Adhesive composition, laminate, optical article, lens, eyeglasses, and method for producing laminate

Abstract

Provided are: a first adhesive composition containing a urethane prepolymer having an isocyanate group at a terminal, a blocked isocyanate having an isocyanate group protected by a blocking agent, and an organic solvent; and a second adhesive composition containing a water-dispersible urethane resin, a blocked isocyanate having an isocyanate group protected by a blocking agent, and water. Also provided are a laminate, an optical article, a lens, and eyeglasses that include a coating film of the first or second adhesive composition, and a method for producing a laminate.

Description

Adhesive composition, laminate, optical article, lens, eyeglasses, and method for producing laminate

[0001] The present disclosure relates to an adhesive composition, a laminate, an optical article, a lens, an eyeglass, and a method for producing a laminate.

[0002] Urethane adhesives are known as one type of adhesive. Urethane adhesives are reactive adhesives that utilize an addition reaction between polyisocyanate and polyol to bond materials. Urethane adhesives are broadly classified into moisture-curing one-component adhesives and two-component adhesives in which a solution containing an isocyanate compound and a solution containing a polyol are mixed immediately before use. Moisture-curing one-component adhesives contain, for example, a urethane prepolymer having an isocyanate group obtained by reacting a polyisocyanate, a polyol, and a chain extender, and a solvent. In moisture-curing one-component adhesives, a coating film with adhesive properties is formed by reacting the urethane prepolymer having an isocyanate group with moisture in the air. To improve the storage stability of one-component adhesives, a technology has been developed to protect the isocyanate groups of the urethane prepolymer with a blocking agent.

[0003] Japanese Patent Application Laid-Open No. 2019-26668 International Publication No. 2018 / 230513 International Publication No. 2021 / 172404 Japanese Patent Application Laid-Open No. 2004-261973

[0004] An object of the present disclosure is to provide an adhesive composition capable of forming a coating film with reproducible adhesiveness, a laminate, an optical article, a lens, and a pair of glasses that include this coating film, and a method for producing the laminate.

[0005] According to the present disclosure, there is provided a first adhesive composition, which contains a urethane prepolymer having an isocyanate group at its terminal, a blocked isocyanate having an isocyanate group protected with a blocking agent, and an organic solvent.

[0006] According to the present disclosure, there is provided a second adhesive composition, which contains a water-dispersible urethane resin, a blocked isocyanate having an isocyanate group protected with a blocking agent, and water.

[0007] According to the present disclosure, there is provided a laminate. The laminate includes a first optical substrate and a urethane (urea) resin layer having a blocked isocyanate group. The urethane (urea) resin layer is laminated on the first optical substrate. The urethane (urea) resin layer is a coating film of the first or second adhesive composition of the present disclosure.

[0008] According to the present disclosure, an optical article is provided. The optical article includes a laminate of the present disclosure.

[0009] According to the present disclosure, a lens is provided, the lens comprising the optical article of the present disclosure.

[0010] According to the present disclosure, eyeglasses are provided, the eyeglasses including lenses of the present disclosure.

[0011] The present disclosure provides a method for producing a laminate, which includes applying a first or second adhesive composition to at least one main surface of a first optical substrate and drying the composition to form a urethane (urea) resin layer having a blocked isocyanate group.

[0012] According to the present disclosure, there are provided an adhesive composition capable of forming a coating film with reproducible adhesiveness, a laminate, an optical article, a lens, and an eyeglass that include this coating film, and a method for producing the laminate.

[0013] Fig. 1 is a cross-sectional view schematically showing an example of a first laminate of the present disclosure; Fig. 2 is a cross-sectional view schematically showing another example of a first laminate of the present disclosure; Fig. 3 is a cross-sectional view schematically showing an example of a second laminate of the present disclosure; Fig. 4 is a cross-sectional view schematically showing another example of a second laminate of the present disclosure; Fig. 5 is a perspective view schematically showing an example of eyeglasses of the present disclosure.

[0014] According to the present disclosure, first and second adhesive compositions are provided. The first adhesive composition contains a urethane prepolymer having an isocyanate group at its terminal, a blocked isocyanate having an isocyanate group protected with a blocking agent, and an organic solvent. The second adhesive composition contains a water-dispersible urethane resin, a blocked isocyanate having an isocyanate group protected with a blocking agent, and water.

[0015] The use of the first and second adhesive compositions makes it possible to form a coating film whose adhesiveness can be restored. The reason for this is believed to be as follows. First, the first adhesive composition is applied, and the organic solvent is removed to obtain a first coating film. In this first coating film, it is believed that the isocyanate groups of some of the urethane prepolymer (-R-N=C=O) react with moisture in the air and hydroxyl groups present on the surface of the coating object, producing carbamic acid (-R-NHCOOH). Carbamic acid is active, so it decomposes to produce amine (-R-NH ２ ) and carbon dioxide. This amine reacts with the isocyanate groups of other urethane prepolymers (-R'-N=C=O) to form a cured product of urethane urea resin (-R-NHCONH-R'-). This urethane urea resin contains isocyanate groups. Therefore, the first coating film has adhesive properties. However, as mentioned above, the adhesive properties of this first coating film are lost over time because the isocyanate groups are lost through reaction with moisture in the air.

[0016] Here, the first adhesive composition contains a blocked isocyanate together with a urethane prepolymer. The blocked isocyanate has a reactive isocyanate group protected with a blocking agent that can be dissociated by heating. The first coating film contains this blocked isocyanate. Heating the first coating film dissociates the blocking agent from the blocked isocyanate in the first coating film, forming an isocyanate group. Therefore, heating the first coating film restores the adhesiveness of the first coating film. In other words, heating the first coating film containing blocked isocyanate groups allows the formation of a coating film containing isocyanate groups.

[0017] Similarly, the first coating film obtained by applying the second adhesive composition and then removing the water also contains a urethane (urea) resin and a blocked isocyanate. Therefore, by heating this first coating film, the adhesiveness of the coating film can be restored in the same manner as described above.

[0018] <First adhesive composition> The first adhesive composition of the present disclosure contains a urethane prepolymer having an isocyanate group at its terminal, a blocked isocyanate having an isocyanate group protected with a blocking agent, and an organic solvent. The first adhesive composition may be a moisture-curable one-component adhesive.

[0019] [Urethane Prepolymer] The urethane prepolymer has an isocyanate group at its terminal. The urethane prepolymer preferably has two or more isocyanate groups, and may have from two to six isocyanate groups, more preferably two. The urethane prepolymer contains at least one bond selected from the group consisting of a urethane bond, a urea bond, a thiourethane bond, and a thiourea bond.

[0020] The number average molecular weight of the urethane prepolymer is, for example, from 800 to 100,000. The number average molecular weight of the urethane prepolymer is preferably from 900 to 50,000, and more preferably from 1,000 to 10,000. This number average molecular weight can be measured by gel permeation chromatography (GPC).

[0021] The proportion of the urethane prepolymer in the first adhesive composition is, for example, 10% by mass or more and 60% by mass or less, and preferably 20% by mass or more and 50% by mass or less.

[0022] The urethane prepolymer may be a first reactant or a second reactant. The first reactant is obtained by reacting a first polyisocyanate with a first poly(thio)ol. The second reactant is obtained by reacting the first reactant with a chain extender. The urethane prepolymer is preferably the second reactant. The first poly(thio)ol includes at least one of a first polyol and a first polythiol. In producing the first reactant or the second reactant, a reaction solvent may be used, or a heat treatment may be performed.

[0023] In producing the first reactant, the ratio M2 / M1 of the molar amount M1 of the first polyisocyanate to the molar amount M2 of the first poly(thiol) is preferably 0.5 or more and 0.95 or less, and more preferably 0.5 or more and 0.9 or less.

[0024] In producing the second reaction product, the chain extender is preferably added so that the ratio M4 / M1 of the molar amount M1 of the first polyisocyanate to the molar amount M4 of the chain extender is 0.1 or more and 0.5 or less.

[0025] (First Polyisocyanate) The first polyisocyanate has two or more isocyanate groups. The first polyisocyanate may have 2 to 6 isocyanate groups, and is more preferably a diisocyanate having two isocyanate groups.

[0026] The relative molecular mass of the first polyisocyanate is, for example, 100 or more and 1,000 or less, and preferably 150 or more and 500 or less.

[0027] The first polyisocyanate includes, for example, at least one selected from the group consisting of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and an aromatic polyisocyanate compound. The first polyisocyanate preferably includes an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, or a mixture thereof. The first polyisocyanate preferably includes an aromatic polyisocyanate compound, and more preferably includes an aromatic diisocyanate compound.

[0028] The aliphatic polyisocyanate compound includes, for example, at least one selected from the group consisting of tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, and 2,2,4-trimethylhexane-1,6-diisocyanate.

[0029] Examples of the alicyclic polyisocyanate compound include cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, an isomer mixture of 4,4'-methylenebis(cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, and hexahydrotoluene. The diisocyanate-containing polymer contains at least one selected from the group consisting of 1,2-bis(isocyanatomethyl)cyclohexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]-1-methylcyclohexane, 2-(3-isocyanatopropyl)cyclohexyl isocyanate, and norbornane diisocyanate.

[0030] Examples of aromatic polyisocyanate compounds include phenylcyclohexylmethane diisocyanate, 4,4'-methylenebis(phenylisocyanate), an isomer mixture of 4,4'-methylenebis(phenylisocyanate), tolylene-2,3-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)benzene, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl ether diisocyanate, and 1,3-diisocyanatomethylbenzene. The isocyanatobenzene may contain at least one member selected from the group consisting of benzene, 4,4'-diisocyanato-3,3'-dimethoxy(1,1'-biphenyl), 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl)methyl]2-methylbenzene, 1-isocyanato-3-[(4-isocyanatophenyl)methyl)-2-methylbenzene, 4-[(2-isocyanatophenyl)oxy]phenyl isocyanate, and diphenylmethane diisocyanate.

[0031] From the viewpoint of increasing the hardness and adhesion of the coating film, it is preferable that the first polyisocyanate contains at least one selected from the group consisting of tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, 4,4'-methylenebis(phenylisocyanate), an isomer mixture of 4,4'-methylenebis(phenylisocyanate), 1,5-naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,2-bis(isocyanatomethyl)cyclohexane, cyclohexane-1,3-diisocyanate, and cyclohexane-1,4-diisocyanate.

[0032] The first polyisocyanate may be used alone or in combination with a plurality of types.

[0033] (First polyol) The first polyol has two or more hydroxyl groups. The first polyol may have two to six hydroxyl groups, and is preferably a diol having two hydroxyl groups. The first polyol preferably has a structure in which hydroxyl groups are bonded to both ends of a long chain containing a repeating unit.

[0034] The number average molecular weight of the first polyol is, for example, from 100 to 5000. The number average molecular weight of the first polyol is preferably from 300 to 2000, and more preferably from 400 to 1500. This number average molecular weight can be measured by GPC.

[0035] The first polyol includes, for example, at least one selected from the group consisting of alkylene glycol, polyether polyol, polycarbonate polyol, polyester polyol, and polycaprolactone polyol.

[0036] The alkylene glycol includes, for example, at least one selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, and diethylene glycol.

[0037] The polyether polyol includes, for example, at least one selected from the group consisting of polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

[0038] Examples of polycarbonate 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, neopentyl glycol, cyclohexane-1,4- The polycarbonate polyol contains at least one selected from the group consisting of polycarbonate polyols obtained by phosgenation of one or more low molecular weight polyols such as diol, cyclohexane-1,4-dimethanol, diol dimer acid, ethylene oxide adduct or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol; and polycarbonate polyols obtained by transesterification with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyol is more preferably a low molecular weight polyol having a linear alkylene chain.

[0039] Examples of polycarbonate polyols that can be used include the "Duranol (registered trademark)" series manufactured by Asahi Kasei Corporation, the "Kuraray Polyol (registered trademark)" series manufactured by Kuraray Co., Ltd., the "Placcel (registered trademark)" series manufactured by Daicel Corporation, the "Nippolan (registered trademark)" series manufactured by Tosoh Corporation, and the "ETERNACOLL (registered trademark)" series manufactured by UBE Inc.

[0040] The polyester polyol may be a polyester polyol obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid. Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, and trimethylolpropane. These may be used alone or in combination of two or more. Examples of polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more.

[0041] Examples of polyester polyols that can be used include the "Polylite (registered trademark)" series manufactured by DIC Corporation, the "Nippolan (registered trademark)" series manufactured by Tosoh Corporation, and the "Maximol (registered trademark)" series manufactured by Air Water Performance Chemicals Inc.

[0042] The polycaprolactone polyol includes, for example, at least one selected from the group consisting of poly-ε-caprolactone, polycaprolactone diol, and polycaprolactone triol.

[0043] As the polycaprolactone polyol, for example, the "Placcel (registered trademark)" series manufactured by Daicel Corporation can be used.

[0044] (First Polythiol) The first polythiol has two or more thiol groups, or one or more hydroxyl groups and one or more thiol groups. The first polythiol may have two to six thiol groups, and is preferably a dithiol having two thiol groups. The first polythiol preferably has a structure in which thiol groups are bonded to both ends of a long chain containing a repeating structure.

[0045] The number average molecular weight of the first polythiol is, for example, from 100 to 2000. The number average molecular weight of the first polythiol is preferably from 300 to 1500, and more preferably from 400 to 1200. This number average molecular weight can be measured by GPC.

[0046] Examples of the first polythiol include 1,10-decanedithiol, 1,8-octanedithiol, tetraethylene glycol bis(3-mercaptopropionate), 1,4-butanediol bis(3-mercaptopropionate), and 1,6-hexanediol bis(3-mercaptopropionate).

[0047] (Chain Extender) A chain extender is added to increase the molecular weight of the urethane prepolymer.

[0048] The chain extender has two or more active hydrogen groups of at least one type selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, and thiol groups. The chain extender preferably has a hydroxyl group or an amino group. The number of active hydrogen groups in the chain extender may be two or more and six or less, and preferably two.

[0049] From the viewpoint of ease of control of the chain extension reaction (ease of control of the increase in molecular weight), the compound having a hydroxyl group is preferably a compound having two hydroxyl groups in the molecule and a molecular weight of 50 to 500. Specific examples of suitable compounds include alkylene glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, and trimethylolpropane; and polyalkylene glycols such as polypropylene glycol.

[0050] As the compound having an amino group, it is more preferable to use 3,3'-dichloro-4,4'-diaminodiphenylmethane, methylenedianiline, a methylenedianiline-sodium chloride complex, isophoronediamine, bis-(4-aminocyclohexyl)methane, or norbornanediamine, and among these, 3,3'-dichloro-4,4'-diaminodiphenylmethane and bis-(4-aminocyclohexyl)methane are particularly preferred.

[0051] [Blocked Isocyanate] The blocked isocyanate has one or more isocyanate groups protected with a blocking agent. The blocked isocyanate preferably has two or more isocyanate groups protected with a blocking agent, more preferably three or more, and may have three to six isocyanate groups protected with a blocking agent. The blocked isocyanate can be obtained, for example, by reacting a second polyisocyanate with a blocking agent. Commercially available blocked isocyanates may be used.

[0052] The content of the blocked isocyanate in the first adhesive composition is, for example, 0.1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 10% by mass or less.

[0053] In the first adhesive composition, the proportion of the blocked isocyanate relative to the total amount of the urethane prepolymer and the blocked isocyanate is, for example, 1% by mass or more and 40% by mass or less.

[0054] The relative molecular mass of the blocked isocyanate is, for example, 200 or more and 5000 or less. The relative molecular mass is preferably 250 or more and 2000 or less.

[0055] The ratio W1 / W2 of the number average molecular weight W1 of the urethane prepolymer to the relative molecular mass W2 of the blocked isocyanate is, for example, 1 or more and 3,000 or less, preferably 1 or more and 1,000 or less.

[0056] (Second Polyisocyanate) The second polyisocyanate has two or more isocyanate groups. The second polyisocyanate may have two to six isocyanate groups, and preferably has three or more isocyanate groups. The second polyisocyanate may be the first polyisocyanate described above. The second polyisocyanate may be at least one selected from the group consisting of a trimer and a biuret of the first polyisocyanate described above.

[0057] Specific examples of the second polyisocyanate include at least one selected from the group consisting of a trimer of hexamethylene diisocyanate, a biuret of hexamethylene diisocyanate, and a trimer of isophorone diisocyanate.

[0058] (Blocking Agent) The blocking agent reacts with the terminal isocyanate group (R-NCO) of the urethane prepolymer to form a blocked isocyanate group (R-NH-CO-B: B is a blocking agent). The blocked isocyanate group does not have reactivity with active hydrogen groups. The blocked isocyanate group can be regenerated by, for example, heating, releasing the terminal blocking agent.

[0059] The blocking agent is not particularly limited, and known compounds can be used. Specifically, at least one blocking agent selected from the group consisting of pyrazoles, acid amides, imidazoles, pyridines, amines, alcohols, lactams, phenols, oximes, and active methylene compounds can be used. The blocking agents may be used alone or in combination of two or more.

[0060] As the blocking agent, it is preferable to use pyrazoles, such as 3,5-dimethylpyrazole.

[0061] Examples of alcohols include aliphatic alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, and trifluoroalcohol.

[0062] Examples of lactams include γ-butyrolactam, ε-caprolactam, and γ-valerolactam.

[0063] Examples of phenols include phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoic acid esters, and mono- or di-alkylphenols having an alkyl group having 4 or more carbon atoms as a substituent. Specific examples include monoalkylphenols such as n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, and n-nonylphenol; and dialkylphenols such as di-n-propylphenol, diisopropylphenol, isopropyl cresol, di-n-butylphenol, di-t-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol.

[0064] Examples of oximes include acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, and cyclohexanone oxime.

[0065] Examples of the active methylene compound include malonic acid diester compounds and acetoacetic acid ester compounds.

[0066] Examples of malonic acid diester compounds include dimethyl malonate, diethyl malonate, diisopropyl malonate, di-n-propyl malonate, di-n-butyl malonate, ethyl n-butyl malonate, methyl n-butyl malonate, ethyl t-butyl malonate, methyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzylmethyl malonate, ethylphenyl malonate, t-butylphenyl malonate, and isopropylidene malonate.

[0067] Examples of the acetoacetate ester compounds include methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, t-butyl acetoacetate, n-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate.

[0068] [Organic Solvent] The organic solvent dissolves or disperses the urethane prepolymer and the blocked isocyanate. To enhance storage stability, the organic solvent preferably does not have an active hydrogen group. Examples of the organic solvent include at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide (DMF), tetrahydrofuran (THF), petroleum ether, and propylene glycol monomethyl ether.

[0069] The content of the organic solvent in the first adhesive composition is, for example, 30% by mass or more and 95% by mass or less, and preferably 60% by mass or more and 90% by mass or less.

[0070] [Other Additives] The first adhesive composition may contain other additives in addition to the above components, such as a leveling agent, a photochromic compound, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, or other stabilizers, additives, a silane coupling agent, a glycidyl compound, etc.

[0071] Examples of the leveling agent that can be used include silicone surfactants, fluorine-containing surfactants, etc. Specific examples of silicone surfactants and fluorine-containing surfactants include "L-7001," "L-7002," "L-7604," "FZ-2123," and "FZ-2104" manufactured by DuPont-Toray Specialty Materials Co., Ltd.; "Megafac F-470," "Megafac F-1405," and "Megafac F-479" manufactured by DIC Corporation; and "Flo-Rad FC-430" manufactured by 3M Japan Ltd. When using surfactants, two or more types may be mixed and used.

[0072] The content of the other additives in the first adhesive composition is, for example, 0.001% by mass or more and 10% by mass or less, and preferably 0.01% by mass or more and 1% by mass or less.

[0073] The first adhesive composition may consist solely of the above-described urethane prepolymer having an isocyanate group at its terminal, a blocked isocyanate having an isocyanate group protected with a blocking agent, an organic solvent, and other additives. In this embodiment, the proportion of the urethane prepolymer is, for example, 10% by mass or more and 60% by mass or less, the proportion of the blocked isocyanate is 1% by mass or more and 20% by mass or less, the proportion of the other additives is 0.01% by mass or more and 5% by mass or less, and the proportion of the organic solvent is the remainder.

[0074] The first adhesive composition typically does not contain a polyol. If a polyol is contained, the stability of the first adhesive composition may be reduced. The polyol content in the first adhesive composition is preferably 1% by mass or less, more preferably 0.1% by mass or less. There is no particular lower limit for the polyol content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0075] The first adhesive composition typically does not contain a polyamine. If a polyamine is contained, the stability of the first adhesive composition may be reduced. The polyamine content in the first adhesive composition is preferably 1% by mass or less, and more preferably 0.1% by mass or less. There is no particular lower limit for the polyamine content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0076] The first adhesive composition typically does not contain a polymer without a reactive group, such as a urethane resin. The content of the polymer without a reactive group in the first adhesive composition is preferably 1% by mass or less, more preferably 0.1% by mass or less. There is no particular lower limit for the polymer content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0077] <Second adhesive composition> The second adhesive composition of the present disclosure contains a water-dispersible urethane resin, a blocked isocyanate having an isocyanate group protected with a blocking agent, and water. The second adhesive composition may be a moisture-curable one-component adhesive.

[0078] The water-dispersible urethane resin may be a reaction product of the first polyisocyanate and the first polyol. The water-dispersible urethane resin does not have an isocyanate group. The water-dispersible urethane resin is preferably in the form of particles, more preferably in the form of colloidal particles.

[0079] The water-dispersible urethane resin has an average particle size measured by a light scattering method of, for example, 0.001 μm or more and 0.100 μm or less, and preferably 0.005 μm or more and 0.050 μm or less. This average particle size can be measured, for example, by a dynamic light scattering method.

[0080] The number average molecular weight of the water-dispersible urethane resin is preferably from 1,000 to 100,000. This number average molecular weight can be measured by GPC.

[0081] The proportion of the water-dispersible urethane resin in the second adhesive composition is, for example, 10% by mass or more and 60% by mass or less, and preferably 20% by mass or more and 50% by mass or less.

[0082] The blocked isocyanate content in the second adhesive composition is, for example, 0.1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 10% by mass or less.

[0083] The proportion of water in the second adhesive composition is, for example, 30% by mass or more and 95% by mass or less, and preferably 60% by mass or more and 90% by mass or less.

[0084] The second adhesive composition may consist solely of a water-dispersible urethane resin, a blocked isocyanate having an isocyanate group protected with a blocking agent, water, and other additives. In this embodiment, the proportion of the water-dispersible urethane resin is, for example, 10% by mass or more and 60% by mass or less, the proportion of the blocked isocyanate is 1% by mass or more and 20% by mass or less, the proportion of the other additives is 0.01% by mass or more and 5% by mass or less, and water is the remainder.

[0085] The second adhesive composition typically does not contain a polyol. If a polyol is contained, the stability of the second adhesive composition may be reduced. The polyol content in the second adhesive composition is preferably 1% by mass or less, and more preferably 0.1% by mass or less. There is no particular lower limit for the polyol content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0086] The second adhesive composition typically does not contain a polyamine. If a polyamine is contained, the stability of the second adhesive composition may be reduced. The polyamine content in the second adhesive composition is preferably 1% by mass or less, and more preferably 0.1% by mass or less. There is no particular lower limit for the polyamine content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0087] The second adhesive composition typically does not contain a prepolymer having a reactive group, such as a urethane prepolymer. The prepolymer content in the second adhesive composition is preferably 1% by mass or less, and more preferably 0.1% by mass or less. There is no particular lower limit for the prepolymer content, but in one example it is 0% by mass, and in another example it is 100 ppm by mass or more.

[0088] <First Laminate> The first laminate of the present disclosure includes a first optical substrate and a urethane (urea) resin layer having a blocked isocyanate group. The urethane (urea) resin layer is laminated on the first optical substrate. The urethane (urea) resin layer is a coating film of the first or second adhesive composition of the present disclosure. Here, the urethane (urea) resin includes at least one of a urethane resin and a urethane urea resin.

[0089] Fig. 1 is a cross-sectional view schematically illustrating an example of a first laminate according to the present disclosure. The first laminate 1a shown in Fig. 1 includes a first optical substrate 2 and a urethane (urea) resin layer 3 having a blocked isocyanate group laminated on one main surface of the first optical substrate 2. The urethane (urea) resin layer 3 having a blocked isocyanate group is a coating film obtained by applying and drying the first or second adhesive composition according to the present disclosure.

[0090] [First Optical Substrate] The first optical substrate includes a resin layer, a resin film, or a resin lens. The first optical substrate may be planar or curved. The resin lens may be a convex lens, a concave lens, or a plano lens. The first optical substrate may be manufactured using a 3D printer. The first optical substrate is preferably a resin lens or a saponified triacetyl cellulose (TAC) film.

[0091] The resin layer is a cured product of a curable composition. The resin layer contains, for example, at least one resin selected from the group consisting of an acrylic resin, a methacrylic resin, a polyurethane resin, an epoxy resin, and a polyurethane-urea resin. The curable composition may contain, for example, a polymerizable monomer such as (meth)acrylate, or may contain a reactive compound such as an isocyanate compound or a polyol. The curable composition may contain a functional dye.

[0092] The resin film contains at least one resin selected from the group consisting of, for example, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin.

[0093] The resin lens contains at least one resin selected from the group consisting of, for example, 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.

[0094] As the cellulose resin, commercially available resins can be used, and examples of suitable cellulose resins include acetyl cellulose such as triacetyl cellulose and diacetyl cellulose; and propyl cellulose such as tripropyl cellulose and dipropyl cellulose.

[0095] Commercially available resins can be used as the polyamide resin. Examples of polyamide resins that can be used include polyamide resins obtained by polycondensation of ω-aminocarboxylic acids such as ε-caprolactam, 10-aminodecanoic acid lactam, and ω-laurin lactam, polyamide resins obtained by co-condensation polymerization of diamines and dicarboxylic acids, and copolymers thereof. From the viewpoints of mechanical strength, solvent resistance, and transparency, polyamide resins obtained by co-condensation polymerization are preferred.

[0096] Specific examples of the alicyclic polyamide resin include "TROGAMID" (registered trademark) manufactured by Polypla-Evonik Co., Ltd., "Grilamid" (registered trademark) and "Grilamid TR" (registered trademark) manufactured by EMS-GRIVORY, Inc. One type of alicyclic polyamide resin may be used alone, or two or more types may be used in combination.

[0097] Commercially available resins can be used as the polyester resin. Examples of the polyester resin include polycondensates of dicarboxylic acids such as terephthalic acid and isophthalic acid with diols such as ethylene glycol, butylene glycol, and 1,4-cyclohexanedimethanol. Among these, polyethylene terephthalate, polybutylene terephthalate, and copolymers thereof can be preferably used.

[0098] As the (meth)acrylic resin, commercially available resins can be used. As the (meth)acrylic resin, for example, a homopolymer such as methyl methacrylate or a resin made of a copolymer of a plurality of (meth)acrylic monomers can be suitably used.

[0099] Commercially available resins can be used as the polyurethane resin and polyurethane urea resin. The polyurethane resin or polyurethane urea resin is a resin having a urethane bond and / or a urea bond in the molecule. Specifically, known resins obtained by reacting a diisocyanate compound such as isophorone diisocyanate with a polyol compound such as polycarbonate polyol or polyester polyol can be used. Furthermore, polyurethane resins or polyurethane urea resins obtained by reacting a chain extender such as a low molecular weight diol, triol, diamine, or triamine can be preferably used.

[0100] As the polyimide resin, commercially available resins can be used. Polymers of aromatic tetracarboxylic acids and aromatic diamines can be suitably used. Examples of aromatic tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3',3,4'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, pyridine-2,3,5,6-tetracarboxylic acid, or aromatic tetracarboxylic acids derived from their acid anhydrides or dianhydrides, or ester compounds or halides of their acids. Examples of aromatic diamines include paraphenylenediamine, metaphenylenediamine, benzidine, paraxylylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis(3-methyl-5-aminophenyl)benzene, and derivatives thereof.

[0101] As the epoxy resin, commercially available resins can be used, such as resins obtained by condensation reaction of bisphenol A, bisphenol F, or the like with epichlorohydrin, other polyfunctional epoxy resins, and biphenyl-type epoxy resins.

[0102] As the polyolefin resin, commercially available resins can be used, such as polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer.

[0103] Commercially available polyvinyl alcohol (PVA) resins can be used. The substrate may consist solely of PVA resin, or may contain other resins. Examples of other resins include aldehyde-modified polyvinyl formal, polyvinyl acetal, and polyvinyl butyral.

[0104] The thickness of the first optical substrate is, for example, 1.0 μm or more and 10 mm or less. The thickness of the first optical substrate may be 10 μm or more and 1000 μm or less.

[0105] (Modification) The first optical substrate may be a laminate. For example, the first optical substrate may be a binder sheet. The binder sheet includes a pair of optical substrates and an adhesive layer positioned between the optical substrates to bond them together. The thickness of the binder sheet may be, for example, 1.0 μm or more and 1 mm or less, and may be 100 μm or more and 1000 μm or less.

[0106] The adhesive layer may be a functional layer containing a resin and a functional dye. The functional layer is, for example, a cured product of an adhesive composition containing a urethane urea resin or a urethane urea prepolymer and a functional dye. The urethane urea prepolymer can be produced, for example, by a method similar to that for the second reactant described above. The urethane urea resin can be obtained, for example, by reacting a urethane prepolymer with an amine compound serving as a reaction terminator and water. The functional dye includes, for example, at least one selected from the group consisting of a photochromic compound, an ultraviolet absorber, a blue light absorber, an infrared absorber, a dye, and an electrochemical compound. The photochromic compound includes, for example, at least one selected from the group consisting of a chromene compound, a fulgide compound, and a spirooxazine compound. The chromene compound includes a compound having a 1-benzopyran skeleton, a spiropyran compound having a spiropyran skeleton, or a naphthopyran compound having a naphthopyran skeleton. The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton.

[0107] Fig. 2 is a cross-sectional view schematically showing another example of the first laminate of the present disclosure. The first laminate 1b shown in Fig. 2 includes a first-A optical substrate 2a, a first-C optical substrate 2c, an adhesive layer 2b located therebetween, a urethane (urea) resin layer 3 having a blocked isocyanate group that coats one surface of the first-A optical substrate 2a, and a urethane (urea) resin layer 3 having a blocked isocyanate group that coats one surface of the first-C optical substrate 2c. The urethane (urea) resin layer 3 having a blocked isocyanate group is a coating film obtained by applying and drying the first or second adhesive composition of the present disclosure.

[0108] The second laminate of the present disclosure includes the first laminate of the present disclosure and a second optical substrate. The second optical substrate is laminated on a urethane (urea) resin layer having a blocked isocyanate group, or a urethane (urea) resin layer having an isocyanate group generated by dissociation of a blocking agent from the blocked isocyanate group.

[0109] The second optical substrate includes a resin layer, a resin film, or a resin lens. The second optical substrate may be the same type as the first optical substrate. The first optical substrate may be a resin film, and the second optical substrate may be a resin lens. Alternatively, the first optical substrate may be a resin lens, and the second optical substrate may be a resin lens. Alternatively, the first optical substrate may be a resin lens, and the second optical substrate may be a resin layer. The second optical substrate may be manufactured using a 3D printer. The second optical substrate preferably includes at least one selected from the group consisting of an acrylic resin, a polyurethane resin, a polyurethane urea resin, a polythiourethane resin, a polythiourethane urea resin, a polythioepoxy resin, and an allyl resin.

[0110] Fig. 3 is a cross-sectional view schematically illustrating an example of a second laminate according to the present disclosure. The second laminate 10a shown in Fig. 3 includes a first optical substrate 2, a urethane (urea) resin layer 3a laminated on one main surface of the second optical substrate 2, and a second optical substrate 4 laminated on the urethane (urea) resin layer 3a.

[0111] Fig. 4 is a cross-sectional view schematically showing another example of the second laminate of the present disclosure. The second laminate 10b shown in Fig. 4 includes a first-A optical substrate 2a, a first-C optical substrate 2c, an adhesive layer 2b located therebetween, a urethane (urea) resin layer 3a covering one surface of the first-A optical substrate 2a, a urethane (urea) resin layer 3a covering one surface of the first-C optical substrate 2c, and a second optical substrate 4 covering the main surface of each urethane (urea) resin layer 3a.

[0112] <Method for producing first and second laminates> A method for producing a first laminate according to the present disclosure includes applying the first or second adhesive composition according to the present disclosure to at least one main surface of a first optical substrate and drying the composition to form a urethane (urea) resin layer having a blocked isocyanate group.

[0113] The method for producing the second laminate of the present disclosure may include heating the first laminate at 60 to 150°C to dissociate the blocking agent from the blocked isocyanate groups, thereby obtaining a urethane (urea) resin layer having an isocyanate group.

[0114] The method for producing the second laminate of the present disclosure may include forming a coating film of a curable composition on a urethane (urea) resin layer having an isocyanate group, and curing the coating film.

[0115] The manufacturing method of the first and second laminates will be described in detail below.

[0116] First, first and second adhesive compositions are prepared by mixing the respective components. These adhesive compositions are applied to at least one main surface of a first optical substrate. The application method may be a dipping method, a coating method, or a 3D printer. The surface of the first optical substrate may be subjected to a surface treatment such as etching, alkali treatment, or corona treatment. The applied film is dried, for example, at a temperature of 25°C or higher and 130°C or lower to form a first coating film. In this way, a first laminate is obtained. The drying temperature may be determined based on the thermal stability of the selected blocked isocyanate. In other words, drying is performed so as not to dissociate the blocking agent of the blocked isocyanate. This first coating film has both an isocyanate group and a blocked isocyanate group.

[0117] Next, the isocyanate groups in this coating film are eliminated, for example, by reaction with moisture in the air. The presence or absence of isocyanate groups in the coating film can be confirmed, for example, by infrared spectroscopy (IR) analysis. The first laminate having the first coating film after the isocyanate groups have been eliminated is heated at a temperature of 60°C to 150°C, for example, for 0.25 hours to 24 hours, to dissociate the blocking agent for the blocked isocyanate groups. This results in a second coating film having isocyanate groups derived from the blocked isocyanate.

[0118] A second optical substrate is laminated on this second coating film to obtain a second laminate. The lamination method of the second optical substrate is not particularly limited. The second optical substrate existing as an independent film may be laminated on the second coating film, or the second optical substrate may be provided by applying a curable composition on the second coating film and curing the resulting coating film by drying. The method of applying the curable composition may be a dipping method, a spin coating method, or a 3D printer.

[0119] A second optical substrate may be laminated on the first coating film before the isocyanate groups disappear, and the laminate thus obtained is subjected to a heat treatment to obtain a second laminate having higher adhesion.

[0120] <Optical Article> The optical article of the present disclosure includes the first or second laminate of the present disclosure.

[0121] Examples of optical articles include binder sheets, lenses, eyeglasses, window materials for houses and automobiles, liquid crystal displays, sun visors, watches, etc. Lenses include semi-finished lenses and finished lenses.

[0122] Fig. 5 is a perspective view schematically illustrating an example of eyeglasses according to the present disclosure. The eyeglasses 100 shown in Fig. 5 include lenses 101 and a frame 102 that supports the lenses 101. The lenses 101 include the optical article according to the present disclosure.

[0123] The present invention will be described in more detail by the following examples, which are merely illustrative of the present invention and are not intended to limit the scope and spirit of the present invention.

[0124] Example 1 Preparation of First Adhesive Composition Into a reaction vessel equipped with a stirrer, 142 g of a polycarbonate diol (Duranol manufactured by Asahi Kasei Corporation) having a number average molecular weight of 500 and made from 1,5-pentanediol and hexanediol, 90 g of a 80% by mass:20% by mass mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI80), and 58 g of toluene were added and mixed uniformly. The mixture was adjusted to 90°C, and a urethanization reaction was carried out.

[0125] Furthermore, 3.9 g of propylene glycol (PG) as a chain extender and 177 g of toluene were added to the solution containing the first precursor obtained by the above method, and the temperature was adjusted to 75°C. A chain extension reaction was carried out to prepare an isocyanate group-containing urethane prepolymer. To 100 g of the obtained urethane prepolymer, 76.6 g of ethyl acetate, and 0.06 g of leveling agent "L7001" manufactured by DuPont-Toray Specialty Materials Co., Ltd., blocked isocyanate (B-1) was added to a solids content of 5.6 g, and the mixture was thoroughly stirred under a nitrogen atmosphere until homogeneous, to obtain a first adhesive composition. "TRIXENE BI 7982" manufactured by GSI Creos Corporation was used as the blocked isocyanate (B-1). The solids content of the first adhesive composition was 30% by mass.

[0126] [Production of First Optical Substrate] A binder sheet was used as the first optical substrate. The binder sheet had a three-layer structure consisting of a first A optical substrate, a photochromic adhesive layer, and a first C optical substrate. The binder sheet was prepared by the following method.

[0127] First, a photochromic adhesive composition for forming a photochromic adhesive layer was prepared. A 2-L reaction vessel was charged with 100 g of isophorone diisocyanate, 315 g of polycarbonate diol having a number-average molecular weight of 1,000, and 40 g of diethyl ketone to obtain a mixture. Under a nitrogen atmosphere, the mixture was stirred at 150 rpm at 100°C for 5 hours to obtain a reaction solution containing a first prepolymer. The end point of the reaction was confirmed by back titration of the isocyanate group.

[0128] To a reaction solution containing the first prepolymer at 10°C, 560 g of diethyl ketone and 150 g of tert-butyl alcohol were added, and the liquid temperature was then maintained at 15°C. 21.3 g of bis-(4-aminocyclohexyl)methane was added dropwise to this reaction solution, and the mixture was allowed to react at 15°C for 1 hour, thereby obtaining a reaction solution containing a second prepolymer. The solids concentration of the reaction solution containing the second prepolymer was 37.6% by mass. The number average molecular weight of the second prepolymer was measured and found to be 13,000. The softening point was 98°C.

[0129] 100 g of the reaction solution containing the second prepolymer, 1.02 g of the photochromic compound PC1, 0.34 g of ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], and 0.05 g of a leveling agent "L7001" manufactured by DuPont Toray Specialty Materials Inc. were mixed and stirred at room temperature to obtain a photochromic adhesive composition.

[0130] The photochromic compound PC1 is a compound represented by the following formula:

[0131]

[0132] Next, a 60 μm thick saponified TAC film was prepared as the 1A and 1C optical substrates. The contact angle of this TAC film was 10°. Hereinafter, this film will also be referred to as TAC1. The contact angle was measured using a DropMaster 500 manufactured by Kyowa Interface Science Co., Ltd. A water droplet was dropped on the surface of the sheet sample, and the angle formed between the water droplet and the sheet sample surface was measured and used as the contact angle.

[0133] Next, the photochromic adhesive composition was applied to a PET (polyethylene terephthalate) film (Purex film with silicone coating, manufactured by Toyobo Film Solutions Co., Ltd.) using a bar coater to obtain a third coating film. This third coating film was dried at 100 ° C. for 5 minutes, and then the PET film was peeled off to obtain a photochromic adhesive sheet with a thickness of approximately 30 μm. The 1A optical substrate, the obtained photochromic adhesive sheet, and the 1C optical substrate were bonded in this order to obtain a structure. The structure was in the shape of a rectangular strip. One end of the long side of the structure was not coated with the adhesive composition and was left as an uncoated portion.

[0134] This structure was degassed for 16 hours under conditions of 40° C. and 13 Torr, and then heated at 100° C. for 6 hours to obtain a binder sheet.

[0135] [Production of First Laminate] The first adhesive composition was applied to the surface of the first A optical substrate and the surface of the first C optical substrate of the binder sheet, and dried at 70° C. for 15 minutes to obtain a coating film of a urethane urea resin. The coating film had a thickness of 10 μm.

[0136] [Production of Second Laminate] The first laminate was subjected to a curved surface processing. The curved first laminate was placed in the notch on the inside of the gasket. This gasket was placed in a glass mold so that the first laminate was located within the hollow portion. 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 for urethane urea resin was injected into the hollow portion of the glass mold. The glass mold after the injection of the curable composition was cured at 120°C for 10 hours using an air oven. After polymerization was completed, the gasket and mold were removed and placed in an oven and heated at 110°C for 1 hour. This operation was repeated to obtain a total of three lenses.

[0137] The curable composition for urethane urea resin was prepared by the following method.

[0138] 100 parts by mass of a polyester polyol composed of adipic acid and 1,6-hexanediol and having a number average molecular weight of 1,000, 78 parts by mass of an isomer mixture of 4,4'-methylenebis(cyclohexyl isocyanate), and 17 parts by mass of 2,4-diamino-3,5-diethyl-toluene / 2,6-diamino-3,5-diethyl-toluene as an aromatic diamine curing agent were prepared.

[0139] A mixture of the polyester polyol and an isomer mixture of 4,4'-methylenebis(cyclohexyl isocyanate) was heated at 140°C for 10 minutes under dry nitrogen to produce a prepolymer. This prepolymer was cooled to 70°C and allowed to stand for 24 hours. An aromatic diamine curing agent was mixed into the prepolymer to obtain a curable composition.

[0140] <Examples 2 to 6 and Comparative Example 1> As shown in Table 1, a first and a second laminate were produced in the same manner as in Example 1, except that a first adhesive composition was used in which the type or amount of blocked isocyanate was changed.

[0141] The following blocked isocyanates were used: B-1: A solution in which molecules in which the three isocyanate groups of a trimer of hexamethylene diisocyanate (HDI) are capped with 3,5-dimethylpyrazole are dissolved in a mixed solvent. The mixed solvent is a mixture of petroleum naphtha and butyl acetate. Solids content: 65% ("TRIXENE BI 7982" manufactured by GSI Creos Co., Ltd.) B-2: A solution in which molecules in which the three isocyanate groups of a trimer of isophorone diisocyanate (IPDI) are capped with 3,5-dimethylpyrazole are dissolved in propylene glycol monomethyl ether. Solids content: 70%. ("TRIXENE BI 7951" manufactured by GSI Creos Co., Ltd.) B-3: A solution obtained by dissolving a molecule in which the three isocyanate groups of a biuret of hexamethylene diisocyanate (HDI) are capped with 3,5-dimethylpyrazole in a mixed solvent of propylene glycol monomethyl ether and ethyl acetate. Solid content: 70%. ("TRIXENE BI 7960" manufactured by GSI Creos Co., Ltd.)

[0142] Example 7 First, a curved first laminate was manufactured using the same method as in Example 1. The curved first laminate was placed in the notch on the inside of the gasket. This gasket was placed in a glass mold so that the first laminate was positioned within the hollow. The glass mold was designed to provide a lens diopter D of 6.00, a lens diameter of 83 mm, and a lens thickness of 7.5 mm. A curable composition for forming a thiourethane resin was injected into the hollow of the glass mold. The glass mold after the curable composition was injected was gradually heated from 35°C to 130°C over 12 hours using an air oven, and then maintained at 130°C for 0.5 hours. After polymerization was completed, the gasket and mold were removed and placed in an oven and heated at 130°C for 3 hours. The outer periphery of the heated cured product was polished using a ball grinder to obtain an optical article with a diameter of 70 mm. This procedure was repeated to obtain a total of three lenses.

[0143] The curable composition for forming a thiourethane resin was prepared by the following method: 43.5 parts by mass of dicyclohexylmethane-4,4′-diisocyanate, 43.5 parts by mass of isophorone diisocyanate, 63.0 parts by mass of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, and 0.1 parts by mass of dibutyltin dilaurate as a polymerization initiator were mixed to obtain a curable composition.

[0144] Example 8 First, a curved first laminate was produced using the same method as in Example 1. The curved first laminate was placed in the notch on the inside of a gasket. This gasket was placed in a glass mold so that the first laminate was positioned within the hollow. The glass mold was designed to provide a lens with a diopter D of 6.00, a lens diameter of 83 mm, and a lens thickness of 7.5 mm. This glass mold was heated at 120°C for 30 minutes to dissociate the blocking agent from the blocked isocyanate and regenerate the isocyanate group. A curable composition for forming a thioepoxy resin was then injected into the hollow of the glass mold. The glass mold after the injection of the curable composition was gradually heated from 20°C to 90°C over 20 hours using an air oven, and then maintained at 90°C for 1 hour. After polymerization was completed, the gasket and mold were removed and placed in an oven and heated at 90°C for 1 hour. The outer periphery of the cured product after heating was ground with a ball grinder to obtain an optical article with a diameter of 70 mm. This operation was repeated to obtain a total of three lenses.

[0145] A curable composition for forming a thioepoxy resin was prepared by the following method: 95 parts by mass of bis(β-epithiopropylthio)ethane, 5 parts by mass of 2-mercaptoethanol, and 0.1 parts by weight of tetrabutylammonium bromide as a polymerization catalyst were mixed to obtain a curable composition.

[0146] Example 9 [Production of First Laminate] A 2.0 mm thick CR-39 (allyl resin plastic lens; refractive index = 1.50) was used as the first optical substrate. This first optical substrate was thoroughly degreased with acetone, immersed in a 10% by mass aqueous sodium hydroxide solution at 50 ° C for 10 minutes, thoroughly washed with warm water, and dried in a 70 ° C dryer for 30 minutes. This first optical substrate was spin-coated with the first adhesive composition obtained in Example 1 using a spin coater 1H-DX2 manufactured by Mikasa Co., Ltd., and dried for 24 hours under conditions of 25 ° C and 50% RH to produce a first laminate in which a urethane urea resin layer was formed on the first optical substrate. At this time, the film thickness of the urethane urea resin layer was set to 10 μm. When the urethane urea resin layer of this structure was confirmed by IR (infrared spectroscopy), a peak intensity of 2200 to 2300 cm was obtained. －１No peaks attributable to isocyanate groups were observed.

[0147] [Production of Second Laminate] The first laminate was heated at 120°C for 0.5 hours to dissociate the blocking agent from the blocked isocyanate and regenerate the isocyanate group. The urethane urea resin layer after heating was observed by IR (infrared spectroscopy) and showed a peak intensity of 2200 to 2300 cm －１ A peak derived from an isocyanate group was confirmed.

[0148] Next, the components described below were mixed to prepare a photochromic (meth)acrylate curable composition. (Meth)acrylate components: 14G (polyethylene glycol dimethacrylate (the average chain length of the ethylene glycol chain is 14 and the average molecular weight is 736)): 40 parts by mass, A-400 (polyethylene glycol diacrylate (the average chain length of the ethylene glycol chain is 9 and the average molecular weight is 508)): 21 parts by mass, TMPT (trimethylolpropane trimethacrylate): 30 parts by mass, PR1 (polyrotaxane synthesized according to the method of Example 10 of WO 2018 / 030257): 3 parts by mass, γ-methacryloyloxypropyltrimethoxysilane: 3 parts by mass, GMA (glycidyl methacrylate): 1 part by mass. Photochromic compound: PC1 (compound represented by the above formula): 2 parts by mass. Photopolymerization initiator: phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (trade name: Omnirad 819, manufactured by IGM): 0.3 parts by mass. Stabilizer: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (molecular weight 508): 3 parts by mass Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (manufactured by BASF, Irganox 245): 1 part by mass

[0149] 2 g of the photochromic (meth)acrylate curable composition was spin-coated onto the urethane urea resin layer of the first laminate at a rotation speed of 100 rpm for 30 seconds, and then at 800 rpm for 10 to 20 seconds, so that the film thickness became 40 μm. Thereafter, the composition was spin-coated in a nitrogen gas atmosphere at an output of 200 mW / cm. ２The photochromic (meth)acrylate curable composition was polymerized by irradiating it with light for 80 seconds using a metal halide lamp, and then heated at 110°C for 3 hours to obtain a second laminate in which a 40 μm-thick acrylic resin-based photochromic layer was formed on the urethane urea resin layer.

[0150] Comparative Example 2 First and second laminates were produced in the same manner as in Example 9, except that the adhesive composition used did not contain the blocked isocyanate.

[0151] <Evaluation Test> [Measurement of Average Molecular Weight of Urethane Prepolymer] The weight-average molecular weight of the urethane prepolymer was measured using GLP under the following conditions. A liquid chromatograph (manufactured by Nihon Waters K.K.) was used as the apparatus. A Shodex GPC KD-806M (exclusion limit molecular weight: 200,000,000) manufactured by Resonaq Co., Ltd. was used as the column. Dimethylformamide (DMF) was used as the developing solution, and measurements were performed at a flow rate of 1 mL / min and a temperature of 40°C. Polystyrene was used as the standard sample, and the weight-average molecular weight and number-average molecular weight were determined by comparative conversion. A differential refractometer was used as the detector. The urethane prepolymer was measured after previously treating it with butylamine to inactivate the isocyanate groups. The number-average molecular weight of the urethane prepolymer determined by this method was 2,000.

[0152] [Measurement of photochromic properties of laminates] The maximum absorption wavelength, color density, and fading speed of the first laminates obtained in Examples 1 to 8 and Comparative Example 1, and the second laminates obtained in Example 9 and Comparative Example 2 were measured.

[0153] Specifically, at a temperature of 23°C, one surface of the laminate was irradiated with a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K. for 120 seconds through an Aeromass filter (manufactured by Corning Inc.) to cause the photochromic compound to develop color. The beam intensity was 365 nm = 2.4 mW / cm. ２ , 245nm=24μW / cm ２ It was decided.

[0154] The maximum absorption wavelength (λmax) after color development was determined using a spectrophotometer (Instant Multichannel PhotoDirector MCPD1000) manufactured by Otsuka Electronics Co., Ltd.

[0155] The absorbance ε(0) of the maximum absorption wavelength of the laminate before irradiation with the xenon lamp was measured. Next, the laminate was irradiated with the xenon lamp at the above beam intensity for 120 seconds, and the absorbance ε(120) of the maximum absorption wavelength of the laminate was measured. The value obtained by subtracting ε(0) from absorbance ε(120) was taken as the color density. The color density was 1.1 in all cases.

[0156] The time required for the color density to decrease to half was measured and taken as the color fading rate [t1 / 2 (sec.)]. The color fading rate was 42 seconds in all cases.

[0157] [Isocyanate Group Regeneration Test] The isocyanate groups in the urethane urea resin layer of the first laminate were eliminated by humidification treatment. This first laminate was heated at 120°C for 30 minutes. After the heat treatment, the urethane urea resin layer of the first laminate was analyzed by Fourier transform infrared spectroscopy (FT-IR) to find that the isocyanate groups in the urethane urea resin layer of the first laminate were quenched at 2200 to 2300 cm. －１ The presence or absence of a peak derived from an isocyanate group located at the position was confirmed, and the evaluation was performed according to the following evaluation criteria. The results are shown in Table 1. -Evaluation criteria- 1: A peak derived from an isocyanate group was detected. 2: A peak derived from an isocyanate group was not detected.

[0158] [Evaluation of Adhesion of Second Laminate (Lens)] The adhesion between the first optical substrate and the second optical substrate in the obtained second laminate (lens) was evaluated by the following method. After cutting the lens into a width of 10 mm, a superhard blade scraper was pressed against the interface with the second optical substrate to check whether peeling was observed, and the evaluation was performed according to the following evaluation criteria. The results are shown in Table 1. -Evaluation criteria- 1: Peeling was easily observed between the first optical substrate and the second optical substrate. 2: Peeling was not easily observed between the first optical substrate and the second optical substrate.

[0159]

[0160] In the above table, the amount of blocked isocyanate means the parts by mass of solid content relative to 100 parts by mass of urethane prepolymer.

[0161] Preferred embodiments of the present disclosure are described below. [1] An adhesive composition containing a urethane prepolymer having an isocyanate group at its terminal, a blocked isocyanate having an isocyanate group protected with a blocking agent, and an organic solvent. [2] The adhesive composition according to [1], wherein the urethane prepolymer comprises a reaction product of an aromatic polyisocyanate compound, a poly(thiol) compound, and a chain extender. [3] The adhesive composition according to [1] or [2], wherein the proportion of the blocked isocyanate relative to the total amount of the urethane prepolymer and the blocked isocyanate is 1 to 40 mass%. [4] The adhesive composition according to any one of [1] to [3], wherein the blocked isocyanate has two or more protected isocyanate groups. [5] The adhesive composition according to any one of [1] to [4], wherein the ratio W1 / W2 of the number-average molecular weight W1 of the urethane prepolymer to the relative molecular mass W2 of the blocked isocyanate is 1 or more and 3,000 or less. [6] The adhesive composition according to any one of [1] to [5], wherein the blocking agent comprises a pyrazole. [7] A laminate comprising: a first optical substrate; and a urethane (urea) resin layer having a blocked isocyanate group, the urethane (urea) resin layer being a coating film of the adhesive composition according to any one of [1] to [6], laminated on the first optical substrate. [8] The laminate according to [7], comprising a urethane (urea) resin layer having an isocyanate group obtained by dissociating the blocking agent from the blocked isocyanate group. [9] The laminate according to [8], further comprising a second optical substrate laminated on the urethane (urea) resin layer having an isocyanate group.

[10] The laminate according to any one of [7] to [9], wherein the first optical substrate comprises a resin film or a resin lens.

[11] The laminate according to

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

[12] The laminate according to

[10] , wherein the resin lens contains at least one resin 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.

[13] An optical article comprising the laminate according to any one of [7] to

[12] .

[14] A lens comprising the optical article according to

[13] .

[15] Eyeglasses comprising the lens according to

[14] .

[16] An adhesive composition comprising: a water-dispersible urethane resin; a blocked isocyanate having an isocyanate group protected with a blocking agent; and water.

[17] A method for producing a laminate, comprising applying the adhesive composition according to any one of [1] to [6] to at least one main surface of a first optical substrate and drying the composition to form a urethane (urea) resin layer having a blocked isocyanate group.

[18] A method for producing a laminate, comprising heating the laminate obtained by the production method according to

[17] at 60 to 150°C to dissociate the blocking agent from the blocked isocyanate groups, thereby obtaining a urethane (urea) resin layer having an isocyanate group.

[19] A method for producing a laminate according to

[18] , comprising forming a coating film of a curable composition on the urethane (urea) resin layer having an isocyanate group, and curing the coating film.

Claims

1. An adhesive composition comprising: a urethane prepolymer having an isocyanate group at its terminal; a blocked isocyanate having an isocyanate group protected with a blocking agent; and an organic solvent.

2. The adhesive composition of claim 1, wherein said urethane prepolymer comprises the reaction product of an aromatic polyisocyanate compound, a poly(thio)ol compound, and a chain extender.

3. The adhesive composition according to claim 1, wherein the proportion of the blocked isocyanate relative to the total amount of the urethane prepolymer and the blocked isocyanate is 1 to 40 mass %.

4. The adhesive composition according to claim 1, wherein said blocked isocyanate has two or more protected isocyanate groups.

5. The adhesive composition according to claim 1, wherein the ratio W1 / W2 of the number average molecular weight W1 of the urethane prepolymer to the relative molecular mass W2 of the blocked isocyanate is 1 or more and 3,000 or less.

6. The adhesive composition of claim 1, wherein said blocking agent comprises a pyrazole.

7. A laminate comprising: a first optical substrate; and a urethane (urea) resin layer having a blocked isocyanate group, the urethane (urea) resin layer being a coating of the adhesive composition according to claim 1 laminated on the first optical substrate.

8. The laminate according to claim 7, further comprising a urethane (urea) resin layer having an isocyanate group obtained by dissociating the blocking agent from the blocked isocyanate group.

9. The laminate according to claim 8, further comprising a second optical substrate laminated on the urethane (urea) resin layer having an isocyanate group.

10. The laminate according to claim 7, wherein the first optical substrate comprises a resin film or a resin lens.

11. The laminate according to claim 10, wherein the resin film contains at least one resin selected from the group consisting of cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, polyvinyl alcohol resin, and polycarbonate resin.

12. The laminate according to claim 10, wherein the resin lens contains at least one resin 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.

13. An optical article comprising the laminate according to claim 7.

14. A lens comprising the optical article of claim 13.

15. Eyeglasses comprising the lens of claim 14.

16. An adhesive composition comprising: a water-dispersible urethane resin; a blocked isocyanate having an isocyanate group protected with a blocking agent; and water.

17. A method for producing a laminate, comprising applying the adhesive composition according to claim 1 onto at least one main surface of a first optical substrate and drying the composition to form a urethane (urea) resin layer having a blocked isocyanate group.

18. A method for producing a laminate, comprising heating the laminate obtained by the method according to claim 17 at 60 to 150°C to dissociate the blocking agent from the blocked isocyanate groups, thereby obtaining a urethane (urea) resin layer having an isocyanate group.

19. A method for producing a laminate according to claim 18, comprising: forming a coating film of a curable composition on the urethane (urea) resin layer having an isocyanate group; and curing the coating film.

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