WO2026004832A1 - Stratifié, article optique, lentille, lunettes et composition durcissable pour couche de protection - Google Patents

Stratifié, article optique, lentille, lunettes et composition durcissable pour couche de protection

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Publication number
WO2026004832A1
WO2026004832A1 PCT/JP2025/022614 JP2025022614W WO2026004832A1 WO 2026004832 A1 WO2026004832 A1 WO 2026004832A1 JP 2025022614 W JP2025022614 W JP 2025022614W WO 2026004832 A1 WO2026004832 A1 WO 2026004832A1
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Prior art keywords
meth
acrylate
group
mass
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/022614
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English (en)
Japanese (ja)
Inventor
康智 清水
真行 宮崎
一石 福田
悠介 橋本
利光 平連
孝翼 藤原
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Tokuyama Corp
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Tokuyama Corp
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Publication of WO2026004832A1 publication Critical patent/WO2026004832A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses

Definitions

  • the present invention relates to laminates, optical articles, lenses, eyeglasses, and curable compositions for protective layers.
  • Functional dyes include compounds that have the ability to selectively absorb visible light, as well as compounds that develop, lose, or change color in response 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.
  • 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.
  • Photochromic eyeglass lenses are obtained, for example, by applying a photochromic curable composition to a plastic lens by spin coating or other methods, and then curing the coating to form a photochromic coating layer.
  • a protective layer may be provided on top of this photochromic coating layer.
  • the object of the present invention is to provide a curable composition for laminates, optical articles, lenses, eyeglasses, and protective layers that exhibit excellent functional dye performance, hardness, and appearance.
  • a 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.
  • 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
  • the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.
  • an optical article includes a laminate according to an embodiment.
  • a lens is provided.
  • the lens includes an optical article according to an embodiment.
  • eyeglasses are provided.
  • the eyeglasses include lenses according to an embodiment.
  • a curable composition for a protective layer in another embodiment, includes a first (meth)acrylate having a relative molecular mass of 550 or less, 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, one (meth)acryloyl group, and occupying a proportion of 0.5% to 15% by weight; and a photopolymerization initiator.
  • the present invention provides a laminate, optical article, lens, eyeglasses, and curable composition for protective layer that exhibits excellent functional dye performance, hardness, and appearance.
  • FIG. 1 is a cross-sectional view schematically illustrating an example of a laminate according to an embodiment.
  • an optical laminate imparted with the functionality of the functional dye can be formed by applying a curable composition containing a functional dye onto an optical substrate and curing the resulting coating to obtain a functional layer.
  • the matrix of the functional layer is required to be less likely to interfere with structural changes in the functional dye in order to bring out the performance of the functional dye.
  • a protective layer can be further provided on the surface of the functional layer.
  • the protective layer can be formed, for example, by applying a curable composition for forming the protective layer onto the functional layer and curing the coating.
  • a protective layer can improve the hardness of the laminate, it can also reduce functionality. This is thought to be because a mixed layer is formed at the interface between the functional layer and the protective layer when the protective layer is formed, and some of the functional dye migrates into this mixed layer. In other words, it was difficult to obtain a protective layer that could impart sufficient hardness without interfering with the functionality of the functional layer. Furthermore, it was found that a protective layer with high hardness can crack during curing, resulting in poor appearance. Further research by the inventors revealed that by controlling the molecular weight and number of polymerizable functional groups of the curable composition used in this protective layer, it is possible to achieve a protective layer that satisfies the functionality, hardness, and appearance of the laminate.
  • 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 the protective layer.
  • the curable composition for the 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.
  • Laminates according to the embodiment which include a protective layer obtained by curing such a curable composition for the protective layer, are less likely to form the mixed layer described above and are more likely to suppress migration of the functional dye, compared to laminates which include protective layers outside the above-mentioned range. They also achieve a hardness that satisfies the function of the protective layer. Therefore, a laminate can be realized which has excellent functional dye performance and also has a satisfactory hardness.
  • 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.
  • the optical substrate may have any shape, such as a flat plate, a circle, a prism, or a cylinder.
  • 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.
  • the optical substrate may be made of an organic material such as resin, or an inorganic material such as glass.
  • the optical substrate preferably contains a resin.
  • the resin may be at least one selected from the group consisting of allyl resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythioepoxy resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin.
  • the resin may be 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 a cured form 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-based materials.
  • 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 one example is 100% by mass or less.
  • 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.
  • the functional layer contains a functional dye and a resin.
  • the functional layer may be a cured product of the curable composition for the functional layer described below.
  • the thickness of the functional layer is, for example, 1.0 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the functional layer is, for example, preferably 10.0 ⁇ m or more and 80.0 ⁇ m or less, and more preferably 20.0 ⁇ m or more and 60.0 ⁇ m 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 observation with a scanning microscope, similar to the method for measuring the thickness of the protective layer described below.
  • the Vickers hardness V2 of the functional layer is 0.5 or greater but less than 1.2, and in another example, 0.7 or greater but less than 1.1.
  • 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 using a method conforming to Japanese Industrial Standards (JIS) Z 2244-2009: Micro Vickers Hardness Test.
  • JIS Japanese Industrial Standards
  • a laminate in which a primer layer is laminated on an optical substrate, with only the functional layer laminated on this primer layer, is used as a sample.
  • a laminate in which the optical substrate, primer layer, and functional layer are laminated in this order is also referred to as the "first laminate.”
  • first laminate a laminate in which a primer layer is laminated on an optical substrate, with the functional layer laminated on this primer layer, with only the protective layer laminated on this functional layer, is used as a sample.
  • the laminate in which the optical substrate, primer layer, functional layer, and protective layer are stacked in this order will also be referred to as the second laminate.
