JP5863317B2 - 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. .

  Such plastic photochromic sunglasses are manufactured by various methods. Specifically, a method of applying a coating composition containing a photochromic dye on the surface of a plastic lens, and a method of forming a lens by mixing a photochromic dye with the plastic lens material itself.

  In addition, the following methods are also being studied in that partial processing can be performed, a smooth photochromic layer can be formed, and photochromic characteristics can be imparted simultaneously when manufacturing a plastic lens by injection molding. Specifically, it is a method of using a photochromic adhesive containing a photochromic dye and an acrylate resin or a polyurethane resin (see Patent Documents 1 to 5). More specifically, the “photochromic laminated sheet” obtained by joining optical sheets made of polycarbonate resin with the photochromic adhesive is mounted in a mold for lens molding, and the laminated sheet is formed by injection molding. It is the method of manufacturing the plastic photochromic sunglasses which have (refer patent documents 1-4).

  The method of using this “photochromic laminated sheet” is a method with high production efficiency, but there is room for improvement in the following points. For example, although it is a method of producing the photochromic laminated sheet itself, Patent Documents 2 and 3 describe a method of continuously producing the photochromic laminated sheet. However, in these methods, when forming the photochromic adhesive layer, a solvent that dissolves an optical sheet such as a polycarbonate sheet such as toluene or tetrahydrofuran is used. For this reason, there has been a problem that the appearance is poor or the photochromic characteristics are deteriorated due to the eluted optical sheet component.

  In addition, in the methods described in Patent Documents 1 to 5, it is considered that the heat resistance of the resin forming the layer made of the adhesive, specifically, the polyurethane resin or the acrylate resin is affected. There is a case where the contact state between the sheet and the injection-molded lens may be poor, and there is a problem that separation or optical distortion occurs in the obtained optical article. Therefore, it has been required to improve the heat resistance of the matrix resin itself of the layer made of the adhesive.

  Furthermore, since plastic photochromic sunglasses are exposed to light, the durability of the photochromic dye is important. In the case of using this photochromic laminated sheet, for example, in the method described in Patent Document 1, a photochromic adhesive containing an antioxidant and an additive such as a hindered amine is used in order to improve durability. ing. By blending the additive, the durability of the photochromic dye can be sufficiently secured. However, according to the study by the present inventors, in the photochromic adhesive, the adhesion between the adhesive layer (photochromic adhesive layer) and the polycarbonate sheet is not sufficient, and the sheet may peel off. there were.

  On the other hand, as a method for improving the durability of a photochromic material, a method of introducing a functional structure such as a hindered amine into a resin molecule serving as a matrix is known. For example, a composition in which a polyurethane resin grafted with a hindered amine functional group and a photochromic dye is combined with a photochromic property without impairing photochromic properties, and a composition superior in durability. Is known (see Patent Document 6). The method described in Patent Document 6 uses a coating composition containing a polyisocyanate compound having three isocyanate groups, a diol compound having two hydroxyl groups, a hindered amine compound having a hydroxyl group, and a photochromic dye, The material is manufactured. In Patent Document 6, as a method for producing a photochromic material, a coating layer containing a polyurethane resin grafted with a hindered amine functional group and a photochromic dye is formed by curing the coating composition on a plastic support. The method is specifically described. Since this coating composition contains a polyisocyanate compound having three isocyanate groups and a diol compound having two hydroxyl groups, a highly crosslinked urethane resin is formed.

  Although the method described in Patent Document 6 is different from the methods described in Patent Documents 1 to 5 in that a coating composition is used, the coating composition disclosed in Patent Document 6 is used, for example, in Patent Document 1 If used as a photochromic adhesive, the amount of additive used can be reduced, and the adhesion can be improved. Further, it is considered that a highly crosslinked polyurethane resin is used, and the heat resistance is also improved.

  However, according to the study by the present inventors, it has been found that the adhesion between polycarbonates cannot be improved by simply using a urethane resin having a hindered amine structure in the molecule and highly crosslinked. In addition, when attempting to polymerize a highly crosslinked urethane resin on a polycarbonate sheet according to the method of Patent Document 6, there is a possibility that the sheet may be deformed due to the influence of polymerization shrinkage or the like, and there is room for improvement.

US Patent Publication No. 20040966666 WO2002 / 099513 pamphlet JP 2002-196103 A Special table 2003-519398 gazette JP 61-5910 A JP 2000-515904 A

  Therefore, the object of the present invention is, first of all, 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. Is to provide.

  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 adhesive layer and the characteristics of the obtained optical article.

  As a result, (1) a photochromic comprising a polyurethane resin and a photochromic compound obtained from a functionality-imparting compound capable of imparting functionality such as a piperidine structure, a specific diisocyanate compound, a specific polydiol compound, and a specific chain extender By using the composition for the photochromic adhesive, the adhesiveness, photochromic property, and durability of the resulting photochromic laminate sheet can be improved, and further, a layer comprising the adhesive and an optical sheet It has been found that the adhesion of can be improved.

  Further, (2) forming the photochromic adhesive layer without using a solvent, or forming a cast film using a solvent and then drying (solvent removal) to form the photochromic adhesive layer. When a photochromic adhesive sheet comprising a specific polyurethane resin having a functional group in the molecule and having a compound dispersed therein is separately prepared and a photochromic laminated sheet is produced using the “photochromic adhesive sheet” Has found that the adverse effects of the solvent can be avoided and the photochromic properties are not lowered, and the present invention has been completed.

  That is, this invention is shown by following [1]-[10].

[1] in the (A) molecule, a polyurethane resin, and (B) a photochromic composition comprising a photochromic compound having a piperidine structure,
The component (A) is
(A1) a polydiol compound having a molecular weight of 400 to 3000 having two hydroxyl groups in the molecule;
(A2) a diisocyanate compound having two isocyanate groups in the molecule;
(A3) a chain extender having a molecular weight of 50 to 300 having a functional group capable of reacting with two isocyanate groups in the molecule;
(A4) having one or two groups capable of reacting with isocyanate groups in the molecule, and, in the molecule, and functionalizing compound having a piperidine structure,
A photochromic composition which is a polyurethane resin obtained by reacting Especially, it is preferable that the said (A4) functionality provision compound is a compound which has a piperidine structure.

[2] The amount ratio of the component (A1), the component (A2), the component (A3), and the component (A4) used when obtaining the polyurethane resin (A) is the hydroxyl group contained in the component (A1). The total number of moles is n1, the total number of isocyanate groups contained in the component (A2) is n2, the total number of functional groups capable of reacting with isocyanate groups in the component (A3) is n3, and the component When the total number of moles of functional groups capable of reacting with isocyanate groups contained in (A4) is n4,
n1: n2: n3: n4 = 0.30-0.89: 1.00: 0.10-0.69: 0.01-0.20 The photochromic composition as described in [1] which is a quantitative ratio used. .

  [3] The photochromic composition according to claim 1, wherein the (A1) polydiol compound is at least one polydiol compound selected from polyether diol, polycarbonate diol, polycaprolactone diol, and polyester diol.

  [4] The photochromic composition according to [1], wherein 30% by mass or more of the (A2) diisocyanate compound is an aliphatic diisocyanate compound.

  [5] The photochromic according to [1], wherein the (A3) chain extender is at least one chain extender selected from a diamine compound, an amino alcohol compound, an aminocarboxylic acid compound, an aminothiol compound, and a diol compound. Composition.

  [6] The photochromic composition according to [1], 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 resin.

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

  [8] An optical article comprising 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 according to [1].

  [9] The optical article according to [8], 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.

