Laminate, optical article, lens, and spectacles

Abstract

Provided is a laminate comprising: an optical substrate; a functional layer that is positioned on the optical substrate and contains a functional dye and a resin; and a protective layer that covers at least a portion of the functional layer, has a thickness of at least 0.3 μm and less than 5 μm as measured by scanning microscope observation, and contains at least one resin selected from the group consisting of thermosetting urethane resins, thermosetting urea resins, thermosetting urethane urea resins, epoxy resins, and (meth)acrylic resins. Also provided are: an optical article including the laminate; a lens; and spectacles.

Description

Laminate, optical article, lens, and eyeglasses

[0001] The present disclosure relates to laminates, optical articles, lenses, and eyeglasses.

[0002] Functional dyes include compounds that have the ability to selectively absorb visible light, as well as compounds that develop, lose, or change color when exposed to energy such as light, heat, an electric field, or pressure. Such functional dyes can exhibit specific functions by undergoing structural changes under specific conditions.

[0003] Photochromic compounds, a type of functional dye, are compounds that can reversibly convert into two isomers with different absorption spectra. Photochromic compounds have the property that when a colorless, bleached compound is irradiated with ultraviolet light, it is isomerizes into a colored state, and when the light exposure is removed and the compound is placed in a dark place, it returns to its original color.

[0004] Photochromic eyeglass lenses are obtained, for example, by applying a photochromic curable composition onto a plastic lens by spin coating or the like and curing the coating to form a photochromic coating layer. A protective layer may be provided on this photochromic coating layer.

[0005] International Publication No. 2005 / 092999 International Publication No. 2021 / 221084

[0006] An object of the present disclosure is to provide a laminate having excellent functional dye performance and hardness, and an optical article, a lens, and a pair of glasses including the laminate.

[0007] According to the present disclosure, a laminate is provided. The laminate includes an optical substrate, a functional layer, and a protective layer. The functional layer is located on the optical substrate. The functional layer includes a functional dye and a resin. The protective layer covers at least a portion of the functional layer. The protective layer has a thickness of 0.3 μm or more and less than 5 μm as measured by scanning microscope observation. The protective layer includes at least one resin selected from the group consisting of a thermosetting urethane resin, a thermosetting urea resin, a thermosetting urethane urea resin, an epoxy resin, and a (meth)acrylic resin.

[0008] The present disclosure also provides an optical article, which includes the laminate of the present disclosure.

[0009] Also provided in accordance with the present disclosure is a lens comprising the optical article of the present disclosure.

[0010] Also provided in accordance with the present disclosure are eyeglasses, the eyeglasses including lenses of the present disclosure.

[0011] According to the present disclosure, there are provided a laminate having excellent performance and hardness of a functional dye, as well as optical articles, lenses, and eyeglasses including the laminate.

[0012] 1 is a cross-sectional view schematically illustrating an example of a laminate according to the present disclosure.

[0013] An optical laminate imparted with the functionality of the functional dye may be formed by applying a curable composition containing a functional dye to an optical substrate and curing the resulting coating to obtain a functional layer. The matrix of the functional layer is required to be less likely to interfere with structural changes in the functional dye in order to bring out the performance of the functional dye. However, such a matrix that is less likely to interfere with structural changes in the functional dye may have high flexibility, resulting in low hardness and being easily scratched. Therefore, to protect the functional layer, a protective layer may be further provided on the surface of the functional layer. The protective layer may be formed, for example, by applying a curable composition for forming the protective layer to the functional layer and curing the coating.

[0014] Through extensive research, the present inventors have found that although providing a protective layer can improve the hardness of the laminate, it can also reduce its functionality. This is thought to be because, during the formation of the protective layer, a mixed layer is formed at the interface between the functional layer and the protective layer, and a portion of the functional dye migrates into this mixed layer. Further research by the present inventors has found that there is a negative correlation between the film thickness of this protective layer and the functionality of the laminate.

[0015] The laminate of the present disclosure comprises an optical substrate, a functional layer, and a protective layer. The functional layer is located on the optical substrate. The functional layer contains a functional dye and a resin. The protective layer covers at least a portion of the functional layer. The protective layer has a thickness of 0.3 μm or more and less than 5 μm as measured by scanning microscope observation. The protective layer contains at least one resin selected from the group consisting of a thermosetting urethane resin, a thermosetting urea resin, a thermosetting urethane urea resin, an epoxy resin, and a (meth)acrylic resin. The term "(meth)acrylic resin" means at least one of an acrylic resin and a methacrylic resin.

[0016] The laminate of the present disclosure, which includes a protective layer having a thickness of 0.3 μm or more but less than 5 μm, is less likely to form the mixed layer described above and can suppress migration of the functional dye, compared to a laminate having a protective layer having a thickness of 5 μm or more. Thus, a laminate with excellent performance of the functional dye can be realized.

[0017] The laminate of the present disclosure will be described in detail below.

[0018] <Laminate> Fig. 1 is a cross-sectional view schematically illustrating an example of a laminate according to the present disclosure. The laminate 1 illustrated in Fig. 1 includes an optical substrate 2, a primer layer 3, a functional layer 4, a protective layer 5, and a hard coat layer 6. The optical substrate 2 is a spherical lens. The primer layer 3, the functional layer 4, the protective layer 5, and the hard coat layer 6 are laminated in this order on the convex surface of the optical substrate 2. The primer layer 3 and the hard coat layer 6 may be omitted. The hard coat layer 6 may have multiple layers with different refractive indices. Further, additional layers such as an anti-reflection film, an anti-fogging layer, and an anti-water-repellent film may be provided.

[0019] [Optical substrate] The optical substrate may have any shape, for example, a flat plate, a circle, a prism, a cylinder, etc. The optical substrate is preferably lenticular. The optical substrate may be a spherical lens or an aspherical lens. The optical substrate may be a convex lens or a concave lens.

[0020] The optical substrate may be made of an organic material such as a resin, or may be made of an inorganic material such as glass.

[0021] The optical substrate preferably contains a resin. The resin may include at least one selected from the group consisting of allyl resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythioepoxy resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin. The resin may include at least one selected from the group consisting of allyl resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, and polycarbonate resin. The optical substrate may be, for example, a cured product of an eyeglass lens material such as CR-39 (registered trademark) or the MR series. The resin may be derived from plant materials or petroleum materials.

[0022] The biomass plastic content of the optical substrate is preferably 25% by mass or more. The biomass plastic content can be calculated using a method in accordance with ISO standard 16620-3. The biomass plastic content of the optical substrate is more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular upper limit to this biomass plastic content, but in one example, it is 100% by mass or less.

[0023] [Functional Layer] The functional layer is located on the optical substrate. The functional layer may be in contact with the optical substrate or may be in contact with the primer layer located on the optical substrate. The portion of the functional layer that is not in contact with the optical substrate or the primer layer is at least partially, preferably entirely, covered with a protective layer.

[0024] The functional layer contains a functional dye and a resin, and may be a cured product of a functional layer-forming curable composition described below.

[0025] The thickness of the functional layer is, for example, 1.0 μm or more and 100 μm or less. The thickness of the functional layer is, for example, preferably 10.0 μm or more and 80.0 μm or less, and more preferably 20.0 μm or more and 60.0 μm or less. The thickness of the functional layer may be thicker or thinner than the thickness of the protective layer. The thickness of the functional layer is preferably thicker than the protective layer. The thickness of the functional layer can be measured by scanning microscope observation, similar to the thickness of the protective layer described below.

[0026] In one example, the Vickers hardness V2 of the functional layer is 0.5 or more and less than 1.2, and in another example, 0.7 or more and 1.1 or less. The Vickers hardness V2 of the functional layer is typically lower than the Vickers hardness V1 of the protective layer. The Vickers hardness is obtained by a method conforming to Japanese Industrial Standards (JIS) Z 2244-2009: Micro Vickers Hardness Test. To measure the Vickers hardness V2 of the functional layer, a laminate in which a primer layer is laminated on an optical substrate and only the functional layer is laminated on this primer layer is used as a sample. Hereinafter, a laminate in which the optical substrate, the primer layer, and the functional layer are laminated in this order is also referred to as the first laminate. To measure the Vickers hardness V1 of the protective layer, a laminate in which a primer layer is laminated on an optical substrate, a functional layer is laminated on this primer layer, and only the protective layer is laminated on this functional layer is used as a sample. Hereinafter, the laminate in which the optical substrate, the primer layer, the functional layer, and the protective layer are laminated in this order will also be referred to as the second laminate.

[0027] In one example, the Bayer value B2 of the functional layer is equal to or greater than 1.0 and less than 2.0. The Bayer value B2 of the functional layer is lower than the Bayer value B1 of the protective layer. The Bayer value can be an indicator of abrasion resistance. A low Bayer value means low abrasion resistance. The Bayer value can be measured using a Bayer abrasion tester manufactured by Colts Laboratories. The first laminate is used as a sample to measure the Bayer value B2 of the functional layer. The second laminate is used as a sample to measure the Bayer value B1 of the protective layer.

[0028] The resin includes at least one selected from the group consisting of, for example, allyl resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythioepoxy resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin. The resin preferably includes at least one selected from the group consisting of acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, and polythiourethane resin. More preferably, the resin includes at least one selected from the group consisting of acrylic resin and methacrylic resin.

[0029] The resin may be a major component of the functional layer. The proportion of the resin in the functional layer is, for example, 80% by mass or more, preferably 90% by mass or more. The upper limit of this proportion is, for example, 95% by mass or less, and, for another example, 99% by mass or less.