  • the resin includes, for example, 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. It is preferable that the resin include at least one selected from the group consisting of acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, and polythiourethane resin. It is more preferable that the resin include at least one selected from the group consisting of (meth)acrylic resin.
  • the resin may be the main component of the functional layer.
  • the proportion of the resin in the functional layer is, for example, 80% by mass or more, and 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.
  • the functional dye may include, 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.
  • the content of the functional dye in the functional layer is, for example, 0.01% by mass or more and 20% by mass or less.
  • the content of the functional dye is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.
  • the photochromic compound may be at least one selected from the group consisting of chromene compounds, fulgide compounds, fulgimide compounds, and spirooxazine compounds.
  • chromene compounds and spirooxazine compounds are preferably used.
  • Chromene compounds include compounds having a 1-benzopyran skeleton, spiropyran compounds containing a spiropyran skeleton, and naphthopyran compounds having a naphthopyran skeleton.
  • the naphthopyran compound preferably includes compounds represented by the following formulas (9), (10), (11), (12), (13), and (14):
  • 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 aromatic heterocycle is fused to the above ring. Ring AA may not be present.
  • 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 aromatic heterocycle is fused to the above ring.
  • R 24 and R 25 each independently represent a hydrogen atom or a substituent, and two or more substituents may be bonded to form a ring structure.
  • 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 hal
  • Q1 is an alkylene group which may contain a halogen atom in the substituent.
  • Q2 is an alkylene group which may contain a halogen atom in the substituent.
  • Q3 is an alkyl group which may contain a halogen atom in the substituent.
  • R700 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.
  • R701 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.
  • aa is 0 or 1 or more and 10 or less.
  • M is CR 26 R 27 , SiR 26 R 27 , GeR 26 R 27 or NR 26.
  • R 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.
  • 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).
  • R 26 and R 27 are taken together to form a ring structure, they preferably 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.
  • 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.
  • R 1003 , R 1004 and R 1005 each independently represent 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.
  • R 1006 , R 1007 and R 1008 each independently represent 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.
  • R 1009 , R 1010 and R 1011 each independently represent 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.
  • 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.
  • Naphthopyran compounds include indenonaphthopyran compounds having an indenonaphthopyran skeleton.
  • the indenonaphthopyran compound has an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.
  • photochromic compounds having oligomer chain groups within the molecule can also be suitably used.
  • the indenonaphthopyran compound preferably includes a compound shown in formula (16) below.
  • R 24 , R 25 , R 26 and R 27 are the same as defined above.
  • r is an integer of 0 to 4.
  • s is an integer of 0 to 4.
  • multiple R 28s may be the same or different.
  • multiple R 29s may be the same or different.
  • the two adjacent R 28s may be joined together with the carbon atoms bonding to those R 28s to form a ring which may contain at least one heteroatom selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms, and the ring may have a substituent.
  • the two adjacent R 29s may be joined together with the carbon atoms bonding to those R 29s to form a ring which may contain at least one heteroatom selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms, and the ring may have a substituent.
  • R 28 and R 29 are each independently 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
  • E is an oxygen atom or NR 101
  • 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.
  • R 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.
  • R 201 is a group other than a hydrogen atom.
  • R400 is a hydrogen atom, an alkyl group, an aryl group, a silyl group having a substituent, a polymerizable group, or a photochromic group.
  • the substituent of the silyl group is an alkyl group, an 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.
  • L1 is a group represented by the following formula (X2).
  • R 30 is a group represented by the following formula (X2a).
  • J represents a divalent group, each independently representing a direct bond or a substituted methylene group, an oxygen atom, a sulfur atom, or NR 301.
  • R 301 represents a hydrogen atom or an alkyl group.
  • L represents an oxygen atom or a sulfur atom.
  • R 300 represents an alkylene group or a silylene group having an alkyl group or an aryl group as a substituent.
  • R 302 , R 303 , and R 304 represent alkylene groups.
  • h, j, k, and l each independently represent 0 or 1.
  • ii represents an integer from 1 to 200. Multiple i units may be the same or different.
  • the dashed line represents a bond to R 400 .
  • the curable composition for the functional layer contains the functional dye and the polymerizable compound described above.
  • the curable composition for the functional layer may further contain an additive and a solvent.
  • Polymerizable compounds that can be used include compounds having a polymerization reactive group, radical polymerizable compounds, and epoxy-based polymerizable compounds.
  • the curable composition for urethane-based resins may contain a compound having a polymerization reactive group and a compound containing an active hydrogen group.
  • An example of a compound having a polymerizable reactive group is an iso(thio)cyanate compound.
  • An iso(thio)cyanate compound is a compound 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 per molecule.
  • polyiso(thio)cyanates examples 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.
  • compounds having an active hydrogen group compounds having at least one of a hydroxyl group and a thiol group are preferred, and polyfunctional compounds having two or more active hydrogen groups per molecule are more preferred.
  • compounds 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.
  • the functional forming curable composition for (meth)acrylic resin may contain a (meth)acrylate having one or more (meth)acryloyl groups.
  • the curable composition for acrylic resin contains at least one selected from the group consisting of mono(meth)acrylate, di(meth)acrylate, and polyfunctional (meth)acrylate having three or more (meth)acryloyl groups.
  • the curable composition for acrylic resin preferably contains a di(meth)acrylate and a tri(meth)acrylate.
  • 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.
  • 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.
  • a cured product with high performance functional dyes tends to be obtained.
  • the fourth (meth)acrylate is a diacrylate.
  • R1 and R7 are each independently a hydrogen atom or a methyl group. That is, the fourth (meth)acrylate component can be a diacrylate, dimethacrylate, or methacrylate acrylate represented by the above formula (2).