[10] A method for producing the optical article according to [9],
(I) The photochromic composition according to [7] above is spread on a smooth substrate and then dried to remove (C) the organic solvent, (A) the polyurethane resin, and (A) the polyurethane resin. A step of preparing a photochromic adhesive sheet comprising (B) a photochromic compound dispersed therein, and (II) interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other. Creating the laminated structure by bonding the two optical sheets or optical films;
A method comprising the steps of:

  The photochromic composition of the present invention functions as an adhesive or a binder, and is obtained when a laminated body (photochromic laminated sheet) is manufactured by bonding an optical sheet or film made of polycarbonate resin or the like with an adhesive layer made of the composition. The resulting laminate exhibits 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 resin having a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule (hereinafter also simply referred to as component A), and (B) a photochromic. It is characterized by comprising a compound (hereinafter also simply referred to as component B). Hereinafter, the A component and the B component will be described.

Component A: Polyurethane resin having piperidine structure, hindered phenol structure, triazine structure, or benzotriazole structure The polyurethane resin used in conventional photochromic adhesives or binders is a hindered amine light stabilizer, antioxidant, UV absorption An agent or the like is added to improve the durability of the photochromic compound and the polyurethane resin. On the other hand, the A component of the photochromic composition of the present invention is a polyurethane resin having in its molecule a structure that imparts functionality such as hindered amine light stability, antioxidant performance, or ultraviolet absorption performance. And the photochromic composition containing the polyurethane resin obtained from a specific monomer component described in detail below exhibits excellent heat resistance, durability, and photochromic properties, and has an adhesive property with an optical sheet such as polycarbonate. Can be improved.

The polyurethane resin used as the component A is a resin having a structure that imparts a function in a molecule such as a side chain, a skeleton, or a terminal of the molecule. In order for the resulting photochromic composition to exhibit excellent heat resistance, adhesion, and photochromic properties,
(A1) a polydiol compound having a molecular weight of 400 to 3000 having two hydroxyl groups in the molecule (hereinafter also simply referred to as A1 component),
(A2) a diisocyanate compound having two isocyanate groups in the molecule (hereinafter also simply referred to as A2 component),
(A3) a chain extender having a molecular weight of 50 to 300 having a functional group capable of reacting with two isocyanate groups in the molecule (hereinafter also simply referred to as A3 component),
(A4) Functionality-imparting compound having a group capable of reacting with one or two isocyanate groups in the molecule and having a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule ( Hereinafter, it is necessary to use a polyurethane resin obtained by simply reacting with A4 component or a function-imparting compound.

  In particular, by using the A4 component, it is possible to introduce a structure having a function of improving durability in the molecule of the polyurethane resin. Hereinafter, these components will be described.

A1 Component: Polydiol Compound The polydiol compound of the A1 component has 2 hydroxyl groups in the molecule because the polyurethane resin does not become a highly cross-linked product as the A component and is soluble in an organic solvent.

  The average molecular weight of the A1 component is 400 to 3000, but the heat resistance of the A component obtained by using the A1 component and photochromic properties (color density, fading speed, weather resistance, etc.), particularly the viewpoint of the weather resistance of the photochromic compound Therefore, the average molecular weight is preferably 400 to 2500, and more preferably 400 to 1500.

  Further, as the A1 component, known polydiol compounds can be used without any limitation, but it is preferable to use polydiol compounds such as polyether diol, polycarbonate diol, polycaprolactone diol, and polyester diol, which are used alone. Or two or more types may be used in combination. Of these, polycarbonate diol and polycaprolactone diol are preferably used from the viewpoints of heat resistance, adhesion, weather resistance, hydrolysis resistance, and the like. Hereinafter, various compounds used as the A1 component will be described in detail.

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

  The “compound having two active hydrogen-containing groups in the molecule” includes water, ethylene glycol, propylene glycol, butanediol, etc., and these may be used alone or in combination of two or more. May be used. 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.

  Such polyether diol is available as a reagent 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 diol : The polycarbonate polyol used as the A1 component includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 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 A ethylene oxide or propylene oxide adduct, bis ( β-hydroxy (Ciethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and other low-molecular polyols such as polycarbonate polyols obtained by phosgenation, or transesterification with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyol obtained by the above can be mentioned.

  These polycarbonate diols 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.

  As A1 component of this invention, it is preferable to use polycarbonate diol from viewpoints, such as heat resistance, adhesiveness, a weather resistance, and hydrolysis resistance. In particular, when an optical sheet or film made of polycarbonate resin is joined to produce a laminate, the adhesive layer and the adherend layer have the same skeleton, and the adhesion is stabilized by improving the affinity. It is preferable to use an A1 component using polycarbonate diol.

Polycaprolactone diol : As the polycaprolactone diol used as the A1 component, a compound obtained by ring-opening polymerization of ε-caprolactone can be used.

  Such polycaprolactone diol is commercially available as a reagent or industrially, and examples of commercially available products include “Placcel (registered trademark)” series manufactured by Daicel Chemical Industries, Ltd.

Polyester diol : Examples of the polyester diol used as the A1 component include a polyester diol obtained by a condensation reaction between a “diol” and a “dibasic acid”. Here, as the “diol”, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexane Examples include diol, 3,3′-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, and the like. Alternatively, two or more types may be mixed and used. Examples of the “dibasic 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.

  These polyester diols are commercially available as reagents or industrially, and examples of commercially available ones include “Polylite (registered trademark)” series manufactured by DIC Corporation, and “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: diisocyanate compound The "diisocyanate compound having two isocyanate groups in the molecule" used as the A2 component in the present invention includes an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, and a mixture thereof. Is used. Among these, it is preferable to use an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound from the viewpoint of weather resistance. For the same reason, 30% by mass or more, particularly 50% by mass or more of the A2 component diisocyanate compound is preferably an aliphatic diisocyanate compound. The reason for using the diisocyanate compound as the A2 component is the result of considering the solubility in an organic solvent. When a polyisocyanate compound having three or more isocyanate groups in the molecule is mainly used, the resulting polyurethane resin has a high crosslink density, and the solubility in an organic solvent is lowered, which is not preferable.

If the diisocyanate compound which can be used conveniently as an A2 component is illustrated,
Aliphatic polyisocyanate compounds such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-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, norbornane diisocyanate, 4 , 4′-methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1, 4-diisocyanate, 1,9-diisocyanato-5-methylnonane, 1,1-bis (isocyanatomethyl) cyclohexane, 2-iso Cycloaliphatic polyisocyanate compounds such as anato-4-[(4-isocyanatocyclohexyl) methyl] -1-methylcyclohexane, 2- (3-isocyanatopropyl) cyclohexyl isocyanate, or phenylcyclohexylmethane diisocyanate, 4,4 ′ -Methylenebis (phenylisocyanate) isomer mixture, toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate 1,3-bis (isocyanatomethyl) benzene, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, 1,3-di Isocyanatomethylbenzene, 4,4′-diisocyanato-3,3′-dimethoxy (1,1′-biphenyl), 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 1,2-diisocyanatobenzene 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl) Aromatic polyisocyanate compounds such as methyl] 2-methylbenzene, 1-isocyanato-3-[(4-isocyanatophenyl) methyl) -2-methylbenzene, 4-[(2-isocyanatophenyl) oxy] phenyl isocyanate Can be mentioned.

  Among these, from the viewpoint of the weather resistance of the obtained polyurethane resin (the obtained photochromic composition), as described above, 30% by mass or more, particularly 50% by mass or more of the diisocyanate compound of component A2 is an aliphatic diisocyanate compound, and It is preferably at least one diisocyanate compound selected from alicyclic diisocyanate compounds. Specific examples of suitable compounds 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, norbornane diisocyanate, 4,4′-methylenebis (cyclohexyl) Isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenyle It is preferred to use 1,3-diisocyanate, hexa hydro-phenylene-1,4-diisocyanate.

