Adhesive composition, cured product, laminate, optical article, lens, and eyewear

Abstract

The purpose of the present disclosure is to provide an adhesive composition capable of realizing an adhesive layer having excellent functionality, and to provide a cured product, a laminate, an optical article, a lens, and glasses thereof. According to one embodiment, an adhesive composition is provided. The adhesive composition contains a polyurethane urea resin and an organic solvent. The polyurethane urea resin has a urea bond, a urethane bond, and a structure represented by formula (I). In formula (I), R1 and R2 are each independently a linear alkylene group having 3-10 carbon atoms (inclusive). And l is 0 or 1-25 (inclusive). And n and m are each independently 2-70 (inclusive).

Description

TECHNICAL FIELD

[0001] The present application relates to an adhesive composition, a cured product, a laminate, an optical article, a lens, and eyeglasses. BACKGROUND

[0002] Plastic eyeglasses are eyeglasses in which a plastic lens is used as a lens. A plastic lens is manufactured, for example, by applying various kinds of processing to a semi-finished lens as a semi-product. On the surface of the convex face of the semi-finished lens, a functional layer such as a hard coat layer, an anti-reflection film, and the like is provided. Further, on the back face of the concave face of the semi-finished lens, cutting and grinding processing is applied.

[0003] In recent years, light-adjustable lenses having photochromic properties in which the color tone changes depending on the amount of ultraviolet light are attracting attention. A light-adjustable lens can be obtained by imparting a photochromic compound to a plastic lens. A photochromic compound is a compound that can reversibly produce two or more isomers having mutually different absorption spectra by the action of light.

[0004] As a method for manufacturing a photochromic lens, 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 have been used in the past.

[0005] The adhesive sheet method is a method for manufacturing a semi-finished lens by integrating an adhesive sheet with a lens base material, the adhesive sheet being formed by sandwiching a resin layer containing a photochromic compound with two optical sheets. In this method, for example, the adhesive sheet is installed in a metal mold, and then a thermoplastic resin is injection-molded toward it, whereby a semi-finished lens is obtained. If the adhesive sheet method is used, a self-supporting article containing a photochromic compound can be used to manufacture a semi-finished lens, and therefore, compared to the kneading method and the lamination method, there is a tendency to improve production efficiency and to easily mass-produce.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Application Publication No. 2016-169363

[0009] Patent Document 2: International Publication No. 2013 / 099640

[0010] Patent Document 3: Japanese Patent Application Publication No. 2013-033131 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] An object of the present application is to provide an adhesive composition capable of achieving an adhesive layer excellent in function, and to provide a cured product, a laminate, an optical article, a lens, and eyeglasses thereof.

[0013] Solution to problem

[0014] An adhesive composition is provided according to the present disclosure. The adhesive composition includes a polyurethane urea resin and an organic solvent. The polyurethane urea resin has a urea bond, a urethane bond, and a structure represented by the following Formula (I).

[0015]

[0016] In Formula (I), R 1 and R 2 each independently is a linear alkylene group having 3 or more and 10 or less carbon atoms. l is 0 or 1 or more and 25 or less. n and m each independently are 2 or more and 70 or less.

[0017] A cured product is provided according to the present disclosure. The cured product is a cured product of the adhesive composition of the embodiment.

[0018] A laminate is provided according to the present disclosure. The laminate includes a resin layer and an optical substrate. The resin layer includes the cured product of the embodiment.

[0019] An optical article is provided according to the present disclosure. The optical article includes the laminate of the embodiment.

[0020] A lens is provided according to the present disclosure. The lens includes the optical article of the embodiment.

[0021] Eyeglasses are provided according to the present disclosure. The eyeglasses include the lens of the other embodiment.

[0022] Effects of the invention

[0023] According to the present application, an adhesive composition capable of achieving an adhesive layer excellent in function is provided, and a cured product, a laminate, an optical article, a lens, and eyeglasses thereof are provided. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a cross-sectional view schematically showing an example of the laminate of the embodiment.

[0025] Figure 2 is a cross-sectional view schematically showing another example of the laminate of the embodiment.

[0026] Figure 3 is a cross-sectional view schematically showing an example of the laminate of the embodiment including a coating layer.

[0027] Figure 4is a cross-sectional view schematically showing an example of an optical article of the embodiment.

[0028] Figure 5 is a perspective view schematically showing an example of eyeglasses of the embodiment. DETAILED DESCRIPTION

[0029] A bonding composition is provided according to the embodiment. The bonding composition contains a polyurethane urea resin and an organic solvent. The polyurethane urea resin has a urea bond, a urethane bond, and a structure represented by the above formula (I).

[0030] If the bonding composition is used, a bonding layer having excellent functionality can be achieved. The reason is considered as described below. First, a functional pigment contains a compound having the ability to selectively absorb visible light, and a compound that develops color, fades, or changes color by energy such as light, heat, electric field, or pressure. Such a functional pigment can exert a specific function by undergoing a structural change under specific conditions. In general, the matrix of a plastic cured product has a rigid structure. Therefore, the functional pigment in the cured product is less likely to undergo a structural change compared to in a solution, and its function can be limited. The bonding composition of the embodiment contains a polyurethane urea resin having a structure represented by the above formula (I). That is, the polyurethane urea resin has a structure in which a linear alkylene glycol having 3 or more and 10 or less carbon atoms is used as a repeating unit. It is considered that in a cured product of a bonding composition containing such a polyurethane urea resin, the alkylene glycol chain structure contributes to providing a matrix in which a functional pigment easily undergoes a structural change.

[0031] That is, the polyurethane urea resin is a resin containing a plurality of urea bonds (-NH-C(=O)-NH-) and urethane bonds (-OC(=O)N(H)-) generated by polyaddition of isocyanate groups (-N=C=O) with hydroxyl groups (-OH) and polyaddition of isocyanate groups with amino groups (-NH2). It is considered that in such a resin, for example, a high molecular chain obtained by reacting a diisocyanate with a diol and then reacting the obtained urethane prepolymer with a diamine has a complex entangled structure. It is considered that in the polyurethane urea resin, intermolecular interactions are generated between the high molecular chains due to hydrogen bonds and the like. The proportion of heteroatoms such as oxygen atoms per unit mass of the structure represented by formula (I) is less than that of a chain composed of only a polypropylene glycol chain structure, a polycarbonate structure, or a polyester polycarbonate structure. Therefore, it is considered that the structure represented by formula (I) has a lower polarity than other structures, and intermolecular interactions are not easily generated. It is considered that in the cured product of the polyurethane urea resin having the structure represented by formula (I), the cohesiveness of the high molecular chains with each other is low, and therefore the distance between the high molecular chains is relatively large, and a matrix having higher flexibility is formed. Therefore, in the cured product, the structural change of the functional pigment is not easily hindered, and excellent functionality can be exerted.

[0032] Hereinafter, the adhesive composition of the embodiment will be described in detail.

[0033] [Adhesive composition]

[0034] The adhesive composition of the embodiment contains a polyurethane urea resin and an organic solvent.

[0035] (Polyurethane urea resin)

[0036] The polyurethane urea resin has urea bonds, urethane bonds, and a structure represented by the following formula (I). The structure represented by the following formula (I) is basically a structure derived from a diol. For example, it can be confirmed by nuclear magnetic resonance spectroscopy (NMR) analysis that the urea urethane resin has the following structure.

[0037]

[0038] In formula (I), R 1 and R 2 are each independently a linear alkylene group having 3 or more and 10 or less carbon atoms. R 1 and R 2 are each independently a linear alkylene group having 4 or more and 8 or less carbon atoms, and more preferably a linear alkylene group having 4 or more and 6 or less carbon atoms. R 1 and R 2 are particularly preferably n-butylene groups. R 1 and R 2 are preferably the same structure.

[0039] l is 0 or 1 or more and 25 or less. From the viewpoint of improving the functionality of the adhesive layer, l is preferably 0. That is, the softness of the polyalkylene glycol structure is high, and thus if a urethane urea resin having such a structure is used, the functionality of the adhesive layer can be improved. On the other hand, from the viewpoint of improving the adhesion of the adhesive layer, l is preferably 1 or more and 25 or less. That is, if a polyurethane urea resin having a polyether (poly) carbonate structure is used, there is a tendency for the adhesion of the optical substrate or the like to the resin to be improved. When the resin has a polycarbonate structure, there is a tendency for the adhesion to be particularly improved. l is preferably 1 or more and 7 or less, and more preferably 2 or more and 6 or less.

[0040] n and m are each independently 2 or more and 70 or less. When l is 0, m is 0. n and m are each the number of repetitions of R 1 O and R 2 O. n and m are preferably 3 or more. If the proportion of the molecular weight of R 1 O or R 2 O is high, there is a tendency for the functionality of the adhesive layer to be improved. On the other hand, from the viewpoint of improving the heat resistance of the adhesive layer, n and m are preferably 16 or less, and more preferably 11 or less. If the proportion of the molecular weight of R 1 O or R 2 O is low, there is a tendency for the softening point of the polyurethane urea resin to be improved and for the heat resistance of the adhesive layer to be improved. n and m can be 7 or more and 10 or less, 9 or more and 15 or less, 20 or more and 40 or less, 25 or more and 35 or less, or 50 or more and 60 or less.

[0041] The softening point of the polyurethane urea resin is, for example, 40°C or more and 200°C or less. The softening point is preferably 50°C or more, and more preferably 60°C or more. If the softening point is high, there is a tendency for the heat resistance of the adhesive layer to be improved. The softening point can be measured, for example, by thermal mechanical analysis (TMA).

[0042] The urethane urea resin can have a structure represented by the following formula (II).

[0043]

[0044] In formula (II), X is a structure represented by formula (I).

[0045] R 3 and R 4 are each independently a substituted or unsubstituted linear or branched alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted bicycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted diarylene group, norbornene, or a divalent group represented by the following formula (III).

[0046] -R 5 -Y-R 5 - (III)

[0047] In formula (III), R 5 is a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group.

[0048] Y is a substituted or unsubstituted linear or branched alkylene group, or an oxygen atom.

[0049] R 3 may be a structure derived from a diisocyanate. R 3 is preferably a substituted or unsubstituted linear or branched alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted bicycloalkylene group, or a divalent group represented by formula (III), more preferably a substituted or unsubstituted cycloalkylene group.

[0050] R 4 may be a structure derived from a diamine. R 4 is preferably a substituted or unsubstituted linear or branched alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted bicycloalkylene group, or a divalent group represented by formula (III), more preferably a substituted or unsubstituted cycloalkylene group, or a divalent group represented by formula (III). R 3 and R 4 are preferably different structures from each other.

[0051] R 3 or R 4 , the number of carbon atoms of the alkylene group is, for example, 1 or more and 10 or less, preferably 3 or more and 8 or less. The alkylene group is preferably an unsubstituted linear alkylene group.

[0052] In Y, the number of carbon atoms of the alkylene group is, for example, 1 or more and 5 or less, preferably 1 or 2. The alkylene group is preferably an unsubstituted methylene group.

[0053] R 3 , R 4 , or R 5 , the number of carbon atoms of the cycloalkylene group is, for example, 4 or more and 20 or less, preferably 6 or more and 15 or less. The cycloalkylene group is preferably an unsubstituted cyclohexyl group, or a cyclohexyl group having an alkyl group as a substituent.

[0054] R 3 , R 4 , or R 5 , the number of carbon atoms of the arylene group is, for example, 4 or more and 20 or less, preferably 6 or more and 15 or less. The arylene group is preferably an unsubstituted phenylene group, or an unsubstituted naphthylene group.

[0055] p is an integer of 1 or more and 9 or less.

[0056] q is an integer of 3 or more and 56 or less. q is preferably 7 or more and 38 or less.

[0057] Both terminals of the urethane urea resin represented by the above formula (II) can be isocyanate groups or hydroxyl groups, or can be modified with a terminating group. As the terminating group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted piperidyl group, or a substituted or unsubstituted alkylene piperidyl group is preferred. The number of carbons of the alkyl group is, for example, 1 or more and 10 or less, and is preferably 2 or more and 7 or less. The piperidyl group is preferably a 2,2,6,6-tetramethylpiperidyl group. If such a structure is present, there is a tendency for the light stability to improve due to the effect of the hindered amine-based light stabilizer.

[0058] (Organic solvent)

[0059] In the adhesive composition, the polyurethane urea resin can be dissolved in the organic solvent or dispersed in the organic solvent. In the adhesive composition, the proportion of the polyurethane urea resin is, for example, 10 mass% or more and 60 mass% or less. The proportion is preferably 15 mass% or more and 50 mass% or less, and more preferably 20 mass% or more and 40 mass% or less.

[0060] The organic solvent is used as a substance capable of dissolving or dispersing the polyurethane urea resin. The organic solvent includes, for example, at least one selected from the group consisting of N,N-dimethylformamide, N-methyl-2-pyrrolidone (NMP), t-butanol, diethyl ketone, tetrahydrofuran, cyclohexanone, cyclopentanone, methyl isobutyl ketone, and toluene. The organic solvent preferably includes at least one selected from the group consisting of N,N-dimethylformamide, t-butanol, diethyl ketone, tetrahydrofuran, and toluene.

[0061] In the adhesive composition, the organic solvent is the remaining portion of the other substances contained in the adhesive composition. The proportion of the organic solvent is, for example, 40 mass% or more and 90 mass% or less. The proportion is preferably 50 mass% or more and 85 mass% or less, and more preferably 60 mass% or more and 80 mass% or less.

[0062] (Functional pigment)

[0063] The adhesive composition can further include a functional pigment.

[0064] The functional pigment includes, for example, at least one selected from the group consisting of a photochromic compound, an ultraviolet absorber, a blue light absorber, a high-energy visible light absorber, an infrared absorber, a dye, and an electrochromic compound.

[0065] As the photochromic compound, at least one selected from the group consisting of a chromene compound, a fulgide compound, and a spirooxazine compound is used, for example. As the photochromic compound, it is preferable to use a chromene compound. The chromene compound includes a compound having a 1-benzopyran skeleton, a spiropyran compound including a spiropyran skeleton, and a naphthopyran compound having a naphthopyran skeleton. The naphthopyran compound includes an indenonaphthopyran compound having an indenonaphthopyran skeleton. The chromene compound preferably includes an indenonaphthopyran compound having an indenonaphtho[2,1-f]naphtho[1,2-b]pyran skeleton. The cured product of the chromene compound including the indenonaphtho[2,1-f]naphtho[1,2-b]pyran skeleton has a tendency that the durability is excellent.

[0066] The indenonaphthopyran compound preferably includes a compound represented by the following formula (IIIa).

[0067]

[0068] In the formula (IIIa), R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently is a hydrogen atom, a hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which can have a substituent, a halogen atom, an alkylthio group, an arylthio group which can have a substituent, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkyl group which can have a substituent, an aralkoxy group which can have a substituent, an aryloxy group which can have a substituent, an aryl group which can have a substituent, a heteroaryl group which can have a substituent, a thiol group, an alkoxyalkylthio group, a halogenated alkylthio group, a cycloalkylthio group which can have a substituent, or an oligomer group.

[0069] The carbon number of the alkyl group is preferably 1 to 10. As the alkyl group, there can be mentioned, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, and a hexyl group.

[0070] The carbon number of the halogenated alkyl group is preferably 1 to 10. As the halogenated alkyl group, an alkyl group substituted with a fluorine atom, a chlorine atom, or a bromine atom is preferable. As an example of the suitable halogenated alkyl group, there can be mentioned a trifluoromethyl group, a tetrafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

[0071] The ring-forming carbon atom number of the cycloalkyl group is preferably 3 to 8. As the cycloalkyl group, there can be mentioned, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Note that the cycloalkyl group can have a substituent, but the above ring-forming carbon atom number (carbon number 3 to 8) is set as the carbon number excluding the carbon number of the substituent.

[0072] The carbon number of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. As examples of the alkoxy group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and t-butoxy can be given.

[0073] The amino group is a primary amino group (-NH2). The substituted amino group can be a secondary amino group or a tertiary amino group in which one or two hydrogen atoms are substituted. As substituents of the substituted amino group, an alkyl group having a carbon number of 1 to 6, a haloalkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, a cycloalkyl group having a carbon number of 3 to 7, an aryl group having a carbon number of 6 to 14, a heteroaryl group having a carbon number of 4 to 14 and the like can be given. As examples of the suitable amino group, amino, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, diphenylamino and the like can be given.

[0074] The ring-forming atom number of the heterocyclic group is preferably 3 to 10. The heterocyclic group can be an aliphatic heterocyclic group or an aromatic heterocyclic group. Specific examples of the aliphatic heterocyclic group can be given as morpholinyl, piperidinyl, pyrrolidinyl, piperazinyl, N-methylpiperazinyl. Specific examples of the aromatic heterocyclic group can be given as indolinyl. The heterocyclic group can have a substituent. As a preferred substituent, an alkyl group having a carbon number of 1 to 10 can be given. As examples of the suitable heterocyclic group having a substituent, 2,6-dimethylmorpholinyl, 2,6-dimethylpiperidinyl, 2,2,6,6-tetramethylpiperidinyl and the like can be given.

[0075] As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be given.

[0076] The carbon number of the alkylthio group is preferably 1 to 10. As examples of the alkylthio group, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio and t-butylthio can be given.

[0077] The carbon number of the arylthio group is preferably 6 to 10. As examples of the arylthio group, phenylthio, 1-naphthylthio and 2-naphthylthio can be given.

[0078] The carbon number of the alkylcarbonyl group is preferably 2 to 10. As examples of the alkylcarbonyl group, acetyl and ethylcarbonyl can be given.

[0079] The carbon number of the alkoxycarbonyl group is preferably 2 to 10. As examples of the alkoxycarbonyl group, methoxycarbonyl and ethoxycarbonyl can be given.

[0080] The carbon number of the aralkyl group is preferably 7 to 11. As examples of the aralkyl group, benzyl, phenethyl, phenylpropyl, phenylbutyl and naphthylmethyl can be given.

[0081] The carbon number of the aralkyl group is preferably 7 to 11. As examples of the aralkyl group, benzyl, phenethyl, phenylpropyl, phenylbutyl and naphthylmethyl can be given.

[0082] The number of carbons of the aryl group is preferably from 6 to 12. As examples of the aryl group, mention can be made of phenyl, 1-naphthyl and 2-naphthyl.

[0083] The number of carbons of the aryloxy group is preferably from 6 to 12. As examples of the aryloxy group, mention can be made of phenoxy and naphthoxy.

[0084] The number of carbons of the heteroaryl group is preferably from 3 to 12. As examples of the heteroaryl group, mention can be made of thienyl, furanyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl and benzopyrrolinyl.

[0085] The number of carbons of the alkoxyalkylthio group is preferably from 2 to 10. As examples of the alkoxyalkylthio group, mention can be made of methoxymethylthio, methoxyethylthio, methoxy-n-propylthio, methoxy-n-butylthio, ethoxyethylthio and n-propyloxypropylthio.

[0086] The number of carbons of the haloalkylthio group is preferably from 1 to 10. As examples of the haloalkylthio group, mention can be made of trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio and bromomethylthio.

[0087] The number of ring-forming carbon atoms of the cycloalkylthio group is preferably from 3 to 8. As examples of the cycloalkylthio group, mention can be made of cyclopropylthio, cyclobutylthio, cyclopentylthio and cyclohexylthio. Note that the cycloalkylthio group can have a substituent, but the number of ring-forming carbon atoms (the number of carbons from 3 to 8) described above is the number of carbons excluding the substituent.

[0088] The oligomer group contains an oligomer chain, a linking group and a terminal group.

[0089] The oligomer chain can contain at least one selected from the group consisting of a polyalkylene oxide chain, a polysiloxane chain and a polyester chain. The oligomer chain is a divalent group.

[0090] The polyalkylene oxide chain has a linear or branched polyalkylene oxide having a number of carbons of 1 or more and 10 or less as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less. The repeating unit is, for example, -CH2O-, -CH2CH2O-, -CH(CH3)CH2O-, -CH2CH(CH3)O-, -CH2CH2CH2O- or -CH2CH2C(CH3)O-.

[0091] The polysiloxane chain has, for example, dimethylsiloxy (-Si(CH3)2O-) as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less.

[0092] The polyester chain has, for example, -OC(=O)CH2-, -OC(=O)CH2CH2CH2CH2C(=O)O-, or -OC(=O)CH2CH2CH2CH2C(=O)OCH2CH2- as a repeating unit. The number of repetitions of the repeating unit is, for example, 3 or more and 1000 or less.

[0093] The linking group bonds the photochromic compound to one end of the oligomer chain. The linking group is, for example, -O-, -O-CH2CH2-O-, -O-CH2CH2-OC(=O)CH2CH2C(=O)-O-, or -O-CH2CH2-OC(=O)CH2CH2C(=O)-O-CH2-. The linking group can be a divalent group, or a group of two or more valences.

[0094] 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 or more and 10 or less carbon atoms, a linear or branched alkoxy group having 1 or more and 10 or less carbon atoms, a linear or branched alkenyl group having 2 or more and 30 or less carbon atoms, or an organic residue having 1 or more and 10 or less carbon atoms and 1 or more and 3 or less oxygen atoms. The terminal group is preferably a methyl group.

[0095] The oligomer group can include a first linking group, an oligomer chain, and a second linking group. The first linking group and the second linking group can have the same structure as each other, or can have different structures from each other. The first linking group is connected to a first photochromic compound. The second linking group is connected to a second photochromic compound. The first photochromic compound and the second photochromic compound can have the same structure as each other, or can have different structures from each other.

[0096] The above-mentioned cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group can be unsubstituted, or can have a substituent.

[0097] The substituent that the cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group can have is selected from the group consisting of a primary amino group, secondary amino group, tertiary amino group, alkyl group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 10 carbon atoms, hydroxyl group, cycloalkyl group having 3 to 8 carbon atoms, aryl group having 6 or more and 12 or more carbon atoms, alkylaryl group having 1 or more and 20 or less carbon atoms, heterocycloalkyl group having 1 or more and 8 or less carbon atoms and including 1 or more and 5 or less heteroatoms, heteroaryl group having 1 or more and 8 or less carbon atoms and including 1 or more and 5 or less heteroatoms, aryloxy group having 6 or more and 12 or more carbon atoms, arylthio group having 6 or more and 12 or more carbon atoms, cyano group, nitro group, and halogen atom. The number of substituents can be 1, or 2 or more.

[0098] two R's adjacent to each other 13 two R's adjacent to each other 14 and R 15 and R 16 may be bonded to each other to form an aliphatic ring having 2 to 5 carbon atoms, an aliphatic heterocyclic ring having 1 or more and 3 or less heteroatoms and 1 to 4 carbon atoms, an aromatic ring having 4 or more and 12 or less carbon atoms, or an aromatic heterocyclic ring having 1 or more and 6 or less heteroatoms and 3 or more and 11 or less carbon atoms. The aliphatic ring, the aliphatic heterocyclic ring, the aromatic ring, and the aromatic heterocyclic ring can be unsubstituted or can have at least one substituent selected from the above-mentioned substituent group. R 15 and R 16 may form a substituted or unsubstituted spiro ring having the carbon atom at the 13-position as a spiro atom. The ring is preferably an aliphatic ring having 5 to 16 ring-forming carbon atoms. The aliphatic ring further preferably has an alkyl group having 1 to 3 carbon atoms as a substituent.

[0099] In formula (IIIa), r and s are each independently an integer of 0 or more and 4 or less. r and s can be 1 or more, or 2 or more.

[0100] The ultraviolet absorber has an absorption wavelength in the ultraviolet (UV) region of 400 nm or less. The ultraviolet absorber can have a maximum absorption wavelength in the region of 330 nm or more and 380 nm or less, or can have a maximum absorption wavelength in the region of 250 nm or more and less than 330 nm. As the ultraviolet absorber, an organic compound can be used. As the ultraviolet absorber, for example, at least one selected from the group consisting of a benzophenone derivative, ethylhexyl methoxy cinnamate, a benzotriazole derivative, and a triazine derivative is used. The ultraviolet absorber preferably contains at least one selected from the group consisting of a benzophenone derivative, ethylhexyl methoxy cinnamate, and a benzotriazole derivative.

[0101] As the blue light absorber, a compound having an absorption peak in the wavelength region of more than 400 nm and 450 nm or less in an absorption spectrum can be used. As such a compound, for example, at least one selected from the group consisting of a perylene-based compound, a porphyrin-based compound, a carotenoid-based compound, and a cyanine-based compound is used. As the blue light absorber, a porphyrin-based compound is preferably used, and a tetraazaporphyrin compound is more preferably used.

[0102] The high-energy visible light absorber is a blue light absorber having an absorption peak in the wavelength region of 400 nm or more and 420 nm or less. As the high-energy visible light absorber, the same substance as the blue light absorber can be used.

[0103] The dye preferably contains a compound having an absorption peak in a wavelength region of 540 nm or more and 650 nm or less in the absorption spectrum, and more preferably a compound having an absorption peak in a wavelength region of 550 nm or more and 600 nm or less. If such a compound is contained, the anti-glare property of the optical article can be improved. As such a compound, a nitro-based compound, an azo-based compound, an anthraquinone-based compound, a threne-based compound, a porphyrin-based compound, a rare earth metal compound, and the like can be listed. As such a compound, at least one selected from the group consisting of a tetraazaporphyrin compound and a neodymium compound is preferably used.

[0104] As the electrochromic compound, an organic compound such as viologen, a polymer having electrochromic property, a metal salt complex having a d atom, and the like can be listed.

[0105] The proportion of the functional pigment in the adhesive composition is, for example, 0.1% by mass or more and 10% by mass or less, and is preferably 1% by mass or more and 5% by mass or less.

[0106] (Second Polyisocyanate)

[0107] The adhesive composition can further contain a second polyisocyanate. The cured product of the adhesive composition containing the second polyisocyanate can have a crosslinked structure of a uretonimine bond, a biuret bond, or the like between the polyurethane urea resins. The cured product having such a crosslinked structure has a tendency that the softening point is improved, and thus the heat resistance is further improved.

[0108] The second polyisocyanate contains two or more isocyanate groups. The second polyisocyanate preferably has two or three isocyanate groups.

[0109] The second polyisocyanate preferably contains at least one selected from the group consisting of an aliphatic isocyanate, an alicyclic isocyanate, and an aromatic isocyanate compound. The second polyisocyanate more preferably contains an alicyclic isocyanate, a trimer of isocyanate (isocyanurate compound), and a biuret compound of isocyanate. As the second polyisocyanate, a single kind can be used, or a plurality of kinds can be used in mixture.

[0110] Examples of the aliphatic isocyanate can include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4,-trimethylhexamethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio)ethane, and the like.

[0111] Examples of the alicyclic isocyanate can include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate (hydrogenated diphenylmethane diisocyanate), norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, and the like.

[0112] Examples of the aromatic isocyanate can include xylene diisocyanate (o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate), toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 4,4'-diphenylmethane diisocyanate, and the like.

[0113] Examples of the second polyisocyanate can include an isomer mixture of 4,4'-methylenebis(cyclohexyl isocyanate), cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydro-toluene-2,4-diisocyanate, hexahydro-toluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate. In addition to these, urea compounds, biuret compounds, adducts, and the like of polyisocyanate compounds can be used without any limitation, and examples can include a trimer of isophorone diisocyanate (isocyanurate compound), hexamethylene diisocyanate, a biuret compound of hexamethylene diisocyanate, an isocyanurate compound of hexamethylene diisocyanate, and an adduct compound of hexamethylene diisocyanate, and the like.

[0114] In addition, a blocked isocyanate in which the isocyanate group of the second polyisocyanate shown above is blocked, and the like can also be used.

[0115] The proportion of the second polyisocyanate in the adhesive composition is, for example, 1% by mass or more and 20% by mass or less, and is preferably 1% by mass or more and 10% by mass or less.

[0116] The ratio S2 / S1 of the mass S2 of the second polyisocyanate to the mass S1 of the polyurethane urea resin is, for example, 0.05 or more and 0.4 or less, and is preferably 0.05 or more and 0.3 or less.

[0117] (Additives)

[0118] The adhesive composition can contain an additive, which is, for example, at least one selected from the group consisting of a polymerization catalyst, a polymerization initiator, an antistatic agent, an internal mold release agent, an antioxidant, a light stabilizer, a coloration preventive agent, a fluorescent dye, a dye, a pigment, a perfume, a solvent, a leveling agent, and a resin modifier. The adhesive composition preferably contains at least one of an antioxidant and a leveling agent.

[0119] As the antioxidant, 2,6-di-tert-butyl-4-methylphenol; IRGANOX 245 (ethylenebis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-3-methylphenyl]propionate) manufactured by BASF Japan Ltd.; IRGANOX 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) manufactured by BASF Japan Ltd.; IRGANOX 1010 (pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) manufactured by BASF Japan Ltd.; IRGANOX 1035, 1075, 104, 3790, 5057, 565, and the like manufactured by BASF Japan Ltd. can be used.

[0120] As the leveling agent, a silicone surfactant, a fluorine-containing surfactant, or the like can be used. Specifically, L-7001, L-7002, L-7604, FZ-2123 manufactured by DOW CORNING TORAY SILICONE CO., LTD.; MEGAFAC F-470, MEGAFAC F-1405, MEGAFAC F-479 manufactured by DIC Corporation; Fluorad FC-430 manufactured by 3M Japan Ltd., and the like can be used.

[0121] As the light stabilizer, a compound of a hindered amine type having a 2, 2, 6, 6-tetramethyl-4-piperidyl skeleton is preferably used, and commercially available products can be used. Examples thereof include bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} -2, 2, 6, 6-tetramethylpiperidine, 4-benzoyloxy-2, 2, 6, 6-tetramethylpiperidine, methyl (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, 1, 2, 2, 6, 6-pentamethyl-4-piperidyl methacrylate, 2- [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl] methyl] -2-butylmalonic acid [1, 2, 2, 6, 6-pentamethyl-4-piperidyl], poly [ {6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl} (2, 2, 6, 6-tetramethyl-4-piperidyl) imino] hexamethylene { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino}, 1, 2, 2, 6, 6-pentamethyl-4-piperidyl methacrylate, and the like. As trade names, ADEKA STAB (registered trademark) LA series (LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-81, LA-82, and the like) manufactured by ADEKA CORPORATION; TINUVIN (registered trademark) series (TINUVIN 123, TINUVIN 171, TINUVIN 249, TINUVIN 292, TINUVIN 765, TINUVIN 622SF, and the like) manufactured by BASF Japan Ltd.; Chimassorb (registered trademark) series (Chimassorb 2020 FDL, CHimassorb 944 FDL), and the like can be cited.

[0122] Method for producing the adhesive composition

[0123] The adhesive composition of the embodiment can be obtained by mixing the polyurethane urea resin with an organic solvent. The polyurethane urea resin can be a third reaction product of a second reaction product having two isocyanate groups and a monoamine. The second reaction product can be a reaction product of a first reaction product having two isocyanate groups and a first diamine. The first reaction product can be a reaction product of a first diol including a compound represented by the following formula (Ia) and a first polyisocyanate. In other words, the polyurethane urea resin can be obtained by reacting a first diol with a first polyisocyanate to obtain a first prepolymer, reacting the first prepolymer with a first diamine to obtain a second prepolymer, and then reacting the second prepolymer with a monoamine. The details of the method for producing the polyurethane urea resin are described below.

[0124] First, the first polyisocyanate is brought into contact with the first diol to obtain a first reaction product. The first reaction product is a urethane prepolymer having two isocyanate groups, that is, a first prepolymer.

[0125] The first diol includes a compound represented by the following formula (Ia).

[0126]

[0127] In formula (Ia), R 1 , R 2 , 1, m, and n are the same as the definitions in formula (I).

[0128] The number average molecular weight of the first diol based on the hydroxyl value is, for example, 500 or more and 4000 or less. The number average molecular weight is preferably 800 or more and 3000 or less, and more preferably 1000 or more and 2000 or less.

[0129] As the first diol, a polyether diol can be used, a polyether (poly)carbonate diol can be used, and a mixture thereof can be used. As the polyether diol, for example, at least one compound selected from the group consisting of polytetramethylene ether diol (PTMG), poly(penta methylene ether) diol, polyhexamethylene ether diol, polyheptamethylene ether diol, polyoctamethylene ether diol, polynonamethylene ether diol, and polydecamethylene ether diol can be used. As the polyether (poly)carbonate diol, a reaction product obtained by subjecting the above-described polyether diol to a polymerization reaction in the presence of a catalyst with a carbonate compound can be used.

[0130] The first diol can include a polyol compound other than the compound represented by formula (Ia). The polyol compound can include at least one selected from the group consisting of a polyether polyol, a polyester polyol, a polycarbonate polyol, and a polycaprolactone polyol.

[0131] As the polycarbonate polyol, "DUALNOL (registered trademark)" series manufactured by Asahi Kasei Chemicals Corporation, "KURARAY POLYOL (registered trademark)" series manufactured by Kuraray Co., Ltd., "PLACCEL (registered trademark)" series manufactured by Daicel Corporation, "Nipporan (registered trademark)" series manufactured by Nippon Shokubai Co., Ltd., "ETERNACOLL (registered trademark)" series manufactured by UBE Industries, Ltd., and the like can be used.

[0132] The polycaprolactone polyol can be obtained by, for example, ring-opening polymerization of ε-caprolactone. As the polycaprolactone polyol, "PLACCEL (registered trademark)" series manufactured by Daicel Corporation, and the like can be used.

[0133] As the polyether polyol, "EXCENOL (registered trademark)" series and "Emulster (registered trademark)" series manufactured by AGC Inc., "ADEKA Polyester" series manufactured by ADEKA Corporation, and the like can be used.

[0134] As the polyester polyol, "POLYLITE (registered trademark)" series manufactured by DIC Corporation, "Nipporan (registered trademark)" series manufactured by Nippon Shokubai Co., Ltd., "MAXIMOL (registered trademark)" series manufactured by Kawaski Kasei Co., Ltd., and the like can be used.

[0135] As the first polyisocyanate, the same compound as the above-mentioned second polyisocyanate can be used. The first polyisocyanate is preferably an alicyclic polyisocyanate, and more preferably contains at least one selected from the group consisting of isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4' diisocyanate (hydrogenated diphenylmethane diisocyanate), norbornane diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane, and 2,6-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane.

[0136] The ratio M2 / M1 of the molar amount M2 of the first diol to the molar amount M1 of the first polyisocyanate compound is preferably adjusted so as to be 0.30 or more and 0.90 or less. If the ratio M2 / M2 is within the above-mentioned range, a sufficient amount of urethane bond is formed in the first prepolymer. From the viewpoint of improving the functionality of the adhesive layer, the ratio M2 / M1 is preferably 0.40 or more, and more preferably 0.50 or more. From the viewpoint of improving the adhesion of the adhesive layer, the ratio M2 / M1 is preferably 0.85 or less, more preferably 0.80 or less, and further preferably 0.70 or less.

[0137] The ratio S4 / S3 of the mass S4 of the first diol to the mass S3 of the first polyisocyanate is preferably 0.1 or greater and 20 or less. If the ratio S4 / S3 is within the above range, a second prepolymer having a sufficient amount of isocyanate groups per unit mass can be obtained. The ratio S4 / S3 is preferably 1 or greater and 7 or less, more preferably 2 or greater and 5 or less.

[0138] The number average molecular weight of the first prepolymer is preferably 500 or greater and 10,000 or less, more preferably 1,000 or greater and 5,000 or less. The number average molecular weight of the first prepolymer can be measured by the same method as the second prepolymer. The number average molecular weight of the first prepolymer can be measured by, for example, gel permeation chromatography (GPC).

[0139] Next, the first reaction product is contacted with the first diamine to obtain a second reaction product. The second reaction product is a urethane urea prepolymer having two isocyanate groups, that is, a second prepolymer.

[0140] The contacting of the first reaction product with the first diamine can be performed in two stages. That is, the first reaction product can be contacted with a part of the first diamine to obtain a second' reaction product, and then the second' reaction product can be contacted with the remaining part of the first diamine to obtain the second reaction product. The proportion of the part of the first diamine in the total amount of the first diamine is, for example, set to 10 mass% or greater and 50 mass% or less, preferably 20 mass% or greater and 40 mass% or less.

[0141] The number average molecular weight of the second prepolymer is preferably 5,000 or greater, more preferably 10,000 or greater, further preferably 13,000 or greater. If a second prepolymer having a large number average molecular weight is used, there is a tendency that the adhesion of the cured product improves. That is, it is considered that a second prepolymer having a large number average molecular weight easily interlaces with each other, and thus the cohesive force increases, whereby the adhesion improves. The number average molecular weight of the second prepolymer is preferably 50,000 or less, more preferably 40,000 or less, further preferably 30,000 or less. A second prepolymer having a too large number average molecular weight contains a small amount of is (thio) cyanate groups per unit mass, and the adhesion can decrease. The number average molecular weight of the second prepolymer can be measured by gel permeation chromatography (GPC).

[0142] The molar mass of the first diamine is preferably 50 or greater and 500 or less. If a diamine having a molar mass within the range is used, there is a tendency that a second prepolymer having a desired number average molecular weight can be obtained. The molar mass of the diamine is more preferably 50 or greater and 300 or less.

[0143] As the first diamine, there can be mentioned isophorone diamine, ethylene diamine, 1,2-diamino propane, 1,3-diamino propane, 1,2-diamino butane, 1,3-diamino butane, 1,4-diamino butane, 1,5-diamino pentane, 1,6-diamino hexane, piperazine, N,N-bis-(2-aminoethyl) piperazine, bis-(4-aminocyclohexyl) methane, bis-(4-amino-3-butylcyclohexyl) methane, 1,2-diamino cyclohexane, 1,3-diamino cyclohexane, 1,4-diamino cyclohexane, norbornane diamine, hydrazine, adipic acid dihydrazine, phenylene diamine, 4,4'-diphenyl methane diamine, N,N'-diethyl ethylene diamine, N,N'-dimethyl ethylene diamine, N,N'-dipropyl ethylene diamine, N,N'-dibutyl ethylene diamine, N-methyl ethylene diamine, N-ethyl ethylene diamine, bis(hexamethylene) triamine, 1,2,5-pentane triamine, and the like.

[0144] The first diamine preferably contains at least one selected from the group consisting of isophorone diamine, ethylene diamine, bis-(4-aminocyclohexyl) methane, and 1,6-diamino hexane.

[0145] The ratio M3 / M1 of the molar amount M3 of the first diamine to the molar amount M1 of the first polyisocyanate is preferably adjusted so as to be 0.1 or more and 0.9 or less. If the ratio M3 / M1 is within the above range, a sufficient amount of the second prepolymer can be produced. From the viewpoint of improving the adhesion of the adhesive layer, the ratio M3 / M1 is preferably 0.20 or more, more preferably 0.3 or more. From the viewpoint of improving the functionality of the adhesive layer, the ratio M3 / M1 is preferably 0.50 or less, more preferably 0.49 or less.

[0146] The ratio M3 / M2 of the molar amount M3 of the first diamine to the molar amount M2 of the first diol is preferably adjusted so as to be 0.01 or more and 0.9 or less. From the viewpoint of improving the adhesion of the adhesive layer, the ratio M3 / M2 is preferably 0.10 or more, more preferably 0.30 or more, further preferably 0.50 or more.

[0147] The ratio S5 / S6 of the mass S5 of the first diamine to the mass S6 of the first prepolymer is preferably 0.01 or more and 0.5 or less. If the ratio S5 / S6 is within the above range, a second prepolymer having a sufficient amount of isocyanate groups per unit mass can be obtained. The ratio S5 / S6 is more preferably 0.04 or more and 0.3 or less.

[0148] Next, the second reaction product is brought into contact with a monoamine to obtain a third reaction product. The third reaction product is a non-reactive urethane urea polymer having no active groups such as isocyanate groups, i.e., the first polymer.

[0149] The monoamine is preferably a primary amine. The monoamine is preferably an alkylamine or an amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety represented by the following formula (3). The number of carbons of the alkylamine is, for example, 1 or more and 10 or less, and is preferably 2 or more and 7 or less. As the alkylamine, n-butylamine is preferably used. From the viewpoint of improving adhesion, an alkylamine is preferably used.

[0150] The amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety can function as a hindered amine, and thus light stability can be improved.

[0151]

[0152] In formula (3), R 21 is a hydrogen atom or an alkyl group having a number of carbons of 1 or more and 3 or less. R 22 is an alkylene group having a number of carbons of 1 or more and 3 or less. a is 0 or 1.

[0153] The monoamine is preferably 1,2,2,6,6-pentamethyl-4-aminopiperidine in which R 21 is a methyl group and a is 0.

[0154] The ratio M4 / M1 of the molar amount M4 of the monoamine to the molar amount M1 of the first polyisocyanate is, for example, 0.01 or more and 0.5 or less, and is preferably 0.02 or more and 0.2 or less.

[0155] The ratio S7 / S8 of the mass S7 of the monoamine to the mass S8 of the second prepolymer is preferably 0.001 or more and 0.100 or less. If the ratio S7 / S8 is within the above range, the first prepolymer having a sufficient amount of isocyanate groups per unit mass can be obtained. The ratio S7 / S8 is more preferably 0.002 or more and 0.030 or less.

[0156] The generation of the above-described first to third reaction products is preferably performed in an atmosphere of an inactive gas such as nitrogen. The generation of these substances can also be performed in the presence of a reaction solvent. The generation of the first reaction product can be performed without a solvent, the obtained first reaction product is dissolved in a reaction solvent, the first diamine is added to the solution, and a solution containing the second reaction product is obtained. The monoamine can be added to the solution, and a solution containing the third reaction product, that is, the adhesion composition, is obtained. As the reaction solvent, the same substance as the above-described organic solvent can be used. The reaction solvent can be the organic solvent of the adhesion composition. Note that the adhesion composition can be obtained by removing the reaction solvent by drying the solution containing the third reaction product, and then dissolving or dispersing the third reaction product in the organic solvent. Any component such as a functional pigment can be further added to the adhesion composition obtained by the above-described method.

[0157] [Layered Body]

[0158] The laminate of the embodiment, as described above, can be used as an adhesive sheet. The laminate of the embodiment can be used as a functional sheet in which a functional pigment such as a photochromic compound is compounded in a resin layer.

[0159] The laminate includes a resin layer including a cured product of the adhesive composition of the embodiment and an optical substrate. The resin layer is laminated on at least one of the main surfaces of the optical substrate. The laminate can include a first optical substrate and a second optical substrate, and a resin layer interposed between and adhering the first and second optical substrates.

[0160] The thickness of the laminate of the embodiment is preferably 100 μm or more, more preferably 120 μm or more, and further preferably 150 μm or more. If the thickness of the laminate is thick, the shape stability tends to be improved. The upper limit of the thickness of the laminate is not particularly limited, and is, for example, 1000 μm or less, and, for another example, 500 μm or less, and further preferably 400 μm or less. By so designing, the operability can be improved when manufacturing a spectacle lens having a thin center thickness.

[0161] Figure 1 is a cross-sectional view schematically showing an example of the laminate of the embodiment. Figure 1 The laminate 1 shown includes a first optical substrate 2, a second optical substrate 3, and a resin layer 4 interposed between the first and second optical substrates. The first optical substrate 2 includes a first main surface 2a and a second main surface 2b. The first main surface 2a constitutes one of the outermost surfaces of the laminate 1. The second main surface 2b is in contact with the resin layer 4. The second optical substrate 3 includes a first main surface 3a and a second main surface 3b. The first main surface 3a constitutes the other of the outermost surfaces of the laminate 1. The second main surface 3b is in contact with the resin layer 4.

[0162] (First and second optical substrates)

[0163] As the first and second optical substrates, an optical film or sheet having visible light transmittance can be used. The first and second optical substrates can be a colorless transparent film, a translucent film, or a colored transparent film.

[0164] The thickness of the first and second optical substrates is, for example, 10 μm or more and 100 μm or less, and is preferably 20 μm or more and 80 μm or less. The thickness of the second optical substrate can be the same as or different from the thickness of the first optical substrate. The thickness of the first and second optical substrates is, for example, 50 μm or more and 1000 μm or less, or 200 μm or more and 500 μm or less.

[0165] The first and second optical substrates can include at least one resin selected from the group consisting of polycarbonate resin, cellulose resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polyamide resin, polyester resin, polyimide resin, epoxy resin, polyolefin resin, and polyvinyl alcohol resin.

[0166] As the polycarbonate resin, an aromatic polycarbonate resin having an aromatic phenol such as a general bisphenol A skeleton as a main body, further a polymer alloy of the aromatic polycarbonate resin and other resins, and the like can be used. As the other resins, synthetic resins such as polyester resin, polysiloxane, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, and the like can be listed. The polycarbonate resin used for the optical sheet or the optical film preferably has a weight average molecular weight of 10,000 to 200,000, and more preferably 15,000 to 80,000.

[0167] As the cellulose resin, for example, diacetyl cellulose, tripropyl cellulose, dipropyl cellulose, and the like can be listed.

[0168] As the polyamide resin, for example, a polyamide resin obtained by polycondensation of ε-caprolactam, 10-amino capric acid lactam, ω-aminocarboxylic acid such as ω-lauryl lactam, a polyamide resin obtained by co-polycondensation of a diamine and a dicarboxylic acid, and further a copolymer thereof can be used. Among the polyamides obtained by the co-polycondensation, an alicyclic polyimide resin or a semi-aromatic polyimide resin is preferable.

[0169] As the polyester resin, for example, a polycondensate of a dicarboxylic acid such as terephthalic acid, isophthalic acid, and a diol such as ethylene glycol, butanediol, 1,4-cyclohexane dimethanol can be listed.

[0170] As the (meth)acrylic resin, for example, a resin composed of a homopolymer of methyl methacrylate or the like, or a copolymer of a plurality of (meth)acrylic monomers can be used.

[0171] As the polyurethane resin and the polyurethane urea resin, a well-known substance obtained by reacting a diisocyanate compound such as isophorone diisocyanate with a polyol compound such as a polycarbonate polyol, a polyester polyol, and the like can be used. Further, a polyurethane resin or a polyurethane urea resin obtained by reacting a chain extender such as a low molecular weight diol, triol, diamine, triamine, and the like can be appropriately used.

[0172] As the polyimide resin, a polymer of an aromatic tetracarboxylic acid and an aromatic diamine can be suitably used. As the aromatic tetracarboxylic acid, for example, pyromellitic acid, 3,3',4,4'-diphenyltetracarboxylic acid, 2,3',3,4'-diphenyltetracarboxylic 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 an acid anhydride or acid dianhydride thereof, or an aromatic tetracarboxylic acid derived from an ester or halide of these acids can be exemplified.

[0173] As the epoxy resin, for example, a resin obtained by subjecting bisphenol A, bisphenol F or the like to a condensation reaction with epichlorohydrin, other functional epoxy resins, a biphenyl type epoxy resin, or the like can be suitably used.

[0174] As the polyolefin resin, for example, polypropylene, polyethylene, an ethylene-propylene copolymer, an ethylene-a-olefin copolymer, a propylene-a-olefin copolymer, or the like can be suitably used.

[0175] As the first optical substrate and the second optical substrate, a polycarbonate resin is preferably used. If a polycarbonate resin is used, a laminate excellent in adhesion and appearance can be obtained. Further, when an adhesive composition containing a urethane urea resin having a polyether polycarbonate structure is used, there is a tendency that the adhesion to an adhesive layer containing a cured product thereof is improved.

[0176] (Resin layer)

[0177] The resin layer is located between the first optical substrate and the second optical substrate. The resin layer can be in contact with the second main surface of the first optical substrate and the second main surface of the second optical substrate. That is, the resin layer can function as an adhesive layer for adhering the first optical substrate and the second optical substrate.

[0178] The resin layer contains a cured product of the adhesive composition of the embodiment. The cured product is considered to contain a structure represented by Formula (I). The resin layer can contain a functional pigment such as a photochromic compound.

[0179] The thickness of the resin layer is, for example, 0.1 μm or more and 100 μm or less. The thickness of the resin layer can be thinner than the thickness of the first substrate and the second substrate, or can be thicker.

[0180] (Method for manufacturing)

[0181] The manufacturing method of the laminate of the embodiment, for example, includes the following steps: a step of applying the above-mentioned adhesive composition on a support to obtain a coating film; a step of peeling the support from the coating film and laminating it on the second main surface of the first optical substrate; a step of laminating the second optical substrate on the coating film in such a way that the second main surface contacts, thereby obtaining a first structure; and a step of heating the first structure to cure the coating film. Note that the coating film can be directly provided by applying the adhesive composition on the first optical substrate and drying it.

[0182] The manufacturing method of the laminate will be described in detail below.

[0183] First, the first optical substrate and the second optical substrate are prepared. As the first optical substrate and the second optical substrate, commercially available resin films or sheets can be used. Non-stretched sheets can be used, or sheets subjected to stretching treatment and dyeing treatment can be used. As the resin film or resin sheet, commercially available products subjected to saponification treatment can be used, or saponification treatment can be applied. In addition, the first optical substrate and the second optical substrate can be subjected to surface treatment such as etching treatment, corona treatment, and the like.

[0184] Next, the above-mentioned adhesive composition is applied on a support to form a coating film. The coating film is dried at a temperature of 70°C or higher and 150°C or lower for 1 minute or longer and 1 hour or shorter, for example, to obtain a coating film. The coating film peeled from the support is laminated on the second main surface of the first optical substrate. The second main surface of the second optical substrate is laminated in contact with the coating film. Thus, a first structure in which the first optical substrate, the coating film, and the second optical substrate are sequentially laminated is obtained.

[0185] Next, the first structure is heated to cure the coating film. Thus, a laminate in which the first optical substrate and the second optical substrate are bonded via the resin layer is obtained. In the heating treatment of the first structure, heating is performed at a temperature of 40°C or higher and 160°C or lower for 1 minute or longer and 10 hours or shorter, for example.

[0186] The obtained laminate can be subjected to a degassing treatment. In the degassing treatment, the laminate can be left to stand at a temperature of 40°C or higher and 80°C or lower under a vacuum of 500 Pa for 5 hours or longer and 20 hours or shorter, for example. The structure after the degassing treatment can be further subjected to a heating treatment.

[0187] <Layered Body Variation Example 1>

[0188] The laminate can further include a first adhesive layer and a second adhesive layer. The first adhesive layer is located between the resin layer and the first optical substrate to bond them. The second adhesive layer is located between the resin layer and the second optical substrate to bond them.

[0189] Figure 2is a cross-sectional view showing another example of the laminate. Figure 2 The laminate 1a shown has the same structure as the laminate 1 except that the first adhesive layer FA is provided between the resin layer 4 and the first optical substrate 2, and the second adhesive layer SA is provided between the resin layer 4 and the second optical substrate 3. Figure 1 The laminate 1a shown has the same structure as the laminate 1 except that the first adhesive layer FA is provided between the resin layer 4 and the first optical substrate 2, and the second adhesive layer SA is provided between the resin layer 4 and the second optical substrate 3.

[0190] The thickness of the first adhesive layer and the second adhesive layer is, for example, 1 μm or more. If the thickness of the first adhesive layer and the second adhesive layer is thick, there is a tendency that the adhesion of the first optical substrate and the second optical substrate to the resin layer improves. The thickness of the first adhesive layer and the second adhesive layer is preferably 3 μm or more, more preferably 5 μm or more. On the other hand, if the thickness of the first adhesive layer and the second adhesive layer is too thick, there is a tendency that the appearance of the laminate deteriorates. The thickness of the first adhesive layer and the second adhesive layer is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less.

[0191] At least one of the first adhesive layer and the second adhesive layer preferably contains a cured product of the adhesive composition of the embodiment. The components and the contents of the adhesive composition are preferably different from those of the adhesive composition used for forming the resin layer. The first adhesive layer and the second adhesive layer can also contain a cured product of an adhesive composition that does not contain a urethane urea resin represented by Formula (I), but from the viewpoint of photochromic properties, it is preferable that at least a part thereof contains a structure of Formula (1). In addition, as to a urethane urea resin that does not contain a structure represented by Formula (1), for example, in addition to the use of polycarbonate diol as the first diol, it can be obtained by the same production method as the adhesive composition of the above embodiment. The first adhesive layer and the second adhesive layer can also contain at least one resin selected from the group consisting of an epoxy resin, an oxetane resin, an acrylic resin, and a methacrylic resin.

[0192] The first adhesive layer and the second adhesive layer can be formed, for example, by applying an adhesive composition to the surface of at least one of the first optical substrate and the second optical substrate and curing it.

[0193] <Layered Body Variation Example 2>

[0194] The laminate of the embodiment can be provided with a release substrate instead of the optical substrate. The laminate of the embodiment can be a laminate of a first optical substrate, a resin layer, and a release substrate. The laminate can be used as a sealant or a sticker, and the adhesive composition of the embodiment can be used as an adhesive for a sealant.

[0195] As the release substrate, there is no particular limitation as long as it is a substrate having a release property. As the release substrate, paper or plastic can be used. The release substrate can be coated with a release agent on the surface of the substrate.

[0196] When used as a sealant, the release substrate is preferably peeled from the laminate, and the adhesive as the resin layer is attached to the adherend, followed by heating. By heating, it is possible to make the adhesion more robust. The heating temperature is, for example, 50°C or higher and 150°C or lower. The adherend is not particularly limited and can be plastic, metal, stone, wood, or the like. The adherend is preferably plastic.

[0197] <Support>

[0198] The laminate of the embodiment can further include a support. The support can be positioned between the resin layer and the first adhesive layer or the second adhesive layer, or between the first adhesive layer or the second adhesive layer and the first optical substrate or the second optical substrate. The support can further improve the shape stability of the laminate. The support can be colorless and transparent, white and transparent, or colored and transparent.

[0199] The support preferably includes, for example, a resin selected from the group consisting of polyethylene terephthalate, triacetyl cellulose, polyamide, polycarbonate sheet, cellulose acetate butyrate, and (meth)acrylic.

[0200] The thickness of the support is preferably 50 μm or more. If the thickness of the support is thick, the strength of the laminate tends to be further improved. The thickness of the support is not particularly limited, and one example is 1000 μm or less, and another example is 500 μm or less.

[0201] (Method for Manufacturing)

[0202] The method for manufacturing the laminate of the embodiment includes, for example, the steps of: applying a second adhesive composition to a main surface of at least one of the first optical substrate and the second optical substrate, and drying it to provide a first coating film and a second coating film; applying the first adhesive composition to a support to obtain a third coating film; peeling the third coating film from the support, and then laminating it on the first coating film of the first optical substrate; laminating the second optical substrate so that the second coating film is on the third coating film laminated on the first coating film, to obtain a first structure; and heating the first structure to cure the first coating film, the second coating film, and the third coating film. Note that the third coating film can be provided directly by applying the adhesive composition to the first coating film and drying it.

[0203] Hereinafter, the method for manufacturing the laminate of the embodiment will be described in detail.

[0204] First, the second adhesive composition is applied to the second principal surface of the first and second optical substrates using, for example, a bar coater, to form a coating film. The coating film is dried at a temperature of, for example, 70°C or higher and 150°C or lower for 1 minute or longer and 1 hour or shorter. Thus, the first optical substrate having the first coating film formed on one principal surface and the second optical substrate having the second coating film formed on one principal surface are obtained.

[0205] Next, the first adhesive composition described above is applied to a support to form a coating film. The coating film is dried at a temperature of, for example, 70°C or higher and 150°C or lower for 1 minute or longer and 1 hour or shorter. Thus, the third coating film is obtained. The third coating film peeled from the support is laminated on the first coating film of the first optical substrate. Thus, a structure in which the first optical substrate, the first coating film, and the third coating film are sequentially laminated is obtained.

[0206] Next, the second coating film on the second optical substrate is laminated in contact with the third coating film. Thus, a first structure in which the first optical substrate, the first coating film, the third coating film, the second coating film, and the first principal surface of the second optical substrate are sequentially laminated is obtained.

[0207] Next, the first structure is heated to cure the first to third coating films. Thus, a laminate in which the first optical substrate and the second optical substrate are bonded by the first adhesive layer, the resin layer, and the second adhesive layer is obtained. In the heating treatment of the first structure, for example, heating is performed at a temperature of 40°C or higher and 160°C or lower for 1 minute or longer and 240 hours or shorter.

[0208] The obtained laminate can be subjected to a degassing treatment. In the degassing treatment, for example, the laminate can be left to stand at a temperature of 40°C or higher and 80°C or lower under a vacuum of 500 Pa for 5 hours or longer and 20 hours or shorter. The structure after the degassing treatment can be further subjected to a heating treatment.

[0209] At least one of the first adhesive composition and the second adhesive composition is the adhesive composition of the embodiment. As the first adhesive composition, it is preferable to use the adhesive composition of the embodiment, and it is more preferable that both the first adhesive composition and the second adhesive composition are the adhesive composition of the embodiment.

[0210] When the adhesive composition of the embodiment is used as the first adhesive composition and the second adhesive composition, their compositions are preferably different from each other. Specifically, the first adhesive composition preferably contains the functional pigment and the second polyisocyanate, and the second adhesive composition preferably does not contain the functional pigment and the second polyisocyanate. Furthermore, the polyurethane urea resin of the first adhesive composition and the polyurethane urea resin of the second adhesive composition preferably have different compositions. That is, the ratio M2 / M1 of the molar amount M2 of the first diol at the time of production of the polyurethane urea resin contained in the first adhesive composition to the molar amount M1 of the first polyisocyanate compound is preferably higher than the ratio M2 / M1 at the time of production of the polyurethane urea resin contained in the second adhesive composition. Furthermore, the ratio M3 / M1 of the molar amount M3 of the first diamine at the time of production of the polyurethane urea resin contained in the first adhesive composition to the molar amount M1 of the first polyisocyanate compound is preferably lower than the ratio M3 / M1 at the time of production of the polyurethane urea resin contained in the second adhesive composition. By thus using the polyurethane urea resins having different ratios M2 / M1 and ratios M3 / M1, a laminate excellent in both adhesiveness and functionality can be achieved.

[0211] [Layered body with coating layer]

[0212] The layered body of the embodiment can include a coating layer. The coating layer coats at least a part of the first optical substrate and the second optical substrate. The coating layer includes at least one resin selected from the group consisting of an epoxy resin, an oxetane resin, an acrylic resin, a methacrylic resin, and a urethane resin. The layered body with a coating layer contains a coating layer, and thus is excellent in process stability. Furthermore, the adhesion to the optical element substrate described below is excellent.

[0213] Figure 3 is a cross-sectional view schematically showing an example of the layered body with a coating layer of the embodiment. Figure 3 The layered body with a coating layer 7 shown in the figure is provided with Figure 1 The layered body 1 shown in the figure, the first coating layer 5 which coats the first main surface 2a of the first optical substrate 2 entirely, and the second coating layer 6 which coats the first main surface 3a of the second optical substrate 3 entirely. The first coating layer 5 can also coat a part of the first main surface 2a, and the second coating layer 6 can also coat a part of the first main surface 3a. One of the first coating layer 5 and the second coating layer 6 can also be omitted. Note that the layered body 1a shown in the figure can also be used instead of the layered body 1. Figure 2 The layered body 1a shown in the figure can also be used instead of the layered body 1.

[0214] <Coating layer>

[0215] The coating layer coats at least a portion of the surface of at least one of the first optical substrate and the second optical substrate. The coating layer preferably coats the surfaces of both the first optical substrate and the second optical substrate. The coating layer preferably coats the entire surfaces of the first optical substrate and the second optical substrate. At the surfaces of the first optical substrate and the second optical substrate, if the area coated by the coating layer is large, there is a tendency for the adhesion of the optical element substrate and the shape stability of the laminate to improve.

[0216] The thickness of the coating layer is, for example, 5 μm or more. If the thickness of the coating layer is thick, there is a tendency for the adhesion of the optical element substrate and the shape stability of the laminate to improve. The thickness of the coating layer is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 25 μm or more. On the other hand, if the thickness of the coating layer is excessively thick, there is a tendency for the appearance of the laminate to deteriorate. The thickness of the coating layer is preferably 100 μm or less, more preferably 75 μm or less, and further preferably 50 μm or less.

[0217] The coating layer contains at least one kind of resin selected from the group consisting of an epoxy resin, an oxetane resin, an acrylic resin, a methacrylic resin, and a urethane resin. The coating layer preferably contains an epoxy resin. The coating layer containing an epoxy resin has a tendency for the appearance to be excellent and for the adhesion to the optical element substrate to be higher. The kind of the resin contained in the coating layer can be confirmed by gas chromatography, Fourier transform infrared spectroscopy (FT-IR) analysis.

[0218] The surface of the coating layer preferably has at least one kind of functional group selected from the group consisting of an epoxy group, an acryloyl group, a methacryloyl group, and a vinyl group. If the coating layer having these functional groups on the surface is provided, there is a tendency for the adhesion to the optical element substrate to improve. The coating layer more preferably contains at least one kind of functional group selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl group and contains an epoxy group. Such a coating layer can further improve the adhesion.

[0219] The fact that the surface of the coating layer has a functional group can be confirmed by, for example, Fourier transform infrared spectroscopy (FT-IR) analysis. That is, when the surface has an acryloyl group, a methacryloyl group, or a vinyl group, a peak is detected in the range of 1600 cm -1 1600 cm -1 -1 and 1680 cm -1 -1 and 1000 cm -1 -1.

[0220] The coating layer can be formed, for example, by applying a coating layer-forming composition on the surface of at least one of the first optical substrate and the second optical substrate and curing it. The coating layer-forming composition contains, for example, at least one resin selected from the group consisting of an epoxy resin, an oxetane resin, an acrylic resin, a methacrylic resin, and a urethane resin, and an organic solvent.

[0221] [Optical article]

[0222] The optical article of the embodiment contains the laminate of the embodiment. The optical article can contain the laminate of the embodiment, and an optical element substrate that covers at least a part of the first optical substrate and the second optical substrate.

[0223] As the optical article, a binder sheet, a lens, eyeglasses, a window material for houses and automobiles, a liquid crystal display, a sun visor, a timepiece, and the like can be cited. The lens contains a semi-finished lens and a finished lens.

[0224] Figure 4 is a cross-sectional view schematically showing an example of the optical article of the embodiment. Figure 4 The optical article 10 shown contains a first optical element substrate 11 and Figure 1 The laminate 1 shown. The optical article 10 has a concave-convex lens shape. The laminate 1 has a curved surface along the lens shape. The first optical element substrate 11 is located on the concave side. The first optical element substrate 11 covers the entire surface of the unshown second optical substrate of the laminate 1. The side surface of the laminate 1 is not covered by the first optical element substrate 11. The side surface of the laminate 1 can also be covered by the first optical element substrate 11. The laminate 1 and the first optical element substrate 11 can be integrated, for example, by heat fusion.

[0225] The optical article of the embodiment can use Figure 2 the laminate 1a shown instead of Figure 1 the laminate 1 shown, and Figure 3 the coating layer-containing laminate 7 shown instead of Figure 1 the laminate 1 shown. The first optical element substrate 11 can cover the entire surface of the first coating layer 5 of the coating layer-containing laminate 7.

[0226] Figure 5 is a perspective view schematically showing an example of the eyeglasses of the embodiment. Figure 5 The eyeglasses 100 shown contain a lens 101 and a frame 102 that supports the lens 101. The lens 101 contains the optical article 10 of the embodiment.

[0227] (Optical element substrate)

[0228] The optical element substrate can include a resin. The resin can include at least one selected from the group consisting of a polyester resin, a polyamide resin, an allyl resin, a (meth)acrylic resin, a polyurethane resin, a polyurethane urea resin, a polythiourethane resin, a polythiourethane urea resin, a polythioepoxy resin, and a polycarbonate resin. The optical element substrate preferably includes a polycarbonate resin.

[0229] Method for manufacturing optical article

[0230] The optical article of the embodiment can be manufactured, for example, by the following method.

[0231] First, the laminate is subjected to shape processing. Specifically, the laminate is set in a mold of a surface processing device. The mold has, for example, a lens shape such as a semispherical shape. A hole is provided on the bottom surface of the mold. A pressure adjusting device such as a vacuum pump is connected to the hole by a pipe. The pressure adjusting device is activated to reduce the pressure of the space between the mold and the laminate. At this time, the ambient temperature can be set to 70°C or higher and 160°C or lower so that the laminate is easily deformed. After a prescribed time has elapsed, the operation of the pressure adjusting device is stopped, and the deformed laminate is taken out of the mold. The taken-out laminate is cooled at a temperature of, for example, 0°C or higher and 40°C or lower. The thus-operated laminate subjected to surface processing is obtained.

[0232] Next, the deformed laminate is set in the inside of a mold for injection molding. A liquid thermoplastic resin is poured into the back surface (concave surface) of the set laminate. The inside of the mold is cooled to solidify the thermoplastic resin. The thus-operated optical article in which the thermoplastic resin of the optical element substrate is integrated with the laminate is obtained.

[0233] Alternatively, a curable composition of a thermosetting resin is poured into a casting mold in which the laminate is set to fill the inside of the mold with the curable composition. The casting mold after the curable composition is filled is subjected to heat treatment to cure the curable composition. At the time of the heat treatment, for example, the temperature is gradually increased from normal temperature to a curing temperature, and after the curing temperature is reached, a prescribed time is kept. The curing temperature is, for example, 60°C or higher and 100°C or lower. The rate of temperature increase is, for example, 1°C / hour or higher and 10°C / hour or lower. The time of keeping at the curing temperature is, for example, 1 hour or longer and 30 hours or shorter. After the heat treatment is completed, the cured product is taken out of the casting mold. The taken-out cured product is further heated at 60°C or higher and 150°C or lower for 1 hour or longer and 10 hours or shorter. The thus-operated optical article in which the surface of the second optical substrate of the laminate is covered with the optical element substrate is obtained.

[0234] Example

[0235] The present application will be further explained in detail by the following examples. These examples are only for illustrating the present application, but the concept and scope of the present application are not limited by these examples.

[0236] Hereinafter, the abbreviations of compounds and the like used as each component in the examples and comparative examples are summarized.

[0237] Photochromic compound

[0238] PC1: Compound represented by the following formula

[0239]

[0240] 1st diol

[0241] PL1: PEPCD NT2006 manufactured by Mitsubishi Chemical Corporation (polyether polycarbonate diol composed of polytetramethylene ether having a number average molecular weight of 650, number average molecular weight 2000)

[0242] PL2: PEPCD NT1002 manufactured by Mitsubishi Chemical Corporation (polyether polycarbonate diol composed of polytetramethylene ether having a number average molecular weight of 250, number average molecular weight 1000)

[0243] PL3: PEPCD NT2002 manufactured by Mitsubishi Chemical Corporation (polyether polycarbonate diol composed of polytetramethylene ether having a number average molecular weight of 250, number average molecular weight 2000)

[0244] PL4: Polytetramethylene ether 1000 manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd. (polyether polyol, number average molecular weight 1000)

[0245] PL5: Polytetramethylene ether 2000 manufactured by Fuji Photo Film Co., Ltd. and Wako Pure Chemical Industries, Ltd. (polyether polyol, number average molecular weight 2000)

[0246] PL6: PTMG4000 manufactured by Mitsubishi Chemical Corporation (polytetramethylene ether diol, number average molecular weight 4000)

[0247] PL7: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 1000)

[0248] PL8: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 2000)

[0249] The properties of the 1st diol are summarized in Table 1 below.

[0250] [Table 1]

[0251]

[0252] First polyisocyanate and second polyisocyanate

[0253] NCO1: isophorone diisocyanate

[0254] NCO2: dicyclohexylmethane-4,4-diisocyanate

[0255] NCO3: DURANATE TPA-100 (polyisocyanate having isocyanurate structure) manufactured by Asahi Kasei Chemicals Corporation

[0256] NCO4: DURANATE 24A-100 (polyisocyanate having biuret structure) manufactured by Asahi Kasei Chemicals Corporation

[0257] NCO5: DURANATE AE700-100 (polyisocyanate having adduct structure) manufactured by Asahi Kasei Chemicals Corporation

[0258] NCO6: DURANATE E402-100 (polyisocyanate having adduct structure) manufactured by Asahi Kasei Chemicals Corporation

[0259] NCO7: DURANATE SBB-70P (polyblocked isocyanate having biuret structure) manufactured by Asahi Kasei Chemicals Corporation

[0260] NCO8: TRIXENE BI7992 (polyblocked isocyanate having biuret structure) manufactured by GSI Creos Corporation

[0261] First diamine

[0262] H1: bis(4-aminocyclohexyl)methane

[0263] H2: isophorone diamine

[0264] Monoamine

[0265] HA1: 1,2,2,6,6-pentamethyl-4-aminopiperidine

[0266] HA2: n-butylamine

[0267] Organic solvent

[0268] D1: mixed solvent of diethyl ketone / tert-butanol = volume ratio 8 / 2

[0269] D2: propylene glycol monomethyl ether

[0270] D3: diethyl ketone

[0271] Other ingredients

[0272] L1: ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]

[0273] L2: FZ2162 manufactured by Dow Chemical Company

[0274] (Synthesis of polyurethane urea resin solutions US1 to US16)

[0275] In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen introduction tube, polyether polycarbonate diol (PL1) having a number average molecular weight of 2000, 269.9 g, and isophorone diisocyanate (NCO1), 50 g, were charged, and the reaction was allowed to proceed at 130°C for 8 hours under a nitrogen atmosphere to synthesize a urethane prepolymer. The end of the reaction was confirmed by a back titration method of isocyanate groups. After the end of the reaction, the reaction liquid was cooled to the vicinity of 30°C, and dissolved in a mixed solvent of diethyl ketone / tert-butanol = 8 / 2 (component of organic solvent), 630 g (D1). After the reaction solution was cooled to 0°C, bis(4-aminocyclohexyl)methane (H1), 4.97 g, was added dropwise as a chain extender. After stirring for 1 hour, the reaction solution was warmed to 25°C. Then, 10.43 g of H1 was further added dropwise, and stirred for 1 hour. Then, 1,2,2,6,6-pentamethyl-4-aminopiperidine (HA1), 4.1 g, was further added dropwise, and allowed to react for 1 hour to obtain a diethyl ketone / tert-butanol solution of a urethane urea resin, US1. For the obtained polyurethane urea resin, infrared absorption spectrum was measured, and as a result, no absorption derived from isocyanate groups was confirmed at the molecular terminal, and it was confirmed that no isocyanate groups remained at the molecular terminal. Further, the softening point measured by TMA was 95°C.

[0276] Polyurethane urea resin solutions US2 to US16 were obtained by the same method as in the polyurethane urea resin solution US1 except that the compounding components were changed as shown in Table 2.

[0277] [Table 2]

[0278]

[0279] Note that in the "compounding molar ratio" in Table 2, the molar ratio of the first diol / the first isocyanate / the first diamine / the monoamine is described.

[0280] Example 1

[0281] (Preparation of photochromic adhesive composition AC1)

[0282] A urethane urea resin solution US 150 g, a photochromic compound (PC1) 1.27 g, dicyclohexylmethane-4,4-diisocyanate 2.8 g as a crosslinking agent, and ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] 0.2 g as an antioxidant, FZ2162 0.016 g as a surfactant were stirred / mixed at room temperature to obtain a mixture for constituting a photochromic adhesive composition.

[0283] <Examples 2 to 13, 27 to 35, Comparative Examples 1 to 3>

[0284] An adhesive composition AC2 to AC16 was obtained by the same method as in Example 1 except that the formulation was changed as shown in Table 3.

[0285] [Table 3]

[0286]

[0287] <Example 14>

[0288] (Production of photochromic laminate)

[0289] A polyurethane urea resin solution US 14 was used as the adhesive composition AC16 for the formation of the adhesive layer. The adhesive composition AC16 was applied to one main surface of a polycarbonate sheet having a thickness of 300 μm, and the coating film was dried at 110°C for 10 minutes to obtain a polycarbonate sheet having an adhesive layer with a film thickness of 10 μm. Two pieces of the polycarbonate sheet were obtained.

[0290] The adhesive composition AC1 was applied to a PET (polyethylene terephthalate) film (PUREX film manufactured by Teijin DuPont Film Co., Ltd., with a silicon coating film), and the coating film was dried at 80°C for 5 minutes to obtain a dried film having a thickness of about 30 μm. The dried film was peeled from the PET film, and the dried film was disposed between the polycarbonate sheets having the adhesive layers in contact with each other. After the laminate was left at 40°C under vacuum for 20 hours, it was subjected to a heat treatment at 100°C for 1 hour, followed by a humidity treatment at 60°C at 80% RH for 22 hours, and finally left at 80°C under vacuum for 6 hours, thereby obtaining a photochromic laminate LB1 in which a first optical substrate, a first adhesive layer, a resin layer, a second adhesive layer, and a second optical substrate were sequentially laminated.

[0291] <Examples 15 to 26, 36 to 44, Comparative Examples 4 and 5>

[0292] A laminate LB2 to LB15 was obtained by the same method as in Example 14 except that the type of the adhesive composition was changed as shown in Table 4 and Table 5.

[0293] Example 45

[0294] A laminate LB25 was obtained in the same manner as in Example 14, except that a polycarbonate sheet having a thickness of 100 μm was used, and the type of the adhesive composition was changed as shown in Table 5.

[0295] Example 46

[0296] A laminate LB25 was obtained in the same manner as in Example 14, except that a polycarbonate sheet having a thickness of 200 μm was used, and the type of the adhesive composition was changed as shown in Table 5.

[0297] Example 47

[0298] (Preparation of the photochromic adhesive composition AC25)

[0299] A photochromic adhesive composition AC25 was obtained by stirring / mixing a urethane urea resin solution US4 50 g, a photochromic compound (PC1) 1.27 g, and as an antioxidant, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] 0.2 g, as a surfactant, FZ2162 0.016 g, at room temperature.

[0300] Comparative Example 6

[0301] An adhesive composition AC26 was obtained in the same manner as in Example 47, except that US9 was used in the urethane urea resin solution as shown in Table 6.

[0302] Example 48

[0303] A saponified TAC (cellulose triacetate) film having a thickness of 60 μm was prepared as a first optical substrate. The adhesive composition AC25 was applied to the TAC film, and the coating film was dried at 80°C for 5 minutes to obtain a dried film having a thickness of about 30 μm. The dried film was disposed in contact with a diethylene glycol bisallyl carbonate resin having a thickness of about 2 mm as a bonded substrate. The laminate was subjected to a heat treatment at 90°C for 1 hour, whereby a photochromic laminate LB28 in which the first optical substrate, the resin layer, and the bonded substrate were sequentially laminated was obtained.

[0304] Comparative Example 7

[0305] A photochromic laminate LB29 was obtained in the same manner as in Example 48, except that the type of the adhesive composition was changed as shown in Table 7.

[0306] Evaluation

[0307] For the obtained laminates in the examples and comparative examples, the photochromic properties and the peeling strength were measured. The results thereof are shown in Tables 4 to 7.

[0308] Photochromic properties

[0309] The obtained laminates were used as a test sample, and a color development was performed by irradiating the surface of the laminate with light having a beam intensity of 365 nm = 2.4 mW / cm 2 , 245 nm = 24 μW / cm 2 for 300 seconds at 23°C using a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K. through an aeromas filter (manufactured by Corning Incorporated), and the photochromic properties of the laminate were measured.

[0310] 1) Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development was measured by a spectrophotometer (MCPD1000, manufactured by Otsuka Electronics Co., Ltd.). The maximum absorption wavelength is related to the color tone at the time of color development.

[0311] 2) Color development concentration [ε(120) - ε(0)]: The difference between the absorbance ε(120) after irradiation for 300 seconds at the aforementioned maximum absorption wavelength and the absorbance ε(0) at the time of non-irradiation at the maximum absorption wavelength. It can be said that the higher the value, the more excellent the photochromic properties.

[0312] 3) Fading speed [t1 / 2 (sec.)]: The time required for the absorbance at the aforementioned maximum wavelength of the test sample to decrease to 1 / 2 of [ε(120) - ε(0)] at the time of stopping the irradiation of light after irradiation for 300 seconds. It can be said that the shorter the time, the more excellent the photochromic properties.

[0313] Peeling strength

[0314] The obtained photochromic laminates were made into test pieces having an adhesive portion of 25 x 100 mm, and mounted to a testing machine (AUTOGRAPH AGS-500NX, manufactured by Shimadzu Corporation) equipped with a constant temperature tank, and after being left at 70°C for 10 minutes, a tensile test was performed at a crosshead speed of 100 mm / min, and the peeling strength was measured.

[0315] [Table 4]

[0316]

[0317] [Table 5]

[0318]

[0319] [Table 6]

[0320]

[0321] [Table 7]

[0322]

[0323] As is clear from the above examples, the laminate obtained by using the photochromic composition mixed with the polyurethane urea resin having the structure represented by Formula (I) has excellent photochromic properties. By using the polyurethane having a high softening point derived from a polyether polycarbonate diol, the peeling strength is increased. Further, by using the polyurethane urea resin having the structure represented by Formula (I) also in the adhesive layer, the excellent photochromic properties are further exhibited. Further, by compounding a triisocyanate into the adhesive composition, it is possible to increase the peeling strength without reducing the discoloration speed.

[0324] On the other hand, when a polycarbonate diol is used as in Comparative Example 1, sufficient photochromic properties cannot be obtained. Further, although the photochromic properties are improved by increasing the molecular weight of the polyol as in Comparative Example 2, the photochromic properties are insufficient compared to the polyurethane urea resin having the structure represented by Formula (I).

[0325] As shown in Table 7, the sheet-shaped laminate of Example 48 exhibits excellent photochromic properties. Further, in the laminate of Example 48, the adhesion of the resin layer to the adherend substrate is high, and the laminate cannot be easily peeled by hand. On the other hand, the sheet-shaped laminate of Comparative Example 7 cannot obtain high adhesion.

[0326] Hereinafter, preferred modes of the present application are described.

[0327] [1] An adhesive composition comprising:

[0328] a polyurethane urea resin having a urea bond, a urethane bond, and a structure represented by the following Formula (I), and

[0329] an organic solvent.

[0330]

[0331] In the aforementioned Formula (I),

[0332] R 1 and R 2 each independently is a linear alkylene group having 3 or more and 10 or less carbon atoms,

[0333] l is 0, or is 1 or more and 25 or less,

[0334] n and m each independently are 2 or more and 70 or less.

[0335] [2] The adhesive composition according to [1], wherein, in the aforementioned formula (I), 1 is 1 or more and 25 or less.

[0336] [3] The adhesive composition according to [1] or [2], further comprising a functional pigment.

[0337] [4] The adhesive composition according to any one of [1] to [3], further comprising a photochromic compound.

[0338] [5] The adhesive composition according to any one of [1] to [4], wherein,

[0339] the aforementioned polyurethane urea resin comprises a third reaction product of a second reaction product having two isocyanate groups and a monoamine,

[0340] the aforementioned second reaction product comprises a reaction product of a first reaction product having two isocyanate groups and a first diamine,

[0341] the aforementioned first reaction product comprises a reaction product of a first diol and a first polyisocyanate, and the aforementioned first diol comprises a compound represented by the following formula (la).

[0342]

[0343] in the aforementioned formula (la), R 1 , R 2 , 1, m, and n are the same as the definitions in the aforementioned formula (I).

[0344] [6] The adhesive composition according to [5], wherein a ratio M3 / M2 of a molar amount M3 of the aforementioned first amine to a molar amount M2 of the aforementioned first diol is 0.1 or more and 0.9 or less.

[0345] [7] The adhesive composition according to [5] or [6], wherein a number average molecular weight based on a hydroxyl value of the aforementioned first diol is 500 or more and 4000 or less.

[0346] [8] The adhesive composition according to any one of [1] to [7], wherein a softening point based on thermal mechanical analysis (TMA) of the aforementioned polyurethane urea resin is 40°C or more and 200°C or less.

[0347] [9] The adhesive composition according to any one of [1] to [8], further comprising a second polyisocyanate compound.

[0348]

[10] A cured product which is a cured product of the adhesive composition according to any one of [1] to [9].

[0349]

[11] A laminate comprising a resin layer and an optical substrate, the aforementioned resin layer comprising the cured product of

[10] .

[0350]

[12] A laminate comprising:

[0351] a first optical substrate and a second optical substrate;

[0352] a resin layer comprising the cured product of

[10] ;

[0353] a first adhesive layer that adheres the aforementioned first optical substrate to the aforementioned resin layer; and,

[0354] a second adhesive layer that adheres the aforementioned second optical substrate to the aforementioned resin layer.

[0355]

[13] The laminate according to

[12] , wherein at least one of the aforementioned first adhesive layer and second adhesive layer comprises the cured product of

[10] .

[0356]

[14] The laminate according to

[11] , wherein the aforementioned optical substrate comprises at least one resin selected from the group consisting of polycarbonate resin, cellulose resin, and polyvinyl alcohol resin.

[0357]

[15] An optical article comprising the laminate of

[11] .

[0358]

[16] A lens comprising the optical article of

[15] .

[0359]

[17] Eyeglasses comprising the lens of

[16] .

Claims

1. An adhesive composition comprising: a polyurethane urea resin having a urea bond, a urethane bond, and a structure represented by the following formula (I); and an organic solvent, in the formula (I), R 1 and R 2 each independently is a linear alkylene group having 3 or more and 10 or less carbon atoms, l is 0, or is 1 or more and 25 or less, n and m are each independently 2 or more and 70 or less.

2. The adhesive composition according to claim 1, wherein, in the formula (I), l is 1 or more and 25 or less.

3. The adhesive composition according to claim 1, further comprising a functional pigment.

4. The adhesive composition according to claim 1, further comprising a photochromic compound.

5. The adhesive composition according to claim 1, wherein the polyurethane urea resin comprises a third reaction product of a second reaction product having two isocyanate groups and a monoamine, the second reaction product comprises a reaction product of a first reaction product having two isocyanate groups and a first diamine, the first reaction product comprises a reaction product of a first diol and a first polyisocyanate, the first diol comprising a compound represented by the following formula (la), In the formula (Ia), R 1 , R 2 , 1, m and n are the same as defined in the formula (I).

6. The adhesive composition according to claim 5, wherein, a ratio M3 / M2 of a molar amount M3 of the first diamine to a molar amount M2 of the first diol is 0.1 or more and 0.9 or less.

7. The adhesive composition according to claim 5, wherein, a number average molecular weight based on a hydroxyl value of the first diol is 500 or more and 4000 or less.

8. The adhesive composition according to claim 1, wherein, a softening point based on thermal mechanical analysis (TMA) of the polyurethane urea resin is 40°C or more and 200°C or less.

9. The adhesive composition according to claim 1, further comprising a second polyisocyanate compound.

10. A cured product, which is a cured product of the adhesive composition according to claim 1.

11. A laminate comprising a resin layer and an optical substrate, the resin layer comprising the cured product according to claim 10.

12. A laminate comprising: a first optical substrate and a second optical substrate; a resin layer comprising the cured product according to claim 10; a first adhesive layer that adheres the first optical substrate to the resin layer; and a second adhesive layer that adheres the second optical substrate to the resin layer.

13. The laminate of claim 12, wherein, at least one of the first adhesive layer and the second adhesive layer comprises the cured product according to claim 10.

14. The laminate of claim 11, wherein, the optical substrate comprises at least one resin selected from the group consisting of a polycarbonate resin, a cellulose resin, and a polyvinyl alcohol resin.

15. An optical article comprising the laminate according to claim 11.

16. A lens comprising the optical article according to claim 15.

17. Eyeglasses comprising the lens according to claim 16.

Images