Laminate, optical article, lens, eyeglasses, and curable composition for protective layer

Abstract

The present disclosure addresses the problem of providing: a laminate having excellent appearance, hardness, and performance of a functional dye; an optical article; a lens; eyeglasses; and a curable composition for a protective layer. One embodiment of the present invention provides a laminate. 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 contains a functional dye and a resin. The protective layer covers at least a portion of the functional layer. The protective layer includes a cured body of a curable composition for a protective layer. The curable composition for a protective layer contains a first (meth)acrylate, a second (meth)acrylate, a third (meth)acrylate, and a photopolymerization initiator. The first (meth)acrylate has three or more (meth)acryloyl groups having a relative molecular mass of 550 or less. The second (meth)acrylate has two (meth)acryloyl groups. The third (meth)acrylate has one (meth)acryloyl group having a relative molecular mass of 300 or less.

Description

Laminates, optical articles, lenses, eyeglasses, and curable compositions for protective layers

[0001] The present invention relates to a laminate, an optical article, a lens, eyeglasses, and a curable composition for a protective layer.

[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 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 colorless state.

[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

[0006] An object of the present invention is to provide a laminate, optical article, lens, eyeglasses, and curable composition for protective layer, which are excellent in performance, hardness, and appearance of a functional dye.

[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 includes a cured product of a curable composition for the protective layer. The curable composition for the protective layer includes a first (meth)acrylate, a second (meth)acrylate, a third (meth)acrylate, and a photopolymerization initiator. The first (meth)acrylate has three or more (meth)acryloyl groups with a relative molecular mass of 550 or less. The second (meth)acrylate has two (meth)acryloyl groups. The third (meth)acrylate has one (meth)acryloyl group with a relative molecular mass of 300 or less. In the curable composition for the protective layer, the proportion of the first (meth)acrylate is 25% by mass or more and 85% by mass or less, the proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.

[0008] According to another embodiment, an optical article is provided, the optical article comprising a laminate according to an embodiment.

[0009] According to another embodiment, a lens is provided, the lens comprising an optical article according to an embodiment.

[0010] According to another embodiment, a pair of eyeglasses is provided, the eyeglasses including a lens according to an embodiment.

[0011] According to another embodiment, there is provided a curable composition for a protective layer, the curable composition for a protective layer including: a first (meth)acrylate having a relative molecular mass of 550 or less, having three or more (meth)acryloyl groups, and occupying a proportion of 25% to 85% by weight, a second (meth)acrylate having two (meth)acryloyl groups, and occupying a proportion of 10% to 70% by weight, a third (meth)acrylate having a relative molecular mass of 300 or less, having one (meth)acryloyl group, and occupying a proportion of 0.5% to 15% by weight, and a photopolymerization initiator.

[0012] According to the present invention, there are provided a laminate, an optical article, a lens, spectacles, and a curable composition for a protective layer, which are excellent in the performance, hardness, and appearance of a functional dye.

[0013] FIG. 1 is a cross-sectional view schematically illustrating an example of a laminate according to an embodiment.

[0014] As described above, 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 hinder the structural change of the functional dye in order to bring out the performance of the functional dye. However, such a matrix that is less likely to hinder the structural change of the functional dye may have high flexibility, and therefore may have low hardness and be 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.

[0015] Through extensive research, the present inventors have found that providing a protective layer can improve the hardness of a laminate, but can also reduce its functionality. This is thought to be due to the formation of a mixed layer at the interface between the functional layer and the protective layer, which causes a portion of the functional dye to migrate into this mixed layer. In other words, it has been difficult to obtain a protective layer that can impart sufficient hardness without interfering with the functionality of the functional layer. Furthermore, it has also been found that a protective layer with high hardness may crack upon curing, resulting in poor appearance. Further research by the present inventors has found that a protective layer that satisfies the functionality, hardness, and appearance of the laminate can be achieved by controlling the molecular weight and the number of polymerizable functional groups of the curable composition used in the protective layer.

[0016] The laminate according to the embodiment 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 includes a cured product of a curable composition for a protective layer. The curable composition for a protective layer includes a first (meth)acrylate having three or more (meth)acryloyl groups and a relative molecular mass of 550 or less, a second (meth)acrylate having two (meth)acryloyl groups, a third (meth)acrylate having one (meth)acryloyl group and a relative molecular mass of 300 or less, and a photopolymerization initiator. The curable composition for a protective layer includes a cured product of a curable composition for a protective layer, in which the proportion of the first (meth)acrylate is 25% by mass or more and 85% by mass or less, the proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less. In this specification and claims, (meth)acrylic means at least one of acrylic and methacrylic.

[0017] The laminate according to the embodiment, which includes a protective layer obtained by curing such a curable composition for a protective layer, is less likely to form the mixed layer described above and is more likely to suppress migration of the functional dye, compared to a laminate including a protective layer outside the above-mentioned range. Furthermore, a hardness that satisfies the function as a protective layer can be achieved. Therefore, a laminate that has excellent performance of the functional dye and also satisfies hardness can be achieved.

[0018] The laminate according to the embodiment will be described in detail below.

[0019] <Laminate> Fig. 1 is a cross-sectional view schematically illustrating an example of a laminate according to an embodiment. 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 a water-repellent film may be provided.

[0020] <Optical substrate> The optical substrate may have any shape, for example, a flat plate, a circle, a prism, a cylinder, etc. The optical substrate preferably has a lens shape. The optical substrate may be a spherical lens or an aspherical lens. The optical substrate may be a convex lens or a concave lens.

[0021] 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.

[0022] The optical substrate preferably contains a resin. The resin preferably contains 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 preferably contains 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.

[0023] 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 preferably 30% by mass or more, and 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.

[0024] <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 a 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.

[0025] The functional layer contains a functional dye and a resin, and may be a cured product of a curable composition for functional layer, which will be described later.

[0026] 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 method for measuring the thickness of the protective layer described below.

[0027] 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.

[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. The resin more preferably includes at least one selected from the group consisting of (meth)acrylic 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, 99% by mass, and, for another example, 95% 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 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 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 at least one selected from the group consisting of a hydroxyl 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 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 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 Q ３ (15) Q１ is an alkylene group which may contain a halogen atom as a substituent. ２ is an alkylene group which may contain a halogen atom as a substituent. ３ is an alkyl group which may contain 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 alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ７０１ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. aa is 0 or 1 to 10.

[0040] 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.

[0041] The substituent is preferably at least one selected from the group consisting of a hydroxyl 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).

[0042] Also, R ２６ and R２７ When two of these 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 an 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 a heterocycle.

[0043]

[0044] In 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). mm is 1 to 10.

[0045]

[0046] In 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). nn is 1 to 10.

[0047]

[0048] In 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 substituents may be the same as those described in formula (9). oo is 1 to 12.

[0049]

[0050] In 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). pp is 1 to 12.

[0051]

[0052] In 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 substituents may be the same as those described in formula (9). qq is 1 to 12.

[0053] 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.

[0054] In addition to the above, photochromic compounds having an oligomer chain group in the molecule can also be suitably used.

[0055] The indenonaphthopyran compound preferably includes a compound represented by the following formula (16).

[0056]

[0057] In the formula, R ２４ , R ２５ , R ２６ and R ２７ is the same as above.

[0058] 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 a２９ 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, or a nitrogen atom, and the ring may further have a substituent.

[0059] R ２８ , and R ２９ each independently represent a group represented by formula (15), a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group which may have a substituent, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group, an arylthio group which may have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, 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 aryl group which may have a substituent, a heteroaryl group which may have a substituent, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or a cycloalkylthio group which may have a substituent, a silyl group which may have a substituent, an oxysilyl group which may have a substituent, a group represented by formula (17) below, or L １ -R ４００ It is a group represented by:

[0060]

[0061] 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 an integer of 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.

[0062] R ４００is a hydrogen atom, an alkyl group, an aryl group, a substituted silyl group, a polymerizable group, or a photochromic group. The substituent of the silyl group is an alkyl group, an alkoxyl 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.

[0063] L １ is a group represented by the following formula (X2).

[0064]

[0065] In formula (X2), R ３０ is a group represented by the following formula (X2a).

[0066]

[0067] In formulas (X2) and (X2a), J is a divalent group, each independently representing a direct bond or a substituted methylene group, an oxygen atom, a sulfur atom, or an NR ３０１ And. R ３０１ is a hydrogen atom or an alkyl group. L in formula (18) 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. ii is an integer from 1 to 200. Multiple i units may be the same or different. The dashed line represents R ４００ Represents a bond with.

