JP5591175B2 - Photochromic polymerizable composition - Google Patents

Description

  The present invention relates to a novel photochromic polymerizable composition. Specifically, the present invention relates to a novel photochromic polymerizable composition that can be suitably used as a photochromic adhesive for joining optical sheets or films made of polycarbonate resin or the like. 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 sheet (layer) made of the photochromic polymerizable composition.

  In recent years, mainly in the United States, plastic lenses using a polycarbonate resin having transparency and excellent impact resistance have been in increasing demand for use in sunglasses having anti-glare properties. Such plastic sunglasses, which contain a photochromic compound, can change the transmittance according to the brightness of the surroundings and adjust the anti-glare property. Plastic photochromic sunglasses (photochromic lenses) are rapidly becoming popular. Have gained.

  Such a photochromic lens is manufactured by various methods. Specifically, a method of applying a coating composition containing a photochromic compound to the surface of a plastic lens, and a method of forming a lens by mixing a photochromic compound with the material of the plastic lens 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 simultaneously imparted when manufacturing a plastic lens by injection molding. That is, this is a method of using a photochromic adhesive containing a photochromic compound and a urethane polymer. Specifically, a “photochromic laminate” is produced by laminating the photochromic adhesive on an optical sheet such as a polycarbonate resin, and then the laminate is mounted in a lens molding die for injection molding or thermocompression bonding. It is a method to do. According to this method, plastic photochromic sunglasses having the laminate can be produced (see Patent Documents 1 to 4). Since the photochromic lens (optical article) obtained by this method has joined the laminated body and the plastic lens by injection molding or thermocompression bonding, the adhesion at the interface between the laminated body and the lens is very high. It will be a thing.

  However, in the optical article by the method described in Patent Documents 1 and 2, it is considered to be due to the structure of the urethane polymer used, but since the adhesion between the optical sheet and the photochromic adhesive is not sufficient, the optical sheet is There was a problem of peeling (the optical sheet might peel off because the adhesiveness of the photochromic laminate itself was not sufficient). Furthermore, since the heat resistance of the urethane polymer is not sufficient, there is a problem that optical distortion occurs when performing injection molding or thermocompression bonding. Therefore, it has been desired to improve the heat resistance of the matrix resin (urethane polymer) itself of the layer made of the adhesive.

  In contrast, the methods described in Patent Documents 3 and 4 employ a two-component urethane polymer (a mixture of a compound having an isocyanate group at the terminal and a compound having a hydroxyl group at the terminal). In this method, a composition containing a two-pack type urethane polymer and a photochromic compound is laminated on an optical sheet, and after the lamination, the two-pack type urethane polymer is reacted to form a high molecular weight urethane resin layer (adhesive). Layer). According to this method, since the composition before lamination has a relatively low molecular weight, there is an advantage that the solubility of the composition itself and the solubility of the photochromic compound are not lowered. Furthermore, since a two-component urethane polymer is reacted after the lamination to obtain a high molecular weight urethane polymer, the heat resistance can also be improved.

  However, even with the photochromic adhesive obtained by this method, the adhesion of the photochromic laminate itself is not sufficient, and the problem that the optical sheet peels cannot be solved. When used in daily life, photochromic lenses may come into contact with hot water or hot water. Even under such circumstances, the adhesion between the optical sheet and the adhesive must be high. . That is, it is desirable that the optical sheet is firmly bonded even when the photochromic laminate itself is placed in the above-described situation. However, in the photochromic adhesive obtained by reacting the two-component urethane polymer, for example, after contacting with hot water while maintaining high photochromic properties, the optical sheet and the adhesive have high adhesion. It was difficult to maintain and there was room for improvement. Further, the two-component urethane polymer has high reactivity between isocyanate groups and hydroxyl groups, so there is room for improvement in terms of storage stability.

  In addition, the following method has been proposed as a method for manufacturing a lens using a “photochromic laminate”, other than the above-described injection molding and thermocompression bonding. Specifically, it is a method of forming a plastic lens by immersing a photochromic laminate in a polymerizable monomer and then polymerizing and curing the polymerizable monomer (see Patent Documents 5 and 6). According to this method, by changing the kind of the polymerizable monomer, the performance of the obtained lens can be easily changed, and lenses having various performances can be manufactured. In addition, as compared with injection molding and thermocompression bonding, a photochromic lens can be produced at a relatively low temperature.

  However, according to studies by the present inventors, it has been found that the methods described in Patent Documents 5 and 6 have room for improvement in the following points. Patent Documents 5 and 6 indicate that a two-component thermosetting urethane polymer composed of a urethane polymer having an isocyanate group and a curing agent is used as a photochromic adhesive. When the thermosetting urethane polymer described in Patent Documents 5 and 6 is used, depending on the type of polymerizable monomer and the polymerization conditions, the thermosetting urethane polymer and the photochromic compound are eluted from the photochromic laminate into the polymerizable monomer. There was a case. This elution occurs at the end portion of the photochromic laminate. Since the portion where the elution of the photochromic laminate has occurred needs to be removed from the lens, the larger the elution portion, the smaller the effective area of the lens, leaving room for improvement. Also, if the eluted part is removed from the lens, the end face of the photochromic laminate will be on the same plane as the end face of the photochromic lens, but the thermosetting urethane polymer may not have sufficient adhesion. There was a risk that the lens would peel off.

US Patent Publication No. 20040966666 Special table 2003-519398 gazette US Published Patent No. 2005050233153 US Patent Publication No. 200202000655 JP 2005-181426 A JP 2005-215640 A

  As described above, in a method for producing a photochromic lens using a photochromic laminate, in the prior art, the adhesion of the photochromic adhesive (photochromic polymerizable composition) to the optical sheet, the heat resistance of the photochromic adhesive itself, and the composition It was necessary to improve the storage stability. Moreover, it was necessary to improve the solubility resistance (hereinafter, sometimes referred to as solvent resistance) to the polymerizable monomer that is polymerized and becomes the base material of the lens. A photochromic polymerizable composition satisfying these performances can be used for both a method for producing a photochromic lens by injection molding and thermocompression bonding and a method for embedding in a polymerizable monomer.

  Therefore, when the first object of the present invention is used as an adhesive layer (adhesive) when joining an optical sheet or film, it has excellent adhesion, heat resistance, and solvent resistance, and is excellent. The object is to provide a photochromic polymerizable composition exhibiting photochromic properties, and further a photochromic polymerizable composition having excellent storage stability.

  A second object of the present invention is an optical article comprising a laminated structure (for example, a photochromic laminate) in which an optical sheet or film is joined by an adhesive layer having photochromic properties. It is to provide an optical article having excellent properties and photochromic properties.

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

  In order to solve the above-mentioned problems, the present inventors have examined the relationship between the structure of the photochromic adhesive layer and the characteristics of the obtained optical article. As a result, polymerizability combining a urethane prepolymer having at least one isocyanate group in the molecule and a compound having at least one oxazolidine ring in the molecule (hereinafter also simply referred to as “oxazolidine ring-containing compound”). It has been found that the above problems can be solved by forming an adhesive layer obtained using the composition as a main component, and the present invention has been completed.

  Furthermore, the photochromic adhesive layer is formed by forming the photochromic adhesive layer without using an organic solvent, or forming a cast film using an organic solvent and then drying (removing the solvent) to form the photochromic adhesive layer. If a photochromic adhesive sheet comprising a specific urethane polymer is prepared separately and a photochromic laminate is produced using the photochromic adhesive sheet, adverse effects due to the solvent can be avoided and the photochromic properties do not deteriorate. As a result, the present invention has been completed.

That is, the first aspect of the present invention is
Urethane prepolymer (A) having at least one isocyanate group in the molecule,
Oxazoline di emissions ring-containing compound having at least one oxazolidine ring in the molecule (B), and photochromic compound (C)
It is a photochromic polymerizable composition characterized by including.

The photochromic polymerizable composition is included in the compound (B) having the oxazolidine ring, where n is the total number of isocyanate groups contained in the urethane prepolymer (A), in order to exhibit a particularly excellent effect. When the total number of moles of the oxazolidine ring is
n: o = 0.5-10: 1
It is preferable that the amount ratio is as follows.

  The second aspect of the present invention is an optical article having a laminated structure in which two optical sheets or optical films facing each other are bonded via an adhesive layer obtained from the photochromic polymerizable composition.

Furthermore, a third aspect of the present invention is a method for producing the optical article,
After spreading the photochromic polymerizable composition containing an organic solvent on a smooth substrate, the organic solvent (D) is removed by drying to remove the urethane prepolymer (A), the oxazolidine ring-containing compound (B), A step of preparing a photochromic adhesive sheet containing the photochromic compound (C), and interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other, and at least in the presence of moisture, the two sheets Producing the laminated structure by bonding an optical sheet or an optical film;
The method characterized by comprising. By interposing the photochromic adhesive sheet and joining the optical sheets or optical films in the presence of water, the isocyanate group of the urethane prepolymer (A) and the oxazolidine ring of the oxazolidine ring-containing compound (B) The reaction (polyaddition reaction) proceeds and the optical sheet or optical film can be firmly bonded.

  The photochromic polymerizable composition of the present invention functions as an adhesive or a binder. The polymerizable composition of the present invention forms an adhesive layer made of a polymer of a urethane prepolymer and an oxazolidine ring-containing compound. A laminate (photochromic laminate) in which an optical sheet or film made of polycarbonate resin or the like is bonded via this adhesive layer uses the polymer, and therefore has excellent adhesion and photochromic properties (color density, fading speed). , Durability), heat resistance, and solvent resistance. Moreover, the polymerizable composition of the present invention has good storage stability.

  In addition, 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 polycarbonate resin thermoplastic resin on the mold, Adhesiveness and photochromic properties are unlikely to deteriorate and optical distortion hardly occurs.

