Hardening composition

Abstract

To provide a curable composition that can suppress thermal degradation of a tetraazaporphyrin compound, achieving a lens having high visibility as well as superior antiglare and contrast-enhancement effects.SOLUTION: A curable composition according to the present disclosure comprises silsesquioxane having a cyclohexeneoxide group and a tetraazaporphyrin compound having an absorption peak in the wavelength region of 570-605 nm, wherein the content of the tetraazaporphyrin compound is 1000-10000 ppm by weight relative to the content of the silsesquioxane.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a curable composition containing a silsesquioxane and a tetraazaporphyrin compound.

Background Art

[0002] It is known that glasses such as sunglasses and goggles can obtain an anti-glare effect and a contrast enhancement effect by restricting the transmission of light of a specific wavelength.

[0003] For example, Patent Document 1 describes that a tetraazaporphyrin compound having a sharp absorption peak around 585 nm is added to a plastic lens material such as a polycarbonate-based thermoplastic resin in an amount of 0.001% by weight, melt-kneaded at 280° C., and then injection-molded to obtain a lens excellent in anti-glare effect and contrast enhancement effect.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As a result of the inventors' examination of the above method, the following problems were found. 1. Since the expensive tetraazaporphyrin compound deteriorates due to high-temperature exposure during melt-kneading with the thermoplastic resin and injection molding, in order to obtain the desired anti-glare effect and contrast enhancement effect, it is necessary to add an extra amount of the tetraazaporphyrin compound to compensate for the deterioration, which increases the cost. 2. The tetraazaporphyrin compound is a compound that exhibits blue to purple. When a large amount of this compound is added to a plastic lens material, the resulting lens is colored in a dark blue to purple, which reduces the design value. 3. When the tetraazaporphyrin compound is exposed to high temperatures, a thermal decomposition product of the tetraazaporphyrin compound is generated, and the thermal decomposition product acts in a direction of broadening the absorption peak, thereby reducing visibility.

[0006] Accordingly, an object of the present disclosure is to provide a curable composition capable of suppressing thermal degradation of a tetraazaporphyrin compound and realizing a lens excellent in visibility, anti-glare effect, and contrast enhancement effect. Another object of the present disclosure is to provide a curable composition having excellent storage stability, suppressing thermal degradation of a tetraazaporphyrin compound, and realizing a lens excellent in visibility, anti-glare effect, and contrast enhancement effect. Another object of the present disclosure is to provide a hard coat film excellent in visibility, anti-glare effect, and contrast enhancement effect and not impairing the color tone of the lens. Another object of the present disclosure is to provide a method for manufacturing a lens capable of suppressing thermal degradation of a tetraazaporphyrin compound and excellent in visibility, anti-glare effect, and contrast enhancement effect. Another object of the present disclosure is to provide a lens excellent in visibility, anti-glare effect, and contrast enhancement effect and having high design value. Another object of the present disclosure is to provide glasses excellent in visibility, anti-glare effect, and contrast enhancement effect and having high design value.

Means for Solving the Problems

[0007] The present inventors have conducted intensive research to solve the above problems, and have found that, instead of kneading a tetraazaporphyrin compound into a lens, by forming a hard coat film containing a tetraazaporphyrin compound on the lens surface, the deterioration of the tetraazaporphyrin compound due to exposure to high temperatures can be minimized, and even if the amount of the tetraazaporphyrin compound is reduced compared to the conventional method, the lens can be given an anti-glare effect and a contrast enhancement effect equivalent to or superior to the conventional method. In addition, since silsesquioxane having a cyclohexene oxide group also shows solubility in a solvent that dissolves a tetraazaporphyrin compound, it has been found that by dissolving a tetraazaporphyrin compound and a silsesquioxane having a cyclohexene oxide group in a solvent, the coating property can be improved, and a hard coat film containing a tetraazaporphyrin compound can be easily formed on the lens surface. The present disclosure has been completed based on these findings.

[0008] That is, the present disclosure relates to a silsesquioxane having a cyclohexene oxide group, A tetraazaporphyrin compound having an absorption peak in the wavelength region of 570 to 605 nm; Contains The content of the tetraazaporphyrin compound in the curable composition is 1,000 to 10,000 ppm by weight of the content of the silsesquioxane.

[0009] The present disclosure also provides a method for preparing a silsesquioxane having the following formula (I): [R a SiO 3 / 2 ] (I) [In formula (I), R a represents a group containing a cyclohexene oxide 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. and a structural unit represented by the following formula (II): [R a SiO 2 / 2(OR b )] (II) [In formula (II), R a is the same as described above. R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] and includes a structural unit represented by the ratio (the former / the latter; molar ratio) of the content of the structural unit represented by the formula (I) to the content of the structural unit represented by the formula (II) is 5 to 500, in the total amount of the structural units of the silsesquioxane, the structural units represented by the formulas (I) and (II), wherein R a in the formula is a group containing a cyclohexene oxide group, and the proportion occupied by the structural unit is 50 to 100 mol%, and the present invention provides the curable composition.

[0010] The present disclosure also provides the curable composition, which is a composition for forming a hard coat layer.

[0011] The present disclosure also provides a hard coat film comprising a cured product of the curable composition.

[0012] The present disclosure also has a minimum value of a downward peak in the wavelength region of 570 to 605 nm in the transmission spectrum, the transmittance (t1) of the minimum value is 80% or less, the ratio (t2 / t1) of the transmittance (t2) at a wavelength of 550 nm to the transmittance (t1) is 1.1 or more, and the present disclosure provides the hard coat film in which the ratio (t3 / t1) of the transmittance (t3) at a wavelength of 625 nm to the transmittance (t1) is 1.1 or more.

[0013] The present disclosure also provides a method for manufacturing a hard coat lens, which comprises applying the curable composition to a lens surface and curing it to obtain a hard coat lens having a hard coat film comprising a cured product of the curable composition.

[0014] The present disclosure also provides a hard coat lens having the hard coat film on a lens surface.

[0015] The present disclosure also provides glasses including the hard coat lens. [Advantages of the Invention]

[0016] Since the curable composition of the present disclosure has the above configuration, it is useful as a composition for forming a hard coat layer. And, if the curable composition is applied to the lens surface and cured, a hard coat lens having an excellent anti-glare effect and contrast enhancing effect can be manufactured while minimizing the high-temperature exposure of the tetraazaporphyrin compound. Therefore, a decrease in visibility due to the thermal decomposition product of the tetraazaporphyrin compound is suppressed, and extremely good visibility can be imparted to the hard coat lens in addition to the excellent anti-glare effect and contrast enhancing effect. Further, according to the curable composition, as described above, by minimizing the high-temperature exposure of the tetraazaporphyrin compound, it is possible to suppress thermal decomposition, so it is not necessary to add a large amount of the tetraazaporphyrin compound to supplement the thermal decomposition product. Therefore, the addition amount of the tetraazaporphyrin compound can be reduced compared to the conventional amount, and it is possible to form a hard coat film in which coloring by the tetraazaporphyrin compound is suppressed. And, in a hard coat lens including a hard coat film with suppressed coloring, the range of selection of the color tone of the lens is widened and the design value is increased. Furthermore, although the tetraazaporphyrin compound is expensive, as described above, the amount used can be reduced, so it is possible to form a hard coat film at low cost. [Brief Description of the Drawings]

[0017]

Figure 1

Figure 2

[0018] [Curable Composition] The curable composition of the present disclosure contains a silsesquioxane having a cyclohexene oxide group and a tetraazaporphyrin compound having an absorption peak in the wavelength range of 570 to 605 nm. The curable composition is useful as a composition for forming a hard coat layer.