[0068] (Curable Composition for Functional Layer) The curable composition for functional layer contains the functional dye and polymerizable compound described above. The curable composition for functional layer may further contain additives and solvents.

[0069] As the polymerizable compound, a compound having a polymerization reactive group, a radical polymerizable compound, an epoxy-based polymerizable compound, or the like can be used.

[0070] The curable composition for the urethane-based resin may contain a compound having a polymerization reactive group and a compound containing an active hydrogen group.

[0071] Examples of compounds having a polymerizable reactive group include iso(thio)cyanate compounds. Iso(thio)cyanate compounds are compounds having an isocyanate group or an isothiocyanate group, and may contain both an isocyanate group and an isothiocyanate group. The iso(thio)cyanate compound preferably includes a polyiso(thio)cyanate compound having at least two iso(thio)cyanate groups in one molecule. 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.

[0072] The compound having an active hydrogen group is preferably a compound having at least one of a hydroxyl 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, and polyfunctional alcohols such as trimethylolpropane and pentaerythritol.

[0073] The curable composition for forming a functional group for a (meth)acrylic resin may contain a (meth)acrylate having one or more (meth)acryloyl groups. The curable composition for an acrylic resin contains at least one selected from the group consisting of a mono(meth)acrylate, a di(meth)acrylate, and a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups. The curable composition for an acrylic resin preferably contains a di(meth)acrylate and a tri(meth)acrylate.

[0074] That is, the curable composition for the functional layer may contain the first (meth)acrylate, second (meth)acrylate, and third (meth)acrylate described in detail in the curable composition for the protective layer.

[0075] The curable composition for the functional layer preferably further contains a fourth (meth)acrylate represented by formula (2). The fourth (meth)acrylate is a type of second (meth)acrylate. When the fourth (meth)acrylate is contained, a cured product with high performance of the functional dye tends to be obtained. The fourth (meth)acrylate is a diacrylate.

[0076]

[0077] In the formula, R １ and R ７ are each independently a hydrogen atom or a methyl group. That is, the quaternary (meth)acrylate component can be a diacrylate, dimethacrylate, or methacrylate acrylate represented by the above formula (2). When a quaternary (meth)acrylate that is a diacrylate is used, a cured product in which the photochromic dye fades at a high rate tends to be obtained. When a quaternary (meth)acrylate that is a dimethacrylate is used, a cured product in which the photochromic dye has a high color density tends to be obtained. R １ and R ７ is preferably a methyl group.

[0078] R ４ is a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent. c is 2 to 100. c is a number larger than a, b, d, and e.

[0079] That is, the repeating unit -(OR ４ )- is a first alkylene oxide unit. The polymer portion formed by this repeating unit can form the soft segment of the cured product. ４ is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 3 or more and 6 or less, and more preferably 4 or more and 5 or less. The greater the number of carbon atoms in the alkylene group, the greater the functionality of the cured body. On the other hand, if the number of carbon atoms in the alkylene group is too large, the amount of soft segments per unit mass decreases, which may reduce the functionality of the cured body.

[0080] From the viewpoint of achieving both functionality and hardness, c is preferably 5 to 85, more preferably 7 to 70, even more preferably 10 to 50, and particularly preferably 13 to 20.

[0081] R ２ , R ３ , R ５ , and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ , R ３ , R ５ , and R ６ are each independently preferably a hydrogen atom or a methyl group. ２ and R ３ are different groups. ５ and R ６ are different groups. ２ and R ６ may be the same group. ３ and R ５ may be the same group.

[0082] a and e are 0 to 10. From the viewpoint of achieving both functionality and hardness, a and e are preferably 0 to 5, more preferably 0 to 2, even more preferably 0 or 1, and most preferably 0.

[0083] b and d are 0 to 20. From the viewpoint of achieving both functionality and hardness, 0 to 15 is preferred, 0 to 10 is more preferred, 0 to 5 is even more preferred, and 0 is particularly preferred.

[0084] In other words, the di(meth)acrylate represented by formula (2) may be a monomer further comprising at least one of a second alkylene oxide unit, which is a repeating unit having b and d attached thereto, and a third alkylene oxide unit, which is a repeating unit having a and e attached thereto.

[0085] The di(meth)acrylate represented by formula (2) preferably has a, b, d, and e all equal to 0, i.e., contains only the first alkylene oxide unit. The use of such a di(meth)acrylate represented by formula (1) tends to increase the hardness of the cured product. c may be 4 or more and 20 or less, or 6 or more and 15 or less.

[0086] Such a compound is represented, for example, by the following formula (3).

[0087]

[0088] In the above formula (3), R １ , R ７ , c has the same meaning as in formula (1).

[0089] R １１ is a linear alkylene group having 3 to 10 carbon atoms. １１ is preferably a linear alkylene group having 3 to 7 carbon atoms, more preferably a linear alkylene group having 3 to 5 carbon atoms, and most preferably a linear alkylene group having 4 carbon atoms.

[0090] Specific examples of the compound represented by the above formula (3) include polytrimethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polypentamethylene glycol di(meth)acrylate, and polyhexamethylene glycol di(meth)acrylate.

[0091] When a di(meth)acrylate represented by formula (1) in which a and e are 0 and b and d are 1 or greater is used, i.e., a di(meth)acrylate represented by formula (1) further containing a second alkylene oxide unit, a cured product with high functionality of the functional dye tends to be obtained. b and d may be 2 or greater and 15 or less, or 4 or greater and 10 or less.

[0092] Specific examples of such di(meth)acrylates represented by formula (2) are as follows:

[0093]

[0094]

[0095] The di(meth)acrylate represented by formula (2) may be a monomer in which a, b, d, and e are each 1 or more, i.e., further comprising both a second alkylene oxide unit and a third alkylene oxide unit, wherein the second alkylene oxide unit and the third alkylene oxide unit have different structures.

[0096] Specific examples of such di(meth)acrylates represented by formula (1) are as follows:

[0097]

[0098] The di(meth)acrylate represented by formula (2) can be produced, for example, by the following method.

[0099] The diacrylate represented by formula (2) having an acryloyl group can be synthesized by esterification of a polyol compound represented by the following formula with acrylic acid. ２ , R ３ , R ４ , R ５ , R ６ , a, b, c, d and e have the same meanings as in formula (2).

[0100]

[0101] Specifically, the polyol compound and acrylic acid dissolved in a solvent such as toluene are stirred in the presence of a mineral acid such as sulfuric acid or hydrochloric acid, an organic acid such as an aromatic sulfonic acid, or a Lewis acid such as boron fluoride ether, while heating as necessary, and the resulting water is removed by azeotropy to cause the reaction. Examples of methods for removing water in the esterification reaction include a method using a drying agent such as anhydrous magnesium sulfate or molecular sieves, and a method in which water is removed in the presence of a dehydrating agent typified by dicyclohexylcarbodiimide.

[0102] Alternatively, the compound can be synthesized by esterification using an acrylic acid halide. Specifically, the polyol compound and acrylic acid dissolved in an ether solvent such as tetrahydrofuran are stirred in the presence of a base such as pyridine or dimethylaniline, with heating as necessary, and the resulting hydrogen halide is removed.

[0103] Furthermore, it can also be synthesized by a transesterification reaction with an ester compound such as acrylic anhydride or methyl acrylate. Specifically, a method can be employed in which the polyol compound and acrylic acid are dissolved in a solvent such as toluene in the presence of an acidic catalyst such as an aromatic sulfonic acid or a basic catalyst such as sodium acetate or pyridine, and then stirred while heating as necessary.

[0104] The compound represented by formula (2) having a methacryloyl group can be synthesized in the same manner as above, for example, by using methacrylic acid instead of acrylic acid.

[0105] Among the above polyol compounds, a polyol compound in which a and e are 0 and b and d are 1 or more, that is, a polyol having a second alkylene oxide unit, can be synthesized, for example, by the following method.

[0106] H-(OR ４ A polyol having a second alkylene oxide unit can be synthesized by reacting c-OH with a cyclic ether compound such as ethylene oxide or propylene oxide. The polyol compound having a second alkylene oxide unit can be synthesized, for example, by carrying out the reaction in a nitrogen-substituted autoclave at high temperature and pressure in the presence of a catalyst such as an alkali metal hydroxide, e.g., potassium hydroxide.

