Curable composition

Abstract

The present invention provides a curable composition which can suppress thermal deterioration of a tetraazaporphyrin compound, and realize a lens excellent in visual confirmation, anti-glare effect, and contrast enhancement effect. The curable composition of the present disclosure contains: a silsesquioxane having an epoxy cyclohexyl group; and a tetraazaporphyrin compound having an absorption peak in a wavelength region of 570 to 605 nm, the content of the tetraazaporphyrin compound being 1000 to 10000 parts by weight per million parts by weight of the silsesquioxane.

Description

Technical Field

[0001] This disclosure relates to a curable composition comprising a silsesquioxane and a tetrazaporphyrin compound. This application claims priority to Japanese Patent Application No. 2021-018313, filed February 8, 2021, the contents of which are incorporated herein by reference. Background Technology

[0002] It is known that sunglasses, goggles, and other eyewear can achieve anti-glare and contrast enhancement effects by limiting the transmission of light of specific wavelengths.

[0003] For example, Patent Document 1 describes a method that, by adding 0.001% by weight of a tetrazaporphyrin compound with a sharp absorption peak around 585 nm to a plastic lens material such as a polycarbonate thermoplastic resin, melting and mixing it at 280°C, and then injection molding it, a lens with excellent anti-glare and contrast enhancement effects can be obtained.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 5626081 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The inventors conducted research on the above method and found the following problems.

[0009] 1. Expensive tetrazaporphyrin compounds deteriorate due to melt mixing with thermoplastic resins and high-temperature exposure during injection molding. Therefore, in order to obtain the desired anti-glare and contrast enhancement effects, additional tetrazaporphyrin compounds need to be added to compensate for the deteriorated parts, which increases costs.

[0010] 2. Tetraazaporphyrin compounds are blue to purple compounds. If they are added in large quantities to plastic lens materials, the resulting lenses will be colored dark blue to purple, thus reducing their design value.

[0011] 3. By exposing a tetrazaporphyrin compound to high temperature, a pyrolysis product of the tetrazaporphyrin compound is generated, but the pyrolysis product acts in the direction that broadens the absorption peak, reducing visual confirmability.

[0012] Therefore, the purpose of this disclosure is to provide a curable composition that can suppress the thermal degradation of tetrazaporphyrin compounds and achieve a lens with excellent visual clarity, anti-glare effect and contrast enhancement effect.

[0013] Another object of this disclosure is to provide a curable composition that has excellent storage stability, can suppress the thermal degradation of tetrazaporphyrin compounds, and achieves a lens with excellent visual clarity, anti-glare effect and contrast enhancement effect.

[0014] Another object of this disclosure is to provide a hard coating that has excellent visual clarity, anti-glare effect and contrast enhancement effect without compromising the hue of the lens.

[0015] Another object of this disclosure is to provide a method for manufacturing a lens that can suppress the thermal degradation of tetrazaporphyrin compounds and has excellent visual clarity, anti-glare effect and contrast enhancement effect.

[0016] Another object of this disclosure is to provide a lens that has excellent visual clarity, anti-glare effect and contrast enhancement effect, and has high design value.

[0017] Another object of this disclosure is to provide eyeglasses that have excellent visual confirmation, anti-glare effect and contrast enhancement effect, and have high design value.

[0018] Technical solution

[0019] To solve the aforementioned problems, the inventors conducted in-depth research and discovered that by forming a hard coating film containing a tetrazaporphyrin compound on the lens surface instead of incorporating the tetrazaporphyrin compound into the lens, the degradation caused by the tetrazaporphyrin compound's exposure to high temperatures can be minimized. Even with a reduction in the amount of tetrazaporphyrin compound used compared to conventional methods, the lens can still achieve anti-glare and contrast enhancement effects equal to or better than those of conventional methods. Furthermore, it was found that silsesquioxanes containing epoxycyclohexyl groups also exhibit solubility in solvents containing tetrazaporphyrin compounds. Therefore, dissolving both the tetrazaporphyrin compound and the epoxycyclohexyl silsesquioxane in a solvent improves coatability, allowing for easy formation of a hard coating film containing the tetrazaporphyrin compound on the lens surface. This disclosure is based on these insights.

[0020] That is, this disclosure provides a curable composition comprising: a silsesquioxane having an epoxycyclohexyl group; and a tetrazaporphyrin compound having an absorption peak in the wavelength region of 570 to 605 nm, wherein the content of the tetrazaporphyrin compound is 1,000 to 10,000 ppm by weight of the silsesquioxane content.

[0021] This disclosure also provides the curable composition wherein the silsesquioxane comprises structural units represented by formula (I) and structural units represented by formula (II).

[0022] [R a SiO 3 / 2(I)

[0023] In formula (I), R a [This refers to a group containing an epoxycyclohexyl 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom.]

[0024] [R a SiO 2 / 2 (OR b (II)

[0025] In formula (II), R a Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0026] The ratio (molar ratio) of the structural unit shown in formula (I) to the structural unit shown in formula (II) is 5 to 500, and the structural unit of the sesquioxane, which is the structural unit shown in formula (I) and (II) in the total amount, is R. a The proportion of structural units containing cyclohexyl epoxide groups is 50–100 mol%.

[0027] This disclosure also provides the curable composition described above, which is a composition for forming a hard coating.

[0028] This disclosure also provides a hard coating film, which is composed of a cured product of the curable composition.

[0029] This disclosure also provides the hard coating film having a minimum downward peak in the wavelength region of 570–605 nm in the transmission spectrum, wherein the transmittance (t1) at the minimum value is less than 80%, the ratio of transmittance (t2) at wavelength 550 nm to the transmittance (t1) (t2 / t1) is more than 1.1, and the ratio of transmittance (t3) at wavelength 625 nm to the transmittance (t1) (t3 / t1) is more than 1.1.

[0030] This disclosure also provides a method for manufacturing a hard-coated lens, which is as follows: applying the curable composition to the lens surface and curing it to obtain a hard-coated lens having a hard coating film composed of the cured product of the curable composition.

[0031] This disclosure also provides a hard-coated lens, which is a hard-coated lens having the hard coating on the lens surface.

[0032] This disclosure also provides eyeglasses having the aforementioned hard-coated lens.

[0033] Invention Effects

[0034] The curable composition disclosed herein has the above-described structure, and is therefore useful as a composition for forming a hard coating. Furthermore, by applying the curable composition to the lens surface and allowing it to cure, the high-temperature exposure of the tetrazaporphyrin compound is minimized, resulting in a hard-coated lens with excellent anti-glare and contrast enhancement effects. Therefore, the reduction in visual clarity caused by the pyrolysis products of the tetrazaporphyrin compound is suppressed, and in addition to imparting excellent anti-glare and contrast enhancement effects to the hard-coated lens, it also imparts extremely good visual clarity.

[0035] Furthermore, by using the aforementioned curable composition, high-temperature exposure can be minimized, thus suppressing the pyrolysis of the tetrazaporphyrin compound and eliminating the need for large amounts of tetrazaporphyrin compound to replenish the pyrolytes. Therefore, the amount of tetrazaporphyrin compound added in the curable composition can be reduced compared to conventional methods, resulting in the formation of a hard coating film that suppresses coloration caused by the tetrazaporphyrin compound. Moreover, in hard-coated lenses with a hard coating film that suppresses coloration, the range of lens hues is expanded, enhancing design value. Furthermore, although tetrazaporphyrin compounds are expensive, a hard coating film can be formed inexpensively by reducing its amount added. Attached Figure Description

[0036] Figure 1 The transmittance curves of the hard-coated lens 1 obtained in the embodiment and the hard-coated lens 2 obtained in the comparative example are shown.

[0037] Figure 2 The transmittance curve of the hard coating film 1 obtained in the embodiment is shown. Detailed Implementation

[0038] [Curing composition]

[0039] The curable composition disclosed herein contains: a silsesquioxane having an epoxycyclohexyl group; and a tetrazaporphyrin compound having an absorption peak in the wavelength region of 570–605 nm. The curable composition is useful as a composition for forming hard coatings.

[0040] In addition to the components mentioned above, the curable composition may also contain one or more other components as needed. Examples of other components include: curing catalysts, solvents, leveling agents, defoamers, foam stabilizers, UV absorbers, heat stabilizers, antioxidants, light stabilizers, plasticizers, lubricants, fillers, flame retardants, antistatic agents, and colorants.

[0041] (Tetraazaporphyrin compounds)

[0042] The tetrazaporphyrin compound has a sharp absorption peak in the wavelength region of 570–605 nm (preferably 575–600 nm, more preferably 580–595 nm, and particularly preferably 580–590 nm) of the absorption spectrum measured with chloroform solution.

[0043] The absorption rate (A1) of the maximum value of the absorption peak is, for example, 80% or more, preferably 90% or more, and particularly preferably 95% or more.