  Further, the diisocyanate compound may be a compound having in its molecule a structure that imparts functionality such as light stability performance, antioxidant performance, or ultraviolet absorption performance. Hereinafter, the diisocyanate compound which has a piperidine structure which exhibits light stability performance is demonstrated to an example. The diisocyanate compound has a triisocyanate compound having three isocyanate groups in the molecule, a group (amino group, hydroxyl group, carboxyl group, or thiol group) that can react with one isocyanate group in the molecule, and a piperidine structure. The reaction product with a compound is mentioned. Examples of the triisocyanate compound include 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2-isocyanatoethyl (2,6-diisocyanate) hexanoate, 1- Methylbenzene-2,4,6-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, etc. Can be mentioned. In addition, examples of the compound having a piperidine structure and a group capable of reacting with one isocyanate group in the molecule include compounds represented by the following general formula (1), which are described in the functional compound having the piperidine structure below. By reacting one isocyanate group of the triisocyanate compound with, for example, a group capable of reacting with an isocyanate group of a compound represented by the following general formula (1), two isocyanate groups exist in the molecule. A compound (diisocyanate compound) can be obtained.

  Further, as the compound to be reacted with the triisocyanate compound, a compound having a group capable of reacting with one isocyanate group and a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule can be used. By using these compounds, a diisocyanate compound having antioxidant performance or ultraviolet absorption performance is obtained.

  In addition, A component which uses A4 component (functionality-imparting compound) described in detail below by using a diisocyanate compound having light stability performance, antioxidant performance, or ultraviolet absorption performance as described above as A2 component. (Polyurethane resin) can be synthesized. Therefore, when using the diisocyanate compound having light stability performance, antioxidant performance, ultraviolet absorption performance, etc. as the A2 component, when synthesizing the A component, the A4 component (functionality-imparting compound) described in detail below is used. It may or may not be used.

  These diisocyanate compounds may be used alone or in combination of two or more.

A3 component: chain extender The chain extender used as the A3 component in the present invention is a compound having a molecular weight of 50 to 300 having a functional group capable of reacting with two isocyanate groups in the molecule. The A3 component functions as a chain extender when synthesizing a polyurethane resin. By using the A3 component as a chain extender, the molecular weight, heat resistance, photochromic properties, etc. of the polyurethane resin of the present invention can be controlled. It becomes possible. When the molecular weight of the chain extender is less than 50, the resulting polyurethane resin tends to be too hard and the heat resistance is improved, but the adhesion and photochromic properties are lowered. On the other hand, when the molecular weight of the chain extender exceeds 300, the resulting polyurethane resin tends to be too soft, and all of heat resistance, adhesion, and photochromic properties are lowered. Therefore, the molecular weight of the chain extender is more preferably 50 to 250, and most preferably 55 to 200.

The A3 component of the present invention is preferably at least one chain extender selected from a diamine compound, an amino alcohol compound, an aminocarboxylic acid compound, an aminothiol compound, and a diol compound. Hereinafter, the diamine compound, amino alcohol compound, aminocarboxylic acid compound, and aminothiol compound may be collectively referred to as an amino group-containing compound. As an amino group-containing compound, at least one of the groups that react with two isocyanate groups in the molecule is an amino group (—NH ₂ group and —NH (R) group), and an isocyanate group other than an amino group. Is a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), or a carboxyl group [—C (═O) OH group].

  Examples of the compound suitably used as the amino group-containing compound of the A3 component include isophorone diamine, ethylene diamine, 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, norbornenediamine, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4 , 4'-diphenylmethanediamine, N, N'-diethyleth Njiamin, N, N'-dimethylethylenediamine, N, N'-di-propyl ethylene diamine, N, N'-di-butyl ethylenediamine, N- methylethylenediamine, mention may be made of N- ethyl ethylenediamine.

  Examples of amino alcohol compounds include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2 -Piperidine ethanol, 4-piperidine ethanol, etc. can be mentioned.

  Examples of aminocarboxylic acids include glycine, alanine, lysine, and leucine.

  Examples of aminothiol include 1-aminothiol and 2-aminoethanethiol.

  Examples of compounds suitably used as the diol compound of the A3 component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3 -Pentanediol, 2,5-hexanediol, 1,6-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexene Examples thereof include sandimethanol, 1,2-bis (hydroxyethyl) -cyclohexane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol and the like.

  The chain extenders such as the above amino group-containing compounds and diol compounds may be used alone or in combination of two or more.

  In the chain extender, an amino group-containing compound is preferably used from the viewpoints of heat resistance, adhesion, durability of the photochromic compound, and the like. The reason for this is that when a polyurethane resin as component A is synthesized, the resulting polyurethane resin has a urea bond by using an amino group-containing compound, resulting in an increase in molecular rigidity and an intermolecular chain. It is presumed that the heat resistance is improved because the hydrogen bond of this becomes stronger. In addition, regarding the improvement of the durability of the photochromic compound, the presence of the urea bond makes the hydrogen bond between the molecular chains more rigid, making it difficult for oxygen in the air to diffuse into the polyurethane resin. It is estimated that this is because photooxidation degradation, which is known as a general degradation mechanism, is suppressed. Furthermore, it is presumed that the adhesion 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.

A4 component: a functional compound having a group capable of reacting with one or two isocyanate groups in the molecule and having a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule The A4 component used in the present invention has a group capable of reacting with one or two isocyanate groups in the molecule, and has a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule. It is a compound which has this.

Examples of the group capable of reacting with the isocyanate group include an amino group (—NH ₂ group and —NH (R) group), a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), a carboxyl group [ -C (= O) OH group], or acid chloride group [-C (= O) OCl group]. In particular, in order to obtain a urethane resin exhibiting excellent effects, it is preferable that the number of groups capable of reacting with this isocyanate group is one in the molecule. The reason for this is not clear, but is considered as follows. By having one group, the functional compound is introduced into the side chain and terminal of the polyurethane resin. For this reason, it is considered that the functionality-imparting compound can efficiently act on a substance that lowers durability such as radicals.

  In addition, the aforementioned piperidine structure, hindered phenol structure, triazine structure, or benzotriazole structure has a light stabilizing effect (piperidine structure), an antioxidant effect (hindered phenol structure), or an ultraviolet absorption effect (triazine structure or benzoid structure). This is a site that exhibits a triazole structure. By using a compound having these structures, the durability (light stability, antioxidant performance, ultraviolet absorption performance) of the polyurethane resin itself as component A and the photochromic compound can be improved. Especially, in order to improve the durability of a photochromic compound, it is preferable to use the compound which has a piperidine structure. Hereinafter, various compounds used as the A4 component will be described in detail.

Functionality-imparting compound having a piperidine structure As the functionality-imparting compound having a piperidine structure used as the A4 component in the present invention, a compound having a structure represented by the following general formula (i) in the molecule can be preferably used.

(Where
R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. ). And the compound which has the group which can react with an isocyanate group in the nitrogen atom of the said piperidine ring or the 4-position carbon atom corresponds to the functional provision compound which has a piperidine structure.

  Hereinafter, more specific compounds will be described.

  Among the functional compounds used as the A4 component in the present invention, as the compound capable of introducing a piperidine structure at the end of the polyurethane resin, it is preferable to use a compound represented by the following general formula (1). Can be mentioned.

(Where
R ¹ , R ² , R ³ , and R ⁴ have the same meaning as in the general formula (i),
R ⁵ is a C 1-10 alkyl group or a hydrogen atom,
R ⁶ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms, a is 0 or 1,
X is a group capable of reacting with an isocyanate group. ).

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, but all four alkyl groups are preferably methyl groups.

R ⁵ is a C 1-10 alkyl group or a hydrogen atom. Especially, it is preferable that it is a C1-C4 alkyl group or a hydrogen atom from a viewpoint of availability. Since R ¹ to R ⁴ is an alkyl group having 1 to 4 carbon atoms, even R ⁵ is a hydrogen atom, a nitrogen atom and an isocyanate group R ⁵ is attached to the influence of steric hindrance to react There is nothing.

R ⁶ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. In addition, although a shows the number of R6, when a is 0, it points to what X has couple | bonded with the piperidine ring directly.

  X is a group capable of reacting with an isocyanate group, and is preferably an amino group, a hydroxyl group, a carboxyl group, or a thiol group. Among these, an amino group and a hydroxyl group are preferable from the viewpoints of reactivity with an isocyanate group and availability.