[0107] Among the above polyol compounds, a polyol compound in which a, b, d, and e are 1 or more, i.e., a di(meth)acrylate represented by formula (2) further containing second and third alkylene oxide units, can be synthesized, for example, by the following method.

[0108] A polyol compound having a second alkylene oxide unit is reacted with a cyclic ether compound to synthesize a polyol compound having a third alkylene oxide unit, and the resulting polyol compound further having a third alkylene oxide unit is reacted with acrylic acid or methacrylic acid in the same manner as described above to synthesize a di(meth)acrylate represented by formula (2) further containing second and third alkylene oxide units.

[0109] The curable composition for the functional layer preferably contains a fifth (meth)acrylate having a number-average molecular weight of 850 to 3,000 as determined by proton nuclear magnetic resonance spectroscopy and having three or more (meth)acryloyl groups. The fifth (meth)acrylate allows for the formation of a polymer solid matrix with high crosslinking density without interfering with the formation of soft segments. The fifth (meth)acrylate is a polyfunctional (meth)acrylate having three or more (meth)acryloyl groups. From the viewpoint of enhancing the functionality of the cured product, the number-average molecular weight of the fifth (meth)acrylate is preferably 950 or more, more preferably 1,000 or more, and even more preferably 1,100 or more. On the other hand, if the number-average molecular weight of the fifth (meth)acrylate is excessively high, the fluidity of the fifth (meth)acrylate may decrease, resulting in poor handling and coating properties. From this viewpoint, the number-average molecular weight of the first (meth)acrylate is preferably 2,500 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.

[0110] In the curable composition for functional layer, the proportion of the fifth (meth)acrylate is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of improving the appearance of the cured body. In terms of improving the functionality of the cured body, the proportion of the fifth (meth)acrylate is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. This proportion can be confirmed, for example, by measuring the mass of the first (meth)acrylate separated by silica gel column chromatography.

[0111] The fifth (meth)acrylate preferably has one or more methacryloyl groups, more preferably has two or more methacryloyl groups, and even more preferably has three or more methacryloyl groups. The presence of methacryloyl groups can suppress deterioration of the functional dye and tends to improve the appearance of the cured product.

[0112] The fifth (meth)acrylate preferably contains an alkylene oxide chain. Use of such a fifth (meth)acrylate tends to enhance the functionality of the cured product. The number of carbon atoms in the alkylene oxide chain is, for example, 1 or more and 10 or less, preferably 2 or more and 4 or less.

[0113] The raw material for the fifth (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource. The first (meth)acrylate containing an alkylene oxide chain can be obtained, for example, by using a plant-derived polyol compound.

[0114] The fifth (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a fifth (meth)acrylate tends to enhance the functionality of the cured product.

[0115] The fifth (meth)acrylate may contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group. Preferably, the first (meth)acrylate does not contain at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group.

[0116] The fifth (meth)acrylate preferably contains a tri- to hexa-functional (meth)acrylate represented by the following formula (I):

[0117]

[0118] In formula (I), Q １０ is a linear or branched alkylene group having 1 to 3 carbon atoms. １０ is preferably a methylene group. a1 is an integer of 0 or 1.

[0119] Q １１ is a linear or branched alkylene group having 1 to 10 carbon atoms. １１ is preferably a linear alkylene group. １１ is preferably an alkylene group having 2 to 5 carbon atoms. １１ is more preferably an ethylene group, an n-propylene group, or an n-butylene group.

[0120] a2 is a number between 3 and 15. a2 is preferably between 5 and 10.

[0121] Q １２ is a hydrogen atom or a methyl group. １２ is preferably a methyl group.

[0122] Q １３ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms. １３ Examples of the organic group represented by Q include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond. １３ is preferably a tetravalent hydrocarbon group or a hexavalent hydrocarbon group. １３ may be a group derived from trimethylolpropane, a group derived from glycerin, a group derived from pentaerythritol, a group derived from ditrimethylolpropane, or a group derived from dipentaerythritol.

[0123] a3 is 3, 4, 5, or 6. a3 is preferably 3 or 4.

[0124] The fifth (meth)acrylate more preferably contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (II):

[0125]

[0126] In formula (II), Q ２０ , Q ２１ , Q ２２ , and Q ２３ are each independently an alkylene group having 1 to 3 carbon atoms. ２０ , Q ２１ , Q２２ , and Q ２３ is preferably a methylene group. a4, a5, a6, and a7 each independently represent an integer of 0 or 1.

[0127] Q ２４ , Q ２５ , and Q ２６ are each independently a monovalent group represented by the following formula (III):

[0128]

[0129] In formula (III), Q １１ , Q １２ , a2 have the same meanings as in formula (I).

[0130] Q ２４ , Q ２５ , and Q ２６ may have different structures from each other or may have the same structure. ２４ , Q ２５ , and Q ２６ Preferably, the structures of the two compounds are the same.

[0131] Q ２７ Q is a hydrogen atom, a linear or branched alkyl group having from 1 to 5 carbon atoms, a linear or branched alkoxy group having from 1 to 5 carbon atoms, or a monovalent group represented by formula (III). ２７ is preferably a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or a monovalent group represented by formula (III).

[0132] Specific examples of the polyfunctional (meth)acrylate represented by the above formula (I) include at least one selected from the group consisting of alkoxylated trimethylolpropane tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, alkoxylated ditrimethylolpropane (meth)acrylate, and alkoxylated dipentaerythritol (meth)acrylate.

[0133] The alkoxylated trimethylolpropane tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, butoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and butoxylated trimethylolpropane triacrylate.

[0134] The alkoxylated glycerin tri(meth)acrylate includes at least one selected from the group consisting of ethoxylated glycerin trimethacrylate, propoxylated glycerin trimethacrylate, butoxylated glycerin trimethacrylate, ethoxylated glycerin triacrylate, propoxylated glycerin triacrylate, and butoxylated glycerin triacrylate.

[0135] The alkoxylated pentaerythritol tetra(meth)acrylate includes at least one selected from the group consisting of ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, butoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and butoxylated pentaerythritol tetraacrylate.

[0136] The polyfunctional (meth)acrylate represented by formula (I) more preferably includes at least one selected from the group consisting of ethoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.

[0137] The fifth (meth)acrylate may contain a polyfunctional (meth)acrylate having a urethane bond. The polyfunctional (meth)acrylate having a urethane bond is obtained by reacting a polyol compound having three or more hydroxyl groups in the molecule with a (meth)acrylate having one isocyanate group in the molecule. Alternatively, it can also be obtained by reacting a polyol compound having a urethane bond and three or more hydroxyl groups in the molecule with a (meth)acrylate. The polyfunctional (meth)acrylate having a urethane bond preferably has four or more (meth)acryloyl groups in the molecule. Commercially available products include U-6HA (molecular weight 1,019, number of functional groups 6) and U-15HA (molecular weight 2,300, number of functional groups 15).

[0138] The fifth (meth)acrylate may include a polyester (meth)acrylate obtained by modifying the terminal of a polyester compound with a (meth)acryloyl group. Various polyester (meth)acrylate compounds with different molecular weights of the raw polyester compound and different amounts of (meth)acryloyl group modification are commercially available as polyester (meth)acrylate compounds, and these can be used. Specific examples include tetrafunctional polyester oligomer (molecular weight 2,500 to 3,000, Daicel-UCB, EB80).

[0139] Specific examples of compounds that can be contained in other functional material-forming curable compositions include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate acrylate, ethylene glycol bisglycidyl (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, tetramethylolmethane 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 having a molecular weight of less than 850, alkoxylated glycol having a molecular weight of less than 850 Serine tri(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate having a molecular weight of less than 850, alkoxylated ditrimethylolpropane having a molecular weight of less than 850, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and the like.

[0140] The proportion of di(meth)acrylate in the (meth)acrylate curable composition for the functional layer is preferably 35% by mass or more. Using a curable composition with a high proportion of di(meth)acrylate makes it difficult to prevent structural changes in the functional dye, resulting in a functional layer with excellent performance. The proportion of di(meth)acrylate is more preferably 40% 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.

[0141] The proportion of trifunctional or higher poly(meth)acrylates in the (meth)acrylate curable composition for the functional layer is preferably 50% by mass or less. Using a curable composition with a low proportion of trifunctional or higher poly(meth)acrylates results in a functional layer with excellent functional dye performance. 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.