[0030] The functional dye includes, for example, at least one selected from the group consisting of a photochromic compound, an ultraviolet absorber, a blue light absorber, an infrared absorber, a thermochromic compound, and an electrochromic compound.

[0031] The content of the functional dye in the functional layer is, for example, 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass.

[0032] (Photochromic Compound) The photochromic compound may be at least one selected from the group consisting of chromene compounds, fulgide compounds, fulgimide compounds, and spirooxazine compounds. Among the photochromic compounds, it is preferable to use at least one selected from the group consisting of chromene compounds and spirooxazine compounds. The chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds containing a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.

[0033] The naphthopyran compound preferably includes compounds represented by the following formula (9), (10), (11), (12), (13), and (14).

[0034]

[0035] In the above formula (9), ring AA is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring. Ring AA may not be present.

[0036] Ring AB is a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocycle, or a substituted or unsubstituted fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the above ring.

[0037] R ２４ and R ２５ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.

[0038] The substituent is, for example, a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, a haloalkylthio group, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, an aryl group which may have a substituent, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, and at least one selected from the group consisting of an oligomeric group, and is preferably at least one selected from the group consisting of a haloalkylthio group, a cycloalkylthio group which may have a substituent, an oligomeric group, and a group represented by the following formula (15):

[0039] -Q １ - (P １ Q ２ ) ａａ -P ２ Q３ (15)

[0040] Q １ is an alkylene group which may have a halogen atom as a substituent. ２ is an alkylene group which may have a halogen atom as a substituent. ３ is an alkyl group which may have a halogen atom as a substituent. １ and P ２ are each independently O, S, or NR ７００ , P.R. ７０１ , or P(=O). ７００ R is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. ７０１ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group. aa represents 0 or a number ranging from 1 to 10.

[0041] M is CR ２６ R ２７ , SiR ２６ R ２７ , GeR ２６ R ２７ , or NR ２６ It is. ２６ and R ２７ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.

[0042] The substituent is preferably at least one selected from the group consisting of a hydroxy group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group which may have a substituent, an aralkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group, an arylthio group which may have a substituent, an aryl group which may have a substituent, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, and a group represented by the above formula (15).

[0043] Also, R ２６ and R ２７ When the two of the above are taken together to form a ring structure, it is preferable that they form an aliphatic ring having 3 to 20 ring carbon atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, a heterocycle having 3 to 20 ring atoms, or a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the heterocycle.

[0044]

[0045] In the above formula (10), R １０００ , R １００１ , and R １００２ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as those described in formula (9) above. mm is 1 to 10.

[0046]

[0047] In the above formula (11), R １００３ , R １００４ , and R １００５ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as those described in formula (9) above. nn is 1 to 10.

[0048]

[0049] In the above formula (12), R １００６ , R １００７ , and R １００８ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The same types of substituents as those explained in formula (9) above can be used as the substituents. oo is 1 to 12.

[0050]

[0051] In the above formula (13), R １００９ , R １０１０ , and R １０１１ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The substituents may be the same as those described in formula (9) above. pp is 1 to 12.

[0052]

[0053] In the above formula (14), R １０１２ , R １０１３ , and R １０１４ are each independently a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure. The same types of substituents as those described in formula (9) above can be used as the substituents. qq is 1 to 12.

[0054] The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton, and the indenonaphthopyran compound preferably has an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

[0055] In addition to the above, photochromic compounds having an oligomer chain group in the molecule can also be suitably used.

[0056] The indenonaphthopyran compound preferably includes a compound represented by the following formula (16):

[0057]

[0058] In the formula, R ２４ , R ２５ , R ２６ , and R２７ is the same as above.

[0059] r is an integer of 0 to 4. s is an integer of 0 to 4. When r is 2 to 4, multiple R ２８ may be the same or different. When s is 2 to 4, multiple R ２９ may be the same or different. ２８ If there is a ２８ Together they ２８ and the carbon atom bonded to the adjacent R may form a ring which may contain at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and the ring may further have a substituent. ２９ If there is a ２９ Together they ２９ and the carbon atom bonded thereto may form a ring which may contain at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and the ring may further have a substituent.

[0060] R ２８ and R ２９ are each independently a group represented by the above formula (15), a hydroxy group, an alkyl group, a haloalkyl group, an optionally substituted cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, an optionally substituted heterocyclic group, a cyano group, a halogen atom, an alkylthio group, an optionally substituted arylthio group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an optionally substituted aralkyl group, an optionally substituted aralkoxy group, an optionally substituted aryloxy group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, an optionally substituted cycloalkylthio group, an optionally substituted silyl group, an optionally substituted oxysilyl group, a group represented by the following formula (17), or L １ -R４００ It is a group represented by the following formula:

[0061]

[0062] E is an oxygen atom or NR １０１ and R １０１ is a hydrogen atom or an alkyl group. F is an oxygen atom or a sulfur atom. G is an oxygen atom, a sulfur atom, or NR ２０２ It is. ２０２ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. gg is 0 or 1. R ２０１ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. When G is an oxygen atom or a sulfur atom, R ２０１ is a group other than a hydrogen atom.

[0063] R ４００ is a hydrogen atom, an alkyl group, an aryl group, a silyl group having a substituent, a polymerizable group, or a photochromic group. The substituent of the silyl group is an alkyl group, an alkoxy group, or an aryl group. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.

[0064] L １ is a group represented by the following formula (X2).

[0065]

[0066] In the above formula (X2), R ３０ is a group represented by the following formula (X2a):

[0067]

[0068] In the formula (X2) and formula (X2a), J is a divalent group, and each J is independently a direct bond, a substituted methylene group, an oxygen atom, a sulfur atom, or NR ３０１ It is. ３０１ is a hydrogen atom or an alkyl group. L is an oxygen atom or a sulfur atom. R ３００ is an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent.３０２ , R ３０３ , and R ３０４ is an alkylene group. h, j, k, and l are each independently 0 or 1. i is an integer of 0 to 200. The structures of groups with multiple i's may be the same or different. The dashed line represents R ４００ Represents a bond with.

[0069] (Curable composition for forming functional layer) The curable composition for forming functional layer contains the functional dye and polymerizable compound described above. The curable composition for forming functional layer may further contain additives and solvents.

[0070] As the polymerizable compound, a compound having a polymerizable group, a radical polymerizable compound, an epoxy-based polymerizable compound, or the like can be used.

[0071] The curable composition for urethane-based resins may contain a compound having a polymerizable group and a compound having an active hydrogen group.

[0072] Examples of compounds having a polyreactive group include iso(thio)cyanate compounds. The iso(thio)cyanate compound is a compound having an isocyanate group or an isothiocyanate group, and may have both an isocyanate group and an isothiocyanate group. The iso(thio)cyanate compound preferably includes a polyiso(thio)cyanate compound having two or more iso(thio)cyanate groups in one molecule. Specific examples of polyiso(thio)cyanates include aromatic polyiso(thio)cyanates having an aromatic ring, such as m-xylene diisocyanate and 4,4'-diphenylmethane diisocyanate; and aliphatic polyiso(thio)cyanates, such as norbornane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate.

[0073] The compound having an active hydrogen group is preferably a compound having at least one of a hydroxy group and a thiol group, and more preferably a polyfunctional compound having two or more active hydrogen groups in one molecule. Specific examples of the compound having an active hydrogen group include polyfunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and 4-mercaptomethyl-3,6-dithia-octanedithiol; polyfunctional alcohols such as trimethylolpropane and pentaerythritol; and the like.

[0074] The curable composition for acrylic resins may contain a (meth)acrylate having one or more (meth)acryloyl groups. The curable composition for acrylic resins contains at least one selected from the group consisting of mono(meth)acrylates, di(meth)acrylates, tri(meth)acrylates, tetra(meth)acrylates, and polyfunctional (meth)acrylates having five or more (meth)acryloyl groups. The curable composition for acrylic resins preferably contains a di(meth)acrylate and a tri(meth)acrylate. The term "(meth)acryloyl" means at least one of acryloyl and methacryloyl. Similarly, the term "(meth)acrylate" means at least one of acrylate and methacrylate.

[0075] Specific examples of (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol bisglycidyl (meth)acrylate, polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, polyhexamethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(3,5-dibromo-4-(meth)acryloyloxyethoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane triacrylate, tetramethylolmethylpropane di ... Examples of the alkoxylated alkyl acrylates include tetramethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, alkylene glycol, alkoxylated trimethylolpropane tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, and alkoxylated ditrimethylolpropane.

[0076] The number average molecular weight of the di(meth)acrylate or tri(meth)acrylate is preferably 600 or more, more preferably 700 or more, and even more preferably 800 or more. Polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and ethoxylated trimethylolpropane trimethacrylate are particularly preferred. A high number average molecular weight tends to improve the performance of the functional layer. The number average molecular weight of the di(meth)acrylate or tri(meth)acrylate can be measured, for example, by gel permeation chromatography (GPC). The number average molecular weight of the di(meth)acrylate or tri(meth)acrylate may be 3,000 or less, 2,000 or less, or 1,500 or less.

[0077] The proportion of di(meth)acrylate in the (meth)acrylate is preferably 40% by mass or more. When a curable composition having a high proportion of di(meth)acrylate is used, the structural change of the functional dye is less likely to be hindered, and a functional layer with excellent performance can be obtained. The proportion of di(meth)acrylate is more preferably 50% by mass or more. There is no particular upper limit for this proportion, but in one example it is 80% by mass or less, and in another example it is 70% by mass or less.

