastics Co., Ltd., thickness 2000 μm, COC substrate) and (a ring-opening metathesis polymer of norbornenes, thickness 2000 μm, COP substrate) using a wire bar #5 so that the thickness after curing became about 1 μm, and then heat treatment was performed in an oven at 120 °C for 2 hours to produce a coating layer of Comparative Example 8.

[0147] Regarding each component described in Table 1, it will be described in detail below. POSS101: Trade name "POSS101", manufactured by Consul Chemical Co., Ltd. (glycidyl epoxy organosiloxane) OX-SQ: Trade name "OX-SQ", manufactured by Toagosei Co., Ltd. (oxetane organosilsesquioxane) KR-470: Trade name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd. (cyclic epoxy silicone resin) Celloxide 2021P: Trade name "Celloxide 2021P", manufactured by Daicel Corporation (alicyclic epoxy resin) YD-128: Trade name "YD-128", manufactured by Nippon Steel Chemical & Material Co., Ltd. (bisphenol A epoxy resin) KER-2500A: Manufactured by Shin-Etsu Chemical Co., Ltd. (two-component addition-curable silicone resin) KER-2500B: Manufactured by Shin-Etsu Chemical Co., Ltd. (two-component addition-curable silicone resin) OE-6630A: Manufactured by Dow Corning Toray Co., Ltd. (two-component silicone resin) OE-6630B: Manufactured by Dow Corning Toray Co., Ltd. (two-component silicone resin) SI-100L: Trade name "SI-100L", manufactured by Sanshin Chemical Co., Ltd. (thermal polymerization initiator)

[0148] [Evaluation] The following evaluations were carried out on the curable resin compositions and coating layers of the examples and comparative examples, and the results are shown in Table 1.

[0149] (1) Viscosity About 1.1 mL of the curable resin compositions of the examples and comparative examples were collected, 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.

[0150] (2) Adhesion test On the surface of the coating layers of the examples and comparative examples, according to JIS K5600-5-6:1999, scratches were made with a cutter blade at intervals of 1 mm to create 100 squares in a grid pattern. An adhesive tape was attached and peeled off in the 90° direction, and it was visually confirmed whether the surface of the coating peeled off after sticking to the adhesive tape. When 90 or more adhered, it was rated as ◎, when 70 or more and less than 90 adhered, it was rated as ○, and when less than 70 adhered, it was rated as ×.

[0151] (3) PCT test (pressure cooker test) Regarding the coating layers that received an evaluation of ○ or higher in the above adhesion test, they were put into a pressure cooker test apparatus (trade name "EHS-411M", manufactured by Espec Corporation) and stored in a constant temperature and humidity chamber at 120°C and 100% RH for 8 hours. The change in appearance after taking it out was visually confirmed, and when there was no change in appearance, it was rated as ○, and when whitening or wrinkles occurred, it was rated as ×.

[0152] (4) Arithmetic mean height (Sa) In accordance with ISO25178, it was placed on the test stand of a laser microscope (trade name "VK-8710", manufactured by Keyence Corporation), and the arithmetic roughness of the surface of the coating layer was measured using a lens manufactured by Nikon Corporation, ×10 / 0.30 OFN25 WP 16.5). The arithmetic mean height of the coating layer was calculated for a size of 200 μm × 200 μm, 10 results were obtained, and the average value of the middle 6 test results was taken as the arithmetic mean height.

[0153]

Table 1

[0154] The curable resin composition of the example contains an alicyclic ketone compound and / or an alicyclic ether compound, and a cationic polymerizable silsesquioxane and / or a cationic polymerizable cyclic siloxane, and thus can be coated in a single layer, has sufficient adhesion to a cycloolefin copolymer substrate, and has been confirmed to be excellent in moisture resistance. On the other hand, when the cationic polymerizable silsesquioxane and / or the cationic polymerizable cyclic siloxane is not used, the moisture resistance is poor or sufficient adhesion to the cycloolefin copolymer substrate cannot be exhibited (Comparative Examples 1 to 4, Comparative Examples 7, 8). Further, when the alicyclic ketone compound and / or the alicyclic ether compound is not used, adhesion to the cycloolefin copolymer substrate cannot be exhibited (Comparative Examples 5, 6).

[0155] Variations of the invention according to the present disclosure are described below. [Appendix 1] A curable resin composition for coating a cycloolefin copolymer substrate, a curable resin composition containing an alicyclic ketone compound and / or an alicyclic ether compound and a cationic polymerizable silsesquioxane and / or a cationic polymerizable cyclic siloxane. [Appendix 2] The curable resin composition according to Appendix 1, having a viscosity at 25 °C of 15 mPa·s or less. [Appendix 3] The curable resin composition according to Appendix 1 or 2, wherein the alicyclic ketone compound is cyclohexanone or cyclopentanone, and the alicyclic ether compound is cyclopentyl methyl ether. [Appendix 4] The curable resin composition according to any one of Appendices 1 to 3, wherein the cationic polymerizable functional group of the cationic polymerizable silsesquioxane has a cyclic ether structure. [Appendix 5] A coating layer which is a cured product of the curable resin composition according to any one of Appendices 1 to 4. [Appendix 6] A laminate in which the coating layer according to Appendix 5 is laminated on at least one of cycloolefin copolymer substrates. [Appendix 7] The laminate according to Supplementary Note 6, wherein 100 meshes are formed in a grid pattern at 1 - mm intervals in the coating layer, an adhesive tape is attached, and when peeled off in the 90° direction, 90 or more meshes remain. [Supplementary Note 8] The laminate according to Supplementary Note 6 or 7, wherein the arithmetic mean height (Sa) of the coating layer is 30 μm. [Supplementary Note 9] The laminate according to any one of Supplementary Notes 6 to 8, wherein the cycloolefin - based copolymer substrate is a substrate for lenses. [Supplementary Note 10] A plastic lens comprising the laminate according to Supplementary Note 9. [Supplementary Note 11] An image display device comprising the laminate according to any one of Supplementary Notes 6 to 9.

Claims

1. A curable resin composition for coating a cycloolefin copolymer substrate, which comprises 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, having a viscosity at 25°C of 15 mPa·s or less.

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 layer which is a cured product of the curable resin composition according to Claim 1 or 2.

6. A laminate in which the coating layer according to Claim 5 is laminated on at least one of cycloolefin copolymer substrates.

7. The laminate according to Claim 6, wherein 100 squares are formed in a grid pattern at 1-mm intervals on the coating layer, an adhesive tape is attached thereto, and when peeled off in the 90°C direction, 90 or more squares remain.

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

9. The laminate according to Claim 6, wherein the cycloolefin 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