[0142] The biomass plastic content of the curable composition for the functional layer is preferably 25% by mass or more. The biomass plastic content of the curable composition is preferably 30% by mass or more, and more preferably 40% by mass or more. There is no particular upper limit to the biomass plastic content of the curable composition, but in one example, it is 100% by mass or less.

[0143] The curable composition for the functional layer can contain various known compounding agents. Examples of the compounding agents include release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and other compounding agents. Solvents and leveling agents can also be added. Thiols such as t-dodecyl mercaptan can be added as polymerization regulators. Known polymerization initiators and polymerization catalysts suitable for the resin can also be added.

[0144] <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.

[0145] 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 is a cured product of the curable composition for the protective layer described below.

[0146] 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.

[0147] The thickness of the protective layer is 2 μm or more and less than 50.0 μm. A laminate having a protective layer thickness within this range can achieve both high hardness and the performance of the functional dye, and can also obtain an excellent appearance of the laminate. From the viewpoint of increasing the hardness of the laminate, the thickness of the protective layer is preferably 2.5 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more. From the viewpoint of improving the performance of the functional dye of the laminate and the appearance of the laminate, the thickness of the protective layer is preferably 20.0 μm or less, more preferably 15.0 μm or less, and even more preferably 10.0 μm or less. The thickness of the protective layer can be measured by observation with a scanning microscope. Specifically, the film thickness is confirmed by cutting out a cross section of the laminate and observing the surface at 1200x magnification.

[0148] 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 for this ratio V1 / V2, but in one example, it is 10.0 or less. This ratio V1 / V2 may be 2.0 or more, 3.0 or more, 4.0 or more, 5.0 or more, or 6.0 or less. The Vickers hardness V1 of the protective layer can be measured using the same method as the Vickers hardness V2 of the functional layer.

[0149] 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 6.0 or less. This Vickers hardness V1 may be 2.0 or more, 3.0 or more, or 4.0 or more.

[0150] The Bayer value B1 of the protective layer superposed on the functional layer is, for example, 1.0 or more. The Bayer value B1 of the protective layer superposed on the functional layer is preferably 1.5 or more, more preferably 2.0 or more, and even more preferably 2.5 or more.

[0151] (Curable Composition for Protective Layer) The curable composition for the protective layer comprises a first (meth)acrylate having three or more (meth)acryloyl groups and a relative molecular mass of 550 or less, a second (meth)acrylate having two (meth)acryloyl groups, a third (meth)acrylate having one (meth)acryloyl group and a relative molecular mass of 300 or less, and a photopolymerization initiator.

[0152] In addition, in the curable composition for the protective layer, the proportion of the first (meth)acrylate is 25% by mass or more and 85% by mass or less, the proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.

[0153] When the proportion of the curable composition for the protective layer is within the above-mentioned range, a laminate having excellent performance of the functional dye and satisfactory hardness can be obtained. Preferably, the proportion of the first (meth)acrylate is 25% by mass or more and 60% by mass or less, the proportion of the second (meth)acrylate is 25% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 1% by mass or more and 15% by mass or less, more preferably, the proportion of the first (meth)acrylate is 25% by mass or more and 60% by mass or less, the proportion of the second (meth)acrylate is 30% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 3% by mass or more and 10% by mass or less.

[0154] Of all compounds having a (meth)acryloyl group contained in the curable composition for the protective layer, from the viewpoint of improving the durability of the laminate, the proportion of compounds containing only methacryloyl groups is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, from the viewpoint of improving the durability of the laminate, the proportion of compounds containing only acryloyl groups is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. On the other hand, from the viewpoint of improving the appearance of the laminate, the proportion of compounds containing only acryloyl groups is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, from the viewpoint of improving the appearance of the laminate, the proportion of compounds containing only methacryloyl groups is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0155] <First (meth)acrylate> The first (meth)acrylate is a poly(meth)acrylate having three or more (meth)acryloyl groups and a relative molecular mass of 550 or less. The number of (meth)acryloyl groups in the first (meth)acrylate is, for example, 3, 4, 5, 6, 7, or 8, preferably 3 or more and 6 or less, and more preferably 3 or 4.

[0156] The relative molecular mass of the first (meth)acrylate is preferably 250 or more and 530 or less, and more preferably 250 or more and 350 or less. By using a first (meth)acrylate with a relatively low relative molecular mass, the hardness of the protective layer tends to be increased.

[0157] The proportion of the first (meth)acrylate in the protective layer curable composition is 25% by mass or more and 85% by mass or less. The proportion of the first (meth)acrylate may be 30% by mass or more, 40% by mass or more, 60% by mass or less, or 50% by mass or less. By using the first (meth)acrylate in the above-mentioned range, a cured product with excellent hardness can be obtained. If the proportion of the first (meth)acrylate is too low, the hardness will not be sufficiently increased, and if it is too high, the functionality of the laminate will be reduced and the cured product will be prone to poor appearance. The ratio A2 / A1 of the proportion A1 of the first (meth)acrylate to the proportion A2 of the second (meth)acrylate in the protective layer curable composition is preferably in the range of 0.8 to 1.2. When this ratio A2 / A1 is less than 1, a laminate with excellent functionality tends to be obtained. When this ratio A2 / A1 is higher than 1, a laminate with excellent hardness tends to be obtained. From the viewpoint of improving the durability of the laminate, the first (meth)acrylate preferably contains a methacryloyl group, and more preferably all of the (meth)acryloyl groups are methacryloyl groups. From the viewpoint of improving the appearance of the laminate, the first (meth)acrylate preferably contains an acryloyl group, and more preferably all of the (meth)acryloyl groups are acryloyl groups.

[0158] The first (meth)acrylate is preferably an acyclic (meth)acrylate that does not contain a cyclic structure such as an aromatic ring or an aliphatic ring. Use of such a first (meth)acrylate tends to enhance the functionality of the cured body.

[0159] The first (meth)acrylate may include at least one structure selected from the group consisting of an ester bond, a urethane bond, a urea bond, and a carbonyl group.

[0160] The raw material of the first (meth)acrylate may be a compound derived from a biological resource or a compound derived from a fossil resource.

[0161] Specific examples of the first (meth)acrylate include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, glycerin trimethacrylate, glycerin triacrylate, glycerin dimethacrylate monoacrylate, and glycerin diacrylate monomethacrylate.

[0162] <Second (meth)acrylate> The second (meth)acrylate is a di(meth)acrylate having two (meth)acryloyl groups. In the curable composition for the protective layer, the proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less. By using the second (meth)acrylate in the above-mentioned range, excellent functionality can be obtained. If the amount of the second (meth)acrylate is too small, the functionality may be reduced, and if the amount is too large, the hardness of the cured product is likely to be insufficient. The proportion of the second (meth)acrylate may be 20% by mass or more, 30% by mass or more, 50% by mass or less, or 40% by mass or less.

[0163] The second (meth)acrylate may be a low-molecular-weight di(meth)acrylate having a relatively low molecular weight, a high-molecular-weight di(meth)acrylate having a relatively high molecular weight, or a mixture thereof. The use of a low-molecular-weight di(meth)acrylate tends to increase the hardness of the laminate. The use of a high-molecular-weight di(meth)acrylate tends to increase the functionality of the laminate. The relative molecular mass of the low-molecular-weight di(meth)acrylate is preferably 200 or more and 500 or less, and more preferably 220 or more and 400 or less. The number-average molecular weight of the high-molecular-weight di(meth)acrylate, as measured by proton nuclear magnetic resonance spectroscopy, is preferably 500 or more and 2000 or less, and more preferably 600 or more and 1000 or less. From the viewpoint of increasing the durability of the laminate, the second (meth)acrylate preferably contains a methacryloyl group, and more preferably has two methacryloyl groups. From the viewpoint of improving the appearance of the laminate, the second (meth)acrylate preferably contains an acryloyl group, and more preferably has two acryloyl groups.

[0164] The second (meth)acrylate preferably contains a di(meth)acrylate represented by the following formula (1): When the di(meth)acrylate represented by formula (1) is contained, a cured product having high performance of the functional dye tends to be obtained.

[0165]

[0166] In formula (1), R １２ and R １３ are each independently a hydrogen atom or a methyl group.

[0167] j and k each independently represent an integer of 0 or greater, and j+k has an average value of 2 or greater but less than 8, or 8 or greater. j+k is preferably 9 or greater but 15.

[0168] Specific examples of compounds represented by the above formula (1) in which j+k is 8 or more are as follows:

[0169] Dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate acrylate.

[0170] The di(meth)acrylate represented by formula (1) preferably includes a polyethylene glycol di(meth)acrylate in which k is 0 and j is 8 or more.

[0171] Specific examples of compounds represented by the above formula (1) in which j+k is 2 or more and less than 8 are as follows:

[0172] Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylates consisting of a mixture of polypropylene glycol and polyethylene glycol (polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate acrylate).

[0173] The second (meth)acrylate is not particularly limited, and known di(meth)acrylates can be used without any restrictions. The aforementioned fourth (meth)acrylate can also be used. Specific examples of other second (meth)acrylates include di(meth)acrylates represented by the following formula (5) or (6), di(meth)acrylates having a urethane bond, and di(meth)acrylates other than those listed above.

[0174] <Second (meth)acrylate represented by the following formula (5)>

[0175]

[0176] R １４ and R １５ are each a hydrogen atom or a methyl group. １６ and R １７ are each a hydrogen atom or a methyl group.

[0177] A is a divalent organic group, which is a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group which may be substituted with a halogen or an alkyl group having 1 to 5 carbon atoms, a cycloalkylene group, a bicycloalkylene group, a tricycloalkylene group, or a group represented by any of the following formulas:

[0178]

[0179]

[0180]

[0181]

[0182]

[0183] In the above formula, R １８Ａ , R １８Ｂ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. xx and xy represent integers of 0 to 4 or 0 to 10. Ring X represents a benzene ring or a cyclohexane ring. YY represents -O-, -S-, -(SO ２ )-,-CO-,-CH ２ -, -CH=CH-, -C(CH ３ )２ -, -C(CH ３ ) (C ６ H ５ )—, or a group represented by any of the following formulae:

[0184]

[0185]

[0186] In the above formula (5), l and m are each an integer of 0 or 1 or more, and l+m is an average value of 0 or 1 or more and 30 or less.

[0187] Specific examples of the di(meth)acrylate represented by the above formula (5) include di(meth)acrylates such as bisphenol A di(meth)acrylate shown below.

[0188] 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane, 2,2-bis(4-(methacryloyloxydipropoxy)phenyl)propane, 2,2-bis[4-(acryloyloxydiethoxy)phenyl]propane, 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane, 1,3-adamantanediol dimethacrylate, ditrimethylolcyclodecane diacrylate, tricyclodecane dimethanol dimethacrylate, tricyclodecane dimethanol diacrylate. The second (meth)acrylate preferably contains a di(meth)acrylate having a cyclic structure, and more preferably contains an alicyclic (meth)acrylate. When such a second (meth)acrylate is contained, the hardness of the protective layer tends to be increased. The second (meth)acrylate having a cyclic structure preferably contains a di(meth)acrylate represented by the above formula (5), and it is particularly preferable that A is any of the following structures: <Second (meth)acrylate represented by the following formula (6)>

[0189]

[0190] R １９ and R ２０ are each a hydrogen atom or a methyl group.

[0191] n is a number between 1 and 20 on average.

[0192] B and B' are each independently a linear or branched alkylene group having 2 to 15 carbon atoms. B and B' may be the same or different. When there are multiple Bs, the multiple Bs may be the same or different groups.

[0193] The di(meth)acrylate represented by the above formula (6) can be produced by reacting a polycarbonate diol with (meth)acrylic acid.

[0194] Examples of the polycarbonate diol to be used here include the following: Specifically, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of octamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation with nonamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of triethylene glycol and tetramethylene glycol Examples thereof include polycarbonate diol (average molecular weight 500 to 2000), polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of 1-methyltrimethylene glycol.

[0195] <Second (meth)acrylate having a urethane bond> Examples of the di(meth)acrylate having a urethane bond include those obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the molecule, a polyol compound having two or more hydroxyl groups in the molecule, and a hydroxyl group-containing (meth)acrylate.

[0196] Suitable examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, and methylcyclohexane diisocyanate.

[0197] Examples of polyols include polyalkylene glycols having 2 to 4 carbon atoms and having repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide, and polyester diols such as polycaprolactone diol. Further examples include polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

[0198] In addition, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of such a polyisocyanate and a polyol with 2-hydroxy(meth)acrylate, or a reaction mixture obtained by directly reacting the diisocyanate with 2-hydroxy(meth)acrylate, such as a urethane(meth)acrylate monomer, can also be used.

[0199] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0200] As the di(meth)acrylate having a urethane bond, commercially available products can be used without any limitation. Examples of commercially available products include U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), and U-122P (molecular weight 1,100) manufactured by Shin-Nakamura Chemical Co., Ltd., and EB4858 (molecular weight 454) manufactured by Daicel-UCB Ltd.

[0201] <Second (meth)acrylate not corresponding to the above> The "di(meth)acrylate not corresponding to the above" other than the di(meth)acrylate represented by the above formula (1), (5) or (6) and the di(meth)acrylate having a urethane bond is not particularly limited, but may also include a di(meth)acrylate containing a sulfur atom. The sulfur atom preferably forms a part of the molecular chain as a sulfide group. Specific examples of the "di(meth)acrylate not falling under the above-mentioned categories" include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide, and 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide.

[0202] The second (meth)acrylate may be a single component of each of the components described individually, or a plurality of components may be used. Furthermore, a plurality of components described individually may be used in combination. When a plurality of components or a plurality of combinations are used, the reference mass is the total amount of the plurality of components.

[0203] <Third (meth)acrylate> The third (meth)acrylate is a mono(meth)acrylate having a relative molecular mass of 300 or less and one (meth)acryloyl group. In the curable composition for protective layer, the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less. By using the third (meth)acrylate in the above-mentioned range, excellent functionality can be obtained. If the amount of the third (meth)acrylate is excessively small, durability may decrease. If the amount is excessively large, hardness may decrease or the cured product may be prone to poor appearance.

[0204] The relative molecular mass of the third (meth)acrylate is preferably 100 or more and 280 or less, and more preferably 120 or more and 250 or less. By using a third (meth)acrylate having a relatively low relative molecular mass, the hardness of the protective layer tends to be increased.

[0205] The third (meth)acrylate may be, for example, a monofunctional (meth)acrylate represented by the following formula (7).

[0206]

[0207] R ２１ is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, a glycidyl group, a pentamethylpiperidino group, or a 2,2,6,6-tetramethylpiperidino group. ２２ is a hydrogen atom or a methyl group. o is an integer of 0 to 10. p is an integer of 0 to 20.

[0208] R ２１ is preferably a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group. When a monofunctional acrylate having such a functional group is contained, the adhesion between the cured product and the substrate tends to be improved.

[0209] Specific examples of the monofunctional (meth)acrylate represented by the above formula (7) include lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

[0210] In particular, from the viewpoint of improving the durability of the functional dye, those having a hindered amine skeleton are preferred, and for example, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate are preferably used.

[0211] <Other (meth)acrylates> The curable composition for a protective layer according to the embodiment may further contain other (meth)acrylates. The other (meth)acrylates are not particularly limited, and known compounds can be used. For example, a (meth)acrylate having three or more (meth)acryloyl groups and a relative molecular weight of more than 550, or a (meth)acrylate having one (meth)acryloyl group and a relative molecular weight of more than 300, such as a quinary methacrylate, can be used. Additionally, (meth)acrylate group-containing polyrotaxanes and (meth)acrylate group-containing silsesquioxane compounds are also preferably used.

[0212] <Polyrotaxanes Having (Meth)Acrylate Groups> Polyrotaxanes have a composite molecular structure consisting of an axis molecule and multiple cyclic molecules that encapsulate the axis molecule. Bulky terminal groups are formed at both ends of the axis molecule, preventing the cyclic molecules from detaching from the axis molecule. Radical-polymerizable polyrotaxanes are polyrotaxanes in which radical-polymerizable groups are introduced into the side chains of cyclic molecules. The radical-polymerizable groups are introduced, for example, by modifying 1 mol % or more but less than 100 mol % of the hydroxyl groups of the cyclic molecules with radical-polymerizable groups. The modification ratio can be calculated by (number of moles of polymerizable groups introduced) / (number of moles of total OH groups in side chains) × 100. From the viewpoints of adhesion and the mechanical strength and functionality of the resulting cured product, the modification ratio is preferably 10 mol % or more but less than 95 mol %.

[0213] If the weight-average molecular weight of the axial molecule is too large, the compatibility with other polymerizable monomers, etc. tends to decrease, while if it is too small, the mobility of the cyclic molecule tends to decrease. The weight-average molecular weight of the axial molecule is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 80,000, and most preferably in the range of 8,000 to 50,000.

[0214] The cyclic molecule is preferably a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring, or a dicyclohexanocrown ring, with a cyclodextrin ring and a crown ether ring being particularly preferred, and a cyclodextrin ring being most preferred. Furthermore, among cyclodextrin rings, there are α-cyclodextrin rings (inner ring diameter 0.45 to 0.6 nm), β-cyclodextrin rings (inner ring diameter 0.6 to 0.8 nm), and γ-cyclodextrin rings (inner ring diameter 0.8 to 0.95 nm), with α-cyclodextrin rings and β-cyclodextrin rings being preferred, and an α-cyclodextrin ring being most preferred. When the inclusion number when all cyclic molecules are introduced into the axial molecule is taken as 1, the inclusion number of the cyclic molecules is preferably in the range of 0.001 to 0.6, more preferably in the range of 0.002 to 0.5, and most preferably in the range of 0.003 to 0.4.

[0215] As the radical polymerizable group, a (meth)acryloyl group is preferred in consideration of reactivity with other polymerizable monomers, etc. The number of radical polymerizable groups is not particularly limited, and is preferably 0 to 5,000 per molecule.

[0216] Such polyrotaxanes having a (meth)acryloyl group are described in WO 2018 / 030257.

[0217] <(Meth)acryloyl Group-Containing Silsesquioxane> (Meth)acryloyl group-containing silsesquioxane has various molecular structures such as cage-like, ladder-like, and random structures, and has three or more (meth)acryloyl groups.

[0218] An example of such a (meth)acryloyl group-containing silsesquioxane is one represented by the following formula (8).

[0219]

[0220] In formula (8), q is the degree of polymerization and is an integer of 3 to 100.

[0221] Multiple R ２３ may be the same or different and are a radical polymerizable group, an organic group containing a radical polymerizable group, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group. ２３ At least one R ２３ is a radically polymerizable group or an organic group containing a radically polymerizable group.

[0222] Here, R ２３ Examples of the radical polymerizable group represented by the formula (I) or the organic group containing a radical polymerizable group include a (meth)acryloyl group; an organic group having a (meth)acryloyl group such as a (meth)acryloyloxypropyl group or a (3-(meth)acryloyloxypropyl)dimethylsiloxy group; an allyl group; an organic group having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; and an organic group having a vinyl group such as a vinylpropyl group or a vinyldimethylsiloxy group. R ２３ At least one of the groups is an organic group having a (meth)acryloyl group.

[0223] From the viewpoint of increasing the hardness of the protective layer, the curable composition for the protective layer preferably contains a (meth)acryloyl group-containing silsesquioxane. The content of the (meth)acryloyl group-containing silsesquioxane in the curable composition for the protective layer may be 1% by mass or more, 5% by mass or more, 8% by mass or more, 15% by mass or less, 20% by mass or less, or 30% by mass or less.

[0224] The curable composition for protective layer contains a photopolymerization initiator. The proportion of the photopolymerization initiator in the curable composition for protective layer is not particularly limited, but is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 1% by mass or more and 3% by mass or less.

[0225] As the photopolymerization initiator, any known photopolymerization initiator can be used without any limitation. Specific examples of the photopolymerization initiator that can be used include the following:

[0226] acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione, methylphenylglycoxylate; acylphosphine oxide compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and the like.

[0227] <Additives> The curable composition for the protective layer may further contain additives, etc. Examples of the additives include 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, and a glycidyl compound.

[0228] The curable composition for the protective layer can further contain inorganic oxide fine particles. The incorporation of inorganic oxide fine particles can further improve the scratch resistance of the resulting protective layer. Specifically, silica is used as the inorganic oxide fine particles. Furthermore, fine particles made of an inorganic oxide or composite inorganic oxide containing at least one element selected from Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W, and Ce are preferred, 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 inorganic oxide fine particles preferably have a primary particle diameter of approximately 1 to 300 nm as observed by transmission electron microscope (TEM). Fine particles of this particle size are typically used in the form of a dispersion in an organic solvent as a dispersant. Generally, particle aggregation is prevented by colloidal dispersion. For example, alcohol solvents such as propylene glycol monomethyl ether, isopropanol, ethanol, methanol, and ethylene glycol, as well as methyl ethyl ketone, methyl isobutyl ketone, and dimethylacetamide can also be used. Sols using organic solvents as dispersion media are commercially available from Nissan Chemical Industries, Ltd. as methanol silica sol, MA-ST-MS (dispersion medium: methanol), IPA-ST (dispersion medium: isopropanol), PGM-ST (dispersion medium: propylene glycol monomethyl ether), and the like.

[0229] 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.

[0230] The curable composition for the protective layer 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.

[0231] Furthermore, the curable composition for the protective layer 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", "Irgafox 168", "Irganox PS 800 FL", and "Irganox PS 802" manufactured by BASF Corporation 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's "ADEKA STAB AO-20", "ADEKA STAB AO-30", "ADEKA STAB AO-40", "ADEKA 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",Examples include "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-63P", "ADK STAB LA-68", "ADK STAB LA-72", "ADK STAB LA-77Y", and "ADK STAB LA-81".

[0232] The amount of the leveling agent blended in the curable composition for the protective layer 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.

[0233] In the curable composition for a protective layer, the blending amounts of the ultraviolet absorber, ultraviolet stabilizer, and antioxidant are, for example, 0.1 wt % or more and 5.0 wt % or less, and preferably 0.5 wt % or more and 2.0 wt % or less. The curable composition for a protective layer typically does not contain a functional dye. The content of the functional dye in the curable composition for a protective layer is preferably 1 wt % or less, and more preferably 100 wt % or less.

[0234] <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.

[0235] The primer layer includes, for example, a polyurethane resin. The primer layer may be a moisture-curing urethane resin.

[0236] 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 polyurethane resin precursors, and a solvent.

[0237] <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.

[0238] 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 that the hard coat layer contains at least one inorganic oxide selected from the group consisting of titanium oxide and cerium oxide.

[0239] 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 or higher. 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 is used as a sample, in which a primer layer is laminated on an optical substrate, a functional layer is laminated on this primer layer, only a protective layer is laminated on this functional layer, and a hard coat layer is laminated on this protective layer. 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.

[0240] 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. 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.

[0241] <Anti-Reflection Film> The anti-reflection film is a film that prevents reflection of light by interference. 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.

[0242] 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 ), a mixture thereof (for example, indium tin oxide (ITO)), or the like is used.

[0243] <Method for Producing Laminate> The laminate according to the embodiment 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.

[0244] The primer layer is formed by applying a primer layer-forming composition to one main surface of the optical substrate and drying the coating. The formation of the primer layer may be omitted.

[0245] A curable composition for the functional layer is applied onto the primer layer by, for example, spin coating to obtain a coating film. The coating film is cured by irradiating it with ultraviolet light, α-rays, β-rays, γ-rays, active energy rays such as LED, 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 nm to 420 nm. ２ The UV light is irradiated for 0.5 to 5 minutes.

[0246] A curable composition for forming a protective layer is applied to the first laminate by spin coating or the like to form a coating film. The optical substrate on which the coating film has been formed is irradiated with ultraviolet light, α-rays, β-rays, γ-rays, active energy rays such as LED, heat, or both, to cure the coating film, thereby obtaining a second laminate provided with a protective layer. The coating film is preferably cured in a nitrogen atmosphere with an oxygen concentration of 10,000 ppm or less. The coating film is also preferably cured by ultraviolet light irradiation. The ultraviolet light irradiation conditions are, for example, 50 to 1,500 mW / cm at a wavelength of 365 nm to 420 nm. ２ The second laminate is irradiated with UV light for 5 seconds to 1 minute. A coating film is formed by, for example, immersing the second laminate in a curable composition for forming a hard coat layer. 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. An additional layer, such as an anti-reflection layer, an anti-fogging layer, or a water-repellent layer, may be provided on the hard coat layer of the third laminate.

[0247] <Optical Articles> The laminates according to the embodiments 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, as well as lenses, window glass for houses and automobiles, liquid crystal displays, sun visors, decorative articles, and window films. Lenses include semi-finished lenses and finished lenses. Lenses are suitable for eyeglasses.

[0248] The laminate according to the embodiment is particularly suitable for use in photochromic lenses, which are suitable as lenses for spectacles such as sunglasses.

[0249] EXAMPLES Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. The notation of each component and the evaluation methods are as follows.

[0250] <Components> Primary (meth)acrylates TMPT: trimethylolpropane trimethacrylate (relative molecular weight 338) M930: glycerin triacrylate (relative molecular weight 254) D-TMP: ditrimethylolpropane tetramethacrylate (relative molecular weight 523) A-TMMT: pentaerythritol tetraacrylate (relative molecular weight 352)

[0251] Secondary (meth)acrylates A-DCP: tricyclodecane dimethanol diacrylate (relative molecular weight 304) DCP: tricyclodecane dimethanol dimethacrylate (relative molecular weight 332) 14G: polyethylene glycol dimethacrylate (number average molecular weight 770) A-PC: dimethacrylate of polycarbonatediol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (number average molecular weight 606) NEOP: neopentyl glycol dimethacrylate (relative molecular weight 240) NK701: 2-hydroxy-1,3-dimethacryloxypropane (relative molecular weight 228)

[0252] Tertiary (meth)acrylates KBM503: γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., relative molecular weight 248) LA-82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by ADEKA Corporation, relative molecular weight 239) GMA: glycidyl methacrylate (relative molecular weight 142) HEMA: hydroxyethyl methacrylate (relative molecular weight 130)

[0253] Quaternary (meth)acrylate M-PTMG100: Polytetramethylene glycol dimethacrylate (average molecular weight 1136)

[0254] Fifth (meth)acrylate TMPT-20E: ethoxylated trimethylolpropane trimethacrylate (average molecular weight 1218)

[0255] Other (meth)acrylates S21: Silsesquioxane monomer (number average molecular weight 3000)

[0256] <Synthesis of S21 (Silsesquioxane Monomer)> 300 ml of ethanol and 54 g (3.0 mol) of water were added to 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate, and 0.20 g (0.005 mol) of sodium hydroxide was added as a catalyst, followed by a reaction at 45°C for 5 hours. After confirming the disappearance of the raw materials, the mixture was neutralized with dilute hydrochloric acid, and 174 ml of toluene, 174 ml of heptane, and 174 g of water were added, followed by removal of the aqueous layer. The organic layer was then washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain a silsesquioxane monomer (S21) having multiple methacryloyl groups. The disappearance of the raw materials was confirmed by １ This was confirmed by H-NMR.

[0257] The resulting silsesquioxane monomer (S21) was analyzed by gel permeation chromatography (GPC) and found to have a number average molecular weight of 3,000.

[0258] Functional dye: Photochromic compound PC1: Compound represented by the following formula.

[0259]

[0260] PC2: A compound represented by the following formula: In the following formula, Me represents a methyl group.

[0261]

[0262] PC3: A compound represented by the following formula: In the following formula, Me represents a methyl group, and Pr represents a propyl group.

[0263]

[0264] PC4: A compound represented by the following formula:

[0265]

[0266] PC5: A compound represented by the following formula:

[0267]

[0268] PC6: A compound represented by the following formula:

[0269]

[0270] (Photochromic Compound Composition) PCF1: A composition consisting of 0.4 parts by mass of PC1, 1.1 parts by mass of PC2, 1.7 parts by mass of PC3, 0.8 parts by mass of PC4, 0.3 parts by mass of PC5, and 0.2 parts by mass of PC6.

[0271] (Photopolymerization initiator) PI: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (manufactured by IGM, Omnirad 819) PII: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM, Omnirad TPO)

[0272] (Leveling agent) FZ-2110: manufactured by Dow Toray Industries, Inc.

[0273] Other compounding agents (stabilizers) HP: ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (manufactured by BASF Japan Ltd., Irganox 245).

[0274] Comparative Example 1 (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.

[0275] Next, using a spin coater (1H-DX2, manufactured by Mikasa Co., Ltd.), the surface of the plastic lens was coated with a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Corporation) at a rotation speed of 70 rpm for 15 seconds, followed by 10 seconds at 1000 rpm.

[0276] Thereafter, the curable composition for functional layer (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 having the curable composition for functional layer coated on its surface was subjected to spin-coating under a nitrogen gas atmosphere with an output of 900 mW / cm. ２ The curable composition for the functional layer was polymerized by irradiating the curable composition for the functional layer with light from an LED lamp (having a peak wavelength of 405 nm) for 40 seconds. Thereafter, the curable composition for the functional layer was further heated at 90°C for 1 hour to obtain a first laminate PL1 in which a primer layer and a 40 μm-thick photochromic resin layer were laminated on the optical substrate.

[0277] The formulation of the curable composition for the functional layer was as follows: 46 parts by mass of the fourth (meth)acrylate M-PTMG100, 46 parts by mass of the fifth (meth)acrylate TMPT-20E, 8 parts by mass of the third (meth)acrylate LA-82, 4.5 parts by mass of the photochromic compound composition PCF1, 0.5 parts by mass of the additive HP, 0.2 parts by mass of the photopolymerization initiator PI, 0.1 parts by mass of the additive FZ-2110, and 6 parts by mass of the third (meth)acrylate KBM-503 were mixed to prepare the curable composition for the functional layer.

[0278] Example 1 Preparation of Curable Composition AP1 for Protective Layer 15 parts by mass of the first (meth)acrylate TMPT, 15 parts by mass of the first (meth)acrylate D-TMP, 44 parts by mass of the second (meth)acrylate 14G, 21 parts by mass of the second (meth)acrylate A-PC, 1 part by mass of the third (meth)acrylate GMA, 4 parts by mass of the third (meth)acrylate LA-82, 0.65 parts by mass of the photopolymerization initiator PII, and 0.03 parts by mass of the additive FZ-2110 were mixed to prepare a curable composition for protective layer AP1. Hereinafter, this composition is also referred to as curable composition for protective layer AP1.

[0279] <Production of second laminate> A coating film was formed by spin coating the photochromic resin layer of the first laminate obtained in the same manner as in Comparative Example 1 with the curable composition AP1 for protective layer (2 g) at a rotation speed of 100 rpm for 10 to 60 seconds, and then at 1200 rpm for 10 to 60 seconds. Thereafter, the lens was subjected to spin coating in a nitrogen gas atmosphere at an output of 200 mW / cm. ２ The coating was irradiated with light for 30 seconds using a metal halide lamp (1000 W / L) to cure the coating. In this way, a second laminate was obtained in which a protective layer was formed on the photochromic resin layer. The thickness of the protective layer was 10 μm.

[0280] Examples 2 to 20 and Comparative Examples 2 to 4 A second laminate was obtained in the same manner as in Example 1, except that the curable composition for protective layer AP1 was replaced with a curable composition for protective layer shown in Table 1. The numbers in parentheses shown in Table 1 indicate the blending amount (parts by mass) of each component.

[0281] <Evaluation Test> (Film Thickness Measurement) For the first laminate obtained in Comparative Example 1, the film thickness of the functional layer was confirmed by scanning microscope observation, in which the laminate was cut out in cross section and the surface was observed at a magnification of 1200 times. As a result, the film thickness of the functional layer was 40 μm.

[0282] 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.

[0283] (Measurement of Vickers hardness) For the first laminate obtained in Comparative Example 1, the Vickers hardness of the functional layer was measured under conditions of a load of 10 gf and a load time of 30 seconds using a micro Vickers hardness tester (model: PMT-X7A) manufactured by Matsuzawa Co., Ltd. As a result, the Vickers hardness of the functional layer was 0.7.

[0284] 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 results are shown in Table 2.

[0285] (Bayer Value Measurement) The Bayer value of the protective layer of the second laminate obtained in Example 1 was measured by the following method. A Bayer abrasion tester manufactured by Colts Laboratories was used, and measurements were taken 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 3.8. The Bayer value of the protective layer was measured by the same method as above using the second laminate obtained in the examples and comparative examples. The results are shown in Table 2.

[0286] (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 had 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.

[0287] (Measurement of luminous transmittance at 23°C and 35°C: T (%)) The luminous transmittance of the first laminate or second laminate obtained in the Examples and Comparative Examples at 23°C and 35°C 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 23°C and 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.

[0288] (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 of the sample at the maximum wavelength 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.

[0289] (Measurement of 23°C Fade Rate T70%) 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). 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 at the time of 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.

[0290] (Durability) To evaluate the durability of the first laminate or second laminate obtained in the Examples and Comparative Examples due to light irradiation, the yellowness index was evaluated before and after an accelerated deterioration test. That is, the first laminate or second laminate was subjected to accelerated deterioration for 96 hours using a Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the yellowness index of the laminate was evaluated before and after the test, and the yellowness index (YI) before the test and the yellowness index (YI96) after the test were measured, and the value of the yellowness index ΔYI {YI96 - YI} was calculated. The smaller the value, the higher the durability. The results are shown in Table 2.

[0291] (Crack evaluation) Five sheets of each of the second laminates obtained in the examples and comparative examples were heated at 110°C for one hour, and then the number of sheets on which cracks occurred on the surface of the laminate was counted. The fewer the number of sheets on which cracks occurred, the higher the crack resistance. The results are shown in Table 2.

[0292] (Adhesion Measurement) The adhesion of the obtained second 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 where the protective layer remained on the optical substrate was counted. Next, the lenses were boiled in distilled water for 3 hours, and then the above-mentioned measurement was performed. As a result, it was confirmed that the protective layer remained on 100 grids in all Examples and Comparative Examples.

[0293]

[0294]

[0295] Preferred embodiments of the present disclosure will be 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 and containing a (meth)acrylic resin, wherein the protective layer contains a cured product of a curable composition for a protective layer, and the curable composition for a protective layer contains a first (meth)acrylate having three or more (meth)acryloyl groups and a relative molecular mass of 550 or less, a second (meth)acrylate having two (meth)acryloyl groups, a third (meth)acrylate having one (meth)acryloyl group and a relative molecular mass of 300 or less, and a photopolymerization initiator, wherein a proportion of the first (meth)acrylate in the curable composition for a protective layer is 25% by mass or more and 85% by mass or less, a proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less, and a proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.

[0296] [2] The laminate according to [1], wherein the content of the functional dye in the curable composition for the protective layer is 100 ppm by mass or less.

[0297] [3] The laminate according to [1] or [2], wherein the second (meth)acrylate includes a di(meth)acrylate having a cyclic structure.

[0298] [4] The laminate according to any one of [1] to [3], wherein the curable composition for the protective layer further contains silsesquioxane having a relative molecular mass of more than 550 and having three or more (meth)acryloyl groups.

[0299] [5] The laminate according to any one of [1] to [4], wherein the first (meth)acrylate includes an acrylate having three or four acryloyl groups, and the second (meth)acrylate includes a diacrylate.

[0300] [6] The laminate according to any one of [1] to [5], wherein the second (meth)acrylate includes a di(meth)acrylate represented by the following formula (1):

[0301]

[0302] In the formula (1), R １２ and R １３ are each independently a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or greater, and j+k has an average value of 8 or greater.

[0303] [7] The laminate according to any one of [1] to [6], wherein a ratio V1 / V2 of a Vickers hardness V1 of the protective layer to a Vickers hardness V2 of the functional layer is 1.1 or more, and the Vickers hardness V1 and the Vickers hardness V2 are values ​​measured by Japanese Industrial Standards Z 2244-2009: Micro Vickers Hardness Test.

[0304] [8] The laminate according to any one of [1] to [7], wherein the protective layer has a Vickers hardness V1 of 1.2 or more as measured by the Micro Vickers Hardness Test according to Japanese Industrial Standards Z 2244-2009.

[0305] [9] The laminate according to any one of [1] to [8], 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.

[0306]

[10] The laminate according to any one of [1] to [9], wherein the functional layer contains a photochromic compound.

[0307]

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

[10] , wherein the functional layer contains a (meth)acrylic resin.

[0308]

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

[11] , wherein the functional layer includes a cured product of a curable composition for functional layer, which contains a fourth (meth)acrylate represented by the following formula (2):

[0309]

[0310] In the formula (2), R １ and R ７ are each independently a hydrogen atom or a methyl group, R ２ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ３ and R５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ４ represents a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent; a and e each independently represent a number from 0 to 10; b and d each independently represent a number from 0 to 20; and c is a number from 2 to 100 and is larger than each of a, b, d, and e.

[0311]

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

[12] , wherein the curable composition for the functional layer has a number average molecular weight of 850 or more and 3,000 or less by proton nuclear magnetic resonance analysis and further contains a fifth (meth)acrylate having three or more (meth)acryloyl groups.

[0312]

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

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

[0313]

[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.

[0314]

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

[15] .

[0315]

[17] A lens comprising the laminate according to any one of [1] to

[15] .

[0316]

[18] Eyeglasses including the lens according to

[17] .

[0317]

[19] A curable composition for a protective layer, comprising: a first (meth)acrylate having a relative molecular mass of 550 or less, having three or more (meth)acryloyl groups, and occupying a proportion of 25% by mass or more and 85% by mass or less; a second (meth)acrylate having two (meth)acryloyl groups, and occupying a proportion of 10% by mass or more and 70% by mass or less; a third (meth)acrylate having a relative molecular mass of 300 or less, having one (meth)acryloyl group, and occupying a proportion of 0.5% by mass or more and 15% by mass or less; and a photopolymerization initiator.

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 and containing a (meth)acrylic resin, wherein the protective layer comprises a cured product of a curable composition for a protective layer, the curable composition for a protective layer comprising: a first (meth)acrylate having three or more (meth)acryloyl groups and a relative molecular mass of 550 or less; a second (meth)acrylate having two (meth)acryloyl groups; a third (meth)acrylate having one (meth)acryloyl group and a relative molecular mass of 300 or less; and a photopolymerization initiator, wherein the proportion of the first (meth)acrylate in the curable composition for a protective layer is 25% by mass or more and 85% by mass or less, the proportion of the second (meth)acrylate is 10% by mass or more and 70% by mass or less, and the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.

2. The laminate according to claim 1, wherein the content of the functional dye in the curable composition for the protective layer is 100 ppm by mass or less.

3. The laminate according to claim 1, wherein the second (meth)acrylate comprises a di(meth)acrylate having a cyclic structure.

4. The laminate according to claim 1, wherein the curable composition for the protective layer further comprises a silsesquioxane having a relative molecular mass of more than 550 and having three or more (meth)acryloyl groups.

5. The laminate according to claim 1, wherein the first (meth)acrylate comprises an acrylate having three or four acryloyl groups, and the second (meth)acrylate comprises a diacrylate.

6. The laminate according to claim 1, wherein the second (meth)acrylate includes a di(meth)acrylate represented by the following formula (1): In the formula (1), R １２ and R １３ are each independently a hydrogen atom or a methyl group, j and k are each independently an integer of 0 or greater, and j+k has an average value of 8 or greater.

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

8. The laminate according to claim 7, 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.

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

2.

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

11. The laminate according to claim 1, wherein the functional layer comprises a (meth)acrylic resin.

12. The laminate according to claim 7, wherein the functional layer comprises a cured product of a curable composition for functional layer, which contains a fourth (meth)acrylate represented by the following formula (2): In the formula (2), R １ and R ７ are each independently a hydrogen atom or a methyl group, R ２ and R ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ３ and R ５ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ４ represents a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent; a and e each independently represent a number from 0 to 10; b and d each independently represent a number from 0 to 20; and c is a number from 2 to 100 and is larger than each of a, b, d, and e.

13. The laminate described in claim 12, wherein the curable composition for the functional layer has a number average molecular weight of 850 or more and 3,000 or less as measured by proton nuclear magnetic resonance spectroscopy and further contains a fifth (meth)acrylate having three or more (meth)acryloyl groups.

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

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. An optical article comprising the laminate of claim 1.

17. A lens comprising the laminate of claim 1.

18. Eyeglasses comprising a lens according to claim 17.

19. A curable composition for a protective layer, comprising: a first (meth)acrylate having a relative molecular mass of 550 or less, having three or more (meth)acryloyl groups, and occupying a proportion of 25% by mass or more and 85% by mass or less; a second (meth)acrylate having two (meth)acryloyl groups and occupying a proportion of 10% by mass or more and 70% by mass or less; a third (meth)acrylate having a relative molecular mass of 300 or less, having one (meth)acryloyl group, and occupying a proportion of 0.5% by mass or more and 15% by mass or less; and a photopolymerization initiator.

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