  Furthermore, the photochromic laminate is also useful in a technique of embedding in a polymerizable monomer that forms a transparent thermosetting resin and producing a lens by thermosetting. That is, since the adhesive layer (sheet) obtained from the photochromic polymerizable composition of the present invention has improved solvent resistance, the urethane polymer that is the matrix of the adhesive layer even when exposed to a polymerizable monomer for a long time Elution of the polymer and the photochromic compound can be suppressed. As a result, the effective area of the photochromic lens can be improved and productivity can be increased.

  In addition, according to the production 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 organic solvents can be avoided, so that photochromic properties can be reduced. Absent.

  The photochromic polymerizable composition of the present invention comprises a urethane prepolymer (A) having at least one isocyanate group in the molecule (hereinafter sometimes referred to simply as component A), an oxazolidine ring-containing compound (B) (hereinafter referred to as “component”). , And may be simply B component), and a photochromic compound (C) (hereinafter sometimes simply referred to as C component).

  In the prior art, the urethane polymer used for the photochromic adhesive is formed by mixing a reactive urethane polymer having an isocyanate group (prepolymer) and a prepolymer having a group capable of reacting with an isocyanate group (polyol) to form a coating film. Thereafter, both were reacted to increase the molecular weight. However, the adhesive layer obtained by this method has a problem that adhesion, heat resistance and solvent resistance are insufficient. Furthermore, since the isocyanate group has high reactivity with the hydroxyl group, there is room for improvement in terms of storage stability.

  In contrast, the photochromic adhesive comprising the polymerizable composition of the present invention comprises a urethane prepolymer (A), an oxazolidine ring-containing compound (B component), and a photochromic compound (C component) described below. The oxazolidine ring is more stable with respect to the isocyanate group than the hydroxyl group. When the adhesive layer (sheet) is formed in the presence of water, or when the optical sheet or the optical film is bonded with the adhesive sheet in the presence of water, the oxazolidine ring is opened to form an isocyanate group. To form a cross-linked urethane polymer containing a urea bond. Therefore, the photochromic polymerizable composition of the present invention can form a urethane polymer having a stronger cohesive force. As a result, it is presumed that the polymer of the photochromic polymerizable composition that is the main component of the adhesive layer has improved heat resistance and solvent resistance and can solve the above-mentioned problems. For the above reasons, it is considered that when the A component and the B component are mixed, they are relatively more stable than the conventional two-component urethane polymer and exhibit excellent storage stability.

  Hereinafter, the A component, the B component, and the C component will be described.

(Component A: urethane prepolymer having at least one isocyanate group in the molecule)
The urethane prepolymer (A) used in the present invention is a urethane prepolymer having at least one isocyanate group in the molecule.

The component A is not particularly limited, but is preferably produced by the following method. Specifically, the component A is from the viewpoint of heat resistance, solvent resistance, adhesion, and photochromic properties.
(A1) a polyol compound having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule (hereinafter also simply referred to as A1 component),
(A2) Polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also simply referred to as A2 component)
It is preferable to make it react. Hereinafter, these components will be described.

(A1 component: polyol compound)
The number of hydroxyl groups contained in the molecule of the A1 component polyol compound is preferably 2 to 6 because the urethane prepolymer (A) does not become a highly crosslinked product. Furthermore, considering the solubility in an organic solvent, the number of hydroxyl groups is more preferably 2 to 3.

  The number average molecular weight of the A1 component is preferably 400 to 3000. This A1 component is a polymer, and therefore the molecular weight is indicated by the number average molecular weight. From the viewpoint of the heat resistance of the obtained component A and the photochromic properties (color development density, fading speed, weather resistance, etc.) of the photochromic polymerizable composition, among them, the number average molecular weight is 400 to 2500 from the viewpoint of the weather resistance of the photochromic compound. It is preferable that it is 400-1500.

  As the A1 component, a known polyol compound can be used without any limitation. Specifically, it is preferable to use polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol. These may be used alone or in combination of two or more. Among these, polycarbonate polyol and polycaprolactone polyol 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 polyol)
The polyether polyol used as the A1 component includes a polyether polyol compound obtained by the reaction of “a compound having two or more active hydrogen-containing groups in the molecule” and “alkylene oxide”, and modification of the polyether polyol compound. Examples thereof include polymer polyols, urethane-modified polyether dipolyols, and polyether ester copolymer polyols.

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

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

(Polycarbonate polyol)
Examples of the polycarbonate polyol used as the A1 component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 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, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxy Ethyl) benzene, xylyl Polycarbonate polyol obtained by phosgenation of one or more low-molecular polyols such as ethylene glycol, glycerin, trimethylolpropane and pentaerythritol, or polycarbonate polyol obtained by transesterification with ethylene carbonate, diethyl carbonate, and diphenyl carbonate Etc.

  These polycarbonate polyols are available as reagents or industrially, and examples of those that are commercially available include "Duranol (registered trademark)" series manufactured by Asahi Kasei Chemicals Corporation, "Kuraray polyol (registered trademark)" manufactured by Kuraray Co., Ltd. ) "Series," Placcel (registered trademark) "series manufactured by Daicel Chemical Industries, Ltd.," Nipporan (registered trademark) "series manufactured by Nippon Polyurethane Industry Co., Ltd.," ETERNACOLL (registered trademark) "series manufactured by Ube Industries, Ltd. be able to.

  As A1 component of this invention, it is preferable to use a polycarbonate polyol 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 A1 component using polycarbonate polyol.

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

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

(Polyester polyol)
Examples of the polyester polyol used as the A1 component include a polyester polyol obtained by a condensation reaction of “polyhydric alcohol” and “polybasic acid”. Here, as the “polyhydric alcohol”, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 3,3'-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. These may be used alone or in combination of two or more. Examples of the “polybasic acid” include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more.

  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: polyisocyanate compound)
Examples of the “polyisocyanate compound having two or more isocyanate groups in the molecule” used as the A2 component in the present invention include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and these A mixture is mentioned. Among these, from the viewpoint of weather resistance, it is preferable to use at least one polyisocyanate compound selected from an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound. Further, from the viewpoint of particularly improving the weather resistance, 30% by mass or more, particularly 50% by mass or more of the polyisocyanate compound of component A2 is at least one selected from aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds. A polyisocyanate compound is preferred. In the most preferred embodiment, 100% by mass of the component A2 is at least one polyisocyanate compound selected from an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound.

  In the A2 component polyisocyanate compound, the number of isocyanate groups contained in the molecule may be two or more.

If the polyisocyanate compound which can be used conveniently as an A2 component is illustrated,
Aliphatic diisocyanate compounds such as diethylene diisocyanate, 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, 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-isocyanato-4-[(4-isocyanate Preparative cyclohexyl) methyl] -1-methyl-cyclohexane, alicyclic diisocyanate compounds such as 2- (3-isocyanatopropyl) cyclohexyl isocyanate,
Phenylcyclohexylmethane diisocyanate, isomer mixture of 4,4′-methylenebis (phenylisocyanate), toluene-2,3-diisocyanate, toluene-2,4-character isocyanate, 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-diisocyanatomethylbenzene, 4,4′-diisocyanato-3,3′-dimethoxy (1,1′-biphenyl), 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4- Bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl) methyl] 2-methyl Aromatic diisocyanate compounds such as benzene, 1-isocyanato-3-[(4-isocyanatophenyl) methyl) -2-methylbenzene, 4-[(2-isocyanatophenyl) oxy] phenyl isocyanate,
1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanato) hexanoate, 1-methylbenzene-2,4,6-tri Is composed of isocyanate, diphenylmethane-2,4,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, and a trimer of the diisocyanate compound. Mention may be made of triisocyanate compounds such as isocyanurate compounds.

  Among these, from the viewpoint of the weather resistance of the resulting photochromic polymerizable composition, as described above, 30% by mass or more, particularly 50% by mass or more of the polyisocyanate compound of component A2 is an aliphatic polyisocyanate compound and an alicyclic ring. It is preferably at least one polyisocyanate compound selected from the formula polyisocyanate compounds. Specific examples of suitable compounds include 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, 4, 4'-methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahi Lophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl (2, 6-diisocyanato) hexanoate; an isocyanurate compound composed of an aliphatic diisocyanate compound and a trimer of an alicyclic diisocyanate compound. These polyisocyanate compounds may be used alone or in combination of two or more.

  The urethane prepolymer (A) used in the present invention can be synthesized from the A1 component and the A2 component. Among them, in order to exhibit a more excellent effect, the component A includes a chain extender having a group capable of reacting with two or more isocyanate groups in the molecule, and a group capable of reacting with an isocyanate group in the molecule. It may be synthesized using a reaction terminator having one. However, when these chain extenders and reaction terminators are used, the component A to be produced is always in such a proportion that it has at least one isocyanate group in the molecule, and the reaction terminator. Must be used. The chain extender (hereinafter also referred to as A3 component) and the reaction terminator (hereinafter also referred to as A4 component) will be described.

(A3 component: chain extender)
The chain extender used as the A3 component is a compound having a molecular weight of 50 to 300 having a group capable of reacting with two or more isocyanate groups in the molecule. Since the chain extender is not a polymer, the molecular weight refers to the molecular weight of the chain extender itself. The group capable of reacting with an isocyanate group is an amino group (—NH ₂ group and —NH (R) group, R is a substituent), a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group). ), A carboxyl group [—C (═O) OH group], or an acid chloride group [—C (═O) OCl group].

  The A3 component functions as a chain extender when the urethane prepolymer (A) is synthesized. By using the A3 component as the chain extender, the molecular weight and heat resistance of the urethane prepolymer (A) of the present invention are increased. Control of photon properties and photochromic characteristics becomes possible. When the molecular weight of the chain extender is less than 50, the resulting urethane prepolymer (A) tends to be too hard. Moreover, although the heat resistance of the photochromic polymerizable composition obtained improves, it exists in the tendency for adhesiveness and a photochromic characteristic to fall. On the other hand, when the molecular weight of the chain extender exceeds 300, the resulting urethane prepolymer (A) tends to be too soft. Therefore, all of the heat resistance, adhesion, and photochromic properties of the resulting photochromic polymerizable composition tend to decrease. From the above, the molecular weight of the chain extender is more preferably 50 to 250, and most preferably 55 to 200.