  • a fourth (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.
  • a fourth (meth)acrylate that is a dimethacrylate a cured product in which the photochromic dye has a high color density tends to be obtained.
  • R1 and R7 are preferably methyl groups.
  • R4 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 greater than a, greater than b, greater than d, and greater than e.
  • the repeating unit -(OR 4 )- to which the subscript c is added is a first alkylene oxide unit.
  • the polymer moiety constituted by this repeating unit can form a soft segment of the cured body.
  • R 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 high, the amount of soft segment per unit mass decreases, which can reduce the functionality of the cured body.
  • c is preferably 5 to 85, more preferably 7 to 70, even more preferably 10 to 50, and particularly preferably 13 to 20.
  • 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.
  • R 2 , R 3 , R 5 , and R 6 are each independently preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are different groups.
  • R 5 and R 6 are different groups.
  • R 2 and R 6 may be the same group.
  • R 3 and R 5 may be the same group.
  • a and e are 0 to 10. From the perspective 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.
  • b and d are between 0 and 20. From the standpoint 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.
  • 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.
  • the di(meth)acrylate represented by formula (2) preferably contains only first alkylene oxide units, with a, b, d, and e being 0.
  • the use of such a di(meth)acrylate represented by formula (1) tends to increase the hardness of the cured body.
  • c may be 4 or more and 20 or less, or 6 or more and 15 or less.
  • Such a compound is, for example, represented by the following formula (3):
  • R 1 , R 7 and c have the same meanings as in formula (1).
  • R 11 is a linear alkylene group having 3 to 10 carbon atoms.
  • R 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.
  • compounds 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.
  • 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.
  • di(meth)acrylates represented by formula (2) are as follows:
  • the di(meth)acrylate represented by formula (2) may be a monomer in which a, b, d, and e are 1 or greater, i.e., further comprising both a second alkylene oxide unit and a third alkylene oxide unit.
  • the second alkylene oxide unit and the third alkylene oxide unit have mutually different structures.
  • di(meth)acrylates represented by formula (1) are as follows:
  • the di(meth)acrylate represented by formula (2) can be produced, for example, by the following method.
  • the diacrylate represented by formula (2) having an acryloyl group can be synthesized by esterifying a polyol compound represented by the following formula with acrylic acid: R2 , R3 , R4 , R5 , R6 , a, b, c, d, and e of the polyol compound below have the same meanings as those in formula (2).
  • 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 allow the reaction to occur.
  • a mineral acid such as sulfuric acid or hydrochloric acid
  • an organic acid such as an aromatic sulfonic acid
  • a Lewis acid such as boron fluoride ether
  • an esterification reaction using an acrylic acid halide can also be synthesized by an esterification reaction using an acrylic acid halide.
  • one method that can be used is to stir the above polyol compound and acrylic acid dissolved in an ether solvent such as tetrahydrofuran in the presence of a base such as pyridine or dimethylaniline, while heating as necessary, and then remove the hydrogen halide that is produced.
  • ester compound such as acrylic anhydride or methyl acrylate.
  • a method can be used in which the above 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.
  • 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.
  • polyol compounds in which a and e are 0 and b and d are 1 or greater can be synthesized, for example, by the following method.
  • a polyol having a second alkylene oxide unit can be synthesized by reacting H—(OR 4 )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.
  • polyol compounds in which a, b, d, and e are 1 or greater i.e., di(meth)acrylates represented by formula (2) that further contain second and third alkylene oxide units, can be synthesized, for example, by the following method.
  • a polyol compound having a second alkylene oxide unit can be synthesized by reacting a polyol compound having a third alkylene oxide unit with a cyclic ether compound, and the resulting polyol compound further having a third alkylene oxide unit can be reacted with acrylic acid or methacrylic acid in a manner similar to that described above to synthesize a di(meth)acrylate represented by formula (2) further containing second and third alkylene oxide units.
  • the curable composition for the functional layer preferably has a number-average molecular weight of 850 to 3,000 as measured by proton nuclear magnetic resonance spectroscopy and contains a fifth (meth)acrylate having three or more (meth)acryloyl groups.
  • the inclusion of 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fifth (meth)acrylate preferably has one or more methacryloyl groups, more preferably two or more methacryloyl groups, and even more preferably three or more methacryloyl groups.
  • the presence of methacryloyl groups helps to suppress deterioration of the functional dye and tends to improve the appearance of the cured product.
  • 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 body.
  • the number of carbon atoms in the alkylene oxide chain is, for example, 1 or more and 10 or less, and preferably 2 or more and 4 or less.
  • the raw material for the fifth (meth)acrylate may be a compound derived from biological resources or a compound derived from fossil resources.
  • the first (meth)acrylate containing an alkylene oxide chain can be obtained, for example, by using a plant-derived polyol compound.
  • 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 body.
  • 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. It is preferable that 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.
  • the fifth (meth)acrylate preferably includes a tri- to hexa-functional (meth)acrylate represented by the following formula (I):
  • Q 10 is a linear or branched alkylene group having from 1 to 3 carbon atoms.
  • Q 10 is preferably a methylene group.
  • a1 is an integer of 0 or 1.
  • Q 11 is a linear or branched alkylene group having from 1 to 10 carbon atoms.
  • Q 11 is preferably a linear alkylene group.
  • Q 11 is preferably an alkylene group having from 2 to 5 carbon atoms.
  • Q 11 is more preferably an ethylene group, an n-propylene group, or an n-butylene group.
  • a2 is a number between 3 and 15. It is preferable that a2 is between 5 and 10.
  • Q 12 is a hydrogen atom or a methyl group, and Q 12 is preferably a methyl group.
  • Q 13 is a trivalent to hexavalent organic group having 1 to 10 carbon atoms.