[0044] The ratio (A1 / A2) of the absorbance (A1) to the absorbance (A2) at a wavelength of 550 nm of the absorption spectrum is, for example, 1.5 or more, preferably 2.0 or more, and particularly preferably 3.0 or more.

[0045] The ratio (A1 / A3) of the absorption rate (A1) to the absorption rate (A3) at a wavelength of 625 nm of the absorption spectrum is, for example, 10 or more, preferably 20 or more.

[0046] Examples of the tetrazaporphyrin compounds include those represented by the following formula (p).

[0047]

[0048] In the above formula (p), A 1 ~A 8 Same or different, representing hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, substituted or unsubstituted amino group, carboxyl group, sulfonic acid group, hydrocarbon group, -OR group, or -SR group (where R represents hydrocarbon group). Selected from A 1 ~A 8 The two groups in the symbol are optionally bonded to each other to form a ring together with the adjacent carbon atom. M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxide metal atom.

[0049] As the substituted amino group, examples include mono- or di(C) amino groups. 1-20 Alkylamino, etc.

[0050] The hydrocarbon group includes aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by their bonding. Preferably, the hydrocarbon group is an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0051] The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms. Examples of aliphatic hydrocarbon groups with 1 to 20 carbon atoms include: alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, decyl, and dodecyl; alkenyl groups with 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as vinyl, allyl, and 1-butenyl; and alkynyl groups with 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as ethynyl and propynyl.

[0052] Examples of aromatic hydrocarbon groups include aryl groups with 6 to 10 carbon atoms, such as phenyl and naphthyl.

[0053] The hydrocarbon group may also have substituents such as halogen atoms.

[0054] As selected from A 1 ~A 8 Two groups are optionally bonded to each other to form a ring together with an adjacent carbon atom. Examples include aliphatic hydrocarbon rings with 3 to 6 carbon atoms and aromatic hydrocarbon rings with 6 to 10 carbon atoms.

[0055] M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxide metal atom, preferably a divalent metal atom or an oxide metal atom.

[0056] Examples of divalent metal atoms include: Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, etc.

[0057] Examples of the oxide metal atoms include: VO, MnO, TiO, etc.

[0058] As the tetrazaporphyrin compound, for example, commercially available products such as "FDG-006" (manufactured by Yamada Chemical Industry Co., Ltd.) may be preferred.

[0059] The content of the tetrazaporphyrin compound is, for example, 1000 to 10000 ppm by weight, the same as the content of the silsesquioxane. From the perspective of achieving excellent anti-glare and contrast enhancement effects, and suppressing design degradation, the upper limit of the content is preferably 8000 ppm by weight, particularly preferably 7000 ppm by weight, most preferably 6000 ppm by weight, and especially preferably 5000 ppm by weight. From the perspective of improving anti-glare and contrast enhancement effects, the lower limit of the content is preferably 2000 ppm by weight, particularly preferably 2500 ppm by weight, and most preferably 3000 ppm by weight.

[0060] Using the curable composition disclosed herein, high-temperature exposure of the tetrazaporphyrin compound can be suppressed, and a hard coating film containing the tetrazaporphyrin compound can be formed on the lens surface. Therefore, it is not necessary to increase the amount of tetrazaporphyrin compound in the composition to anticipate thermal degradation. Thus, costs associated with the tetrazaporphyrin compound can be reduced.

[0061] (Silsesquioxane)

[0062] The silsesquioxane is a compound having a main chain backbone composed of siloxane bonds (Si-O-Si bonds) and an epoxy cyclohexyl group bonded to the main chain backbone.

[0063] The silsesquioxane may also be a compound having a main chain backbone composed of siloxane bonds; and a group containing an epoxycyclohexyl group and a substituted or unsubstituted aryl group (e.g., phenyl) bonded to the main chain backbone.

[0064] The epoxycyclohexyl group is represented by formula (1a) or (1b) below. In the following formula, R 1a R 1b "Same" or "Different" indicates alkylene groups with 1 to 10 carbon atoms. The bonds marked with a wavy line are bonded to the main chain backbone composed of siloxane bonds.

[0065]

[0066] Examples of alkylene groups having 1 to 10 carbon atoms include: methylene, methylmethylene, ethylene, dimethylene, dimethylmethylene, propylene, trimethylene, and other straight-chain or branched alkylene groups.

[0067] The silsesquioxanes include silsesquioxanes with various structures such as ladder structure, complete cage structure, incomplete cage structure, and random structure. Among them, silsesquioxanes with incomplete cage structure are preferred from the perspective of forming a cured product with high hardness.

[0068] The silsesquioxane having an incomplete cage-like structure comprises structural units shown in formula (I) and formula (II).

[0069] [R a SiO 3 / 2 (I)

[0070] In formula (I), R a [This refers to a group containing an epoxycyclohexyl 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom.]

[0071] [R a SiO 2 / 2 (OR b (II)

[0072] In formula (II), R a Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0073] In the total amount of the structural units of formula (I) and formula (II) constituting the silsesquioxane, at least one is R. a It is a structural unit containing an epoxycyclohexyl group.

[0074] The structural unit shown in formula (I) above is the structural unit shown in formula (I') below, and is called the T3 body. Furthermore, the structural unit shown in formula (II) above is the structural unit shown in formula (II') below, and is called the T2 body. These structural units are all T units. In the structure shown in formula (I') below, the three oxygen atoms bonded to the silicon atom are bonded to other silicon atoms (silicon atoms not shown in formula (I')). Furthermore, in the structure shown in formula (II') below, the two oxygen atoms located above and below the silicon atom are also bonded to other silicon atoms (silicon atoms not shown in formula (II')).

[0075]

[0076] The above R a It represents a group containing an epoxycyclohexyl 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom.

[0077] Examples of aryl groups include phenyl, naphthyl, and other aryl groups with 6 to 10 carbon atoms.

[0078] Examples of aralkyl groups include benzyl, phenethyl, and other aralkyl groups with 7 to 12 carbon atoms.

[0079] Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, and other cycloalkyl groups with 3 to 6 carbon atoms.

[0080] Examples of alkyl groups include straight-chain or branched alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl.

[0081] Examples of alkenyl groups include, for example, straight-chain or branched alkenyl groups with 2 to 6 carbon atoms, such as vinyl, allyl, and isopropenyl.

[0082] Examples of substituted aryl, substituted aralkyl, substituted cycloalkyl, substituted alkyl, and substituted alkenyl groups include those in which at least one of the hydrogen atoms bonded to the main chain backbone of the aforementioned aryl, aralkyl, cycloalkyl, alkyl, or alkenyl groups is selected from the group consisting of at least one group formed by substituting one or all of the hydrogen atoms of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, a RO group, an RCOO group, an RCO group, a siloxane group, a halogen atom, a mercapto group, an amino group, and a hydroxyl group. It should be noted that R represents a hydrocarbon group, such as alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and monovalent groups formed by two or more of them bonded by single bonds.

[0083] The above (OR) b The ) group represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. Examples of alkoxy groups having 1 to 4 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc.

[0084] The silsesquioxane may also include: as a structural unit of formula (I) or (II), where R is a structural unit of formula (I) or (II). a Structural units comprising groups containing an epoxycyclohexyl group; and R as a structural unit shown in (I) or (II) where R is a group containing an epoxycyclohexyl group. a The structural unit is a substituted or unsubstituted aryl group (e.g., phenyl).

[0085] That is, the silsesquioxane may also comprise: the structural unit shown in formula (I-1) or the structural unit shown in formula (II-1) below; and the structural unit shown in formula (I-2) or the structural unit shown in formula (II-2) below. It should be noted that the structural unit shown in formula (I-1) and the structural unit shown in formula (I-2) are T3 bodies, and the structural unit shown in formula (II-1) and the structural unit shown in formula (II-2) are T2 bodies.

[0086] [R a1 SiO 3 / 2 (I-1)

[0087] In formula (I-1), R a1 [Represents a group containing an epoxycyclohexyl group]

[0088] [R a1 SiO 2 / 2 (OR b (II-1)

[0089] In formula (II-1), R a1 Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0090] [R a2 SiO 3 / 2 (I-2)

[0091] In equation (I-2), R a2 [Indicates substituted or unsubstituted aryl]

[0092] [R a2 SiO 2 / 2 (OR b (II-2)

[0093] In formula (II-2), R a2 R b Same as described above]

[0094] The T3 / T2 molar ratio, i.e., the ratio of the content of the structural unit shown in formula (I) to that of the structural unit shown in formula (II) (the former / the latter; molar ratio), or the ratio of the total of the structural units shown in formulas (I-1)(I-2) to the total of the structural units shown in formulas (II-1)(II-2) (the former / the latter; molar ratio), is, for example, 5 to 500. From the viewpoint of achieving improved hardness and scratch resistance of the obtained cured product, the lower limit of the T3 / T2 molar ratio is preferably 7, particularly preferably 8, most preferably 9, and especially preferably 10. The upper limit of the T3 / T2 molar ratio is preferably 50, particularly preferably 30, most preferably 20, and especially preferably 15. The T3 / T2 molar ratio can be, for example, determined by... 29 The result is determined by Si-NMR spectroscopy. 29 In Si-NMR spectra, silicon atoms in the T3 phase and silicon atoms in the T2 phase exhibit signals (peaks) at different positions (chemical shifts). Therefore, the molar ratio mentioned above can be determined by calculating the integral ratio of each peak.