[0078] The proportion of trifunctional or higher poly(meth)acrylates in the (meth)acrylates is preferably 50% by mass or less. Using a curable composition with a low proportion of trifunctional or higher poly(meth)acrylates can provide a functional layer with excellent performance of functional dyes. The proportion of trifunctional or higher poly(meth)acrylates is more preferably 30% by mass or less. There is no particular lower limit for this proportion, but in one example, it is 10% by mass or more, and in another example, it is 20% by mass or more.

[0079] The biomass degree of the curable composition for forming a functional layer is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. There is no particular upper limit to the biomass degree of the curable composition for forming a functional layer, but in one example, it is 100% by mass or less.

[0080] The curable composition for forming a functional layer can contain various known compounding agents. Examples of compounding agents include various stabilizers such as release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. Solvents, leveling agents, and the like can also be added. Thiols such as tert-dodecyl mercaptan can also be added as polymerization regulators.

[0081] [Protective Layer] The protective layer is located on the functional layer. The protective layer is in direct contact with at least a portion of the functional layer. The portion of the protective layer that is not in contact with the functional layer may be covered with a hard coat layer, an anti-reflection film, or the like.

[0082] The protective layer contains at least one resin selected from the group consisting of a thermally cured urethane resin, a thermally cured urea resin, a thermally cured urethane urea resin, an epoxy resin, and a (meth)acrylic resin. The urethane resin refers to a polymer having a urethane bond. The urethane resin is typically produced by polyaddition of a compound having an isocyanate group and a compound having a hydroxy group. The urea resin refers to a resin having a urea bond. The urea resin is typically produced by polyaddition of a compound having an isocyanate group and a compound having an amino group. The urethane urea resin refers to a resin containing a urethane bond and a urea bond. The urethane urea resin is typically produced by polyaddition of a compound having an isocyanate group and a compound having a hydroxy group and an amino group. The protective layer preferably contains a urethane resin in terms of high adhesion.

[0083] The proportion of the resin in the protective layer is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more. The proportion of the resin may be 100% by mass. The protective layer typically does not contain any component other than the resin. The protective layer may be a cured product of the curable composition for forming a protective layer described below.

[0084] The protective layer may contain inorganic oxide particles. The inorganic oxide particles may be the same as those used in the hard coat layer described later. The proportion of the inorganic oxide particles in the protective layer is, for example, 0.01% by mass or more and 5.0% by mass or less, and preferably 0.1% by mass or more and 1.0% by mass or less.

[0085] The thickness of the protective layer is 0.3 μm or more and less than 5.0 μm. A laminate having a protective layer thickness within this range can achieve both high hardness and the performance of the functional dye. From the viewpoint of increasing the hardness of the laminate, the thickness of the protective layer is preferably 0.5 μm or more, more preferably 0.75 μm or more, even more preferably 1.0 μm or more, and particularly preferably 1.5 μm or more. The thickness of the protective layer may be 2.0 μm or more. From the viewpoint of improving the performance of the functional dye of the laminate, the thickness of the protective layer is preferably 4.5 μm or less, more preferably 4.0 μm or less, and even more preferably 3.0 μm or less. The thickness of the protective layer can be measured by observation with a scanning microscope. Specifically, the film thickness can be measured by cutting out a cross section of the laminate and observing the surface at 1200x magnification.

[0086] The Vickers hardness V1 of the protective layer superposed on the functional layer is typically higher than the Vickers hardness V2 of the functional layer. The ratio V1 / V2 of the Vickers hardness V1 of the protective layer to the Vickers hardness V2 of the functional layer is, for example, 1.1 or more. This ratio V1 / V2 is preferably 1.2 or more, more preferably 1.3 or more, and even more preferably 1.5 or more. There is no particular upper limit to this ratio V1 / V2, but in one example it is 3.0 or less, and in another example it is 2.5 or less.

[0087] The Vickers hardness V1 of the protective layer overlaid on the functional layer is, for example, 1.2 or more. The Vickers hardness V1 of the protective layer overlaid on the functional layer is preferably 1.3 or more, more preferably 1.4 or more, and even more preferably 1.5 or more. There is no particular upper limit to this Vickers hardness V1, but in one example it is 3.0 or less, and in another example it is 2.5 or less.

[0088] The Bayer value B1 of the protective layer superimposed on the functional layer is higher than the Bayer value B2 of the functional layer. The ratio B1 / B2 of the Bayer value B1 of the protective layer to the Bayer value B2 of the functional layer is, for example, 1.1 or more. This ratio B1 / B2 is preferably 2.0 or more, more preferably 2.5 or more, and even more preferably 3.0 or more. There is no particular upper limit to this ratio B1 / B2, but in one example it is 10.0 or less, and in another example it is 6.0 or less.

[0089] The Bayer value B1 of the protective layer overlaid on the functional layer is, for example, 2.0 or more. The Bayer value B1 of the protective layer overlaid on the functional layer is preferably 3.0 or more, more preferably 3.5 or more, and even more preferably 4.0 or more. There is no particular upper limit to this Bayer value B1, but in one example it is 8.0 or less, and in another example it is 6.0 or less.

[0090] (Curable composition for forming protective layer) As the curable composition for forming a protective layer, for example, a first curable composition for forming a protective layer containing a urethane resin, a second curable composition for forming a protective layer containing an epoxy resin, or a third curable composition for forming a protective layer containing a (meth)acrylic resin can be used.

[0091] The first curable composition contains, for example, an isocyanate compound, an active hydrogen group-containing compound, and a solvent.

[0092] The isocyanate compound is a compound having one or more isocyanate groups. The isocyanate compound includes a diisocyanate having two isocyanate groups, a triisocyanate having three isocyanate groups, and a polyisocyanate having four or more isocyanate groups. The isocyanate compound preferably includes at least one of a diisocyanate and a triisocyanate, and more preferably includes only a diisocyanate, a triisocyanate, or a mixture thereof.

[0093] The relative molecular mass of the isocyanate compound is preferably 1500 or less. When the molecular weight of the isocyanate compound is low, the hardness of the protective layer tends to increase. The relative molecular mass of the isocyanate compound is more preferably 1200 or less, and even more preferably 1000 or less. The lower limit of the relative molecular mass is, for example, 400 or more, preferably 500 or more.

[0094] The isocyanate compound includes, for example, at least one selected from the group consisting of an alicyclic isocyanate, an aliphatic isocyanate, and an aromatic isocyanate. The isocyanate compound preferably includes at least one selected from the group consisting of an alicyclic isocyanate and an aliphatic isocyanate, and more preferably includes both.

[0095] Specific examples of aliphatic isocyanates include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, and 1,2-bis(2-isocyanatoethylthio)ethane.

[0096] Specific examples of alicyclic isocyanates include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated diphenylmethane diisocyanate), norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, and 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane.

[0097] Specific examples of aromatic isocyanates include xylene diisocyanate (o-, m-, p-), toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and 4,4'-diphenylmethane diisocyanate.

[0098] The isocyanate compound preferably includes a diisocyanate trimer. The trimer may be a triisocyanate having three isocyanate groups. The trimer may be an isocyanurate or a biuret.

[0099] The isocyanate compound preferably contains at least one compound selected from the group consisting of aliphatic isocyanates, biuret compounds of aliphatic isocyanates, isocyanurates of aliphatic isocyanates, alicyclic isocyanates, biuret compounds of alicyclic isocyanates, isocyanurates of alicyclic isocyanates, aromatic isocyanates, biuret compounds of aromatic isocyanates, and isocyanurates of aromatic isocyanates, and more preferably contains at least one compound selected from the group consisting of isocyanurates of alicyclic isocyanates, isocyanurates of aliphatic isocyanates, and biuret compounds of aliphatic isocyanates. Specific examples of isocyanurates of alicyclic isocyanates include isocyanurates of isophorone diisocyanate, isocyanurates of dicyclohexylmethane 4,4'-diisocyanate, and isocyanurates of 1,3-bis(isocyanatomethyl)cyclohexane. Specific examples of isocyanurates of aliphatic isocyanates include isocyanurates of hexamethylene diisocyanate, etc. Specific examples of biuret compounds of aliphatic isocyanates include biuret compounds of hexamethylene diisocyanate, etc.

[0100] The isocyanate compound preferably contains at least one first isocyanate selected from the group consisting of aliphatic isocyanates, biurets of aliphatic isocyanates, and isocyanurates of aliphatic isocyanates. The first isocyanate more preferably contains at least one of an isocyanurate of aliphatic isocyanates and a biuret of aliphatic isocyanates. Use of a curable composition containing the first isocyanate tends to result in a protective layer that has high adhesion to the hard coat layer.

[0101] The isocyanate compound preferably contains at least one second isocyanate selected from the group consisting of alicyclic isocyanates, biuret derivatives of alicyclic isocyanates, and isocyanurates of alicyclic isocyanates. The second isocyanate more preferably contains an isocyanurate derivative of alicyclic isocyanates. Use of a curable composition containing a second isocyanate compound tends to result in a protective layer with high hardness.

[0102] The isocyanate compound may include both a first isocyanate and a second isocyanate. The ratio S3 / S4 of the mass S3 of the first isocyanate to the mass S4 of the second isocyanate is, for example, 0.1 or more and 10 or less. This ratio S3 / S4 is preferably 0.2 or more and 5 or less, more preferably 0.5 or more and 4 or less, and even more preferably 1 or more and 3 or less.