The A3 component is preferably at least one chain extender selected from diamine compounds, triamine compounds, aminoalcohol compounds, aminocarboxylic acid compounds, aminothiol compounds, diol compounds, and triol compounds. Hereinafter, a diamine compound, a triamine compound, an amino alcohol compound, an aminocarboxylic acid compound, and an aminothiol compound may be collectively used as an amino group-containing compound. The amino group-containing compound has a group that reacts with at least two or more isocyanate groups in the molecule, at least one of which is an amino group (—NH ₂ group and —NH (R) group, and R is a substituted group. Group) and a reactive group with an isocyanate group other than an amino group is a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), a carboxyl group [—C (═O) OH group], or It is an acid chloride group [—C (═O) OCl group].

  If the compound used suitably as an amino group containing compound of A3 component is illustrated, as a diamine compound and a triamine compound, isophorone diamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2- Diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- ( 4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, hydrazine, adipic acid dihydrazine, phenylenediamine 4,4'-diphenylmethanediamine, N, N'-diethyl Ethylenediamine, N, N′-dimethylethylenediamine, N, N′-dipropylethylenediamine, N, N′-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) triamine, 1,2,5- A pentane triamine etc. can be mentioned.

  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 A3 component diol compounds and compounds suitably used as triol compounds 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-cyclohexanedio 1,4-cyclohexanedimethanol, 1,2-bis (hydroxyethyl) -cyclohexane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, etc. be able to.

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

  In the chain extender, an amino group-containing compound is preferably used, and a diamine compound is more preferably used from the viewpoints of heat resistance, adhesion, durability of the photochromic compound, and the like. This is because the urethane prepolymer (A) has a urea bond by using an amino group-containing compound when the component A is synthesized, and the molecular rigidity is increased and the hydrogen between the molecular chains is increased. It is thought that the bond becomes stronger. As a result, it is estimated that the heat resistance of the photochromic polymerizable composition is improved. In addition, regarding the improvement in durability of photochromic compounds, the presence of urea bonds makes hydrogen bonds between molecular chains stronger, making it difficult for oxygen in the air to diffuse into the urethane polymer. It is presumed that photooxidation deterioration was 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: reaction stopper having a group capable of reacting with one isocyanate group in the molecule (reaction stopper))
When synthesizing the urethane prepolymer (A) used in the present invention, a reaction terminator having a group capable of reacting with one isocyanate group in the molecule (hereinafter also simply referred to as A4 component) can be used in combination. is there.

  The A4 component is a reaction terminator having a group capable of reacting with one isocyanate group in the molecule. By using the A4 component, the end of the urethane prepolymer (A) is non-reactive group other than the isocyanate group. Can be converted to However, the urethane prepolymer (A) of the present invention must always have one isocyanate group in the molecule.

The group capable of reacting with the isocyanate group includes 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].

  This reaction terminator has only one group in the molecule that can react with an isocyanate group. When two or more such groups are present, the A component obtained by reaction with the A4 component has a high molecular weight and becomes highly viscous when diluted with an organic solvent, which may make the coating difficult. Moreover, it exists in the tendency to reduce the adhesiveness (adhesion with an optical sheet) of the photochromic adhesive agent obtained. By introducing the reaction terminator into the urethane prepolymer (A), the number average molecular weight of the urethane prepolymer can be controlled, and the adhesion, heat resistance, and photochromic properties can be easily adjusted to the desired physical properties. .

  The reaction terminator is preferably a compound having a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule. The reason for this is that the 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, This is because it becomes a site exhibiting a benzotriazole structure). By using a reaction terminator having these structures, it is possible to improve the durability (light stability, antioxidant performance, ultraviolet absorption performance) of the urethane prepolymer itself, which is the component A, and the photochromic compound. Moreover, since the addition amount of additives, such as a hindered amine and antioxidant, can be reduced, the adhesive fall by addition of an additive 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.

  Examples of the reaction terminator preferably used as the A4 component include the following compounds as those having a piperidine structure. Specifically, 1-methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 1-methyl-2,2,6,6-tetramethyl-4-aminopiperidine, 2,2,6 And a reaction terminator having a piperidine structure such as, 6-tetramethyl-4-aminopiperidine in the molecule and a group capable of reacting with one isocyanate group. In addition, a reaction terminator having a hindered phenol structure, a triazine structure, or a benzotriazole structure in the molecule and a group capable of reacting with one single isocyanate group can also be used.

  The A4 component is preferably introduced into the molecular end of the urethane prepolymer (A) for the purpose of improving the weather resistance of the resulting photochromic polymerizable composition. By introducing it at the molecular end, there is an advantage that the original heat resistance and mechanical strength (peel strength) of the urethane resin are not impaired.

  The above reaction terminators may be used alone or as a mixture of two or more. From the viewpoint of improving the durability of the urethane prepolymer (A) and the photochromic compound, the piperidine structure is used. It is preferable to use a reaction terminator having the same.

(Method for synthesizing component A)
When the A component is obtained by reacting these A1 component, A2 component, and further, if necessary, the A3 component and A4 component, the A component can be suitably obtained by the following method, for example.

(Synthesis method)
A urethane prepolymer can be obtained by reacting the A1 component and the A2 component. As needed, A component can also be manufactured by making the terminal isocyanate group which remains in the obtained urethane prepolymer, A3 component, and A4 react.

  In the above method, the reaction between the A1 component and the A2 component is carried out by reacting both in the presence or absence of a solvent at 25 to 120 ° C. for 0.5 to 24 hours in an inert gas atmosphere such as nitrogen or argon. Just do it. As the solvent, organic solvents such as methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the polyisocyanate compound as the A2 component and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to a dehydration treatment in advance and sufficiently dried. In carrying out the 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.

  When the urethane prepolymer (A) having an isocyanate group at the end of the molecular chain is produced by the reaction, it can be used as it is. However, in order to further improve the heat resistance of the photochromic polymerizable composition, it is preferable to react the A3 component with the isocyanate group.

  The reaction of the component A3 and the urethane prepolymer (A) 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, methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

  When the urethane prepolymer (A) having an isocyanate group at the end of the molecular chain is produced by the reaction, it can be used as it is. However, in order to further improve the weather resistance of the photochromic polymerizable composition, it is preferable to react the A4 component with the isocyanate group. The reaction between the A4 component and the urethane prepolymer (A) 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, methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

(Combination ratio of each component)
What is necessary is just to determine suitably the quantity ratio of A1 component used for reaction in the said method, A2 component, A3 component used as needed, and also A4 component. However, since the component A has at least one isocyanate group in the molecule, it is necessary to change the blending amount depending on the component used. From the viewpoint of the balance between the resulting photochromic polymerizable composition and the heat resistance, adhesive strength, and photochromic properties (color density, fading speed, weather resistance, etc.) of the photochromic adhesive sheet (layer) obtained from the polymerizable composition, It is preferable that the quantity ratio is as follows. When the A component is composed of A1 and A2 components, when it is formed from A1, A2, and A3 components, when it is formed from A1, A2, and A4 components, or A1, A2, A3, and The case where it is comprised from A4 component is demonstrated.

(When composed of A1 and A2 components)
When A component is comprised from A1 component and A2 component, it is preferable that the quantity ratio of each component satisfies the following quantity ratios. In particular,
The total number of moles of hydroxyl groups contained in the component (A1) is n1,
The total number of moles of isocyanate groups contained in the component (A2) is n2,
It is preferable that the quantity ratio is n1: n2 = 0.4 to 0.9: 1. In order to exhibit particularly excellent adhesion and heat resistance, 0.5 to 0.85: 1 is preferable.

(When composed of A1, A2, and A3 components)
When the A component is composed of the A1, A2, and A3 components, it is preferable that the amount ratio of each component satisfies the following amount ratio. In particular,
In addition to n1 of the component (A1) and n2 of the component (A2), when the total number of moles of groups capable of reacting with the isocyanate group of the component (A3) is n3,
n1: n2: n3 = It is preferable to set it as the quantity ratio used as 0.4-0.85: 1: 0.05-0.5. In particular, 0.45 to 0.8: 1: 0.05 to 0.3 is preferable in order to exhibit excellent adhesion and heat resistance.

(When composed of A1, A2, and A4 components)
When the A component is composed of the A1, A2, and A4 components, it is preferable that the amount ratio of each component satisfies the following amount ratio. In particular,
In addition to n1 of the component (A1) and n2 of the component (A2), when the total number of moles of groups capable of reacting with the isocyanate group of the component (A4) is n4,
n1: n2: n4 = It is preferable to set it as the quantity ratio used as 0.4-0.90: 1: 0.01-0.09. In particular, in order to exhibit excellent adhesion, heat resistance, and photochromic characteristics, 0.45 to 0.85: 1: 0.01 to 0.07 is preferable. Since the obtained A component has one isocyanate group in the molecule, the A4 component must be a blending amount satisfying it within the above range. Therefore, when the A4 component is reacted with the reactant obtained from the A1 and A2 components to produce the A component, the reactant has at least 1.5 isocyanate groups in the molecule, preferably 2 or more 4 in the molecule. There must be no more.

That is, n4 must be less than half the number of moles of remaining isocyanate groups (n2-n1). (N4 ≦ (n2−n1) / 2 must be satisfied). Above all, considering heat resistance and photochromic characteristics,
n1: n2: n4 = 0.6 to 0.85: 1: 0.01 to 0.07 was satisfied, and (n2-n1) / 5 ≦ n4 ≦ (n2-n1) / 2
Is preferably satisfied. In addition, when A4 component is used, the number of the isocyanate groups contained in the molecule | numerator of A component can be calculated | required from the preparation ratio of each component, the number average molecular weight of A component, and the titration result of an isocyanate group. In this case, the number of isocyanate groups is an average value.

(When composed of A1, A2, A3 and A4 components)
When the A component is composed of the A1 component, A2, A3, and A4 components, it is preferable that the amount ratio of each component satisfies the following amount ratio. Specifically, it is preferable that the ratio is n1: n2: n3: n4 = 0.3 to 0.8: 1: 0.05 to 0.5: 0.01 to 0.1. In particular, n1: n2: n3: n4 = 0.35 to 0.75: 1: 0.05 to 0.3: 0.01 to 0 in order to exhibit excellent adhesion, heat resistance and photochromic properties. 0.08 is preferable. Also in this case, since the A4 component is used, when the A4 component is reacted with the reactant obtained from the A1, A2, and A3 components to produce the A component, the reactant has at least an isocyanate group in the molecule. There must be 2 or more, preferably 3 or more and 4 or less. That is, n4 must be less than half of the number of moles of remaining isocyanate groups (n2-n1-n3). (N4 ≦ (n2-n1-n3) / 2 must be satisfied). Above all, considering heat resistance, adhesion, and photochromic properties,
n1: n2 :: n3: n4 = 0.4 to 0.65: 1: 0.1 to 0.3: 0.01 to 0.08, and
(N2-n1-n3) / 5 ≦ n4 ≦ (n2-n1-n3) / 2
Is preferably satisfied. Also in this case, the number of isocyanate groups in the obtained component A can be obtained as an average value.

  The n1, n2, n3, and n4 can be determined as the product of the number of moles of the compound used as each component and the number of groups present in one molecule of the compound.

(Physical properties of component A, number of isocyanate groups)
The component A obtained by the above method has a number average molecular weight of 1,000 to 5 from the viewpoint of heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.) of the formed adhesive layer. It is preferably 10,000, more preferably 1,000 to 20,000, and most preferably 2,000 to 10,000. The number average molecular weight of the urethane polymer is determined by using gel permeation chromatograph (GPC) in terms of polyethylene oxide, columns: Shodex KD-805, KD-804 (manufactured by Showa Denko KK), eluent. : Number average molecular weight measured under conditions of LiBr (10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, urethane polymer sample solution: 0.5% dimethylformamide (DMF) solution.

  The component A has at least one isocyanate group in the molecule. The number of isocyanate groups contained in the molecule is preferably 1.5 to 5 and more preferably 1.5 to 4 in the molecule in view of adhesion and heat resistance. The number of isocyanate groups contained in the molecule of component A can be determined from the charge ratio of each component, the number average molecular weight of component A, and the titration result of isocyanate groups. In this case, the number of isocyanate groups is an average value.

(Component B: Oxazolidine ring-containing compound)
Component B is a compound having one or more oxazolidine rings in the molecule (an oxazolidine ring-containing compound). The oxazolidine ring-containing compound is a compound having a saturated 5-membered heterocyclic ring containing oxygen and nitrogen, and has an oxazolidine ring that opens in the presence of moisture (water) and cures by reacting with an isocyanate group. A compound. Specifically, the following formula

It is a compound which has a ring shown.

Mechanisms by which oxazoline di down ring is ring-opened by reaction with water are as follows. And the produced amino group and hydroxyl group react with the isocyanate group contained in the urethane prepolymer (A).

  In the photochromic polymerizable composition of the present invention, the crosslinking density of the urethane polymer forming the photochromic adhesive sheet (layer) can be improved by using the oxazolidine ring-containing compound (component B). Therefore, the heat resistance and solvent resistance of the urethane polymer can be improved, the durability of the photochromic compound, and the adhesion between the optical sheet and the photochromic adhesive sheet (layer) can be improved. Furthermore, since the A component and the B component are not mixed, they do not react instantaneously, so that the storage stability of the photochromic polymerizable composition itself is also improved.

  Examples of the oxazolidine ring-containing compound (component B) include N-hydroxyalkyl oxazolidine and its adduct with a polyisocyanate compound, oxazolidine silyl ether, carbonate oxazolidine, ester oxazolidine and the like.

  As hydroxyalkyl oxazolidine, it can carry out by the dehydration condensation reaction of an alkanolamine and a ketone or an aldehyde, for example. Specific examples of hydroxyalkyl oxazolidine include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3- (2- Hydroxyethyl) oxazolidine, 2- (p-methoxyphenyl) -3- (2-hydroxyethyl) oxazolidine, 2- (2-methylbutyl) -3- (2-hydroxyethyl) -5-methyloxazolidine and the like.

  Oxazolidine silyl ether includes the above-mentioned N-hydroxyalkyl oxazolidine, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, It can be obtained by reaction with an alkoxysilane such as γ-glycidoxypropyltriethoxysilane.

  Examples of the carbonate oxazolidine include carbonate oxazolidine obtained by the method of JP-A No. 5-117252.

  As the ester oxazolidine, for example, various ester oxazolidines such as ester oxazolidine obtained by the methods of US Pat. No. 3,661,923 and US Pat. No. 4,138,545 can be used.

  Among them, the number of oxazolidine rings contained in the component B is preferably 2 or more in the molecule from the viewpoint of improving the crosslinking density of the urethane polymer obtained by reacting with the urethane prepolymer (A). More preferably, it is 2 or more and 3 or less.

(Compound having two or more oxazolidine rings in the molecule (polycyclic compound))
The compound (polycyclic compound) having two or more oxazolidine rings in the molecule is preferably a reaction product of an N-hydroxyalkyloxazolidine represented by the following general formula (2) and a polyisocyanate compound.

(Where
R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ are each independently hydrogen or a monovalent hydrocarbon group having 1 to 20 carbon atoms,
R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms. )
In the general formula ^{(2), R 1, R} 2, R 3, and ^{R 4} is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an optionally substituted aromatic hydrocarbon group. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferred because of easy availability of raw materials and good curability.
R ⁵ and R ⁶ are a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an optionally substituted aromatic hydrocarbon group.

R ⁷ is a divalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, it is an aliphatic hydrocarbon group having a linear or branched chain. Among these, an ethylene group and a propylene group are preferable because they are easily available.

(Synthesis of N-hydroxyalkyloxazolidine represented by the general formula (2))
The N-hydroxyalkyloxazolidine represented by the general formula (2) can be obtained by reacting a corresponding aldehyde or ketone with N-hydroxyalkylamine.

  Examples of aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, hexylaldehyde, 2-methylpentylaldehyde, octylaldehyde, 3,5,5- Aliphatic aldehydes such as trimethylhexyl aldehyde; aromatic aldehydes such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutyl and benzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, trimethoxybenzaldehyde, and the like.

  Examples of the ketone include ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, diethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl-t-butyl ketone, diisobutyl ketone, cyclopentanone, and cyclohexanone.

  N-hydroxyalkylamines include aminoethylethanolamine, diethylethanolamine, dimethylethanolamine, (2-hydroxyethyl) amine, (2-hydroxypropyl) amine, bis-N- (2-hydroxyethyl) amine, bis -N- (2-hydroxypropyl) amine, N-2- (hydroxyethyl) -N- (2-hydroxypropyl) amine and the like. This N-hydroxyalkyloxazolidine can be synthesized by the following method.

  The synthesis of N-hydroxyalkyloxazolidine is carried out while refluxing the aldehyde or ketone and hydroxyalkylamine in toluene. The reaction time is preferably 5 to 20 hours, and more preferably 8 to 15 hours. If the reaction time is short, the reaction may be insufficient, and if the reaction time is too long, a colored component that is assumed to be a decomposition product of the reactive organism is generated.

  In this synthesis, it is preferable to use an excessive amount of aldehyde or ketone relative to N-hydroxyalkylamine. Specifically, it is preferable to use an aldehyde or a ketone in excess within a range of 1.01 to 1.1 mol with respect to 1 mol of N-hydroxyalkylamine. This is because it is difficult to separate and produce N-hydroxyalkyloxazolidine as a reaction product and N-hydroxyalkylamine as a raw material.

(Synthesis of polycyclic compound (component B))
The polycyclic compound (component B) can be obtained by reacting the N-hydroxyalkyloxazolidine with polyisocyanate.

  As the polyisocyanate compound, any of the polyisocyanate compounds exemplified for the component A2 can be used without any limitation. Two or more kinds can be used alone or in combination. Among these, it is preferable to use an aliphatic diisocyanate compound or an alicyclic diisocyanate compound. Moreover, as a polyisocyanate compound, the urethane prepolymer which is said A component can also be used conveniently.

  When synthesizing a polycyclic compound, the amount ratio of the N-hydroxyalkyloxazolidine to the polyisocyanate compound is equivalent to the number of moles of isocyanate groups contained in the polyisocyanate compound relative to the number of moles of the N-hydroxyalkyloxazolidine. It is preferable to use it.

  The reaction between the N-hydroxyalkyloxazolidine and the polyisocyanate compound 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 24 hours. You can do it. As the solvent, organic solvents such as methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the polyisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried. In carrying out the 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 of this polyisocyanate compound.

  Examples of the component B used in the present invention include the exemplified oxazolidine ring-containing compounds and the polycyclic compounds produced by the above method. Next, the compounding quantity of this B component is demonstrated.

(B component content)
In the photochromic polymerizable composition of the present invention, the component B is obtained so that the resulting photochromic adhesive layer exhibits excellent adhesion, heat resistance, and photochromic properties.
The total number of moles of isocyanate groups contained in the urethane prepolymer (A) is n,
When the total number of moles of the oxazolidine ring contained in the oxazolidine ring-containing compound (B) is o,
n: o = 0.5-10: 1
It is preferable to blend so as to satisfy the above.

  When the ratio of n is less than 0.5, the resulting photochromic adhesive layer may have insufficient heat resistance and solvent resistance. Moreover, when the ratio of n exceeds 10, the crosslinking density of the resulting photochromic adhesive layer tends to be too high, and although heat resistance and solvent resistance are improved, adhesion and photochromic characteristics may be deteriorated. There is.