[0095] It should be noted that silsesquioxanes 29 Si-NMR spectra can be measured, for example, using the following apparatus and conditions.

[0096] Measurement device: Trade name "JNM-ECA500NMR" (manufactured by Nippon Electronics Co., Ltd.).

[0097] Solvent: deuterated chloroform.

[0098] Points earned: 1800.

[0099] Measurement temperature: 25℃.

[0100] In addition to the T unit, the silsesquioxane may also have [R] a 3SiO 1 / 2 The structural unit shown is the so-called M-unit, [R] a At least one of the group consisting of the structural unit shown in [2SiO] (the so-called D unit) and the structural unit shown in [SiO2] (the so-called Q unit). It should be noted that R in the above formula... a Same as described above.

[0101] From the perspective of having high curability and being able to form a cured product with high hardness, the proportion of T units in the total amount of the structural units of silsesquioxane [total structural units; total amount of M units, D units, T units and Q units] (100 mol%) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, further preferably 65 to 100 mol%, particularly preferably 70 to 100 mol%, and most preferably 80 to 100 mol%.

[0102] Considering its high curability and ability to form a cured product with high hardness, the structural units of the silsesquioxane, in all quantities, are structural units represented by formulas (I) and (II), and R in the formula... a The proportion of structural units containing cyclohexyl epoxide groups [i.e., the sum of the structural units shown in formula (I-1) and formula (II-1)] is preferably 50-100 mol%, more preferably 60-100 mol%, even more preferably 65-100 mol%, particularly preferably 70-100 mol%, most preferably 80-99 mol%, and especially preferably 85-96 mol%. It should be noted that the proportion of these structural units is determined based on the composition of the silsesquioxane raw material. Alternatively, it can be determined by NMR spectroscopy of the silsesquioxane.

[0103] Furthermore, considering the ability to form a cured product with high hardness, the structural units of the silsesquioxane, in all quantities, those that are structural units represented by formula (I) or (II) and where R is a structural unit in the formula... aThe proportion of substituted or unsubstituted aryl (e.g., phenyl) structural units [i.e., the total of the structural units shown in formula (I-2) and formula (II-2) above] is preferably 50 mol% or less, more preferably 40 mol% or less, particularly preferably 30 mol% or less, most preferably 20 mol% or less, and especially preferably 10 mol% or less. It should be noted that the lower limit of the stated proportion is, for example, 1 mol%, preferably 2 mol%, particularly preferably 3 mol%, and most preferably 4 mol%.

[0104] The T units constituting the silsesquioxane [= the total amount of structural units shown in formula (I) and structural units shown in formula (II)] that have an epoxycyclohexyl group [= as a structural unit shown in formula (I) or a structural unit shown in formula (II) and where R is a structural unit shown in formula (II)] a The proportion of the total amount of structural units containing cyclohexyl epoxide groups is preferably 50-100 mol%, more preferably 60-100 mol%, further preferably 65-100 mol%, particularly preferably 70-100 mol%, and most preferably 80-99 mol%.

[0105] Therefore, the proportion of T units having an epoxycyclohexyl group in the total amount of structural units of silsesquioxane [all structural units; including T units, M units, D units, and Q units] (100 mol%) [= as a structural unit shown in formula (I) or a structural unit shown in formula (II) where R...] a The total amount of structural units containing cyclohexyl epoxide groups is, for example, 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 65 to 100 mol%, particularly preferably 70 to 100 mol%, and most preferably 80 to 99 mol%.

[0106] The molecular weight distribution (Mw / Mn) of the silsesquioxane, converted from standard polystyrene obtained by GPC, is, for example, 1.0 to 3.0, preferably 1.1 to 2.0, more preferably 1.2 to 1.9, particularly preferably 1.45 to 1.80, and most preferably 1.45 to 1.70. By making the molecular weight distribution below 3.0, there is a tendency for the surface hardness of the cured product to increase further. On the other hand, by making the molecular weight distribution above 1.0, there is a tendency for it to easily become liquid and for its workability to improve.

[0107] The number-average molecular weight (Mn) of the silsesquioxane, converted from standard polystyrene obtained by GPC, is, for example, 500 to 10,000, preferably 1,000 to 8,000, particularly preferably 1,200 to 6,000, most preferably 1,300 to 3,000, and especially preferably 1,400 to 2,500. If the number-average molecular weight is 500 or higher, there is a tendency to obtain cured products with high hardness, excellent scratch resistance, and excellent heat resistance. On the other hand, if the number-average molecular weight is 10,000 or lower, there is a tendency to have good compatibility with other components and excellent usability.

[0108] The epoxy equivalent of the silsesquioxane is, for example, 50 to 3000 g / eq, with an upper limit preferably of 2000 g / eq, more preferably 1500 g / eq, further preferably 1000 g / eq, particularly preferably 500 g / eq, and most preferably 300 g / eq. The lower limit is preferably 100 g / eq, more preferably 150 g / eq. By making the epoxy equivalent below 3000 g / eq, there is a tendency to obtain cured products with high hardness, excellent scratch resistance, and excellent heat resistance. Furthermore, by making the epoxy equivalent above 50 g / eq, there is a tendency to obtain products with moderate flowability and excellent workability.

[0109] The silsesquioxane can be manufactured by hydrolyzing and polycondensing a hydrolyzable silane compound.

[0110] The hydrolyzable silane compound comprises at least the compound represented by formula (a) below. The compound represented by formula (a) below is as follows.

[0111] R a Si(X 1 )3(a)

[0112] (where X) 1 OR b Radix or halogen atom. R a R b Same as above)

[0113] The hydrolyzable silane compound comprises at least a compound represented by formula (a) and R in the formula. a It is a compound containing an epoxycyclohexyl group.

[0114] The compound shown in formula (a) can also be used in combination of two or more depending on the structural unit of the manufactured silsesquioxane. For example, in the case of manufacturing a silsesquioxane having a main chain backbone composed of siloxane bonds; and an epoxycyclohexyl group and a substituted or unsubstituted aryl group (e.g., phenyl) bonded to the main chain backbone, it is preferable to use the compound shown in formula (a) where R is a silsesquioxane. aA compound containing an epoxycyclohexyl group and a compound represented by formula (a) wherein R is a group containing an epoxycyclohexyl group. a Used in combination of compounds with substituted or unsubstituted aryl groups (e.g., phenyl).

[0115] In addition to the compound shown in formula (a) above, the hydrolyzable silane compound may also contain other hydrolyzable silane compounds (e.g., hydrolyzable trifunctional silane compounds other than those shown in formula (a), hydrolyzable monofunctional silane compounds forming M units, hydrolyzable difunctional silane compounds forming D units, hydrolyzable tetrafunctional silane compounds forming Q units, etc.). By adjusting the amount and composition of the hydrolyzable silane compound used, the desired silsesquioxane can be produced.

[0116] From the perspective of suppressing the decomposition of epoxycyclohexyl groups and preventing the formation of siloxane bonds, the hydrolysis and condensation reactions of hydrolyzable silane compounds are preferably carried out in the presence of an alkali metal catalyst. Examples of such alkali metal catalysts include alkali metal hydroxides, carbonates, bicarbonates, organic acid salts, alkoxides, and aromatic oxides. They can be used alone or in combination of two or more. Furthermore, they can be used in a dissolved or dispersed state in water, solvents, etc.

[0117] Examples of hydroxides of the alkali metals include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.

[0118] Examples of carbonates of the alkali metals include lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate.

[0119] Examples of alkali metal bicarbonates include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate.

[0120] The organic acid salt of the alkali metal is preferably a salt of an alkali metal and a monocarboxylic acid. Examples include carboxylates of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (preferably salts of alkali metals and monocarboxylic acids, and particularly preferably acetates of alkali metals).

[0121] Examples of alkane oxides of the aforementioned alkali metals include: lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium tert-butoxide, and other alkali metal C-type oxides. 1-5 Alkyl oxides.

[0122] Aryl oxides of the alkali metals mentioned above include, for example, sodium phenolate and other alkali metal C oxides. 6-11 Aromatic oxides.

[0123] The amount of alkali metal catalyst used is, for example, about 0.002 to 0.200 moles relative to 1 mole of hydrolyzable silane compound.

[0124] Water is used in the hydrolysis and condensation reactions of the aforementioned hydrolyzable silane compounds. The amount of water used is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 moles relative to 1 mole of the hydrolyzable silane compound.