[0103] In the first curable composition, the content of the isocyanate compound is, for example, 10% by mass or more and 50% by mass or less, and may be 20% by mass or more and 40% by mass or less.

[0104] In the first curable composition, the isocyanate compound may be in the form of a blocked isocyanate in which the isocyanate group is protected with a blocking agent. The first curable composition may contain the blocked isocyanate, an active hydrogen group-containing compound, a blocking agent dissociation catalyst, and a solvent.

[0105] In the first curable composition, the content of the blocked isocyanate is, for example, 10% by mass or more and 50% by mass or less, and may be 20% by mass or more and 40% by mass or less.

[0106] The blocking agent can react with an isocyanate group (R-NCO) to form a blocked isocyanate group (R-NH-CO-B; B is a blocking agent). The blocked isocyanate group does not have reactivity with active hydrogen groups. The blocked isocyanate group can be regenerated by releasing the terminal blocking agent, for example, by heating.

[0107] Examples of the blocking agent include alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds, and includes at least one selected from the group consisting of alcohol compounds, lactam compounds, oxime compounds, and pyrazole compounds.

[0108] Specific examples of the alcohol compound include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, and trifluoroethanol.

[0109] Specific examples of the phenol compound include monoalkylphenols such as n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, and n-nonylphenol; and dialkylphenols such as di-n-propylphenol, diisopropylphenol, isopropyl cresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol.

[0110] Specific examples of the amine compound include diphenylamine, carbazole, di-n-propylamine, diisopropylamine, dibutylamine, aniline, N-methylaniline, bis(2,2,6,6-tetramethylpiperidinyl)amine, isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3,5,5-trimethylcyclohexyl)amine, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, and 6-methyl-2-piperidine.

[0111] Specific examples of lactam compounds include γ-butyrolactam, ε-caprolactam, and γ-valerolactam.

[0112] Specific examples of the oxime compound include acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, and cyclohexanone oxime.

[0113] Specific examples of ketoenol compounds include acetylacetone.

[0114] Specific examples of the active methylene compound include malonic acid diester compounds and acetoacetic acid ester compounds.

[0115] Specific examples of the malonic acid diester compound include dimethyl malonate, diethyl malonate, diisopropyl malonate, di-n-propyl malonate, di-n-butyl malonate, ethyl n-butyl malonate, methyl n-butyl malonate, ethyl tert-butyl malonate, methyl tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzylmethyl malonate, ethylphenyl malonate, tert-butylphenyl malonate, and isopropylidene malonate.

[0116] Specific examples of acetoacetate ester compounds include methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, tert-butyl acetoacetate, n-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate.

[0117] Specific examples of the pyrazole compound include pyrazole, 1,2-dimethylpyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

[0118] Specific examples of the triazole compound include triazole, 1,2,4-triazole, 4-amino-1,2,4-triazole, and benzotriazole.

[0119] Specific examples of the imide compound include succinimide, maleimide, phthalimide, succinimide, methsuximide, ethosuximide, and phensuximide.

[0120] Specific examples of the mercaptan compound include n-butyl mercaptan, n-dodecyl mercaptan, n-hexyl mercaptan, thiophenol, and pyridine-2-thiol.

[0121] Specific examples of the imine compound include ethyleneimine, polyethyleneimine, and 1,4,5,6-tetrahydropyrimidine.

[0122] Specific examples of the urea compound include urea, thiourea, and ethyleneurea.

[0123] Specific examples of diaryl compounds include diaryl carbonates.

[0124] The blocking agent preferably contains at least one selected from the group consisting of alcohol compounds, lactam compounds, oxime compounds, and pyrazole compounds, since these can be dissociated at a relatively low temperature of 60 to 140°C.

[0125] The blocking agent dissociation catalyst can accelerate the dissociation reaction of the blocking agent of the blocked isocyanate.

[0126] The blocking agent dissociation catalyst includes, for example, at least one selected from the group consisting of zwitterionic compounds, organotin compounds, organobismuth compounds, organozinc compounds, organotitanium compounds, and organozirconium compounds.

[0127] Specific examples of zwitterionic compounds include N,N,N-triethyl-N-methylammonium chloride, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium chloride, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium chloride, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium chloride, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium chloride, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium chloride, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium chloride, N,N-di(2-methoxyethyl)-N,N-dimethylammonium chloride, and N,N-di(2-ethoxyethyl)-N,N-dimethylammonium chloride. Chloride, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium chloride, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium chloride, tri-n-butyl-n-hexylphosphonium chloride, 1,3-di(tert-butyl)imidazolium chloride, 1,3-bis(1,1-dimethylethyl)imidazolium chloride, 1,3-bis(1,1-dimethylpropyl)imidazolium chloride, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium chloride, 1,3-bis(1-methyl-1-phenylethyl)imidazolium chloride, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium Chloride, 1,3-bis(1-adamantyl)imidazolium chloride, 1-hexadecylpyridinium chloride, N-octyl-N,N,N-trimethylammonium bromide, N,N,N-triethyl-N-methylammonium bromide, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium bromide, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bromide, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium bromide, N,N-Diethyl-N-propyl-N-(2-ethoxyethyl)ammonium bromide, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bromide, N,N-Diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium bromide, N,N-Di(2-methoxyethyl)-N,N-dimethylammonium bromide, N,N-Di(2-ethoxyethyl)-N,N-dimethylammonium bromide, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium bromide, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bromide, Tri-n-butyl-n-hexylphosphonium bromide, 1,3-Di(tert-butyl)imidazolium Bromide, 1,3-bis(1,1-dimethylethyl)imidazolium bromide, 1,3-bis(1,1-dimethylpropyl)imidazolium bromide, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium bromide, 1,3-bis(1-methyl-1-phenylethyl)imidazolium bromide, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium bromide, 1,3-bis(1-adamantyl)imidazolium bromide, 1-hexadecylpyridinium bromide, 1,3-dioctylimidazolium acetate, 1,3-bis(2-ethylhexyl)imidazolium acetate, 1,3-dibenzylimidazolium acetate, 1,3-dibutylimidazolium acetate, 3-dioctylimidazolium formate, 1,3-dioctylimidazolium-2-N-phenylamidate, 1,3-bis(2-ethylhexyl)imidazolium-2-N-phenylamidate, 1,3-dibenzylimidazolium-2-N-phenylamidate], 1,3-dibutylimidazolium-2-N-phenylamidate, 1-ethyl-3-methylimidazolium-2-N-phenylamidate, 1-methyl-3-octylimidazolium-2-N-phenylamidate, 1-methyl-3-octylimidazolium-2-N-phenylamidate, 1,3-di-n-octylimidazolium-2-N-phenylamidate, 1,3-Di-tert-butylimidazolium-2-N-phenylamidate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium-2-N-phenylamidate, 1-octyl-3-methylimidazolium-2-N-phenylamidate, N-octyl-N,N,N-trimethylammonium iodide, N,N,N-triethyl-N-methylammonium iodide, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium iodide, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium iodide, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium iodide, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium iodide, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium Iodide, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium Iodide, N,N-di(2-methoxyethyl)-N,N-dimethylammonium Iodide, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium Iodide, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium Iodide, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium Iodide, tri-n-butyl-n-hexylphosphonium Iodide, 1,3-di(tert-butyl)imidazolium Iodide, 1,3-bis(1,1-dimethylethyl)imidazolium Iodide, 1,3-bis(1,1-dimethylpropyl)imidazolium iodide, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium iodide, 1,3-bis(1-methyl-1-phenylethyl)imidazolium iodide, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium iodide, 1,3-bis(1-adamantyl)imidazolium iodide, 1-hexadecylpyridinium iodide, etc.

[0128] Specific examples of organotin compounds include dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, dibutyltin dilaurate, dimethyldichlorotin, and tin laurate.

[0129] Specific examples of the organic bismuth compound include bismuth octoate, bismuth naphthenate, and bismuth acetylacetonate.

[0130] Specific examples of the organic zinc compound include zinc octoate, zinc naphthenate, and zinc acetylacetonate.

[0131] Specific examples of the organic titanium compound include tetra-n-butyl titanate, tetraisopropyl titanate, and titanium terephthalate.

[0132] Specific examples of the organic zirconium compound include zirconium octylate, zirconium naphthenate, and zirconium acetylacetonate.

[0133] As the blocking agent dissociation catalyst, the compounds described in Patent Document 2 may be used.

[0134] In the first curable composition, the content of the blocking agent dissociating catalyst is, for example, 0.1% by mass or more and 10% by mass or less, and may be 1% by mass or more and 5% by mass or less.

[0135] The active hydrogen group-containing compound has two or more active hydrogen groups. The active hydrogen group-containing compound may have 2, 3, 4, 5, 6, or 7 or more active hydrogen groups. The active hydrogen group is a functional group that can react with an isocyanate group. Examples of the active hydrogen group include a hydroxy group, an amino group, a carboxy group, and a thiol group. The active hydrogen group-containing compound may have only one type of active hydrogen group or may have multiple types. The active hydrogen group-containing compound preferably includes at least one compound selected from the group consisting of a compound having only two or three hydroxy groups and a compound having one or two hydroxy groups and one or two amino groups.