Therefore, in order to fully demonstrate all physical properties such as adhesion, heat resistance, solvent resistance, and photochromic properties,
n: o = 1 to 8: 1 is preferable, and
Most preferably, n: o = 1.5 to 5: 1.

(C component: photochromic compound)
As the photochromic compound used as the component C in the photochromic polymerizable 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 are described in, for example, JP-A-2-28154, JP-A-62-2288830, WO94 / 22850 pamphlet, WO96 / 14596 pamphlet and the like. 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.

(Amount of component C)
In the photochromic polymerizable composition of the present invention, the blending amount of the C component is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass in total of the A component and the B 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, photochromic polymerizability with respect to the A and B components. Not only does the composition become difficult to dissolve 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 C added is 100 parts by mass in total of component A and component B. On the other hand, it is more preferable to set it as 0.5-10 mass parts, especially 1-5 mass parts.

  In addition, the photochromic polymerizable composition of the present invention may contain an organic solvent (D) (hereinafter sometimes referred to simply as “component D”), water, an isocyanate compound, and other additives.

(D component: organic solvent)
By mix | blending an organic solvent with the photochromic polymerizable composition of this invention, a urethane prepolymer (A), an oxazolidine ring containing compound (B component), a photochromic compound (C component), and another component become easy to mix. As a result, the uniformity of the photochromic polymerizable composition can be improved. Furthermore, the viscosity of the photochromic polymerizable composition can be appropriately adjusted by using an organic solvent. And the operativity when apply | coating the photochromic polymerizable composition of this invention to an optical sheet or a film, and the uniformity of the thickness of a coating film can also be made high.

  When an optical sheet or film made of a material that is easily affected by an organic solvent is used, there is a concern that problems such as poor appearance or reduced photochromic characteristics may occur. However, such a problem can be avoided by adopting the method of the present invention described below. In the photochromic polymerizable composition of the present invention, various types of solvents can be used as described later. Therefore, the occurrence of the above problem can also be prevented by selecting and using a solvent that does not easily attack the optical sheet or film as the organic solvent.

  Examples of the organic solvent that can be suitably used as the component D include diacetone alcohol; methyl ethyl ketone; toluene; hexane; heptane; ethyl acetate; DMF; DMSO; THF: cyclohexanone; 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.

  Considering the smoothness of the coating layer when the photochromic polymerizable composition of the present invention is applied to an optical sheet or film, or the smoothness of the photochromic adhesive layer (sheet) when the method of the present invention described below is adopted Then, the organic solvent is preferably used by mixing 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. By using an organic solvent in such a combination, in addition to the smoothness, the organic solvent can be easily removed and the drying rate can be increased. What is necessary is just to determine suitably the mixture ratio of the organic solvent whose boiling point is less than 90 degreeC and 90 degreeC or more according to the other component to be used. Among them, in order to exert an excellent effect, when the total amount of organic solvent is 100% by mass, the organic solvent having a boiling point of less than 90 ° C. is 20 to 80% by mass, and the organic solvent having a boiling point of 90 ° C. or more is 80 to 80%. It is preferable to set it as 20 mass%.

  Moreover, the compounding quantity in the case of using D component is 5-900 mass parts with respect to a total of 100 mass parts of A component and B component from the viewpoint of the effect acquired by D component addition as mentioned above, especially. It is preferable to set it as 100-750 mass parts, and it is most preferable to set it as 200-600 mass parts.

(water)
By adding water to the photochromic polymerizable composition of the present invention, the oxazolidine ring-containing compound (B) is opened, and the reaction between the urethane prepolymer (A) and the oxazolidine ring-containing compound (B) at the time of coating is performed. It can be easily advanced.

  When water is blended, it is preferably blended within a range of 0.1 to 5 moles per mole of the oxazolidine ring contained in the oxazolidine ring-containing compound (B). Moreover, when mix | blending water, it is preferable to mix just before using the photochromic polymerization composition of this invention. Further, water can be substituted by moisture in the atmosphere.

(Isocyanate compound having at least one isocyanate group in the molecule)
It is also possible to mix | blend the isocyanate compound which has at least 1 isocyanate group in a molecule | numerator with the photochromic polymerizable composition of this invention. As this isocyanate compound, a well-known isocyanate compound can be used without any limitation. These may be used alone or in combination of two or more.

  Examples of the isocyanate compound include 1-adamantyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, hexane isocyanate, nonyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, in addition to the polyisocyanate compound exemplified as the A2 component. And compounds having one isocyanate group in the molecule, such as 4-methylcyclohexyl isocyanate. Among these, it is preferable to use an isocyanate compound having 2 to 3 isocyanate groups in the molecule. Further, these isocyanate compounds preferably have a molecular weight of 1000 or less. Since the isocyanate compound is not a polymer, the molecular weight refers to the molecular weight of the compound itself.

When blending the isocyanate compound, the amount thereof is too large, the reaction proceeds with oxazoline di emissions ring-containing compound (B), which may reduce the effect of the present invention. Therefore, when mix | blending this isocyanate compound, it mix | blends in the range from which the mole number of the isocyanate group of this isocyanate compound becomes 0.05 to 0.5 time the mole number of the isocyanate group of a urethane prepolymer (A). It is preferable.

(Other ingredients)
Further, the photochromic polymerizable composition used in the present invention includes a surfactant, an antioxidant, and a radical scavenging agent for the purpose of improving the durability of the photochromic compound, improving the color developing speed, improving the fading speed, and forming the film. Additives such as additives, 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 polymerizable 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 1 part by mass with respect to 100 parts by mass of the urethane polymer (component A) having a polymerizable group.

  Antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenolic radical scavengers, sulfur antioxidants, phosphorus antioxidants, A triazine compound, a benzotriazole compound, a benzophenone compound, or the like can be preferably used. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. Furthermore, when using these additives, surfactants and antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination. The addition amount of these antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers is 0.001 to 20 masses per 100 mass parts in total of the urethane prepolymer (A) and the oxazolidine ring-containing compound (B). A range of parts is preferred. However, if these additives are used excessively, the adhesiveness of the photochromic polymerizable composition to an optical sheet or film made of polycarbonate resin is lowered, so the amount added is preferably 7 parts by mass or less, more preferably 3 parts by mass or less, most preferably 1 part by mass or less.

  An adhesive may be added to the photochromic polymerizable composition used in the present invention for the purpose of improving the adhesion between the photochromic adhesive sheet and the optical sheet. Specific examples include terpene resins, terpene phenol resins, phenol resins, hydrogenated terpene resins, rosin resins, xylene resins, acrylic adhesives, silicone adhesives, urethane adhesives, and the like.

  To the photochromic polymerizable composition used in the present invention, inorganic oxide fine particles and organic / inorganic composite materials are added for the purpose of improving the heat resistance of the photochromic adhesive sheet and reducing the solubility in the polymerizable monomer. May be. Inorganic oxide fine particles include metal oxide sols such as silica sol dispersed in organic solvents such as methanol, methyl ethyl ketone, propylene glycol monomethyl ether, etc., and organic / inorganic hybrid materials include silica / melamine hybrid materials, silica / Examples thereof include a urethane hybrid material, a silica / acrylic hybrid material, and a silica / epoxy resin hybrid material.

(Method for producing photochromic polymerizable composition)
The photochromic polymerizable composition of the present invention can be produced by mixing the A component, the B component, the C component, and other components. The order in which the components are mixed is not particularly limited.

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

Photochromic polymerizable composition of the present invention, water may be mixed, but in this case, it is preferable that the blended so as not to contact oxazoline di emissions ring-containing compound (B) at an early stage. Therefore, when water is blended, it is preferable to blend water immediately before use.

  Further, as described above, this water can be replaced with moisture. Therefore, if at least one of the step of forming the adhesive layer described in detail below and the step of bonding the optical sheet or optical film through the adhesive layer is performed in the presence of moisture, water is added. Effect. In particular, it is preferable to perform the step of bonding the optical sheet or the optical film in the presence of moisture.

  The photochromic polymerizable composition of the present invention thus obtained can be suitably used as a photochromic adhesive, particularly a photochromic adhesive (layer) for joining optical sheets or films made of polycarbonate resin. And the optical article of this invention can be obtained by joining an optical sheet or an optical film mutually through the contact bonding layer which consists of a photochromic polymeric composition of this invention. Hereinafter, the optical article of the present invention and the method for producing the optical article will be described.

(Optical article of the present invention)
The optical article of the present invention comprises a laminated structure in which two optical sheets or optical films facing each other are bonded via an adhesive layer made of the photochromic polymerizable composition of the present invention. As such an optical article,
A photochromic laminated sheet or film comprising only the laminated structure (hereinafter, also simply referred to as a laminate of the present invention);
A composite laminate in which an optical sheet or a film is further laminated on these laminates, or a coat layer such as a hard coat layer is formed on the surface;
These laminates, and optical articles obtained by integrating the composite laminate with an optical substrate such as a plastic lens body can be exemplified. As a method for integrating with an optical substrate such as a plastic lens body, for example, heat for forming an optical substrate (for example, a lens body) such as a polycarbonate resin after mounting the laminate of the present invention in a mold. A method of injection-molding a plastic resin (hereinafter also simply referred to as an injection molding method), a method of sticking the laminate of the present invention to the surface of an optical substrate with an adhesive or the like, and embedding the laminate in a polymerizable monomer And a method of polymerizing a polymerizable monomer. Hereinafter, these materials or members constituting the optical article of the present invention will be described.

(Optical sheet and film)
In the present invention, as the optical sheet and the optical film, a light-transmitting sheet and film can be used without any particular limitation. It is preferable to do. Examples of resins suitable as raw materials for optical sheets and optical films include polycarbonate resins, polyethylene terephthalate resins, nylon resins, triacetyl cellulose resins, acrylic resins, urethane resins, allyl resins, epoxy resins, and polyvinyl alcohol resins. It is done. 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.