  Specific examples of the reaction terminator represented by the above formula (1) include 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, 1,2,2,6,6-pentamethyl-4- Aminopiperidine, 2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-aminopiperidine, 1,2,2,6,6-pentamethyl-4-amino Examples include methylpiperidine, 1,2,2,6,6-pentamethyl-4-aminobutylpiperidine, and the like.

  Moreover, as a compound which can introduce | transduce a piperidine structure into the terminal of a polyurethane resin, the following compound which is a reaction material of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol is also used. I can do it.

  In the above compound, n preferably satisfies the range of 5-20.

  Among the A4 components used in the present invention, compounds represented by the following general formulas (2), (3), and (4) are used as compounds that can introduce a piperidine structure into the main chain of the polyurethane resin. It is preferable to do.

  Following formula (2)

(Where
R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each an alkyl group having 1 to 4 carbon atoms,
R ¹¹ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms,
R ¹² is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms, b is 0 or 1,
Y is a group capable of reacting with an isocyanate group. The compound represented by) can also be suitably used.

In the general formula (2), R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each an alkyl group having 1 to 4 carbon atoms, but all four alkyl groups are preferably methyl groups.

R ¹¹ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms.

R ¹² is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. When b is 0, Y is directly bonded to the piperidine ring.

  Y is the same as X in the general formula (1).

  Examples of the function-imparting compound represented by the above formula (2) include the following compounds.

  Following formula (3)

(Where
R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms,
R ¹⁷ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms, c is 0 or 1,
R ¹⁸ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
Z is a group capable of reacting with an isocyanate group. The compound represented by) can also be suitably used.

In the general formula (3), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms, but all four alkyl groups are preferably methyl groups.

R ¹⁷ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. When c is 0, it means that Z is directly bonded to the piperidine ring.

R ¹⁸ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms.

  Z is the same as X in the general formula (1).

  Examples of the piperidine ring-containing compound represented by the general formula (3) include bis (2,2,6,6-tetramethyl-1-methoxy-4-piperidinyl) sebacate.

(Where
R ¹⁹ , R ²⁰ , R ²¹ , and R ²² are each an alkyl group having 1 to 4 carbon atoms,
R ²³ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms, R ²⁴ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
V and W are groups that can react with an isocyanate group, respectively. )
In the general formula (4), R ¹⁹ , R ²⁰ , R ²¹ , and R ²² are each independently an alkyl group having 1 to 4 carbon atoms, but all four alkyl groups are preferably methyl groups.

R ²³ is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, or a polymethylene group having 3 to 10 carbon atoms,
R ²⁴ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. Here, d is 0 or 1, and when d is 0, it means that V is directly bonded to the piperidine ring.

  V and W are the same as X in the general formula (1), and may be the same group or different groups.

  Examples of the piperidine ring-containing compound represented by the general formula (4) include 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.

Functionality-imparting compound having a hindered phenol structure As the functionality-imparting compound having a hindered phenol structure used as the A4 component in the present invention, a compound having a structure represented by the following general formula (ii) in the molecule is suitable. Can be used for

(Where
R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom,
At least one of R ²⁵ and R ²⁶ is an alkyl group having 4 or more carbon atoms. ). And the compound which has a group which can react with an isocyanate group in the 1st-position carbon atom of the said structure turns into a functional provision compound which has a hindered phenol structure. The hydroxyl group at the 4-position in the above formula (ii) is unlikely to react with an isocyanate group due to the steric hindrance because at least one of R ²⁵ and R ²⁶ is an alkyl group. Therefore, the hydroxyl group at the 4-position is not a group capable of reacting with an isocyanate group.

  The compound having the above-described structure in the molecule and having two groups capable of reacting with an isocyanate group is present in the main chain of the polyurethane resin of component A as described in the functional compound having the piperidine structure. A hindered phenol structure can be introduced. Moreover, when there is one group capable of reacting with an isocyanate group, a hindered phenol structure can be introduced into the side chain and terminal of the polyurethane resin.

  Among the function-imparting compounds having a hindered phenol structure, a preferable compound includes the following general formula (5).

(Where
R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom, and at least one of R ²⁵ and R ²⁶ has 4 or more carbon atoms. An alkyl group,
R ²⁹ is an alkylene group having 1 to 10 carbon atoms, or a polymethylene group having 3 to 10 carbon atoms, e is 0 or 1,
U is a group capable of reacting with an isocyanate group. ).

In the general formula (5), R ²⁵ and R ²⁶ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom, and either one is an alkyl group having 4 or more carbon atoms. Preferably, one of R ²⁵ and R ²⁶ is a tert-butyl group. When one group is an alkyl group having 4 or more carbon atoms, the durability of the resulting photochromic composition can be further improved.

R < ²⁷ > and R < ²⁸ > are a C1-C18 alkyl group or a hydrogen atom, More preferably, a C1-C10 alkyl group or a hydrogen atom.

  U is a group capable of reacting with an isocyanate group, and is an amino group, a hydroxyl group, a thiol group, a carboxyl group, or an acid chloride group, and particularly preferably an amino group, a hydroxyl group, a thiol group, or a carboxyl group. .

R ²⁹ is an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms or a polymethylene group having 3 to 5 carbon atoms. E represents the number of R29, and is 0 or 1. When e is 0, it means that U is directly bonded to the benzene ring. A compound in which e is 0 is preferable.

  Specific examples of the functional compound having a hindered phenol structure include 3-methyl-4-hydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, and 3,5-dimethyl- 4-hydroxybenzoic acid, 3-t-butyl-4-hydroxybenzoic acid, 3-t-butyl-5-methyl-4-hydroxybenzoic acid, 3-t-butyl-6-methyl-4-hydroxybenzoic acid, 3-t-butyl-5-ethyl-4-hydroxybenzoic acid, 3-t-butyl-6-ethyl-4-hydroxybenzoic acid, 3-t-octyl-4-hydroxybenzoic acid, 3-t-octyl- 5-methyl-4-hydroxybenzoic acid, 3-t-octyl-5-ethyl-4-hydroxybenzoic acid, 3-t-octyl-6-methyl-4-hydroxybenzoic acid, 2- (3-methyl- -Hydroxyphenyl) acetic acid, 2- (3,5-dimethyl-4-hydroxyphenyl) acetic acid, 2- (3,5-di-t-butyl-4-hydroxyphenyl) acetic acid, 2- (3-t-butyl) -4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-5-methyl-4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-6-methyl-4-hydroxyphenyl) acetic acid, 2- (3-t-butyl-5-ethyl-4-hydroxyphenyl) acetic acid, 2- (3-t-octyl-4-hydroxyphenyl) acetic acid, 2- (3-t-octyl-5-methyl-4-hydroxy) Phenyl) acetic acid, 2- (3-t-octyl-6-methyl-4-hydroxyphenyl) acetic acid, 3- (3-methyl-4-hydroxyphenyl) propionic acid, 3- (3,5-dimethyl-4-phenyl) Hydro Phenyl) propionic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, 3- (3-t-butyl-4-hydroxyphenyl) propionic acid, 3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-6-methyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-5-ethyl-4-) Hydroxyphenyl) propionic acid, 3- (3-t-butyl-6-ethyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-4-hydroxyphenyl) propionic acid, 3- (3-t -Octyl-5-methyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-6-methyl-4-hydroxyphenyl) propionic acid, 3- (3,5-di- Dodecyl-4-hydroxyphenyl) propionic acid, 4- (3-methyl-4-hydroxyphenyl) butyric acid, 4- (3,5-dimethyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-4 -Hydroxyphenyl) butyric acid, 4- (3,5-di-t-butyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-5-methyl-4-hydroxyphenyl) butyric acid, 4- (3 -T-butyl-5-ethyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-6-methyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-6-ethyl-4) -Hydroxyphenyl) butyric acid, 4- (3-t-octyl-4-hydroxyphenyl) butyric acid, 4- (3-t-octyl-5-methyl-4-hydroxyphenyl) butyric acid, 4- (3-t-octyl) -6 Til-4-hydroxyphenyl) butyric acid, 3,5-dimethyl-4-hydroxyphenylamine, 3,5-diisopropyl-4-hydroxyphenylamine, 3,5-di-t-butyl-4-hydroxyphenylamine, etc. Can be mentioned.

  Among these, more preferable compounds include 3,5-di-t-butyl-4-hydroxybenzoic acid, 3-t-butyl-4-hydroxybenzoic acid, and 3-t-butyl-5-methyl-4-hydroxybenzoic acid. 3-t-butyl-6-methyl-4-hydroxybenzoic acid, 3-t-butyl-5-ethyl-4-hydroxybenzoic acid, 3-t-butyl-6-ethyl-4-hydroxybenzoic acid, 2 -(3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-5-methyl-4-) Hydroxyphenyl) acetic acid, 2- (3-tert-butyl-6-methyl-4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-5-ethyl-4-hydroxyphenyl) acetic acid, 3- (3 5-di-t-butyl- -Hydroxyphenyl) propionic acid, 3- (3-t-butyl-4-hydroxyphenyl) propionic acid, 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionic acid, 3- (3- t-butyl-6-methyl-4-hydroxyphenyl) propionic acid, 3- (3-t-butyl-5-ethyl-4-hydroxyphenyl) propionic acid, 3- (3-t-butyl-6-ethyl- 4-hydroxyphenyl) propionic acid, 4- (3-t-butyl-4-hydroxyphenyl) butyric acid, 4- (3,5-di-t-butyl-4-hydroxyphenyl) butyric acid, 4- (3-t -Butyl-5-methyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-5-ethyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-6-methyl-4-hydroxy) Rokishifeniru) butyric acid, 4- (3-t- butyl-6-ethyl-4-hydroxyphenyl) butyric acid, may be mentioned 3,5-di -t- butyl-4-hydroxyphenyl amine.

Functionality-imparting compound having a triazine structure or a benzotriazole structure The functionality-imparting compound having a triazine structure or a benzotriazole structure used as the A4 component in the present invention is represented by the following general formulas (iii) and (iv). A compound having such a structure in the molecule can be preferably used.

  The compound having the above-described structure in the molecule and having two groups capable of reacting with an isocyanate group is present in the main chain of the polyurethane resin of component A as described in the functional compound having the piperidine structure. A triazine structure or a benzotriazole structure can be introduced. When there is one group that can react with an isocyanate group, a triazine structure or a benzotriazole structure can be introduced into the side chain or terminal of the polyurethane resin.

  Among the functional compounds having a triazine structure or a benzotriazole structure, preferred compounds include the following general formulas (6) and (7). First, a compound having a triazine structure will be described.

  The following general formula (6)

(Where
R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group, a hydrogen atom, an amino group, a hydroxyl group, a carboxyl group, or a thiol. Group,
The alkyl group and the alkyloxy group may have a substituent selected from an amino group, a hydroxyl group, a carboxyl group, and a thiol group,
However, one or two groups among R ^{30 to} R ³⁵ are groups capable of reacting with an isocyanate group. ) Can be preferably used.

In the general formula (6), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are each independently an alkyl group having 1 to 10 carbon atoms or an alkyloxy group having 1 to 10 carbon atoms. is there. More preferably, it is a C1-C5 alkyl group or a C1-C5 alkyloxy group. These groups may have a group capable of reacting with an isocyanate group, preferably an amino group, a hydroxyl group, a carboxyl group, or a thiol group as a substituent.

Further, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ in the general formula (6) may be a hydrogen atom or a group capable of undergoing an isocyanate reaction, preferably a hydrogen atom, An amino group, a hydroxyl group, a carboxyl group, or a thiol group.

However, one or two groups out of R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ can react with an isocyanate group, preferably an amino group, a hydroxyl group, or a carboxyl group Or a thiol group.

Among them, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁵ are methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, hydroxymethyl group, 2- Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxyethyloxy group, 3-hydroxypropyloxy group, 2-hydroxypropyloxy group, hydrogen It is preferably an atom or a hydroxyl group. One or two of them are a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, or a 2-hydroxyethyl group. It is preferably an oxy group, a 3-hydroxypropyloxy group, a 2-hydroxypropyloxy group, or a hydroxyl group.

  Specific examples of the compound include 2- (2,4-dihydroxyphenyl) -4,6-diphenyl-s-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4- Dimethylphenyl) -s-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2-methoxyphenyl) -s-triazine, 2- (2,4-dihydroxyphenyl) -4, 6- Bis (4-methoxyphenyl) -s-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethoxyphenyl) -s-triazine, 2- (2-hydroxy-4- Hydroxymethylphenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4-hydroxymethylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine 2- (2-hydroxy-4- (2-hydroxyethyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxyethyl) phenyl) -4,6- Bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxyethyloxy) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4 -(2-hydroxyethyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxypropyl) phenyl) -4,6 -Diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxypropyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- ( -Hydroxy-4- (3-hydroxypropyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (3-hydroxypropyl) phenyl) -4,6-bis (2,4 -Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxypropyloxy) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxy) Propyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (4-hydroxybutyl) phenyl) -4,6-diphenyl-s- Triazine, 2- (2hydroxy-4- (4-hydroxybutyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy Droxy-4- (3-hydroxybutyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (3-hydroxybutyl) phenyl) -4,6-bis (2,4- Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (4-hydroxybutyloxy) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (4-hydroxybutyl) Oxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2-phenyl-4,6-bis (4-hydroxyphenyl) -s-triazine, 2- (2,4- Dimethoxyphenyl) -4,6-bis (2-hydroxyphenyl) -s-triazine, 2- (2,4-dimethylphenyl) -4,6-bis (2-hydroxy-4-dimethylphenol) ) -S-triazine, 2-phenyl-4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- (2-methoxy-4-ethylphenyl) -4,6-bis ( 2-hydroxy-4-methylphenyl) -s-triazine, 2- (2-ethoxy-4-methylphenyl) -4,6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- ( 2-methyl-4propylphenyl) -4,6-bis (2- (4-hydroxybutyloxy) -4-methylphenyl) -s-triazine, 2- (2-methoxy-4-propylphenyl) -4, 6-bis (2-hydroxy-4-methylphenyl) -s-triazine, 2- (2-ethoxy-4-propylphenyl) -4,6-bis (2-hydroxypropyloxy-4-dimethylphenol) Le) -s-triazine, and the like.

  Next, a preferred functional compound having a benzotriazole structure will be described. A preferable compound includes a compound represented by the following general formula (7).

(Where
R ³⁶ and R ³⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a hydrogen atom, or an aryl group,
The alkyl group and the alkyloxy group may have a group capable of reacting with an isocyanate group, provided that only one group can react with the isocyanate group,
The aryl group may have an alkyl group having 1 to 5 carbon atoms as a substituent,
^R38 is a hydrogen atom or a halogen atom. )
In the said General formula (7), ^R36 and ^R37 are respectively independently a C1-C10 alkyl group or a C1-C10 alkyloxy group. These groups may have a group capable of reacting with an isocyanate group, specifically an amino group, a hydroxyl group, a carboxyl group, an acid chloride group, or a thiol group. However, there is only one group that can react with the isocyanate group.

R ³⁶ and R ³⁷ are each an aryl group having an alkyl group having 1 to 5 carbon atoms as a substituent, preferably a phenyl group having an alkyl group having 1 to 5 carbon atoms as a substituent, or a hydrogen atom. May be.

Examples of suitable R ³⁶ and R ³⁷ are methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, hexyl group, 1,1,3,3-tetramethylbutyl group. , Phenyl group, benzyl group, 1,1-dimethylbenzyl group, carboxyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, amino group, aminomethyl group, aminoethyl group, aminopropyl group, and carboxyl group, carboxy group Examples thereof include an acid chloride group corresponding to a methyl group, a carboxyethyl group, and a carboxypropyl group.

  Specific examples of the compound include 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -4′-hydroxyphenyl] propionic acid, 3- [3 ′-(2 ″ H— Benzotriazol-2 ″ -yl) -5′-methyl-4′-hydroxyphenyl] propionic acid, 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -5′-ethyl -4′-hydroxyphenyl] propionic acid, 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -5′-t-butyl-4′-hydroxyphenyl] propionic acid, 3- [3 ′-(5 ″ -Chloro-2 ″ H-benzotriazol-2 ″ -yl) -5′-t-butyl-4′-hydroxyphenyl] propionic acid, 3- [3 ′-(2 '' H-benzotriazol-2 ''-yl) -4 ' -Hydroxy-5 "-(1 ', 1'-dimethylbenzyl) phenyl] propionic acid, 3- [3'-(2" H-benzotriazol-2 "-yl) -4" -hydroxy- 5 "-(1", 1 ", 3", 3 "-tetramethylbutyl) phenyl" propionic acid and their acid chloride compounds, 2- (5-methyl-2-hydroxyphenyl) benzo Triazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′-t-octylphenyl] benzotriazole, 2 -[2'-hydroxy-5 '-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(hydroxyethyl) phenyl] -2H-benzoto Riazole, 2- [2′-hydroxy-5 ′-(hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-methyl-5 ′-(hydroxymethyl) phenyl] -2H— Benzotriazole, 2- [2′-hydroxy-3′-methyl-5 ′-(hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-methyl-5 ′-(hydroxypropyl) ) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′- t-butyl-5 '-(hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5 -(Hydroxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-octyl-5 '-(hydroxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy -3'-t-octyl-5 '-(hydroxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-octyl-5'-(hydroxypropyl) phenyl] -2H- And benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(hydroxyethyl) phenyl] -5-chloro-2H-benzotriazole, and the like.

  The A4 component can be introduced into any of the terminal, main chain, side chain and the like of the obtained polyurethane resin for the purpose of improving the weather resistance of the polyurethane resin and the photochromic compound. From the viewpoint of not impairing heat resistance and mechanical strength (peel strength), it is preferably introduced at the end of the polyurethane resin.

  Next, a method for synthesizing the component A using the components A1 to A4 will be described.

Method for synthesizing component A When the component A1, component A2, component A3 and component A4 are reacted to obtain component A, a so-called one-shot method or prepolymer method can be employed. The component A can be suitably obtained.

Synthesis method 1 (A component having a functional structure at the end)
The urethane prepolymer is obtained by reacting the A1 component and the A2 component, and then the urethane prepolymer and the A3 component are reacted. The A component of the present invention can be produced by reacting the terminal isocyanate group remaining in the obtained urethane polymer with the A4 component having a group capable of reacting with one isocyanate group in the molecule.

  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 the isocyanate group in the diisocyanate compound which is the A2 component 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, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

  Furthermore, the reaction between the urethane polymer obtained and the A4 component was conducted 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 24 hours. You can do it. As the solvent, methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

Synthesis method 2 (A component having a functional structure in the main chain)
A urethane prepolymer having a functional structure is obtained by reacting the A1 component and the A2 component to obtain a urethane prepolymer, and further mixing and reacting an A4 component having a group capable of reacting with two isocyanate groups in the molecule. Next, the A component of the present invention can be produced by reacting the urethane prepolymer with the A3 component.

  In the above method, the reaction between the A1 component and the A2 component, and further the reaction with the A4 component is carried out at 25 to 120 ° C. in an inert gas atmosphere such as nitrogen or argon in the presence or absence of a solvent. What is necessary is just to make it react for 5 to 24 hours. As the solvent, organic solvents such as methyl ethyl ketone, diethyl 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, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

Synthesis method 3 (A component having a functional structure in the side chain)
First, an A4 component having a group capable of reacting with one isocyanate group in the molecule is reacted with a triisocyanate compound having three isocyanate groups to synthesize a diisocyanate compound having a functional structure in the side chain. The A component of the present invention can be produced by reacting the diisocyanate compound with the A1 component and the A2 component to obtain a urethane prepolymer and then reacting with the A3 component.

  In the above method, the reaction between the triisocyanate compound and the A4 component is performed 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 24 hours. You can do it. As the solvent, organic solvents such as methyl ethyl ketone, diethyl 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.

  The reaction with the diisocyanate compound having a functional structure in the side chain obtained by the above method, the A1 component, and the A2 component is carried out in an inert gas atmosphere such as nitrogen or argon in the presence or absence of a solvent. The reaction may be performed at 25 to 120 ° C. for 0.5 to 24 hours. As the solvent, organic solvents such as methyl ethyl ketone, diethyl 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 100 mass parts in total 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, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

The mixing ratio of each component, the characteristics of the A component The amount ratio of the A1, A2, A3, and A4 components used for the reaction in the above method may be determined as appropriate, but the heat resistance and adhesive strength of the resulting polyurethane resin From the viewpoint of balance such as photochromic characteristics (color density, fading speed, weather resistance, etc.), the following quantitative ratio is preferable. That is, the total number of moles 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 The total number of moles of “functional group capable of reacting with isocyanate group” (specifically, amino group, hydroxyl group, mercapto group and / or carboxyl group) contained in is n3, and “reacts with isocyanate group contained in A4 component” N1: n2: n3: n4 = 0.30-0.89, where n4 is the total number of moles of “functional group” (specifically, amino group, hydroxyl group, mercapto group and / or carboxyl group). 1.00: 0.1-0.69: 0.01-0.20, especially n1: n2: n3: n4 = 0.35-0.84: 1.00: 0.15-0 .64: 0.01-0.18 It is preferable that the quantity ratio is n1: n2: n3: n4 = 0.40 to 0.79: 1.00: 0.20 to 0.59: 0.01 to 0.15. Most preferred.

  The polyurethane resin obtained by such a reaction may be used while dissolved in the reaction solvent, but if necessary, the solvent is distilled off or the reaction solution is dropped into a poor solvent such as water. Then, the polyurethane resin may be used as the component A after being subjected to a post-treatment such as precipitation, filtration, and drying.

  The component A polyurethane resin has a molecular weight of 10,000 to 1,000,000, particularly 30,000 to 30,000, from the viewpoint of heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.) of the obtained polyurethane resin. 900,000 is preferable, and 50,000 to 800,000 is most preferable. The molecular weight of the polyurethane resin was determined by using gel permeation chromatography (GPC) in terms of polystyrene, columns: Shodex KD-805, KD-804 (manufactured by Showa Denko KK), eluent: LiBr ( 10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, polyurethane resin sample solution: number average molecular weight measured under the conditions of 0.5% dimethylformamide (DMF) solution.

  Moreover, if the molecular weight (number average molecular weight) of the polyurethane resin measured on the same conditions as the above is converted into polyethylene oxide, the molecular weight is preferably 5,000 to 150,000, and more preferably 8,000 to 100,000. It is preferable that it is 10,000 to 60,000 especially.

The polyurethane resin as component A is a workability when an optical sheet or film is pasted using the photochromic composition of the present invention to form a laminate, or when an optical article using the obtained laminate is produced. In addition, in the case of forming a hard coat layer on the surface of the laminate or optical article, from the viewpoint of workability when a hard coat solution is applied or cured, 60 to 200 ° C., particularly 80 It preferably has a heat resistance of ˜150 ° C. 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.

  Next, the photochromic compound that is the B component will be described.

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, the polyurethane resin (component A) and the photochromic compound (component B), and other components added as necessary, are mixed. It becomes easy 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 [10] 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 and ethylene glycol dimethyl ether; diacetone alcohol; methyl ethyl ketone, diethyl ketone, etc. Ketones; toluene; hexane; heptane: ethyl acetate, 2-methoxyethyl, acetate such as 2-ethoxyethyl acetate; DMF; DMSO; 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 film. 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.

  In addition, 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 the above [10] is adopted, the 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 surfactants 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 resin (component A).