  • Examples of the organic group represented by Q 13 include a group derived from a polyol, a trivalent to hexavalent hydrocarbon group, and an organic group containing a trivalent to hexavalent urethane bond.
  • Q 13 is preferably a tetravalent hydrocarbon group or a hexavalent hydrocarbon group.
  • Q 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.
  • a3 is 3, 4, 5, or 6. It is preferable that a3 is 3 or 4.
  • the fifth (meth)acrylate contains a tri- or tetrafunctional (meth)acrylate represented by the following formula (II):
  • Q 20 , Q 21 , Q 22 and Q 23 are each independently an alkylene group having 1 to 3 carbon atoms.
  • Q 20 , Q 21 , Q 22 and Q 23 are preferably a methylene group.
  • a4, a5, a6 and a7 are each independently an integer of 0 or 1.
  • Q 24 , Q 25 , and Q 26 are each independently a monovalent group represented by the following formula (III).
  • Q 24 , Q 25 and Q 26 may have different structures or the same structure, and it is preferred that Q 24 , Q 25 and Q 26 have the same structure.
  • Q27 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).
  • Q27 is preferably a hydrogen atom, a linear alkyl group having from 1 to 3 carbon atoms, or a monovalent group represented by formula (III).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the fifth (meth)acrylate may contain a polyfunctional (meth)acrylate having a urethane bond.
  • a 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 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).
  • the fifth (meth)acrylate may include a polyester (meth)acrylate obtained by modifying the end 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, and these can be used. Specific examples include tetrafunctional polyester oligomer (molecular weight 2,500 to 3,000, Daicel-UCB, EB80).
  • compounds that can be included in other functional 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, Acrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate acrylate,
  • the proportion of di(meth)acrylate is preferably 35% by mass or more.
  • a curable composition with a high proportion of di(meth)acrylate makes it less likely that structural changes in the functional dye will be hindered, resulting in a functional layer with excellent performance.
  • the proportion of di(meth)acrylate be 40% by mass or more. There is no particular upper limit to this proportion, but in one example it is 80% by mass or less, and in another example it is 70% by mass or less.
  • the proportion of tri- or higher functional poly(meth)acrylates is preferably 50% by mass or less.
  • Using a curable composition with a low proportion of tri- or higher functional poly(meth)acrylates will result in a functional layer with excellent functional dye performance.
  • the proportion of tri- or higher functional poly(meth)acrylates is 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.
  • 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 this curable composition, but in one example, it is 100% by mass or less.
  • the curable composition for the functional layer can be blended with various known compounding agents. These include, for example, release agents, UV absorbers, infrared absorbers, UV stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and other compounding agents. Solvents and leveling agents can also be blended. Thiols such as t-dodecyl mercaptan can be blended as polymerization modifiers. Known polymerization initiators and polymerization catalysts suitable for the resin can also be blended.
  • the protective layer is located on the functional layer and 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.
  • the proportion of 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 resin may be 100% by mass.
  • the protective layer typically does not contain any components other than the resin.
  • the protective layer is a cured product of the curable composition for the protective layer, which will be described later.
  • 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 below.
  • the proportion of 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.
  • the thickness of the protective layer is at least 2 ⁇ m and less than 50.0 ⁇ m.
  • a laminate with a protective layer thickness within this range can achieve both high hardness and functional dye performance, and can also achieve an excellent laminate appearance.
  • the protective layer thickness is preferably at least 2.5 ⁇ m, more preferably at least 3 ⁇ m, and particularly preferably at least 5 ⁇ m.
  • the protective layer thickness is preferably no more than 20.0 ⁇ m, more preferably no more than 15.0 ⁇ m, and even more preferably no more than 10.0 ⁇ m.
  • the thickness of the protective layer can be measured by observation with a scanning electron microscope. Specifically, the film thickness is confirmed by cutting out a cross section of the laminate and observing the surface at 1200x magnification.
  • the Vickers hardness V1 of the protective layer overlying 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 greater. This ratio V1/V2 is preferably 1.2 or greater, more preferably 1.3 or greater, and even more preferably 1.5 or greater. There is no particular upper limit to this ratio V1/V2, but in one example, it is 10.0 or less. This ratio V1/V2 may be 2.0 or greater, 3.0 or greater, 4.0 or greater, 5.0 or greater, 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.
  • 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.
  • This Vickers hardness V1 may be 2.0 or more, 3.0 or more, or 4.0 or more.
  • the Bayer value B1 of the protective layer overlaid on the functional layer is, for example, 1.0 or greater.
  • the Bayer value B1 of the protective layer overlaid on the functional layer is preferably 1.5 or greater, more preferably 2.0 or greater, and even more preferably 2.5 or greater.
  • the curable composition for the 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 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
  • the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.
  • 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
  • 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
  • the proportion of the third (meth)acrylate is 3% by mass or more and 10% by mass or less.
  • 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.
  • 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.
  • 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.
  • 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. Using a first (meth)acrylate with a relatively low relative molecular mass tends to increase the hardness of the protective layer.
  • 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.
  • 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.
  • this ratio A2/A1 is less than 1, a laminate with excellent functionality tends to be obtained.
  • this ratio A2/A1 is higher than 1, a laminate with excellent hardness tends to be obtained.
  • the first (meth)acrylate preferably contains a methacryloyl group, and more preferably all of the (meth)acryloyl groups are methacryloyl groups.
  • the first (meth)acrylate preferably contains an acryloyl group, and more preferably all of the (meth)acryloyl groups are acryloyl groups.
  • 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.
  • the first (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.
  • the raw material for the first (meth)acrylate may be a compound derived from biological resources or a compound derived from fossil resources.
  • the first (meth)acrylate examples 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.