  In addition, the two optical sheets facing each other in the present invention may be sheets made of the same resin or sheets made of different resins.

  The thickness of the optical sheet or optical film is not particularly limited, but is usually 50 μm to 1 mm, preferably 0.1 mm to 0.5 mm. When the thickness is less than 50 μm, the optical sheet or film is distorted when cured in a state where the optical sheet or film is embedded in a polymerizable monomer as a base material. On the other hand, when the thickness of the optical sheet or film exceeds 1 mm, the resulting photochromic lens becomes thick, which is not preferable for eyeglass use, and curved surface processing becomes difficult.

  The optical sheet or optical film used in the present invention may be modified by a known method. For example, in order to further improve the adhesion due to the photochromic polymerizable composition, it is possible to use a surface modified one. The modification method is not particularly limited, and examples thereof include plasma discharge treatment, corona treatment, flame treatment, chemical treatment with acid, alkali chemicals, and the like. In addition to improving adhesion, a multilayer optical sheet or film and an optical sheet or film having a coating layer can also be used to provide other functions.

Method for Producing Photochromic Laminate The laminate of the present invention is produced by joining two optical sheets or optical films facing each other via an adhesive layer (sheet) made of the photochromic polymerizable 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 adhesive layer can be obtained by the following method depending on the properties of the photochromic polymerizable composition to be used. That is, when the photochromic polymerizable composition of the present invention is prepared to have an appropriate viscosity by blending an organic solvent or the like, the photochromic polymerizable composition of the present invention is applied onto one optical sheet or optical film. If necessary, after drying (heating), another optical sheet or optical film may be (heated) pressure bonded. At this time, as a method for applying the photochromic polymerizable composition, known methods such as a spin coating method, a spray coating method, a dip coating method, a dip-spin coating method, and a dry laminating method are used without any limitation. The photochromic polymerizable composition is applied, and the drying is preferably performed at a temperature of room temperature to 100 ° C. and a humidity of 10 to 100% RH. By carrying out the drying under these conditions, the hydrolysis reaction of the B component oxazolidine ring is accelerated, and better adhesion, heat resistance, and solvent resistance can be obtained.

  Moreover, when using the photochromic polymerizable composition of the present invention containing an organic solvent, after spreading the photochromic polymerizable composition of the present invention on a smooth substrate, the organic solvent (D) is dried and dried. Removing and preparing a photochromic adhesive sheet containing a urethane prepolymer (A), an oxazolidine ring-containing compound (B), and a photochromic compound (C), and between two optical sheets or optical films facing each other The laminate of the present invention can also be produced by performing the step of joining the two optical sheets or optical films in the presence of water with the photochromic adhesive sheet interposed therebetween.

  As the material for the smooth base material, those which are resistant to the solvent used in the present invention and those in which the urethane polymer of the present invention is easy to peel off are preferable. Specific examples include glass, stainless steel, polytetrafluoro Examples thereof include ethylene and polyethylene terephthalate. 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.

  Next, the photochromic adhesive sheet produced on the smooth base material is peeled off from the base material and interposed between two optical sheets or optical films facing each other. And what is necessary is just to join an optical sheet or an optical film by a well-known method, for example, pressure bonding (heat pressure bonding). Under the present circumstances, a laminated structure is formed by setting it as the conditions which the said urethane prepolymer (A) and the said oxazolidine ring containing compound (B) contained in a photochromic adhesive sheet react.

  The conditions under which the urethane prepolymer (A) and the oxazolidine ring-containing compound (component B) are reacted may be those under which the oxazolidine ring is hydrolyzed with water. Although this water may be mix | blended with a photochromic polymerizable composition, it can substitute by joining an optical sheet or an optical film in a humid atmosphere. By hydrolyzing the oxazolidine ring, the produced amino alcohol reacts with the isocyanate group of the urethane prepolymer (A) to form a crosslinked structure. By forming this crosslinked structure, the resulting photochromic adhesive layer exhibits excellent heat resistance, solvent resistance, and adhesion. Specifically, it is preferably performed at a temperature of room temperature to 100 ° C. and a humidity of 10 to 100% RH, and at a temperature of room temperature to 80 ° C. and a humidity of 50 to 100% RH. Is more preferable.

  When using the photochromic polymerizable composition of the present invention that does not contain an organic solvent, it is also possible to produce a photochromic adhesive sheet by coextrusion molding or the like. And what is necessary is just to manufacture a photochromic laminated body using this adhesive sheet.

The photochromic laminate obtained by the above method can be used as it is, but it can also be used by stabilizing the state by the following method. In the stabilization treatment, the urethane prepolymer (A) and the oxazolidine ring-containing compound (component B) can be reacted. Specifically, it is preferable to leave the laminated body just joined at a temperature of 20 ° C. or more and 60 ° C. or less for 12 hours or more. The upper limit of the standing time is not particularly limited, but 50 hours is sufficient. 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). By this heat treatment, oxazoline di emissions ring-containing compound ring-opening (B), and the isocyanate group of the urethane prepolymer (A) is really what the command is considered to react. Therefore, the photochromic adhesive sheet is interposed between two optical sheets or optical films facing each other, and then the bonded laminate is left to stand under the above conditions, and then the heat treatment is performed, whereby the photochromic lamination is performed. The body is preferable.

Example of use of photochromic laminate (photochromic lens)
The photochromic laminated sheet is preferably used with an optical substrate bonded to at least one surface thereof. Examples of the optical substrate include thermoplastic resins such as the polycarbonate resin described above. In this case, the thermoplastic resin can be laminated on the photochromic laminate by injection molding / thermocompression bonding. Since the adhesive sheet made of the photochromic polymerizable composition of the present invention has improved adhesion and heat resistance, it can be suitably used when a photochromic lens is produced by such a method.

  Moreover, after the said photochromic laminated body is embed | buried in a polymerizable monomer, a thermosetting resin can be laminated | stacked on this laminated body by hardening this polymerizable monomer. Examples of the polymerizable monomer include those capable of forming a thermosetting resin such as a (meth) acrylate monomer composition, an allyl monomer composition, a thiourethane monomer composition, a urethane monomer composition, and a thioepoxy monomer composition. Can do. Since the adhesive sheet made of the photochromic polymerizable composition of the present invention has improved solvent resistance, it can also be suitably used when producing a photochromic lens by such a method.

  The present invention is further illustrated by the following examples. These examples are merely to illustrate the present invention, and the spirit and scope of the present invention are not limited to these examples. The abbreviations of the compounds used as the respective components in the examples and comparative examples are summarized below.

(A1 component; polyol compound)
PL1: Duranol (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 800) manufactured by Asahi Kasei Chemicals Corporation.
PL2: Polypropylene diol (number average molecular weight 700) manufactured by Asahi Glass Co., Ltd.
(A2 component; polyisocyanate compound)
NCO1: isophorone diisocyanate.
NCO2: 4,4′-methylenebis (cyclohexyl isocyanate).
NCO3: Toluene-2,4-diisocyanate.

(A3 component; chain extender)
CE1: Isophorone diamine.

(A4 component; reaction terminator)
S1: 1-methyl-2,2,6,6-tetramethyl-4-aminopiperidine.

(Component B: Oxazolidine ring-containing compound)
OX1; a polycyclic compound obtained by reacting 2 mol of N-hydroxyethyl-2-ethyloxazolidine with 1 mol of isophorone diisocyanate.

Synthesis method of OX1 A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 2 mol (262 g) of N-hydroxyethyl-2-ethyloxazolidine and 1 mol (222 g) of isophorone diisocyanate in a nitrogen atmosphere. The reaction was allowed to proceed at 80 ° C. for 8 hours to obtain OX1 represented by the following formula.

  OX2: a polycyclic compound obtained by reacting 2 mol of N-hydroxyethyl-2-phenyloxazolidine with 1 mol of isophorone diisocyanate.

Synthesis method of OX2 A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 2 mol (358 g) of N-hydroxyethyl-2-phenyloxazolidine and 1 mol (222 g) of isophorone diisocyanate in a nitrogen atmosphere. The reaction was allowed to proceed at 80 ° C. for 8 hours to obtain OX2 represented by the following formula.

(C component: photochromic compound)
PC1: Compound represented by the following formula.

(D component: organic solvent)
D1: THF (tetrahydrofuran).
D2: Toluene.
D3: Ethyl acetate.

(Component A: Synthesis of urethane prepolymer (U1))
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 216 g of polycarbonate polyol (PL1) having a number average molecular weight of 800 and 100 g of isophorone diisocyanate (NCO1), and reacted at 80 ° C. for 6 hours in a nitrogen atmosphere. To obtain a urethane prepolymer (U1). The number average molecular weight of the obtained urethane prepolymer (U1) was 1,800 (theoretical value: 1,700) in terms of polyoxyethylene. The theoretical value of the number average molecular weight referred to here is the molecular weight when the A1 component and A2 component used as raw materials theoretically form a urethane prepolymer without cross-linking. Moreover, when the isocyanate group of (U1) obtained was quantified, it confirmed that it has an average of two isocyanate groups in 1 molecule.

  In addition, the quantification of the isocyanate group was confirmed by the following back titration method and the number average molecular weight. In this back titration method, first, n-butylamine having an excess amount and a known concentration is added to the isocyanate group contained in the obtained urethane prepolymer. n-Butylamine is partially consumed by reacting with isocyanate groups. The system is then titrated with acid to determine the amount of n-butylamine consumed, thereby determining the isocyanate group content. The consumed n-butylamine and the isocyanate group are the same amount.

  The isocyanate group was calculated from the content of the isocyanate group determined by the back titration method and the measurement result of the number average molecular weight.

(Component A: Synthesis of urethane prepolymer (U2))
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 216 g of polycarbonate polyol (PL1) having a number average molecular weight of 800 and 100 g of isophorone diisocyanate (NCO1), and reacted at 80 ° C. for 6 hours in a nitrogen atmosphere. I let you. Thereafter, 500 ml of THF was added, and 7.7 g of isophoronediamine (CE1) was added dropwise under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was reacted at 25 ° C. for 1 hour, and the solvent was distilled off under reduced pressure to obtain a urethane prepolymer ( U2) was synthesized. The number average molecular weight of the obtained urethane prepolymer (U2) was 3,000 (theoretical value: 2,000) in terms of polyoxyethylene. The number of isocyanate groups in the molecule was 2 on average.

(Component A: Synthesis of urethane prepolymer (U3))
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 216 g of polycarbonate polyol (PL1) having a number average molecular weight of 800 and 100 g of isophorone diisocyanate (NCO1), and reacted at 80 ° C. for 6 hours in a nitrogen atmosphere. I let you. Thereafter, 500 ml of THF was added, and 7.7 g of isophoronediamine (CE1) was added dropwise under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was reacted at 25 ° C. for 1 hour, and then 1-methyl-2,2,6,6. -Tetramethyl-4-aminopiperidine (S1) 7.7g was added, it was made to react at 25 degreeC for 1 hour, and the urethane prepolymer (U3) was obtained by depressurizingly distilling a solvent. The number average molecular weight of the obtained urethane prepolymer (U3) was 4,000 (theoretical value: 3,000) in terms of polyoxyethylene. In addition, the average number of isocyanate groups in the molecule was 1.3.

(Component A: Synthesis of urethane prepolymers (U4) to (U11))
Except for using the polyol compound (A1 component), the polyisocyanate compound (A2 component), the chain extender (A3 component), the reaction terminator, and the reaction solvent shown in Table 1, except that the reaction conditions shown in Table 1 were used. In the same manner as in U1 to U3, U4 to U11 were synthesized. Tables 1 and 2 summarize the results of the blending ratio, synthesis conditions, number average molecular weight, and number of isocyanate groups of the obtained urethane prepolymer.

Example 1
(Preparation of photochromic polymerizable composition)
14.5 g of THF as an organic solvent was added to 4.35 g of urethane prepolymer (U1), and dissolved by stirring. After confirming that the urethane prepolymer (U1) was dissolved, the mixture was cooled to room temperature, 0.25 g of the photochromic compound (PC1) and 0.65 g of the oxazolidine-containing compound (OX1) were added, and mixed by stirring to obtain a photochromic polymerizable composition. Obtained. When the storage stability of this photochromic polymerizable composition was evaluated, it was 1 of the following evaluation methods.

[Evaluation Item: Photochromic Polymerizable Composition]
(Storage stability)
The obtained photochromic polymerizable composition was sealed with nitrogen sealed in a glass container, and the storage stability was evaluated by measuring the molecular weight after standing at 25 ° C. for 1 month. Evaluation criteria were implemented by the evaluation of 1-3 steps shown below.
1: The molecular weight is 1.0 to 1.2 times lower than the molecular weight at the start of storage.
2: Compared with the molecular weight at the start of storage, the molecular weight is 1.3 to 2.0 times or less.
3: The molecular weight is 2.1 times or more compared to the molecular weight at the start of storage.

(Production of photochromic laminate (optical article))
The obtained photochromic polymerizable composition was applied to a PET film (Purex film manufactured by Teijin DuPont Films, Inc., with a silicon coating), and in a laboratory in the presence of moisture (23 ° C., humidity 50%), It was dried at 50 ° C. for 30 minutes to obtain a photochromic adhesive sheet having a thickness of about 40 μm. Next, the obtained photochromic adhesive sheet is sandwiched between two 400 μm-thick polycarbonate sheets, allowed to stand at 40 ° C. for 24 hours, and further heat-treated at 110 ° C. for 60 minutes, thereby having the desired photochromic characteristics. A laminate was obtained.

  When the obtained photochromic laminate was evaluated by the following method, the peel strength was 130 N / 25 mm in the initial stage and 115 N / 25 mm after the boiling test. Moreover, about solvent resistance, it was 1 with the following evaluation criteria with respect to any polymerizable monomer composition, and was favorable.

[Evaluation item: Photochromic laminate]
(Peel strength)
The obtained laminate is used as a test piece having an adhesive part of 25 × 100 mm, mounted on a testing machine (Autograph AG5000D, manufactured by Shimadzu Corporation), subjected to a tensile test at a crosshead speed of 100 mm / min, and a peel strength is measured. did. The photochromic laminate used as the test piece is the one before and after the boiling test. In addition, the photochromic laminated body of a boiling test refers to what was left to stand in the boiling water for 1 hour.

(Solvent resistance)
The obtained photochromic laminate was cut into a circle having a diameter of 65 mm and immersed in various polymerizable monomer compositions shown below at room temperature for 12 hours, and then the appearance of the photochromic laminate was visually evaluated. Further, the elution amount of the photochromic compound was quantified using high performance liquid chromatography. The evaluation criteria were implemented by four-step evaluation of 1-4 as shown below.

(Evaluation criteria for solvent resistance)
1: Elution of a urethane resin and a photochromic compound is observed at least partially at a portion of 0.2 mm or less from the end of the photochromic laminate, but peeling between the optical sheet and the photochromic adhesive layer is not observed. The elution amount of the photochromic compound was 0.5 wt% or less of the total amount contained in the photochromic laminate.
2: Elution of the urethane resin and the photochromic compound is observed at least partially at a portion of 0.5 mm or less from the end of the photochromic laminate, but peeling between the optical sheet and the photochromic adhesive layer is not observed. The elution amount of the photochromic compound was 1.0 wt% or less of the total amount contained in the photochromic laminate.
3: The elution of the urethane resin and the photochromic compound is observed at least partially at a portion of less than 1.0 mm from the end of the photochromic laminate, but peeling between the optical sheet and the photochromic adhesive layer is not observed. The elution amount of the photochromic compound was less than 2.0 wt% of the total amount contained in the photochromic laminate.
4: Elution of the urethane resin and the photochromic compound is observed at least partially at a portion of 1.0 mm or more from the end of the photochromic laminate, and further, peeling between the optical sheet and the photochromic adhesive layer is observed. The elution amount of the photochromic compound was 2.0 wt% or more in the amount contained in the entire photochromic laminate.

(Polymerizable monomer composition used for solvent resistance evaluation)
Z1 (acrylate monomer composition); a mixture of 20 parts by mass of trimethylolpropane trimethacrylate, 40 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 522, and 40 parts by mass of urethane acrylate (EBECRYL4858 manufactured by Daicel Chemical Industries).
Z2 (allyl monomer composition); diethylene glycol bisallyl carbonate.
Z3 (thiourethane-based monomer composition): a mixture of 100 parts by mass of dicyclohexylmethane-4,4′-diisocyanate and 63.0 parts by mass of 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane .
Z4 (urethane-based monomer composition); 100 parts by mass of a polyester polyol having a number average molecular weight of 1000 consisting of adipic acid and 1,6-hexanediol, 78 parts by mass of an isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate), and Mixture of 17 parts by mass of 2,4-diamino-3,5-diethyl-toluene / 2,6-diamino-3,5-diethyl-toluene as an aromatic diamine curing agent.
Z5 (thioepoxy monomer composition); a mixture of 95 parts by mass of bis (β-epithiopropylthio) ethane and 5 parts by mass of 2-mercaptoethanol.

(Manufacture of photochromic lenses (optical articles))
Next, the obtained photochromic laminate was cut into a circle having a diameter of 65 mm and placed in a glass mold having a gasket (0.00D, lens diameter 70 mm, wall thickness set to 3.0 mm). A mixture of 3 parts by weight of diisopropyl peroxydicarbonate as a polymerization initiator and 100 parts by weight of diethylene glycol bisallyl carbonate, which was prepared as a thermosetting composition, was filled on the top and bottom of the installed laminate.

  A glass mold filled with the thermosetting composition was placed in an air furnace, gradually heated from 40 to 90 ° C. over 20 hours, and further held at 90 ° C. for 1 hour for polymerization. After completion of the polymerization, the gasket and the mold were removed, and then heat treatment was performed at 120 ° C. for 2 hours to obtain a photochromic lens.

  When the obtained photochromic lens was evaluated by the following method, the color density as a photochromic characteristic was 1.2, the color fading speed was 55 seconds, and the durability was 95%. In addition, the appearance of the obtained photochromic lens was satisfactory because it did not show elution of the photochromic compound or the polyurethane resin layer, and was one of the following evaluation criteria.

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

  Maximum absorption wavelength (λmax): 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.

  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) at the maximum absorption wavelength when not irradiated. It can be said that the higher this value, the better the photochromic properties.

  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 ½ of [ε (120) −ε (0)]. The time it takes to drop. It can be said that the shorter this time is, the better the photochromic property is.

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

(Appearance evaluation)
The obtained photochromic lens was visually evaluated. The evaluation criteria were implemented by four-step evaluation of 1-4 as shown below.
1: The elution of the urethane resin and the photochromic compound is observed in at least part of the portion of 0.2 mm or less from the end of the photochromic laminate, but “optical sheet and photochromic adhesive layer” and “optical sheet and thermosetting” No peeling is observed in any of “between the functional resins”.
2: Elution of urethane resin and photochromic compound is observed in at least part of the portion of 0.5 mm or less from the end of the photochromic laminate, but “optical sheet and photochromic adhesive layer” and “optical sheet and thermosetting” No peeling is observed in any of “between the functional resins”.
3: Elution of urethane resin and photochromic compound is observed in at least part of the portion less than 1.0 mm from the edge of the photochromic laminate, but “optical sheet and photochromic adhesive layer” and “optical sheet and thermosetting” No peeling is observed in any of “between the functional resins”.
4: Elution of urethane resin and photochromic compound was observed in at least part of the portion of 1.0 mm or more from the end of the photochromic laminate, and “optical sheet and photochromic adhesive layer” and “optical sheet and thermosetting” Peeling is observed in any of “between the functional resins”.

  The above results are summarized in Tables 3 and 4.