[0125] The above reaction is preferably carried out in the presence of a solvent. Examples of such solvents include: aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, isopropanol, and butanol. One or more of these solvents may be used alone or in combination. Among these solvents, ketones and / or ethers are preferred, especially ketones, considering their excellent solubility in water and silsesquioxanes and their ability to not hinder the hydrolysis and polycondensation reactions of hydrolyzable silane compounds.

[0126] The amount of solvent used is, for example, 0 to 20 parts by weight relative to 1 part by weight of the hydrolyzable silane compound.

[0127] The preferred reaction temperature for the hydrolysis and polycondensation reaction of the above-mentioned hydrolyzable silane compound is 40–100°C, more preferably 45–80°C. Furthermore, the preferred reaction time for the hydrolysis and polycondensation reaction is 0.1–10 hours, more preferably 1.5–8 hours. Moreover, the hydrolysis and polycondensation reaction can be carried out under normal pressure, or under pressure or reduced pressure. It should be noted that the atmosphere for the reaction can be any of the following: an inert gas atmosphere such as nitrogen, an inert gas atmosphere such as argon, or an atmosphere containing oxygen such as air.

[0128] After the reaction is complete, the resulting reaction product can be separated and purified by conventional precipitation / washing / filtration.

[0129] In this disclosure, it is preferable to perform a water washing process until the reaction solution becomes neutral after the hydrolysis and polycondensation reaction of the hydrolyzable silane compound is completed. This is because using a silsesquioxane that has undergone water washing improves the storage stability of the resulting cured composition.

[0130] The curable composition obtained using silsesquioxane that has undergone water washing treatment exhibits excellent storage stability. When the curable composition is stored at 5°C for 180 days, the viscosity increase rate calculated according to the following formula is, for example, 10% or less, preferably 5% or less, particularly preferably 3% or less, and especially preferably 1% or less.

[0131] Viscosity increase rate (%) = [(V2-V1) / V1] × 100

[0132] (V1 represents the viscosity of the cured composition before storage, and V2 represents the viscosity of the cured composition after storage.)

[0133] The content of the silsesquioxane is preferably 70% by weight or more, more preferably 75% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more, of the total amount of the non-volatile components of the curable composition disclosed herein.

[0134] The curable composition disclosed herein may also contain compounds other than the silsesquioxane as curable compounds. The proportion of the silsesquioxane in all curable compounds contained in the curable composition is preferably 70% by weight or more, more preferably 75% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. If the curable composition contains the silsesquioxane within the specified range, the refractive index of the cured product of the curable composition can be increased. This reduces the difference in refractive index between the cured product and plastic lenses formed from resin materials such as polyamide resins, which have a refractive index (e.g., around 1.49 to 1.61) commonly used in displays, thus suppressing the generation of interference fringes. Furthermore, the heat resistance and crack resistance of the cured product of the curable composition are improved.

[0135] (solvent)

[0136] The curable composition may also contain a solvent. When the curable composition contains a solvent, the coatability is improved by reducing viscosity, and a uniform coating can be formed.

[0137] As the solvent, considering the ability to evaporate rapidly after coating the curable composition and to prevent the formation of solvent-induced bubbles in the cured product, it is preferable to use a solvent that has excellent solubility in the silsesquioxane and tetrazaporphyrin compounds and a boiling point of 150°C or less at normal pressure (preferably 130°C or less, particularly preferably 120°C or less. The lower limit of the boiling point is, for example, 50°C, preferably 60°C, and particularly preferably 70°C).

[0138] Examples of solvents include ketone solvents and alcohol solvents. They can be used alone or in combination of two or more. Among these solvents, ketone solvents are preferred due to their particularly excellent solubility in tetrazaporphyrin compounds.

[0139] It should be noted that when using ketone-based solvents, the cured composition may sometimes gel, resulting in reduced storage stability. However, if a silsesquioxane that has undergone water washing treatment is used, the cured composition will not gel even when using a ketone-based solvent. In other words, by using a water-washed silsesquioxane and a ketone-based solvent, a cured composition with excellent visual clarity, anti-glare effect, contrast enhancement effect, and excellent storage stability can be produced.

[0140] As the ketone solvent, acetone (boiling point 56°C), methyl ethyl ketone (boiling point 80°C), and methyl isobutyl ketone (boiling point 116°C) are preferred, for example.

[0141] The solvent may contain other solvents besides ketone solvents, but from the viewpoint of improving the solubility of tetrazaporphyrin compounds, the proportion of ketone solvents in the total amount of solvent is preferably 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0142] In addition, the solvent may also contain solvents whose boiling points at atmospheric pressure are outside the above range. However, from the perspective of having both good coating properties and easy drying properties after coating, the proportion of the solvent in the total amount of the solvent is preferably 40% by weight or less, more preferably 30% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.

[0143] The content of the solvent (the total amount if it contains two or more) is, for example, 0.5 to 3 times by weight (preferably 1.0 to 2.5 times by weight) of the content of the silsesquioxane containing epoxycyclohexyl groups. Within this range, the content can be adjusted according to the viscosity required by the curable composition.

[0144] For example, in the case of use for coating curable compositions by impregnation, the viscosity of the curable composition at 25°C and 60 rpm, as measured using a type B viscometer (rotor 1), is preferably about 3.0 to 5.5 mPa·s, more preferably 3.5 to 5.0 mPa·s, and particularly preferably 4.0 to 4.5 mPa·s. In this case, the content of the solvent is preferably about 1.0 to 2.0 times by weight of the content of the silsesquioxane having an epoxy cyclohexyl group, and particularly preferably 1.5 to 2.0 times by weight.

[0145] (Catalyst solidification)

[0146] The curing catalyst is a compound that can initiate or promote the cationic polymerization reaction of the silsesquioxane.

[0147] In the curable compositions disclosed herein, a cationic polymerization initiator is preferably used as the curing catalyst. The cationic polymerization initiator is a compound that generates a cation as an active species and initiates a curing reaction of the cationic curable compound contained in the curable composition.

[0148] The cationic polymerization initiators include thermal cationic polymerization initiators that generate cations by heating and photocationic polymerization initiators that generate cations by ultraviolet irradiation. They can be appropriately selected and used depending on the application.

[0149] Examples of initiators for thermal cationic polymerization include: 4-hydroxyphenyl-methyl-benzylsulfonylphenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonylphenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonylphenyltris(pentafluorophenyl)borate, and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonylphenyltris(pentafluorophenyl)borate.

[0150] Examples of photocationic polymerization initiators include: (4-hydroxyphenyl)methylbenzylsulfonium tetra(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tetra(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium phenyl tri(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium phenyl tri(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenylsulfonium]hexafluoroantimonate, and diphenyl[4-(phenylthio)phenylsulfonium]hexafluoroantimonate. [4-(phenylthio)phenyl]sulfonium tri(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetra(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tri(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonium)phenyl]sulfide phenyl tri(pentafluorophenyl)borate, [4-(2-thioxanthoneylthio)phenyl]phenyl-2-thioxanthoneylsulfonium phenyl tri(pentafluorophenyl)borate, etc.

[0151] The content of the cationic polymerization initiator is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight, relative to 100 parts by weight of the curing compound contained in the curing composition.

[0152] [Hard coating]

[0153] The hard coating disclosed herein is a film or thin film structure composed of a cured product of the above-described curable composition. The thickness of the hard coating can be appropriately selected according to the application; for example, it is 0.5 to 5 μm, preferably 1 to 3 μm, when the hard coating is bonded to the lens surface to form a hard-coated lens.

[0154] The hard coating film can be manufactured, for example, by a process of forming a coating film of the above-described curable composition on the surface of a substrate and a process of curing the formed coating film. If necessary, a pre-drying (pre-curing) process can also be provided before curing the coating film.

[0155] As for the method of forming the coating film of the curable composition, there are no particular limitations as long as the curable composition can be applied to the surface of the substrate. Examples include printing, coating, dipping, spraying, spin coating, etc.

[0156] The curing method for the coating film of the curable composition can be appropriately selected according to the type of cationic polymerization initiator contained in the curable composition.

[0157] For example, if the curable composition contains a thermo-cationic polymerization initiator, it can be cured by heat treatment of the coating film of the curable composition. Furthermore, if the curable composition contains a photo-cationic polymerization initiator, it can be cured by ultraviolet irradiation of the coating film of the curable composition.

[0158] The heat treatment conditions are not particularly limited, and the curing temperature is, for example, 80–200°C. When the substrate is plastic, from the viewpoint of preventing deformation or discoloration of the substrate due to heat, the curing temperature is preferably 90–150°C, and particularly preferably 95–130°C. The curing time is preferably set appropriately according to the curing temperature and the thickness of the coating; for example, at a curing temperature of 100°C, the curing time is approximately 0.5–5 hours.

[0159] When conducting the aforementioned ultraviolet irradiation, the light source for ultraviolet light can be, for example, a UV-LED, a mercury lamp such as a low-pressure, medium-pressure, or high-pressure mercury lamp, a mercury-xenon lamp, a metal halide lamp, a tungsten lamp, an arc lamp, an excimer lamp, an excimer laser, a semiconductor laser, a YAG laser, a laser system combining a laser and a nonlinear optical crystal, or a high-frequency induction ultraviolet light generating device. The ultraviolet irradiation dose (cumulative light intensity) is, for example, 100–500 mJ / cm². 2 .

[0160] The hard coating film has high surface hardness. The hard coating film (film thickness: 2.0 μm) formed on a polyamide resin (trade name "TROGAMID CX7323", manufactured by Daicel Evonik Co., Ltd.) film (thickness: 100 μm) has a pencil hardness of, for example, HB or higher, preferably F or higher. Therefore, it exhibits excellent scratch resistance. It should be noted that pencil hardness can be evaluated according to the method described in JISK 5600-5-4.

[0161] The hard coating film selectively absorbs light in the wavelength region of 570–605 nm (preferably 575–600 nm, more preferably 580–595 nm, and particularly preferably 580–590 nm). Therefore, the hard coating film has excellent anti-glare and contrast enhancement effects.

[0162] The transmission spectrum of the hard coating film has a sharp downward peak in the wavelength region of 570–605 nm, and no peaks in other visible light regions.

[0163] The transmittance (t1) at the minimum value of the downward peak is, for example, 85% or less, preferably 80% or less, and particularly preferably 75% or less. Furthermore, the transmittance (t1) is, for example, 30% or more, preferably 40% or more, and particularly preferably 45% or more.

[0164] Furthermore, the transmittance (t2) at a wavelength of 550 nm of the transmission spectrum is, for example, 75% or more, preferably 80% or more, and particularly preferably 85% or more.

[0165] The transmittance (t3) at a wavelength of 625 nm of the transmission spectrum is, for example, 75% or more, preferably 80% or more, further preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0166] Furthermore, the ratio of the transmittance (t2) to the transmittance (t1) (t2 / t1) is, for example, 1.1 or more, preferably 1.12 or more, particularly preferably 1.13 or more, and most preferably 1.15 or more.

[0167] The ratio of the transmittance (t3) to the transmittance (t1) (t3 / t1) is, for example, 1.1 or more, preferably 1.15 or more, particularly preferably 1.2 or more, and most preferably 1.25 or more.

[0168] Furthermore, the hard coating film has a low content of tetrazaporphyrin compounds, thus suppressing coloration caused by these compounds. Therefore, the hard coating film exhibits light transmittance of, for example, 80% or more in the visible light region, such as the wavelength region of 450–550 nm (preferably 450–560 nm, particularly preferably 450–570 nm) and the wavelength region of 625–700 nm (preferably 605–700 nm, particularly preferably 600–700 nm). Therefore, even when the hard coating film is applied to the surface of a lens, the lens's hue is not impaired.

[0169] The hard coating film has a high light transmittance, for example, 78% or more, preferably 78.5% or more, more preferably 79% or more, even more preferably 80% or more, particularly preferably 83% or more, and especially preferably 85% or more. Therefore, it has excellent visual confirmability.

[0170] It should be noted that the light transmittance (τv) of the hard coating film is a function of the spectral transmittance of the hard coating film, and is calculated according to the following formula (1).

[0171]

[0172] τ(λ) represents the spectral transmittance of the hard coating.

[0173] V(λ)Sc(λ) is a weighted average of visual sensitivity in light adaptation, and its values ​​are shown in Table 1 below.

[0174] [Table 1]

[0175]

[0176]

[0177] Hard-coated lens

[0178] The hard-coated lens disclosed herein has a configuration in which the aforementioned hard coating film is present on the lens surface. In addition to the aforementioned configuration, the hard-coated lens may also have other configurations (e.g., polarizing film, anti-reflective film, specular coating, protective film, etc.).

[0179] The lens is preferably a plastic lens. Examples of lens materials include, for instance, polyamide resins, polycarbonate resins, acrylic resins, allyl resins (diethylene glycol dielyl carbonate homopolymers or copolymers), urethane resins, and thiourethane resins. One or more of these materials may be used alone or in combination.

[0180] The thickness of the lens can be appropriately selected according to the application, and is approximately 1.0 to 3.0 mm. The surface shape of the lens is not particularly limited; it can be any shape, such as a flat surface, a curved surface (convex or concave).

[0181] The hard-coated lens can be manufactured by a process of forming a coating film of the above-described curable composition on the lens surface and a process of curing the formed coating film. The same methods as those used in the manufacturing method of the hard coating film described above can be employed as the coating method and the curing method of the curable composition.

[0182] The hard-coated lens has the aforementioned hard coating on its surface, thus selectively absorbing light in the wavelength region of 570–605 nm (preferably 575–600 nm, more preferably 580–595 nm, and particularly preferably 580–590 nm). The transmission spectrum of the hard-coated lens has a sharp downward peak in this wavelength region. Therefore, it exhibits excellent anti-glare and contrast enhancement effects.

[0183] There are no particular limitations on the lenses constituting the hard-coated lenses, such as those formed from polyamide resin (trade name "TROGAMID CX7323", manufactured by Daicel Evonik Co., Ltd.). When the surface of the lens with a central thickness of 2.2 mm (equivalent to a curvature of 6) has the above-described hard coating, the transmittance (t1') of the minimum value of the downward peak appearing in the wavelength region of 570-605 nm, the transmittance (t2') at a wavelength of 550 nm, and the transmittance (t3') at a wavelength of 625 nm in the transmission spectrum of the hard-coated lens have the following characteristics.

[0184] The transmittance (t1') is, for example, 85% or less, preferably 80% or less, particularly preferably 75% or less, and most preferably 70% or less. Furthermore, the transmittance (t1') is, for example, 30% or more, preferably 40% or more, and particularly preferably 45% or more.

[0185] The transmittance (t2') at a wavelength of 550 nm of the transmission spectrum is, for example, 73% or more, preferably 75% or more, and particularly preferably 80% or more.

[0186] The transmittance (t3') at a wavelength of 625 nm of the transmission spectrum is, for example, 73% or more, preferably 75% or more, particularly preferably 80% or more, and most preferably 85% or more.

[0187] Furthermore, the ratio of the transmittance (t2') to the transmittance (t1') (t2' / t1') is, for example, 1.05 or more, preferably 1.1 or more, particularly preferably 1.12 or more, and most preferably 1.13 or more.

[0188] The ratio of the transmittance (t3') to the transmittance (t1') (t3' / t1') is, for example, 1.05 or more, preferably 1.1 or more, particularly preferably 1.15 or more, and most preferably 1.2 or more.

[0189] Furthermore, the hard-coated lens exhibits a light transmittance of, for example, 80% or more in the visible light region, such as the wavelength region of 450–550 nm (preferably 450–560 nm, particularly preferably 450–570 nm) and the wavelength region of 625–700 nm (preferably 605–700 nm, particularly preferably 600–700 nm). Therefore, it possesses high visual confirmability.

[0190] The hard-coated lens [for example, in a lens formed of the polyamide resin ( The hard-coated lens, with a central thickness of 2.2 mm (equivalent to a curvature of 6), has a high light transmittance, for example, 78% or more, preferably 78.5% or more, particularly preferably 79% or more, and most preferably 79.5% or more. Therefore, it exhibits excellent visual clarity.

[0191] The light transmittance of the hard-coated lens is a function of the spectral transmittance of the hard-coated lens. The light transmittance of the hard-coated lens can be calculated by replacing the spectral transmittance [τ(λ)] of the hard coating film with the spectral transmittance [τ(λ)'] of the hard-coated lens in the above equation (1).

[0192] The hard-coated lens possesses the aforementioned characteristics, thus exhibiting excellent visual clarity. Furthermore, it offers excellent anti-glare and contrast enhancement effects, as well as superior scratch resistance.

[0193] Moreover, the aforementioned hard-coated lenses exhibit excellent heat resistance and crack resistance. Furthermore, they can suppress the generation of interference fringes caused by the refractive index difference between the lens and the hard coating.

[0194] Furthermore, the aforementioned hard coating suppresses coloration caused by tetrazaporphyrin compounds, thus expanding the range of hue selection for the hard-coated lens of this disclosure, which possesses the aforementioned hard coating. In addition, in corrective lenses (for myopia, astigmatism, hyperopia, etc.), the power is adjusted by varying the lens thickness. However, when tetrazaporphyrin compounds are mixed into the lens, a hue difference arises between the thick and thin portions of the lens. But in the hard-coated lens of this disclosure, it is not necessary to contain tetrazaporphyrin compounds in the lens, thus preventing hue difference due to lens thickness. As described above, using the hard-coated lens of this disclosure provides eyeglasses with high design value.

[0195] [Glasses]

[0196] The eyeglasses disclosed herein are devices worn around the eyes and have the aforementioned hard-coated lenses. The eyeglasses include not only ordinary eyeglasses but also sunglasses and safety goggles.

[0197] The glasses offer excellent visual clarity, high anti-glare performance, enhanced contrast, and significant design value. Furthermore, the surface of the glasses is highly hard and exhibits excellent scratch resistance.

[0198] The above-described components and combinations thereof are merely examples, and appropriate additions, omissions, substitutions, and modifications can be made to the components without departing from the spirit of this disclosure. Furthermore, this disclosure is not limited by the embodiments, but only by the description in the patent claims.

[0199] Example

[0200] The present disclosure will now be described in more detail based on embodiments, but the present disclosure is not limited to these embodiments.

[0201] Preparation Example 1 (Preparation of SQ1)

[0202] In a 300 mL reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet, 161.5 mmol (39.79 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter referred to as "EMS"), 9 mmol (1.69 g) of phenyltrimethoxysilane (hereinafter referred to as "PMS"), and 165.9 g of acetone were added under a nitrogen stream, and the mixture was heated to 50 °C. Then, 4.70 g (1.7 mmol of potassium carbonate) of a 5% aqueous solution was added dropwise over 5 minutes, followed by 1700 mmol (30.60 g) of water over 20 minutes. It should be noted that no significant temperature rise occurred during the addition. The mixture was then maintained at 50 °C under a nitrogen stream for 4 hours for polycondensation.

[0203] The products in the reaction solution after the polycondensation reaction were analyzed, and the results showed that the number average molecular weight was 1911 and the molecular weight distribution was 1.47. The ratio of the T2 to T3 forms of the above products [T3 form / T2 form] was 10.3.

[0204] The reaction solution was then cooled and washed with water until the lower layer became neutral. After separating the upper layer, the solvent was removed by distillation at 1 mmHg and 40 °C to obtain a colorless and transparent liquid product (sesquioxane containing 2-(3,4-epoxycyclohexyl)ethyl, epoxy equivalent: 195 g / eq; SQ1).

[0205] Preparation Examples 2-5 (Preparation of SQ2-5)

[0206] By changing the reaction conditions as described in Table 2 below, except that, sesquioxanes containing 2-(3,4-epoxycyclohexyl)ethyl were obtained in the same manner as in Preparation Example 1, sesquioxanes (SQ2-5).

[0207] [Table 2]

[0208]

[0209]

[0210] Comparative preparation example 1 (preparation of SQ6)

[0211] 300.0 mmol (70.9 g) of 3-glycidoxypropyltrimethoxysilane and 283.6 g of acetone were added to a 1000 mL reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet under a nitrogen stream, and the mixture was heated to 50 °C. Then, 8.29 g (3.0 mmol of potassium carbonate) of a 5% aqueous solution was added dropwise over 5 minutes, followed by the addition of 3000.0 mmol (54.00 g) of water over 20 minutes. It should be noted that no significant temperature rise occurred during the addition. The mixture was then maintained at 50 °C under a nitrogen stream for 5 hours for polycondensation.

[0212] Then, while cooling the reaction solution, 141.8 g of MIBK and 104.2 g of 5% saline were added. The solution was transferred to a 1 L separatory funnel, and 141.8 g of MIBK was added again for washing with water. After separation, the aqueous layer was extracted and washed with water until the lower layer became neutral. After separating the upper layer, the solvent was removed by distillation at 1 mmHg and 50 °C, yielding 67.40 g of a colorless, transparent, and liquid product (a polyorganosilsesquioxane containing 3-glycidoxypropyl groups, epoxy equivalent: 160 g / eq; SQ6) containing 28.28 wt% MIBK.

[0213] The number-average molecular weight (Mn), molecular weight distribution, and the ratio of T2 to T3 products [T3 / T2] were determined using the following methods for the preparation examples and comparative preparation examples. The results are summarized in Table 3 below.

[0214] Number-average molecular weight (Mn) and molecular weight distribution were determined by GPC analysis under the following conditions.

[0215] Alliance HPLC system 2695 (Waters).

[0216] Refractive Index Detector 2414 (manufactured by Waters).

[0217] Column: Tskgel GMH HR -M (Tosoh Corporation) × Two.

[0218] Column protection: Tskgel guard column H HR L (manufactured by Tosoh Corporation).

[0219] Column drying oven: COLUMN HEATER U-620 (manufactured by Sugai).

[0220] Solvent: THF.

[0221] Measurement conditions: 40℃.

[0222] The ratio of T2 to T3 in the product [T3 / T2] was determined using a JEOL ECA500 (500MHz) [JEOL ECA500 (500MHz)]. 29 This is performed using Si-NMR spectroscopy. Specifically, it is done by... 29 The signal in the Si-NMR spectrum is between -64 and -70 ppm (R). a The signal of silicon atoms in the T3 body of 2-(3,4-epoxycyclohexyl)ethyl and the signal of -54 to -60 ppm (R b The integral ratio of the silicon atom signal of the T2 body of 2-(3,4-epoxycyclohexyl)ethyl is calculated to obtain [T3 body / T2 body].

[0223] [Table 3]

[0224]

[0225] Reference Example 1

[0226] The SQ1 (100 parts by weight) obtained in Preparation Example 1, MIBK (manufactured by Kanto Chemical Co., Ltd.; 20 parts by weight) and the curing catalyst ([diphenyl[4-(phenylthio)phenyl]sulfonium tri(pentafluoroethyl)trifluorophosphate]; 1 part by weight) were mixed to obtain a hard coating liquid.

[0227] Using the obtained hard coating liquid, a hard coating film was prepared by the following method, and the surface hardness and scratch resistance of the obtained hard coating film were evaluated.

[0228] <Surface Hardness Evaluation>

[0229] Using a wire-winding bar, the obtained hard coating liquid was applied to a transparent polyamide resin (refractive index 1.52, trade name "TROGAMID CX7323", manufactured by Daicel·Evonik Co., Ltd.) film (thickness: 100 μm) to achieve a cured thickness of 40 μm. It was then placed in an oven at 70°C for 10 minutes (pre-baking), followed by irradiation with ultraviolet light (irradiation conditions (irradiation dose): 312 mJ / cm²). 2 Irradiation intensity: 80W / cm 2 Finally, it is heat-treated (cured) at 80°C for 2 hours. This cures the coating film of the above-mentioned hard coating liquid, resulting in a hard coating film with a hard coating layer.

[0230] The scratch resistance of the obtained hard coating film was evaluated using the following method.

[0231] At 1000g / cm 2The load was applied to the surface of the hard coating film of #0000 steel wool 100 times to check for scratches and their number on the surface of the hard coating film. The scratch resistance was evaluated according to the following criteria.

[0232] ◎(Extremely good): No marks or damage.

[0233] 〇 (Good): There are scratches, but the number of scratches is 1 to 10.

[0234] Δ (Slightly unsatisfactory): There are scratches, with more than 10 but less than 20 scratches.

[0235] × (Poor): There are scratches, and the number of scratches exceeds 20.

[0236] <Surface Hardness Evaluation>

[0237] The coating was applied in such a way that the thickness after curing of the hard coating liquid was 2.0 μm. Otherwise, a hard coating film with a hard coating layer (thickness: 2.0 μm) was obtained in the same manner as in Reference Example 1 above.

[0238] The pencil hardness of the hard coating surface of the obtained hard coating film was evaluated according to the method of JIS K5600-5-4.

[0239] See Examples 2-6

[0240] SQ1 was modified as described in Table 4 below, except that it was performed in the same manner as in Reference Example 1, and a hard-coated film was obtained and evaluated. The results are summarized in Table 4.

[0241] [Table 4]

[0242]

[0243] Example 1 (Preparation of Curable Composition 1)

[0244] In a 3-liter stainless steel container equipped with a stirrer and a nitrogen inlet tube, 516 g of methyl ethyl ketone, 451 g of the MIBK solution of SQ1 obtained in Preparation Example 1 (77.5% solid content), 6.8 g of curing catalyst (trade name "SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.), 1.1 g of leveling agent (trade name "Surflon S-243", manufactured by AGC seimichemical Co., Ltd.), 27 g of benzotriazole UV absorber (trade name "TINUVIN 1130", manufactured by BASF Japan Co., Ltd.), and 1.4 g of tetraazaporphyrin compound (the compound shown in formula (p-1) below, with selective light absorption wavelengths in the range of 570-605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.) as pigment powder (the content of the compound is equivalent to 4000 ppm by weight of the content of SQ1) were added under a nitrogen flow. The mixture was stirred at 25°C for 10 minutes to prepare curable composition 1. The viscosity (V1) of curable composition 1 at 25°C and 60 rpm is 4.2 mPa·s. It should be noted that this viscosity was measured using a type B viscometer (rotor 1).

[0245]

[0246] The storage stability of the cured composition 1 was evaluated using the following method.

[0247] Specifically, the curable composition 1 was sealed in a sealed container and stored at 5°C for 180 days. Then, the viscosity (V2) of the stored composition at 25°C and 60 rpm was measured, and the viscosity increase rate was calculated using the following formula. The result showed a viscosity increase rate of 1%, confirming good storage stability.

[0248] Viscosity increase rate (%) = [(V2-V1) / V1] × 100

[0249] Example 2 (Manufacturing of Hard Coated Lens 1)

[0250] 4970g of transparent polyamide resin (refractive index 1.52, trade name "TROGAMIDCX7323", manufactured by Daicel·Evonik Co., Ltd.) and 30g of benzotriazole UV absorber (trade name "TINUVIN326", manufactured by BASF Japan Co., Ltd.) were mixed for 5 minutes using a cylindrical rotary drum mixer. Then, the mixture was dried at 100°C for 3 hours using a dehumidifying small hopper dryer to obtain mixed material 1.

[0251] Using an injection molding machine (trade name "Tuparl TR150S", manufactured by Sodic Plastech) equipped with a lens mold, the mixed sample 1 was injection molded to produce a plastic lens 1. The central thickness is 2.2mm, equivalent to a curve with a curvature of 6.

[0252] The curable composition 1 obtained in Example 1 was applied to the convex and concave surfaces of the plastic lens 1 by dip coating with a hard coating thickness of 2.0 μm after curing. The lens was then heated in an oven at 100°C for 2 hours to obtain the hard-coated lens 1.

[0253] The light transmittance of the obtained hard-coated lens 1 was measured using the following method. The results are shown below. Figure 1 .

[0254] <Transmittance Evaluation Methods>

[0255] The light transmittance was measured using a spectrophotometer "CM-5" (manufactured by KONICA MINOLTA Co., Ltd.) under the following conditions. The results are shown below. Figure 1 .

[0256] Light source: pulsed xenon lamp.

[0257] Measurement wavelength range: 360~740nm.

[0258] Diffuse lighting.

[0259] Light reception method at 0° direction.

[0260] The light transmittance of hard-coated lens 1 is 79.7%.

[0261] according to Figure 1 The transmittance (t1') of light with a wavelength of 585nm, the transmittance (t2') of light with a wavelength of 550nm, and the transmittance (t3') of light with a wavelength of 625nm for the hard-coated lens 1 are as follows.

[0262] t1' = 70%.

[0263] t2' = 80%.

[0264] t3' = 87%.

[0265] t2' / t1' = 1.14.

[0266] t3' / t1' = 1.24.

[0267] The hard-coated lens 1 was heated in an electric dryer at 90°C for 60 minutes and placed at 25°C for 1 hour. Visual inspection was then performed using an LED light source for lens inspection (a visual inspection light manufactured by Nagata Corporation, trade name "NS-100NW(Y)", with an illuminance of 30,000 lux and a distance of 200 mm between the light source and the measurement area). The result was that no crack was detected.

[0268] Furthermore, when observing the hard-coated lens 1 using a three-wavelength fluorescent lamp, no interference fringes caused by the refractive index difference were detected.

[0269] Example 3 (Manufacturing of Hard Coating Film 1)

[0270] Using a winding rod, the curable composition 1 obtained in Example 1 was coated onto a glass plate to a cured thickness of 2 μm. The coated film was then heat-treated in an oven at 100°C for 2 hours to cure. A 5 cm square slit was then cut using a cutting machine, and the film was peeled off the glass plate to produce a hard coating film 1 (thickness: 2.0 μm). The light transmittance of the obtained hard coating film 1 was measured using the <transmittance evaluation method> described above. The results are shown below. Figure 2 The light transmittance of hard coating 1 is 87.1%.

[0271] In addition, according to Figure 2 The transmittance (t1) of light with a wavelength of 585 nm, the transmittance (t2) of light with a wavelength of 550 nm, and the transmittance (t3) of light with a wavelength of 625 nm of the hard coating film 1 are as follows.

[0272] t1 = 75%.

[0273] t2 = 88%.

[0274] t3 = 95%.

[0275] t2 / t1 = 1.17.

[0276] t3 / t1 = 1.27.

[0277] according to Figure 2 It is evident that the hard coating 1 can selectively and significantly reduce the transmittance of light at 585nm. Therefore, it is clear that by using the hard coating 1, eyeglasses with excellent visual clarity, anti-glare effect, and contrast enhancement effect can be obtained.

[0278] Comparative Example 1 (Preparation of Curable Composition 2)

[0279] 534 g of methyltriethoxysilane, 162 g of water, and 0.5 mL of 0.1 equivalent hydrochloric acid were added to a 1-liter reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet under a nitrogen stream. The mixture was thoroughly mixed and heated under reflux at 80°C for 4 hours. The initially heterogeneous liquid then became a transparent, homogeneous layer. Next, the ethanol (containing some water) produced as a byproduct of the reaction was distilled off, and the mixture was concentrated to obtain a 50% solids solution. This solution was further aged under reflux for 20 hours. Solvent evaporation was then performed using a thin-film evaporator within a short time (less than 1 minute) to obtain solid, flake-like methyl-containing silsesquioxanes.

[0280] In a 500 mL flask, 27 g of ethanol and 3 g of deionized water were mixed to prepare 10% aqueous ethanol. 30 g of the methyl-containing silsesquioxane obtained above was added to the mixture, and the mixture was stirred vigorously at 25 °C for about 40 minutes. As a result, the methyl-containing silsesquioxane was completely dissolved, and a 50% solution was obtained.

[0281] In addition, 23g of ethanol, 2g of deionized water, 1g of phenolic salt of 1,8-diazabicyclo[5.4.0]undecene-7 (a strong base curing agent), 1g of fluorine leveling agent (trade name "FTERGENT 100", manufactured by NEOS Co., Ltd.), and 13g of acetic acid were added in sequence to obtain a catalyst solution.

[0282] A 50% solution of the methyl-containing silsesquioxane was mixed with the catalyst solution, and 0.1 g of a tetrazaporphyrin compound (the compound shown in formula (p-1) above, with selective light absorption wavelengths in the range of 570–605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.) as a pigment powder was added (the amount is equivalent to 3300 ppm by weight of the methyl-containing silsesquioxane content), and the mixture was stirred at 25°C for 30 minutes. However, the undissolved pigment powder was in a state that could be visually confirmed.

[0283] Comparative Example 2 (Preparation of Curable Composition 3)

[0284] Without adding tetrazaporphyrin compounds, curable composition 3 was prepared in the same manner as in Example 1.

[0285] Comparative Example 3 (Manufacturing of Hard Coated Lens 2)

[0286] 9940 g of transparent polyamide resin (refractive index 1.52, trade name "TROGAMIDCX7323", manufactured by Daicel Evonik Co., Ltd.), 60 g of benzotriazole UV absorber (trade name "TINUVIN326", manufactured by BASF Japan Co., Ltd.), and 0.15 g of tetrazaporphyrin compound (the compound shown in formula (p-1) below, with selective light absorption wavelengths in the range of 570–605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.) as pigment powder were mixed for 5 minutes. Then, the mixture was dried at 100°C for 3 hours using a dehumidifying small hopper dryer to obtain mixture 2. Mixture 2 was granulated by extruding mixture 2 using a non-vented single-screw extruder under the following conditions.

[0287] Extrusion conditions: C1 = 250℃, C2 = 260℃, C3 = 270℃, C4 = 280℃, die head = 270℃, screw speed 60rpm, extrusion rate 15kg / hr.

[0288] Using the granulated mixed sample 2 described above instead of mixed sample 1, a plastic lens 2 was obtained in the same manner as in Example 2. The central thickness is 2.2mm, equivalent to a curve with a curvature of 6.

[0289] Curable composition 3 was used instead of curable composition 1, and plastic lens 2 was used instead of plastic lens 1. Otherwise, a hard-coated lens 2 was obtained in the same manner as in Example 2.

[0290] The tetrazaporphyrin compound content of the hard-coated lens 2 is approximately three times the tetrazaporphyrin compound content of the hard-coated lens 1 by weight.

[0291] The light transmittance of the hard-coated lens 2 was measured using the same method as in Example 2. The results are shown below. Figure 1 The light transmittance of hard-coated lens 2 is 77.7%.

[0292] according to Figure 1 The transmittance (t1') of light with a wavelength of 585nm, the transmittance (t2') of light with a wavelength of 550nm, and the transmittance (t3') of light with a wavelength of 625nm for the hard-coated lens 2 are as follows.

[0293] t1' = 73%.

[0294] t2' = 75%.

[0295] t3' = 84%.

[0296] t2' / t1' = 1.03.

[0297] t3' / t1' = 1.15.

[0298] according to Figure 1 Regarding the hard-coated lens 1, although the content of tetrazaporphyrin compound is approximately one-third that of the hard-coated lens 2, the reduction in light transmittance in the wavelength region of 570–605 nm is also superior to that of the hard-coated lens 2. Furthermore, compared to the hard-coated lens 2, the reduction in light transmittance outside the aforementioned wavelength region is suppressed in the hard-coated lens 1. Moreover, since the content of tetrazaporphyrin compound in the hard-coated lens 1 is approximately one-third that of the hard-coated lens 2, lens tinting is suppressed, resulting in higher light transmittance compared to the hard-coated lens 2.

[0299] As described above, when using hard-coated lens 1, compared to using hard-coated lens 2, it can more evenly and effectively capture light of wavelengths easily perceived by the human eye, thus resulting in clearer contrast. In other words, using hard-coated lens 1 ensures a good field of vision and reduces eye fatigue.

[0300] In summary, the following notes pertain to the composition and variations of this disclosure.

[0301] [1] A curable composition comprising: a silsesquioxane having an epoxycyclohexyl group; and a tetrazaporphyrin compound having an absorption peak in the wavelength region of 570 to 605 nm, wherein the content of the tetrazaporphyrin compound is 1,000 to 10,000 ppm by weight of the silsesquioxane content.

[0302] [2] The curable composition according to [1], wherein the silsesquioxane comprises the structural unit shown in formula (I) and the structural unit shown in formula (II).

[0303] [R a SiO 3 / 2 (I)

[0304] In formula (I), R a [This refers to a group containing an epoxycyclohexyl 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom.]

[0305] [R a SiO 2 / 2 (OR b (II)

[0306] In formula (II), R a Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0307] The ratio (molar ratio) of the structural unit shown in formula (I) to the structural unit shown in formula (II) is 5 to 500, and the structural unit of the sesquioxane, which is the structural unit shown in formula (I) and (II) in the total amount, is R. a The proportion of structural units containing cyclohexyl epoxide groups is 50–100 mol%.

[0308] [3] The curable composition according to [1], wherein the silsesquioxane is a compound having a main chain backbone consisting of siloxane bonds; and a group containing an epoxy cyclohexyl group and substituted or unsubstituted aryl groups bonded to the main chain backbone.

[0309] [4] The curable composition according to [1], wherein the silsesquioxane comprises: a structural unit represented by formula (I-1) or a structural unit represented by formula (II-1); and a structural unit represented by formula (I-2) or a structural unit represented by formula (II-2).

[0310] [R a1 SiO 3 / 2 (I-1)

[0311] In formula (I-1), R a1 [Represents a group containing an epoxycyclohexyl group]

[0312] [R a1 SiO 2 / 2 (OR b (II-1)

[0313] In formula (II-1), R a1 Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0314] [R a2 SiO 3 / 2 (I-2)

[0315] In equation (I-2), R a2 [Indicates substituted or unsubstituted aryl]

[0316] [R a2 SiO 2 / 2 (OR b (II-2)

[0317] In formula (II-2), R a2 R b Same as described above]

[0318] [5] According to the curable composition of [1], wherein the silsesquioxane comprises a structural unit represented by formula (I-1) or a structural unit represented by formula (II-1); and a structural unit represented by formula (I-2) or a structural unit represented by formula (II-2).

[0319] The proportion of the total structural units of the silsesquioxane, including the structural units shown in formula (I-1) and the structural units shown in formula (II-1), is 50 to 99 mol, and the proportion of the total structural units of the silsesquioxane, including the structural units shown in formula (I-2) and the structural units shown in formula (II-2), is 1 to 50 mol.

[0320] [R a1 SiO 3 / 2 (I-1)

[0321] In formula (I-1), R a1 [Represents a group containing an epoxycyclohexyl group]

[0322] [R a1 SiO 2 / 2 (OR b (II-1)

[0323] In formula (II-1), R a1 Same as described above. R b [Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms]

[0324] [R a2 SiO 3 / 2 (I-2)

[0325] In equation (I-2), R a2 [Indicates substituted or unsubstituted aryl]

[0326] [R a2 SiO 2 / 2 (OR b (II-2)

[0327] In formula (II-2), R a2 R b Same as described above]

[0328] [6] The curable composition according to [4] or [5], wherein the ratio of the sum of the structural units shown in formula (I-1) and the structural units shown in formula (I-2) to the sum of the structural units shown in formula (II-1) and the structural units shown in formula (II-2) (the former / the latter; molar ratio) is 5 to 500.

[0329] [7] The curable composition according to any one of [1] to [6], wherein the number average molecular weight of the silsesquioxane, converted from standard polystyrene obtained by GPC, is 500 to 10000.

[0330] [8] The curable composition according to any one of [1] to [7], wherein the epoxy equivalent of the sesquioxane is 50 to 3000 g / eq.

[0331] [9] The curable composition according to any one of [1] to [8], wherein the curable composition is a hard coating forming composition.

[0332]

[10] The use of a curable composition as described in any one of [1] to [8] as a composition for forming a hard coating.

[0333]

[11] A method for manufacturing a hard coating film, comprising: a step of coating a curable composition as described in any one of [1] to [8].

[0334]

[12] A method for manufacturing a hard coating film, comprising the following steps: applying a curable composition as described in any one of [1] to [8] to obtain a hard coating film with a pencil hardness of HB or higher as determined by the method according to JIS K 5600-5-4.

[0335]

[13] A hard coating film, which is composed of a cured product of any one of the curable compositions described in [1] to [8].

[0336]

[14] According to the hard coating described in

[13] , the pencil hardness measured by means of JIS K 5600-5-4 is HB or higher.

[0337]

[15] According to the hard coating film of

[13] or

[14] , in the transmission spectrum, there is a minimum value of a downward peak in the wavelength region of 570 to 605 nm, the transmittance (t1) of the minimum value is less than 80%, the ratio of the transmittance (t2) at wavelength 550 nm to the transmittance (t1) (t2 / t1) is more than 1.1, and the ratio of the transmittance (t3) at wavelength 625 nm to the transmittance (t1) (t3 / t1) is more than 1.1.

[0338]

[16] A method for manufacturing a hard-coated lens is as follows: applying a curable composition as described in any one of [1] to [8] onto the surface of a lens and curing it to obtain a hard-coated lens having a hard coating film composed of the cured product of the curable composition.

[0339]

[17] A hard-coated lens, which is a hard-coated lens having a hard coating as described in any one of

[13] to

[15] on the lens surface.

[0340]

[18] The hard-coated lens according to

[17] has a light transmittance of 78% or more.

[0341]

[19] The hard-coated lens according to

[17] or

[18] , wherein, in the transmission spectrum, there is a minimum value of a downward peak in the wavelength region of 570 to 605 nm, the transmittance (t1') of the minimum value is 85% or less, the ratio of the transmittance (t2') at wavelength 550 nm to the transmittance (t1') (t2' / t1') is 1.05 or more, and the ratio of the transmittance (t3') at wavelength 625 nm to the transmittance (t1') (t3' / t1') is 1.05 or more.

[0342]

[20] An eyeglass having a hard-coated lens as described in any one of

[17] to

[19] .

[0343]

[21] A pair of sunglasses having a hard-coated lens as described in any one of

[17] to

[19] .

[0344]

[22] A pair of goggles having a hard-coated lens as described in any one of

[17] to

[19] .

[0345] Industrial availability

[0346] If the curable composition of this disclosure is applied to the surface of a lens and cured, a hard-coated lens with excellent anti-glare and contrast enhancement effects can be manufactured. Therefore, the curable composition is preferably used as a composition for forming a hard coating.

Claims

1. A hard coating film comprising a cured product of a curable composition, said curable composition comprising: Silsesquioxanes containing an epoxycyclohexyl group; and Tetraazaporphyrin compounds with absorption peaks in the wavelength region of 570–605 nm The content of the tetrazaporphyrin compound is 1000 to 10000 ppm by weight, which is the same as the content of the sesquioxane. The light transmittance of the hard coating is above 78%.

2. The hard coating film according to claim 1, wherein, The silsesquioxane comprises structural units shown in formula (I) and structural units shown in formula (II). [R] a SiO 3 / 2 ](I) In equation (I), R a This indicates a group containing an epoxycyclohexyl 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom. [R a SiO 2 / 2 (OR b )](II) In equation (II), R a Similar to the above, R b Indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. The ratio of the content of the structural unit shown in formula (I) to that of the structural unit shown in formula (II), i.e., the former / the latter, is 5 to 500 in molar ratio. Of the total amount of structural units of the silsesquioxane, the structural unit represented by formulas (I) and (II), and R in the formula a The proportion of structural units containing epoxycyclohexyl groups is 50–100 moles.

3. The hard coating film according to claim 1 or 2, wherein, In the transmission spectrum, there is a minimum value with a downward peak in the wavelength region of 570–605 nm. The minimum transmittance t1 is below 80%. The ratio of transmittance t2 to transmittance t1 at a wavelength of 550 nm, i.e., t2 / t1, is greater than 1.

1. The ratio of the transmittance t3 to the transmittance t1 at a wavelength of 625 nm, i.e., t3 / t1, is greater than 1.

1.

4. A hard-coated lens, wherein the hard-coated lens is a lens having a hard coating as described in claim 1 or 2 on its lens surface.

5. A pair of eyeglasses, the eyeglasses comprising a hard-coated lens as described in claim 4.

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