[0136] The relative molecular mass of the active hydrogen group-containing compound is, for example, 500 or less. When an active hydrogen group-containing compound with a low molecular weight is used, the hardness of the protective layer tends to increase. The relative molecular mass of the active hydrogen group-containing compound is preferably 300 or less, more preferably 250 or less, and even more preferably 200 or less. In one example, the lower limit of the relative molecular mass is 50 or more, and in another example, 100 or more.

[0137] The ratio MW1 / MW2 of the relative molecular mass MW1 of the isocyanate compound to the relative molecular mass MW2 of the active hydrogen group-containing compound is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 5 or more and 10 or less.

[0138] Specific examples of active hydrogen group-containing compounds having only hydroxy groups include low molecular weight polyol compounds such as ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, and 1,2,6-hexanetriol. Polymer polyols such as alkylene glycol, alkoxylated trimethylolpropane, alkoxylated glycerin, alkoxylated pentaerythritol, and alkoxylated ditrimethylolpropane may also be used.

[0139] Specific examples of active hydrogen group-containing compounds having only amino groups include isophoronediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylene)methane, and the like. Examples of the diaminocyclohexane include tris(2-aminoethyl)amine (N,N'-dimethylethylenediamine), N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, and tris(2-aminoethyl)amine (TREN).

[0140] Specific examples of the active hydrogen group-containing compound having both a hydroxy group and an amino group include monoaminediol, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 2-amino-2-ethyl-1,3-propanediol, and 2-amino-2-hydroxymethyl-1,3-propanediol.

[0141] Furthermore, compounds having both an amino group and a carboxy group can also be used as the compound having an amino group. Specific examples of aminocarboxylic acids include glycine, alanine, lysine, and leucine.

[0142] In addition, compounds having both an amino group and a thiol group can also be used as the compound having an amino group. Specific examples of aminothiols include 1-aminothiol and 2-aminoethanethiol.

[0143] In the first curable composition, the active hydrogen group-containing compound is preferably blended so that the total number of moles of active hydrogen functional groups is the same as or less than the total number of moles of isocyanate groups or isocyanate groups protected with a blocking agent. That is, when the total number of moles of isocyanate groups or isocyanate groups protected with a blocking agent is taken as 1 mole, the total number of moles of active hydrogen functional groups is preferably 0.1 moles or more and 2.0 moles or less, more preferably 0.5 moles or more and 1.5 moles or less.

[0144] In the first curable composition, the ratio M1 / M2 of the molar amount M1 of isocyanate contained in the blocked isocyanate to the molar amount M2 of active hydrogen contained in the active hydrogen group-containing compound may be 0.67 or more and 1.5 or less.

[0145] In the first curable composition, the content of the active hydrogen group-containing compound is, for example, 0.1 mass% or more and 10 mass% or less, preferably 0.5 mass% or more and 8 mass% or less, and more preferably 1 mass% or more and 5 mass% or less.

[0146] The solvent is used to adjust the solids concentration of the first curable composition. The solvent is water or an organic solvent. The solvent is preferably an organic solvent, and more preferably does not have an active hydrogen group. As the solvent, for example, at least one selected from the group consisting of 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, methanol, ethanol, 2-propanol, tert-butyl alcohol, 2-methyl-2-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide, and tetrahydrofuran is used.

[0147] In the first curable composition, the content of the solvent is, for example, 20% by mass or more and 80% by mass or less, and may be 50% by mass or more and 70% by mass or less.

[0148] The first curable composition may further contain an additive such as a leveling agent, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, a stabilizer, a silane coupling agent, or a glycidyl compound.

[0149] The first curable composition can further contain inorganic oxide fine particles. By incorporating inorganic oxide fine particles, the scratch resistance of the resulting protective layer can be further improved. Examples of inorganic oxide fine particles include silica. Furthermore, it is preferable to use fine particles made of an inorganic oxide or composite inorganic oxide containing at least one element selected from the group consisting of Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W, and Ce, particularly inorganic oxide fine particles or composite inorganic oxide fine particles containing at least one element selected from the group consisting of Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, and W. The particle diameter of the inorganic oxide fine particles is preferably about 1 to 300 nm as observed by transmission electron microscope (TEM). Fine particles of such particle diameters are typically used in the form of a dispersion in an organic solvent as a dispersion medium. Generally, particle aggregation is prevented by colloidal dispersion. For example, alcohol solvents such as propylene glycol monomethyl ether, isopropanol, ethanol, methanol, ethylene glycol, etc., as well as methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, etc. Sols using organic solvents as dispersion media are commercially available from Nissan Chemical Industries, Ltd. as methanol silica sol, MA-ST-MS (dispersion media: methanol), IPA-ST (dispersion media: isopropanol), PGM-ST (dispersion media: propylene glycol monomethyl ether), etc.

[0150] The sol of composite inorganic oxide fine particles can also be commercially available, for example, OZ series, OT series, HT series manufactured by Nissan Chemical Industries, Ltd., and Optolake series manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0151] The first curable composition preferably contains a leveling agent. A surfactant may be used as the leveling agent. Examples include silicone surfactants and fluorine-containing surfactants. Specific examples of silicone surfactants and fluorine-containing surfactants include "L-7001", "L-7002", "L-7604", "FZ-2123", "FZ-2104", and "FZ-2110" manufactured by Dow-Toray Industries, Inc.; "Megafac F-470", "Megafac F-1405", and "Megafac F-479" manufactured by DIC Corporation; and "Flo-Rad FC-430" manufactured by 3M Japan Ltd. When using surfactants, two or more types may be mixed and used.

[0152] Furthermore, the first curable composition preferably contains at least one selected from the group consisting of an ultraviolet absorber, an ultraviolet stabilizer, and an antioxidant, for the purpose of improving the durability of the functional dye. For example, "Irganox 1010", "Irganox 1035", "Irganox 1076", "Irganox 1098", "Irganox 1141", "Irganox 1330", "Irganox 1425 WL", "Irganox 1520 L", "Irganox 245", "Irganox 249", "Irganox 3114", "Irganox 565", "Irganox 168", "Irganox PS 800 FL", and "Irganox PS 802" manufactured by BASF are included. FL'', ``Irganox5057'', ``Irganox1135'', ``Tinuvin123'', ``Tinuvin144'', ``Tinuvin765'', ``Tinuvin770'', ``Tinuvin324'', ``Tinuvin 326", "Tinuvin329", "Tinuvin360", "Tinuvin213", "Tinuvin120", Tinuvin571", "Tinuvin1400", "Tinuvin1577ED", "Uvinul 3030 FF”, “Uvinul 3035”, “Uvinul 3039”, “Uvinul MC80”;ADEKA CORPORATION manufactured "ADK STAB AO-20", "ADK STAB AO-30", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-80", "ADK STAB AO-330", "ADK STAB PEP-8", "ADK STAB PEP-36", "ADK STAB HP-10", "ADK STAB 2112", "ADK STAB 1178", "ADK STAB 1500", "ADK STAB C", "ADK STAB 135A", "ADK STAB 3010", "ADK STAB TPP", "ADK STAB AO-412S", "ADK STAB AO-503", "ADK STAB AO-26", "ADK STAB LA-24", "ADK STAB LA-29", "ADK STAB LA-31", "ADK STAB LA-32", "ADK STAB LA-36", "ADK STAB LA-46", "ADK STAB LA-F70", "ADK STAB 1413", "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-63P", "ADK STAB LA-68", "ADK STAB LA-72", "ADK STAB LA-77Y", "ADK STAB LA-81", "ADK STAB LA-82", "ADK STAB LA-87", and the like.

[0153] In the first curable composition, the content of the leveling agent is, for example, 0.001% by mass or more and 1% by mass or less, and preferably 0.01% by mass or more and 0.1% by mass or less.

[0154] In the first curable composition, the content of the ultraviolet absorber, ultraviolet stabilizer, and antioxidant is, for example, 0.1 mass % or more and 2 mass % or less, and preferably 0.5 mass % or more and 1.0 mass % or less.

[0155] The second curable composition contains, for example, an epoxy compound having two or more epoxy groups in the molecule, a catalyst, and a solvent.

[0156] Examples of the epoxy compound include 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexane carboxylate, an isomer mixture of dodecahydro-2,6:3,5-dimethano-2H-oxireno[3',4']cyclopenta[1',2':6,7]naphtho[2,3-b]oxirene, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, 4-cyclohexene-1,2-dicarboxylate diglycidyl, 5,12-dioxahexacyclo[7.6.1.0]diol ... ２，８ .0 ４，６ .0 １０，１５ .0 １１，１３ ] At least one selected from the group consisting of an isomer mixture of hexadecane, etc.

[0157] In the second curable composition, the content of the epoxy compound is, for example, 20% by mass or more and 70% by mass or less, and preferably 30% by mass or more and 60% by mass or less.

[0158] As the catalyst, for example, at least one catalyst or a composite catalyst of at least two catalysts selected from the group consisting of aluminum complexes, triphenylsilanol, tertiary amines, etc. is used.

[0159] In the second curable composition, the catalyst content is, for example, 0.1% by mass or more and 10% by mass or less, and preferably 1% by mass or more and 6% by mass or less.

[0160] The solvent may be the same as that used in the first curable composition. The solvent content of the second curable composition may be, for example, 20% by mass or more and 80% by mass or less. The solvent content may be 40% by mass or more and 60% by mass or less.

[0161] The second curable composition may further contain an additive. The additive may be the same as that used in the first curable composition. The second curable composition preferably contains a leveling agent.

[0162] The third curable composition contains, for example, a (meth)acrylate having one or more (meth)acryloyl groups.

[0163] The (meth)acrylate may be the same as that used in the functional layer-forming curable composition containing an acrylic resin. The third curable composition preferably contains a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups. From the viewpoint of increasing the hardness of the protective layer, the number-average molecular weight of the polyfunctional (meth)acrylate is preferably low, for example, from 40 to 1,000. From the viewpoint of increasing the hardness of the protective layer, the content of the polyfunctional (meth)acrylate in the third curable composition is preferably from 50% by mass to 99% by mass, more preferably from 60% by mass to 90% by mass.

[0164] The third curable composition may further contain a polymerization initiator, a solvent, and any additives, including the same additives as those that can be used in the first curable composition.

[0165] [Primer Layer] The primer layer is located between the optical substrate and the functional layer, and can function as an adhesive layer that bonds the optical substrate and the functional layer together.

[0166] The primer layer includes, for example, a polyurethane resin. The primer layer may be a moisture-curing urethane resin.

[0167] The primer layer can be obtained, for example, by applying a primer layer-forming composition to an optical substrate and drying the resulting coating. The primer layer-forming composition contains, for example, at least one selected from the group consisting of polyurethane resins and precursors of polyurethane resins, and a solvent.

[0168] [Hard Coat Layer] The hard coat layer covers, for example, at least a part of the surface of the protective layer, and preferably covers the entire surface.

[0169] The hard coat layer contains, for example, a silicon-containing compound such as an organic silane or an inorganic silane, and an inorganic oxide. Examples of the inorganic oxide include titanium oxide (TiO ２ ), zirconium oxide (ZrO ２ ), cerium oxide (CeO ２Materials with high refractive indexes, such as titanium oxide and cerium oxide, are used. These inorganic oxides have ultraviolet absorbing properties. Therefore, lenses provided with a hard coat layer containing these inorganic oxides are less likely to discolor. In terms of high ultraviolet absorbing properties, it is preferable to include at least one inorganic oxide selected from the group consisting of titanium oxide and cerium oxide.

[0170] The Vickers hardness V3 of the hard coat layer is typically higher than the Vickers hardness V2 of the protective layer. The Vickers hardness V3 of the hard coat layer is, for example, 1.5 or higher. The Vickers hardness V3 of the hard coat layer is preferably 1.6 or higher, more preferably 1.8 or higher, and even more preferably 2.0. There is no particular upper limit to the Vickers hardness V3, but in one example, it is 4.0 or lower, and in another example, it is 3.5 or lower. The Vickers hardness is obtained by a method in accordance with Japanese Industrial Standards (JIS) Z 2244-2009: Micro Vickers Hardness Test. To measure the Vickers hardness V3 of the hard coat layer, a laminate in which a primer layer is laminated on an optical substrate, a functional layer is laminated on this primer layer, a protective layer is laminated on this functional layer, and only the hard coat layer is laminated on this protective layer is used as a sample. Hereinafter, the laminate in which the optical substrate, the primer layer, the functional layer, the protective layer, and the hard coat layer are laminated in this order will also be referred to as a third laminate.

[0171] The Bayer value B3 of the hard coat layer is typically higher than the Bayer value B2 of the protective layer. The Bayer value B3 of the hard coat layer is, for example, 4.0 or more. The Bayer value B3 of the hard coat layer is preferably 4.2 or more, more preferably 4.4 or more, and even more preferably 4.5 or more. There is no particular upper limit for this Bayer value B3, but in one example it is 6.0 or less, and in another example it is 5.0 or less. The Bayer value can be measured using a Bayer abrasion tester manufactured by Colts Laboratories. To measure the Bayer value B3 of the hard coat layer, the third laminate is used as a sample.

[0172] [Anti-Reflection Film] The anti-reflection film is a film that prevents reflection of light by interference action. For example, the anti-reflection film covers at least a part of the surface of the hard coat layer, and preferably covers the entire surface.

[0173] The anti-reflection film has a multi-layer structure in which a high refractive index film and a low refractive index film are laminated. The low refractive index film is, for example, a silicon dioxide (SiO ２ The high refractive index film is made of a material having a higher refractive index than the low refractive index layer. Examples of such materials include zirconium oxide (ZrO ２ ), tin oxide (SnO ２ ), niobium oxide (Nb ２ O ５ ), tantalum oxide (Ta ２ O ５ ), titanium oxide (TiO ２ ), yttrium oxide (Y ２ O ３ ), aluminum oxide (Al ２ O ３ ), mixtures thereof (for example, indium tin oxide (ITO)), and the like.

[0174] <Method for Producing Laminate> The laminate of the present disclosure is produced, for example, by the following method: First, an optical substrate is prepared. The surface of the optical substrate may be subjected to a chemical treatment using an alkaline solution, an acid solution, or the like, or a physical treatment using corona discharge, plasma discharge, polishing, or the like.

[0175] Next, a primer layer-forming composition is applied to one main surface of the optical substrate, and the coating is dried to form a primer layer. The formation of the primer layer may be omitted.

[0176] Next, a curable composition for forming a functional layer is applied onto the primer layer by, for example, spin coating to obtain a coating film. This coating film is cured by irradiating it with active energy rays such as ultraviolet rays, α-rays, β-rays, γ-rays, and LEDs; heat; or both, to obtain a first laminate provided with a functional layer. When the functional layer contains an acrylic resin, the coating film is preferably cured in a nitrogen atmosphere with an oxygen concentration of 500 ppm or less. The coating film is also preferably cured by ultraviolet irradiation. The ultraviolet irradiation conditions are, for example, 50 to 1500 mW / cm at a wavelength of 365 to 420 nm. ２ The UV light is irradiated for 0.5 to 5 minutes.

[0177] Next, the first laminate is immersed in, for example, the first curable composition or the second curable composition for forming the protective layer to form a coating film. The optical substrate on which this coating film has been formed is heated to obtain a second laminate provided with a protective layer. The heating temperature is, for example, 70°C or higher and 130°C or lower, preferably 90°C or higher and 110°C or lower. The heating time is, for example, 0.1 hours or higher and 3 hours or lower, preferably 0.5 hours or higher and 1 hour or lower. The thickness of the protective layer can be adjusted, for example, by the solids concentration of the first or second curable composition, the coating method, etc.

[0178] Next, the second laminate is immersed in a curable composition for forming a hard coat layer, for example, to form a coating film. The optical substrate on which this coating film has been formed is heated to obtain a third laminate provided with a hard coat layer. The heating temperature is, for example, 80°C or higher and 150°C or lower. The heating time is, for example, 0.5 hours or higher and 5 hours or lower. The formation of the hard coat layer may be omitted. Further layers, such as an anti-reflection film, an anti-fogging layer, or an anti-water-repellent film, may be provided on the hard coat layer of the third laminate.

[0179] <Optical Articles> The laminate of the present disclosure can be used in a wide range of optical articles, including various memory materials such as various memory materials replacing silver halide photosensitive materials, copying materials, printing photoreceptors, memory materials for cathode ray tubes, photosensitive materials for lasers, and photosensitive materials for holography; lenses, window glass for houses and automobiles, liquid crystal displays, sun visors, decorative articles, window films, etc. Lenses include semi-finished lenses and finished lenses. Lenses are suitable for eyeglasses.

[0180] The laminate of the present disclosure is particularly suitable for use in photochromic lenses, which are suitable as lenses for spectacles such as sunglasses.

[0181] EXAMPLES The present invention will be described in detail below using examples and comparative examples, but the present invention is not limited to these examples.

[0182] Comparative Example 1 (Preparation of curable composition for forming functional layer) 7.5 parts by mass of trimethylolpropane trimethacrylate, 50 parts by mass of polytetramethylene glycol dimethacrylate, 42.5 parts by mass of ethoxylated trimethylolpropane trimethacrylate, 1.1 parts by mass of a photochromic compound represented by the following formula (20), 2.0 parts by mass of a photochromic compound represented by the following formula (Chemical Formula 21), 1.0 part by mass of a photochromic compound represented by the following formula (Chemical Formula 22), 0.4 parts by mass of a photochromic compound represented by the following formula (23), 0.5 parts by mass of Irganox 245 manufactured by BASF, 0.1 parts by mass of Omnirad 819 manufactured by IGM Resins BV, 0.1 parts by mass of FZ-2110 manufactured by Dow Toray Industries, Inc., and 6 parts by mass of KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. were mixed to prepare a curable composition for forming a functional layer. In the formula, "Me" represents a methyl group, and "Pr" represents a propyl group.

[0183]

[0184]

[0185]

[0186]

[0187] (Production of First Laminate) First, a thiourethane-based plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and then thoroughly washed with distilled water.

[0188] Next, using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) was spin-coated onto the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds.

[0189] Thereafter, the functional layer-forming curable composition (2 g) was spin-coated onto the moisture-curable primer layer of the optical substrate at a rotation speed of 100 rpm for 30 seconds, followed by 1000 rpm for 10 to 20 seconds, so as to form a film thickness of 40 μm. Thereafter, the lens on whose surface the functional layer-forming curable composition was coated was subjected to spin-coating at an output of 900 mW / cm in a nitrogen gas atmosphere. ２ The curable composition for forming the functional layer was polymerized by irradiating the curable composition for forming the functional layer with light from a 1000 kJ LED lamp (having a peak wavelength of 405 nm) for 40 seconds. The curable composition for forming the functional layer was then heated at 90°C for 1 hour to obtain a first laminate in which the primer layer and the photochromic resin layer having a thickness of 40 μm were laminated on the optical substrate.

[0190] Comparative Example 2 Preparation of Curable Composition UP1 for Forming Urethane-Based Protective Layer 40 parts by mass of IPDI nurate, 60 parts by mass of HDI biuret, 9.3 parts by mass of 2-amino-2-ethyl-1,3-propanediol, 5 parts by mass of a zwitterionic compound, 0.14 parts by mass of FZ-2104, and 166 parts by mass of a solvent were mixed to prepare a curable composition UP1 for forming a urethane-based protective layer.

[0191] IPDI nurate: isophorone diisocyanate trimer (nurate) blocked with trifluoroethanol (molecular weight after deblocking: approximately 669) HDI biuret: hexamethylene diisocyanate trimer (biuret) blocked with trifluoroethanol (molecular weight after deblocking: approximately 479) Active hydrogen group-containing compound: 2-amino-2-ethyl-1,3-propanediol (molecular weight: approximately 119) Dissociation catalyst: zwitterionic compound (URECKO-C021, manufactured by Koei Chemical Co., Ltd.) Solvent: propylene glycol monomethyl ether Leveling agent: FZ-2104 (manufactured by Dow Toray Industries, Inc.)

[0192] (Production of Second Laminate) After chemically treating the first laminate obtained in the same manner as in Comparative Example 1 with a 5% sodium hydroxide solution, the urethane-based curable composition for forming a protective layer UP1 was applied by dip coating to form a coating film. Pre-curing was performed at 85°C for 5 minutes, followed by heating at 95°C for 1 hour. In this way, a second laminate was obtained in which a protective layer was formed on the photochromic resin layer. The film thickness of the protective layer was 0.2 μm.

[0193] (Preparation of hard coat layer-forming composition) A hard coat layer-forming composition was prepared by mixing 100 parts by mass of methanol silica sol, 0.1 parts by mass of leveling agent L-7001 manufactured by Dow Toray Industries, Inc., 29.7 parts by mass of 3-glycidoxypropyltrimethoxysilane, 23.9 parts by mass of methylethoxysilane, 9 parts by mass of ethylene glycol isopropyl ether, 6.4 parts by mass of acetylacetone, 20.9 parts by mass of tert-butyl alcohol, 12.5 parts by mass of 0.5N hydrochloric acid, 1.1 parts by mass of aluminum acetylacetonate, and 0.3 parts by mass of 3-aminopropyltrimethoxysilane.

[0194] (Production of third laminate) After chemically treating the second laminate with a 5% sodium hydroxide solution, a hard coat layer-forming composition was applied by dip coating to form a coating film. After pre-curing at 70°C for 5 minutes, the coating was heated at 110°C for 3 hours. In this way, a third laminate was obtained in which a hard coat layer was formed on the protective layer. The film thickness of the hard coat layer was 2 μm.

[0195] Examples 1 to 19 and Comparative Examples 3 and 4 A second laminate and a third laminate were obtained in the same manner as in Comparative Example 2, except that the thickness of the protective layer or the curable composition for forming the protective layer was changed as shown in Table 2.

[0196] Comparative Example 5 Preparation of Curable Composition UP16 for Forming Urethane-Based Protective Layer 100 parts by mass of Takeseal PFR402TP-4 manufactured by Takebayashi Chemical Industry Co., Ltd., 200 parts by mass of ethyl acetate, and 0.06 parts by mass of leveling agent FZ-2104 manufactured by Dow Toray Industries, Inc. were mixed under a nitrogen atmosphere to prepare a curable composition UP16 for forming a urethane-based protective layer.

[0197] (Production of second laminate) A first laminate obtained in the same manner as in Comparative Example 1 was chemically treated with a 5% sodium hydroxide solution, and then a curable composition for forming a urethane-based protective layer UP16, which is a moisture-curable urethane resin solution, was applied by spin coating to form a coating film, which was then dried for 10 minutes under conditions of 25°C and 50% RH. In this way, a second laminate was obtained in which a moisture-curable urethane resin protective layer was formed on the photochromic resin layer.

[0198] Example 20 Preparation of curable composition EP1 for forming epoxy-based protective layer 100 parts by mass of 5,12-dioxahexacyclo[7.6.1.0 ２，８ .0 ４，６ .0 １０，１５ .0 １１，１３ ] A mixture of hexadecane isomers, 33 parts by mass of methyl ethyl ketone, 66 parts by mass of methanol, 0.4 parts by mass of leveling agent L-7001 manufactured by Dow Toray Industries, Inc., 6 parts by mass of aluminum acetylacetonate, and 12 parts by mass of triphenylsilanol was mixed to prepare a curable composition EP1 for forming an epoxy-based protective layer.

[0199] (Production of second laminate and third laminate) A second laminate and a third laminate were obtained in the same manner as in Example 1, except that the curable composition for forming an epoxy-based protective layer EP1 was used as the curable composition for forming a protective layer. The heating temperature for curing the coating film of the curable composition for forming an epoxy-based protective layer was 110°C, and the heating time was 1 hour.

[0200] The compositions of the urethane-based curable compositions for forming a protective layer UP1 to UP15 are summarized in Table 1 below.

[0201]

[0202] The components shown in Table 1 are as follows: (NCO compounds) IPDI nurate: isophorone diisocyanate trimer (nurate) blocked with trifluoroethanol (molecular weight after deblocking: approximately 669) HDI biuret: hexamethylene diisocyanate trimer (biuret) blocked with trifluoroethanol (molecular weight after deblocking: approximately 479) HDI nurate: hexamethylene diisocyanate trimer (nurate) blocked with DMP / DEM (molecular weight after deblocking: approximately 505) (Blocking agents) TFE: trifluoroethanol DMP / DEM: complex of diethyl malonate and 3,5-dimethylpyrazole (Active hydrogen group-containing compounds) A0620: 2-amino-2-ethyl-1,3-propanediol (molecular weight: approximately 119) TMP: trimethylolpropane (molecular weight: approximately 134) TREN: tris(2-aminoethyl)amine (molecular weight: approximately 146) TMPT-20EO: Ethoxylated trimethylolpropane (molecular weight: approximately 1014) PPG: Polypropylene glycol (triol type) (molecular weight: approximately 700) (dissociation catalyst) URECKO-C021: Manufactured by Koei Chemical Co., Ltd. Zinc catalyst: K-KAT XK-635 (Manufactured by Kusumoto Chemical Co., Ltd.) (solvent) PGME: Propylene glycol monomethyl ether (leveling agent) FZ-2104: Manufactured by Dow Toray Industries, Inc.

[0203] <Evaluation Test> (Storage Stability) The storage stability of each of the protective layer-forming curable compositions UP1 to UP15 was confirmed by leaving them to stand at 23° C. for 7 days. The results are shown in Table 1.

[0204] (Film Thickness Measurement) The first laminate obtained in Comparative Example 1 was cut into a cross section, and the film thickness was confirmed by observing the surface of the functional layer under a scanning electron microscope at a magnification of 1200. As a result, the film thickness of the functional layer was 40 μm.

[0205] The thickness of the protective layer was measured in the same manner as above using the second laminates obtained in the examples and comparative examples. The results are shown in Table 2.

[0206] (Measurement of Vickers Hardness) For the first laminate obtained in Comparative Example 1, the Vickers hardness of the functional layer was measured by the following method. That is, using a micro Vickers hardness tester (model: PMT-X7A) manufactured by Matsuzawa Co., Ltd., measurement was performed under conditions of a load of 10 kgf and a load time of 30 seconds. As a result, the Vickers hardness V2 of the functional layer was 1.0.

[0207] The Vickers hardness of the protective layer was measured in the same manner as above using the second laminates obtained in the examples and comparative examples. The ratio V1 / V2 of the Vickers hardness V1 of each protective layer to the Vickers hardness V2 of the functional layer is shown in Table 2.

[0208] (Bayer Value Measurement) The Bayer value of the functional layer of the first laminate obtained in Comparative Example 1 was measured by the following method. That is, using a Bayer abrasion tester manufactured by Colts Laboratories, measurement was performed under the conditions of 500 g of test abrasive per test and 500 reciprocations. As a result, the Bayer value of the functional layer was 1.2.

[0209] The Bayer value of the protective layer was measured in the same manner as above using the second laminate obtained in Example 9. As a result, the Bayer value of the protective layer was 4.5.

[0210] (Photochromic Properties) The obtained laminate was used as a sample, and the surface of the laminate was irradiated with light at a specified temperature of ±1° C. for 300 seconds to develop color using a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K., which has an illuminance of 50,000 lux at the sample and an irradiance value specified in ISO 8980-3, as an irradiation light source, to measure the photochromic properties of the laminate. Each photochromic property was evaluated by the following method.

[0211] (Measurement of 35°C Luminous Transmittance: Y) The luminous transmittance at 35°C of the first laminate or second laminate obtained in the Examples and Comparative Examples was measured by the following method. The laminate was irradiated with the above-mentioned light (light having an illuminance of 50,000 lux at the sample and an irradiance value specified in ISO 8980-3) for 300 seconds at 35°C, and then the spectral transmittance was measured using a spectrophotometer (Instant Multichannel Photo Director MCPD1000) manufactured by Otsuka Electronics Co., Ltd., and the luminous transmittance upon color development was calculated based on ISO 8980-3. The smaller this value, the better the photochromic properties. The results are shown in Table 2.

[0212] (Measurement of 23°C Half-Life: τ1 / 2) The half-life at 23°C of the first laminate or second laminate obtained in the Examples and Comparative Examples was measured using the following method. The maximum absorption wavelength after color development was determined using a spectrophotometer (Instant Multichannel Photodirector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. Next, the difference [ε(300) - ε(0)] between the absorbance ε(300) after 300 seconds of irradiation at the maximum absorption wavelength and the absorbance ε(0) at the maximum absorption wavelength without irradiation was determined. After 300 seconds of irradiation, the time required for the absorbance at the maximum absorption wavelength of the sample to decrease to half of [ε(300) - ε(0)] was determined (fading rate). The shorter this time, the better the photochromic properties. The results are shown in Table 2.

[0213] (Measurement of T70 at 23°C) The T70 at 23°C of the first laminate or second laminate obtained in the Examples and Comparative Examples was measured using the following method. The laminate was irradiated with the above-mentioned light (light having an illuminance of 50,000 lux at the sample and an irradiance value specified in ISO 8980-3) at 23°C for 300 seconds (defined as 0 seconds) and then the spectral transmittance was measured every 10 seconds using a spectrophotometer (Instant Multichannel Photo Director MCPD1000) manufactured by Otsuka Electronics Co., Ltd., and the luminous transmittance during color development was calculated based on ISO 8980-3. The time required for the luminous transmittance to reach 70% was measured. The shorter this time, the better the photochromic properties. The results are shown in Table 2.

[0214] (Appearance) The appearance of the second laminate obtained in the examples and comparative examples was judged by the following method. The obtained second laminate was lightly wiped once with a Bemcot PS-2 manufactured by Asahi Kasei Corporation soaked in acetone, and then visually evaluated in a dark room using a Color Cabin III manufactured by Cabin Kogyo Co., Ltd. The judgment criteria were as follows. The results are shown in Table 2. -Judgment criteria- 1: Defects in the film are observed even in part 2: No defect in the film is observed Cloudy: If it is not colorless and transparent, it is judged to be cloudy.

[0215] (Adhesion Measurement) The adhesion of the obtained laminate was evaluated by the following method. The evaluation was performed by a cross-cut test. That is, each laminate was cut at approximately 1 mm intervals using a cutter knife to create 100 grids. Cellophane adhesive tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached to these grids, and the tape was pulled in a 90° direction from the surface, and then peeled off. After peeling off the adhesive tape, the number of grids of the laminate remaining on the optical substrate was counted. Next, the lenses were boiled in distilled water for 3 hours, and then the above-mentioned measurements were performed. The results are shown in Table 3.

[0216]

[0217]

[0218] Preferred aspects of the present disclosure are described below. [1] A laminate comprising: an optical substrate; a functional layer located on the optical substrate and containing a functional dye and a resin; and a protective layer covering at least a portion of the functional layer, the protective layer having a thickness of 0.3 μm or more and less than 5 μm as measured by scanning microscope observation, and containing at least one resin selected from the group consisting of thermosetting urethane resins, thermosetting urea resins, thermosetting urethane urea resins, epoxy resins, and (meth)acrylic resins. [2] The laminate according to [1], wherein the ratio V1 / V2 of the Vickers hardness V1 of the protective layer to the Vickers hardness V2 of the functional layer measured by the Micro Vickers Hardness Test according to Japanese Industrial Standards Z 2244-2009 is 1.1 or more. [3] The laminate according to [1] or [2], wherein the ratio B1 / B2 of the Bayer value B1 of the protective layer to the Bayer value B2 of the functional layer is 1.1 or more. [4] The laminate according to any one of [1] to [3], wherein the protective layer has a Vickers hardness V1 of 1.2 or more as measured by the Japanese Industrial Standards Z 2244-2009 Micro Vickers Hardness Test. [5] The laminate according to any one of [1] to [4], wherein the protective layer has a Bayer value B1 of 2.0 or more. [6] The laminate according to any one of [1] to [5], wherein the protective layer has a thickness of 0.5 μm or more and 3.0 μm or less. [7] The laminate according to any one of [1] to [6], wherein the functional layer has a Vickers hardness V2 of 0.5 or more and less than 1.2 as measured by the Japanese Industrial Standards Z 2244-2009 Micro Vickers Hardness Test. [8] The laminate according to any one of [1] to [7], wherein the functional layer has a Bayer value B2 of 1.0 or more and less than 2.0. [9] The laminate according to any one of [1] to [8], further comprising a hard coat layer covering at least a portion of the protective layer and containing an inorganic oxide.

[10] The laminate according to [9], wherein the hard coat layer has a Vickers hardness V3 of 1.5 or more as measured by the Micro Vickers Hardness Test according to Japanese Industrial Standards Z 2244-2009.

[11] The laminate according to [9] or

[10] , wherein the hard coat layer has a Bayer value B3 of 4.0 or more.

[12] The laminate according to any one of [1] to

[11] , further comprising a primer layer located between the optical substrate and the functional layer and containing a urethane resin.

[13] The laminate according to any one of [1] to

[12] , wherein the functional layer contains a photochromic compound.

[14] The laminate according to any one of [1] to

[13] , wherein the functional layer contains at least one resin selected from the group consisting of an acrylic resin and a methacrylic resin.

[15] The laminate according to any one of [1] to

[14] , wherein the optical substrate contains at least one resin selected from the group consisting of an allyl resin, a cellulose resin, an acrylic resin, a methacrylic resin, a polyurethane resin, a polyurethane urea resin, a polythiourethane resin, a polythioepoxy resin, a polyamide resin, a polyester resin, a polyimide resin, an epoxy resin, a polyolefin resin, a polyvinyl alcohol resin, and a polycarbonate resin.

[16] The laminate according to any one of [1] to

[15] , wherein the protective layer is a cured product of a curable composition containing a blocked isocyanate, an active hydrogen group-containing compound, and a solvent.

[17] The laminate according to

[16] , wherein in the curable composition, the ratio M1 / M2 of the molar amount M1 of isocyanate contained in the blocked isocyanate to the molar amount M2 of active hydrogen contained in the active hydrogen group-containing compound is 0.67 or more and 1.5 or less.

[18] The laminate according to any one of [1] to

[17] , wherein the functional layer is a cured product of a curable composition containing the functional dye, a di(meth)acrylate, and a tri(meth)acrylate.

[19] An optical article comprising the laminate according to any one of [1] to

[18] .

[20] A lens comprising the optical article according to

[19] .

[21] Eyeglasses comprising the lens according to

[20] .

Claims

1. A laminate comprising: an optical substrate; a functional layer located on the optical substrate and containing a functional dye and a resin; and a protective layer covering at least a portion of the functional layer, having a thickness of 0.3 μm or more and less than 5 μm as measured by scanning microscope observation, and containing at least one resin selected from the group consisting of thermosetting urethane resin, thermosetting urea resin, thermosetting urethane urea resin, epoxy resin, and (meth)acrylic resin.

2. The laminate according to claim 1, wherein the ratio V1 / V2 of the Vickers hardness V1 of the protective layer measured according to Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test to the Vickers hardness V2 of the functional layer is 1.1 or more.

3. The laminate according to claim 1, wherein the ratio B1 / B2 of the Bayer value B1 of the protective layer to the Bayer value B2 of the functional layer is 1.1 or more.

4. The laminate according to claim 1, wherein the protective layer has a Vickers hardness V1 of 1.2 or more according to Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test.

5. The laminate according to claim 1, wherein the protective layer has a Bayer value B1 of 2.0 or more.

6. The laminate according to claim 1, wherein the thickness of the protective layer is 0.5 μm or more and 3.0 μm or less.

7. The laminate according to claim 1, wherein the functional layer has a Vickers hardness V2 measured according to Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test of 0.5 or more and less than 1.

2.

8. The laminate according to claim 1, wherein the Bayer value B2 of the functional layer is equal to or greater than 1.0 and less than 2.

0.

9. The laminate according to claim 1, further comprising a hard coat layer containing an inorganic oxide and covering at least a portion of the protective layer.

10. The laminate according to claim 9, wherein the hard coat layer has a Vickers hardness V3 of 1.5 or more according to Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test.

11. The laminate according to claim 9, wherein the Bayer value B3 of the hard coat layer is 4.0 or more.

12. The laminate according to claim 1, further comprising a primer layer containing a urethane resin, located between the optical substrate and the functional layer.

13. The laminate according to claim 1, wherein the functional layer comprises a photochromic compound.

14. The laminate according to claim 1, wherein the functional layer comprises at least one resin selected from the group consisting of acrylic resins and methacrylic resins.

15. The laminate according to claim 1, wherein the optical substrate comprises at least one resin selected from the group consisting of allyl resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythioepoxy resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin.

16. The laminate according to claim 1, wherein the protective layer is a cured product of a curable composition containing a blocked isocyanate, an active hydrogen group-containing compound, and a solvent.

17. The laminate according to claim 16, wherein in the curable composition, the ratio M1 / M2 of the molar amount M1 of isocyanate contained in the blocked isocyanate to the molar amount M2 of active hydrogen contained in the active hydrogen group-containing compound is 0.67 or more and 1.5 or less.

18. The laminate according to claim 1, wherein the functional layer is a cured product of a curable composition containing the functional dye, a di(meth)acrylate, and a tri(meth)acrylate.

19. An optical article comprising the laminate of claim 1.

20. A lens comprising the optical article of claim 19.

21. Eyeglasses comprising a lens according to claim 20.

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