[0019] In addition to the above components, the curable composition may contain one or more other components as necessary. Examples of other components include a curing catalyst, a solvent, a leveling agent, an antifoaming agent, a foam stabilizer, an ultraviolet absorber, a heat stabilizer, an antioxidant, a light stabilizer, a plasticizer, a lubricant, a filler, a flame retardant, an antistatic agent, a coloring material, and the like.

[0020] (Tetraazaporphyrin compound) The absorption spectrum of the tetraazaporphyrin compound measured in a chloroform solution has a sharp absorption peak in the wavelength range of 570 to 605 nm (preferably 575 to 600 nm, more preferably 580 to 595 nm, particularly preferably 580 to 590 nm).

[0021] The absorption rate (A1) at the maximum value of the absorption peak is, for example, 80% or more, preferably 90% or more, particularly preferably 95% or more.

[0022] The ratio (A1 / A2) of the absorption rate (A1) to the absorption rate (A2) at a wavelength of 550 nm in the absorption spectrum is, for example, 1.5 or more, preferably 2.0 or more, particularly preferably 3.0 or more.

[0023] The ratio (A1 / A3) of the absorption rate (A1) to the absorption rate (A3) at a wavelength of 625 nm in the absorption spectrum is, for example, 10 or more, preferably 20 or more.

[0024] Examples of the tetraazaporphyrin compound include a compound represented by the following formula (p).

Chemical formula

[0025] In the above formula (p), A 1 ~A 8 are the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, a substituted or unsubstituted amino group, a carboxyl group, a sulfonic acid group, a hydrocarbon group, an -OR group, or an -SR group (wherein R represents a hydrocarbon group). Two groups selected from A 1 ~A 8 may be bonded to each other to form a ring together with the adjacent carbon atoms. 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 oxidized metal atom.

[0026] Examples of the substituted amino group include a mono- or di(C 1-20 )alkylamino group and the like.

[0027] The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by bonding these. As the hydrocarbon group, an aliphatic hydrocarbon group and / or an aromatic hydrocarbon group are preferable.

[0028] As the hydrocarbon group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, a dodecyl group; an alkenyl group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, particularly preferably 2 to 3 carbon atoms) such as a vinyl group, an allyl group, a 1-butenyl group; an alkynyl group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, particularly preferably 2 to 3 carbon atoms) such as an ethynyl group, a propynyl group, and the like.

[0029] Examples of the aromatic hydrocarbon group include an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

[0030] The hydrocarbon group may have a substituent such as a halogen atom.

[0031] Said A 1 ~A 8 Examples of the ring that may be formed by two groups selected from the above and bonded to each other together with adjacent carbon atoms include aliphatic hydrocarbon rings having 1 to 6 carbon atoms, aromatic hydrocarbon rings having 6 to 10 carbon atoms, and the like.

[0032] Said M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or a metal oxide atom, and preferably a divalent metal atom or a metal oxide atom.

[0033] Examples of the divalent metal atom include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, and the like.

[0034] Examples of the metal oxide atom include VO, MnO, TiO, and the like.

[0035] As the tetraazaporphyrin compound, for example, commercially available products such as the product name "FDG-006" (manufactured by Yamada Chemical Industry Co., Ltd.) can be preferably used.

[0036] The content of the tetraazaporphyrin compound is, for example, 1000 to 10000 weight ppm of the content of the silsesquioxane. The upper limit value of the content is preferably 8000 weight ppm, particularly preferably 7000 weight ppm, most preferably 6000 weight ppm, and especially preferably 5000 weight ppm in terms of suppressing the reduction of the design value while having an excellent anti-glare effect and an excellent contrast enhancement effect. The lower limit value of the content is preferably 2000 weight ppm, particularly preferably 2500 weight ppm, and most preferably 3000 weight ppm in terms of enhancing the anti-glare effect and the contrast enhancement effect.

[0037] By using the curable composition of the present disclosure, it is possible to form a hard coat film containing the tetraazaporphyrin compound on the lens surface while suppressing the high-temperature exposure of the tetraazaporphyrin compound. Therefore, it is not necessary to increase the amount of the tetraazaporphyrin compound in the composition in anticipation of thermal degradation. As a result, the cost associated with the tetraazaporphyrin compound can be reduced.

[0038] (Silsesquioxane) The silsesquioxane is a compound having a main chain skeleton composed of siloxane bonds (Si-O-Si bonds) and a group containing a cyclohexene oxide group bonded to the main chain skeleton.

[0039] The silsesquioxane may be a compound having a main chain skeleton composed of siloxane bonds and a group containing a cyclohexene oxide group and a substituted or unsubstituted aryl group (for example, a phenyl group) bonded to the main chain skeleton.

[0040] The group containing a cyclohexene oxide group is represented by the following formula (1a) or (1b). In the following formula, R 1a , R 1b are the same or different and each represents an alkylene group having 1 to 10 carbon atoms. The wavy bond is bonded to the main chain skeleton composed of siloxane bonds. [Chemical formula]

[0041] Examples of the alkylene group having 1 to 10 carbon atoms include linear or branched alkylene groups such as a methylene group, a methylmethylene group, an ethylene group, a dimethylene group, a dimethylmethylene group, a propylene group, and a trimethylene group.

[0042] The silsesquioxane includes those having various structures such as a ladder-type structure, a complete cage-type structure, an incomplete cage-type structure, and a random-type structure. Among them, the silsesquioxane having an incomplete cage-type structure is preferable in terms of forming a cured product having high hardness.

[0043] The silsesquioxane having the incomplete cage structure is represented by the following formula (I) [R a SiO 3 / 2 (I) [In formula (I), R a represents a group containing a cyclohexene oxide 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] and a structural unit represented by the following formula (II) [R a SiO 2 / 2 (OR b )] (II) [In formula (II), R a is the same as defined above. R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] and contains a structural unit represented by in the total amount of the structural unit represented by the above formula (I) and the structural unit represented by the above formula (II) constituting the silsesquioxane, at least one is a structural unit in which R a is a group containing a cyclohexene oxide group.

[0044] The structural unit represented by the above formula (I) is a structural unit represented by the following formula (I’), and is referred to as a T3 unit. Further, the structural unit represented by the above formula (II) is a structural unit represented by the following formula (II’), and is referred to as a T2 unit. All of these structural units are T units. 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’)). Also, 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’)).

Chemical formula

[0045] The above R a represents a group containing a cyclohexene oxide 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.

[0046] Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

[0047] Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms such as a benzyl group and a phenethyl group.

[0048] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 6 carbon atoms such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0049] Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group.

[0050] Examples of the alkenyl group include linear or branched alkenyl groups having 2 to 6 carbon atoms such as a vinyl group, an allyl group, and an isopropenyl group.

[0051] Examples of the substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include groups in which some or all of the hydrogen atoms bonded to the main chain skeletons of the above-described aryl group, aralkyl group, cycloalkyl group, alkyl group, or alkenyl group are substituted with at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an RO group, an RCOO group, an RCO group, a siloxane group, a halogen atom, a mercapto group, an amino group, and a hydroxyl group. Here, R represents a hydrocarbon group, and examples thereof include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent group in which two or more of these are bonded via a single bond.

[0052] The above (OR b ) group represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, an isobutyloxy group, and the like.