  Antioxidants, radical scavengers, UV stabilizers, and UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, and phosphorus antioxidants. , Triazine compounds, benzotriazole compounds, benzophenone compounds, and the like can be suitably 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. The addition amount of these antioxidants, radical scavengers, ultraviolet stabilizers and ultraviolet absorbers is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the polyurethane resin (component A). However, if these additives are used excessively, the adhesiveness of the photochromic composition to an optical sheet or film made of polycarbonate resin is lowered, so the addition amount is preferably 7 parts by mass or less, more preferably 3 masses. Part or less, most preferably 1 part by weight or less.

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. The order in which the components are mixed is not particularly limited, and the photochromic composition may be mixed so that the components satisfy the preferable range.

  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. And an optical sheet or an optical film is bonded to each other through an adhesive layer made of the photochromic composition of the present invention, whereby the optical article of the present invention shown as [8] can be obtained. 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. In addition, after immersing the laminate (which may be a composite laminate) in a polymerizable monomer capable of forming an optical substrate, the polymerizable monomer is cured to thereby form the laminate in the optical substrate. It can also be embedded and integrated. Therefore, the optical article may be one obtained by laminating the above laminate (may be a composite laminate) on a plastic optical substrate made of a thermoplastic resin or a thermosetting resin, The above-mentioned laminated body (may be a composite laminated body) may be embedded in a plastic optical substrate. 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 (for example, a polarizing film made of polyvinyl alcohol sandwiched by a triacetyl cellulose resin film) 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. When such a method is adopted, a laminated body can be continuously produced using an apparatus as described in Patent Document 3.

  Moreover, when using the photochromic composition of this invention containing a solvent, (C) Solvent is removed by drying after extending the photochromic composition of this invention on a smooth base material, A photochromic adhesive sheet comprising an A component and a B component dispersed in the A component is prepared, and then (2) 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.

  As the material of the smooth base material, those which are resistant to the solvent used in the present invention and those in which the polyurethane resin of the present invention is easy to peel off are preferable. For example, glass, stainless steel, Teflon (registered) Trademark), polyethylene terephthalate, polypropylene, and a plastic film on which a coating layer for improving the peelability of silicon or fluorine is laminated. The photochromic adhesive sheet can be obtained by peeling off the substrate.

  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.

  The obtained photochromic adhesive sheet is interposed between two optical sheets or optical films facing each other. And both are joined. The laminated sheet obtained in the step of joining the optical sheet or the optical film can be used as it is, but the state can be stabilized and used by the following method. Specifically, it is preferable to leave the laminated body just joined at a temperature of 20 ° C. or higher and 60 ° C. or lower for 4 hours or longer. The upper limit of the standing time is not particularly limited, but 50 hours is sufficient. In addition, when standing, it can be left at normal pressure or left under vacuum. Furthermore, it is preferable to leave this standing laminate at a temperature of 80 ° C. to 130 ° C. for 30 minutes to 3 hours (hereinafter referred to as heat treatment). The laminate obtained by this heat treatment has a very stable state.

  When the photochromic composition of the present invention containing no organic solvent is used, a photochromic adhesive sheet can be produced by coextrusion molding or the like. Even when the adhesive sheet obtained by such a method is used, after bonding the optical sheet, in order to stabilize the state, a time for standing still in the same manner as described above is provided and heat treatment is performed. Is preferred.

  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: Polydiol compound PL1: Exenol (polypropylene glycol, average molecular weight 400) manufactured by Asahi Glass Co., Ltd.
PL2: Exenol (polypropylene glycol, average molecular weight 1000) manufactured by Asahi Glass Co., Ltd.
PL3: Exenol (polypropylene glycol, average molecular weight 2000) manufactured by Asahi Glass Co., Ltd.
PL4: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, average molecular weight 500).
PL5: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, average molecular weight 800).
PL6: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, average molecular weight 1000).
PL7: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, average molecular weight 3000).
PL8: Plaxel (polycaprolactone diol, average molecular weight 500) manufactured by Daicel Chemical Industries, Ltd.
PL9: Polylite manufactured by DIC Corporation (polyester diol composed of adipic acid and 1,4-butanediol, average molecular weight 1000).
PL10: ETERNACOLL manufactured by Ube Industries, Ltd. (polycarbonate diol using 1,4-cyclohexanedimethanol as a raw material, average molecular weight 1000).
PL11: Exenol manufactured by Asahi Glass Co., Ltd. (polypropylene glycol, average molecular weight 4000), molecular weight exceeds 3000, and does not correspond to the A1 component of the present invention.

A2 component; diisocyanate compound NCO1: isophorone diisocyanate.
NCO2: hydrogenated diphenylmethane diisocyanate.
NCO3: Hexamethylene-1,6-diisocyanate.
NCO4: Toluene-2,4-diisocyanate.
NCO5: norbornane diisocyanate.
NCO6: 1,3,6-hexamethylene triisocyanate. Since it has three isocyanate groups, it does not correspond to the A2 component of the present invention.
NCO7: reaction product of 1-methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and 1-methylbenzene-2,4,6-triisocyanate.
NCO8: reaction product of 1-methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and 1,6,11-undecane triisocyanate.

A3 component; chain extender CE1: isophoronediamine.
CE2: ethylenediamine.
CE3: 1,6-diaminohexane.
CE4: 2-aminoethanol.
CE5: 6-aminohexanol.
CE6: 1,4-butanediol.
CE7; 2-aminoethanethiol.
CE8: Piperazine.
CE9: N, N′-diethylethylenediamine.
CE10: 1,10-decanediol.

A4 component; Functionality-imparting compound HA1; 1,2,2,6,6-pentamethyl-4-hydroxypiperidine.
HA2; 1,2,2,6,6-pentamethyl-4-aminopiperidine.
HA3; a compound represented by the following formula (Cinu Specialty Chemicals Co., Ltd. Tinuvin 622LD, average molecular weight 3100 to 4000).

HA4; 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.
HA6; 3-t-butyl-5-methyl-4-hydroxybenzoic acid.
HA7; 3- [3 ′-(2 ″ H-benzotriazol-2 ″ -yl) -4′-hydroxyphenyl] propionic acid.

Component B: photochromic compound PC1: a 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.
C7: Diethyl ketone.

Other components Irganox 245: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], manufactured by Ciba Specialty Chemicals
Synthesis of polyurethane resin (U1) A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 90 g of polyether diol having an average molecular weight of 400, 100 g of isophorone diisocyanate, and 800 ml of DMF at 120 ° C. in a nitrogen atmosphere. The mixture was allowed to react for 5 hours, then cooled to 25 ° C., 34 g of isophoronediamine as a chain extender was added dropwise, reacted at 25 ° C. for 1 hour, and then 1,2,2,6,6-pentamethyl-4-hydroxy 8 g of piperidine was added and reacted at 120 ° C. for 5 hours. The solvent was distilled off under reduced pressure to obtain a polyurethane resin (U1) having a piperidine ring at the end of the urethane resin. The number average molecular weight of the obtained polyurethane resin was 150,000 in terms of polystyrene, 10,000 (theoretical value; 10,000) in terms of polyoxyethylene, and the heat resistance was 120 ° C. The theoretical value of the number average molecular weight here refers to the molecular weight when the A1 component, A2 component, A3 component, and A4 component used as raw materials are theoretically linearly purified without cross-linking the polyurethane resin. It is. Table 1 shows the reaction conditions.

Synthesis of polyurethane resins (U2) to (U30) and (U33) to (U45) Polydiol compound (A1 component), diisocyanate compound (A2 component), chain extender (A3 component) shown in Table 1, Table 2, and Table 3 ), A functional compound (A4 component), and a reaction solvent, and using the reaction conditions shown in Table 1, Table 2, and Table 3, U2-U30, And U33 to U45 were synthesized.

