WO2023085051A1

WO2023085051A1 - Optical laminated sheet, optical article, lens, spectacles, and method for manufacturing optical laminated sheet

Info

Publication number: WO2023085051A1
Application number: PCT/JP2022/039379
Authority: WO
Inventors: 力宏森
Original assignee: 株式会社トクヤマ
Priority date: 2021-11-10
Filing date: 2022-10-21
Publication date: 2023-05-19

Abstract

The purpose of the present invention is to provide an optical laminated sheet having excellent adhesion and appearance, a method for manufacturing the same, and an optical article, lens, and spectacles that include the optical laminated sheet.　According to an embodiment of the present invention, an optical laminated sheet 1 is provided. The optical laminated sheet 1 includes a first optical sheet 2, a second optical sheet 3, and a photochromic adhesive layer 4. The first and second optical sheets include a polyvinyl alcohol resin. The photochromic adhesive layer 4 is interposed between the first optical sheet 2 and the second optical sheet 3, and bonds said sheets. The photochromic adhesive layer 4 includes a cured body of an adhesive composition including a photochromic compound, either a second prepolymer or a first polymer, and the second prepolymer or a third prepolymer.

Description

Optical laminated sheet, optical article, lens, spectacles, and method for producing optical laminated sheet

The present invention relates to an optical laminated sheet, an optical article, a lens, spectacles, and a method for producing an optical laminated sheet.

　Plastic glasses are glasses that use plastic lenses. A plastic lens is manufactured, for example, by subjecting a semi-finished lens, which is a semi-finished product, to various processes. A functional layer such as a hard coat layer or an antireflection film is provided on the convex surface of the semi-finished lens. In addition, cutting and polishing are applied to the back surface, which is the concave surface of the semi-finished lens.

In recent years, attention has been focused on photochromic lenses that change color depending on the amount of ultraviolet light. A photochromic lens is obtained by applying a photochromic compound to a plastic lens. A photochromic compound is a compound that can reversibly generate two or more isomers having different light absorption spectra by the action of light.

Conventional methods for producing photochromic lenses include a kneading method in which a photochromic compound is dispersed in the matrix of a semi-finished lens, and a lamination method in which a layer containing a photochromic compound is provided on the surface of a semi-finished lens. .

The binder sheet method is a method of manufacturing a semi-finished lens by integrating a binder sheet in which a resin layer containing a photochromic compound is sandwiched between two optical sheets with a lens substrate. According to the binder sheet method, a semi-finished lens can be produced using a self-supporting article containing a photochromic compound. Therefore, compared to the kneading method and the lamination method, the production efficiency tends to be higher and mass production tends to be easier. .

　The use of a polyurethane resin or a polyuretaurea resin as a matrix for a resin layer containing a photochromic compound is under study. Also, the use of polyvinyl alcohol resin as the optical sheet is being studied.

JP 2013-033131 A WO2019/163728 WO2019/194281 WO2012/018070 Japanese Patent Application Publication No. 2018-514817 WO2017/115874

An object of the present invention is to provide an optical laminated sheet excellent in adhesion and appearance, a method for producing the same, and an optical article, lens, and spectacles including this optical laminated sheet.

According to embodiments, an optical laminated sheet is provided. The optical laminate sheet includes a first optical sheet, a second optical sheet, and a photochromic adhesive layer. The first and second optical sheets contain polyvinyl alcohol resin. The photochromic adhesive layer is interposed between and adheres the first optical sheet and the second optical sheet. The photochromic adhesive layer contains a cured adhesive composition containing a photochromic compound and a polymerizable component. The polymerized component includes any one of the second prepolymer, the first polymer and the second prepolymer, the first polymer and the third prepolymer, and the first polymer, the second prepolymer and the third prepolymer. The second prepolymer is obtained by reacting the first prepolymer and the second polyfunctional active hydrogen compound. The second prepolymer is a compound having two or more iso(thio)cyanate groups. The second polyfunctional active hydrogen compound has two or more active hydrogen groups. The first prepolymer is obtained by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound. The first prepolymer is a compound having two or more iso(thio)cyanate groups. The first polyfunctional active hydrogen compound has two or more active hydrogen groups. The first iso(thio)cyanate compound has two or more iso(thio)cyanate groups. The first polymer is a compound obtained by reacting the second prepolymer with a monofunctional active hydrogen compound. A monofunctional active hydrogen compound has one active hydrogen group. The third prepolymer is obtained by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound. The third prepolymer has two or more iso(thio)cyanate groups.

According to embodiments, an optical article is provided. An optical article includes an optical laminate sheet according to an embodiment and an optical element substrate. The optical element substrate covers the surface of at least one of the first optical sheet and the second optical sheet, and contains a resin.

According to embodiments, lenses are provided that include optical articles according to other embodiments.

According to embodiments, spectacles including lenses according to other embodiments are provided.

According to the embodiment, a first method for manufacturing an optical laminated sheet is provided. This production method comprises reacting a first polyfunctional active hydrogen compound with a first iso(thio)cyanate compound to obtain a first prepolymer, and reacting the first prepolymer with a second polyfunctional active hydrogen compound. obtaining a second prepolymer; mixing the second prepolymer and a photochromic compound to obtain an adhesive composition; and coating the adhesive composition on at least one major surface of the first optical sheet. obtaining a coating film; and laminating a second optical sheet on the coating film.

According to the embodiment, a second method for manufacturing an optical laminate sheet is provided. This production method comprises reacting a first polyfunctional active hydrogen compound with a first iso(thio)cyanate compound to obtain a first prepolymer, and reacting the first prepolymer with a second polyfunctional active hydrogen compound. obtaining a second prepolymer by reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a first polymer; mixing the first polymer, the second prepolymer, and the photochromic compound obtaining an adhesive composition; coating the adhesive composition on at least one main surface of a first optical sheet to obtain a coating film; and laminating a second optical sheet on the coating film. include.

According to the present invention, an optical laminated sheet excellent in adhesion and appearance, a method for producing the same, and an optical article, lens, and spectacles including this optical laminated sheet are provided.

Sectional drawing which shows an example of a 1st optical lamination sheet roughly. Sectional drawing which shows an example of a 2nd optical lamination sheet roughly. BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing which shows schematically an example of the optical article which concerns on embodiment. BRIEF DESCRIPTION OF THE DRAWINGS The perspective view which shows schematically an example of the spectacles which concern on embodiment.

The photochromic adhesive layer of the optical laminate sheet is sometimes required to have high photochromic properties in addition to the adhesive ability to bond two optical sheets. That is, photochromic compounds exhibit photochromic properties by repeating structural changes between isomers. The matrix of the adhesive layer containing the photochromic compound is required to have properties that do not interfere with this structural change. (Thio)urethane resins, (thio)urea resins, or (thio)urethane urea resins are sometimes used to provide such matrices. Since these resins are reaction products of iso(thio)cyanate and compounds containing active hydrogen groups, resins having desired properties can be obtained by appropriately selecting each component. Furthermore, by using a chain extender having an active hydrogen group, it is possible to further bond the above-mentioned reaction product, so that the structure capable of exhibiting desired properties can be designed in more detail.

Here, (thio)urethane resin means at least one of urethane resin and thiourethane resin. (Thio)urea resin means at least one of urea resin and thiourea resin. A (thio)urethane urea resin means at least one of a urethane urea resin and a thiourethane urea resin. An iso(thio)cyanate group means at least one of an isocyanate group (-C=N=O) and an isothiocyanate group (-C=N=S). A (thio)urethane urea resin is a resin having both a (thio)urethane bond and a (thio)urea bond. A (thio)urethane bond can be produced by a reaction between a compound having an iso(thio)cyanate group and a compound having a hydroxyl group (--OH). A (thio)urea bond can result from a reaction between a compound having an iso(thio)cyanate group and a compound having an amine group (--NH ₂ ). A (thio)urethane urea resin can be obtained by reacting a compound having a (thio)urethane bond and an isocyanate group with an amine.

In the optical laminate sheet according to the embodiment, the photochromic adhesive layer is a cured adhesive composition containing a photochromic compound and a polymerizable component. The polymerized component includes any one of the second prepolymer, the first polymer and the second prepolymer, the first polymer and the third prepolymer, and the first polymer, the second prepolymer and the third prepolymer.

The second prepolymer is obtained by reacting a first prepolymer obtained by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound with a second polyfunctional active hydrogen compound as a chain extender. It is an iso(thio)cyanate compound obtained by The first polyfunctional active hydrogen compound and the second polyfunctional active hydrogen compound may be the same compound or different compounds. Since the second prepolymer is composed of at least two or more components, a cured product in which the photochromic compound is susceptible to structural change can be produced.

Also, the first polymer has a structure in which the iso(thio)cyanate group of the second prepolymer is bonded to a compound having a monofunctional active hydrogen group. The first polymer does not react with iso(thio)cyanate groups at normal temperature and normal pressure, but reacts with the second prepolymer and/or the third prepolymer at high temperature to form two or more iso(thio)cyanate groups. and these are believed to polymerize to give a cured product. Since the first polymer is composed of at least three or more components and also reacts with the second prepolymer and/or the third prepolymer, it is thought that the photochromic compound produces a cured product that is susceptible to structural change.

Further, in the optical laminated sheet according to the embodiment, two optical sheets containing polyvinyl alcohol (PVA) are adhered by an adhesive layer containing a photochromic compound. PVA is a highly hydrophilic resin having —CH ₂ CH(OH)— as a repeating unit, and has hydroxyl groups (—OH) on its surface. In the method for producing an optical laminated sheet according to the embodiment, for example, the second prepolymer, the first polymer and the second prepolymer, the first polymer and the third prepolymer, and the first polymer are formed on the surface of the first optical sheet. and the second prepolymer and the third prepolymer, and then laminating the second optical sheet on the obtained coating film. At this time, the iso(thio)cyanate groups of the second prepolymer chemically react with hydroxyl groups on the surface of PVA contained in the first and second optical sheets. In addition, the iso(thio)cyanate groups contained in the reactants of the first polymer and the second prepolymer and/or the third prepolymer chemically react with the hydroxyl groups on the surface of the PVA contained in the first and second optical sheets. . This increases the bonding strength between the photochromic adhesive layer and the first and second optical sheets. That is, in the optical laminated sheet according to the embodiment, high adhesiveness can be achieved without subjecting the surfaces of the first and second sheets to treatment for imparting hydroxyl groups or the like or using other adhesives or the like.

As described above, the optical laminated sheet according to the embodiment has excellent photochromic properties, high adhesion between the first and second optical sheets, and excellent appearance. Such an optical laminated sheet is suitable for use in optical articles such as sunglasses.

[First optical laminated sheet]
The first optical laminate sheet includes a first optical sheet, a second optical sheet, and a photochromic adhesive layer. The first optical sheet and the second optical sheet are adhered by a photochromic adhesive layer. The photochromic adhesive layer is in direct contact with at least one major surface of the first and second optical sheets.

FIG. 1 is a cross-sectional view schematically showing an example of the first optical laminate sheet. The optical laminated sheet 1 shown in FIG. 1 includes a first optical sheet 2, a second optical sheet 3, and a photochromic adhesive layer 4 interposed therebetween. The photochromic adhesive layer 4 covers the entire one main surface of the first optical sheet 2 and the entire one main surface of the second optical sheet 3 . The photochromic adhesive layer 4 may cover both the entire principal surfaces of the first optical sheet 2 and both the entire principal surfaces of the second optical sheet 3, or may cover only a portion of each principal surface. may

(First and second optical sheets)
The first and second optical sheets contain polyvinyl alcohol (PVA) resin. The first and second optical sheets may be composed only of PVA resin, or may contain other resins. Other resins include aldehyde-modified polyvinyl formal, polyvinyl acetal, polyvinyl butyral, and the like.

The first and second optical sheets may be unstretched, uniaxially stretched, or biaxially stretched. The stretching direction may be the machine direction (MD) of the unstretched film, the direction perpendicular thereto (TD), or the direction oblique to the machine direction. Here, the unstretched sheet is a sheet that is not stretched, and the uniaxially stretched sheet is an unstretched sheet that is stretched in one of the above directions. A biaxially stretched sheet is a sheet stretched in two of the stretching directions described above. It may be an axially stretched sheet. In the case of a biaxially stretched sheet, it is usually preferable to stretch it in MD or TD. The draw ratio is preferably 2 to 8 times.

The average degree of polymerization of the PVA resin is, for example, 100 or more and 10000 or less, preferably 1500 or more and 8000 or less, more preferably 2000 or more and 5000 or less. The average degree of polymerization of PVA resin is determined by a method based on Japanese Industrial Standards (JIS) K6726;1994.
The PVA resin may contain boric acid. Boric acid is used as a cross-linking agent for cross-linking PVA. The boric acid content of the PVA resin is, for example, 1% by mass or more and 20% by mass or less, preferably 3% by mass or more and 18% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. . The boric acid content can be calculated by inductively coupled plasma (IPC) emission spectrometry. Specifically, first, the first or second optical sheet is dissolved in an aqueous nitric acid solution to obtain a solution. IPC analysis is performed using this solution to calculate the boron content. This boron content is converted to the boric acid content.

At least one of the first and second optical sheets may be a polarizing film having polarizing properties. The first and second polarizing optical sheets preferably have a luminous transmittance of 10% or more and 80% or less and a degree of polarization of 30% or more and 99.9% or less.

The polarizing first and second optical sheets contain a dichroic substance. Dichroic substances include iodine and dichroic dyes. The dichroic dye may be an azo dye or an anthraquinone dye. Specific examples of dichroic dyes are Chloranthin Fast Red (CI 28160), Congo Red (CI 22120), Brilliant Blue B (CI 24410), Benzopurpurine (CI 24410). 23500), Chlorazole Black BH (CI 22590), Direct Blue 2B (CI 22610), Diamine Green (CI 30295), Chrysophenine (CI 24895), Sirius Yellow (CI 24895). I.29000), Direct Fast Red (CI23630), Acid Black (CI20470), Direct Sky Blue (CI24400), Solophenyl Blue 4GL (CI34200), Direct Includes Copper Blue 2B (CI 24185) and Nippon Brilliant Violet BKconc (CI 27885).

The thickness of the first optical sheet is, for example, 10 μm or more and 100 μm or less. The thickness of the second optical sheet may be the same as or different from the thickness of the first optical sheet.

(Photochromic adhesive layer)
The photochromic adhesive layer is interposed between and adheres the first optical sheet and the second optical sheet. The photochromic adhesive layer contains a cured adhesive composition, which will be described later. The cured product contains at least one selected from the group consisting of polyurethane resins, polyurethane urea resins, polythiourethane resins, and polythiourethane urea resins, and a photochromic compound.

The thickness of the photochromic adhesive layer is, for example, 0.1 μm or more and 100 μm or less. The thickness of the photochromic adhesive layer may be thinner than or thicker than the thicknesses of the first and second optical sheets.

(Adhesive composition)
The adhesive composition contains a photochromic compound and a polymerizable component. The polymerized component becomes the matrix of the photochromic adhesive layer. The polymerized component includes any one of the second prepolymer, the first polymer and the second prepolymer, the first polymer and the third prepolymer, and the first polymer, the second prepolymer and the third prepolymer. In other words, the adhesive composition comprises a first combination of a polymerized component comprising the second prepolymer and the photochromic compound, a second combination of the polymerized component comprising the first polymer and the second prepolymer and the photochromic compound, a second A third combination of a polymerized component comprising a first polymer and a third prepolymer and a photochromic compound, and a fourth combination of a polymerized component comprising a first polymer, a second prepolymer and a third prepolymer and a photochromic compound. can include

(Photochromic compound)
As the photochromic compound, for example, at least one selected from the group consisting of chromene compounds, fulgide compounds, and spirooxazine compounds is used. A chromene compound is preferably used as the photochromic compound. Chromene compounds include compounds having a 1-benzopyran skeleton. The following formula (I) shows a 2H-1-benzopyran skeleton.

Chromene compounds include spiropyran compounds containing a spiropyran skeleton and naphthopyran compounds having a naphthopyran skeleton. A spiropyran skeleton is a 1-benzopyran skeleton containing a spiro atom. The formula (II) below shows a naphthopyran skeleton.

Naphthopyran compounds include indenonaphthopyran compounds having an indenonaphthopyran skeleton. The chromene compound preferably contains an indenonaphthopyran compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton. A resin composition containing a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton tends to be more excellent in durability. The following formula (III) shows an indeno[2,1-f]naphtho[1,2-b]pyran skeleton.

The indenonaphthopyran compound preferably contains a compound represented by the following formula (IIIa).

In formula (IIIa), the Z ring is a substituted or unsubstituted spiro ring having a spiro atom at the 13-position carbon atom. Z ring, together with the carbon atom at the 13-position, may form an aliphatic ring, may form a condensed polycyclic ring, may form a heterocyclic ring, or may form a heterocyclic aromatic ring. may be formed.

The number of ring member carbon atoms in the aliphatic ring is preferably 3 or more and 20 or less, more preferably 5 or more and 16 or less, and even more preferably 6 or more and 10 or less. Specific examples of aliphatic rings include cyclopentane ring, cyclohexane ring, cyclooctane ring, cycloheptane ring, norbornane ring, bicyclononane ring, adamantane ring, and spirodicyclohexane ring. The aliphatic ring is preferably a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, or spirodicyclohexane ring.

The number of ring member carbon atoms in the condensed polycyclic ring is preferably 3 or more and 20 or less, more preferably 5 or more and 10 or less. A specific example of the condensed polycyclic ring includes a phenanthrene ring.

The number of ring member atoms of the heterocyclic ring is preferably 3 or more and 20 or less. Specific examples of heterocyclic ring include thiophene ring, furan ring and pyridine ring.

The number of ring member atoms in the heterocyclic aromatic ring is preferably 3 or more and 20 or less. Specific examples of heterocyclic aromatic rings include phenylfuran rings and biphenylthiophene rings.

These aliphatic rings, condensed polycyclic rings, heterocyclic rings, or heterocyclic aromatic rings may have substituents. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, and at least one substituent selected from the group consisting of halogen atoms. The substituent is preferably at least one substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a haloalkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. . The number of substituents on the Z ring is, for example, 0 or more and 10 or less, preferably 2 or more and 4 or less.

The Z ring is preferably an aliphatic ring having 5 to 16 ring member carbon atoms. The first chromene compound having such a structure tends to have a high fading rate. The aliphatic ring more preferably has an alkyl group having 1 to 3 carbon atoms as a substituent. In addition, the aliphatic ring also includes an aliphatic condensed ring in which rings are bonded between two atoms.

The Z ring preferably has a structure represented by the following formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), or (Ih). Structures represented by (Ib), (Ig) or (Ih) are more preferred. In the formula, the carbon atom with the broken line bond is the carbon atom at the 13th position.

In formula (IIIa), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an alkyl group, Cycloalkyl group, haloalkyl group, alkoxy group, amino group, substituted amino group, optionally substituted heterocyclic group, halogen atom, alkylthio group, optionally substituted arylthio group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, optionally substituted aralkyl group, optionally substituted aralkoxy group, optionally substituted aryloxy group, substituent , an optionally substituted heteroaryl group, a thiol group, an alkoxyalkylthio group, a haloalkylthio group, or an optionally substituted cycloalkylthio group.
b is an integer of 0 to 4; When b is 2 or more and 4 or less, a plurality of R ⁷ may have the same structure or different structures.

The number of carbon atoms in the alkyl group is preferably 1-10. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

The haloalkyl group preferably has 1 to 10 carbon atoms. As the haloalkyl group, an alkyl group substituted with a fluorine atom, a chlorine atom or a bromine atom is preferred. Examples of suitable haloalkyl groups include trifluoromethyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl and bromomethyl groups.

The number of ring member carbon atoms in the cycloalkyl group is preferably 3-8. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The cycloalkyl group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.

The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy groups.

An amino group is a primary amino group (—NH ₂ ) and a substituted amino group is a secondary or tertiary amino group in which one or two hydrogen atoms have been substituted. Substituents possessed by the substituted amino group include alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 7 carbon atoms, and 6 carbon atoms. to 14 aryl groups, and heteroaryl groups having 4 to 14 carbon atoms. Examples of suitable amino groups include amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, phenylamino group, diphenylamino group and the like.

The number of atoms in the heterocyclic group is preferably 3-10. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Specific examples of aliphatic heterocyclic groups include morpholino, piperidino, pyrrolidinyl, piperazino and N-methylpiperazino groups. Specific examples of aromatic heterocyclic groups include indolinyl groups. The heterocyclic group may have a substituent. Preferred substituents include alkyl groups having 1 to 10 carbon atoms. Suitable heterocyclic groups having substituents include, for example, 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group and 2,2,6,6-tetramethylpiperidino group.

Halogen atoms include, for example, fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

The number of carbon atoms in the alkylthio group is preferably 1-10. Examples of alkylthio groups include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, and t-butylthio groups.

The arylthio group preferably has 6 to 10 carbon atoms. Examples of arylthio groups include phenylthio, 1-naphthylthio, and 2-naphthylthio groups.

The number of carbon atoms in the alkylcarbonyl group is preferably 2-10. Examples of alkylcarbonyl groups include acetyl and ethylcarbonyl groups.

The alkoxycarbonyl group preferably has 2 to 10 carbon atoms. Alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups.

The aralkyl group preferably has 7 to 11 carbon atoms. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, phenylbutyl, and naphthylmethyl groups.

The aralkoxy group preferably has 7 to 11 carbon atoms. Examples of aralkoxy groups include benzyloxy and naphthylmethoxy groups.

The aryl group preferably has 6 to 12 carbon atoms. Examples of aryl groups include phenyl, 1-naphthyl, and 2-naphthyl groups.

The aryloxy group preferably has 6 to 12 carbon atoms. Examples of aryloxy groups include phenyloxy and naphthyloxy groups.

The heteroaryl group preferably has 3 to 12 carbon atoms. Examples of heteroaryl groups include thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, and benzopyrrolinyl groups.

The alkoxyalkylthio group preferably has 2 to 10 carbon atoms. Examples of alkoxyalkylthio groups include methoxymethylthio, methoxyethylthio, methoxy n-propylthio, methoxy n-butylthio, ethoxyethylthio, n-propoxypropylthio and the like.

The haloalkylthio group preferably has 1 to 10 carbon atoms. Examples of haloalkylthio groups include trifluoromethylthio, tetrafluoroethylthio, chloromethylthio, 2-chloroethylthio, and bromomethylthio groups.

The cycloalkylthio group preferably has 3 to 8 carbon atoms. Examples of cycloalkylthio groups include cyclopropylthio, cyclobutylthio, cyclopentylthio, and cyclohexylthio groups. The cycloalkylthio group may have a substituent, but the number of carbon atoms (3 to 8 carbon atoms) does not include the number of carbon atoms in the substituent.

The cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group, and cycloalkylthio group described above may be unsubstituted or may have a substituent.

Substituents that the cycloalkyl group, arylthio group, aralkyl group, aralkoxy group, aryloxy group, aryl group, heteroaryl group and cycloalkylthio group may have are primary amino group, secondary amino group, tertiary class 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, A hydroxyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkylaryl group having 1 to 20 carbon atoms, and a heteroatom having 1 to 5 carbon atoms having 1 to 8 carbon atoms. a heterocycloalkyl group, a heteroaryl group containing 1 to 5 heteroatoms and having 1 to 8 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, a cyano group, It may be selected from the group of substituents consisting of nitro groups and halogen atoms. The number of substituents may be one, or two or more.

R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are bonded to each other to form an aliphatic ring having 2 or more and 5 or less carbon atoms, or It may form an aliphatic heterocyclic ring, an aromatic ring having 4 or more and 12 or less carbon atoms, or an aromatic heterocyclic ring having 3 or more and 11 or less carbon atoms containing 1 or more and 6 or less hetero atoms. An aliphatic ring, an aliphatic heterocyclic ring, an aromatic ring, and an aromatic heterocyclic ring may be unsubstituted or may have at least one substituent selected from the group of substituents described above.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an oligomer group represented by the following formula (IB) or an oligomer group represented by the following formula (IC) , an oligomer group represented by the following formula (ID), an oligomer group represented by the following formula (IE), or an oligomer group represented by the following formula (X). In addition, substituents that R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ may have include an oligomer group represented by the following formula (IB) and a substituent represented by the following formula (IC). at least one selected from the group consisting of an oligomer group represented by the following formula (ID), an oligomer group represented by the following formula (IE), and an oligomer group represented by the following formula (X) It may also be an oligomeric group of species.

In Formula (IB), X ¹ is an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a (thio)amide group, a (thio)ester group, or an alkylene group having 1 to 10 carbon atoms. Y ¹ and Y ² are each an alkylene group having 1 to 20 carbon atoms. W ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. c is 0 or 1; d and e are each 0 or an integer of 1 to 10; m is an integer of 3 or more and 200 or less.

In Formula (IC), X ¹ , Y ¹ , Y ² , c, d, e, and m have the same meanings as in Formula (IB). ^X2 is an oxygen atom, a sulfur atom, an amino group, a substituted amino group, a (thio)amide group, a (thio)ester group, or an alkylene group having 1 to 10 carbon atoms. ^W2 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a photochromic moiety. f is 0 or 1;

In formula (ID), ^W3 is an alkyl group having 1 to 20 carbon atoms. g is 0 or 1; n is an integer of 3 or more and 200 or less.

In Formula (IE), ^W4 is an alkyl group having 1 to 20 carbon atoms or a photochromic moiety. g and n have the same definitions as in formula (ID). h is 0 or 1;

In formula (X), E is an oxygen atom or ^NR101 . F is an oxygen atom or a sulfur atom. G is an oxygen atom, a sulfur atom, or ^NR202 . j is an integer of 0 or 1; R ¹⁰¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ²⁰¹ and R ²⁰² are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon containing 1 to 5 hetero atoms It is a heteroaryl group having a number of 1 or more and 8 or less, and when G is an oxygen atom or a sulfur atom, R ²⁰¹ is a group other than a hydrogen atom.

The naphthopyran compound preferably contains a compound represented by the following formula (IIa).

In formula (IIa), Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ are respectively R ¹ , R ² , R 3 , R ⁴ ^, R ⁵ , R ⁶ , and groups similar to ^R7 can be used.

The proportion of the photochromic compound in the solid content of the adhesive composition is, for example, 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less.

(Second prepolymer)
The second prepolymer is obtained by reacting a first prepolymer obtained by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound with a second polyfunctional active hydrogen compound as a chain extender. Let it be obtained. The second prepolymer has two or more iso(thio)cyanate groups. The second prepolymer preferably has iso(thio)cyanate groups at both ends of the main chain. The second prepolymer contains at least one selected from the group consisting of urethane prepolymers, urea prepolymers, urethane urea prepolymers, thiourethane prepolymers, thiourea prepolymers, and thiourethane urea prepolymers. The second prepolymer is composed of (thio)urethane resin, (thio)urea resin, and (thio)urethaneurea resin chemically bonded to water in the atmosphere and hydroxyl groups on the surfaces of the first and second optical sheets. At least one selected from the group is produced.

The second prepolymer may contain a structure represented by formula (1) below.

In formula (1), I1 represents a portion other than the terminal of the first iso(thio)cyanate compound. FA1 represents a portion other than the terminal of the first polyfunctional active hydrogen compound. SA1 represents a portion other than the terminal of the second polyfunctional active hydrogen compound. X and Y each represent a urethane bond, a urea bond, a thiourethane bond, or a thiourea bond. X is preferably a urethane bond and Y is preferably a urea bond.

The number average molecular weight of the second prepolymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. The use of a second prepolymer having a large number average molecular weight tends to increase the peel strength of the optical laminated sheet. That is, the second prepolymer having a large number-average molecular weight is likely to be entangled with each other, so that the cohesive force is increased, and therefore the adhesive force is considered to be increased.

The number average molecular weight of the second prepolymer is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. If the number average molecular weight of the second prepolymer is excessively large, the peel strength of the optical laminated sheet tends to decrease. That is, the second prepolymer having a large number-average molecular weight contains a small amount of iso(thio)cyanate groups per unit mass, and therefore tends to have weak adhesion.

The number average molecular weight of the second prepolymer can be measured by gel permeation chromatography (GPC). For measurement, two columns: Shodex KD-806M (manufactured by Showa Denko KK) were connected in series, eluent: LiBr (10 mmol/L)/DMF solution, flow rate: 1 ml/min, detector: RI detector, 2 Prepolymer sample solution: Measured under the condition of 1.0% dimethylformamide (DMF) solution. As analysis software, GPC analysis software "Empower Personal GPC Option" manufactured by Japan Waters Co., Ltd. is used.

The softening point of the second prepolymer is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. When the softening point of the second prepolymer is high, the heat resistance of the optical laminated sheet tends to improve, and the adhesion tends to increase. Although there is no particular upper limit to the softening point of the second prepolymer, it is 200° C. or lower in one example, and 160° C. or lower in another example.

　The softening point of the second prepolymer is measured, for example, by the following method. First, the second prepolymer is dissolved in an organic solvent to obtain a solution. The concentration of the second prepolymer in the solution is, for example, 34% by mass. This solution is poured into a stainless container and dried at 40° C. for 10 hours, 60° C. for 10 hours, and further dried at 60° C. for 12 hours in a vacuum dryer to prepare a test piece with a thickness of 1 mm. The resulting test piece is analyzed using a thermomechanical measuring device (manufactured by Seiko Instruments Inc., TMA120C) to obtain the softening point. The measurement conditions are a temperature rise rate of 10° C./min, a measurement temperature range of 30 to 200° C., and a penetrating probe with a tip diameter of 0.5 mm.

The second prepolymer can occupy the main component in the solid content of the adhesive composition. The proportion of the second prepolymer in the solid content of the adhesive composition is, for example, 90% by mass or more and 99% by mass or less. In addition, when the adhesive composition is the second or fourth combination of the polymer component containing the first polymer and the second prepolymer and the photochromic compound, the ratio of the second prepolymer to the solid content of the adhesive composition is, for example, 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 40% by mass or less.

(First prepolymer)
The first prepolymer is obtained by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound. The first prepolymer has two or more iso(thio)cyanate groups. The first prepolymer preferably has iso(thio)cyanate groups at both ends of the main chain. The first prepolymer contains at least one selected from the group consisting of urethane prepolymers, urea prepolymers, thiourethane prepolymers, and thiourea prepolymers. The first prepolymer serves as a raw material for the second prepolymer.

The first prepolymer may contain a structure represented by the following formula (2).

In formula (2), I1, FA1, and X are synonymous with those in formula (1).

The number average molecular weight of the first prepolymer is preferably 500 or more and 10000 or less, more preferably 1000 or more and 5000 or less. The number average molecular weight of the first prepolymer can be measured in the same manner as for the second prepolymer.

(First iso(thio)cyanate compound)
The first iso(thio)cyanate compound has two or more iso(thio)cyanate groups. The first iso(thio)cyanate compound preferably has two iso(thio)cyanate groups. More preferably, the first iso(thio)cyanate compound is a diisocyanate compound containing two isocyanate groups.

The molar mass of the first iso(thio)cyanate compound is preferably 100 or more and 500 or less. Using the first iso(thio)cyanate compound within this range tends to result in the desired number average molecular weight of the second prepolymer and the first polymer. The molar mass of the first iso(thio)cyanate compound is more preferably 150 or more and 300 or less.

The first iso(thio)cyanate compound includes at least one selected from the group consisting of aliphatic iso(thio)cyanate compounds, alicyclic iso(thio)cyanate compounds, and aromatic iso(thio)cyanate compounds. The first iso(thio)cyanate compound is preferably an alicyclic iso(thio)cyanate compound. As the first iso(thio)cyanate compound, a single type may be used, or a plurality of types may be mixed and used.

Examples of aliphatic isocyanate compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, 1,2-bis(2-isocyanatoethylthio) ethane and the like.

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

Examples of aromatic isocyanate compounds include xylene diisocyanate (o-, m-, p-), 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.

Examples of aliphatic isothiocyanate compounds include hexamethylene diisothiocyanate, 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diiso thiocyanatohexane, 2,4,4-trimethylhexanemethylene diisothiacinate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), dithiobis(2-isothiocyanatoethane) and the like.

Examples of alicyclic isothiocyanate compounds include isophorone diisothiocyanate, cyclohexane diisothiocyanate, 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6 -bis(isothiocyanatomethyl)norbornane, 3,5-bis(isothiocyanatomethyl)norbornane, norbornane diisocyanate, and the like.

Examples of aromatic isothiocyanate compounds include p-phenylenediisopropylidene diisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4 -diisothiocyanatotoluene, xylene diisothiocyanate (o-, m-, p-), 2,4-tolylene diisothiocyanate, 2,6-tolylene diisothiocyanate, 1,1'-methylenebis(4-isothiocyanate) benzene), 1,1′-methylenebis(4-isothiocyanate-2-methylbenzene), 1,1′-methylenebis(4-isothiocyanate-3-methylbenzene), and the like.

(First polyfunctional active hydrogen compound)
The first polyfunctional active hydrogen compound has two or more active hydrogen groups. The first polyfunctional active hydrogen compound preferably has two active hydrogen groups. Active hydrogen groups include at least one selected from the group consisting of hydroxyl groups, amino groups, carboxy groups, and thiol groups. The first polyfunctional active hydrogen compound includes, for example, a polyol compound containing two or more hydroxyl groups, a polyamine compound containing two or more amino groups, a dicarboxylic acid containing two carboxy groups, and a polythiol compound containing two or more thiol groups. At least one selected from the group consisting of As the first polyfunctional active hydrogen compound, a single type may be used, or a plurality of types may be mixed and used.

The first polyfunctional active hydrogen compound preferably contains a polyol compound. Using a polyol compound yields a first prepolymer having (thio)urethane bonds. The repeating structural portion of the polyol compound can contribute to providing a matrix that does not easily hinder the structural change of the photochromic compound in the photochromic adhesive layer. The use of a polyol compound tends to enhance the photochromic properties of the optical laminated sheet.

The number average molecular weight of the polyol compound is preferably 500 or more and 3000 or less. Using a polyol compound containing a number average molecular weight within this range tends to result in the desired number average molecular weight of the second prepolymer and the first polymer. More preferably, the number average molecular weight of the polyol compound is 800 or more and 2000 or less.

The polyol compound may contain at least one selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. Preferably, the polyol compound comprises a polycarbonate polyol. The use of polycarbonate polyol tends to increase the adhesion of the optical laminated sheet.

Polycarbonate polyols can be obtained, for example, by monophosgenation of low-molecular-weight polyols, or transesterification of ethylene carbonate, diethyl carbonate, diphenyl carbonate, and the like. Examples of low molecular polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5- Pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol Examples include ethylene oxide and propylene oxide adducts of A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

Polycarbonate polyols include "Duranol (registered trademark)" series manufactured by Asahi Kasei Corporation, "Kuraray Polyol (registered trademark)" series manufactured by Kuraray Co., Ltd., "Placcel (registered trademark)" series manufactured by Daicel Corporation, " NIPPORUN (registered trademark)" series, UBE Corporation "ETERNACOLL (registered trademark)" series, and the like can be used.

Polycaprolactone polyol is obtained, for example, by ring-opening polymerization of ε-caprolactone. As the polycaprolactone polyol, the "Plaxel (registered trademark)" series manufactured by Daicel Corporation can be used.

A polyether polyol can be obtained, for example, by reacting a compound having two or more active hydrogen groups in its molecule with an alkylene oxide. Compounds having two or more active hydrogen-containing groups include water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, trimethylolpropane, hexanetriol, and the like. is mentioned. Alkylene oxides include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran.

Examples of polyether polyols include the "Exenol (registered trademark)" series and "Emulstar (registered trademark)" series manufactured by AGC Co., Ltd., and the "ADEKA Polyether" series manufactured by ADEKA Corporation.

A polyester polyol is obtained, for example, by condensation reaction between a polyhydric alcohol and a polybasic acid. Polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3, 3′-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like. Examples of polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

Polyester polyols include the "Polylight (registered trademark)" series manufactured by DIC Corporation, the "Nipporan (registered trademark)" series manufactured by Tosoh Corporation, and the "Maximol (registered trademark)" series manufactured by Air Water Performance Chemicals Co., Ltd. can be used.

The polythiol compound may contain at least one selected from the group consisting of aliphatic polythiols, aromatic polythiols, and polythiols containing sulfur atoms in addition to mercapto groups.

Examples of aliphatic polythiols include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6- Hexanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethyl)methane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4 -dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-mercaptoethyl ester) thiomalate, 2,3-dimercaptosuccinate acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis(2-mercaptoacetate), Diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, etc. be

Examples of aromatic polythiols include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercapto methyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethoxy)benzene, 1, 3-bis(mercaptomethoxy)benzene, 1,4-bis(mercaptomethoxy)benzene, 1,2-bis(mercaptoethoxy)benzene, 1,3-bis(mercaptoethoxy)benzene, 1,4-bis(mercaptoethoxy) ) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2, 4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1, 3,5-tris(mercaptoethyl)benzene, 1,2,3-tris(mercaptomethoxy)benzene, 1,2,4-tris(mercaptomethoxy)benzene, 1,3,5-tris(mercaptomethoxy)benzene, 1,2,3-tris(mercaptoethoxy)benzene, 1,2,4-tris(mercaptoethoxy)benzene, 1,3,5-tris(mercaptoethoxy)benzene, 1,2,3,4-tetramercaptobenzene , 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene and the like.

Examples of polythiols containing sulfur atoms in addition to mercapto groups include bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio ) methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio) Ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2-bis(2-mercapto ethylthio)-3-mercaptopropane, 2-mercaptoethylthio-1,3-propanedithiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane etc. are included.

The amount of the first polyfunctional active hydrogen compound is the molar amount M1 of the active hydrogen groups contained in the first polyfunctional active hydrogen compound and the molar amount M1 of the iso(thio)cyanate groups contained in the first iso(thio)cyanate compound. The ratio M1/M2 to M2 is preferably adjusted to be 0.1 or more and 0.5 or less. When the ratio M1/M2 is within the above range, a sufficient amount of at least one of urethane bonds and urea bonds is formed in the first prepolymer, and a flexible photochromic adhesive layer that hardly inhibits structural changes of the photochromic compound. can be formed. The ratio M1/M2 is preferably 0.30 or more and 0.50 or less, more preferably 0.5.

The ratio S1/S2 between the mass S1 of the first polyfunctional active hydrogen compound and the mass S2 of the first iso(thio)cyanate compound is preferably 0.1 or more and 10 or less. When the ratio S1/S2 is within the above range, a second prepolymer having a sufficient amount of isocyanate groups per unit mass is obtained. The ratio S1/S2 is preferably 0.8 or more and 5 or less, more preferably 1 or more and 3 or less.

(Second polyfunctional active hydrogen compound)
The second polyfunctional active hydrogen compound has two or more active hydrogen groups. The second polyfunctional active hydrogen compound reacts with the first prepolymer to produce a second prepolymer. The second polyfunctional active hydrogen compound functions as a chain extender that connects the first prepolymers. The second polyfunctional active hydrogen compound preferably has two active hydrogen groups. As the second polyfunctional active hydrogen compound, the compounds listed for the first polyfunctional active hydrogen compound can be used.

The second polyfunctional active hydrogen compound preferably contains polyamine. Using a polyamine results in a second prepolymer with (thio)urethane urea linkages. The use of such a second prepolymer tends to increase the adhesion of the optical laminated sheet. The molar mass of the polyamine is preferably 50 or more and 500 or less. Using a polyamine having a molar mass within this range tends to give the desired number average molecular weight of the second prepolymer. More preferably, the polyamine has a molar mass of 50 or more and 300 or less. Polyamines include diamines and triamines, preferably diamines.

Polyamines include isophoronediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, piperazine, N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylcyclohexyl)methane, 1, 2-, 1,3- and 1,4-diaminocyclohexane, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4'-diphenylmethanediamine, N,N'-diethylethylenediamine, N,N'-dimethyl ethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis(hexamethylene)triamine, 1,2,5-pentanetriamine and the like.

The polyamine preferably contains at least one selected from the group consisting of isophoronediamine, ethylenediamine, bis-(4-aminocyclohexyl)methane, and 1,6-diaminohexane.

The amount of the second polyfunctional active hydrogen compound is the ratio of the molar amount M3 of the active hydrogen groups contained in the second polyfunctional active hydrogen compound to the molar amount M4 of the iso(thio)cyanate groups contained in the first prepolymer. Preferably, M3/M4 is adjusted to be 0.21 or more and 0.50 or less. A sufficient amount of the second prepolymer is produced when the ratio M1/M2 is within the above range.

The ratio S3/S4 between the mass S3 of the second polyfunctional active hydrogen compound and the mass S4 of the first prepolymer is preferably 0.01 or more and 0.5 or less. When the ratio S3/S4 is within the above range, a second prepolymer having a sufficient amount of isocyanate groups per unit mass is obtained. The ratio S3/S4 is more preferably 0.08 or more and 0.3 or less.

(first polymer)
The first polymer is obtained by reacting the second prepolymer with a monofunctional active hydrogen compound having one active hydrogen group. The first polymer typically does not have iso(thio)cyanate groups. The ends of the first polymer are modified with non-reactive functional groups. The first polymer contains at least one selected from the group consisting of urethane polymer, urea polymer, urethane urea polymer, thiourethane polymer, thiourea polymer, and thiourethane urea polymer.

The first polymer chemically bonds with hydroxyl groups on the surfaces of the second prepolymer and/or the third prepolymer and the first and second optical sheets at a high temperature to form (thio)urethane resin, (thio)urea At least one selected from the group consisting of resins and (thio)urethane urea resins is produced.

The number average molecular weight of the first polymer is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. Using a first polymer having a large number average molecular weight tends to increase the peel strength of the optical laminated sheet. The number average molecular weight of the first polymer is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less. When the number average molecular weight of the first polymer is excessively large, the peel strength of the optical laminated sheet tends to decrease. This number average molecular weight can be measured by the same method as for the second prepolymer.

The softening point of the first polymer is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. When the softening point of the first polymer is high, the heat resistance of the optical laminated sheet tends to improve, and the adhesion tends to increase. Although there is no particular upper limit to the softening point of the first polymer, it is 200° C. or lower in one example, and 160° C. or lower in another example. The softening point of the mixture can be measured in the same manner as for the second prepolymer.

The first polymer can exist as a mixture with the second prepolymer. A mixture of the first polymer and the second prepolymer is obtained by adjusting the amount of the monofunctional active hydrogen compound. That is, the ratio M5/M6 between the molar amount M5 of the iso(thio)cyanate groups contained in the second prepolymer and the molar amount M6 of the active hydrogen groups contained in the monofunctional active hydrogen compound is adjusted to be less than 1. As a result, a mixture of the second prepolymer and the first polymer in which the iso(thio)cyanate group of the second prepolymer is protected with the monofunctional active hydrogen compound is produced. The ratio M5/M6 is preferably 0.75 or more and 0.95 or less.

The number average molecular weight of this mixture is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. The use of a mixture with a large number average molecular weight tends to increase the peel strength of the optical laminated sheet. The number average molecular weight of the mixture is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less. If the number average molecular weight of the mixture is excessively high, the peel strength of the optical laminated sheet tends to decrease. This number average molecular weight can be measured by the same method as for the second prepolymer.

The softening point of this mixture is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and even more preferably 120°C or higher. When the softening point of the mixture is high, the heat resistance of the optical laminated sheet tends to improve, and the adhesion tends to increase. Although there is no particular upper limit to the softening point of the mixture, it is 200° C. or lower in one example, and 160° C. or lower in another example. The softening point of the mixture can be measured in the same manner as for the second prepolymer.

The proportion of the first polymer in the solid content of the adhesive composition is, for example, 75% by mass or more and 95% by mass or less.

The mixture of the first polymer and the second prepolymer may contain the fourth prepolymer. The fourth prepolymer is a compound in which a portion of the iso(thio)cyanate groups of the second prepolymer are protected with a monofunctional active hydrogen compound and the remainder are unprotected. The fourth prepolymer may contain one iso(thio)cyanate group and one monofunctional active hydrogen compound protecting group. Since the fourth prepolymer has an iso(thio)cyanate group, it can enhance the adhesion of the optical laminated sheet, like the second prepolymer.

In the mixture of the first polymer, the second prepolymer, and the fourth prepolymer, the ratio of the first polymer is, according to one example, 1% by mass or more and 40% by mass or less, and according to another example, 10% by mass. It is more than 30 mass % or less. In one example, the ratio of the second prepolymer in the mixture is 1% by mass or more and 40% by mass or less, and in another example, 10% by mass or more and 30% by mass or less. In one example, the proportion of the fourth prepolymer in the mixture is 1% by mass or more and 80% by mass or less, and according to another example, it is 40% by mass or more and 80% by mass or less.

The photochromic adhesive layer may be a cured adhesive composition containing a photochromic compound, a first polymer, a second prepolymer, and a fourth prepolymer, wherein the photochromic compound, the first polymer, and the fourth prepolymer are It may be a cured body of the adhesive composition containing.

(Monofunctional active hydrogen compound)
A monofunctional active hydrogen compound has one active hydrogen group. The monofunctional active hydrogen compound reacts with the iso(thio)cyanate groups of the second prepolymer to produce the first polymer and terminate further reaction. Active hydrogen groups include at least one selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, and thiol groups.

The monofunctional active hydrogen compound is, for example, a monool compound containing one hydroxyl group, a monoamine compound containing one amino group, a carboxylic acid containing one carboxyl group, and a monothiol compound containing one thiol group. At least one selected is included. As the monofunctional active hydrogen compound, a single type may be used, or a plurality of types may be mixed and used.

The monofunctional active hydrogen compound is preferably a monoamine compound. Using a monoamine compound results in a first polymer with (thio)urea linkages.

The monofunctional active hydrogen compound preferably contains an amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety, as represented by the following formula (3). Amines having 2,2,6,6-pentamethyl-4-piperidyl moieties can function as hindered amines, thus enhancing the photostability of the optical laminated sheet.

In formula (3), R ²¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ²² is an alkylene group having 1 to 3 carbon atoms. a is 0 or 1;

The monofunctional active hydrogen compound is preferably 1,2,2,6,6-pentamethyl-4-aminopiperidine, wherein R ²¹ is a methyl group and a is 0.

The ratio S5/S6 between the mass S5 of the monofunctional active hydrogen compound and the mass S6 of the second prepolymer is preferably 0.001 or more and 0.100 or less. When the ratio S5/S6 is within the above range, a first polymer having a sufficient amount of isocyanate groups per unit mass is obtained. The ratio S5/S6 is more preferably 0.010 or more and 0.030 or less.

(Third prepolymer)
The third prepolymer is a compound having two or more iso(thio)cyanate groups obtained by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound. That is, the third prepolymer is the same compound as the first prepolymer. The third prepolymer chemically bonds with the hydroxyl groups on the surfaces of the first prepolymer and the first and second optical sheets at high temperature to form (thio)urethane resin, (thio)urea resin, and (thio)urethane. At least one selected from the group consisting of urea resins is produced.

When the adhesive composition is the third or fourth combination of the polymerizable component containing the first polymer and the third prepolymer and the photochromic compound, the proportion of the third prepolymer in the solid content of the adhesive composition is For example, it is 5 mass % or more and 20 mass % or less.

(Additive)
The adhesive composition includes, for example, a polymerization catalyst, a polymerization initiator, an antistatic agent, an internal release agent, an antioxidant, a light stabilizer, an anti-coloring agent, a fluorescent dye, a dye, a pigment, a fragrance, a solvent, a leveling agent, At least one additive selected from the group consisting of resin modifiers, infrared absorbers, ultraviolet absorbers, and visible light absorbers may be included. The adhesive composition preferably contains at least one of an antioxidant and a leveling agent.

As an antioxidant, 2,6-di-t-butyl-4-methyl-phenol, manufactured by BASF Japan Ltd. IRGANOX245: ethylenebis(oxyethylene)bis[3,5-tert-butyl-4-hydroxy-m -toluyl] propionate], manufactured by BASF Japan Ltd. IRGANOX1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Japan Ltd. IRGANOX1010: pentaerythritol tetrakis [3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], IRGANOX1035, 1075, 104, 3790, 5057, 565, etc. manufactured by BASF Japan Ltd. can be used.

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 Toray Co., Ltd., Megafac F-470 manufactured by DIC Corporation, Megafac F-1405, Megafac F-479, 3M Florad FC-430 manufactured by Japan Co., Ltd. can be used.

Examples of dyes and visible light absorbers include nitro-based compounds, azo-based compounds, anthraquinone-based compounds, threne-based compounds, porphyrin-based compounds, and rare earth metal compounds. Among them, porphyrin compounds and rare earth compounds are preferred in view of the balance between antiglare properties and visibility. Furthermore, from the viewpoint of dispersion stability in plastic materials, porphyrin compounds are most preferable.

Examples of the rare earth metal compound include aquahydroxy(1-phenyl-1,3-butanedionato)neodymium, aquahydroxy(phenacylphenylketonato)neodymium, and aquahydroxy(1-phenyl-2-methyl-1,3-butanedionato)neodymium. , aquahydroxy(1-thiophenyl-1,3-butanedionato)neodymium, aquahydroxy(1-phenyl-1,3-butanedionato)erbium, and aquahydroxy(1-phenyl-1,3-butanedionato)holonium. I can.

The porphyrin-based compound is a compound that may have various substituents on the porphyrin skeleton. For example, JP-A-5-194616, JP-A-5-195446, JP-A-2003-105218, JP-A-2008-134618, JP-A-2013-61653, JP-A-2015-180942, Compounds described in WO2012/020570 pamphlet, Japanese Patent No. 5626081, Japanese Patent No. 5619472, Japanese Patent No. 5778109, etc. can be preferably used.

As the light stabilizer, it is preferable to use a hindered amine compound having a 2,2,6,6-tetramethyl-4-piperidyl skeleton, and a commercially available one can be used. For example, 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-t-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-4-{3- (3,5-di-t-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-piperidinyl methacrylate, 2-[[3,5-bis(1, 1-dimethylethyl)-4-hydroxyphenyl]methyl]-2-butylpropanedioic acid [1,2,2,6,6-pentamethyl-4-piperidinyl], 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 a product name, ADEKA Co., Ltd. ADEKA STAB (registered trademark) LA series (LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-81, LA-82, etc.) , BASF Japan Co., Ltd. Tinubin (registered trademark) series (TinuVin 123, TinuVin 171, TinuVin249, TinuVin292, TinuVin665, TinuVin 622SF, etc.), CHIMASSORB (registered Trademark) Series (chimassorb2020FDL, chimassorb94444FDL), etc. are listed.

The proportion of the additive in the solid content of the adhesive composition is, for example, 0.1% by mass or more and 1% by mass or less.

(organic solvent)
The adhesive composition may contain an organic solvent in order to adjust its viscosity. The organic solvent may contain at least one selected from the group consisting of tetrahydrofuran, diethylketone, t-butyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, toluene, ethyl acetate, and cyclohexanone.

The proportion of the organic solvent in the adhesive composition is, for example, 30% by mass or more and 80% by mass or less.

(Method for producing adhesive composition)
The adhesive composition is obtained, for example, by the following first to fourth manufacturing methods.

A first method for producing an adhesive composition comprises: obtaining a first prepolymer by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound; reacting with a functional active hydrogen compound to obtain a second prepolymer; and mixing the second prepolymer with the photochromic compound and optional additives.

A second method for producing an adhesive composition comprises: obtaining a first prepolymer by reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound; reacting with a functional active hydrogen compound to obtain a second prepolymer; reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a mixture of the first polymer and the second prepolymer; mixing the polymer, the second prepolymer, the photochromic compound and any additives.

A third method for producing an adhesive composition comprises reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer and a third prepolymer; reacting the polymer with a second polyfunctional active hydrogen compound to obtain a second prepolymer; reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a first polymer; the first polymer; mixing the third prepolymer, the photochromic compound and any additives.

A fourth method for producing an adhesive composition includes: reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer; reacting with a functional active hydrogen compound to obtain a second prepolymer; and reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a mixture of the first polymer, the second prepolymer and the fourth prepolymer. and mixing the first polymer, second prepolymer, fourth prepolymer, photochromic compound and optional additives.

A fifth method for producing an adhesive composition comprises reacting a first polyfunctional active hydrogen compound and a first iso(thio)cyanate compound to obtain a first prepolymer and a third prepolymer; reacting the polymer with a second polyfunctional active hydrogen compound to obtain a second prepolymer; reacting the second prepolymer with a monofunctional active hydrogen compound to obtain a first polymer; the first polymer; mixing the second prepolymer, the third prepolymer, the photochromic compound and any additives.

The reaction between the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound is preferably carried out in the presence of an organic solvent. As the organic solvent, those mentioned above can be used. This reaction is preferably carried out under a nitrogen atmosphere. Moreover, this reaction is carried out at a reaction temperature of, for example, 60° C. or higher and 150° C. or lower for 3 hours or longer and 10 hours or shorter. The reaction is preferably carried out until the endpoint is confirmed by back titration of isocyanate groups.

The reaction between the first prepolymer and the second polyfunctional active hydrogen compound is preferably carried out in the presence of an organic solvent. As the organic solvent, those mentioned above can be used. This reaction is preferably carried out under a nitrogen atmosphere. Moreover, this reaction is performed at a reaction temperature of, for example, 10° C. or higher and 30° C. or lower for 0.1 hour or more and 5 hours.

The reaction between the second prepolymer and the monofunctional active hydrogen compound is preferably carried out in the presence of an organic solvent. As the organic solvent, those mentioned above can be used. This reaction is preferably carried out under a nitrogen atmosphere. Also, this reaction is carried out at a reaction temperature of, for example, −10° C. or higher and 10° C. or lower for 0.1 hour or longer and 5 hours or shorter.

(Manufacturing method of optical laminated sheet)
A method for producing an optical laminated sheet according to an embodiment includes: applying the adhesive composition described above to at least one main surface of a first optical sheet to obtain a coating film; and forming a second optical sheet on the coating film. and laminating.
A method for manufacturing the optical laminated sheet will be described in detail below.

First, prepare the first and second optical sheets. As the first and second optical sheets, commercially available unstretched sheets of polyvinyl alcohol resin may be used, or stretched and dyed sheets may be used.

Next, an adhesive composition is applied on at least one main surface of the first optical sheet using, for example, a bar coater to form a coating film. This coating film is dried, for example, at a temperature of 60° C. or higher and 150° C. for 1 minute or longer and 1 hour or shorter. A second optical sheet is laminated on the dried coating film so as to face each other, and laminated using, for example, a lamination roll to obtain a structure.

Next, the resulting structure is subjected to degassing treatment. In the degassing treatment, the structure is allowed 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 degassing is subjected to heat treatment. During the heat treatment, the structure is heated, for example, at a temperature of 60° C. or higher and 150° C. or lower for 0.5 hours or more and 5 hours or less. When the adhesive composition contains the first polymer and the second prepolymer or the third polymer, the heat treatment forms a composite having iso(thio)cyanate groups, which is crosslinked with the first and second optical laminated sheets. Conceivable. The structure after heat treatment may be left at room temperature for one week or more.

In the optical laminated sheet according to the embodiment thus obtained, the photochromic adhesive layer contains a cured adhesive composition containing the second prepolymer or the first polymer and the second prepolymer or the third polymer. , excellent photochromic properties, and excellent adhesion and appearance.

(Second optical laminated sheet)
The second optical laminate sheet includes a first optical sheet and a second optical sheet, a transparent support, a first adhesive layer, and a second adhesive layer. A transparent support is located between the first optical sheet and the second optical sheet. The first adhesive layer adheres the first optical sheet and the transparent support, and contains a photochromic compound. The second adhesive layer adheres the transparent support and the second optical sheet.

The manufacturing process of a photochromic lens using an optical laminated sheet includes a step of integrating at least one main surface of the optical laminated sheet with the lens substrate. In this process, a curved photochromic lens may be manufactured using an optical laminated sheet that has been processed into a curved shape along the intended lens shape.

The curved surface processing of the optical laminated sheet is performed, for example, by decompressing one main surface side of the heated optical laminated sheet, placing the optical laminated sheet along a mold having a curved surface shape, and then cooling the optical laminated sheet. will be At this time, if the thickness of the optical laminated sheet is thin and the strength is not sufficient, the edge of the optical laminated sheet along the mold may be deformed. An optical laminated sheet with deformed edges is not suitable for manufacturing a photochromic lens. Therefore, when such an optical laminated sheet is manufactured, the manufacturing efficiency of the photochromic lens is lowered.

The second optical laminated sheet has a transparent support between the first optical sheet and the second optical sheet. The transparent support enhances the strength of the optical laminated sheet and enhances the self-standing. Therefore, the optical laminated sheet according to the embodiment is less likely to be deformed during curved surface processing. Therefore, the use of the second optical laminated sheet can increase the yield of optical articles.

FIG. 2 is a cross-sectional view schematically showing an example of the second optical laminated sheet. The optical laminated sheet 1 a shown in FIG. 2 includes a first optical sheet 3 , a second optical sheet 2 , a first adhesive layer 4 , a transparent support 5 and a second adhesive layer 6 . At least part of one main surface of the transparent support 5 is covered with the first adhesive layer 4 . At least part of the other main surface of the transparent support 5 is covered with a second adhesive layer 6 . The transparent support 5 is adhered to the first optical sheet 3 via the first adhesive layer 4 and adhered to the second optical sheet 2 via the second adhesive layer 6 .

(First adhesive layer)
The first adhesive layer may have the same structure as the photochromic adhesive layer.

(Second adhesive layer)
The second adhesive layer preferably contains a resin. The resin includes, for example, at least one selected from the group consisting of polyvinyl alcohol resins, (meth)acrylic resins, urethane acrylate resins, polyurethane resins, polyurethane urea resins, polythiourethane resins, and polythiourethane urea resins. is preferred.

The second adhesive layer may or may not contain a photochromic compound. When the second adhesive layer contains a photochromic compound, its structure may be the same as or different from the photochromic compound contained in the first adhesive layer. Also, the second adhesive layer may contain a coloring agent such as a dye or a pigment. When the second adhesive layer contains a coloring agent, the type of the coloring agent may be the same as or different from the coloring agent contained in the first adhesive layer.

The thickness of the second adhesive layer may be the same as that of the first adhesive layer, thicker, or thinner. When the second adhesive layer contains a photochromic compound, it is preferably as thick as the first adhesive layer. When the second adhesive layer does not contain a photochromic compound, it is preferably thinner than the first adhesive layer. The thickness of the second adhesive layer is, for example, 0.1 μm or more and 100 μm or less, preferably 10 μm or more and 50 μm or less. The thickness of the second adhesive layer may be thinner or thicker than the thicknesses of the first and second optical sheets. The thickness of the second adhesive layer can be measured, for example, by the same method as the thickness of the PVA sheet.

(Transparent support)
The transparent support is, for example, a self-supporting film that can improve the strength of the optical laminated sheet. The transparent support may be optically transparent. The transparent support may be colorless and transparent, white and transparent, or colored and transparent. The luminous transmittance of the transparent support is preferably 30% or more. The luminous transmittance of the transparent support can be measured with a UV-Vis spectrophotometer.

The material of the transparent support is not particularly limited. A transparent support is, for example, a resin film or a ceramic film. The transparent support preferably contains at least one resin selected from the group consisting of polyethylene terephthalate, triacetyl cellulose, polyamide, polycarbonate sheet, cellulose acetate butyrate, and (meth)acryl. More preferably, it contains at least one resin selected from the group consisting of acetylcellulose, polyamide, and polycarbonate sheets.

The thickness of the transparent support is preferably thicker than the thickness of the first and second optical sheets. The thickness of the transparent support is preferably 50 μm or more, preferably 100 μm or more, more preferably 200 μm or more. A thick transparent support tends to increase the strength of the optical laminated sheet. Although there is no particular upper limit to the thickness of the transparent support, it is 1000 μm or less in one example, and 500 μm or less in another example. The thickness of the transparent support can be measured, for example, by the same method as the thickness of the PVA sheet.

The transparent support preferably has a surface-modified region on its surface, like the other resin sheets described above. The use of a transparent support having a surface-modified region tends to increase adhesion to the first and second adhesive layers. Surface-modified regions are preferably provided on both major surfaces of the transparent support.

(Method for producing second optical laminated sheet)
A second method for producing an optical laminated sheet comprises: applying the first adhesive composition described above to at least one main surface of the first optical sheet to obtain a first coating film; on at least one main surface of the second optical sheet to obtain a second coating; , laminating the first optical sheet, the transparent support, and the second optical sheet.

A method for manufacturing the optical laminated sheet will be described in detail below.
First, the first and second optical sheets are prepared. Commercially available resin sheets can be used as the first and second optical sheets. As the resin sheet, a non-stretched sheet may be used, or a stretched and dyed sheet may be used. A surface modified region may be provided on each main surface of the first and second optical sheets by the method described above.

Next, the first adhesive composition is applied on at least one main surface of the first optical sheet using, for example, a bar coater to form a first coating film. This coating film is dried, for example, at a temperature of 60° C. or higher and 150° C. for 1 minute or longer and 1 hour or shorter.

Next, the second adhesive composition is applied on at least one main surface of the second optical sheet using, for example, a bar coater to form a second coating film. This coating film is dried, for example, at a temperature of 60° C. or higher and 150° C. for 1 minute or longer and 1 hour or shorter.

Next, a transparent support is placed between the first coating film and the second coating film so as to be in contact with them to obtain a laminate. This laminate is laminated using, for example, lamination rolls to obtain a structure. A surface-modified region may be provided on at least one main surface of the transparent support by the method described above.

Next, the resulting structure is subjected to degassing treatment. In the degassing treatment, the structure is allowed 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 degassing is subjected to heat treatment. During the heat treatment, the structure is heated, for example, at a temperature of 60° C. or higher and 150° C. or lower for 0.5 hours or more and 5 hours or less. The structure after heat treatment may be left at room temperature for one week or longer. By the above method, the optical laminated sheet according to the embodiment is obtained.

[Optical article]
An optical article according to embodiments includes an optical laminated sheet according to embodiments. An optical article according to an embodiment may include the optical laminate sheet according to the embodiment, and an optical element substrate that covers at least one surface of the first optical sheet and the second optical sheet and contains a resin. The optical element substrate may cover the surfaces of both the first optical sheet and the second optical sheet that are not in contact with the photochromic adhesive layer. The optical laminate sheet may be housed inside the optical element substrate.

Optical articles include lenses, window glass for houses and automobiles, liquid crystal displays, sun visors, and clocks. Lenses include semi-finished lenses and finished lenses.

FIG. 3 is a cross-sectional view schematically showing an example of the optical article according to the embodiment. The optical article 10 shown in FIG. 3 includes a first optical element substrate 11, a second optical element substrate 12, and an optical laminated sheet 1 interposed therebetween. The optical laminated sheet 1 is the first optical laminated sheet shown in FIG. As the optical laminated sheet 1, the second optical laminated sheet 1a shown in FIG. 2 may be used. The optical article 10 has a concave-convex lens shape. The optical laminated sheet 1 has a curved surface along the shape of the lens. The first optical element substrate 11 is located on the concave side, and the second optical element substrate 12 is located on the convex side. The first optical element substrate 11 covers the entire surface of the first optical sheet (not shown) of the optical substrate sheet 1 . The second optical element substrate 12 covers the entire surface of the second optical sheet (not shown) of the optical substrate sheet 1 . The side surfaces of the optical substrate sheet 1 are not covered with the first and second optical substrates. The side surfaces of the optical substrate sheet 1 may be covered with the first and second optical substrates.

FIG. 4 is a perspective view schematically showing an example of eyeglasses according to the embodiment. Spectacles 100 shown in FIG. 4 include lenses 101 and a frame 102 that supports the lenses 101 . Lens 101 includes an optical article according to embodiments.

(Optical element substrate)
The optical element substrate may contain a resin. The resin is selected from the group consisting of polyester resins, polyamide resins, allyl resins, acrylic resins, methacrylic resins, polyurethane resins, polyurethane urea resins, polythiourethane resins, polythiourethane urea resins, polythioepoxy resins, and polycarbonate resins. At least one may be included.

The resin preferably contains at least one selected from the group consisting of polyurethane resins, polyurethane urea resins, polythiourethane resins, polythiourethane urea resins, and polythioepoxy resins. These resins tend to have high adhesion to the optical base sheet because the constituent monomers can chemically bond with the hydroxyl groups on the surfaces of the first and second optical sheets of the optical base sheet. More preferably, it is at least one selected from the group consisting of polythiourethane resins, polythioepoxy resins, and polyurethaneurea resins.

(Method for manufacturing optical article)
An optical article according to an embodiment is manufactured, for example, by the following method.
First, a curable composition for forming an optical element substrate is prepared. A known composition corresponding to each resin can be used as the curable composition. Next, prepare the mold and gasket. The mold includes an upper mold and a lower mold. A hollow portion is formed inside by combining the upper mold and the lower mold. A gasket is installed on the interface between the upper mold and the lower mold. The inside of the gasket is provided with cuts for fixing the optical laminated sheet according to the embodiment. The inside of the gasket may be provided with protrusions or recesses instead of cuts. The molds and gaskets are, for example, known for molding plastic lenses.

Next, the end of the optical laminate sheet according to the embodiment is inserted into the notch of the gasket and fixed. This gasket is placed at the interface of the mold. As a result, the optical laminate sheet is installed so as to extend over the inside of the hollow portion of the mold. Next, the hollow part of this mold is filled with a curable composition. The mold filled with the curable composition is heat-treated to cure the curable composition. During the heat treatment, for example, the temperature is gradually raised from normal temperature to the curing temperature, and after reaching the curing temperature, the temperature is maintained for a certain period of time. The curing temperature is, for example, 60° C. or higher and 200° C. or lower, although it varies depending on the type of resin of the optical element substrate. The heating rate is, for example, 1° C./hour or more and 10° C./hour or less. The retention time at the curing temperature is, for example, 0.1 hours or more and 10 hours or less.

After the heat treatment is completed, the hardened body is removed from the mold. The cured body taken out is further heated within the range of the above-mentioned curing temperature for the above-mentioned holding time. Thus, an optical article according to an embodiment is obtained in which the surfaces of the first and second optical sheets of the optical laminated sheet are coated with the optical element substrate.

The optical article according to the embodiment may be obtained by the following method. First, part of the curable composition is filled into the lower mold of the mold. An optical laminate sheet is placed on the surface of the curable composition after filling. Next, an upper mold is installed so as to face the lower mold to form a hollow portion. The remainder of the curable composition is filled into this hollow portion. The resulting mold is heated in the same manner as above to obtain a cured product. In this way, an optical article according to an embodiment is obtained in which the main surface and the entire side surface of the optical laminated sheet are coated with the optical element base material.

Also, the optical article according to the embodiment may be obtained by the following method. First, an optical laminate sheet is placed along the upper surface of the mold. The surface of the optical laminate sheet that does not come into contact with the upper surface of the mold, that is, the back side, is filled with the curable composition and heat-treated under the same conditions as above to obtain the first cured body. The first cured body is a laminate in which an optical laminate sheet is laminated on one main surface of the first optical element substrate. This first cured body is placed in a mold. The curable composition is filled toward the surface of the second optical sheet of the first cured body and heat-treated under the same conditions as above to obtain the second cured body. The second cured body is a laminate in which an optical laminate sheet is laminated on one main surface of the first optical element substrate, and the second optical element substrate is laminated on this optical laminate sheet. In this way, an optical article according to an embodiment is obtained in which the main surface and optionally the side surfaces of the optical laminate sheet are coated with the optical element substrate.

The curable composition for each resin of the optical element substrate is described in detail below.
A curable composition for an allyl-based resin contains an allyl monomer having an allyl group and a polymerization initiator. Allyl monomers include, for example, at least one selected from the group consisting of diethylene glycol bisallyl carbonate, diallyl isophthalate, and diallyl terephthalate. Polymerization initiators include, for example, diisopropyl peroxycarbonate.

A curable composition for a (meth)acrylic resin contains a (meth)acrylic monomer having a (meth)acrylate group and a polymerization initiator. (Meth)acrylic monomers include, for example, glycidyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, trimethylolpropane triethylene glycol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol hexa (meth) acrylate, urethane acrylate, urethane oligomer tetra (meth) acrylate, urethane oligomer hexa (meth) acrylate, polyester oligomer hexa (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, average 2,2-bis(4-(meth)acryloyloxypolyethylene glycol phenyl)propane with a molecular weight of 776, methyl ether polyethylene glycol (meth)acrylate with an average molecular weight of 475, polyethylene glycol diacrylate with an average molecular weight of 522, methyl (meth)acrylate, etc. contains at least one selected from the group consisting of (meth)acrylate monomers having at least one (meth)acrylate group in the molecule. Polymerization initiators include, for example, t-butyl peroxyneodecanate.

A curable composition for a urethane urea resin contains a prepolymer of a polyisocyanate compound and a polyol compound, and a diamine compound. As the polyisocyanate compound, the polyol compound, and the diamine compound, those described above for the adhesive composition can be used. The polyisocyanate compound preferably contains an isomeric mixture of 4,4'-methylenebis(cyclohexylisocyanate). The polyol compound preferably contains a polyester polyol obtained by reacting 1,6-hexanediol with adipic acid. Diamine compounds include 2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene, 4,4′-methylenebis(3-chloro-2,6-diethylaniline) , paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, diaminodiphenylmethane, bis-4-(4-aminophenoxy)phenylsulfone, bis-4-(3-aminophenoxy)phenylsulfone, 2,2- bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenoxy)hexafluoropropane, 1 , 3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene , and 4,4′-bis(4-aminophenoxy)biphenyl.

The curable composition for thiourethane resin contains a polyisocyanate compound, a polythiol compound and a polymerization catalyst. As the polyisocyanate compound, those mentioned above in the adhesive composition can be used. Polyisocyanate compounds include dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-bis(4-isocyanato-2-thiabutyl)-1 ,4-dithiane, 2,5-bis(3-isocyanatomethyl-4-isocyanato-2-thiabutyl)-1,4-dithiane, 2,5-bis(3-isocyanato-2-thiapropyl)-1 ,4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris(isocyanatomethyl)cyclohexane, bis(isocyanatomethylthio)methane, 1,5-diisocyanato-2-isocyanatomethyl-3- Thiapentane, 1,2,3-tris(isocyanatoethylthio)propane, 1,2,3-tris(isocyanatomethylthio)propane, 1,1,6,6-tetrakis(isocyanatomethyl)-2,5-dithiahexane, 1 , 1,5,5-tetrakis(isocyanatomethyl)-2,4-dithiapentane, 1,2-bis(isocyanatomethylthio)ethane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane It is preferable to include at least one selected.

Polythiol compounds include, for example, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1, 4-dimercaptobutane, 1,6-dimercaptohexane, bis(2-mercaptoethyl)sulfide, bis(2,3-dimercaptopropyl)sulfide, 1,2-bis(2-mercaptoethylthio)ethane, 1 ,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2-(2-mercaptoethylthio)-1,3-dimercaptopropane, 1,2-bis( 2-mercaptoethylthio)-3-mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-bis(mercaptomethyl)-1,5-dimercapto-3-thiapentane, 4 ,8-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiundecane, 4,7-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiundecane , 5,7-bis(mercaptomethyl)-1,11-dimercapto-3,6,9-trithiundecane, 1,2,7-trimercapto-4,6-dithiaheptane, 1,2,9-trimercapto -4,6,8-trithianone, 1,2,8,9-tetramercapto-4,6-dithianone, 1,2,10,11-tetramercapto-4,6,8-trithiundecane, 1,2 , 12,13-tetramercapto-4,6,8,10-tetrathiatridecane, 1,1,1-tris(mercaptomethyl)propane, tetrakis(mercaptomethyl)methane, tetrakis(4-mercapto-2-thiabutyl ) methane, tetrakis (7-mercapto-2,5-dithiaheptyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercapto acetate), 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercapto acetate), pentaerythritol tetrakis(3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4 -bis(mercaptomethyl)cyclohexane, 1,3-bis(mercaptomethyl)cyclohexane, 2,5-bis(mercaptomethyl)-1,4-dithiane, 2,5-bis(2-mercaptoethyl)-1,4 -dithiane, 2,5-bis(mercaptomethyl)-1-thiane, 2,5-bis(2-mercaptoethyl)-1-thiane, 1,4-bis(mercaptomethyl)benzene, 1,3-bis( mercaptomethyl)benzene, bis(4-mercaptophenyl)sulfide, bis(4-mercaptophenyl)ether, bis(4-mercaptomethylphenyl)methane, 2,2-bis(4-mercaptophenyl)propane, bis(4- mercaptomethylphenyl)sulfide, bis(4-mercaptomethylphenyl)ether, 2,2-bis(4-mercaptomethylphenyl)propane, 2,5-dimercapto-1,3,4-thiadiazole, 3,4-thiophenedithiol , 1,2-dimercapto-3-propanol, 1,3-dimercapto-2-propanol, glyceryl dithioglycolate, 1,1,2,2-tetrakis(mercaptomethylthio) ethane, 1,1,3,3-tetrakis At least one selected from the group consisting of (mercaptomethylthio)propane and 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane.

Polymerization catalysts include, for example, triethylenediamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis ( 1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene, dimethyltin dichloride, dimethyltin bis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, Dibutyltin Maleate Polymer, Dibutyltin Diricinolate, Dibutyltin Bis (Dodecyl Mercaptide), Dibutyltin Bis (isooctylthioglycolate), Dioctyltin Dichloride, Dioctyltin Maleate, Dioctyltin Maleate Polymer, Dioctyltin Bis(butyl maleate) ), dioctyltin dilaurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltin bis(isooctylthioglycolate), and didodecyltin diricinolate At least one selected is included.

A curable composition for a thioepoxy-based resin contains a monomer having a thioepoxy group, a curing agent, and a polymerization catalyst. Monomers having a thioepoxy group include, for example, compounds having two or more β-epithiopropylthio groups, preferably bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropyl thio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β- epithiopropylthiomethyl)propane, 1,4-bis(β-epithiopropylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3 -(β-epithiopropylthiomethyl)butane, 1,5-bis(β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane , 1,6-bis(β-epithiopropylthio)hexane, 1-(β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl)thio]ethane and 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl] thio] ethane at least one selected from the group consisting of. The curing agent includes, for example, a compound having a thiol group, preferably 2-mercaptoethanol. Polymerization catalysts include, for example, tetrabutylammonium bromide.

The present invention will be explained in more detail by some examples illustrated below. These examples are merely illustrative of the invention, and the spirit and scope of the invention are not limited to these examples.

<Example 1>
(Production of first prepolymer FPP1)
225 g of the first isocyanate compound FI1, 100 g of the first polyfunctional active hydrogen compound FA1, and 200 g of the organic solvent OS1 were charged into a 2 L reactor to obtain a mixture. Isophorone diisocyanate was used as the first isocyanate compound FI1. As the first polyfunctional active hydrogen compound FA1, a polyether diol having a number average molecular weight of 1000 (Exenol manufactured by AGC Inc.) was used. Toluene was used as the organic solvent OS1. This mixture was stirred at 1000 rpm at 100° C. for 7 hours under a nitrogen atmosphere to obtain a reaction liquid containing the first prepolymer. Hereinafter, this first prepolymer is also referred to as first prepolymer FPP1. The end point of the reaction was confirmed by back titration of isocyanate groups.

(Production of second prepolymer SPP1)
After adding 500 g of organic solvent OS2 to the reaction liquid containing the first prepolymer FPP1 at 10°C, the liquid temperature was kept at 15°C. Diethyl ketone was used as the organic solvent OS2. 34 g of the second polyfunctional active hydrogen compound SA1 was added dropwise to this reaction liquid, and reacted at 15° C. for 1 hour to obtain a reaction liquid containing a second prepolymer. Isophoronediamine was used as the second polyfunctional active hydrogen compound SA1. Hereinafter, this second prepolymer is also referred to as second prepolymer SPP1. In addition, in the reaction liquid containing the second prepolymer SPP1, the solid content concentration was 33.9% by mass.

(Preparation of adhesive composition AC1)
100 g reaction solution containing second prepolymer SPP1, 1.02 g photochromic compound PC1, 0.34 g ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate ], and 0.05 g of DOW CORNING TORAY L-7001 were mixed and stirred at room temperature to obtain an adhesive composition. Hereinafter, this adhesive composition is also referred to as adhesive composition AC1.

(Production of optical laminated sheet OL1)
Adhesive composition AC1 was applied onto polyvinyl alcohol film PVF1 using a bar coater to form a coating film. The thickness of the polyvinyl alcohol film PVF1 was 75 μm. This coating film was dried at a temperature of 100° C. for 5 minutes. The film thickness of the coating film after drying was 30 μm. A polyvinyl alcohol film PVF1 was laminated on the dried coating film using a laminate roll to obtain a structure. The structure was in the shape of a rectangular strip. One end of the structure in the long side direction was not coated with the adhesive composition, and was used as an uncoated portion.

This structure was degassed by leaving it at 60°C under a vacuum of 500 Pa for 12 hours. The degassed structure was heated at 90° C. for 2 hours. The structure after heating was left at room temperature for about one week to obtain an optical laminated sheet. Hereinafter, this optical laminated sheet is also referred to as optical laminated sheet OL1.

(Manufacture of lens LS1)
First, the optical laminated sheet OL1 was vacuum-dried under conditions of 80° C. and 13 Torr for 15 hours. The vacuum-dried optical laminated sheet OL1 was placed in the notch on the inner side of the gasket. This gasket was placed in a glass mold so that the optical laminated sheet OL1 was positioned inside the hollow portion. The glass mold was set so that the lens power D was 0.00, the lens diameter was 70 mm, and the lens thickness was 3.0 mm. A thiourethane-based curable composition was injected into the hollow portion of the glass mold. The glass mold after the thiourethane-based curable composition was injected was gradually heated from 35° C. to 110° C. over 12 hours using an air furnace, and then held at 110° C. for 1 hour to obtain the curable composition. Hardened things. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 110° C. and heated for 3 hours. The outer periphery of the cured product after heating was polished with a lens grinder to obtain a lens having a diameter of 60 mm as shown in FIG. This operation was repeated to obtain a total of 10 lenses. Hereinafter, this lens is also referred to as lens LS1.

The thiourethane-based curable composition includes 43.5 parts by mass of dicyclohexylmethane-4,4′-diisocyanate, 43.5 parts by mass of isophorone diisocyanate, 1,2-bis[(2-mercaptoethyl)thio]-3- A mixture of 63.0 parts by weight of mercaptopropane and 0.1 parts by weight of dibutyltin dilaurate was used.

<Examples 2 to 11, and Examples 14, 16 to 19>
An adhesive composition, an optical laminated sheet and a lens were obtained in the same manner as in Example 1, except that each component was changed as shown in Tables 1 and 2.

<Example 12>
(Production of mixture of first polymer FP1 and second prepolymer SPP12)
First, a reaction solution containing the second prepolymer SPP12 was obtained in the same manner as in Example 1, except that the amount of the second polyfunctional active hydrogen compound SA1 added was changed from 34 g to 31 g. 5 g of monofunctional active hydrogen compound MA1 was added to this reaction liquid and stirred to obtain a mixture of the first polymer and the second prepolymer. Hereinafter, the first polymer will also be referred to as the first polymer FP1, and the second prepolymer will also be referred to as the second prepolymer SPP12.

An adhesive composition, an optical laminate sheet and a lens were prepared in the same manner as in Example 1, except that a mixture of the first polymer FP1 and the second prepolymer SPP12 was used instead of the reaction solution of the second prepolymer SPP1. Obtained.

<Example 13>
(Production of first polymer FP2)
First, a reaction solution containing the second prepolymer SPP13 was obtained in the same manner as described in Example 1, except that the amount of the organic solvent OS1 was changed from 500 g to 520 g. 8.5 g of monofunctional active hydrogen compound MA1 was added to this reaction liquid and stirred to obtain a reaction liquid containing the first polymer. Hereinafter, this first polymer is also referred to as first polymer FP2.

An adhesive composition, an optical laminated sheet and a lens were obtained in the same manner as in Example 1, except that the reaction liquid of the first polymer FP2 was used instead of the reaction liquid of the second prepolymer SPP1.

<Example 15>
Instead of 200 g of the reaction mixture of the second prepolymer SPP1, the reaction mixture of the first polymer FP2 obtained in the same manner as described in Example 13 and the reaction mixture of the first polymer FP2 obtained in the same manner as described in Example 14. An adhesive composition, an optical laminate sheet, and a lens were obtained in the same manner as in Example 1, except that a mixed solution of the reaction solution of the second prepolymer SPP13 obtained above was used. The amount of the reaction liquid of the first polymer FP2 in the mixed liquid was 70 g, and the amount of the reaction liquid of the second prepolymer SPP13 was 30 g.

<Example 20>
A lens was obtained in the same manner as in Example 1, except that an allyl-based curable composition was used as the curable composition and the heating conditions were changed.

A mixture of 3 parts by mass of diisopropyl peroxydicarbonate (polymerization initiator) and 100 parts by mass of diethylene glycol bisallyl carbonate was used as the allyl-based curable composition.

The glass mold after injection of the allyl-based curable composition was gradually heated from 30° C. to 90° C. over 20 hours using an air oven, and then held at 90° C. for 1 hour to obtain the curable composition. was cured. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 100° C. and heated for 2 hours.

<Example 21>
A lens was obtained in the same manner as in Example 1, except that an acrylic curable composition was used as the curable composition and the heating conditions were changed.

As the acrylic curable composition, first, 20 parts by mass of trimethylolpropane trimethacrylate, 40 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 522, and 40 parts by mass of urethane acrylate (EBECRYL4858 manufactured by Daicel Corporation) are mixed to form radicals. A polymerizable monomer was obtained. 100 parts by mass of this radically polymerizable monomer was mixed with 1.0 parts by mass of t-butyl peroxyneodecanate to obtain an acrylic curable composition.

The glass mold after injection of the acrylic curable composition was gradually heated from 33 ° C. to 90 ° C. over 17 hours using an air furnace, and then held at 90 ° C. for 2 hours to obtain a curable composition. was cured. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 110° C. and heated for 3 hours.

<Example 22>
A lens was obtained in the same manner as in Example 1, except that a thioepoxy-based curable composition was used as the curable composition and the heating conditions were changed.

A mixture of 95 parts by weight of bis(β-epithiopropylthio)ethane, 5 parts by weight of 2-mercaptoethanol, and 0.1 parts by weight of tetrabutylammonium bromide as a polymerization catalyst was used as the thioepoxy-based curable composition.

The glass mold after injection of the thioepoxy-based curable composition was gradually heated from 20° C. to 90° C. over 20 hours using an air oven, and then held at 90° C. for 1 hour to obtain a curable composition. was cured. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 90° C. and heated for 1 hour.

<Example 23>
A lens was obtained in the same manner as in Example 1, except that a urethane urea-based curable composition was used as the curable composition and the heating conditions were changed.

In the preparation of the urethane urea-based curable composition, first, 100 parts by mass of a polyester polyol composed of adipic acid and 1,6-hexanediol and having a number average molecular weight of 1,000 and an isomer of 4,4'-methylenebis(cyclohexyl isocyanate) 78 parts by mass of the mixture were heated at 140° C. for 10 minutes under dry nitrogen to obtain a prepolymer. The prepolymer was cooled to 70° C. and allowed to stand for 24 hours. 17 parts by mass of a mixture of 2,4-diamino-3,5-diethyl-toluene and 2,6-diamino-3,5-diethyl-toluene was mixed with the prepolymer after standing to obtain a urethane urea curability. A composition was obtained.

The glass mold after injection of the urethane urea-based curable composition was held at 120°C for 10 hours to cure the curable composition. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 110° C. and heated for 1 hour.

<raw materials>
(First polyfunctional active hydrogen compound)
FA1: Exenol manufactured by AGC Co., Ltd. (polyether diol, number average molecular weight 1000)
FA2: Exenol manufactured by AGC Corporation (polyether diol, number average molecular weight 2000)
FA3: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol, number average molecular weight 500)
FA4: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol, number average molecular weight 800)
FA5: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol, number average molecular weight 1000)
FA6: Duranol manufactured by Asahi Kasei Corporation (polycarbonate diol, number average molecular weight 3000)
FA7: Polylight manufactured by DIC Corporation (polyester diol, number average molecular weight 1000)
FA8: ETERNACOLL manufactured by UBE Corporation (polycarbonate diol made from 1,4-cyclohexanedimethanol, number average molecular weight 1000).

(First isocyanate compound)
FI1: isophorone diisocyanate FI2: hydrogenated diphenylmethane diisocyanate FI4: toluene-2,4-diisocyanate FI5: norbornane diisocyanate.

(Second polyfunctional active hydrogen compound: chain extender)
SA1: isophoronediamine SA2: ethylenediamine SA3: 1,6-diaminohexane SA4: bis-(4-aminocyclohexyl)methane.

(Monofunctional active hydrogen compound)
HA1; 1,2,2,6,6-pentamethyl-4-aminopiperidine.

(Photochromic compound)
PC1: A compound represented by the following formula.

PC2: A compound represented by the following formula.

　PC3: A compound represented by the following formula.

(organic solvent)
OS1: toluene OS2: diethyl ketone OS3: isopropyl alcohol OS4: ethyl acetate OS5: cyclohexanone OS6: tetrahydrofuran

(Other additives)
HP: ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]
CF: Dow Corning Toray L-7001
HA: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate DY: Tetraazaporphyrin compound (manufactured by Yamada Kagaku Kogyo Co., Ltd.: FDG-007) (as a result of measurement in chloroform, the absorption peak (maximum The absorption wavelength) was 594 nm, and the absorption intensity at 594 nm was 1.5×10 ⁵ ml/g·cm).

(polyvinyl alcohol film)
PVF1: polyvinyl alcohol film (thickness 75 μm)

PVF2: Polyvinyl alcohol film (thickness: 30 μm) with a draw ratio of 4 times and cross-linked with boric acid
PVF3: Polyvinyl alcohol polarizing film containing a dichroic dye with a luminous transmittance of 44%, a degree of polarization of 94.4%, and a gray tone (thickness: 27 μm)

<Evaluation test>
(Measurement of number average molecular weight of second prepolymer and first polymer)
The number average molecular weights of the second prepolymer, the first polymer, and the mixture of the second prepolymer and the first polymer obtained in Examples 1 to 14 were measured by the method described above. Table 2 shows the results.

(Measurement of softening points of second prepolymer and first polymer)
The softening points of the second prepolymer, the first polymer, and the mixture of the second prepolymer and the first polymer obtained in Examples 1 to 14 were measured by the method described above. Table 2 shows the results.

(Measurement of photochromic property of optical laminated sheet and lens)
The maximum absorption wavelength, color density, and fading rate of the optical laminated sheets obtained in Examples 1 to 23 were measured by the following methods.

Specifically, first, at a temperature of 23° C., a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics K.K. was irradiated for 120 seconds to develop the color of the photochromic compound. The beam intensity was 365 nm=2.4 mW/cm ² and 245 nm=24 μW/cm ² .

The maximum absorption wavelength (λmax) after color development was determined using a spectrophotometer (instantaneous multi-channel photo director MCPD1000) manufactured by Otsuka Electronics Co., Ltd.

The absorbance ε(0) of the maximum absorption wavelength of the optical laminated sheet was measured when the xenon lamp was not irradiated. Next, the optical laminated sheet was irradiated with a xenon lamp for 120 seconds at the above beam intensity, and the absorbance ε (120) of the maximum absorption wavelength of the optical laminated sheet was measured. A value obtained by subtracting ε(0) from the absorbance ε(120) was taken as the color density. It can be said that the higher this value, the better the photochromic properties.

The time required for the color density to decrease to 1/2 was measured, and this was defined as the fading speed [t1/2 (sec.). It can be said that the shorter this time, the better the photochromic properties.

The maximum absorption wavelength, color density, and fading speed of the lenses obtained in Examples 1 to 23 were measured under the same conditions as above. The results were the same as the values for the optical laminated sheets, respectively.

(Measurement of peel strength of optical laminated sheet)
The optical laminate sheets obtained in Examples 1 to 23 were cut into strips of 50 mm×100 mm to obtain test pieces. At this time, it was cut out so as to include one long side end portion that did not include the coating film of the adhesive composition. The portions of the first optical sheet and the second optical sheet of this test piece that were not coated with the adhesive composition were sandwiched between an upper jig and a lower jig, respectively. was installed in The upper jig was pulled at a crosshead speed of 100 mm/min to measure the maximum peel force. This maximum peel strength is shown in Table 4 as the peel strength.

(Lens adhesion evaluation)
The adhesion between the optical laminated sheet and the optical element substrate was evaluated for the lenses according to Examples 1 to 23 by the following method. First, the lens was visually checked to see if any peeling of the optical laminate sheet was observed, and evaluated according to the following evaluation criteria. The results are listed in Table 4.

<Evaluation Criteria>
0: No peeling observed between layers.
1: Peeling is observed in less than 5% of the area between the photochromic laminate and the resin layer.
2: Peeling is observed in less than 10% of the area between the photochromic laminate and the resin layer.
3: Peeling is observed in 10% or more portions between the photochromic laminate and the resin layer.

In Table 2, the column labeled "n1/n2/n3" contains the first polyfunctional active hydrogen compound when the total molar amount (n2) of the isocyanate groups contained in the first isocyanate compound is 1. The ratio of the total molar amount (n1) of active hydrogen groups and the ratio of the total molar amount (n3) of active hydrogen groups contained in the second polyfunctional active hydrogen compound are described.

As is clear from Tables 1 to 4, peeling of the optical laminated sheets according to Examples 1 to 12 and Examples 14 to 23 using the adhesive composition containing the second prepolymer or the second prepolymer and the first polymer The strength was superior to the peel strength of the optical laminate sheet according to Example 13 using an adhesive composition containing only the first polymer.

<Example 24>
(Production of optical laminated sheet OL24)
The first adhesive composition AC1 was applied on one side of the first polyvinyl alcohol film PVF1 using a bar coater to form a first coating film. The thickness of the polyvinyl alcohol film PVF1 was 75 μm. This first coating film was dried at a temperature of 100° C. for 5 minutes. The film thickness of the first coating film after drying was 30 μm.

Also, the second adhesive composition AC2 was applied on one side of the second polyvinyl alcohol film PVF1 using a bar coater to form a second coating film. This second coating was dried at a temperature of 100° C. for 5 minutes. The film thickness of the second coating film after drying was 30 μm.

Next, the first coating film was in contact with one main surface of the polyethylene terephthalate sheet PET, and the second coating film was in contact with the other main surface of the sheet PET, using lamination rolls to obtain a structure. . The structure was a rectangle of about 15 cm×20 cm. One end of the structure in the long side direction was not coated with the adhesive composition, and was used as an uncoated portion.

This structure was degassed by leaving it at 60°C under a vacuum of 500 Pa for 12 hours. The degassed structure was heated at 90° C. for 2 hours. The structure after heating was left at room temperature for about one week to obtain an optical laminated sheet. Hereinafter, this optical laminated sheet is also referred to as an optical laminated sheet OL24. Ten optical laminated sheets OL24 were produced.

Before use, both surfaces of the polyethylene terephthalate sheet PET were subjected to corona discharge treatment using Multidyne manufactured by Navitas.

(Manufacture of lens LS24)
First, the optical laminated sheet OL24 was vacuum-dried under conditions of 80° C. and 13 Torr for 15 hours. The vacuum-dried optical laminated sheet OL1 was placed in a curved surface processing apparatus and subjected to curved surface processing. Specifically, the obtained optical laminated sheet was die-cut to obtain a disk-shaped sheet with a diameter of 80 mm. The obtained disk-shaped sheet was processed into a spherical shape by vacuum suction processing (thermal bending processing). This vacuum suction processing was carried out by placing a concave four-curve mold with a diameter of 90 mm in an atmosphere of 140° C. and performing vacuum suction from a hole in the center of the concave mold with a vacuum pump. The processing time was about 2 minutes per sheet.

The optical laminated sheet OL24 after curved surface processing was placed in the notch inside the gasket. This gasket was placed in a glass mold so that the optical laminated sheet OL24 was positioned inside the hollow portion. The glass mold was set so that the lens power D was 0.00, the lens diameter was 70 mm, and the lens thickness was 3.0 mm. A thiourethane-based curable composition was injected into the hollow portion of the glass mold. The glass mold after the thiourethane-based curable composition was injected was gradually heated from 35° C. to 110° C. over 12 hours using an air furnace, and then held at 110° C. for 1 hour to obtain the curable composition. Hardened things. After heating, the cured body was taken out from the gasket and the glass mold, placed in an oven at 110° C. and heated for 3 hours. The outer periphery of the cured body after heating was polished with a lens grinder to obtain a lens having a diameter of 60 mm as shown in FIG. This operation was repeated to obtain a total of 10 lenses. Hereinafter, this lens is also referred to as lens LS24.

<Example 25 to Example 34>
An optical laminate sheet and a lens were obtained in the same manner as in Example 24, except that the first and second optical sheets or the transparent support was changed as shown in Table 5. The details of the abbreviations in Table 5 are as follows.

PVF1: polyvinyl alcohol film (thickness 75 μm)
PVF2: Polyvinyl alcohol film (thickness: 30 μm) with a draw ratio of 4 times and cross-linked with boric acid
PVF3: Polyvinyl alcohol polarizing film containing a dichroic dye with a luminous transmittance of 44%, a degree of polarization of 94.4%, and a gray tone (thickness: 27 μm)
PET: 300 μm thick sheet made of polyethylene terephthalate TAC: 300 μm thick sheet made of triacetyl cellulose APA1: 300 μm thick alicyclic polyamide sheet sheet mainly composed of group polyamide)
APA2: Stretched alicyclic polyamide sheet with a thickness of 200 μm (a sheet mainly composed of alicyclic polyamide composed of 4,4′-diaminodicyclohexylmethane and 1,10-decanedicarboxylic acid)
PC1: Polycarbonate sheet with a thickness of 200 μm PC2: Stretched polycarbonate sheet with a thickness of 125 μm

<Evaluation test>
(Measurement of photochromic property of optical laminated sheet and lens)
The maximum absorption wavelength, color density, and fading rate of the optical laminated sheets obtained in Examples 24 to 34 were measured by the following methods.

The time required for the color density to decrease to 1/2 was measured, and this was defined as the fading rate [t1/2 (sec.). It can be said that the shorter this time, the better the photochromic properties.
The maximum absorption wavelength, color density, and fading speed of the lenses obtained in Examples 1 to 11 were measured under the same conditions as above. The results were the same as the values for the optical laminated sheets, respectively.

(Measurement of peel strength of optical laminated sheet)
The optical laminate sheets obtained in Examples 24 to 34 were cut into strips of 50 mm×100 mm to obtain test pieces. At this time, it was cut out so as to include one long side end portion that did not include the coating film of the adhesive composition. The portions of the first optical sheet and the second optical sheet of this test piece that were not coated with the adhesive composition were sandwiched between an upper jig and a lower jig, respectively. was installed in The upper jig was pulled at a crosshead speed of 100 mm/min to measure the maximum peel force. This maximum peel strength is shown in Table 5 as the peel strength.

(Yield evaluation of optical laminated sheet after curved surface processing)
The optical laminated sheets according to Examples 24 to 34 were evaluated for yield after curved surface processing. For the evaluation, out of 10 optical laminated sheets that were processed, the number of optical laminated sheets that did not deform at the edges and had a curvature of 4 curves after being placed in an environment of 40°C and 60% RH for 4 hours was counted. , and its ratio was calculated as the yield (%). This value is shown in Table 5.
, listed in Table 1.

(Lens adhesion evaluation)
The adhesion between the optical laminated sheet and the optical element substrate was evaluated for the lenses according to Examples 24 to 34 by the following method. First, the lens was visually checked to see if any peeling of the optical laminate sheet was observed, and evaluated according to the following evaluation criteria. The results are listed in Table 5.

Claims

a first optical sheet and a second optical sheet containing polyvinyl alcohol resin;
a photochromic adhesive layer interposed between the first optical sheet and the second optical sheet to bond them together;
The photochromic adhesive layer comprises a cured adhesive composition containing a photochromic compound and a polymerizable component,
The polymerized component is selected from the second prepolymer, the first polymer and the second prepolymer, the first polymer and the third prepolymer, and the first polymer, the second prepolymer and the third prepolymer. including any
The second prepolymer is a compound having two or more iso(thio)cyanate groups obtained by reacting the first prepolymer with a second polyfunctional active hydrogen compound having two or more active hydrogen groups, The first prepolymer is obtained by reacting a first polyfunctional active hydrogen compound having two or more active hydrogen groups with a first iso(thio)cyanate compound having two or more iso(thio)cyanate groups. A compound having an iso (thio) cyanate group above,
The first polymer is a compound obtained by reacting the second prepolymer with a monofunctional active hydrogen compound having one active hydrogen group, and the third prepolymer is the first polyfunctional active hydrogen compound. A compound having two or more iso(thio)cyanate groups obtained by reacting the first iso(thio)cyanate compound with
Optical laminate sheet.
The optical laminated sheet according to claim 1, wherein the adhesive composition contains the second prepolymer.
The optical laminated sheet according to claim 1 or 2, wherein the first polyfunctional active hydrogen compound contains a polyol compound having a number average molecular weight of 500 or more and 3000 or less.
The optical laminated sheet according to claim 1 or 2, wherein the first iso(thio)cyanate compound contains an iso(thio)cyanate having a molar mass of 100 or more and 500 or less.
The optical laminated sheet according to claim 1 or 2, wherein the second polyfunctional active hydrogen compound contains a polyamine having a molar mass of 50 or more and 500 or less.
The optical laminate sheet according to claim 1 or 2, wherein the monofunctional active hydrogen compound contains an amine having a 2,2,6,6-pentamethyl-4-piperidyl moiety.
The optical laminated sheet according to claim 1, further comprising a transparent support positioned between the first optical sheet and the second optical sheet.
The optical laminated sheet according to claim 7, wherein the transparent support contains at least one resin selected from the group consisting of polyethylene terephthalate, triacetylcellulose, polyamide, and polycarbonate sheets.
An optical laminated sheet according to claim 1 or 2;
An optical article comprising: an optical element base material covering at least one surface of the first optical sheet and the second optical sheet and containing a resin.
The optical article according to claim 9, wherein the optical element substrate covers both surfaces of the first optical sheet and the second optical sheet.
A lens comprising the optical article according to claim 9.
Glasses including the lens according to claim 11.
3. The method for producing an optical laminated sheet according to claim 1, wherein the adhesive composition contains the second prepolymer,
obtaining the first prepolymer by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound;
obtaining the second prepolymer by reacting the first prepolymer with the second polyfunctional active hydrogen compound;
mixing the second prepolymer and the photochromic compound to obtain the adhesive composition;
obtaining a coating film by coating the adhesive composition on at least one main surface of the first optical sheet;
laminating the second optical sheet on the coating film;
A method for producing an optical laminated sheet, comprising:
3. The method for producing an optical laminated sheet according to claim 1, wherein the adhesive composition contains the first polymer and the second prepolymer,
obtaining the first prepolymer by reacting the first polyfunctional active hydrogen compound and the first iso(thio)cyanate compound;
obtaining the second prepolymer by reacting the first prepolymer with the second polyfunctional active hydrogen compound;
reacting the second prepolymer with the monofunctional active hydrogen compound to obtain the first polymer;
mixing the first polymer, the second prepolymer, and the photochromic compound to obtain the adhesive composition;
obtaining a coating film by coating the adhesive composition on at least one main surface of the first optical sheet;
and laminating the second optical sheet on the coating film.