  • the second (meth)acrylate is a di(meth)acrylate having two (meth)acryloyl groups.
  • the proportion of the second (meth)acrylate in the curable composition for the protective layer is 10% by mass or more and 70% by mass or less.
  • 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, 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, more preferably 600 or more and 1000 or less.
  • the second (meth)acrylate preferably contains a methacryloyl group, more preferably two methacryloyl groups, from the viewpoint of improving the durability of the laminate, and preferably contains an acryloyl group, more preferably two acryloyl groups, from the viewpoint of improving the appearance of the laminate.
  • the second (meth)acrylate preferably contains a di(meth)acrylate represented by the following formula (1).
  • a cured product with high performance functional dyes tends to be obtained.
  • R 12 and R 13 each independently represent a hydrogen atom or a methyl group.
  • j and k are each independently an integer of 0 or greater, and j+k is an average value of 2 or greater but less than 8, or 8 or greater. j+k is preferably 9 or greater but less than 15.
  • 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.
  • 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 greater.
  • the second (meth)acrylate is not particularly limited, and any known di(meth)acrylate can be used without any restrictions.
  • the fourth (meth)acrylate described above can also be used.
  • Specific examples of other second (meth)acrylates include di(meth)acrylates shown in formula (5) or (6) below, di(meth)acrylates having a urethane bond, and di(meth)acrylates other than those described above.
  • R 14 and R 15 are each a hydrogen atom or a methyl group
  • R 16 and R 17 are each a hydrogen atom or a methyl group.
  • A is a divalent organic group.
  • A is a linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group optionally 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 one of the following formulas:
  • R 18A and R 18B are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or halogen atoms.
  • xx and xy are integers of 0 to 4 or 0 to 10.
  • Ring X is a benzene ring or a cyclohexane ring.
  • YY is —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 formulas:
  • l and m are each an integer of 0 or 1 or greater, and l+m has an average value of 0 or a value between 1 and 30.
  • di(meth)acrylate represented by the above formula (5) examples include di(meth)acrylates such as the following bisphenol A di(meth)acrylate:
  • the second (meth)acrylate preferably contains a di(meth)acrylate having a cyclic structure, and more preferably contains an alicyclic (meth)acrylate.
  • the second (meth)acrylate having a cyclic structure preferably contains a di(meth)acrylate represented by the above formula (5), and it is particularly preferred that A is any of the following structures: ⁇ Second (meth)acrylate represented by the following formula (6)>
  • R 19 and R 20 are each a hydrogen atom or a methyl group.
  • n is the average value and is a number between 1 and 20.
  • 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.
  • the di(meth)acrylate represented by the above formula (6) can be produced by reacting polycarbonate diol with (meth)acrylic acid.
  • the polycarbonate diols used here include, for example, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of trimethylene glycol, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of tetramethylene glycol, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of pentamethylene glycol, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of hexamethylene glycol, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of octamethylene glycol, polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of nonamethylene glycol, and polycarbonate diols (average molecular weight 500-2000) obtained by the phosgenation of triethylene glycol and tetramethylene glyco
  • Examples include polycarbonate diol (average molecular weight 500-2000), polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of tetramethylene glycol and octamethylene glycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of 1-methyltrimethylene glycol.
  • di(meth)acrylates having a urethane bond examples 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.
  • polyisocyanates 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.
  • polyols examples include polyalkylene glycols having 2 to 4 carbon atoms and repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide, and polyester diols such as polycaprolactone diol.
  • polyester diols such as polycaprolactone diol.
  • Other 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.
  • reaction mixtures in which a urethane prepolymer obtained by reacting these polyisocyanates with polyols is further reacted with 2-hydroxy(meth)acrylate, or urethane(meth)acrylate monomers, which are reaction mixtures in which the diisocyanates are directly reacted with 2-hydroxy(meth)acrylate, can also be used.
  • hydroxyl group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • Any commercially available di(meth)acrylate having a urethane bond can be used without any restrictions.
  • 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.
  • di(meth)acrylates other than the di(meth)acrylates represented by the above formula (1), (5) or (6) and di(meth)acrylates having a urethane bond are not particularly limited, but may also include di(meth)acrylates containing a sulfur atom, preferably a sulfide group forming part of the molecular chain.
  • 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(methacryloyloxyisopropylthioisopropylthioisopropy
  • the second (meth)acrylate described above may be a single component of each of the individually described components, or multiple components may be used. Furthermore, multiple components described individually may be used in combination. When multiple components or multiple combinations are used, the reference mass is the total amount of the multiple components.
  • the third (meth)acrylate is a mono(meth)acrylate having a relative molecular mass of 300 or less and one (meth)acryloyl group.
  • the proportion of the third (meth)acrylate is 0.5% by mass or more and 15% by mass or less.
  • 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.
  • An example of the third (meth)acrylate is a monofunctional (meth)acrylate represented by the following formula (7):
  • R21 is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, a glycidyl group, a pentamethylpiperidino group, or a 2,2,6,6-tetramethylpiperidino group.
  • R22 is a hydrogen atom or a methyl group.
  • o is an integer of 0 to 10.
  • p is an integer of 0 to 20.
  • R21 is preferably a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group.
  • a monofunctional acrylate having such a functional group is contained, the adhesion between the cured product and the substrate tends to be improved.
  • monofunctional (meth)acrylates represented by the above formula (7) include lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -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.
  • 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.
  • 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.
  • 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.
  • (meth)acrylate group-containing polyrotaxanes and (meth)acrylate group-containing silsesquioxane compounds are also preferably used.
  • Polyrotaxane having a (meth)acrylate group 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 radically polymerizable groups are introduced into the side chains of cyclic molecules. The radically 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 radically polymerizable groups.
  • the modification ratio can be calculated by (number of moles of polymerizable groups introduced) / (number of moles of total OH groups in the 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 95 mol% or less.
  • 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.
  • cyclodextrin rings include ⁇ -isomers (inner ring diameter 0.45-0.6 nm), ⁇ -isomers (inner ring diameter 0.6-0.8 nm), and ⁇ -isomers (inner ring diameter 0.8-0.95 nm), with ⁇ -cyclodextrin rings and ⁇ -cyclodextrin rings being preferred, and ⁇ -cyclodextrin rings being most preferred.
  • 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 0.001-0.6, more preferably in the range of 0.002-0.5, and most preferably in the range of 0.003-0.4.
  • radical polymerizable group a (meth)acryloyl group is preferred, taking into consideration factors such as reactivity with other polymerizable monomers. There are no particular restrictions on the number of radical polymerizable groups, and it is preferable to have 0 to 5,000 groups per molecule.
  • the (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.
  • q is the degree of polymerization and is an integer from 3 to 100.
  • the multiple R23s may be the same or different and are each 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. At least one R23 among the multiple R23s is a radical polymerizable group or an organic group containing a radical polymerizable group.
  • examples of the radical polymerizable group or organic group containing a radical polymerizable group represented by R 23 include a (meth)acryloyl group; organic groups having a (meth)acryloyl group such as a (meth)acryloyloxypropyl group or a (3-(meth)acryloyloxypropyl)dimethylsiloxy group; an allyl group; organic groups having an allyl group such as an allylpropyl group or an allylpropyldimethylsiloxy group; a vinyl group; and organic groups having a vinyl group such as a vinylpropyl group or a vinyldimethylsiloxy group.
  • At least one of R 23 is an organic group having a (meth)acryloyl group.
  • the curable composition for the protective layer 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.
  • the curable composition for the protective layer contains a photopolymerization initiator.
  • the proportion of the photopolymerization initiator in the curable composition for the 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.
  • photopolymerization initiator any known photopolymerization initiator can be used without any restrictions.
  • Specific examples of photopolymerization initiators that can be used include the following:
  • Acetophenone compounds 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, ⁇ -Dicarbonyl compounds: 1,2-diphenylethanedione, methylphenylglycoxylate, Acylphosphine oxide compounds: 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, etc.
  • the curable composition for the protective layer may further contain additives, etc.
  • 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.
  • the curable composition for the protective layer can further contain inorganic oxide microparticles.
  • inorganic oxide microparticles By incorporating inorganic oxide microparticles, the scratch resistance of the resulting protective layer can be further improved.
  • silica is used as the inorganic oxide microparticles.
  • microparticles made of an inorganic oxide or composite inorganic oxide containing at least one element selected from the group consisting of Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W, and Ce particularly inorganic oxide microparticles or composite inorganic oxide microparticles containing at least one element selected from the group consisting of Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, and W.
  • Inorganic oxide microparticles with a primary particle diameter of approximately 1 to 300 nm as observed by transmission electron microscope (TEM) are suitable for use.
  • Microparticles of this size are typically used in the form of a dispersion in an organic solvent as a dispersant.
  • organic solvent 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 the dispersion medium are commercially available from Nissan Chemical Industries, Ltd., such as methanol silica sol, MA-ST-MS (dispersion medium: methanol), IPA-ST (dispersion medium: isopropanol), and PGM-ST (dispersion medium: propylene glycol monomethyl ether).
  • sols of composite inorganic oxide microparticles can also be used, such as the OZ series, OT series, and HT series manufactured by Nissan Chemical Industries, Ltd., and the Optolake series manufactured by JGC Catalysts and Chemicals Co., Ltd.
  • the curable composition for the protective layer preferably contains a leveling agent.
  • a surfactant can 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.
  • surfactants two or more types may be mixed together.
  • the curable composition for the protective layer preferably contains at least one selected from the group consisting of UV absorbers, UV stabilizers, and antioxidants.
  • the group consisting of UV absorbers, UV stabilizers, and antioxidants for example, BASF's "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,” “Irganox PS 802 FL,” “Irganox 5057,” and “Irganox 113" are examples.
  • the amount of the leveling agent blended 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.
  • the blending amount of the ultraviolet absorber, ultraviolet stabilizer, and antioxidant is, 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% by mass or less, and more preferably 100 ppm by mass or less.
  • 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.
  • the primer layer contains, for example, a polyurethane resin.
  • the primer layer may be a moisture-curing urethane resin.
  • 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.
  • the hard coat layer covers, for example, at least a part of the surface of the protective layer, and preferably covers the entire surface.
  • the hard coat layer contains a silicon-containing compound such as an organic silane or an inorganic silane, and an inorganic oxide.
  • a silicon-containing compound such as an organic silane or an inorganic silane
  • an inorganic oxide Materials with high refractive indexes, such as titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), and cerium oxide (CeO 2 ), are used as the inorganic oxide.
  • These inorganic oxides have ultraviolet absorption capabilities. Therefore, lenses equipped with a hard coat layer containing these inorganic oxides are less likely to discolor.
  • 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.
  • the Vickers hardness is obtained using a method in accordance with Japanese Industrial Standards (JIS) Z 2244-2009: Micro Vickers Hardness Test.
  • a laminate is used as the sample, which includes an optical substrate, an optical substrate, an optical substrate, a functional layer, and a protective layer, and the hard coat layer is laminated on the protective layer.
  • the laminate in which the optical substrate, primer layer, functional layer, protective layer, and hard coat layer are laminated in this order will also be referred to as the third laminate.
  • 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 greater.
  • the Bayer value B3 of the hard coat layer is preferably 4.2 or greater, more preferably 4.4 or greater, and even more preferably 4.5.
  • the Bayer value can be measured using a Bayer abrasion tester manufactured by Colts Laboratories.
  • the third laminate is used as a sample to measure the Bayer value B3 of the hard coat layer.
  • the anti-reflection film is a film that prevents reflection of light by interference.
  • the anti-reflection film covers at least a part of the surface of the hard coat layer, and preferably covers the entire surface.
  • the anti-reflection film has a multilayer structure in which a high-refractive index film with a relatively high refractive index and a low-refractive index film with a low refractive index are stacked.
  • the low-refractive index film is made of, for example, silicon dioxide (SiO 2 ) with a refractive index of approximately 1.43 to 1.47.
  • the high-refractive index film is made of a material with a refractive index higher than that of 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 ), and mixtures thereof (e.g., indium tin oxide (ITO)).
  • ZrO 2 zirconium oxide
  • 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.
  • a primer layer-forming composition is applied to one main surface of the optical substrate, and the coating is dried to form a primer layer. Formation of the primer layer may be omitted.
  • 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, alpha rays, beta rays, gamma rays, active energy rays such as LED, heat, or both, to obtain a first laminate provided with a functional layer.
  • 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, UV light with a wavelength of 365 nm to 420 nm and an intensity of 50 to 1500 mW/ cm2 for 0.5 to 5 minutes.
  • 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 then irradiated with ultraviolet light, alpha rays, beta rays, gamma 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, UV light with a wavelength of 365 nm to 420 nm and an intensity of 50 to 1,500 mW/ cm2 for 5 seconds to 1 minute.
  • the second laminate is immersed in a curable composition for forming a hard coat layer, for example, to form a coating film.
  • the optical substrate on which this coating film has been formed is heated to obtain a third laminate provided with a hard coat layer.
  • the heating temperature is, for example, 80°C or higher and 150°C or lower.
  • the heating time is, for example, 0.5 hours or higher and 5 hours or lower.
  • the formation of the hard coat layer may be omitted.
  • An additional layer such as an anti-reflection film, an anti-fogging layer, or a water-repellent film, may be provided on the hard coat layer of the third laminate.
  • the laminate according to the embodiment 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.
  • the laminate according to the embodiment is particularly suitable for use in photochromic lenses.
  • Photochromic lenses are suitable for eyeglass lenses such as sunglasses.
  • 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)
  • 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 polycarbonated diol 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)
  • KBM503 ⁇ -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)
  • Quaternary (meth)acrylate M-PTMG100 Polytetramethylene glycol dimethacrylate (average molecular weight 1136)
  • TMPT-20E ethoxylated trimethylolpropane trimethacrylate (average molecular weight 1218)
  • the resulting silsesquioxane monomer (S21) was analyzed by gel permeation chromatography (GPC) and found to have a number average molecular weight of 3,000.
  • Photochromic compound PC1 A compound represented by the following formula.
  • PC2 A compound represented by the following formula. In the formula below, Me represents a methyl group.
  • PC3 A compound represented by the following formula. In the formula below, Me represents a methyl group. Pr represents a propyl group.
  • PC4 A compound represented by the following formula:
  • PC5 A compound represented by the following formula:
  • PC6 A compound represented by the following formula:
  • PCF1 A composition consisting of 0.4 parts by weight of PC1, 1.1 parts by weight of PC2, 1.7 parts by weight of PC3, 0.8 parts by weight of PC4, 0.3 parts by weight of PC5, and 0.2 parts by weight of PC6.
  • PI phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (manufactured by IGM, Omnirad 819)
  • PII 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM, Omnirad TPO)
  • thiourethane-based plastic lens with 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 solution of sodium hydroxide at 50°C for 5 minutes, and then thoroughly washed with distilled water.
  • 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.
  • a moisture-curing primer product name: TR-SC-P, manufactured by Tokuyama Corporation
  • the functional layer curable composition (2 g) was spin-coated onto the moisture-curable primer layer of the optical substrate at a rotation speed of 100 rpm for 30 seconds, followed by 1000 rpm for 10 to 20 seconds to a film thickness of 40 ⁇ m.
  • the lens on whose surface the functional layer curable composition was coated was then irradiated with light for 40 seconds using an LED lamp (with a peak wavelength of 405 nm) with an output of 900 mW/cm 2 in a nitrogen gas atmosphere, polymerizing the functional layer curable composition.
  • the resulting mixture was then further heated at 90 ° C for 1 hour to obtain a first laminate PL1 in which a primer layer and a 40 ⁇ m-thick photochromic resin layer were laminated on the optical substrate.
  • 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.
  • Example 1 Preparation of curable composition AP1 for protective layer>
  • a curable composition for protective layer AP1 was prepared by mixing 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.
  • this composition is also referred to as curable composition for protective layer AP1.
  • the photochromic resin layer of the first laminate obtained in the same manner as in Comparative Example 1 was spin-coated with 2 g of protective layer curable composition AP1 by spin coating at 100 rpm for 10 to 60 seconds, followed by 1200 rpm for 10 to 60 seconds to form a coating film.
  • the lens was then irradiated with light for 30 seconds using a metal halide lamp with an output of 200 mW/ cm2 in a nitrogen gas atmosphere to cure the coating.
  • a second laminate was obtained in which a protective layer was formed on the photochromic resin layer.
  • the protective layer had a thickness of 10 ⁇ m.
  • 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 protective layer curable composition shown in Table 1 was used instead of the protective layer curable composition AP1.
  • the numbers in parentheses shown in Table 1 indicate the blending amount (parts by mass) of each component.
  • the thickness of the protective layer was measured using the same method as above using the second laminates obtained in the examples and comparative examples. The results are shown in Table 2.
  • 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.
  • the Vickers hardness of the protective layer was measured using the same method as above using the second laminates obtained in the examples and comparative examples. The results are shown in Table 2.
  • Bayer value measurement The Bayer value of the protective layer of the second laminate obtained in Example 1 was measured using 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 using the second laminate obtained in the examples and comparative examples in the same manner as above. The results are shown in Table 2.
  • 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 (300W) SHL-100 manufactured by Hamamatsu Photonics, which has an illuminance of 50,000 lux at the sample and an irradiance value specified in ISO 8980-3, as the irradiation light source, and the photochromic properties of the laminate were measured.
  • Each photochromic property was evaluated by the following method.
  • the luminous transmittance at 23°C and 35°C of the first laminate or second laminate obtained in the Examples and Comparative Examples was measured by the following method.
  • the laminate was irradiated with the above-mentioned light (light having an illuminance of 50,000 lux at the sample and an irradiance value specified in ISO 8980-3) for 300 seconds at 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 at the time of 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.
  • 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.
  • the difference [ ⁇ (300) - ⁇ (0)] between the absorbance ⁇ (300) after 300 seconds of irradiation at the maximum absorption wavelength and the absorbance ⁇ (0) at the maximum absorption wavelength without irradiation was determined.
  • 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 upon 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.
  • the yellowness index was evaluated before and after an accelerated deterioration test. Specifically, 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. The yellowness index of the laminate was then evaluated before and after the test, measuring the yellowness index (YI) before the test and the yellowness index (YI96) after the test, and the value of the yellowness index ⁇ YI (YI96-YI) was calculated. The smaller the value, the higher the durability. The results are shown in Table 2.
  • 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.
  • R 12 and R 13 each independently represent a hydrogen atom or a methyl group; j and k are each independently an integer of 0 or more, and j+k has an average value of 8 or more.
  • 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;
  • R1 and R7 are each independently a hydrogen atom or a methyl group
  • R2 and R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R3 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R4 is a linear or branched alkylene group having 3 to 10 carbon atoms which may have a substituent
  • a and e each independently represent 0 to 10
  • b and d each independently represent 0 to 20
  • c is a number between 2 and 100 and is greater than each of a, b, d, and e.
  • a lens comprising the laminate according to any one of [1] to [15].

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  • Laminated Bodies (AREA)

Abstract

La présente divulgation aborde le problème consistant à fournir : un stratifié ayant un excellent aspect, une excellente dureté et une excellente performance d'un colorant fonctionnel ; un article optique ; une lentille ; des lunettes ; et une composition durcissable pour une couche de protection. À cet effet, un mode de réalisation de la présente invention concerne un stratifié. Le stratifié comprend un substrat optique, une couche fonctionnelle et une couche de protection. La couche fonctionnelle est située sur le substrat optique. La couche fonctionnelle contient un colorant fonctionnel et une résine. La couche de protection recouvre au moins une partie de la couche fonctionnelle. La couche de protection comprend un corps durci d'une composition durcissable pour une couche de protection. La composition durcissable pour une couche de protection contient un premier (méth) acrylate, un deuxième (méth) acrylate, un troisième (méth) acrylate et un initiateur de photopolymérisation. Le premier (méth) acrylate a trois groupes (méth) acryloyle ou plus ayant une masse moléculaire relative de 550 ou moins. Le deuxième (méth) acrylate a deux groupes (méth) acryloyle. Le troisième (méth) acrylate a un groupe (méth) acryloyle ayant une masse moléculaire relative inférieure ou égale à 300.
PCT/JP2025/022614 2024-06-27 2025-06-24 Stratifié, article optique, lentille, lunettes et composition durcissable pour couche de protection Pending WO2026004832A1 (fr)

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JP2024-104341 2024-06-27
JP2024104341 2024-06-27

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WO2026004832A1 true WO2026004832A1 (fr) 2026-01-02

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008825A1 (fr) * 2011-07-11 2013-01-17 株式会社トクヤマ Composition photochromique polymérisable
WO2019189855A1 (fr) * 2018-03-30 2019-10-03 ホヤ レンズ タイランド リミテッド Article optique
JP2021107909A (ja) * 2019-12-27 2021-07-29 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ フォトクロミック物品の保護層形成用重合性組成物、フォトクロミック物品および眼鏡
WO2021172512A1 (fr) * 2020-02-27 2021-09-02 株式会社トクヤマ Article optique photochrome
WO2021201166A1 (fr) * 2020-03-31 2021-10-07 ホヤ レンズ タイランド リミテッド Composition polymérisable pour article optique, article optique et lunettes
JP2022135955A (ja) * 2021-03-04 2022-09-15 ホヤ レンズ タイランド リミテッド フォトクロミック物品の製造方法
WO2024128158A1 (fr) * 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013008825A1 (fr) * 2011-07-11 2013-01-17 株式会社トクヤマ Composition photochromique polymérisable
WO2019189855A1 (fr) * 2018-03-30 2019-10-03 ホヤ レンズ タイランド リミテッド Article optique
JP2021107909A (ja) * 2019-12-27 2021-07-29 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ フォトクロミック物品の保護層形成用重合性組成物、フォトクロミック物品および眼鏡
WO2021172512A1 (fr) * 2020-02-27 2021-09-02 株式会社トクヤマ Article optique photochrome
WO2021201166A1 (fr) * 2020-03-31 2021-10-07 ホヤ レンズ タイランド リミテッド Composition polymérisable pour article optique, article optique et lunettes
JP2022135955A (ja) * 2021-03-04 2022-09-15 ホヤ レンズ タイランド リミテッド フォトクロミック物品の製造方法
WO2024128158A1 (fr) * 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes

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