Synthesis of polyurethane resin (U31) A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 180 g of polycarbonate diol having an average molecular weight of 800, 100 g of isophorone diisocyanate, and 1200 ml of DMF, and 5 ° C. at 100 ° C. in a nitrogen atmosphere. Reacted for hours. Next, 4.5 g of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol was added to the reaction solution, and the mixture was further reacted at 100 ° C. for 5 hours under a nitrogen atmosphere. Then, it is cooled to 25 ° C., 30.4 g of isophorone diamine, which is a chain extender, is dropped, reacted at 25 ° C. for 1 hour, the solvent is distilled off under reduced pressure, and a polyurethane resin having a piperidine ring in the main chain of the urethane resin. (U31) was obtained. The number average molecular weight of the obtained polyurethane resin was 270,000 in terms of polystyrene, 9000 (theoretical value; 7,000) in terms of polyoxyethylene, and the heat resistance was 130 ° C. Table 3 shows the reaction conditions.

Synthesis of polyurethane resin (U32) a) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 6.5 g of 1,6,11-undecane triisocyanate, 1,2,2,6,6 -8 g of pentamethyl-4-hydroxypiperidine was added and reacted at 120 ° C for 5 hours. In this way, a diisocyanate compound in which 1,2,2,6,6-pentamethyl-4-hydroxypiperidine and 1,6,11-undecane triisocyanate were reacted was obtained.

  b) A three-necked flask having a stirring blade, a cooling pipe, a thermometer, and a nitrogen gas introduction pipe was charged with 180 g of polycarbonate diol having an average molecular weight of 800, 100 g of isophorone diisocyanate, a), and 1200 ml of DMF, and a nitrogen atmosphere. The reaction was carried out at 80 ° C. for 5 hours.

  c) Next, 30.7 g of isophoronediamine, which is a chain extender, is dropped into the reaction product obtained from b), and the mixture is reacted at 25 ° C. for 1 hour. The solvent is distilled off under reduced pressure, and the side chain has a piperidine ring. A polyurethane resin (U32) was obtained. The number average molecular weight of the obtained polyurethane resin was 320,000 in terms of polystyrene, 9000 (theoretical value; 7,000) in terms of polyoxyethylene, and the heat resistance was 150 ° C.

  Table 3 shows the reaction conditions.

  Table 4 summarizes the blending ratio, number average molecular weight, and heat resistance results of the A1, A2, A3, and A4 components of the polyurethane resins U1 to U45.

Example 1
Preparation of photochromic composition 20 g of isopropyl alcohol as an organic solvent is added to 5 g of polyurethane-urea resin (U1) and 0.25 g of photochromic compound (PC1), and the mixture is stirred at 80 ° C. and dissolved by ultrasonic waves. Got.

Preparation of Photochromic Laminate After the obtained photochromic composition was applied on a glass plate and dried at 80 ° C. for 1 hour, the glass plate was separated to obtain a photochromic sheet having a thickness of 30 μm. Subsequently, the obtained photochromic sheet was sandwiched between two 400 μm-thick polycarbonate sheets, allowed to stand at 40 ° C. for 12 hours, and further heated at 100 ° C. for 30 minutes to obtain a laminate having the desired photochromic properties. Obtained.

  When the obtained photochromic laminate was evaluated, the color density as the photochromic property was 1.0, the fading speed was 90 seconds, and the durability was 95%. The peel strength of the photochromic laminate was 60 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 (%) = [(A48 / A0) × 100]: The following deterioration acceleration test was conducted to evaluate the durability of color development by light irradiation. 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.

  The above evaluation results are shown in Table 5.

Examples 2-41
Except having used the polyurethane resin and organic solvent which are shown in Table 5, Table 6, adjustment of the photochromic composition and preparation of the photochromic laminated body were implemented by the method similar to Example 1. FIG. Tables 5 and 6 show the evaluation results of the obtained various photochromic laminates.

Comparative Examples 1-6
Except having used the polyurethane resin shown in Table 7, and the organic solvent, adjustment of the photochromic composition and preparation of the photochromic laminated body were implemented by the method similar to Example 1. FIG. Table 7 shows the evaluation results of the obtained various photochromic laminates.

  As apparent from Examples 1-41 above, according to the present invention, a polydiol compound (A1 component), a diisocyanate compound (A2 component), a chain extender (A3 component), and a piperidine structure, a hindered phenol structure in the molecule , A synthesized polyurethane resin using a functional compound (A4 component) having a triazine structure or a benzotriazole structure in a suitable ratio has excellent photochromic properties, peel strength (adhesion), and heat resistance. I understand that.

  On the other hand, when a hindered amine light stabilizer (compound having a piperidine ring) is added to a polyurethane resin having no piperidine ring in the molecule as in Comparative Example 1, the peel strength is reduced. However, all physical properties could not be satisfied at the same time. In Comparative Example 2, the weather resistance and heat resistance were reduced by using a polydiol compound having a molecular weight of 4000 for the polyurethane resin. In Comparative Example 3, using a polydiol compound having a molecular weight of 400 as the chain extender (A3 component) lowered the weather resistance, heat resistance, and peel strength. Further, Comparative Example 4 (polyurethane resin; U41) using a triisocyanate compound could not be evaluated because it could not be dissolved in an organic solvent. Further, when a diol compound having a molecular weight of 400 or less was used as the A1 component as in Comparative Example 5, the softening point was too high, and the photochromic properties such as the color density and the fading speed were lowered, and the peel strength was also significantly lowered. When the urethane resin was synthesized without using the A3 component that is a chain extender as in Comparative Example 6, the softening point was too low and durability (photochromic characteristics) and peel strength were lowered.

Claims (10)

(A) in the molecule, a polyurethane resin, and (B) a photochromic composition comprising a photochromic compound having a piperidine structure,
The component (A) is
(A1) a polydiol compound having a molecular weight of 400 to 3000 having two hydroxyl groups in the molecule;
(A2) a diisocyanate compound having two isocyanate groups in the molecule;
(A3) a chain extender having a molecular weight of 50 to 300 having a functional group capable of reacting with two isocyanate groups in the molecule;
(A4) having one or two groups capable of reacting with isocyanate groups in the molecule, and, in the molecule, and functionalizing compound having a piperidine structure,
A photochromic composition which is a polyurethane resin obtained by reacting The (A) component used to obtain the polyurethane resin (A1), (A2) component, (A3) component, and (A4) component quantity ratio is the total number of moles of hydroxyl groups contained in the component (A1) N1, the total number of moles of isocyanate groups contained in the component (A2) is n2, the total number of moles of functional groups capable of reacting with isocyanate groups contained in the component (A3) is n3, and the component (A4) When the total number of moles of functional groups capable of reacting with isocyanate groups in n is n4,
The photochromic composition according to claim 1, wherein the ratio is n1: n2: n3: n4 = 0.30-0.89: 1.00: 0.1-0.69: 0.01-0.20. .   The photochromic composition according to claim 1, wherein the (A1) polydiol compound is at least one polydiol compound selected from polyether diol, polycarbonate diol, polycaprolactone diol, and polyester diol.   The photochromic composition according to claim 1, wherein 30% by mass or more of the (A2) diisocyanate compound is an aliphatic diisocyanate compound.   The photochromic composition according to claim 1, wherein the (A3) chain extender is at least one chain extender selected from a diamine compound, an amino alcohol compound, an aminocarboxylic acid compound, an aminothiol compound, and a diol compound.   2. The photochromic composition according to claim 1, 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 resin. The photochromic composition of Claim 6 which further contains 5-900 mass parts (C) organic solvent with respect to 100 mass parts of said (A) polyurethane resins.   An optical article comprising 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 according to claim 1. The optical article according to claim 8 , 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 9 , comprising:
(I) The photochromic composition according to claim 7 is spread on a smooth substrate and then dried to remove (C) the organic solvent, and (A) the polyurethane resin and the (A) polyurethane resin (B) preparing a photochromic adhesive sheet comprising the photochromic compound dispersed in (II), and (II) interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other, Creating the laminated structure by joining two optical sheets or optical films;
A method comprising the steps of: