WO2024018902A1 - 積層体、光学物品、レンズ、及び眼鏡 - Google Patents

積層体、光学物品、レンズ、及び眼鏡 Download PDF

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Publication number
WO2024018902A1
WO2024018902A1 PCT/JP2023/025033 JP2023025033W WO2024018902A1 WO 2024018902 A1 WO2024018902 A1 WO 2024018902A1 JP 2023025033 W JP2023025033 W JP 2023025033W WO 2024018902 A1 WO2024018902 A1 WO 2024018902A1
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Prior art keywords
group
base material
resin
laminate
compound
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Ceased
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PCT/JP2023/025033
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English (en)
French (fr)
Japanese (ja)
Inventor
康智 清水
力宏 森
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Tokuyama Corp
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Tokuyama Corp
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Priority to JP2024535014A priority Critical patent/JPWO2024018902A1/ja
Priority to EP23842827.0A priority patent/EP4560367A4/en
Priority to US18/993,219 priority patent/US20250355282A1/en
Priority to CN202380054156.5A priority patent/CN119604790A/zh
Publication of WO2024018902A1 publication Critical patent/WO2024018902A1/ja
Priority to MX2025000689A priority patent/MX2025000689A/es
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • G02C7/102—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
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • G02C7/108—Colouring materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
    • G02C2202/16—Laminated or compound lenses

Definitions

  • the present invention relates to a laminate, an optical article, a lens, and glasses.
  • Plastic glasses are glasses that use plastic lenses.
  • Plastic lenses are manufactured, for example, by subjecting semi-finished lenses, which are semi-finished products, to various processes.
  • a functional layer such as a hard coat layer or an antireflection film is provided on the convex surface of the semi-finished lens. Further, the concave back surface of the semi-finished lens is subjected to cutting and polishing processing.
  • a photochromic lens is obtained by applying a photochromic compound to a plastic lens.
  • a photochromic compound is a compound that can reversibly generate two or more isomers having different light absorption spectra by the action of light.
  • methods for manufacturing photochromic lenses include a kneading method in which a photochromic compound is dispersed in the matrix of a semi-finished lens, and a lamination method in which a layer containing a photochromic compound is provided on the surface of a semi-finished lens. .
  • the binder sheet method is a method for manufacturing semi-finished lenses by integrating a binder sheet in which a resin layer containing a photochromic compound is sandwiched between two optical sheets with a lens base material.
  • a binder sheet is placed in a mold and a thermoplastic resin is injection molded onto the binder sheet, thereby obtaining a semi-finished lens.
  • semi-finished lenses can be manufactured using self-standing articles containing photochromic compounds, so compared to the kneading method and lamination method, production efficiency tends to be higher and mass production is easier. .
  • An object of the present invention is to provide a laminate that has excellent adhesion to an optical element substrate and shape stability, and optical articles, lenses, and eyeglasses that include this laminate.
  • the present disclosure relates to a laminate.
  • the laminate includes a first base material, a second base material, an adhesive layer, and a coat layer.
  • the first base material and the second base material contain polyvinyl alcohol resin or cellulose resin.
  • the adhesive layer is interposed between the first base material and the second base material to adhere them.
  • the coating layer covers at least a portion of the surface of at least one of the first base material and the second base material, and contains resin.
  • the resin includes at least one selected from the group consisting of epoxy resin, urethane resin, and acrylic resin.
  • the present disclosure also relates to optical articles.
  • the optical article includes the laminate described above.
  • the present disclosure also relates to lenses.
  • the lens includes the optical article described above.
  • the present disclosure also relates to eyeglasses.
  • the glasses include the above lenses.
  • a laminate with excellent adhesion to an optical element substrate and shape stability, and optical articles, lenses, and eyeglasses including this laminate are provided.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate according to an embodiment.
  • FIG. 1 is a cross-sectional view schematically showing an example of an optical article according to an embodiment.
  • FIG. 1 is a perspective view schematically showing an example of eyeglasses according to an embodiment.
  • a laminate includes a first base material, a second base material, an adhesive layer, and a coat layer.
  • the first and second base materials contain polyvinyl alcohol resin or cellulose resin.
  • the adhesive layer is interposed between the first base material and the second base material to adhere them.
  • the coating layer covers at least a portion of the surface of at least one of the first base material and the second base material, and contains resin.
  • the resin includes at least one selected from the group consisting of epoxy resin, urethane resin, and acrylic resin.
  • the laminate according to the embodiment may be used, for example, as the above-mentioned binder sheet, and may be integrated with an optical element base material such as a lens base material.
  • a binder sheet using first and second base materials containing a polyvinyl alcohol resin or a cellulose resin is integrated with a thermosetting resin by, for example, a cast polymerization method.
  • the temperature of the thermosetting resin composition in the cast polymerization method is lower than the temperature of the thermoplastic resin composition for injection molding. Therefore, in an optical article produced by cast polymerization, the adhesion between the binder sheet and the optical element substrate may be lower than the adhesion between the binder sheet and the optical element substrate in an optical article produced by injection molding.
  • a coat layer is provided on at least one surface of the first and second base materials. Since this coat layer contains resin such as epoxy resin, urethane resin, and acrylic resin, it has better adhesion to the optical element base material than the first and second base materials.
  • the binder sheet may be subjected to shape processing, such as being curved to match the shape of the lens. Since polyvinyl alcohol resin has many hydroxyl groups on its surface, its film is easily affected by moisture in the air. Therefore, binder sheets used for base materials containing polyvinyl alcohol resin tend to have low shape stability. Since the laminate according to the embodiment has the coating layer, it is possible to suppress moisture in the air from adhering to at least one of the first and second base materials. Therefore, the laminate according to the embodiment has excellent shape stability compared to a laminate that does not have a coat layer.
  • the laminate according to the embodiment can be used as a binder sheet, as described above.
  • the laminate according to the embodiment can be used particularly as a functional sheet in which a functional dye such as a photochromic compound is blended in the adhesive layer.
  • the thickness of the laminate according to the embodiment is preferably 100 ⁇ m or more, more preferably 150 ⁇ m or more, and even more preferably 200 ⁇ m or more. As the thickness of the laminate increases, its shape stability tends to increase. Although there is no particular upper limit to the thickness of the laminate, one example is 1000 ⁇ m or less, and another example is 500 ⁇ m or less.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate.
  • the laminate 1 shown in FIG. 1 includes a first base material 2, a second base material 3, an adhesive layer 4 interposed between them, a first coat layer 5 covering the first base material 2, and a first base material 3. 2 and a second coat layer 6 that covers the base material 3 .
  • At least one of the first coat layer and the second coat layer may cover the side surface of the laminate 1. In this case, the first coat layer and the second coat layer may be integrated.
  • the first and second base materials include polyvinyl alcohol (PVA) resin or cellulose resin.
  • the base material may be composed only of PVA resin or cellulose resin, or may contain other resins.
  • PVA polyvinyl alcohol
  • cellulose resin for example, acetyl cellulose such as triacetyl cellulose and diacetyl cellulose may be used, and propyl cellulose such as tripropyl cellulose and dipropyl cellulose may be used.
  • examples of other resins include polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like.
  • the cellulose resin of the present invention can be used without particular limitation, but one with a luminous transmittance higher than 92.5% is preferable.
  • the base material may be unstretched, uniaxially stretched, or biaxially stretched.
  • the stretching direction may be any of the machine flow direction (MD) of the unstretched film, a direction perpendicular thereto (TD), and a direction oblique to the machine flow direction.
  • MD machine flow direction
  • TD direction perpendicular thereto
  • the unstretched sheet is a sheet that has not been stretched
  • the uniaxially stretched sheet is a sheet that has been stretched in one of the above directions.
  • a biaxially stretched sheet is one that has been stretched in two of the above-mentioned stretching directions. It may also be an axially stretched sheet. In the case of biaxially stretched sheets, those stretched in MD and TD are generally preferred.
  • the stretching ratio is preferably 1.5 to 8 times.
  • the average degree of polymerization of the PVA resin is, for example, 100 or more and 10,000 or less, preferably 1,500 or more and 8,000 or less, and more preferably 2,000 or more and 5,000 or less.
  • the average degree of polymerization of the PVA resin is determined by a method based on Japanese Industrial Standards (JIS) K6726; 1994.
  • PVA resin may contain boric acid. Boric acid is used as a crosslinking agent to crosslink PVA.
  • the boric acid content of the PVA resin is, for example, 1% by mass or more and 20% by mass or less, preferably 3% by mass or more and 18% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. .
  • This boric acid content can be calculated by inductively coupled plasma (IPC) emission spectrometry. Specifically, first, the base material is dissolved in an aqueous nitric acid solution to obtain a solution. IPC analysis is performed using this solution to calculate the boron content. This boron content is converted into boric acid content.
  • IPC inductively coupled plasma
  • the base material may be a polarizing film having polarizing properties.
  • at least one of the first and second base materials may be a polarizing film.
  • the polarizing base material preferably has a luminous transmittance of 10% or more and 80% or less, and a polarization degree of 30% or more and 99.9% or less.
  • the polarizing base material contains a dichroic substance.
  • Dichroic substances include iodine and dichroic dyes.
  • the dichroic dye may be azo-based or anthraquinone-based. Specific examples of dichroic dyes include chloranthine fast red (C.I. 28160), Congo red (C.I. 22120), brilliant blue B (C.I. 24410), benzopurpurin (C.I. 23500), Chlorazole Black BH (C.I. 22590), Direct Blue 2B (C.I. 22610), Diamine Green (C.I. 30295), Chrysophenine (C.I. 24895), Sirius Yellow (C.I.
  • the thickness of the base material is, for example, 10 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the second base material may be the same as or different from the thickness of the first base material.
  • the adhesive layer may contain at least one selected from the group consisting of polyurethane resin, polyurethane urea resin, polythiourethane resin, and polythiourethane urea resin.
  • the adhesive layer may contain a functional dye such as a photochromic compound.
  • the adhesive layer may contain a cured product of the adhesive composition described below.
  • the thickness of the adhesive layer is, for example, 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the adhesive layer may be thinner or thicker than the thickness of the first and second base materials.
  • the adhesive composition contains a functional dye and a polymeric component.
  • the polymeric component becomes the matrix of the adhesive layer.
  • the polymerization component includes a second prepolymer or first polymer and a second prepolymer or third prepolymer.
  • the adhesive composition includes a first combination of a polymer component including a second prepolymer and a functional dye, and a second combination of a polymer component and a functional dye including a first polymer and a second prepolymer.
  • a fourth combination may be included.
  • the functional dye includes, for example, at least one selected from the group consisting of photochromic compounds, ultraviolet absorbers, blue light absorbers, infrared absorbers, and electromic compounds.
  • the photochromic compound for example, at least one selected from the group consisting of chromene compounds, fulgide compounds, and spirooxazine compounds is used.
  • a chromene compound includes a compound having a 1-benzopyran skeleton, a spiropyran compound having a spiropyran skeleton, and a naphthopyran compound having a naphthopyran skeleton.
  • Naphthopyran compounds include indenonaphthopyran compounds having an indenonaphthopyran skeleton.
  • the chromene compound preferably includes an indenonaphthopyran compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.
  • a cured product containing a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton tends to have excellent durability.
  • the indenonaphthopyran compound preferably contains a compound represented by the following formula (IIIa).
  • the Z ring is a substituted or unsubstituted spiro ring in which the 13th-position carbon atom is a spiro atom.
  • the Z ring may form an aliphatic ring, a fused polycyclic ring, a heterocyclic ring, or a heteroaromatic ring together with the carbon atom at the 13th position. It may be formed.
  • the Z ring is preferably an aliphatic ring having 5 to 16 carbon atoms. More preferably, the aliphatic ring has an alkyl group having 1 to 3 carbon atoms as a substituent.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 each independently represent a hydrogen atom, a hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an alkyl group, Cycloalkyl group, haloalkyl group, alkoxy group, amino group, substituted amino group, heterocyclic group that may have a substituent, halogen atom, alkylthio group, arylthio group that may have a substituent, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, aralkyl group that may have a substituent, aralkoxy group that may have a substituent, aryloxy group that may have a substituent, substituent An aryl group that may have a substituent, a heteroaryl group that may have a substituent, a thiol group, an alk
  • the number of carbon atoms in the alkyl group is preferably 1 to 10.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and hexyl.
  • the haloalkyl group preferably has 1 to 10 carbon atoms.
  • the haloalkyl group is preferably an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom.
  • suitable haloalkyl groups include trifluoromethyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, and bromomethyl.
  • the number of ring carbon atoms in the cycloalkyl group is preferably 3 to 8.
  • Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Note that the cycloalkyl group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.
  • the number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6.
  • suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.
  • the amino group is a primary amino group (-NH 2 ).
  • a substituted amino group is a secondary or tertiary amino group in which one or two hydrogen atoms are substituted.
  • substituents contained in the substituted amino group include alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 7 carbon atoms, and 6 carbon atoms. Examples thereof include an aryl group having 1 to 14 carbon atoms, a heteroaryl group having 4 to 14 carbon atoms, and the like.
  • suitable amino groups include amino, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, and diphenylamino groups.
  • the number of atoms in the heterocyclic group is preferably 3 to 10.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Specific examples of the aliphatic heterocyclic group include morpholino group, piperidino group, pyrrolidinyl group, piperazino group, and N-methylpiperazino group. A specific example of the aromatic heterocyclic group includes an indolinyl group.
  • the heterocyclic group may have a substituent. Preferred substituents include alkyl groups having 1 to 10 carbon atoms. Suitable heterocyclic groups having substituents include, for example, 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, and 2,2,6,6-tetramethylpiperidino group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of carbon atoms in the alkylthio group is preferably 1 to 10.
  • alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, and t-butylthio.
  • the number of carbon atoms in the arylthio group is preferably 6 to 10.
  • arylthio groups include phenylthio, 1-naphthylthio, and 2-naphthylthio.
  • the number of carbon atoms in the alkylcarbonyl group is preferably 2 to 10.
  • alkylcarbonyl groups include acetyl and ethylcarbonyl groups.
  • the alkoxycarbonyl group preferably has 2 to 10 carbon atoms.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 11.
  • aralkyl groups include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl.
  • the number of carbon atoms in the aralkoxy group is preferably 7 to 11.
  • Examples of aralkoxy groups include benzyloxy and naphthylmethoxy groups.
  • the number of carbon atoms in the aryl group is preferably 6 to 12.
  • aryl groups include phenyl, 1-naphthyl, and 2-naphthyl.
  • the number of carbon atoms in the aryloxy group is preferably 6 to 12.
  • Examples of aryloxy groups include phenyloxy and naphthyloxy groups.
  • the number of carbon atoms in the heteroaryl group is preferably 3 to 12.
  • heteroaryl groups include thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, and benzopyrrolinyl groups.
  • the number of carbon atoms in the alkoxyalkylthio group is preferably 2 to 10.
  • Examples of the alkoxyalkylthio group include methoxymethylthio group, methoxyethylthio group, methoxy n-propylthio group, methoxy n-butylthio group, ethoxyethylthio group, and n-propoxypropylthio group.
  • the haloalkylthio group preferably has 1 to 10 carbon atoms.
  • Examples of haloalkylthio groups include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio.
  • the number of carbon atoms in the cycloalkylthio group is preferably 3 to 8.
  • Examples of cycloalkylthio groups include cyclopropylthio, cyclobutylthio, cyclopentylthio, and cyclohexylthio. Note that the cycloalkylthio group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms of the substituent.
  • the oligomer group includes an oligomer chain, a linking group, and a terminal group.
  • the oligomer chain may include at least one selected from the group consisting of polyalkylene oxide chains, polysiloxane chains, and polyester chains. Oligomer chains are divalent groups.
  • the repeating unit of the polyalkylene oxide chain is a linear or branched polyalkylene oxide having 1 to 10 carbon atoms.
  • the number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less.
  • Repeating units include, for example, -CH 2 O-, -CH 2 CH 2 O-, -CH(CH 3 )CH 2 O-, -CH 2 CH(CH 3 )O-, -CH 2 CH 2 CH 2 O -, or -CH 2 CH 2 C(CH 3 )O-.
  • the polysiloxane chain has, for example, dimethylsilyleneoxy (-Si(CH 3 ) 2 O-) as a repeating unit.
  • the number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less.
  • the number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less.
  • the linking group connects the photochromic compound and one end of the oligomer chain.
  • the linking group may be a divalent group or a divalent or more valent group.
  • the terminal group is bonded to the other end of the oligomer chain.
  • the terminal group is, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 2 to 30 carbon atoms. It is a branched alkenyl group.
  • the terminal group is a methyl group.
  • the oligomer group may include a first linking group, an oligomer chain, and a second linking group.
  • the first linking group and the second linking group may have the same structure or different structures.
  • the first linking group connects to the first photochromic compound.
  • the second linking group connects to the second photochromic compound.
  • the first photochromic compound and the second photochromic compound may have the same structure or different structures.
  • cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group may be unsubstituted or may have a substituent.
  • a cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group may have include a primary amino group, a secondary amino group, a tertiary amino group, and a cycloalkylthio group.
  • the substituents may be selected from the group consisting of: The number of substituents may be one or two or more.
  • R 13 and R 14 , R 14 and R 15 , and R 15 and R 16 are bonded to each other to form an aliphatic ring having 2 to 5 carbon atoms, an aliphatic ring having 1 to 4 carbon atoms containing 1 to 3 heteroatoms;
  • a group heterocycle, an aromatic ring having 4 to 12 carbon atoms, or an aromatic heterocycle having 3 to 11 carbon atoms containing 1 to 6 heteroatoms may be formed.
  • the aliphatic ring, aliphatic heterocycle, aromatic ring, and aromatic heterocycle may be unsubstituted or may have at least one substituent selected from the above substituent group.
  • the ultraviolet absorber has an absorption wavelength in the ultraviolet (UV) region of 400 nm or less.
  • the ultraviolet absorber may have a maximum absorption wavelength in a range from 330 nm to 380 nm, or may have a maximum absorption wavelength in a range from 250 nm to less than 330 nm.
  • An organic compound can be used as the ultraviolet absorber.
  • As the ultraviolet absorber for example, at least one selected from the group consisting of benzophenone derivatives, ethylhexyl methoxycinnamate, benzotriazole derivatives, and triazine derivatives is used.
  • the ultraviolet absorber preferably contains at least one selected from the group consisting of benzophenone derivatives, ethylhexyl methoxycinnamate, and benzotriazole derivatives.
  • the blue light absorber a compound having an absorption peak in the wavelength region higher than 400 nm and lower than 450 nm in the absorption spectrum can be used.
  • a compound is, for example, at least one selected from the group consisting of perylene compounds, porphyrin compounds, carotenoid compounds, and cyanine compounds.
  • the blue light absorber it is preferable to use a porphyrin compound, and it is more preferable to use a tetraazaporphyrin compound.
  • the high-energy visible light absorber is a blue light absorber that has an absorption peak in a wavelength range of 400 nm or more and 420 nm or less.
  • the high-energy visible light absorber those similar to the blue light absorber can be used.
  • the dye preferably contains a compound that has an absorption peak in the wavelength region of 540 nm or more and 650 nm or less, and more preferably contains a compound that has an absorption peak in the wavelength region of 550 nm or more and 600 nm or less in the absorption spectrum.
  • a compound that has an absorption peak in the wavelength region of 540 nm or more and 650 nm or less preferably contains a compound that has an absorption peak in the wavelength region of 550 nm or more and 600 nm or less in the absorption spectrum.
  • examples of such compounds include nitro compounds, azo compounds, anthraquinone compounds, threne compounds, porphyrin compounds, and rare earth metal compounds.
  • electromic compound examples include organic substances such as viologen, polymers having electromic properties, metal salt complexes having a d atom, and the like.
  • the proportion of the functional dye in the solid content of the adhesive composition is, for example, 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less.
  • the second prepolymer is a first prepolymer obtained by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound, and a second polyfunctional active hydrogen compound that is a chain extender. You can get it.
  • the second prepolymer has two or more iso(thio)cyanate groups.
  • the second prepolymer preferably has iso(thio)cyanate groups at both ends of the main chain.
  • the second prepolymer includes at least one selected from the group consisting of urethane prepolymer, urea prepolymer, urethaneurea prepolymer, thiourethane prepolymer, thiourea prepolymer, and thiourethane urea prepolymer.
  • the second prepolymer is chemically bonded to water in the atmosphere and hydroxyl groups on the surfaces of the first and second base materials, and is composed of a (thio)urethane resin, a (thio)urea resin, and a (thio)urethane urea resin. At least one type selected from the group is generated.
  • the number average molecular weight of the second prepolymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more.
  • the peel strength of the laminate tends to increase. That is, it is considered that the second prepolymers having a large number average molecular weight tend to become entangled with each other, thereby increasing the cohesive force and therefore the adhesive force.
  • the number average molecular weight of the second prepolymer is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. If the number average molecular weight of the second prepolymer is excessively large, the peel strength of the laminate tends to decrease. That is, the second prepolymer having a large number average molecular weight contains a small amount of iso(thio)cyanate groups per unit mass, and therefore tends to have a weak adhesive force.
  • the number average molecular weight of the second prepolymer can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • GPC analysis software "Empower Personal GPC Option" manufactured by Nippon Waters Co., Ltd. is used.
  • the softening point of the second prepolymer is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.
  • the softening point of the second prepolymer in one example it is 200°C or lower, and in another example it is 160°C or lower.
  • the softening point of the second prepolymer is measured, for example, by the following method.
  • the concentration of the second prepolymer in the solution is, for example, 34% by mass.
  • This solution is poured into a stainless steel container and dried at 40° C. for 10 hours, at 60° C. for 10 hours, and then in a vacuum dryer at 60° C. for 12 hours to prepare a test piece with a thickness of 1 mm.
  • the obtained test piece is analyzed using a thermomechanical measuring device (TMA120C, manufactured by Seiko Instruments) to obtain the softening point.
  • the measurement conditions are a temperature increase rate of 10° C./min, a measurement temperature range of 30 to 200° C., and a penetrating probe with a tip diameter of 0.5 mm.
  • the second prepolymer may occupy the main component.
  • the proportion of the second prepolymer in the solid content of the adhesive composition is, for example, 90% by mass or more and 99% by mass or less.
  • the proportion of the second prepolymer in the solid content of the adhesive composition is, for example, 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 40% by mass or less.
  • the first prepolymer is obtained by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound.
  • the first prepolymer has two or more iso(thio)cyanate groups.
  • the first prepolymer preferably has iso(thio)cyanate groups at both ends of the main chain.
  • the first prepolymer includes at least one selected from the group consisting of a urethane prepolymer, a urea prepolymer, a thiourethane prepolymer, and a thiourea prepolymer.
  • the first prepolymer becomes a raw material for the second prepolymer.
  • the number average molecular weight of the first prepolymer is preferably 500 or more and 10,000 or less, more preferably 1,000 or more and 5,000 or less.
  • the number average molecular weight of the first prepolymer can be measured in the same manner as the second prepolymer.
  • the first iso(thio)cyanate compound has two or more iso(thio)cyanate groups. It is preferable that the first iso(thio)cyanate compound has two iso(thio)cyanate groups. More preferably, the first iso(thio)cyanate compound is a diisocyanate compound containing two isocyanate groups.
  • the molar mass of the first iso(thio)cyanate compound is preferably 100 or more and 500 or less. When the first iso(thio)cyanate compound within this range is used, the second prepolymer and the first polymer having the desired number average molecular weights tend to be obtained.
  • the molar mass of the first iso(thio)cyanate compound is more preferably 150 or more and 300 or less.
  • the first iso(thio)cyanate compound includes at least one selected from the group consisting of aliphatic iso(thio)cyanate compounds, alicyclic iso(thio)cyanate compounds, and aromatic iso(thio)cyanate compounds.
  • the first iso(thio)cyanate compound is preferably an alicyclic iso(thio)cyanate compound.
  • As the first iso(thio)cyanate compound a single type may be used, or a plurality of types may be mixed and used.
  • aliphatic isocyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4,-trimethylhexamethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio) Examples include ethane.
  • alicyclic isocyanate compounds include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated diphenylmethane) diisocyanate), norbornane diisocyanate, 2,5-bis(isocyanatemethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatemethyl)-bicyclo[2,2,1]-heptane, etc. It will be done.
  • aromatic isocyanate compounds include xylene diisocyanate (o-, m-, p-), toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, Examples include 1,4-bis(isocyanatomethyl)cyclohexane and 4,4'-diphenylmethane diisocyanate.
  • aliphatic isothiocyanate compounds include hexamethylene diisothiocyanate, 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, and 1,6-diisothiocyanate.
  • alicyclic isothiocyanate compounds include isophorone diisothiocyanate, cyclohexane diisothiocyanate, 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6 -bis(isothiocyanatomethyl)norbornane, 3,5-bis(isothiocyanatomethyl)norbornane, norbornane diisocyanate, and the like.
  • aromatic isothiocyanate compounds include p-phenylene diisopropylidene diisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4 -diisothiocyanate toluene, xylene diisothiocyanate (o-, m-, p-), 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate, 1,1'-methylenebis(4-isothiocyanate) benzene), 1,1'-methylenebis(4-isothiocyanate 2-methylbenzene), 1,1'-methylenebis(4-isothiocyanate 3-methylbenzene), and the like.
  • the first polyfunctional active hydrogen compound has two or more active hydrogen groups. It is preferable that the first polyfunctional active hydrogen compound has two active hydrogen groups.
  • the active hydrogen group includes at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxy group, and a thiol group.
  • the first polyfunctional active hydrogen compound is, for example, a polyol compound containing two or more hydroxyl groups, a polyamine compound containing two or more amino groups, a dicarboxylic acid containing two carboxyl groups, and a polythiol compound containing two or more thiol groups. At least one selected from the group consisting of: As the first polyfunctional active hydrogen compound, a single type may be used, or a plurality of types may be mixed and used.
  • the first polyfunctional active hydrogen compound contains a polyol compound.
  • a polyol compound When a polyol compound is used, a first prepolymer having (thio)urethane bonds is obtained.
  • the repeating structural portion of the polyol compound can contribute to providing a matrix in the adhesive layer that is less likely to hinder the structural change of the photochromic compound.
  • the photochromic properties of the laminate tend to increase.
  • the number average molecular weight of the polyol compound is preferably 500 or more and 3000 or less. When a polyol compound having a number average molecular weight within this range is used, it is likely that the second prepolymer and first polymer having the desired number average molecular weight can be obtained.
  • the number average molecular weight of the polyol compound is more preferably 800 or more and 2000 or less.
  • the polyol compound may include at least one selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.
  • the polyol compound includes a polycarbonate polyol. When polycarbonate polyol is used, the adhesion of the laminate tends to increase.
  • Polycarbonate polyols can be obtained, for example, by monophosgenation of low-molecular polyols, or by transesterification of ethylene carbonate, diethyl carbonate, diphenyl carbonate, and the like.
  • low molecular weight polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5- Pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol,
  • polycarbonate polyols examples include the "Duranol (registered trademark)” series manufactured by Asahi Kasei Corporation, the “Kuraray Polyol (registered trademark)” series manufactured by Kuraray Co., Ltd., the “Plaxel (registered trademark)” series manufactured by Daicel Corporation, and the “Duranol (registered trademark)” series manufactured by Tosoh Corporation.
  • the Nipporan (registered trademark) series, the ETERNACOLL (registered trademark) series manufactured by UBE Corporation, etc. can be used.
  • Polycaprolactone polyol is obtained, for example, by ring-opening polymerization of ⁇ -caprolactone.
  • the polycaprolactone polyol the "Plaxel (registered trademark)" series manufactured by Daicel Corporation, etc. can be used.
  • a polyether polyol can be obtained, for example, by reacting a compound having two or more active hydrogen groups in the molecule with an alkylene oxide.
  • compounds having two or more active hydrogen-containing groups include water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, trimethylolpropane, hexanetriol, etc. can be mentioned.
  • the alkylene oxide include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran.
  • polyether polyols examples include the "Excenol (registered trademark)” series and “Emulstar (registered trademark)” series manufactured by AGC Corporation, and the “ADEKA Polyether” series manufactured by ADEKA Corporation.
  • a polyester polyol can be obtained, for example, by a condensation reaction between a polyhydric alcohol and a polybasic acid.
  • polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3, Examples include 3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, and trimethylolpropane.
  • polybasic acids examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, and the like.
  • polyester polyols examples include the "Polylite (registered trademark)” series manufactured by DIC Corporation, the “Nipporan (registered trademark)” series manufactured by Tosoh Corporation, and the “Maximol (registered trademark)” series manufactured by Air Water Performance Chemical Co., Ltd. can be used.
  • the polythiol compound may include at least one selected from the group consisting of aliphatic polythiols, aromatic polythiols, and polythiols containing a sulfur atom in addition to a mercapto group.
  • aliphatic polythiols examples include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6- Hexanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4 -dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, thiomalic acid bis(2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid acid (2-mercaptoethyl este
  • aromatic polythiols examples include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptobenzene).
  • polythiols containing sulfur atoms in addition to mercapto groups include bis(mercaptomethyl) sulfide, bis(mercaptoethyl) sulfide, bis(mercaptopropyl) sulfide, bis(mercaptomethylthio)methane, and bis(2-mercaptoethylthio).
  • the amount of the first polyfunctional active hydrogen compound is determined by the molar amount M11 of active hydrogen groups contained in the first polyfunctional active hydrogen compound and the molar amount M11 of iso(thio)cyanate groups contained in the first iso(thio)cyanate compound. It is preferable that the ratio M11/M12 with M12 is adjusted to be 0.30 or more and 0.90 or less. When the ratio M11/M12 is within the above range, a sufficient amount of at least one of urethane bonds and urea bonds is formed in the first prepolymer, and a flexible adhesive layer that does not easily inhibit structural changes of the photochromic compound is formed. Can be formed.
  • the ratio M11/M12 is preferably 0.40 or more and 0.850 or less, more preferably 0.50 or more and 0.80 or less.
  • the ratio S1/S2 of the mass S1 of the first polyfunctional active hydrogen compound and the mass S2 of the first iso(thio)cyanate compound is preferably 0.1 or more and 10 or less.
  • the ratio S1/S2 is preferably 0.8 or more and 5 or less, more preferably 1 or more and 4 or less.
  • the second polyfunctional active hydrogen compound has two or more active hydrogen groups.
  • the second polyfunctional active hydrogen compound reacts with the first prepolymer to produce a second prepolymer.
  • the second polyfunctional active hydrogen compound functions as a chain extender that connects the first prepolymers. It is preferable that the second polyfunctional active hydrogen compound has two active hydrogen groups.
  • the compounds mentioned for the first polyfunctional active hydrogen compound can be used.
  • the second polyfunctional active hydrogen compound contains a polyamine.
  • a polyamine When a polyamine is used, a second prepolymer having (thio)urethane urea bonds is obtained. When such a second prepolymer is used, the adhesion of the laminate tends to increase.
  • the molar mass of the polyamine is preferably 50 or more and 500 or less. When a polyamine having a molar mass within this range is used, a second prepolymer having a desired number average molecular weight tends to be obtained.
  • the molar mass of the polyamine is more preferably 50 or more and 300 or less.
  • Polyamines include diamines and triamines, and preferably include diamines.
  • polyamines examples include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, and 1,5-diaminopentane.
  • 1,6-diaminohexane piperazine, N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylcyclohexyl)methane, 1, 2-, 1,3- and 1,4-diaminocyclohexane, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4'-diphenylmethanediamine, N,N'-diethylethylenediamine, N,N'-dimethyl
  • Examples include ethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis(hexamethylene)triamine, and 1,2,5-pentanetriamine.
  • the polyamine preferably contains at least one selected from the group consisting of isophoronediamine, ethylenediamine, bis-(4-aminocyclohexyl)methane, and 1,6-diaminohexane.
  • the amount of the second polyfunctional active hydrogen compound is the ratio of the molar amount M13 of active hydrogen groups contained in the second polyfunctional active hydrogen compound to the molar amount M14 of iso(thio)cyanate groups contained in the first prepolymer. It is preferable that M13/M14 is adjusted to be 0.21 or more and 0.9 or less. When the ratio M13/M14 is within the above range, a sufficient amount of the second prepolymer is produced.
  • the ratio S3/S4 of the mass S3 of the second polyfunctional active hydrogen compound and the mass S4 of the first prepolymer is preferably 0.01 or more and 0.5 or less. When the ratio S3/S4 is within the above range, a second prepolymer having a sufficient amount of isocyanate groups per unit mass can be obtained.
  • the ratio S3/S4 is more preferably 0.05 or more and 0.3 or less.
  • the first polymer is obtained by reacting the second prepolymer with a monofunctional active hydrogen compound having one active hydrogen group.
  • the first polymer typically does not have iso(thio)cyanate groups.
  • the terminal end of the first polymer is modified with a non-reactive functional group.
  • the first polymer includes at least one selected from the group consisting of urethane polymer, urea polymer, urethaneurea polymer, thiourethane polymer, thiourea polymer, and thiourethane urea polymer.
  • the first polymer chemically bonds with the second prepolymer and/or the third prepolymer and the hydroxyl groups on the surfaces of the first and second base materials under high temperature to form a (thio)urethane resin and a (thio)urea resin. At least one selected from the group consisting of resin and (thio)urethane urea resin is produced.
  • the number average molecular weight of the first polymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. When a first polymer having a large number average molecular weight is used, the peel strength of the laminate tends to increase.
  • the number average molecular weight of the first polymer is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. If the number average molecular weight of the first polymer is excessively large, the peel strength of the laminate tends to decrease. This number average molecular weight can be measured in the same manner as the second prepolymer.
  • the softening point of the first polymer is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.
  • the softening point of the first polymer in one example it is 200°C or lower, and in another example it is 160°C or lower.
  • the softening point of the mixture can be measured in the same manner as for the second prepolymer.
  • the first polymer may be present as a mixture with the second prepolymer.
  • a mixture of the first polymer and the second prepolymer is obtained by adjusting the amount of monofunctional active hydrogen compound. That is, the ratio M5/M6 of the molar amount M6 of iso(thio)cyanate groups contained in the second prepolymer and the molar amount M5 of active hydrogen groups contained in the monofunctional active hydrogen compound is adjusted to be less than 1. By doing so, a mixture of the second prepolymer and the first polymer in which the iso(thio)cyanate group of the second prepolymer is protected with a monofunctional active hydrogen compound is produced.
  • the ratio M5/M6 is preferably 0.75 or more and 0.95 or less.
  • the number average molecular weight of this mixture is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. When a mixture with a high number average molecular weight is used, the peel strength of the laminate tends to increase.
  • the number average molecular weight of the mixture is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. If the number average molecular weight of the mixture is excessively large, the peel strength of the laminate tends to decrease. This number average molecular weight can be measured in the same manner as the second prepolymer.
  • the softening point of this mixture is preferably 90°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher.
  • the softening point of the mixture is high, the heat resistance of the laminate tends to improve, and the adhesion tends to further increase.
  • the softening point of the mixture in one example it is 200°C or lower, and in another example it is 160°C or lower.
  • the softening point of the mixture can be measured in the same manner as for the second prepolymer.
  • the proportion of the first polymer in the solid content of the adhesive composition is, for example, 75% by mass or more and 95% by mass or less.
  • the mixture of the first polymer and the second prepolymer may include a fourth prepolymer.
  • the fourth prepolymer is a compound in which a portion of the iso(thio)cyanate groups of the second prepolymer are protected with a monofunctional active hydrogen compound, and the remainder is not protected.
  • the fourth prepolymer may include one iso(thio)cyanate group and one monofunctional active hydrogen compound protecting group. Since the fourth prepolymer has an iso(thio)cyanate group, it can improve the adhesion of the laminate like the second prepolymer.
  • the proportion occupied by the first polymer is, in one example, 1% by mass or more and 40% by mass or less, and in another example, 10% by mass.
  • the content is 30% by mass or less.
  • the proportion occupied by the second prepolymer is, according to one example, 1% by mass or more and 40% by mass or less, and according to another example, the proportion occupied by the second prepolymer is 10% by mass or more and 30% by mass or less.
  • the proportion occupied by the fourth prepolymer is, according to one example, 1% by mass or more and 80% by mass or less, and according to another example, the proportion occupied by the fourth prepolymer is 40% by mass or more and 80% by mass or less.
  • the adhesive layer may be a cured adhesive composition containing a first polymer, a second prepolymer, and a fourth prepolymer, and may be a cured adhesive composition containing the first polymer and a fourth prepolymer. It may be the body.
  • a monofunctional active hydrogen compound has one active hydrogen group.
  • the monofunctional active hydrogen compound reacts with the iso(thio)cyanate groups of the second prepolymer to form the first polymer and terminate further reaction.
  • the active hydrogen group includes at least one selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and a thiol group.
  • Monofunctional active hydrogen compounds are, for example, from the group consisting of monool compounds containing one hydroxyl group, monoamine compounds containing one amino group, carboxylic acids containing one carboxyl group, and monothiol compounds containing one thiol group. Contains at least one selected type. As the monofunctional active hydrogen compound, a single type may be used, or a mixture of multiple types may be used.
  • the monofunctional active hydrogen compound is preferably a monoamine compound.
  • a monoamine compound When a monoamine compound is used, a first polymer having (thio)urea bonds is obtained.
  • the monofunctional active hydrogen compound preferably contains an amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety, as represented by the following formula (3).
  • An amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety can function as a hindered amine, thereby increasing the photostability of the laminate.
  • R 21 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 22 is an alkylene group having 1 to 3 carbon atoms.
  • a is 0 or 1.
  • the monofunctional active hydrogen compound is preferably 1,2,2,6,6-pentamethyl-4-aminopiperidine in which R 21 is a methyl group and a is 0.
  • the ratio S5/S6 of the mass S5 of the monofunctional active hydrogen compound to the mass S6 of the second prepolymer is preferably 0.001 or more and 0.100 or less. When the ratio S5/S6 is within the above range, a first polymer having a sufficient amount of isocyanate groups per unit mass can be obtained.
  • the ratio S5/S6 is more preferably 0.010 or more and 0.030 or less.
  • the third prepolymer is a compound having two or more iso(thio)cyanate groups obtained by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound. That is, the third prepolymer is a compound similar to the first prepolymer.
  • the third prepolymer chemically bonds with the first prepolymer and the hydroxyl groups on the surfaces of the first and second base materials under high temperature to form a (thio)urethane resin, a (thio)urea resin, and a (thio)urethane resin. At least one selected from the group consisting of urea resins is produced.
  • the proportion of the third prepolymer in the solid content of the adhesive composition is: For example, it is 5% by mass or more and 20% by mass or less.
  • the adhesive composition includes, for example, a polymerization catalyst, a polymerization initiator, an antistatic agent, an internal mold release agent, an antioxidant, a light stabilizer, an anti-coloring agent, a fluorescent dye, a dye, a pigment, a fragrance, a solvent, a leveling agent, and a resin modifier.
  • the adhesive composition contains at least one of an antioxidant and a leveling agent.
  • IRGANOX245 ethylenebis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-m -Toluyl] propionate], BASF Japan Co., Ltd.
  • IRGANOX1076 Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF Japan Co., Ltd.
  • IRGANOX1010 Pentaerythritol tetrakis [3-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], IRGANOX 1035, 1075, 104, 3790, 5057, 565 manufactured by BASF Japan Co., Ltd., etc. can be used.
  • silicone surfactants As the leveling agent, silicone surfactants, fluorine-containing surfactants, etc. can be used. Specifically, Dow Toray Industries, Ltd. L-7001, L-7002, L-7604, FZ-2123, DIC Corporation Megafac F-470, Megafac F-1405, Megafac F-479, 3M Fluorad FC-430 manufactured by Japan Co., Ltd., etc. can be used.
  • a hindered amine compound having a 2,2,6,6-tetramethyl-4-piperidyl skeleton 2,2,6,6-tetramethyl-4-piperidyl skeleton
  • commercially available ones can be used.
  • Product names include ADEKA STAB (registered trademark) LA series (LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-81, LA-82, etc.) manufactured by ADEKA Co., Ltd. ), TINUVIN (registered trademark) series (TINUVIN123, TINUVIN171, TINUVIN249, TINUVIN292, TINUVIN765, TINUVIN622SF, etc.) manufactured by BASF Japan Co., Ltd., Chimassorb (registered trademark) series (Chimassorb202 0FDL, Chimassorb944FDL), etc.
  • the proportion of the additive in the solid content of the adhesive composition is, for example, 0.1% by mass or more and 1% by mass or less.
  • the adhesive composition may contain an organic solvent to adjust its viscosity.
  • the organic solvent may include at least one selected from the group consisting of tetrahydrofuran, diethyl ketone, t-butyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, toluene, ethyl acetate, and cyclohexanone.
  • the proportion of the organic solvent is, for example, 30% by mass or more and 80% by mass or less.
  • the adhesive composition can be obtained, for example, by the following first to fourth manufacturing methods.
  • a first method for producing an adhesive composition includes reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer, and reacting the first prepolymer and a second polyfunctional hydrogen compound.
  • the method includes reacting a functionally active hydrogen compound to obtain a second prepolymer, and mixing the second prepolymer, a photochromic compound, and optional additives.
  • a second method for producing an adhesive composition includes reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer; reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a second prepolymer; reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a mixture of the first polymer and the second prepolymer; mixing the polymer, second prepolymer, photochromic compound, and optional additives.
  • a third method for producing an adhesive composition includes reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer and a third prepolymer; Reacting a polymer and a second polyfunctional active hydrogen compound to obtain a second prepolymer; Reacting the second prepolymer and a monofunctional active hydrogen compound to obtain a first polymer; and mixing a third prepolymer, a photochromic compound, and optional additives.
  • a fourth method for producing an adhesive composition includes reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer; reacting with a functionally active hydrogen compound to obtain a second prepolymer; and reacting the second prepolymer with a monofunctionally active hydrogen compound to obtain a mixture of the first polymer, the second prepolymer, and the fourth prepolymer. and mixing the first polymer, second prepolymer, fourth prepolymer, photochromic compound, and optional additives.
  • the reaction between the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound is preferably performed in the presence of an organic solvent.
  • an organic solvent those mentioned above can be used.
  • This reaction is preferably carried out under a nitrogen atmosphere. Further, this reaction is carried out, for example, at a reaction temperature of 60° C. or more and 150° C. or less, for 3 hours or more and 10 hours or less. This reaction is preferably carried out until the end point is confirmed by back titration of isocyanate groups.
  • the reaction between the first prepolymer and the second polyfunctional active hydrogen compound is preferably performed in the presence of an organic solvent.
  • an organic solvent those mentioned above can be used.
  • This reaction is preferably carried out under a nitrogen atmosphere. Further, this reaction is carried out, for example, at a reaction temperature of 10° C. or more and 30° C. or less for 0.1 hour or more and 5 hours.
  • the reaction between the second prepolymer and the monofunctional active hydrogen compound is preferably carried out in the presence of an organic solvent.
  • an organic solvent those mentioned above can be used.
  • This reaction is preferably carried out under a nitrogen atmosphere. Further, this reaction is carried out, for example, at a reaction temperature of -10° C. or more and 10° C. or less for 0.1 hour or more and 5 hours or less.
  • the coating layer covers at least a portion of the surface of at least one of the first and second base materials.
  • the coating layer preferably covers the surfaces of both the first and second base materials.
  • the coating layer preferably covers the entire surfaces of the first and second base materials.
  • the thickness of the coating layer is, for example, 5 ⁇ m or more.
  • the thickness of the coating layer is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 25 ⁇ m or more.
  • the thickness of the coat layer is preferably 100 ⁇ m or less, more preferably 75 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the coating layer contains at least one resin selected from the group consisting of epoxy resin, urethane resin, and acrylic resin. It is preferable that the coat layer contains an epoxy resin.
  • a coat layer containing an epoxy resin has excellent appearance and tends to have higher adhesion to the optical element substrate.
  • the type of resin contained in the coating layer can be confirmed by gas chromatography or Fourier transform infrared spectroscopy (FT-IR) analysis.
  • the surface of the coating layer preferably has at least one functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl group. Providing a coating layer having these functional groups on the surface tends to improve the adhesion to the optical element substrate.
  • FT-IR Fourier transform infrared spectroscopy
  • the coat layer can be formed, for example, by applying the following coat layer forming composition onto the surface of at least one of the first and second base materials and curing it.
  • the coating layer forming composition may contain at least one resin selected from the group consisting of epoxy resins, urethane resins, and acrylic resins, and an organic solvent that dissolves or disperses these resins.
  • the organic solvent is, for example, at least one selected from the group consisting of methyl ethyl ketone, toluene, methanol, ethanol, normal propanol, isopropanol, acetone, phenol, diethyl ketone, and xylene.
  • the proportion of the resin is, for example, 10% by mass or more and 50% by mass or less, preferably 20% by mass or more and 30% by mass or less.
  • the coating layer forming composition may further contain a first compound having at least one polymerizable functional group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.
  • a first compound having at least one polymerizable functional group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.
  • the first compound having a (meth)acryloyl group is, for example, a (meth)acrylate having one or more (meth)acryloyl groups.
  • the first compound may be an acrylate, a methacrylate, or a mixture thereof. It is preferable that the first compound has a methacryloyl group.
  • (meth)acrylates include methacrylic acid, acrylic acid, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, In addition to octyl acrylate, lauryl acrylate, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, etc., the following formula (11 ) Compounds having an epoxy group shown in the following are mentioned.
  • R 13 and R 14 are each a hydrogen atom or a methyl group.
  • R 15 and R 16 are each an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxy group or a group represented by the following formula (12).
  • h and i are each a number from 0 to 20 as an average value.
  • examples of the alkylene group represented by R 15 and R 16 include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, and a tetramethylene group.
  • the compound represented by the above formula (11) may be obtained in the form of a mixture of molecules having different molecular weights. Therefore, h and i are shown as average values.
  • Examples of the compound represented by the above formula (11) include glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl methacrylate, and polyethylene glycol glycidyl methacrylate with an average molecular weight of 406.
  • polyethylene glycol glycidyl methacrylate with an average molecular weight of 538 polyethylene glycol glycidyl methacrylate with an average molecular weight of 1022
  • polypropylene glycol glycidyl methacrylate with an average molecular weight of 664 bisphenol A-monoglycidyl ether-methacrylate, 3-(glycidyl-2-oxyethoxy)-2- Hydroxypropyl methacrylate, glycidyl acrylate, glycidyloxymethyl acrylate, 2-glycidyloxyethyl acrylate, 3-glycidyloxypropyl acrylate, 4-glycidyloxybutyl acrylate, polyethylene glycol glycidyl acrylate with an average molecular weight of 406, polyethylene glycol glycidyl acrylate with an average molecular weight of 538 , polyethylene glycol glycidyl acrylate with an average molecular weight
  • the (meth)acrylate at least one selected from the group consisting of glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, and glycidyl acrylate may be used.
  • the first compound having a vinyl group or an allyl group is, for example, a compound having one or more of at least one of a vinyl group and an allyl group.
  • Examples of the first compound having a vinyl group or allyl group include methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, styrene, vinylcyclohexane, butadiene, 1,4-pentadiene, divinyl sulfide, divinyl sulfone, 1,2-divinylbenzene, 1,3-divinyl-1,1,3,3-tetramethylpropane disiloxane, diethylene glycol divinyl ether, divinyl adipate, divinyl sebacate, ethylene glycol divinyl ether, divinyl sulfoxide, divinyl persulfide, dimethyl divinyl silane, 1, 2,4-trivinylcyclohexane, methyltrivinylsilane, N-vinylpyrrolidone, ⁇ -methylstyrene and ⁇ -methylstyrene dimer, (vinyloxy)methanol g
  • the first compound includes methacrylic acid, acrylic acid, glycidyl methacrylate (GMA), glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, and 1, It is preferable to contain at least one member selected from the group consisting of 2-epoxy-4-vinylcyclohexane.
  • glycidyl methacrylate is preferably added to the coating layer forming composition containing the epoxy resin. When such a composition is used, a coat layer with excellent adhesion can be obtained.
  • the proportion of the first compound is, for example, 0.05% by mass or more and 5% by mass or less, preferably 0.1% by mass or more and 1% by mass or less.
  • the proportion occupied by the first compound may be 1% by mass or more and 20% by mass or less, 3% by mass or more and 15% by mass or less, or 5% by mass or more and 10% by mass or less.
  • the proportion occupied by the first compound is high, the adhesion of the coating layer tends to increase.
  • the proportion occupied by the first compound is low, the appearance of the laminate tends to improve.
  • a commercially available adhesive or surface treatment agent may be used as the coating layer forming composition.
  • a commercially available adhesive for example, the Aron Mighty (registered trademark) series manufactured by Toagosei Co., Ltd. is used.
  • the laminate according to the embodiment may further include a support.
  • the support may be located between the adhesive layer and the first or second base material, or between the first or second base material and the coating layer.
  • the support can further enhance the shape stability of the laminate.
  • the support may be colorless and transparent, white and transparent, or colored and transparent.
  • the support preferably contains at least one resin selected from the group consisting of, for example, polyethylene terephthalate, triacetylcellulose, polyamide, polycarbonate sheet, cellulose acetate butyrate, and (meth)acrylic.
  • the thickness of the support is preferably 50 ⁇ m or more, preferably 100 ⁇ m or more, and more preferably 200 ⁇ m or more. As the thickness of the support increases, the strength of the laminate tends to increase. Although there is no particular upper limit to the thickness of the support, one example is 1000 ⁇ m or less, and another example is 500 ⁇ m or less.
  • the method for manufacturing the laminate includes applying the above-described composition for forming a coat layer on the main surface of at least one of the first base material and the second base material, and curing the coating film to form a coat layer.
  • the adhesive composition described above is applied to the other main surface of the first base material and the second base material provided with the layer, or to the main surface of the first base material and the second base material not provided with the coat layer. obtaining a coating film, and laminating a second base material on the coating film.
  • first and second base materials are prepared.
  • a commercially available unstretched sheet of polyvinyl alcohol resin may be used, or a sheet that has been subjected to stretching treatment and dyeing treatment may be used.
  • the first and second base materials may be subjected to surface treatments such as etching treatment, alkali treatment, and corona treatment.
  • a coat layer forming composition is applied onto the main surface of one of the first base material and the second base material using, for example, a bar coater to form a coating film.
  • This coating film is dried, for example, at a temperature of 40° C. or higher and 70° C. for 1 minute or more and 1 hour or less. Note that the coating film may be provided on only one of the first base material and the second base material.
  • the dried coating film is cured by thermal polymerization to form a coat layer. Thermal polymerization may be carried out either before or after applying the adhesive composition on the other main surface of the first base material on which the coating layer is not provided. It is also possible to thermally polymerize the coat layer simultaneously with the heat treatment described below.
  • the thermal polymerization conditions are, for example, at a temperature of 40° C. or higher and 160° C. for 1 minute or more and 10 hours or less. If the heating temperature is set to an excessively high temperature, the first base material and the second base material may shrink.
  • the adhesive composition is applied to the other main surface of the first base material on which the coating layer is not provided, using, for example, a bar coater to form a coating film.
  • This coating film is dried, for example, at a temperature of 60° C. or more and 150° C. for 1 minute or more and 1 hour or less.
  • the second base material is laminated so that the main surface on which the coating layer of the second base material is not provided is in contact with the paint film so as to directly face the dried paint film, and the second base material is pasted together using, for example, a laminating roll. , get the structure.
  • an adhesive layer film may be formed by applying an adhesive composition onto a resin film such as polyethylene terephthalate, and curing the resulting coating film. A structure is obtained by peeling off the adhesive layer from this adhesive film and sandwiching it between first and second base materials.
  • the obtained structure is subjected to deaeration treatment.
  • the structure is left standing under a vacuum of 500 Pa, for example, at a temperature of 40° C. or more and 80° C. or less for 5 hours or more and 20 hours or less.
  • the degassing treatment may be performed under a vacuum of 15 Torr or less at a temperature range of 30° C. or higher and 60° C. or lower.
  • the structure after the deaeration treatment is subjected to a heat treatment.
  • degassing process may be omitted.
  • the structure without degassing is subjected to heat treatment.
  • humidification treatment may be performed instead of deaeration treatment.
  • the humidification treatment is performed, for example, at a temperature of 60° C. or higher and 100° C. or lower, in an environment of 40% RH or higher and 95% RH or lower, for 0.1 hour or more and 10 hours or less.
  • the structure after the moisture treatment is subjected to a heat treatment.
  • the structure is heated, for example, at a temperature of 60° C. or higher and 150° C. or lower for 0.5 hours or more and 10 hours or less.
  • the adhesive composition includes a first polymer and a second prepolymer or a third polymer, it is believed that this heat treatment forms a composite having an iso(thio)cyanate group and crosslinks with the first and second base materials. It will be done.
  • the structure after the heat treatment may be left at room temperature for one week or more.
  • the optical article according to the embodiment includes the laminate according to the embodiment.
  • the optical article according to the embodiment may include the laminate according to the embodiment and an optical element base material that covers at least a portion of the coating layer.
  • optical articles include binder sheets, lenses, eyeglasses, window glass for houses and automobiles, liquid crystal displays, sun visors, watches, and the like. Lenses include semi-finished lenses and finished lenses.
  • FIG. 2 is a cross-sectional view schematically showing an example of the optical article according to the embodiment.
  • the optical article 10 shown in FIG. 2 includes a first optical element base material 11, a second optical element base material 12, and a laminate 1 interposed between them.
  • the optical article 10 has a concave-convex lens shape.
  • the laminate 1 has a curved surface that follows the shape of the lens.
  • the first optical element base material 11 is located on the concave side
  • the second optical element base material 12 is located on the convex side.
  • the first optical element base material 11 covers the entire surface of a first coating layer (not shown) of the laminate 1.
  • the second optical element base material 12 covers the entire surface of a second coating layer (not shown) of the laminate 1.
  • the side surfaces of the laminate 1 are not covered with the first and second optical element base materials.
  • the side surfaces of the laminate 1 may be covered with the first and second optical element base materials.
  • FIG. 3 is a perspective view schematically showing an example of glasses according to the embodiment.
  • Eyeglasses 100 shown in FIG. 3 include a lens 101 and a frame 102 that supports this lens 101.
  • Lens 101 includes the optical article according to the embodiment.
  • the optical element base material may contain resin.
  • the resin is selected from the group consisting of polyester resin, polyamide resin, allyl resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythiourethane urea resin, polythioepoxy resin, and polycarbonate resin. It may contain at least one kind.
  • the optical element base material contains an allyl resin. Allyl resin tends to have high adhesion to the coat layer of the laminate.
  • the curable composition for allyl-based resin contains an allyl monomer having an allyl group and a polymerization initiator.
  • the allyl monomer includes, for example, at least one selected from the group consisting of diethylene glycol bisallyl carbonate, diallyl isophthalate, and diallyl terephthalate.
  • the polymerization initiator includes, for example, diisopropyl peroxycarbonate.
  • the curable composition for (meth)acrylic resin contains a (meth)acrylic monomer having a (meth)acrylate group and a polymerization initiator.
  • the curable composition for urethane urea resin includes a prepolymer of a polyisocyanate compound and a polyol compound, and a diamine compound.
  • a polyisocyanate compound polyol compound, and diamine compound, those mentioned above in the adhesive composition can be used.
  • the curable composition for thiourethane resin contains a polyisocyanate compound, a polythiol compound, and a polymerization catalyst.
  • a polyisocyanate compound those mentioned above in the adhesive composition can be used.
  • the curable composition for thioepoxy resin contains a monomer having a thioepoxy group, a curing agent, and a polymerization catalyst.
  • the optical article according to the embodiment is manufactured, for example, by the following method.
  • the mold includes an upper mold and a lower mold. By combining the upper mold and the lower mold, a hollow part is formed inside.
  • the gasket is installed at the interface between the upper mold and the lower mold.
  • a notch for fixing the laminate is provided inside the gasket.
  • a protrusion or a recess may be provided inside the gasket instead of the notch.
  • the mold and gasket are, for example, those used for molding a well-known plastic lens.
  • the laminate may be subjected to shape processing such as being curved to match the shape of the mold.
  • shape processing such as being curved to match the shape of the mold.
  • the laminate is installed in a mold of a curved surface processing device.
  • the mold has, for example, a lens shape such as a hemispherical shape. Holes are provided in the bottom of the mold.
  • a pressure regulating device such as a vacuum pump is connected to the hole via a pipe. Activate the pressure regulator to reduce the pressure in the space between the mold and the laminate.
  • the second base material of the laminate is deformed so as to stick to the bottom surface of the mold.
  • the environmental temperature may be set at 70° C. or higher and 160° C. or lower so that the laminate is easily deformed.
  • the operation of the pressure regulating device is stopped and the deformed laminate is removed from the mold.
  • the removed laminate is cooled, for example, at a temperature of 0° C. or higher and 40° C. or lower. In this way, a curved laminate is obtained.
  • the hollow part of this mold is filled with a curable composition for forming an optical element substrate.
  • the mold filled with the curable composition is heat treated to harden the curable composition.
  • the temperature is gradually raised from room temperature to the curing temperature, and after reaching the curing temperature, it is held for a certain period of time.
  • the curing temperature is, for example, 60°C or higher and 100°C or lower.
  • the temperature increase rate is, for example, 1° C./hour or more and 10° C./hour or less.
  • the holding time at the curing temperature is, for example, 1 hour or more and 30 hours or less.
  • the optical article according to the embodiment may be obtained by the following method. First, a portion of the curable composition is filled into the lower mold of the mold. A laminate is installed on the surface of the curable composition after filling. Next, an upper mold is installed to face the lower mold to form a hollow part. This hollow space is filled with the remainder of the curable composition. The obtained mold is heated in the same manner as above to obtain a cured body. In this way, an optical article is obtained in which the entire main surface and side surfaces of the laminate are covered with the optical element base material according to the embodiment. Moreover, the optical article according to the embodiment may be obtained by the following method. First, a laminate is placed along the top surface of the mold.
  • a curable composition is filled toward the surface of the laminate that is not in contact with the upper surface of the mold, that is, toward the back surface, and heat-treated under the same conditions as above to obtain a first cured body.
  • This first cured body is placed in a mold.
  • a curable composition is filled toward the surface of the laminate that is not covered by the cured product, and heat treated under the same conditions as above to obtain a second cured product. In this way, an optical article is obtained in which the main surface and optionally the side surfaces of the laminate are covered with the optical element base material.
  • Example 1> Manufacture of first prepolymer FPP1
  • a mixture was obtained by charging 100 g of the first isocyanate compound FI1, 315 g of the first polyfunctional active hydrogen compound FA1, and 40 g of the organic solvent OS1 into a 2 L reaction vessel. Isophorone diisocyanate was used as the first isocyanate compound FI1.
  • As the first polyfunctional active hydrogen compound FA1 polycarbonate diol having a number average molecular weight of 1000 was used. Diethyl ketone was used as the organic solvent OS1.
  • This mixture was stirred at 150 rpm for 5 hours at 100° C. under a nitrogen atmosphere to obtain a reaction solution containing the first prepolymer.
  • this first prepolymer will also be referred to as first prepolymer FPP1. The end point of the reaction was confirmed by back titration of isocyanate groups.
  • Second prepolymer SPP1 After adding 560 g of organic solvent OS1 and 150 g of organic solvent OS2 to the 10°C reaction solution containing the first prepolymer FPP1, the liquid temperature was maintained at 15°C. Tert-butyl alcohol was used as the organic solvent OS2. 21.3 g of the second polyfunctional active hydrogen compound SA1 was added dropwise to this reaction solution, and the reaction was carried out at 15° C. for 1 hour to obtain a reaction solution containing the second prepolymer. As this second polyfunctional active hydrogen compound SA1, bis-(4-aminocyclohexyl)methane was used. Hereinafter, this second prepolymer will also be referred to as second prepolymer SPP1. In addition, in the reaction liquid containing the second prepolymer SPP1, the solid content concentration was 37.6% by mass.
  • the number average molecular weight of the second prepolymer SPP1 was measured and found to be 13,000. Moreover, the softening point was 98°C.
  • adhesive composition AC1 100 g of reaction solution containing second prepolymer SPP1, 1.02 g of photochromic compound PC1, 0.34 g of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate ], and 0.05 g of DOW CORNING TORAY L-7001 were mixed and stirred at room temperature to obtain an adhesive composition.
  • this adhesive composition will also be referred to as adhesive composition AC1.
  • PC1 A compound represented by the following formula.
  • a coat layer forming composition was applied onto one main surface of the polyvinyl alcohol film PVF1 using a bar coater to obtain a coating film. This coating was dried at 60°C for 5 minutes. In this way, a first base material having a first coating film provided on one main surface was obtained. A second base material having a second coating film provided on one main surface was obtained in a similar manner. The thickness of the first and second coating films was 10 ⁇ m.
  • the coating layer forming composition a solution in which an epoxy resin was dissolved in a mixed solvent of toluene and methanol was used.
  • this coat layer forming composition is also referred to as coat layer forming composition CF1.
  • adhesive composition AC1 was applied to a PET (polyethylene terephthalate) film (Purex film manufactured by Teijin DuPont Films Ltd., with silicone coating) using a bar coater to obtain a third coating film. .
  • the PET film was peeled off to obtain a photochromic adhesive sheet with a thickness of about 30 ⁇ m.
  • the obtained photochromic adhesive sheet is sandwiched between the main surface of the first base material on which the first coating film is not provided and the main surface of the second base material on which the second coating film is not provided, and these are pasted. Together, we obtained a structure. Note that the structure was in the shape of a rectangular strip. One end of the structure in the long side direction was not coated with the adhesive composition, leaving an uncoated portion.
  • the first coating film, the second coating film, and the photochromic adhesive sheet were cured by heating this structure at 100° C. for 6 hours while suppressing it on all sides so as not to shrink.
  • this laminate will also be referred to as laminate OL1.
  • curable composition CC1 (Preparation of curable composition CC1) A curable composition was obtained by mixing 97 parts by mass of diethylene glycol bisallyl carbonate and 3 parts by mass of diisopropyl peroxydicarbonate.
  • this curable composition will also be referred to as curable composition CC1.
  • the laminate OL1 was vacuum dried at 80° C. and 13 Torr for 15 hours.
  • the vacuum-dried laminate OL1 was placed in a curved surface processing device and subjected to curved surface processing.
  • the obtained laminate was cut out into a 10 cm square, left to stand for 30 minutes at 45°C and 90% RH, and then cut into a spherical shape using a convex 6-curve mold with a diameter of 83 mm. Processed into. By drying the processed sheet, a six-curve sheet with a diameter of 83 mm was obtained.
  • the curved laminate OL1 was placed in the notch inside the gasket. This gasket was installed in a glass mold so that the laminate OL1 was located in the hollow part. The glass mold was set so that the lens power D was 6.00, the lens diameter was 83 mm, and the lens thickness was 7.5 mm. A curable composition CC1 was injected into the hollow part of this glass mold. The temperature of the glass mold injected with the curable composition CC1 was gradually raised from 35°C to 85°C over 17 hours using an air furnace. After heating, the cured product was taken out from the gasket and the glass mold, and placed in an oven at 90° C. and heated for 3 hours.
  • lens LS1 After heating, the outer periphery of the cured product was polished using a polishing machine to obtain a laminate having a diameter of 70 mm as shown in FIG. 2. This operation was repeated to obtain a total of three lenses.
  • this lens will also be referred to as lens LS1.
  • Example 2 A lens was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed to 25 ⁇ m.
  • Example 3 A lens was obtained in the same manner as in Example 1 except that the coating layer forming composition CF2 was used as the coating layer forming composition.
  • Coat layer forming composition CF2 was prepared by mixing coat layer forming composition CF1 and glycidyl methacrylate (GMA). The amount of GMA in the coating layer forming composition CF2 was 2% by mass.
  • Examples 4 to 6 Lenses were obtained in the same manner as in Example 3, except that the thickness of the coating layer was changed to 25 ⁇ m, 50 ⁇ m, and 75 ⁇ m, respectively.
  • Example 7 A lens was obtained in the same manner as in Example 2, except that the coating layer forming composition CF3 was used as the coating layer forming composition.
  • the coating layer forming composition CF3 a solution in which a urethane resin was dissolved in methyl ethyl ketone was used.
  • Coat layer forming composition CF4 was prepared by mixing coat layer forming composition CF1 and allyl glycidyl ether. The amount of allyl glycidyl ether in the coating layer forming composition CF4 was 10% by mass.
  • Example 9 A lens was obtained in the same manner as in Example 5, except that the coating layer forming composition CF5 was used as the coating layer forming composition.
  • Coat layer forming composition CF5 was prepared by mixing coat layer forming composition CF1 and 1,2-epoxy-4-vinylcyclohexane. The amount of 1,2-epoxy-4-vinylcyclohexane in the coating layer forming composition CF5 was 5% by mass.
  • Example 10> triacetyl cellulose with a thickness of 60 ⁇ m (hereinafter, this film is also referred to as film TAC1) was prepared, and after obtaining the structure, it was heated at 100 ° C. for 6 hours while holding down on all sides to prevent shrinkage. By doing this, instead of curing the first coating film, second coating film, and photochromic adhesive sheet, they are degassed for 16 hours at 40°C and 13 Torr, and then cured by heating at 100°C for 6 hours. A lens was obtained in the same manner as in Example 8, except that a laminate was obtained.
  • film TAC1 triacetyl cellulose with a thickness of 60 ⁇ m
  • Example 11 A lens was obtained in the same manner as in Example 10, except that the coating layer forming composition CF5 was used as the coating layer forming composition.
  • Example 12 A lens was obtained in the same manner as in Example 10, except that the coating layer forming composition CF6 was used as the coating layer forming composition.
  • Coat layer forming composition CF6 was prepared by mixing coat layer forming composition CF1 and methacrylic acid. The amount of methacrylic acid in the coating layer forming composition CF6 was 20% by mass.
  • the maximum absorption wavelength ( ⁇ max) after color development was determined using a spectrophotometer (instant multichannel photo director MCPD1000) manufactured by Otsuka Electronics Co., Ltd.
  • the absorbance ⁇ (0) of the maximum absorption wavelength of the laminate was measured when it was not irradiated with a xenon lamp.
  • the laminate was irradiated with a xenon lamp at the above beam intensity for 120 seconds, and the absorbance ⁇ (120) of the maximum absorption wavelength of the laminate was measured.
  • the value obtained by subtracting ⁇ (0) from the absorbance ⁇ (120) was defined as the color density. It can be said that the higher this value is, the better the photochromic properties are.
  • the color density was 1.1 and the fading speed was 40 seconds.
  • the shape stability of the laminate was evaluated using the following method. First, a laminate having a curved surface processed in the same manner as described in Example 1 was prepared. This laminate was left standing in a constant temperature bath at 25° C. and relative humidity 60% RH. The laminate was taken out from the thermostatic chamber every 30 minutes, placed in a mold, and visually checked for any change in shape. The time until it did not match the mold and a change in shape was confirmed was measured. Similar tests were conducted in an environment of 40° C. and a relative humidity of 35% RH, and in an environment of 5° C. and a relative humidity of 90% RH. The results of these tests are shown in Table 1.
  • the adhesion between the laminate and the optical element base material in the obtained lens was evaluated by the following method. First, a carbide blade scraper was pressed against the interface between the laminate and the optical element base material to check whether any peeling was observed. Next, after boiling the lens in distilled water for a test period, a carbide blade scraper was pressed against the interface between the laminate and the optical element base material to check whether any peeling was observed.
  • the evaluation criteria were as follows. The results are shown in Table 1.
  • the shape stability and lens adhesion of the laminates according to Examples 1 to 12 with a coating layer are the same as those of the laminates according to Comparative Examples 1 to 2 without a coating layer. and lens adhesion.
  • the coat layer has a thickness of 5 ⁇ m or more and 50 ⁇ m or less.
  • the composition for forming a coat layer further includes a first compound having at least one polymerizable functional group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group.
  • the described laminate [7]
  • the first compound further contains at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, an isocyanate group, an isothiocyanate group, an amino group, a hydroxyl group, and a carboxylic acid group, [5] or [6] The laminate described in ].
  • the first compound includes methacrylic acid, acrylic acid, glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, and 1,2-
  • the laminate according to [6] or [7] which contains at least one member selected from the group consisting of epoxy-4-vinylcyclohexane.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Health & Medical Sciences (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Surface Treatment Of Optical Elements (AREA)
PCT/JP2023/025033 2022-07-21 2023-07-05 積層体、光学物品、レンズ、及び眼鏡 Ceased WO2024018902A1 (ja)

Priority Applications (5)

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JP2024535014A JPWO2024018902A1 (https=) 2022-07-21 2023-07-05
EP23842827.0A EP4560367A4 (en) 2022-07-21 2023-07-05 LAMINATED BODY, OPTICAL ITEM, LENS AND EYEGLASSES
US18/993,219 US20250355282A1 (en) 2022-07-21 2023-07-05 Layered body, optical article, lens, and spectacles
CN202380054156.5A CN119604790A (zh) 2022-07-21 2023-07-05 层叠体、光学物品、镜片及眼镜
MX2025000689A MX2025000689A (es) 2022-07-21 2025-01-16 Cuerpo en capas, articulo optico, lentes y anteojos

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2022-116137 2022-07-21
JP2022116137 2022-07-21
JP2023-053170 2023-03-29
JP2023053170 2023-03-29

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WO2024018902A1 true WO2024018902A1 (ja) 2024-01-25

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JP (1) JPWO2024018902A1 (https=)
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MX (1) MX2025000689A (https=)
TW (1) TW202408813A (https=)
WO (1) WO2024018902A1 (https=)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004518165A (ja) * 2000-11-29 2004-06-17 ゼットエムエス エルエルシー フォトクロミック物質およびその製造法
WO2019163728A1 (ja) * 2018-02-23 2019-08-29 株式会社トクヤマ 機能性積層体、及び機能性積層体を用いた機能性レンズ

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004518165A (ja) * 2000-11-29 2004-06-17 ゼットエムエス エルエルシー フォトクロミック物質およびその製造法
WO2019163728A1 (ja) * 2018-02-23 2019-08-29 株式会社トクヤマ 機能性積層体、及び機能性積層体を用いた機能性レンズ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4560367A4

Also Published As

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TW202408813A (zh) 2024-03-01
JPWO2024018902A1 (https=) 2024-01-25
US20250355282A1 (en) 2025-11-20
EP4560367A1 (en) 2025-05-28
MX2025000689A (es) 2025-03-07
EP4560367A4 (en) 2025-11-12
CN119604790A (zh) 2025-03-11

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