[0053] The silsesquioxane is a structural unit represented by the above formula (I) or (II), and together with a structural unit in which R a in the formula is a group containing a cyclohexene oxide group, it may contain a structural unit represented by the above formula (I) or (II), in which R a in the formula is a substituted or unsubstituted aryl group (for example, a phenyl group).

[0054] That is, the silsesquioxane may contain a structural unit represented by the following formula (I-1) or (II-1) and a structural unit represented by the following formula (I-2) or (II-2). The structural unit represented by the formula (I-1) and the structural unit represented by the formula (I-2) are T3 bodies, and the structural unit represented by the formula (II-1) and the structural unit represented by the formula (II-2) are T2 bodies. [R a1 SiO 3 / 2 (I-1) [In the formula (I), R a1 represents a group containing a cyclohexene oxide group] [R a1 SiO 2 / 2 (OR b )] (II-1) [In formula (II), R a1 is the same as described above. R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] [R a2 SiO 3 / 2 (I-2) [In formula (I), R a2 represents a substituted or unsubstituted aryl group] [R a2 SiO 2 / 2 (OR b )] (II-2) [In formula (II), R a2 , R b are the same as described above]

[0055] The molar ratio of the T3 form to the T2 form, that is, the ratio of the content of the structural unit represented by formula (I) to the content of the structural unit represented by the above formula (II) (former / latter; molar ratio), or the ratio of the total of the structural units represented by the above formulas (I-1) and (I-2) to the total of the structural units represented by the above formulas (II-1) and (II-2) (former / latter; molar ratio) is, for example, 5 to 500. The lower limit value of the molar ratio of the T3 form to the T2 form is preferably 7, particularly preferably 8, most preferably 9, especially 10, in terms of the effect of improving the hardness and scratch resistance of the resulting cured product. The upper limit value of the molar ratio of the T3 form to the T2 form is preferably 50, particularly preferably 30, most preferably 20, especially 15. The molar ratio of the T3 form to the T2 form can be determined, for example, 29 by Si-NMR spectrum measurement. 29 In the Si-NMR spectrum, since the silicon atoms in the T3 form and the silicon atoms in the T2 form show signals (peaks) at different positions (chemical shifts), the above molar ratio can be determined by calculating the integral ratio of each peak.

[0056] Incidentally, the 29 Si-NMR spectrum of the silsesquioxane can be measured, for example, by the following apparatus and conditions. Measuring device: Trade name "JNM-ECA500 NMR" (manufactured by JEOL Ltd.) Solvent: Deuterated chloroform Number of integrations: 1800 times Measurement temperature: 25 °C

[0057] In addition to the above T units, the silsesquioxane may also have at least one selected from the group consisting of structural units represented by [R a 3SiO 1 / 2 (so-called M units), structural units represented by [R a 2SiO] (so-called D units), and structural units represented by [SiO2] (so-called Q units). In the above formula, R a is the same as defined above.

[0058] In terms 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 structural units of the 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%, still more preferably 65 to 100 mol%, particularly preferably 70 to 100 mol%, and most preferably 80 to 100 mol%.

[0059] Among the total amount of structural units of the silsesquioxane, the structural units represented by the above formulas (I) and (II), where R a in the formula is a group containing a cyclohexene oxide group [that is, the total of the structural units represented by the above formula (I-1) and the structural units represented by the above formula (II-1)] preferably occupies a proportion of 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 65 to 100 mol%, particularly preferably 70 to 100 mol%, most preferably 80 to 99 mol%, and especially preferably 85 to 96 mol% in terms of having high curability and being able to form a cured product with high hardness. The proportion of the above structural units is determined from the composition of the raw materials of the silsesquioxane. In addition, it can also be determined by subjecting the silsesquioxane to NMR spectrum measurement.

[0060] Also, among the total amount of the structural units of the silsesquioxane, the structural unit represented by the formula (I) or (II), wherein R a is a substituted or unsubstituted aryl group (e.g., phenyl group) [i.e., the total of the structural unit represented by the above formula (I-2) and the structural unit represented by the above formula (II-2)] preferably accounts for 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 in terms of forming a cured product having high hardness. The lower limit of the ratio is, for example, 1 mol%, preferably 2 mol%, particularly preferably 3 mol%, and most preferably 4 mol%.

[0061] Among the total amount of T units [= the total amount of the structural unit represented by the formula (I) and the structural unit represented by the formula (II)] constituting the silsesquioxane, the T unit having a group containing a cyclohexene oxide group [= the structural unit represented by the formula (I) or the structural unit represented by the formula (II), wherein R a is a group containing a cyclohexene oxide group] preferably accounts for 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 65 to 100 mol%, particularly preferably 70 to 100 mol%, and most preferably 80 to 99 mol%.

[0062] Therefore, among the total amount of the structural units of the silsesquioxane [total structural units; including T units, M units, D units, and Q units] (100 mol%), the ratio of the T unit having a group containing a cyclohexene oxide group [= the structural unit represented by the formula (I) or the structural unit represented by the formula (II), wherein R a is a group containing a cyclohexene oxide group] 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%.

[0063] The molecular weight distribution (Mw / Mn) in terms of standard polystyrene of silsesquioxane 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 setting the molecular weight distribution to 3.0 or less, the surface hardness of the cured product tends to be higher. On the other hand, by setting the molecular weight distribution to 1.0 or more, it tends to become liquid and the handleability tends to be improved.

[0064] The number average molecular weight (Mn) in terms of standard polystyrene of silsesquioxane 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. When the number average molecular weight is 500 or more, a cured product having high hardness and excellent scratch resistance and heat resistance tends to be obtained. On the other hand, when the number average molecular weight is 10,000 or less, the compatibility with other components is good and the usability tends to be excellent.

[0065] The epoxy equivalent of silsesquioxane is, for example, 50 to 3,000 g / eq, and the upper limit is preferably 2,000 g / eq, more preferably 1,500 g / eq, still more preferably 1,000 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 setting the epoxy equivalent to 3,000 g / eq or less, a cured product having high hardness and excellent scratch resistance and heat resistance tends to be obtained. Also, by setting the epoxy equivalent to 50 g / eq or more, appropriate fluidity is obtained and the handleability tends to be excellent.

[0066] The silsesquioxane can be produced by subjecting a hydrolyzable silane compound to hydrolysis and polycondensation reactions.

[0067] The hydrolyzable silane compound contains at least a compound represented by the following formula (a). The compound represented by the following formula (a) is R aSi(X 1 )3(a) (wherein X 1 represents an OR b group or a halogen atom. R a , R b are the same as defined above)

[0068] The hydrolyzable silane compound is a compound represented by the above formula (a), and at least includes a compound in which R a in the formula is a group containing a cyclohexene oxide group.

[0069] The compounds represented by the formula (a) can also be used in combination of two or more according to the constitutional units of the silsesquioxane to be produced. For example, when producing a silsesquioxane having a main chain skeleton composed of siloxane bonds and a group containing a cyclohexene oxide group and a substituted or unsubstituted aryl group (for example, a phenyl group) bonded to the main chain skeleton, the compound represented by the formula (a) in which R a in the formula is a group containing a cyclohexene oxide group and the compound represented by the formula (a) in which R a in the formula is a substituted or unsubstituted aryl group (for example, a phenyl group) are preferably used in combination.

[0070] In addition to the compound represented by the above formula (a), the hydrolyzable silane compound may also contain other hydrolyzable silane compounds (for example, hydrolyzable trifunctional silane compounds other than the compound represented by the above formula (a), hydrolyzable monofunctional silane compounds forming M units, hydrolyzable bifunctional silane compounds forming D units, hydrolyzable tetrafunctional silane compounds forming Q units, etc.). By adjusting the usage amount and composition of the hydrolyzable silane compound, a desired silsesquioxane can be produced.

[0071] The hydrolysis and polycondensation reactions of the hydrolyzable silane compound are preferably carried out in the presence of an alkali metal catalyst in that a siloxane bond can be formed while suppressing the decomposition of the cyclohexene oxide group. Examples of the alkali metal catalyst include alkali metal compounds such as hydroxides, carbonates, hydrogen carbonates, organic acid salts, alkoxides, and aryloxides of alkali metals. These can be used alone or in combination of two or more. Also, these can be used in a state dissolved or dispersed in water, a solvent, or the like.

[0072] Examples of the hydroxide of the alkali metal include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and the like.

[0073] Examples of the carbonate of the alkali metal include lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and the like.

[0074] Examples of the hydrogen carbonate of the alkali metal include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, and the like.

[0075] The organic acid salt of the alkali metal is preferably a salt of an alkali metal and a monovalent organic acid. Examples thereof include carboxylates of alkali metals (preferably salts of alkali metals and monovalent carboxylic acids, particularly preferably acetates of alkali metals) such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, and the like.

[0076] Examples of the alkoxide of the alkali metal include C 1-5 alkoxides of alkali metals such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide, and the like.

[0077] Examples of the aryloxide of the alkali metal include C 6-11Examples include aryloxide.

[0078] The usage amount of the alkali metal catalyst is, for example, about 0.002 to 0.200 mol with respect to 1 mol of the hydrolyzable silane compound.

[0079] Water is used for the hydrolysis and polycondensation reactions of the above hydrolyzable silane compound. The usage amount of water is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the hydrolyzable silane compound.

[0080] The above reaction is preferably carried out in the presence of a solvent. Examples of the solvent 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; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol. These can be used alone or in combination of two or more. Among these solvents, ketones and / or ethers are preferable in that they have excellent solubility in water and silsesquioxane and do not inhibit the hydrolysis and polycondensation reactions of the hydrolyzable silane compound, and ketones are particularly preferable.

[0081] The usage amount of the solvent is, for example, 0 to 20 parts by weight with respect to 1 part by weight of the hydrolyzable silane compound.

[0082] When performing the hydrolysis and polycondensation reactions of the above hydrolyzable silane compound, the reaction temperature is preferably 40 to 100°C, more preferably 45 to 80°C. Also, the reaction time for the above hydrolysis and polycondensation reactions is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. Further, the above hydrolysis and polycondensation reactions can be carried out under normal pressure, or under pressure or reduced pressure. Incidentally, as the atmosphere for the above reaction, for example, it may be any of an inert gas atmosphere such as a nitrogen atmosphere, an argon atmosphere, etc., or an oxygen presence such as an air atmosphere.

[0083] After the completion of this reaction, the obtained reaction product can be separated and purified by general precipitation, washing, and filtration.

[0084] In the present disclosure, it is preferable to provide a water washing step of performing a water washing treatment until the reaction solution becomes neutral after the completion of the hydrolysis and polycondensation reactions of the hydrolyzable silane compound. This is because the storage stability of the resulting curable composition can be improved by using the silsesquioxane subjected to the water washing treatment.

[0085] The curable composition obtained by using the silsesquioxane subjected to the water washing treatment is excellent in storage stability. When the curable composition is stored at 5°C for 180 days, the viscosity increase rate calculated from the following formula is, for example, 10% or less, preferably 5% or less, particularly preferably 3% or less, and most preferably 1% or less. Viscosity increase rate (%) = [(V2 - V1) / V1] × 100 (V1 represents the viscosity of the curable composition before storage, and V2 represents the viscosity of the curable composition after storage)

[0086] The content of the above silsesquioxane is preferably, for example, 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 non-volatile content of the curable composition of the present disclosure.

[0087] The curable composition of the present disclosure may contain a compound other than the silsesquioxane as a curable compound. However, the proportion of the content of the silsesquioxane in all the curable compounds contained in the curable composition is preferably, for example, 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 above range, the refractive index of the cured product of the curable composition can be increased, thereby reducing the difference in refractive index from a plastic lens formed of a resin material having a medium refractive index (for example, a refractive index of about 1.49 to 1.61) such as a polyamide-based resin. Therefore, an effect of suppressing the generation of interference fringes can be obtained. In addition, the heat resistance of the cured product of the curable composition is improved, and the crack resistance is improved.

[0088] (Solvent) The curable composition may contain a solvent. When the curable composition contains a solvent, the viscosity can be reduced, the coatability can be improved, and the formation of a uniform film becomes possible.

[0089] As the solvent, a solvent that has excellent solubility with the silsesquioxane and the tetraazaporphyrin compound and has a boiling point of 150 ° C or lower (preferably 130 ° C or lower, particularly preferably 120 ° C or lower. The lower limit of the boiling point is, for example, 50 ° C, preferably 60 ° C, particularly preferably 70 ° C) under normal pressure is used. After applying the curable composition, the solvent can be quickly volatilized, which is preferable in that no bubbles caused by the solvent are generated in the cured product.

[0090] Examples of the solvent include ketone solvents and alcohol solvents. These can be used alone or in combination of two or more. Among these, using a ketone solvent is preferable in that it has particularly excellent solubility for the tetraazaporphyrin compound.

[0091] When using a ketone-based solvent, the curable composition may tend to gel and the storage stability may decrease. However, if a silsesquioxane subjected to a water washing treatment is used, the curable composition will not gel even when a ketone-based solvent is used. That is, by using a silsesquioxane subjected to a water washing treatment and a ketone-based solvent, a curable composition having excellent visibility, an anti-glare effect, and a contrast enhancing effect and excellent storage stability can be produced.

[0092] Examples of the ketone-based solvent include acetone (boiling point 56°C), methyl ethyl ketone (boiling point 80°C), methyl isobutyl ketone (boiling point 116°C), etc., which are preferable.

[0093] As the solvent, other solvents may be contained in addition to the ketone-based solvent. However, the proportion of the ketone-based solvent in the total amount of the solvent is preferably, for example, 60% by weight or more in terms of improving the solubility of the tetraazaporphyrin compound, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0094] Also, the solvent may contain a solvent whose boiling point under normal pressure is outside the above range. However, in terms of having good coatability and easy drying property after coating, the proportion of the solvent in the total amount of the solvent is preferably, for example, 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.

[0095] The content of the solvent (when two or more kinds are contained, the total amount thereof) 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 having a cyclohexene oxide group, and within the above range, the content can be adjusted according to the viscosity required for the curable composition.

[0096] For example, when used for the application of coating a curable composition by the dipping method, the viscosity of the curable composition measured at 25 °C and 60 rpm using a B-type viscometer (rotor No. 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 a cyclohexene oxide group, and particularly preferably 1.5 to 2.0 times by weight.

[0097] (Curing catalyst) The curing catalyst is a compound capable of initiating or promoting the cationic polymerization reaction of the silsesquioxane.

[0098] In the curable composition of the present disclosure, it is preferable to use a cationic polymerization initiator as the curing catalyst. The cationic polymerization initiator is a compound that generates a cation as an active species and initiates the curing reaction of the cation-curable compound contained in the curable composition.

[0099] The cationic polymerization initiator includes a thermal cationic polymerization initiator that generates a cation by heating and a photo cationic polymerization initiator that generates a cation by ultraviolet irradiation. These can be appropriately selected and used according to the application.

[0100] Examples of the thermal cationic polymerization initiator include 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonium phenyltris(pentafluorophenyl)borate, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium phenyltris(pentafluorophenyl)borate, p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium phenyltris(pentafluorophenyl)borate, and the like.

[0101] Examples of the photo cationic polymerization initiator include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenylsulfonium] hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl) trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide phenyltris(pentafluorophenyl)borate, [4-(2-thioxanthonylthio)phenyl]phenyl-2-thioxanthonylsulfonium phenyltris(pentafluorophenyl)borate, and the like.

[0102] 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 with respect to 100 parts by weight of the curable compound contained in the curable composition.

[0103] [Hard coat film] The hard coat film of the present disclosure is a film-like or film-shaped structure composed of a cured product of the above curable composition. The thickness of the hard coat film can be appropriately selected according to the application. When the hard coat film is laminated on the lens surface to form a hard coat lens, it is, for example, 0.5 to 5 μm, preferably 1 to 3 μm.

[0104] The hard coat film can be manufactured, for example, through a process of forming a coating film of the curable composition on the surface of a substrate and a process of curing the formed coating film. If necessary, a pre-drying (pre-cure) process may be provided before curing the coating film.

[0105] As a method for forming the coating film of the curable composition, there is no particular limitation as long as the curable composition can be applied to the surface of the substrate. For example, printing methods, coating methods, dipping methods, spraying methods, spin coating methods, etc. can be mentioned.

[0106] The curing method of the coating film of the curable composition can be appropriately selected according to the type of cationic polymerization initiator contained in the curable composition.

[0107] For example, when the curable composition contains a thermal cationic polymerization initiator, it can be cured by subjecting the coating film of the curable composition to a heat treatment. Also, when the curable composition contains a photo cationic polymerization initiator, it can be cured by irradiating the coating film of the curable composition with ultraviolet rays.

[0108] The heat treatment conditions are not particularly limited, but the curing temperature is, for example, 80 to 200°C. When the substrate is plastic, from the viewpoint of preventing the substrate from deforming or discoloring due to heat, the curing temperature is preferably 90 to 150°C, particularly preferably 95 to 130°C. The curing time is preferably set appropriately according to the curing temperature and the thickness of the coating film. For example, when the curing temperature is 100°C, the curing time is about 0.5 to 5 hours.

[0109] When performing the ultraviolet irradiation, as the light source of ultraviolet rays, for example, UV-LED, mercury lamps such as low, medium, or high-pressure mercury lamps, mercury xenon lamps, metal halide lamps, tungsten lamps, arc lamps, excimer lamps, excimer lasers, semiconductor lasers, YAG lasers, laser systems combining lasers and nonlinear optical crystals, high-frequency induction ultraviolet generators, etc. can be used. The ultraviolet irradiation dose (integrated light quantity) is, for example, 100 to 500 mJ / cm 2 is.

[0110] The hard coat film has high surface hardness, and the pencil hardness of the hard coat film (film thickness: 2.0 μm) formed on a polyamide resin (trade name "TROGAMID CX7323", manufactured by Daicel-Evonik Corporation) film (thickness: 100 μm) is, for example, HB or higher, preferably F or higher. Therefore, it has excellent abrasion resistance. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0111] The hard coat film has the property of selectively absorbing light in the wavelength range of 570 to 605 nm (preferably 575 to 600 nm, more preferably 580 to 595 nm, particularly preferably 580 to 590 nm). Therefore, it has excellent anti-glare effect and contrast enhancement effect.

[0112] The transmission spectrum of the hard coat film has a sharp downward peak in the wavelength range of 570 to 605 nm and no peak in other visible light regions.

[0113] The transmittance (t1) at the minimum value of the downward peak is, for example, 85% or less, preferably 80% or less, particularly preferably 75% or less. Also, the transmittance (t1) is, for example, 30% or more, preferably 40% or more, particularly preferably 45% or more.

[0114] Also, the transmittance (t2) at a wavelength of 550 nm in the transmission spectrum is, for example, 75% or more, preferably 80% or more, particularly preferably 85% or more. The transmittance (t3) at a wavelength of 625 nm in the transmission spectrum is, for example, 75% or more, preferably 80% or more, more preferably 85% or more, particularly preferably 90% or more, and most preferably 95% or more.

[0115] And the ratio (t2 / t1) of the transmittance (t2) to the transmittance (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. The ratio (t3 / t1) of the transmittance (t3) to the transmittance (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.

[0116] Furthermore, since the content of the tetraazaporphyrin compound in the hard coat film is low, coloring by the tetraazaporphyrin compound is suppressed. Therefore, in the visible light region, the transmittance of light in a wavelength region of, for example, 450 to 550 nm (preferably 450 to 560 nm, particularly preferably 450 to 570 nm) and a wavelength region of, for example, 625 to 700 nm (preferably 605 to 700 nm, particularly preferably 600 to 700 nm) of the hard coat film is, for example, 80% or more. Therefore, even when the hard coat film is applied to the surface of the lens, the color tone of the lens is not impaired.

[0117] The hard coat film has a high visual transmittance, for example, 78% or more, preferably 78.5% or more, more preferably 79% or more, further preferably 80% or more, particularly preferably 83% or more, and especially preferably 85% or more. Therefore, it has excellent visibility.

[0118] In addition, the visual transmittance (τv) of the hard coat film is a function of the spectral transmittance of the hard coat film and is calculated from the following formula (1).

Equation

[0119]

Table 1

[0120] [Hard coat lens] The hard coat lens of the present disclosure has a configuration in which the above hard coat film is provided on the lens surface. In addition to the above configuration, the hard coat lens may be provided with other configurations (for example, a polarizing film, an antireflection film, a mirror coat film, a protective film, etc.).

[0121] The lens is preferably a plastic lens. Examples of the lens material include plastics such as polyamide resins, polycarbonate resins, acrylic resins, allyl resins (diethylene glycol bisallyl carbonate homopolymers or copolymers), urethane resins, and thiourethane resins. These can be used alone or in combination of two or more.

[0122] The thickness of the lens can be appropriately selected according to the application, but is about 1.0 to 3.0 mm. The surface shape of the lens is not particularly limited, and any shape such as a flat surface, a curved surface (convex surface or concave surface) can be selected.

[0123] The hard coat lens can be manufactured through a step of forming a coating film of the above curable composition on the lens surface and a step of curing the formed coating film. As the coating method of the curable composition and the curing method of the coating film, the same methods as the manufacturing method of the above hard coat film can be adopted.

[0124] Since the hard coat lens is provided with the above hard coat film on the lens surface, it selectively absorbs light in the wavelength region of 570 to 605 nm (preferably 575 to 600 nm, more preferably 580 to 595 nm, particularly preferably 580 to 590 nm), and the transmission spectrum of the hard coat lens has a sharp downward peak in the wavelength region. Therefore, it exhibits excellent anti-glare effect and contrast enhancement effect.

[0125] There is no particular limitation on the lens constituting the hard coat lens. However, when the hard coat lens has a configuration in which, for example, a hard coat film is provided on the surface of a lens (76φmm, center thickness 2.2 mm, equivalent to 6 curves) formed of a polyamide resin (trade name "TROGAMID CX7323", manufactured by Daicel - Evonik Corporation), the transmittance (t1') of the minimum value of the downward peak that appears in the wavelength range of 570 to 605 nm in the transmittance spectrum of the hard coat lens, the transmittance (t2') at a wavelength of 550 nm in the transmittance spectrum, and the transmittance (t3') at a wavelength of 625 nm in the transmittance spectrum have the following characteristics.

[0126] The transmittance (t1') is, for example, 85% or less, preferably 80% or less, particularly preferably 75% or less, and most preferably 70% or less. Also, the transmittance (t1') is, for example, 30% or more, preferably 40% or more, and particularly preferably 45% or more.

[0127] The transmittance (t2') at a wavelength of 550 nm in the transmittance spectrum is, for example, 73% or more, preferably 75% or more, and particularly preferably 80% or more.

[0128] The transmittance (t3') at a wavelength of 625 nm in the transmittance spectrum is, for example, 73% or more, preferably 75% or more, particularly preferably 80% or more, and most preferably 85% or more.

[0129] And the ratio (t2' / t1') of the transmittance (t2') to the transmittance (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. The ratio (t3' / t1') of the transmittance (t3') to the transmittance (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.

[0130] In addition, for the hard coat lens, in the visible light region, the transmittance of light in a wavelength region of, for example, 450 to 550 nm (preferably 450 to 560 nm, particularly preferably 450 to 570 nm) and a wavelength region of, for example, 625 to 700 nm (preferably 605 to 700 nm, particularly preferably 600 to 700 nm) is, for example, 80% or more. Therefore, it has high visibility.

[0131] The hard coat lens [for example, a hard coat lens having a configuration in which the above hard coat film is provided on the surface of a lens (76φmm, center thickness 2.2 mm, equivalent to 6 curves) formed of the above polyamide resin] has a high visual 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 has excellent visibility.

[0132] The visual transmittance of the hard coat lens is a function of the spectral transmittance of the hard coat lens. The visual transmittance of the hard coat lens can be calculated by substituting the spectral transmittance [τ(λ)] of the hard coat film with the spectral transmittance [τ(λ)'] of the hard coat lens in the above formula (1).

[0133] Since the hard coat lens has the above characteristics, it has excellent visibility. In addition, it is excellent in anti-glare effect and contrast enhancement effect, and also excellent in scratch resistance.

[0134] Furthermore, the above hard coat lens is excellent in heat resistance and crack resistance. In addition, the generation of interference fringes due to the refractive index difference between the lens and the hard coat film is suppressed.

[0135] Furthermore, since the coloring by the tetraazaporphyrin compound is suppressed in the hard coat film, the hard coat lens of the present disclosure including the hard coat film has a wider range of color tone selection. In addition, in corrective lenses (such as myopia, astigmatism, hyperopia), the power is adjusted by changing the lens thickness. However, when the tetraazaporphyrin compound is kneaded into the lens, it was a problem that chromatic aberration occurred between the thick and thin parts of the lens. However, in the hard coat lens of the present disclosure, since it is not necessary to contain the tetraazaporphyrin compound in the lens, it is possible to prevent chromatic aberration from occurring due to the lens thickness. From the above, by using the hard coat lens of the present disclosure, it is possible to provide glasses having high design value.

[0136] [Glasses] The glasses of the present disclosure are devices worn around the eyes and include the hard coat lens. The glasses include not only ordinary glasses but also sunglasses and goggles.

[0137] The glasses have excellent visibility, a high anti-glare effect, a contrast enhancement effect, and high design value. In addition, the surface of the glasses is highly hard and excellent in scratch resistance.

[0138] As described above, each configuration of the present disclosure and their combinations are examples, and additions, omissions, substitutions, and changes of the configuration can be appropriately made without departing from the gist of the present disclosure. In addition, the present disclosure is not limited by the embodiments and is limited only by the description of the claims.

Example

[0139] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.

[0140] Preparation Example 1 (Preparation of SQ1) Into a 300-milliliter reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube, 161.5 millimoles (39.79 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter referred to as "EMS"), 9 millimoles (1.69 g) of phenyltrimethoxysilane (hereinafter referred to as "PMS"), and 165.9 g of acetone were charged and heated to 50°C. To the mixture thus obtained, 4.70 g of a 5% aqueous potassium carbonate solution (1.7 millimoles as potassium carbonate) was added dropwise over 5 minutes, and then 1700 millimoles (30.60 g) of water was added dropwise over 20 minutes. During the addition, no significant temperature rise occurred. Thereafter, the polycondensation reaction was carried out under a nitrogen stream at 50°C for 4 hours. When the product in the reaction solution after the polycondensation reaction was analyzed, the number average molecular weight was 1911 and the molecular weight distribution was 1.47. The ratio [T3 body / T2 body] of the T2 body and the T3 body of the above product was 10.3. Thereafter, the reaction solution was cooled and washed with water until the lower layer liquid became neutral. After separating the upper layer liquid, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 40°C to obtain a colorless and transparent liquid product (2-(3,4-epoxycyclohexyl)ethyl group-containing silsesquioxane, epoxy equivalent: 195 g / eq; SQ1).

[0141] Preparation Examples 2 to 5 (Preparation of SQ2 to 5) 2-(3,4-Epoxycyclohexyl)ethyl group-containing silsesquioxanes (SQ2 to 5) were obtained in the same manner as in Preparation Example 1 except that the reaction conditions were changed as shown in Table 2 below.

[0142]

Table 2

[0143] Comparative Preparation Example 1 (Preparation of SQ6) A 1000-milliliter reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 300.0 millimoles (70.9 g) of 3-glycidyloxypropyltrimethoxysilane and 283.6 g of acetone under a nitrogen stream, and the temperature was raised to 50 °C. To the mixture thus obtained, 8.29 g of a 5% aqueous potassium carbonate solution (3.0 millimoles as potassium carbonate) was added dropwise over 5 minutes, and then 3000.0 millimoles (54.00 g) of water was added dropwise 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, 141.8 g of MIBK and 104.2 g of 5% brine were added. This solution was transferred to a 1-L separatory funnel, and 141.8 g of MIBK was added again for washing with water. After liquid separation, the aqueous layer was withdrawn, washed with water until the lower layer solution became neutral, and the upper layer solution was separated. Then, the solvent was distilled off from the upper layer solution under the conditions of 1 mmHg and 50 °C to obtain 67.40 g of a colorless and transparent liquid product (3-glycidyloxypropyl group-containing polyorganosilsesquioxane, epoxy equivalent: 160 g / eq; SQ6) containing 28.28% by weight of MIBK.

[0144] The number average molecular weight (Mn), molecular weight distribution, and ratio of T2 form to T3 form [T3 form / T2 form] of the products obtained in the preparation examples and comparative preparation examples were determined by the following method. The results are summarized in Table 3 below.

[0145] The number average molecular weight (Mn) and molecular weight distribution were determined by GPC analysis under the following conditions Alliance HPLC system 2695 (manufactured by Waters) Refractive Index Detector 2414 (manufactured by Waters) Column: Tskgel GMH HR -M (manufactured by Tosoh Corporation) × 2 pieces Guard column: Tskgel guard column H HR L (manufactured by Tosoh Corporation) Column oven: COLUMN HEATER U-620 (manufactured by Sugai) Solvent: THF Measurement conditions: 40 °C

[0146] The ratio of T2 form to T3 form [T3 form / T2 form] in the product was determined by 29 Si-NMR spectrum measurement using JEOL ECA500 (500 MHz). Specifically, 29 the integral ratio of the signal at -64 to -70 ppm in the Si-NMR spectrum (R a is the signal of the silicon atom of the T3 form where R is 2-(3,4-epoxycyclohexyl)ethyl) and the signal at -54 to -60 ppm (R b is the signal of the silicon atom of the T2 form where R is 2-(3,4-epoxycyclohexyl)ethyl) was calculated to obtain [T3 form / T2 form].

[0147]

Table 3

[0148] Reference Example 1 SQ1 (100 parts by weight) obtained in Preparation Example 1, MIBK (manufactured by Kanto Chemical Co., Inc.; 20 parts by weight), and a curing catalyst ([diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate]; 1 part by weight) were mixed to obtain a hard coat solution.

[0149] Using the obtained hard coat solution, a hard coat film was prepared by the following method, and the surface hardness and scratch resistance of the obtained hard coat film were evaluated.

[0150] <Surface hardness evaluation> The obtained hard coat solution was applied onto a transparent polyamide resin (refractive index 1.52, trade name "TROGAMID CX7323", manufactured by Daicel-Evonik Corporation) film (thickness: 100 μm) using a wire bar so that the thickness after curing was 40 μm, then left in an oven at 70 °C for 10 minutes (pre-bake), and then irradiated with ultraviolet light (irradiation conditions (irradiation dose): 312 mJ / cm 2 , irradiation intensity: 80 W / cm 2) Finally, heat treatment (aging) was performed at 80 °C for 2 hours. As a result, the coating film of the above hard coat liquid was cured to obtain a hard coat film having a hard coat layer.

[0151] The scratch resistance of the obtained hard coat film was evaluated by the following method. With respect to the surface of the hard coat layer of the hard coat film, #0000 steel wool was reciprocated 100 times under a load of 1000 g / cm 2 to check the presence and number of scratches on the surface of the hard coat layer, and the scratch resistance was evaluated according to the following criteria. ◎ (Extremely good): No scratches 〇 (Good): There are scratches, but the number of scratches is 1 to 10 △ (Slightly poor): There are scratches, and the number of scratches exceeds 10 and is 20 or less × (Poor): There are scratches, and the number of scratches exceeds 20

[0152] <Surface hardness evaluation> A hard coat film having a hard coat layer (thickness: 2.0 μm) was obtained in the same manner as in Reference Example 1 except that the coating was performed so that the thickness after coating and curing of the hard coat liquid was 2.0 μm. The pencil hardness of the surface of the hard coat layer of the obtained hard coat film was evaluated by a method according to JIS K5600-5-4.

[0153] Reference Examples 2 to 6 A hard coat film was obtained in the same manner as in Reference Example 1 except that SQ1 was changed as shown in Table 4 below, and this was evaluated. The results are summarized in Table 4.

[0154]

Table 4

[0155] Example 1 (Preparation of curable composition 1) In a 3-liter stainless steel container equipped with a stirring device and a nitrogen inlet tube, under a nitrogen stream, 516 g of methyl ethyl ketone, 451 g of an MIBK solution of SQ1 obtained in Preparation Example 1 (solid content 77.5%), 6.8 g of a curing catalyst (trade name "SI-100L", manufactured by Sanshin Chemical Industry Co., Ltd.), 1.1 g of a leveling agent (trade name "Surflon S-243", manufactured by AGC Seimi Chemical Co., Ltd.), 27 g of a benzotriazole-based ultraviolet absorber (trade name "Tinuvin 1130", manufactured by BASF Japan Ltd.), and 1.4 g of a tetraazaporphyrin compound which is a pigment powder (a compound represented by the following formula (p-1), having a selective light absorption wavelength in the range of 570 to 605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.) (the above contents correspond to 4000 weight ppm of the content of SQ1) were added, and 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 was 4.2 mPa·s. The viscosity was measured using a B-type viscometer (rotor No. 1).

[0156] [Chemical formula]

[0157] The storage stability of Curable Composition 1 was evaluated by the following method. That is, Curable Composition 1 was sealed in a closed container and stored at 5°C for 180 days. Then, the viscosity (V2) of the composition after storage at 25°C and 60 rpm was measured, and the viscosity increase rate was calculated from the following formula. As a result, the viscosity increase rate was 1%, and it was confirmed that the storage stability was good. Viscosity increase rate (%) = [(V2 - V1) / V1] × 100

[0158] Example 2 (Manufacture of Hard Coat Lens 1) 4,970 g of a transparent polyamide resin (refractive index 1.52, trade name "TROGAMID CX7323", manufactured by Daicel - Evonik Corporation) and 30 g of a benzotriazole - type ultraviolet absorber (trade name "Tinuvin 326", manufactured by BASF Japan Ltd.) were mixed in a cylindrical tumbler - type mixer for 5 minutes, and then dried at 100 °C for 3 hours using a dehumidifying small hopper dryer to obtain a mixed material 1. Using an injection molding machine (trade name "Tuparl TR150S", manufactured by Sodic Plastech) equipped with a mold for lenses, the mixed sample 1 was injection - molded to produce a plastic lens 1 (76 φmm, center thickness 2.2 mm, equivalent to 6 - curve curvature).

[0159] On the convex and concave surfaces of the plastic lens 1, the curable composition 1 obtained in Example 1 was applied by the dipping method so that the thickness of the cured hard - coat layer was 2.0 μm, and then heat - treated in an oven at 100 °C for 2 hours to obtain a hard - coat lens 1.

[0160] For the obtained hard - coat lens 1, the light transmittance was measured by the following method. The results are shown in Figure 1. <Transmittance evaluation method> Using a spectrophotometer "CM - 5" (manufactured by Konica Minolta, Inc.), the light transmittance was measured under the following conditions. The results are shown in Figure 1. Light source: Pulse xenon lamp light source Measurement wavelength range: 360 - 740 nm Diffuse illumination 0° direction light - receiving method

[0161] The visual transmittance of the hard - coat lens 1 was 79.7%.

[0162] From Figure 1, the transmittance of light with a wavelength of 585 nm (t1'), the transmittance of light with a wavelength of 550 nm (t2'), and the transmittance of light with a wavelength of 625 nm (t3') of the hard - coat lens 1 were as follows. t1' = 70% t2' = 80% t3' = 87% t2' / t1' = 1.14 t3' / t1'=1.24

[0163] The hard-coated lens 1 was heat-treated in an electric dryer at 90°C for 60 minutes and then left in an environment at 25°C for 1 hour. Thereafter, the lens was visually observed using an LED light source for lens inspection (visual inspection light manufactured by Nagata Seisakusho Co., Ltd., product name "NS-100NW(Y)", set illuminance 30,000 lux, distance between light source and measurement point 200 mm). No cracks were found.

[0164] Furthermore, when the hard-coated lens 1 was observed using a three-wavelength fluorescent light source, no interference fringes due to differences in refractive index were observed.

[0165] Example 3 (Production of hard coat film 1) The curable composition 1 obtained in Example 1 was applied to a glass plate using a wire bar so that the thickness after curing was 2 μm, and then the coating film was cured by heat treatment for 2 hours in an oven at 100° C. Then, a 5 cm square cut was made using a cutter, and the film was peeled off from the glass plate to prepare a hard coat film 1 (thickness: 2.0 μm). The light transmittance of the obtained hard coat film 1 was measured by the above-mentioned <Transmittance evaluation method>. The results are shown in FIG. 2. The luminous transmittance of the hard coat film 1 was 87.1%. Also, from FIG. 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 coat film 1 were as follows. t1=75% t2=88% t3=95% t2 / t1=1.17 t3 / t1=1.27

[0166] 2, it is understood that the transmittance of light of 585 nm can be selectively and significantly reduced by the hard coat film 1. From this, it is understood that the use of the hard coat film 1 can provide spectacles having excellent visibility, anti-glare effect, and contrast enhancement effect.

[0167] Comparative Example 1 (Preparation of Curable Composition 2) In a 1-liter reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 534 g of methyltriethoxysilane, 162 g of water, and 0.5 ml of 0.1 N hydrochloric acid were charged under a nitrogen stream, mixed well, and heated under reflux at 80 °C for 4 hours. Then, the initially non-uniform liquid became a transparent homogeneous layer. Next, ethanol (partially containing water) by-produced in the above reaction was expelled by distillation and concentrated to obtain a solution with a solid content of 50%, and further aged under reflux for 20 hours. This was subjected to solvent evaporation in a short time of within 1 minute using a thin-film evaporator to obtain a solid flaky methyl group-containing silsesquioxane. 27 g of ethanol and 3 g of deionized water were mixed in a 500-ml flask to prepare 10% water-containing ethanol, and 30 g of the methyl group-containing silsesquioxane obtained above was added thereto. When vigorously stirred at 25 °C for about 40 minutes, the methyl group-containing silsesquioxane completely dissolved to obtain a 50% solution.

[0168] Separately, 23 g of ethanol, 2 g of deionized water, 1 g of a phenol salt of 1,8-diazabicyclo[5.4.0]undecene-7 (strong alkali-based curing agent), 1 g of a fluorine-based leveling agent (trade name "Fujagent 100", manufactured by Neos Co., Ltd.), and 13 g of acetic acid were added in this order to obtain a catalyst solution.

[0169] The 50% solution of the methyl group-containing silsesquioxane and the catalyst solution were mixed, and 0.1 g of a tetraazaporphyrin compound (compound represented by the above formula (p-1), having a selective light absorption wavelength in the range of 570 to 605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.), which is a pigment powder (the above content corresponds to 3300 weight ppm of the content of the methyl group-containing silsesquioxane), was added thereto, and the mixture was stirred at 25 °C for 30 minutes. However, undissolved pigment powder was visually confirmed.

[0170] Comparative Example 2 (Preparation of Curable Composition 3) A curable composition 3 was prepared in the same manner as in Example 1 except that the tetraazaporphyrin compound was not added.

[0171] Comparative Example 3 (Manufacture of Hard Coat Lens 2) 9940 g of a transparent polyamide resin (refractive index 1.52, trade name "TROGAMID CX7323", manufactured by Daicel-Evonik Corporation), 60 g of a benzotriazole-based ultraviolet absorber (trade name "Tinuvin 326", manufactured by BASF Japan Ltd.), and 0.15 g of a tetraazaporphyrin compound which is a pigment powder (a compound represented by the following formula (p-1), having a selective light absorption wavelength in the range of 570 to 605 nm, trade name "FDG-006", manufactured by Yamada Chemical Industry Co., Ltd.) were mixed in a cylindrical tumbler mixer for 5 minutes, and then dried at 100°C for 3 hours using a dehumidifying small hopper dryer to obtain a mixed material 2. Using a non-vent type single-screw extruder, the mixed sample 2 was extruded and pelletized under the following conditions. Extrusion conditions: C1 = 250°C, C2 = 260°C, C3 = 270°C, C4 = 280°C, Die = 270°C, screw rotation speed 60 rpm, extrusion rate 15 kg / hr

[0172] A plastic lens 2 (76φmm, center thickness 2.2 mm, equivalent to 6 curves) was obtained in the same manner as in Example 2, except that the pelletized mixed sample 2 was used instead of the mixed sample 1.

[0173] A hard coat lens 2 was obtained in the same manner as in Example 2, except that the curable composition 3 was used instead of the curable composition 1 and the plastic lens 2 was used instead of the plastic lens 1. The content of the tetraazaporphyrin compound in the hard coat lens 2 was approximately 3 times by weight the content of the tetraazaporphyrin compound in the hard coat lens 1.

[0174] The light transmittance of the hard coat lens 2 was measured in the same manner as in Example 2. The results are shown in Fig. 1. The visual transmittance of the hard coat lens 2 was 77.7%.

[0175] From Figure 1, the transmittance (t1’) of the hard coat lens 2 for light with a wavelength of 585 nm, the transmittance (t2’) for light with a wavelength of 550 nm, and the transmittance (t3’) for light with a wavelength of 625 nm were as follows. t1’ = 73% t2’ = 75% t3’ = 84% t2’ / t1’ = 1.03 t3’ / t1’ = 1.15

[0176] From Figure 1, although the content of the tetraazaporphyrin compound in the hard coat lens 1 was approximately one-third of that in the hard coat lens 2, the degree of decrease in the transmittance of light in the wavelength range of 570 to 605 nm was better than that of the hard coat lens 2. In addition, in the hard coat lens 1, the decrease in the transmittance of light outside the above wavelength range was suppressed compared to the hard coat lens 2. Furthermore, since the content of the tetraazaporphyrin compound in the hard coat lens 1 was approximately one-third of that in the hard coat lens 2, the coloring of the lens was suppressed, and the visual transmittance was higher than that of the hard coat lens 2. From the above, by using the hard coat lens 1, compared with the case of using the hard coat lens 2, light with wavelengths that are easily perceived by the human eye can be incorporated in a well-balanced manner, so that the contrast can be made clear. That is, by using the hard coat lens 1, a good visual field can be ensured and eye fatigue can be suppressed.

Claims

Claim 1 A silsesquioxane having a cyclohexene oxide group, a tetraazaporphyrin compound having an absorption peak in a wavelength region of 570 to 605 nm, and a solvent, wherein the content of the tetraazaporphyrin compound is 1000 to 10000 weight ppm of the content of the silsesquioxane, and the content of the solvent is 0.5 to 3 times by weight of the content of the silsesquioxane having a cyclohexene oxide group, and is composed of a cured product of a curable composition, a hard coat film having a visual transmittance of 78% or more. Claim 2 wherein the silsesquioxane contains a structural unit represented by the following formula (I) [R ａ SiO ３／２ (I) [In formula (I), R ａ represents a group containing a cyclohexene oxide 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] and a structural unit represented by the following formula (II) [R ａ SiO ２／２ (OR ｂ )](II) [In formula (II), R ａ is the same as described above. R ｂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] and the ratio (former / latter; molar ratio) of the content of the structural unit represented by the formula (I) to the content of the structural unit represented by the formula (II) is 5 to 500, Claim 3 Among all the constituent units of the silsesquioxane, the constituent units represented by the formulas (I) and (II), wherein R in the formula ａ is a group containing a cyclohexene oxide group, and the proportion occupied by the constituent units is 50 to 100 mol%, The hard coat film according to claim 1. In the transmission spectrum, having a minimum value of a downward peak in a wavelength region of 570 to 605 nm, wherein the transmittance (t1) of the minimum value is 80% or less, the ratio (t2 / t1) of the transmittance (t2) at a wavelength of 550 nm to the transmittance (t1) is 1.1 or more, and the ratio (t3 / t1) of the transmittance (t3) at a wavelength of 625 nm to the transmittance (t1) is 1.1 or more, the hard coat film according to Claim 1 or 2. Claim 4 A method for manufacturing a hard coat lens, comprising applying the curable composition onto a lens surface and curing it to obtain a hard coat lens provided with the hard coat film according to Claim 1 or 2, which is composed of a cured product of the curable composition. Claim 5 A hard coat lens provided with the hard coat film according to Claim 1 or 2 on a lens surface. Claim 6 Glasses provided with the hard coat lens according to Claim 5. ​

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