Examples 2-17
A photochromic polymerizable composition was prepared in the same manner as in Example 1 except that the urethane prepolymer (A) and the oxazolidine ring-containing compound (component B) shown in Table 3 were used. As in Example 1, 5 parts by mass (actual use amount 0.25 g) of the photochromic compound (PC1) with respect to the total mass of the urethane prepolymer (A) and the oxazolidine ring-containing compound (B component), and an organic solvent (D component) was mix | blended. Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic polymerizable composition, and also the photochromic lens was produced. Table 3 and Table 4 show the evaluation results of various photochromic laminates and photochromic lenses obtained.

Comparative Examples 1 and 2
A photochromic polymerizable composition was prepared in the same manner as in Example 1 except that the urethane polymer shown in Table 1 was used. As in Example 1, the photochromic compound (PC1) was added in an amount of 5 parts by mass (actual amount used: 0.25 g) based on the total mass of the urethane prepolymer (A) and the oxazolidine ring-containing compound (component B). , And an organic solvent (component D). Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic polymerizable composition, and also the photochromic lens was produced. Table 3 and Table 4 show the evaluation results of various photochromic laminates and photochromic lenses obtained.

Comparative Example 3
The urethane prepolymer (U13-a) having an isocyanate group at the end of the molecular chain and the urethane prepolymer (U13-b) having a hydroxyl group at the end of the molecular chain were synthesized by the following methods.

Synthesis of urethane prepolymer (U13-a) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 211 g of a polyol compound (PL2: polypropylene glycol) having a number average molecular weight of 700, 4,4′-methylenebis 118 g of (cyclohexyl isocyanate) (NCO2) was charged and reacted at 80 ° C. for 9 hours in a nitrogen atmosphere to obtain a urethane prepolymer (U13-a) having an NCO group at the terminal. The number average molecular weight of the urethane prepolymer (U13-a) was 2,200 (theoretical value; 2,200) in terms of polyoxyethylene.

Synthesis of urethane prepolymer (U13-b) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 241 g of a polyol compound (PL2: polypropylene glycol) having a number average molecular weight of 700, toluene-2,4- 30 g of diisocyanate (NCO3) was charged and reacted at 80 ° C. for 9 hours under a nitrogen atmosphere to obtain a urethane prepolymer (U13-b) having an OH group at the terminal. The number average molecular weight of the urethane prepolymer (U13-b) was 1,600 (theoretical value: 1,600) in terms of polyoxyethylene.

  Using the urethane prepolymer (U13-a) and urethane prepolymer (U13-b) obtained as described above in the amounts shown in Table 5, THF (D1) 20 g as an organic solvent, and a photochromic compound (PC1) 0.25 g was used, and a photochromic polymerizable composition was prepared in the same manner as in Example 1. Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic polymerizable composition, and also the photochromic lens was produced. The evaluation results are shown in Table 5. The synthesis conditions of the urethane prepolymer used are shown in Table 1, and the ratio of each component of the urethane prepolymer and other physical properties are shown in Table 2.

Comparative Example 4
By the following methods, a urethane prepolymer (U14-a) having an isocyanate group at the end of the molecular chain and a urethane prepolymer (U14-b) having a hydroxyl group at the end of the molecular chain were synthesized.

Synthesis of urethane prepolymer (U14-a) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 289 g of a polyol compound (PL1: polycarbonate diol) having a number average molecular weight of 800 and 120 g of isophorone diisocyanate (NCO1) Was reacted at 80 ° C. for 9 hours under a nitrogen atmosphere to obtain a urethane prepolymer (U14-a) having an NCO group at the terminal. The number average molecular weight of the urethane prepolymer (U14-a) was 2,300 (theoretical value; 2,300) in terms of polyoxyethylene.

Synthesis of urethane prepolymer (U14-b) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 276 g of a polyol compound (PL1: polycarbonate diol) having a number average molecular weight of 800, toluene-2,4- 30 g of diisocyanate (NCO 3) was charged and reacted at 80 ° C. for 9 hours under a nitrogen atmosphere to obtain a urethane prepolymer (U14-b) having an OH group at the terminal. The number average molecular weight of the urethane prepolymer (U14-b) was 1,800 (theoretical value: 1,800) in terms of polyoxyethylene.

  The urethane prepolymer (U14-a) and urethane prepolymer (U14-b) obtained as described above were used in the amounts shown in Table 5, 20 g of THF (D1) as an organic solvent, and a photochromic compound (PC1) 0.25 g was used, and a photochromic polymerizable composition was prepared in the same manner as in Example 1. Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic polymerizable composition, and also the photochromic lens was produced. The evaluation results are shown in Table 5. The synthesis conditions of the urethane prepolymer used are shown in Table 1, and the ratio of each component of the urethane prepolymer and other physical properties are shown in Table 2.

  As apparent from Examples 1 to 17, in the photochromic polymerizable composition containing the urethane prepolymer (A), the oxazolidine ring-containing compound (component B) and the photochromic compound (component C), excellent solvent resistance, It can be seen that it has photochromic properties, peel strength (adhesion), heat resistance, and storage stability.

  On the other hand, as in Comparative Examples 1 to 4, the oxazolidine ring-containing compound was not added (Comparative Example 1), a urethane polymer having no isocyanate group (Comparative Example 2), or a two-component urethane polymer (Comparative Examples 3 and 3). 4), the physical properties such as solvent resistance, photochromic properties, peel strength (adhesiveness), heat resistance and storage stability cannot be satisfied at the same time, and any of the physical properties is insufficient. It was.

Claims (11)

Urethane prepolymer (A) having at least one isocyanate group in the molecule,
Oxazoline di emissions ring-containing compound having at least one oxazolidine ring in the molecule (B), and photochromic compound (C)
A photochromic polymerizable composition comprising: The total number of moles of isocyanate groups contained in the urethane prepolymer (A) is n,
When the total number of moles of the oxazolidine ring contained in the oxazolidine ring-containing compound (B) is o,
n: o = 0.5-10: 1
The photochromic polymerizable composition according to claim 1, which has a quantitative ratio of The urethane prepolymer (A) is
A polyol compound (A1) having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule;
A urethane prepolymer obtained by reacting a polyisocyanate compound (A2) having two or more isocyanate groups in the molecule,
The total number of moles of hydroxyl groups contained in the component (A1) is n1,
The total number of moles of isocyanate groups contained in the component (A2) is n2,
And when
The photochromic polymerizable composition according to claim 1, which is reacted at a quantitative ratio of n1: n2 = 0.4 to 0.9: 1. The urethane prepolymer (A) is
A polyol compound (A1) having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule;
A polyisocyanate compound (A2) having two or more isocyanate groups in the molecule;
A urethane prepolymer obtained by reacting a chain extender (A3) having a molecular weight of 50 to 300 having a group capable of reacting with two or more isocyanate groups in the molecule,
The total number of moles of hydroxyl groups contained in the component (A1) is n1,
The total number of moles of isocyanate groups contained in the component (A2) is n2,
When the total number of moles of the group capable of reacting with the isocyanate group contained in the component (A3) is n3,
2. The photochromic polymerizable composition according to claim 1, wherein the photochromic polymerizable composition is reacted at a ratio of n1: n2: n3 = 0.4 to 0.85: 1: 0.05 to 0.5. The urethane prepolymer (A) is
A polyol compound (A1) having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule;
A polyisocyanate compound (A2) having two or more isocyanate groups in the molecule;
A urethane prepolymer obtained by reacting a reaction terminator (A4) having a piperidine structure in the molecule and having a group capable of reacting with one isocyanate group,
The total number of moles of hydroxyl groups contained in the component (A1) is n1,
The total number of moles of isocyanate groups contained in the component (A2) is n2,
When the total number of moles of the group capable of reacting with the isocyanate group contained in the component (A4) is n4,
The photochromic polymerizable composition according to claim 1, wherein the photochromic polymerizable composition is reacted at a quantitative ratio of n1: n2: n4 = 0.4-0.90: 1: 0.01-0.09. The urethane prepolymer (A) is
A polyol compound (A1) having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule;
A polyisocyanate compound (A2) having two or more isocyanate groups in the molecule;
A chain extender (A3) having a molecular weight of 50 to 300 having a group capable of reacting with two or more isocyanate groups in the molecule;
A urethane prepolymer obtained by reacting a reaction terminator (A4) having a piperidine structure in the molecule and having a group capable of reacting with one isocyanate group,
The total number of moles of hydroxyl groups contained in the component (A1) is n1,
The total number of moles of isocyanate groups contained in the component (A2) is n2,
The total number of moles of the group capable of reacting with the isocyanate group contained in the component (A3) is n3,
When the total number of moles of the group capable of reacting with the isocyanate group contained in the component (A4) is n4,
2. The reaction according to claim 1, wherein n1: n2: n3: n4 = 0.3 to 0.8: 1: 0.05 to 0.5: 0.01 to 0.1. Photochromic polymerizable composition. For a total of 100 parts by mass of the urethane prepolymer (A) and the oxazolidine ring-containing compound (B),
The photochromic polymerizable composition according to claim 1, comprising 0.1 to 20 parts by mass of the photochromic compound (C).   The photochromic polymerizable composition according to claim 7, further comprising 5 to 900 parts by mass of an organic solvent (D) with respect to 100 parts by mass of the urethane prepolymer (A) and the oxazolidine ring-containing compound (B) in total. .   An optical article comprising a laminated structure in which two optical sheets or optical films facing each other are bonded via an adhesive layer obtained from the photochromic polymerizable composition according to claim 1.   The optical article according to claim 9, 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:
After extending the photochromic polymerizable composition according to claim 8 on a smooth substrate, the organic solvent (D) is removed by drying to remove the urethane prepolymer (A) and the oxazolidine ring-containing compound (B). And a step of preparing a photochromic adhesive sheet containing the photochromic compound (C), and interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other, in the presence of water Producing the laminated structure by joining two optical sheets or optical films;
A method comprising the steps of: