JP5743616B2 - Photochromic composition - Google Patents

Description

  The present invention relates to a novel photochromic composition that can be suitably used as a photochromic adhesive, particularly a photochromic adhesive for joining optical sheets or films made of polycarbonate resin. The present invention also relates to an optical article including a laminated structure in which optical sheets or optical films are bonded to each other via an adhesive layer made of the photochromic composition.

  In recent years, mainly in the United States, the demand for plastic substrates using transparent and excellent impact-resistant polycarbonate for sunglasses having anti-glare properties and the like is rapidly increasing. And in such plastic sunglasses, plastic photochromic sunglasses that can adjust the antiglare property by changing the transmittance according to the surrounding brightness by combining with the photochromic dye are rapidly gaining popularity. .

  However, processing of plastic photochromic sunglasses is not always easy. For example, a method of injection molding a polycarbonate resin in a mold in which a composite film in which a photochromic coating is formed on the surface of a polycarbonate film using a photochromic paint in which a photochromic agent is added to an acrylate copolymer is mounted (see Patent Document 1) Then, it was difficult to obtain sunglasses having good photochromic properties. Moreover, as a method for producing a synthetic resin laminate having good photochromic properties, a resin layer having photochromic properties is continuously applied to one side of a transparent synthetic resin layer such as a polycarbonate sheet that moves continuously, and then There has been proposed a method of pasting another transparent resin layer after drying the resin layer (see Patent Document 2 and Patent Document 3). However, in these methods, since the resin composition (specifically, polyurethane resin composition) used for forming the resin layer having the photochromic property contains a solvent such as tetrahydrofuran or toluene, the resin composition When a product is applied to a transparent synthetic resin layer such as a polycarbonate sheet, the transparent synthetic resin layer dissolves, resulting in poor appearance, or the photochromic properties are degraded by the synthetic resin eluted in the urethane resin. There was a problem.

  Further, in the method described in Patent Document 1, there is a method of using “a laminated sheet in which a polycarbonate sheet is bonded by a polyurethane resin adhesive layer containing a photochromic dye” instead of the composite film (Patent Document 4 and Patent Document). 5). However, in this method, the adhesion and heat resistance of the polycarbonate sheet in the laminated sheet were insufficient. For this reason, when an optical article is manufactured by mounting the laminate on a mold and then injection-molding a polycarbonate resin on the mold, the resulting optical article may be peeled off or optical distortion may occur. There was a problem.

JP 61-5910 A WO2002 / 099513 JP 2002-196103 A Special table 2003-519398 gazette US Patent Application Publication No. 2004-096666

  The object of the present invention is to provide a photochromic composition that has excellent adhesion and heat resistance and exhibits excellent photochromic properties when used as an adhesive layer when bonding optical sheets or films. It is to be.

  The second object of the present invention is an optical article comprising a laminated structure in which an optical sheet or film is joined by an adhesive layer having photochromic properties, and has excellent adhesion in the laminated structure, as well as excellent An optical article having excellent heat resistance and excellent photochromic properties.

  Furthermore, the third object of the present invention is to produce an optical article as described above, without causing poor appearance even when an optical sheet or film made of a thermoplastic resin such as polycarbonate is used. It is to provide a method by which an optical article can be manufactured.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the relationship between the structure of the photochromic polyurethane resin adhesive layer and the properties of the obtained optical article. As a result, (1) when a photochromic polyurethane resin adhesive layer formed using a polyurethane-urea resin is used, the resulting laminate has excellent adhesion, heat resistance, photochromic properties, durability, and the like. And (2) forming the photochromic polyurethane resin adhesive layer without using a solvent, or forming a cast film using a solvent and then drying (solvent removal) to form the photochromic polyurethane. Separately prepare a “photochromic adhesive sheet comprising a polyurethane-urea resin and a photochromic compound dispersed in the polyurethane-urea resin” to be a resin adhesive layer, and laminate using the “photochromic adhesive sheet” If the body is manufactured, the adverse effects of the solvent can be avoided. The photochromic property is not lowered, find, and have completed the present invention.

That is, this invention is shown by following [1]-[ 8 ].
[1] opposing two optical sheets or optical films to one another, a polyurethane having a urea bond in the (A) molecular chain - consists of urea resin, and (B) photochromic composition ing comprising a photochromic compound adhesion An optical article comprising a laminated structure bonded through layers .

[2] The (A) polyurethane-urea resin includes (A1) at least one polyol compound selected from (A1) polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol, and (A2) two or more in the molecule. A polyurethane-urea resin obtained by reacting a polyisocyanate compound having an isocyanate group of (A3) with at least one amino group-containing compound selected from (A3) diamine, triamine, aminoalcohol, aminocarboxylic acid, and aminothiol. The optical article according to the above [1].

[3] The amount ratio of the components (A1), (A2) and (A3) used in obtaining the polyurethane-urea resin is the “functional group capable of reacting with an isocyanate group” contained in the component (A1). When the total number is n1, the total number of isocyanate groups contained in the component (A2) is n2, and the total number of “functional groups capable of reacting with isocyanate groups” contained in the component (A3) is n3, n1: The optical article according to the above [2], wherein the quantity ratio is n2: n3 = 0.3 to 0.9: 1: 0.1 to 0.7.

[4] The optical article according to any one of [1] to [3], wherein 30% by mass or more of the (A2) polyisocyanate compound is an aliphatic polyisocyanate compound.

[5] The optical article according to [2] or [3], wherein the content of the (B) photochromic compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyurethane-urea resin. .

[6] The optical article according to [5], further comprising 5 to 900 parts by mass of (C) an organic solvent with respect to 100 parts by mass of the (A) polyurethane-urea resin.

[ 7 ] The optical article according to any one of [1] to [ 6 ] , wherein at least one of the two optical sheets or optical films facing each other in the laminated structure is made of a polycarbonate resin. .

[ 8 ] A method for producing the optical article according to [ 7 ], wherein (I) the photochromic composition according to [6] is spread on a smooth substrate and then dried (C ) Removing the solvent, and preparing a photochromic adhesive sheet comprising (A) a polyurethane-urea resin and (B) a photochromic compound dispersed in the (A) polyurethane-urea resin, and (II) Forming the laminated structure by joining the two optical sheets or optical films with the photochromic adhesive sheet interposed between the two optical sheets or optical films facing each other. A method characterized by.

  When the photochromic composition of the present invention functions as an adhesive or a binder and an optical sheet or film made of polycarbonate resin or the like is bonded to the adhesive layer made of the composition to produce a laminated body, the obtained laminated body is Excellent adhesion and photochromic properties. Furthermore, since the adhesive layer exhibits excellent heat resistance, even when an optical article is manufactured by mounting the laminate on a mold and then injection-molding a thermoplastic resin such as polycarbonate resin on the mold. Properties and photochromic properties are not easily lowered, and optical distortion hardly occurs.

  Further, according to the method of the present invention, even if an optical sheet or film made of a thermoplastic resin such as polycarbonate having poor solvent resistance is used, adverse effects due to the solvent can be avoided, so that photochromic properties can be reduced. Absent.

  The photochromic composition of the present invention comprises (A) a polyurethane-urea resin having a urea bond in the molecular chain (hereinafter also simply referred to as component A) and (B) a photochromic compound (hereinafter also simply referred to as component B). It is characterized by comprising. Hereinafter, these components A and B will be described.

Component A: Polyurethane-urea resin The polyurethane resin used in conventional photochromic adhesives or binders is a urethane resin chain-extended by a urethane bond using a diol compound such as 1,4-butanediol, and the resin. There was no urea bond in the molecule. On the other hand, the A component of the photochromic composition of the present invention is a polyurethane-urea resin having a urea bond in the molecular chain, and the photochromic composition of the present invention is bonded by including such a resin as a resin component. When used as an agent or binder, it is possible to improve heat resistance, adhesion, and durability of the photochromic compound.

  The reason why such an effect is obtained is not necessarily clear, but the present inventors estimate as follows. That is, it is presumed that the heat resistance is improved because the polyurethane resin has a urea bond, so that the rigidity of the molecule becomes high and the hydrogen bond between the molecular chains becomes stronger. In addition, regarding the improvement of the durability of the photochromic compound, the presence of urea bonds makes the hydrogen bonds between the molecular chains stronger, making it difficult for oxygen in the air to diffuse into the polyurethane-urea resin. It is presumed that this is because the photo-oxidative deterioration known as a general deterioration mechanism of the compound was suppressed. Furthermore, it is presumed that the adhesive strength is improved because the hydrogen bond between the molecular chains is strengthened due to the presence of the urea bond, and the cohesive failure of the resin hardly occurs.

  The polyurethane-urea resin used as the component A is not particularly limited as long as it is a polyurethane resin having a urea bond in the molecular chain. However, since the photochromic characteristics when used in the composition of the present invention are good, It is preferable that it is a polyurethane-urea resin which does not have an isocyanate group at the terminal. From the viewpoint of easy production, (A1) at least one polyol compound selected from polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol (hereinafter also simply referred to as A1 component), ( A2) a polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also simply referred to as A2 component), and (A3) at least one selected from diamine, triamine, aminoalcohol, aminocarboxylic acid, and aminothiol. A polyurethane-urea resin obtained by reacting a kind of amino group-containing compound (hereinafter also simply referred to as “A3 component”) is preferable. In such a polyurethane-urea resin, a urea bond is introduced into the molecule due to the use of a compound having an amino group as the A3 component as a raw material. Hereinafter, these components will be described.

A1 component: polyol compound As the polyol compound of the A1 component, it is preferable that the number of hydroxyl groups contained in the molecule is 2 to 6 because the polyurethane-urea resin to be produced does not become a highly crosslinked product. In consideration of solubility, the number of hydroxyl groups contained in the molecule is more preferably 2 to 3. In addition, the above-mentioned polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol and polyester polyol may be used alone or in combination of two or more, but heat resistance, adhesion, weather resistance From the viewpoints of properties and hydrolysis resistance, it is preferable to use polycarbonate polyol and polycaprolactone polyol. Hereinafter, various compounds used as the A1 component will be described in detail.

Polyether polyol : The polyether polyol used as the A1 component includes a polyether polyol compound obtained by the reaction of “a compound having two or more active hydrogen-containing groups in the molecule” and “alkylene oxide” and the polyether. Examples thereof include polymer polyols, urethane-modified polyether polyols, polyether ester copolymer polyols, and the like, which are modified products of polyol compounds.

  The above “compound having two or more active hydrogen-containing groups in the molecule” includes water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol. , Trimethylolpropane, hexanetriol and the like. These may be used alone or in combination of two or more. Examples of the “alkylene oxide” include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran. These may be used alone or in combination of two or more.

  In the polyether polyol of component A1, the number average molecular weight is 500 from the viewpoint of the heat resistance of the resulting polyurethane-urea resin and photochromic properties (color density, fading speed, weather resistance, etc.), particularly the weather resistance of the photochromic compound. ˜3000, especially 500˜2000 is preferred, and 500˜1500 is most preferred.

  Such polyether polyols are available as reagents or industrially, and examples of commercially available ones include “Excenol (registered trademark)” series, “Emulster (registered trademark)” manufactured by Asahi Glass Co., Ltd. ADEKA Co., Ltd. “ADEKA Polyether” series and the like can be mentioned.

Polycarbonate polyol : Examples of the polycarbonate polyol used as the A1 component include a polycarbonate polyol obtained by phosgenation of a polyol, a polycarbonate polyol obtained by a transesterification method using diphenyl carbonate, and the like. In the polycarbonate polyol as the A1 component, the number average molecular weight is preferably 500 to 3000, particularly 500 to 2000, and most preferably 500 to 1500 for the same reason as in the polyether polyol. These polycarbonate polyols are available as reagents or industrially, and examples of those that are commercially available include "Duranol (registered trademark)" series manufactured by Asahi Kasei Chemicals Corporation, "Kuraray polyol (registered trademark)" manufactured by Kuraray Co., Ltd. ) "Series," Placcel (registered trademark) "series manufactured by Daicel Chemical Industries, Ltd.," Nipporan (registered trademark) "series manufactured by Nippon Polyurethane Industry Co., Ltd.," ETERNACOLL (registered trademark) "series manufactured by Ube Industries, Ltd. be able to.

Polycaprolactone polyol : As the polycaprolactone polyol used as the A1 component, a compound obtained by ring-opening polymerization of ε-caprolactone can be used. In the polycaprolactone polyol as the A1 component, the number average molecular weight is preferably 500 to 3000, particularly 500 to 2000, and most preferably 500 to 1500 for the same reason as in the polyether polyol. Such polycaprolactone polyol is commercially available as a reagent or industrially. Examples of commercially available products include “Placcel (registered trademark)” series manufactured by Daicel Chemical Industries, Ltd.

Polyester polyol : Examples of the polyester polyol used as the component A1 include a polyester polyol obtained by a condensation reaction of “polyhydric alcohol” and “polybasic acid”. Here, as the “polyhydric alcohol”, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 3,3'-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. These may be used alone or in combination of two or more. Examples of the “polybasic acid” include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more. In the polyester polyol as the component A1, the number average molecular weight is preferably 500 to 3000, particularly 500 to 2000, and most preferably 500 to 1500 for the same reason as in the polyether polyol. These polyester polyols are available as reagents or industrially, and examples of commercially available ones include “Polylite (registered trademark)” series manufactured by DIC Corporation, “Nipporan (registered trademark)” manufactured by Nippon Polyurethane Industry Co., Ltd. ) ”Series,“ Maximol (registered trademark) ”series manufactured by Kawasaki Kasei Kogyo Co., Ltd., and the like.

A2 component: Polyisocyanate compound As the “polyisocyanate compound having two or more isocyanate groups in the molecule” used as the A2 component in the present invention, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanates are used. Isocyanate compounds and mixtures thereof are used. Among these, it is preferable to use an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound from the viewpoint of weather resistance. For the same reason, it is preferable that 30% by mass or more, particularly 50% by mass or more of the polyisocyanate compound of the A2 component is an aliphatic polyisocyanate compound. In the A2 component polyisocyanate compound, the number of isocyanate groups contained in the molecule may be two or more, but from the viewpoint of solubility in an organic solvent, the number of isocyanate groups contained in the molecule is 2. It is preferable that

  Examples of polyisocyanate compounds that can be suitably used as the A2 component include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, cyclobutane- 1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4'-methylenebis (Cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenol Len-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, phenylcyclohexylmethane diisocyanate, 4,4′-methylenebis (phenylisocyanate) isomer mixture, toluene-2,4-diisocyanate, toluene-2, Examples include 6-diisocyanate, phenylene-1,3-diisocyanate, and phenylene-1,4-diisocyanate. Among these, from the viewpoint of the weather resistance of the obtained polyurethane-urea resin, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4 ′ Isomer mixtures of methylenebis (cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenol Ren-1,3-diisocyanate, it is preferable to use a hexa hydro-phenylene-1,4-diisocyanate. These isocyanate compounds may be used alone or in combination of two or more.

A3 component: amino group-containing compound The amino group-containing compound used as the A3 component in the present invention comprises at least one compound selected from diamine, triamine, aminoalcohol, aminocarboxylic acid, and aminothiol. These compounds have a group that reacts with two or more isocyanate groups in the molecule, and at least one of them is an amino group (—NH ₂ group or —NH (R), provided that R is provided. Is an alkyl group, particularly an alkyl group having 1 to 5 carbon atoms. Here, reactive groups with isocyanate groups other than amino groups are a hydroxyl group (—OH group), a mercapto group (—SH group), and a carboxyl group [—C (═O) OH group].

  The A3 component functions as a chain extender when synthesizing the polyurethane resin, and by using the A3 component as the chain extender, a urea bond is introduced into the polyurethane resin to become a polyurethane-urea resin.

  Examples of compounds suitably used as the amino group-containing compound of component A3 include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane as diamines and triamines. 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- (4-amino Cyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, hydrazine, adipic acid dihydrazine, phenylenediamine, 4, 4'-diphenylmethanediamine, N, N'-diethylethylenedi Min, N, N'- dimethylethylenediamine, N, N'- di-ethylenediamine, N, may be mentioned N'- dibutyl ethylenediamine.

  Examples of amino alcohol include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2- Examples of the aminocarboxylic acid include glycine, alanine, lysine, and leucine. Examples of the aminothiol include 1-aminothiol and 2-aminoethanethiol. Can be mentioned. These amino group-containing compounds may be used alone or in combination of two or more.

  In the chain extender, it is particularly preferable to use a diamine compound from the viewpoints of adhesion, durability of the photochromic compound, and the like.

Method for synthesizing component A When the component A1 is obtained by reacting the component A1, component A2, and component A3, a so-called one-shot method or prepolymer method can be employed. A component can be obtained.

  That is, first, the A1 component and the A2 component are reacted to obtain a urethane prepolymer, and then the urethane prepolymer and the A3 component are reacted to produce the A component. In addition, since the said urethane prepolymer itself is a polyurethane-urea resin, it can also be used with A component as it is.

  In the above method, the reaction between the A1 component and the A2 component is carried out by reacting both in the presence or absence of a solvent at 25 to 120 ° C. for 0.5 to 24 hours in an inert gas atmosphere such as nitrogen or argon. Just do it. As the solvent, organic solvents such as methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the polyisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried. In carrying out the above reaction, dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, 1,4-diazabicyclo [2,2, 2] A catalyst such as octane may be added. As an addition amount at the time of using a catalyst, it is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of this A component.

  The reaction between the urethane prepolymer thus obtained and the A3 component is carried out in the presence or absence of a solvent in an inert gas atmosphere such as nitrogen or argon at 25 to 120 ° C. for 0.5 to What is necessary is just to make it react for 24 hours. As the solvent, methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

  Furthermore, when an isocyanate group remains at the end of the polyurethane-urea resin obtained by the above reaction, an active hydrogen compound that reacts with the isocyanate group may be added to inactivate the end. preferable. As the active hydrogen compound, a compound having one amino group, hydroxyl group, mercapto group, and carboxyl group in the molecule can be used. Specific examples include normal butylamine, sec-butylamine, tert-butylamine, dibutylamine, diisopropylamine, methanol, ethanol, isopropanol, normal butanol, sec-butanol, tert-butanol, and acetic acid.

  When a polyurethane-urea resin having an isocyanate group remaining at the terminal is used, the photochromic property tends to be lowered. Whether or not an isocyanate group remains can be determined by measuring an infrared absorption spectrum.

  The amount ratio of the A1, A2 and A3 components used in the reaction in the above method may be determined as appropriate, but the resulting polyurethane-urea resin has heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance). From the viewpoint of balance such as That is, the total number of “functional groups capable of reacting with isocyanate groups” (specifically, hydroxyl groups) contained in the A1 component is n1, the total number of isocyanate groups contained in the A2 component is n2, and the A3 component contains “ When the total number of functional groups capable of reacting with isocyanate groups (specifically, amino groups, hydroxyl groups, mercapto groups and / or carboxyl groups) is n3, n1: n2: n3 = 0.3 to 0.9: 1: It is preferable that the amount ratio is 0.1 to 0.7, particularly n1: n2: n3 = 0.35 to 0.85 / 1 / 0.15 to 0.65, and n1: n2: Most preferably, the quantity ratio is such that n3 = 0.4 to 0.8 / 1 / 0.2 to 0.6. Here, said n1-n3 can be calculated | required as a product of the use mole number of the compound used as each component, and the number of each group which exists in this compound 1 molecule.

  For the polyurethane-urea resin obtained by such a reaction, if necessary, the solvent is distilled off, or the reaction solution is dropped into a poor solvent such as water, and the polyurethane-urea resin is precipitated, filtered, and dried. The post-treatment may be performed and used as the A component.

The polyurethane-urea resin of component A has a molecular weight of 10,000 to 1,000,000 from the viewpoint of heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.) of the obtained polyurethane-urea resin. In particular, it is preferably 30,000 to 900,000, and most preferably 50,000 to 800,000. The molecular weight of the polyurethane-urea resin is determined by using gel permeation chromatograph (GPC) in terms of polystyrene, columns: Shodex KD-805, KD-804 (manufactured by Showa Denko KK), eluent: It means the molecular weight measured by the conditions of LiBr (10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, polyurethane-urea resin sample solution: 0.5% dimethylformamide (DMF) solution.
Further, when the molecular weight of the polyurethane-urea resin measured under the same conditions as above is converted into polyethylene oxide, the preferred range is 5,000 to 150,000, particularly 8,000 to 100,000, and 10,000 to 60,000. Most preferably.

In addition, the polyurethane-urea resin which is the component A is a laminate obtained by attaching optical sheets or films using the photochromic composition of the present invention, or an optical article using the obtained laminate is produced. 60 to 200 from the viewpoint of workability when applying a hard coat liquid or curing in the case of forming a hard coat layer on the surface of the laminate or optical article. It is preferable that it has heat resistance of 80 degreeC, especially 80-150 degreeC. In addition, heat resistance here means the softening point measured on the following conditions using the thermomechanical measuring apparatus (The Seiko Instruments company make, TMA120C).
[Measurement Conditions] Temperature rising rate: 10 ° C./min, measurement temperature range: 30 to 200 ° C., probe: needle-inserted probe with a tip diameter of 0.5 mm.

Component B: Photochromic Compound As the photochromic compound used as the component B in the photochromic composition of the present invention, known photochromic compounds such as a chromene compound, a fulgimide compound, a spirooxazine compound, and a spiropyran compound can be used without any limitation. These may be used alone or in combination of two or more.

  Examples of the fulgimide compound, spirooxazine compound, spiropyran compound and chromene compound described in JP-A-2-28154, JP-A-62-2288830, WO94 / 22850, WO96 / 14596, etc. Can be mentioned.

  In particular, chromene compounds having excellent photochromic properties other than those described in the above-mentioned patent documents are known as chromene compounds, and such chromene compounds can be suitably used as the B component. Examples of such chromene compounds include JP2001-031670, JP2001-011067, JP2001-011066, JP2000-344761, JP2000-327675, JP2000-256347, JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229993, JP 2000-229972, JP 2000-219678, JP 2000-219686, Special Kaihei 11-322739, JP 11-286484, JP 11-279171, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139, JP 08-157467, US Pat. No. 56457 No. 7, U.S. Pat. No. 5,658,501, U.S. Pat. No. 5,961,892, U.S. Pat. No. 6,296,785, Japanese Patent No. 4424981, Japanese Patent No. 4424962, WO2009 / 136668, WO2008 / 023828, Japanese Patent No. 4369754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, WO2007 / 086532 Pamphlet, JP2009-120536A, JP2009-67754A, JP2009-67680A. JP-A-2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 41588881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent No. 4157227 Gazette, Japanese Patent No. 4118458, Japanese Patent Laid-Open No. 2008-74832, Japanese Patent No. 3984770, Japanese Patent No. 3801386, WO 2005/028465 pamphlet, WO 2003/042203 pamphlet, JP 2005-289812, JP No. 2005-289807, JP-A-2005-112772, Japanese Patent No. 3522189, WO2002 / 090342 pamphlet, Japanese Patent No. 3471703, JP-A 2003-277381, WO2001 / 060811, pamphlet WO00 / 71544 No. pamphlet etc.

  Among these other photochromic compounds, a chromene compound having an indenonaphth “2,1-f” naphtho “2,1-b” pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloration, durability, and fading speed. It is more preferable to use one or more types. Further, among these chromene compounds, compounds having a molecular weight of 540 or more are preferable because they are particularly excellent in color density and fading speed. Specific examples thereof include the following.

  The blending amount of the B component in the photochromic composition of the present invention is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the A component from the viewpoint of photochromic properties. When the amount is too small, sufficient color density and durability tend not to be obtained. When the amount is too large, depending on the type of photochromic compound, the photochromic composition dissolves in the A component. Not only does this tend to be difficult and the uniformity of the composition tends to decrease, but also the adhesive strength (adhesion) tends to decrease. In order to maintain sufficient adhesion to an optical substrate such as a plastic film while maintaining photochromic properties such as color density and durability, the amount of component B added is 0.5 parts per 100 parts by mass of component A. It is more preferable to set it as 10 to 10 weight, especially 1 to 7 parts by mass.

Optional Components The photochromic composition of the present invention may contain (C) an organic solvent (hereinafter also simply referred to as C component) and other components as optional components in addition to the A component and the B component. Hereinafter, these optional components will be described.

Component C: Organic solvent By adding an organic solvent to the photochromic composition of the present invention, a polyurethane-urea resin (component A) and a photochromic compound (component B), and other components added as necessary, It becomes easy to mix and the uniformity of a composition can be improved. Further, the viscosity of the photochromic composition of the present invention can be appropriately adjusted, and the operability and the uniformity of the coating layer thickness when applying the photochromic composition of the present invention to an optical sheet or film can also be increased. . If an optical sheet or film that is easily affected by an organic solvent is used, there may be a problem that appearance defects may occur or photochromic properties may deteriorate. This problem can be avoided by adopting the method of the present invention shown as [9] above. Further, in the photochromic composition of the present invention, since various types of solvents can be used as described later, the occurrence of the above problem can be achieved by selecting and using a solvent that does not easily attack the optical sheet or film as the solvent. Can be prevented.

  Examples of organic solvents that can be suitably used as component C include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, 2-butanol; ethylene glycol monomethyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n- Polyhydric alcohol derivatives such as butyl ether; diacetone alcohol; methyl ethyl ketone; toluene; hexane; heptane; ethyl acetate; O; THF; cyclohexanone; and combinations thereof can be exemplified. What is necessary is just to select suitably from these according to the kind of A component to be used, and the material of an optical sheet or a fill. For example, when an optical sheet or film made of polycarbonate resin is used and the photochromic composition of the present invention is directly applied, it is preferable to use alcohols or polyhydric alcohol derivatives as the solvent.

  Further, while maintaining the smoothness of the photochromic adhesive sheet when the coating layer when the photochromic composition of the present invention is applied to an optical sheet or film or the method of the present invention shown in [9] above is employed, an organic solvent Therefore, it is preferable to use a mixture of an organic solvent having a boiling point of less than 90 ° C. and an organic solvent having a boiling point of 90 ° C. or more as the component C because the drying rate can be increased.

  Moreover, the addition amount in the case of adding C component is 5-900 mass parts with respect to 100 mass parts of A component especially from 20-750 mass parts from a viewpoint of the effect acquired by above-mentioned C component addition. It is preferable to set it to 40 to 400 parts by mass.

Other components Further, the photochromic composition used in the present invention includes a surfactant, an antioxidant, a radical for improving the durability of the photochromic compound, improving the color development speed, improving the fading speed, and forming a film. Additives such as supplements, ultraviolet stabilizers, ultraviolet absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers may be added. As these additives to be added, known compounds are used without any limitation.

  For example, as the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in the photochromic composition. Specific examples of nonionic correct surface active agents that can be suitably used include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensate, a single-chain polyoxyethylene alkyl ethers, and more may be mentioned surfactants of the silicone-based or fluorine. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the polyurethane-urea resin (component A).

  Antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, phosphorus antioxidants, sulfur antioxidants. , Benzotriazole compounds, benzophenone compounds and the like can be preferably used. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. Furthermore, when using these additives, surfactants and antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination. These antioxidants, radical scavengers, UV stabilizers, and UV absorbers are preferably added in an amount of 0.001 to 20 parts by mass with respect to 100 parts by mass of the polyurethane-urea resin (component A).

Production Method of Photochromic Composition The photochromic composition of the present invention can be produced by mixing the A component and the B component, and the C component and other components used as necessary.

  For example, when an organic solvent is not used, each main component can be melt-kneaded to form a photochromic composition and pelletized, or a sheet can be formed as it is. Moreover, when using an organic solvent, a photochromic composition can be obtained by dissolving each main component in an organic solvent.

  The photochromic composition of the present invention thus obtained can be suitably used as a photochromic adhesive, particularly a photochromic adhesive for joining optical sheets or films made of polycarbonate resin. The optical article of the present invention shown as [7] can be obtained by bonding the optical sheet or the optical film to each other via the adhesive layer made of the photochromic composition of the present invention. Hereinafter, the optical article of the present invention and the method for producing the optical article will be described.

Optical Article of the Present Invention The optical article of the present invention comprises a laminated structure in which two optical sheets or optical films facing each other are bonded via an adhesive layer made of the photochromic composition of the present invention. As such an optical article, a laminated sheet or film comprising only the above laminated structure (hereinafter, also simply referred to as a laminated sheet of the present invention); an optical sheet or film further laminated on the laminated sheet or film, or a surface A composite laminated sheet or film having a coating layer such as a hard coat layer formed thereon; a laminated sheet or film, or a composite laminated sheet or film (hereinafter collectively referred to simply as a laminated sheet of the present invention). An optical article integrated with an optical substrate such as a plastic lens body can be used. As a method for integrating with an optical substrate such as a plastic lens body, for example, an optical substrate such as a polycarbonate resin (for example, a lens body) is formed after the laminated sheet of the present invention is mounted in a mold. Examples thereof include a method of injection molding a thermoplastic resin (hereinafter also simply referred to as an injection molding method), a method of sticking the laminated sheet of the present invention to the surface of an optical substrate with an adhesive or the like. Hereinafter, these materials or members constituting the optical article of the present invention will be described.

Optical sheet or film and optical substrate In the present invention, as the optical sheet or optical film and the optical substrate, a light-transmitting sheet or film and an optical substrate can be used without any particular limitation, but they are easily available. It is preferable to use a resin-made one from the viewpoints of properties and ease of processing. For example, polycarbonate resin, polyethylene terephthalate resin, nylon resin, triacetyl cellulose resin, acrylic resin, urethane resin, allyl resin, epoxy resin, polyvinyl alcohol Resin etc. are mentioned. Among these, polycarbonate resin is particularly preferable because it has good adhesion and high applicability to the injection molding method. A polarizing film (a polyvinyl alcohol polarizing film sandwiched between triacetyl cellulose resin films) can also be used as the optical film of the present invention.

Production method of laminated sheet of the present invention The laminated sheet of the present invention is produced by joining two optical sheets or optical films facing each other through an adhesive layer comprising the photochromic composition of the present invention. The thickness of the adhesive layer is preferably 5 to 100 μm, particularly 10 to 50 μm, from the viewpoint of the color density of the photochromic compound, weather resistance, adhesive strength, and the like.

  The said adhesive layer can be obtained with the following methods according to the property of the photochromic composition to be used. That is, when the photochromic composition of the present invention is adjusted to an appropriate viscosity by adding a solvent, etc., the photochromic composition of the present invention is applied on one optical sheet or optical film, and if necessary After (heating) drying, another optical sheet or optical film may be (heated) pressure bonded. At this time, as a method for applying the photochromic composition, a known method such as a spin coating method, a spray coating method, a dip coating method, a dip-spin coating method, or a dry laminating method is used without any limitation. Further, the optical sheet or optical film used in the present invention may be washed and degreased with an organic solvent such as methanol in advance. Furthermore, corona discharge treatment, plasma discharge treatment, UV ozone treatment, or the like can be performed. When such a method is adopted, a laminated body can be continuously produced using an apparatus as described in Patent Document 3.

  In addition, when using the photochromic composition of the present invention containing a solvent, (I) (C) the solvent is removed by drying after spreading the photochromic composition of the present invention on a smooth substrate, A photochromic adhesive sheet comprising an A component and a B component dispersed in the A component is prepared, and then (II) the photochromic adhesive sheet is placed between two optical sheets or optical films facing each other. The laminated body of the present invention can also be produced by bonding the two optical sheets or optical films to intervene. When such a method is adopted, it is possible to eliminate adverse effects caused by the use of the solvent regardless of the type of solvent and the type of optical sheet or optical film.

  Furthermore, when using the photochromic composition of the present invention which does not contain a solvent, a photochromic sheet can be prepared by coextrusion molding or the like.

  The present invention is further illustrated by the following examples. These examples are merely to illustrate the present invention, and the spirit and scope of the present invention are not limited to these examples.

  The abbreviations of the compounds used as the respective components in the examples and comparative examples are summarized below.

A1 component; polyol compound PL1: Exenol manufactured by Asahi Glass Co., Ltd. (polyether diol, number average molecular weight 400)
PL2: Exenol manufactured by Asahi Glass Co., Ltd. (polyether diol, number average molecular weight 1000)
PL3: Exenol manufactured by Asahi Glass Co., Ltd. (polyether diol, number average molecular weight 2000)
PL4: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 500)
PL5: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 800)
PL6: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 1000)
PL7: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol, number average molecular weight 3000)
PL8: Plaxel manufactured by Daicel Chemical Industries, Ltd. (polycaprolactone diol, number average molecular weight 500)
PL9: Polylite manufactured by DIC Corporation (polyester diol, number average molecular weight 1000)
PL10: ETERNACOLL manufactured by Ube Industries, Ltd. (polycarbonate diol using 1,4-cyclohexanedimethanol as a raw material, number average molecular weight 1000)
PL11: Exenol manufactured by Asahi Glass Co., Ltd. (polypropylene glycol, number average molecular weight 4000)
PL12: 1,10-decanediol.

A2 component; polyisocyanate compound NCO1: isophorone diisocyanate NCO2: hydrogenated diphenylmethane diisocyanate NCO3: hexamethylene-1,6-diisocyanate NCO4: toluene-2,4-diisocyanate NCO5: norbornane diisocyanate.

A3 component; amino compound (chain extender)
AM1: isophoronediamine AM2: ethylenediamine AM3: 1,6-diaminohexane AM4: 2-aminoethanol AM5: 6-aminohexanol AM6: glycine AM7; 2-aminoethanethiol AM8; piperazine AM9: N, N'-diethylethylenediamine.

Component B: Photochromic compound PC1: Compound represented by the following formula

Component C: organic solvent C1: isopropyl alcohol C2: propylene glycol mono-methyl ether C3: toluene C4: ethyl acetate C5: cyclohexanone C6: THF.

Synthesis of polyurethane-urea resin (U1) In a three-necked flask having a stirrer chip, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 9.0 g of polyether diol having a number average molecular weight of 400, 10.0 g of isophorone diisocyanate, and 80 ml of DMF are added. Charge and react at 120 ° C. for 5 hours under a nitrogen atmosphere, then cool to 25 ° C., drop 3.4 g of isophoronediamine as a chain extender, react for 1 hour at 25 ° C., and distill off the solvent under reduced pressure. A polyurethane-urea resin (U1) was obtained. The molecular weight of the obtained polyurethane-urea resin was 150,000 in terms of polystyrene, 10,000 (theoretical value; 10,000) in terms of polyoxyethylene, and the heat resistance was 140 ° C. The theoretical value of the number average molecular weight referred to here is the molecular weight when the A1 component, the A2 component, and the A3 component used as raw materials theoretically form a polyurethane resin without cross-linking.

Synthesis of polyurethane-urea resins (U2) to (U10) and (U21) to (U41) Polyol compounds (A1 component), polyisocyanate compounds (A2 components), amine compounds (A3 components) shown in Tables 1, 3 and 4 In addition, U2-U10 and U21-U41 were synthesized in the same manner as the synthesis method of U1 described above, except that the reaction conditions shown in Tables 1, 3, and 4 were used. The properties of the resulting polyurethane-urea resin are also shown in Tables 1, 3 and 4. Incidentally, polyurethane - about urea resin U1~10 and U21～41, was measured infrared absorption spectrum, absorption derived from the isocyanate groups at the molecular ends was observed in the vicinity of 2250 cm ^-1.

Synthesis of polyurethane-urea resin (U11) In a three-necked flask having a stirrer chip, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 9.0 g of polyether diol having a number average molecular weight of 400, 10.0 g of isophorone diisocyanate, and 80 ml of DMF are added. The mixture was charged and reacted at 120 ° C. for 5 hours under a nitrogen atmosphere, then cooled to 25 ° C., 3.4 g of isophoronediamine as a chain extender was dropped, and reacted at 25 ° C. for 1 hour. .35 g was added and reacted at 25 ° C. for 1 hour, and the solvent was distilled off under reduced pressure to obtain a polyurethane-urea resin (U11). When the infrared absorption spectrum of the obtained polyurethane-urea resin was measured, the absorption derived from the isocyanate group at the molecular terminal was not confirmed, and it was confirmed that the isocyanate group did not remain at the molecular terminal. The molecular weight of the obtained polyurethane-urea resin was 150,000 in terms of polystyrene, 10,000 (theoretical value; 10,000) in terms of polyoxyethylene, and the heat resistance was 140 ° C. The theoretical value of the number average molecular weight referred to here is the molecular weight when the A1 component, A2 component, and A3 component used as raw materials are theoretically purified from a polyurethane resin without cross-linking.

Synthesis of polyurethane-urea resins (U12) to (U20) Reaction conditions shown in Table 1 using a polyol compound (A1 component), a polyisocyanate compound (A2 component), an amine compound (A3 component) and a reaction solvent shown in Table 2 Was used to synthesize U12 to U20 in the same manner as the above-described synthesis method of U11. When the infrared absorption spectrum of the obtained polyurethane-urea resin was measured, no absorption derived from the isocyanate group at the molecular end was confirmed in any of the resins. The properties of the obtained polyurethane-urea resin are also shown in Table 2.

Synthesis of polyurethane resins (U42) to (U46) having no urea bond Table 5 is used instead of A3 component, using the polyol compound (A1 component), polyisocyanate compound (A2 component) and reaction solvent shown in Table 5. U42 to U46 were synthesized under the conditions shown in Table 5 in the same manner as the synthesis method of U1 described above except that a diol compound (chain extender) was used. The characteristics of the obtained polyurethane resin are also shown in Table 5. The polyurethane resin U22-46 does not have a urea bond in the molecule due to the use of the diol compound shown in Table 5 as the chain extender.

Example 1
Preparation of photochromic composition 5 g of polyurethane-urea resin (U1), 0.25 g of photochromic compound (PC1), 20 g of isopropyl alcohol as an organic solvent, and bis (1,2,2,6,6-pentamethyl as a photooxidant) -4-piperidyl) sebacate 0.25g was added, and it melt | dissolved by the ultrasonic wave, stirring at 80 degreeC, and obtained the photochromic composition.

Preparation of Photochromic Laminate The obtained photochromic composition was applied on a fluororesin sheet having a smooth surface and dried at 80 ° C. for 1 hour, and the resulting photochromic sheet having a thickness of 30 μm was obtained by two polycarbonate sheets having a thickness of 400 μm. To obtain a laminate having the desired photochromic characteristics.

  When the obtained photochromic laminate was evaluated, the color density as a photochromic property was 1.0, the fading speed was 80 seconds, and the durability was 95%. The peel strength of the photochromic laminate was 30 N / 25 mm. These evaluations were performed as follows.

A laminate obtained with photochromic properties was used as a sample, and a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was passed through an aeromass filter (manufactured by Corning) at 23 ° C. The film was irradiated for 120 seconds with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² to develop color, and the photochromic characteristics of the laminate were measured.

  1) Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photo director MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

  2) Color density [ε (120) −ε (0)]: difference between absorbance ε (120) after irradiation for 120 seconds at the maximum absorption wavelength and absorbance ε (0) without irradiation at the maximum absorption wavelength . It can be said that the higher this value, the better the photochromic properties.

  3) Fading speed [t1 / 2 (sec.)]: When light irradiation is stopped after irradiation for 120 seconds, the absorbance at the maximum wavelength of the sample is 1 / ([ε (120) −ε (0)]). Time required to drop to 2. It can be said that the shorter this time is, the better the photochromic property is.

  4) Durability (%) = [(A24 / A0) × 100]: In order to evaluate the durability of color development by light irradiation, the following deterioration acceleration test was conducted. That is, the obtained laminate was accelerated and deteriorated for 48 hours using a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, the color density before the test (A0) and the color density after the test (A48) were measured, and the value of [(A48) / A0] × 100] was determined as the residual rate. (%) And used as an index of color durability. The higher the remaining rate, the higher the durability of coloring.

Peel strength The obtained laminate was used as a test piece having an adhesive part of 25 × 100 mm, mounted on a testing machine (Autograph AG5000D, manufactured by Shimadzu Corporation), and subjected to a tensile test at a crosshead speed of 100 mm / min. Was measured.

Examples 2-41
A photochromic composition was prepared and a photochromic laminate was prepared in the same manner as in Example 1 except that the polyurethane-urea resin and organic solvent shown in Table 2 were used. Tables 6 and 7 show the evaluation results of the obtained various photochromic laminates.

Comparative Examples 1-5
A photochromic composition was prepared and a photochromic laminate was prepared in the same manner as in Example 1 except that the polyurethane-urea resin and organic solvent shown in Table 3 were used. Table 8 shows the evaluation results of the obtained various photochromic laminates.

  As is clear from Examples 1-41 above, a synthesized polyurethane using a polyol compound (A1 component), a polyisocyanate compound (A2 component), and an amino group-containing compound (A3) in suitable ratios according to the present invention It can be seen that the urea resin has excellent photochromic properties, peel strength, and heat resistance.

  On the other hand, in Comparative Examples 1-5, since the diol compound is used instead of the amino group-containing compound, the polyurethane resin does not have a urea bond, and the peel strength and heat resistance are reduced. Could not be satisfied at the same time.

Claims (8)

Together two optical sheets or optical films facing the polyurethane having a urea bond in the (A) molecular chain - consists of a photochromic composition characterized by comprising a urea resin, and (B) a photochromic compound adhesion An optical article comprising a laminated structure bonded through layers . The (A) polyurethane-urea resin is (A1) at least one polyol compound selected from polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol, and (A2) two or more isocyanate groups in the molecule. And (A3) a polyurethane-urea resin obtained by reacting (A3) at least one amino group-containing compound selected from diamine, triamine, aminoalcohol, aminocarboxylic acid, and aminothiol. The optical article according to 1. The amount ratio of the components (A1), (A2) and (A3) used for obtaining the polyurethane-urea resin is the total number of “functional groups capable of reacting with isocyanate groups” contained in the component (A1). N1: n2: n3 where n2 is the total number of isocyanate groups contained in component (A2) and n3 is the total number of “functional groups capable of reacting with isocyanate groups” contained in component (A3). The optical article according to claim 2, which has a quantitative ratio of 0.3 to 0.9: 1: 0.1 to 0.7. The optical article according to claim 2 or 3, wherein 30% by mass or more of the (A2) polyisocyanate compound is an aliphatic polyisocyanate compound. The optical article according to any one of claims 1 to 4, wherein a content of the (B) photochromic compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) polyurethane-urea resin. The optical article according to claim 5, further comprising 5 to 900 parts by mass of (C) an organic solvent based on 100 parts by mass of the (A) polyurethane-urea resin. The optical article according to any one of claims 1 to 6, wherein at least one of the two optical sheets or optical films facing each other in the laminated structure is made of a polycarbonate resin. A method for producing the optical article according to claim 7 , wherein (I) the photochromic composition according to claim 6 is spread on a smooth substrate and then dried to remove (C) the solvent. (A) preparing a photochromic adhesive sheet comprising (A) a polyurethane-urea resin and (B) a photochromic compound dispersed in the (A) polyurethane-urea resin, and (II) two sheets facing each other A step of forming the laminated structure by interposing the photochromic adhesive sheet between the optical sheet or optical film and joining the two optical sheets or optical films. .