JP2012207198A - Photochromic composition and optical article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic composition which can function as an adhesive layer for bonding optical sheets made from a polycarbonate resin or the like and which can yield a laminate that exhibits excellent tight adhesion, heat resistance and photochromic properties, and to especially provide a photochromic composition that can form an adhesive layer that does not decrease the adhesion between optical sheets even if contacting with hot water.SOLUTION: The photochromic composition includes: a non-reactive polyurethane resin (component A); an isocyanate compound (component B); and a photochromic compound (component C).

Description

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

  In recent years, mainly in the United States, demand for plastic lenses using sunglasses having antiglare properties and polycarbonate having transparency and excellent impact resistance is rapidly increasing. Such plastic sunglasses, which contain a photochromic compound, are capable of adjusting the antiglare property by changing the transmittance according to the ambient brightness, and the plastic photochromic sunglasses are rapidly gaining popularity. .

  Such plastic photochromic sunglasses are 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, it is a method using a photochromic adhesive containing a photochromic compound and a polyurethane resin. 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, and injection molding or heat This is a method of pressure bonding. According to this method, plastic photochromic sunglasses having the laminate can be produced (see Patent Documents 1 to 4).

  Since the plastic photochromic sunglasses (optical article) obtained by this method have joined the surface of the laminate and the plastic lens by injection molding or thermocompression bonding, the adhesion at the interface between the laminate and the lens Is very expensive.

  In the optical article according to the method described in Patent Documents 1 and 2 above, it is considered to be due to the structure of the used polyurethane resin, but the optical sheet peels off because the adhesion between the optical sheet and the photochromic adhesive is not sufficient. (There was a case where the optical sheet peeled off because the adhesiveness of the photochromic laminate itself was not sufficient). Furthermore, since the heat resistance of the polyurethane resin is not sufficient, there is a problem that optical distortion occurs when performing injection molding or thermocompression bonding. Therefore, it has been required to improve the heat resistance of the matrix resin (polyurethane resin) itself of the layer made of the adhesive.

  On the other hand, the methods described in Patent Documents 3 and 4 employ a two-pack type polyurethane resin (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-component polyurethane resin and a photochromic compound is laminated on an optical sheet, and after the lamination, the two-component polyurethane resin 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 polyurethane resin is reacted after lamination to obtain a high molecular weight polyurethane resin, 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 everyday life, plastic photochromic sunglasses may come into contact with high humidity or hot water. Even under such circumstances, the adhesion between the optical sheet and the adhesive must be high. I must. However, in the photochromic adhesive obtained by reacting the two-component polyurethane resin, the optical sheet and the adhesive have high adhesion after being brought into contact with hot water, for example, while maintaining high photochromic properties. It was difficult to maintain and there was room for improvement.

US Patent Publication No. 20040966666 Special table 2003-519398 gazette US Published Patent No. 2005050233153 US Patent Publication No. 200202000655

  Therefore, the first object of the present invention is a photochromic composition having excellent adhesion and heat resistance and exhibiting excellent photochromic properties when used as an adhesive layer when bonding optical sheets or films. To provide things.

  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, the 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 conducted intensive studies on the relationship between the structure of the photochromic adhesive layer and the characteristics of the obtained optical article. As a result, a photochromic laminate obtained by using a photochromic composition containing an end-stopped polyurethane resin (non-reactive polyurethane resin), an isocyanate compound having an isocyanate group, and a photochromic compound for the photochromic adhesive. It has been found that the adhesion of the sheet itself (adhesion between the adhesive layer and the optical sheet), photochromic properties and durability can be improved.

  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. When a photochromic adhesive sheet comprising a specific polyurethane resin in which is dispersed is separately prepared and a photochromic laminate is produced using the “photochromic adhesive sheet”, adverse effects due to solvents can be avoided, and photochromic properties can be avoided. The inventors have found that the temperature does not decrease and have completed the present invention.

  That is, the present invention is shown in the following [1] to [13].

  [1] A photochromic composition comprising a non-reactive polyurethane resin (A), an isocyanate compound (B) having at least one isocyanate group in the molecule, and a photochromic compound (C).

[2] The non-reactive polyurethane resin (A) comprises a polyol compound (A1) having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule and a polysiloxane having two or more isocyanate groups in the molecule. An isocyanate group is formed at the end of the molecular chain obtained by reacting the isocyanate compound (A2) with 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 reactive polyurethane resin (A4) having,
Reaction stopper having a group capable of reacting with one isocyanate group in the molecule (A5)
The photochromic composition of [1], which is a non-reactive urethane resin obtained by reacting

[3] The component ratio (A1), component (A2), component (A3), and component (A5) used in obtaining the non-reactive polyurethane resin (A) is included in the component (A1). The total number of moles of hydroxyl groups is n1, the total number of isocyanate groups contained in the component (A2) is n2, the total number of moles of isocyanate group-reactive groups 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 (A5) is n5,
n1: n2: n3: n5 = 0.30-0.89: 1: 0.1-0.69: 0.01-0.20 The photochromic composition of [2] above.

  [4] The photochromic composition according to [1], wherein the isocyanate compound (B) has a molecular weight of less than 1000.

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

  [6] The photochromic composition according to [1], wherein 30% by mass or more of the polyisocyanate compound (A2) is at least one polyisocyanate compound selected from an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound. .

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

  [8] The photochromic composition according to [1], wherein the reaction terminator (A5) is a compound having a piperidine structure, a hindered phenol structure, a triazine structure, a benzotriazole structure, or an alkyl chain in the molecule.

  [9] The said isocyanate compound (B) containing 0.01-20 mass parts and said photochromic compound (C) 0.1-20 mass parts with respect to 100 mass parts of said non-reactive polyurethane resin (A). [1] The photochromic composition.

  [10] The photochromic composition according to [9], further including 5 to 900 parts by mass of an organic solvent (D) with respect to 100 parts by mass of the non-reactive polyurethane resin (A).

  [11] 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 composition of [1].

  [12] The optical article according to [11], 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.

[13] A method for producing the optical article according to [12],
After spreading the photochromic composition of [10] on a smooth substrate, the organic solvent (D) is removed by drying to remove the non-reactive polyurethane resin (A), the isocyanate compound (B), and the photochromic. A step of preparing a photochromic adhesive sheet containing the compound (C), and the two sheets in the presence of at least moisture by interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other. The step of producing the laminated structure by bonding the optical sheet or optical film of
A method comprising the steps of:

  The photochromic composition of the present invention functions as an adhesive or binder. A laminate (photochromic laminate) obtained by joining an optical sheet or film made of polycarbonate resin with an adhesive layer made of the composition exhibits excellent adhesion and excellent photochromic properties. Furthermore, since the adhesive layer exhibits excellent heat resistance, even when an optical article is manufactured by mounting the laminate on a mold and then injection molding a polycarbonate resin thermoplastic resin on the mold, Adhesiveness and photochromic properties are unlikely to deteriorate and optical distortion hardly occurs.

  Further, according to the method of the present invention, even if an optical sheet or film made of a thermoplastic resin such as polycarbonate having poor solvent resistance is used, adverse effects due to an organic solvent can be avoided, so that photochromic properties are not lowered. .

  The photochromic composition of the present invention includes a non-reactive polyurethane resin (A) (hereinafter also simply referred to as component A) and (B) an isocyanate compound having at least one isocyanate group in the molecule (hereinafter also simply referred to as component B). And (C) a photochromic compound (hereinafter also simply referred to as C component). Hereinafter, the A component, the B component, and the C component will be described.

Component A: Non-reactive polyurethane resin As described above, in the prior art, the polyurethane resin used for the photochromic adhesive is a group that can react with a reactive polyurethane resin (prepolymer) having an isocyanate group and an isocyanate group. After the prepolymer (polyol) having a mixture was mixed to form a coating film, both were reacted to increase the molecular weight. On the other hand, the component A used in the photochromic composition of the present invention is a non-reactive polyurethane resin, and the end of the polyurethane resin is inactivated. That is, the non-reactive polyurethane resin is a resin that does not react with the following isocyanate compound (B). The non-reactive polyurethane resin means a resin that does not cause a polymerization reaction such as addition polymerization, polycondensation, radical polymerization, ionic polymerization, or ring-opening polymerization. Specifically, the non-reactive polyurethane resin is an isocyanate group, hydroxyl group, amino group (—NH ₂ group), carboxyl group, thiol group, acid chloride group, epoxy group, alkoxysilyl group, hydrolysis of the alkoxysilyl group. The group which reacts with the other polymer or isocyanate compound (B) explained in full detail below, such as the group, (meth) acryloyl group, vinyl group, allyl group, etc. is pointed out. In order to obtain the non-reactive polyurethane resin, a reaction terminator (A5) having a group capable of reacting with one isocyanate group in the molecule described later is reacted with an isocyanate group remaining at the end of the polyurethane resin. , A non-reactive group can be introduced at the end of the polyurethane resin (a polyurethane resin having a terminated end can be produced).

  It is possible to use it as a photochromic adhesive by mixing a photochromic compound with the component A. However, the present invention combines the component A and the component B described in detail below to form a matrix resin of a photochromic adhesive (layer), thereby improving heat resistance, adhesion, and photochromic. The characteristic can be exhibited.

The non-reactive polyurethane resin as component A is a resin that does not have a reactive group such as an isocyanate group or a hydroxyl group in the molecule, and its production method is not particularly limited. Especially, in order that the obtained photochromic composition exhibits the outstanding heat resistance, adhesiveness, and a photochromic characteristic, it is preferable to manufacture with the following method. Specifically, first,
(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) a polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also simply referred to as A2 component),
(A3) A chain extender having a molecular weight of 50 to 300 (hereinafter also simply referred to as A3 component) having a functional group capable of reacting with two or more isocyanate groups in the molecule is reacted to form isocyanate at the end of the molecular chain. A reactive polyurethane resin having a group ((A4), hereinafter also simply referred to as A4 component) is obtained.

Next, this reactive polyurethane resin (A4),
(A5) A non-reactive polyurethane resin (A) can be produced by reacting a reaction terminator having a group capable of reacting with one isocyanate group in the molecule (hereinafter also simply referred to as A5 component). preferable. A non-reactive polyurethane resin (A) can be obtained by reacting a terminal isocyanate group of the reactive polyurethane resin (A4) with a group capable of reacting with the isocyanate group of the reaction terminator (A5). Hereinafter, these components will be described.

A1 component: polyol compound The polyol compound of the A1 component preferably has 2 to 6 hydroxyl groups in the molecule because the non-reactive polyurethane resin does not become a highly crosslinked product as the A component to be produced. Furthermore, considering the solubility in an organic solvent, the number of hydroxyl groups is more preferably 2 to 3.

  It is preferable that the number average molecular weight of A1 component is 400-3000. 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 density, fading speed, weather resistance, etc.) of the photochromic composition, among them, the number average molecular weight is 400 to 2500 from the viewpoint of the weather resistance of the photochromic compound. Preferably, 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 the polyether. Polymer polyols, urethane-modified polyether dipolyols, polyether ester copolymer polyols, etc., which are modified products of polyol compounds, can be mentioned.

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

  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 : The polycarbonate polyol used as the A1 component includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1 , 3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A ethylene oxide or propylene oxide adduct, bis ( β-hydro Transesterification method with polycarbonate polyol obtained by phosgenation of one or more kinds of low molecular polyols such as xylethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, or ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyol obtained by the above can be mentioned.

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

  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 As the “polyisocyanate compound having two or more isocyanate groups in the molecule” used as the A2 component in the present invention, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanates are used. Examples thereof include isocyanate compounds and mixtures thereof. 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. However, considering the solubility of the resulting non-reactive polyurethane resin, the number of isocyanate groups contained in the molecule is preferably 2. When a polyisocyanate compound having three or more isocyanate groups in the molecule is mainly used, the crosslinking density of the resulting non-reactive polyurethane resin is increased, and the solubility in an organic solvent may be reduced.

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

  Among these, from the viewpoint of the weather resistance of the resulting non-reactive polyurethane resin (the resulting photochromic composition), as described above, 30% by mass or more, particularly 50% by mass or more of the polyisocyanate compound of component A2 is aliphatic. It is preferably at least one polyisocyanate compound selected from a polyisocyanate compound and an alicyclic polyisocyanate compound. 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, norbornane diisocyanate , 4,4′-methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2, - diisocyanate, hexamethylene hydro-phenylene-1,3-diisocyanate are hexahydrophthalate phenylene-1,4-diisocyanate. These isocyanate compounds may be used alone or in combination of two or more.

  In addition, the polyisocyanate compound may be a compound having in its molecule a structure that imparts functionality such as light stability performance, antioxidant performance, or ultraviolet absorption performance. Hereinafter, a polyisocyanate compound having a piperidine structure that exhibits light stability is described as an example. The polyisocyanate compound includes a triisocyanate compound having three isocyanate groups in the molecule, a group capable of reacting with one isocyanate group in the molecule (amino group, hydroxyl group, carboxyl group, or thiol group) and a piperidine structure. And a reaction product with the compound. Examples of the triisocyanate compound include 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanato) hexanoate, and 1-methylbenzene-2. , 4,6-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate and the like. it can. In addition, examples of the compound having a piperidine structure and a group capable of reacting with one isocyanate group in the molecule include compounds represented by the general formula (1) described in the reaction terminator (A5) having the following piperidine structure. It is done. By reacting one isocyanate group of the triisocyanate compound with, for example, a group capable of reacting with an isocyanate group of a compound represented by the following general formula (1), two isocyanate groups exist in the molecule. A compound (diisocyanate compound) can be obtained.

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

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

A3 component: chain extender The chain extender used as the A3 component in the present invention is a compound having a molecular weight of 50 to 300 having a functional group capable of reacting with two 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 A3 component functions as a chain extender when synthesizing a polyurethane resin. By using the A3 component as a chain extender, the molecular weight, heat resistance, photochromic characteristics, etc. of the non-reactive polyurethane resin of the present invention Can be controlled. When the molecular weight of the chain extender is less than 50, the resulting non-reactive polyurethane resin tends to be too hard. Moreover, although the heat resistance of the obtained photochromic composition 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 non-reactive polyurethane resin tends to be too soft. Therefore, all of the heat resistance, adhesion, and photochromic properties of the obtained photochromic 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 of the present invention is preferably at least one chain extender selected from diamine compounds, triamine compounds, amino alcohol 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. The reactive group with an isocyanate group other than an amino group is a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), or a carboxyl group [—C (═O) OH group]. is there.

  Examples of suitable compounds as the amino group-containing compound of component A3 include diamine compounds and triamine compounds such as isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- (4-amino (Cyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, norbornanediamine, hydrazine, adipic acid dihydrazine, phenylenediamine 4,4′-diphenylmethanediamine, N, '-Diethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dipropylethylenediamine, N, N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) triamine, 1,2 , 5-pentanetriamine and the like.

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

A4 component: Reactive polyurethane resin having an isocyanate group at the end of the molecular chain The A4 component in the present invention is a reactive polyurethane resin having an isocyanate group at the end of the molecular chain obtained by reacting the components A1, A2 and A3. That is.

  When synthesizing the A4 component, a general one-shot method or a prepolymer method can be employed using the A1 component, the A2 component, and the A3 component. For example, as a prepolymer method, an A1 component and an A2 component are reacted to obtain a urethane prepolymer, and then the urethane prepolymer and an A3 component are reacted to form an isocyanate group at the end of the molecular chain that is the A4 component of the present invention. The reactive polyurethane resin which has can be manufactured.

  The amount ratio of the A1 component, the A2 component, and the A3 component will be described in detail below, but the amount ratio may be such that an isocyanate group is present at the end of the obtained A4 component. Specifically, the total number of moles of functional groups (specifically, hydroxyl groups) capable of reacting with the isocyanate group of the A1 component is n1, the total number of isocyanate groups contained in the A2 component is n2, and included in the A3 component When the total number of moles of the functional group that can react with the isocyanate group (specifically, an amino group, a hydroxyl group, a thiol group, or a carboxyl group) is n3, the total sum (n1 + n3) of n1 and n3 is from n2. The quantity ratio may be made smaller. Specifically, it is preferable to satisfy 0.01 ≦ n2− (n1 + n3) ≦ 0.2. The above n1, n2, and n3 can be determined as the product of the number of moles of the compound used as each component and the number of each group present in one molecule of the compound.

  The number average molecular weight of the A4 component obtained is preferably 5,000 to 150,000, more preferably 8,000 to 100,000, and particularly preferably 10,000 to 60,000. In addition, the molecular weight of this reactive polyurethane resin (A4 component) was measured using gel permeation chromatograph (GPC) in terms of polyethylene oxide, columns: Shodex KD-805, KD-804 (manufactured by Showa Denko KK). ), Eluent: LiBr (10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, polyurethane resin sample solution: 0.5% dimethylformamide (DMF) solution measured number average Refers to molecular weight.

A5 component: a reaction terminator having a group capable of reacting with one isocyanate group in the molecule A5 component used in the present invention is a reaction terminator having a group capable of reacting with one isocyanate group in the molecule, By using the A5 component, a nonreactive group can be introduced at the end of the nonreactive polyurethane resin of the present invention.

Examples of the group capable of reacting with the isocyanate group include an amino group (—NH ₂ group and —NH (R) group), a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), a carboxyl group [ -C (= O) OH group], or acid chloride group [-C (= O) OCl group].

  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 upon reaction with the A4 component has a high molecular weight and becomes highly viscous when diluted with an organic solvent, which makes coating difficult. Moreover, the adhesiveness (adhesion with an optical sheet) of the obtained photochromic adhesive will be reduced. By introducing the reaction terminator into the terminal of the non-reactive urethane resin of the present invention, it becomes possible to control the number average molecular weight of the non-reactive urethane resin, and the adhesion, heat resistance, and photochromic properties can be easily achieved. It can be 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 non-reactive polyurethane resin itself as component A and the photochromic compound. . Especially, in order to improve the durability of a photochromic compound, it is preferable to use the compound which has a piperidine structure. Hereinafter, various reaction terminators used as the A5 component will be described in detail.

Reaction Terminator Having Piperidine Structure As the reaction terminator having a piperidine structure used as the A5 component in the present invention, a compound having a structure represented by the following general formula (i) in the molecule can be preferably used.

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

  Hereinafter, more specific compounds will be described.

  Among the reaction terminators used as the A5 component in the present invention, as the compound capable of introducing a piperidine structure at the end of the reactive polyurethane resin, it is preferable to use a compound represented by the following general formula (1). It is mentioned in.

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

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

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

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

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

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

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

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

Reaction Terminator Having a Hindered Phenol Structure As a reaction terminator having a hindered phenol structure used as the A5 component in the present invention, a compound having a structure represented by the following general formula (ii) in the molecule is preferably used. it can.

(Where
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom,
At least one of R ⁷ and R ⁸ is an alkyl group having 4 or more carbon atoms. ). And the compound which has a group which can react with an isocyanate group in the 1st-position carbon atom of the said structure turns into a reaction terminator which has a hindered phenol structure. The hydroxyl group at the 4-position in the formula (ii) does not react with an isocyanate group due to the influence of the steric hindrance because at least one of R ⁷ and R ⁸ is an alkyl group. Therefore, the hydroxyl group at the 4-position is considered to be excluded from the group that can react with the isocyanate group.

  Having a structure as described above in the molecule and further having one group capable of reacting with an isocyanate group, a hindered phenol structure as a non-reactive group is formed at the end of the non-reactive polyurethane resin of component A. Can be introduced.

  Among the reaction terminators having a hindered phenol structure, a preferred compound includes the following general formula (2).

(Where
R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom, and at least one of R ⁷ and R ⁸ has 4 or more carbon atoms. An alkyl group,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms, or a polymethylene group having 3 to 10 carbon atoms, b is 0 or 1,
Y is a group capable of reacting with an isocyanate group. ).

In the general formula (2), R ⁷ and R ⁸ are an alkyl group having 1 to 18 carbon atoms or a hydrogen atom, and either one is an alkyl group having 4 or more carbon atoms. Preferably, one of R ⁷ and R ⁸ is a tert-butyl group. When one group is an alkyl group having 4 or more carbon atoms, the durability of the resulting photochromic composition can be further improved.

R ⁹ and R ¹⁰ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom, and more preferably an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

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

R ¹¹ is an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms or a polymethylene group having 3 to 5 carbon atoms. B represents the number of R ¹¹ and is 0 or 1. When b is 0, it means that Y is directly bonded to the benzene ring. A compound in which b is 0 is preferable.

  Specific examples of the reaction terminator having a hindered phenol structure include 3-methyl-4-hydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, and 3,5-dimethyl-4. -Hydroxybenzoic acid, 3-t-butyl-4-hydroxybenzoic acid, 3-t-butyl-5-methyl-4-hydroxybenzoic acid, 3-t-butyl-6-methyl-4-hydroxybenzoic acid, 3 -T-butyl-5-ethyl-4-hydroxybenzoic acid, 3-t-butyl-6-ethyl-4-hydroxybenzoic acid, 3-t-octyl-4-hydroxybenzoic acid, 3-t-octyl-5 -Methyl-4-hydroxybenzoic acid, 3-t-octyl-5-ethyl-4-hydroxybenzoic acid, 3-t-octyl-6-methyl-4-hydroxybenzoic acid, 2- (3-methyl-4- Hi Loxyphenyl) acetic acid, 2- (3,5-dimethyl-4-hydroxyphenyl) acetic acid, 2- (3,5-di-t-butyl-4-hydroxyphenyl) acetic acid, 2- (3-t-butyl- 4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-5-methyl-4-hydroxyphenyl) acetic acid, 2- (3-tert-butyl-6-methyl-4-hydroxyphenyl) acetic acid, 2- ( 3-t-butyl-5-ethyl-4-hydroxyphenyl) acetic acid, 2- (3-t-octyl-4-hydroxyphenyl) acetic acid, 2- (3-t-octyl-5-methyl-4-hydroxyphenyl) ) Acetic acid, 2- (3-t-octyl-6-methyl-4-hydroxyphenyl) acetic acid, 3- (3-methyl-4-hydroxyphenyl) propionic acid, 3- (3,5-dimethyl-4-hydroxy) Fe L) propionic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, 3- (3-t-butyl-4-hydroxyphenyl) propionic acid, 3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-6-methyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-5-ethyl-4-) Hydroxyphenyl) propionic acid, 3- (3-t-butyl-6-ethyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-4-hydroxyphenyl) propionic acid, 3- (3-t -Octyl-5-methyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-6-methyl-4-hydroxyphenyl) propionic acid, 3- (3,5-didodeci 4-hydroxyphenyl) propionic acid, 4- (3-methyl-4-hydroxyphenyl) butyric acid, 4- (3,5-dimethyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-4) -Hydroxyphenyl) butyric acid, 4- (3,5-di-t-butyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-5-methyl-4-hydroxyphenyl) butyric acid, 4- (3 -T-butyl-5-ethyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-6-methyl-4-hydroxyphenyl) butyric acid, 4- (3-t-butyl-6-ethyl-4) -Hydroxyphenyl) butyric acid, 4- (3-t-octyl-4-hydroxyphenyl) butyric acid, 4- (3-t-octyl-5-methyl-4-hydroxyphenyl) butyric acid, 4- (3-t-octyl) -6-methyl 4-hydroxyphenyl) butyric acid, 3,5-dimethyl-4-hydroxyphenylamine, 3,5-diisopropyl-4-hydroxyphenylamine, 3,5-di-t-butyl-4-hydroxyphenylamine, etc. Can do.

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

Reaction Terminator Having Triazine Structure or Benzotriazole Structure As the reaction terminator having a triazine structure or benzotriazole structure used as the A5 component in the present invention, structures represented by the following general formulas (iii) and (iv) Are preferably used in the molecule.

  By having one of the above groups in the molecule and one group capable of reacting with an isocyanate group, a triazine structure or benzoate as a non-reactive group is formed at the end of the non-reactive polyurethane resin of component A. A triazole structure can be introduced.

  Among the reaction terminators having a triazine structure or a benzotriazole structure, preferred compounds include the following general formulas (3) and (4). First, the reaction terminator having a triazine structure will be described.

  The following general formula (3)

(Where
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group, a hydrogen atom, an amino group, or a hydroxyl group,
The alkyl group and the alkyloxy group may have a substituent selected from an amino group, a hydroxyl group, a carboxyl group, and a thiol group,
However, one of R ^{12 to} R ¹⁷ is a group that can react with an isocyanate group or a group that has a substituent that can react with an isocyanate group. ) Can be preferably used.

In the general formula (3), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an alkyloxy group having 1 to 10 carbon atoms. is there. More preferably, it is a C1-C5 alkyl group or a C1-C5 alkyloxy group. These groups may have a group capable of reacting with an isocyanate group, preferably an amino group, a hydroxyl group, a carboxyl group, or a thiol group as a substituent.

In the general formula (3), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are a hydrogen atom, a group that can react with an isocyanate group, or a substituent that can react with an isocyanate group. R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ may be a group that can react with an isocyanate group, or a group that reacts with an isocyanate group. Group having a substituent.

Among them, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, hydroxymethyl group, 2- Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxyethyloxy group, 3-hydroxypropyloxy group, 2-hydroxypropyloxy group, hydrogen It is preferably an atom or an amino group. And one of them is a hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxyethyloxy group, 3 It is preferably a -hydroxypropyloxy group, 2-hydroxypropyloxy group, or amino group.

In the general formula (3), when a hydroxyl group is directly bonded to the benzene ring (when R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , or R ¹⁷ is a hydroxyl group), this hydroxyl group is Low reactivity with isocyanate groups due to electronic influence. Therefore, when R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , or R ¹⁷ is a hydroxyl group, it does not correspond to a group that can react with an isocyanate group.

Specific examples of the compound include 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-hydroxymethylphenyl) -4,6- Bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxyethyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxyethyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxyethyloxy) phenyl) -4,6- Diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxyethyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine 2- (2-hydroxy-4- (2-hydroxypropyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (2-hydroxypropyl) phenyl) -4,6-bis (2,4-Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (3-hydroxypropyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- ( 3-hydroxypropyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (2-hydroxypropyloxy) phenyl) -4,6-diphenyl -S-triazine, 2- (2hydroxy-4- (2-hydroxypropyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (4-hydroxybutyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- (4-hydroxybutyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (3-hydroxybutyl) phenyl) -4,6-diphenyl-s-triazine, 2- (2hydroxy-4- ( 3-hydroxybutyl) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4- (4-hydroxybutyloxy) phenyl) -4,6-diphenyl -S-triazine, 2- (2hydroxy-4- (4-hydroxybutyloxy) phenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2,4-bis 2-methoxy-4-ethylphenyl) -6- (2-hydroxymethyl-4-methylphenyl) -s-triazine, 2,4-bis (2-ethoxy-4-methylphenyl) -6- (2-hydroxy Methyl-4-methylphenyl) -s-triazine,
2,4-bis (2-methyl-4propylphenyl) -6- (2- (4-hydroxybutyloxy) -4-methylphenyl) -s-triazine, 2,4-bis (2-methoxy-4-) Propylphenyl) -6- (2-hydroxymethyl-4-methylphenyl) -s-triazine, 2,4- (2-ethoxy-4-propylphenyl) -6- (2-hydroxypropyloxy-4-dimethylphenyl) ) -S-triazine and the like.

  Next, a preferred reaction terminator having a benzotriazole structure will be described. A preferable compound includes a compound represented by the following general formula (4).

(Where
R ¹⁸ and R ¹⁹ each independently react with an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, a hydrogen atom, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or an isocyanate group. Possible group,
The alkyl group and the alkyloxy group may have a group capable of reacting with an isocyanate group, provided that in R ¹⁸ and R ¹⁹ , there is only one group capable of reacting with an isocyanate group,
The aryl group and aralkyl group may have an alkyl group having 1 to 5 carbon atoms as a substituent,
R ²⁰ is a hydrogen atom or a halogen atom. )
In the general formula (4), the hydroxyl group directly bonded to the benzene ring has low reactivity with the isocyanate group due to its electronic influence. Therefore, the hydroxyl group does not correspond to a group that can react with an isocyanate group.

In the general formula (4), R ¹⁸ and R ¹⁹ are each independently an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms, a hydrogen atom, an aryl group, an aralkyl group, an alkyloxy group. It is a group capable of reacting with a carbonyl group or an isocyanate group.

  The alkyl group and alkyloxy group may have a group capable of reacting with an isocyanate group, specifically an amino group, a hydroxyl group, a carboxyl group, an acid chloride group, or a thiol group. However, there is only one group that can react with the isocyanate group.

R ¹⁸ and R ¹⁹ are an aryl group or an aralkyl group having an alkyl group having 1 to 5 carbon atoms as a substituent, preferably a phenyl group having an alkyl group having 1 to 5 carbon atoms as a substituent. It is.

Examples of suitable R ¹⁸ and R ¹⁹ are hydrogen atom, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, hexyl group, 1,1,3,3-tetra Examples include methylbutyl group, phenyl group, benzyl group, 1,1-dimethylbenzyl group, carboxyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, amino group, aminomethyl group, aminoethyl group, and aminopropyl group. . Moreover, the acid chloride group etc. of a carboxyl group can also be mentioned.

Among suitable groups, R ¹⁸ and R ¹⁹ must always have a group capable of reacting with one isocyanate group in one group.

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

  The A5 component can be introduced into the terminal of the non-reactive polyurethane resin obtained for the purpose of improving the weather resistance of the non-reactive polyurethane resin and photochromic compound of the present invention. It can be considered that there is an advantage that the inherent heat resistance and mechanical strength (peeling strength) of the urethane resin are not impaired by introducing it at the end.

Other reaction terminators As the A5 component in the present invention, in addition to the above-mentioned reaction terminators for improving the weather resistance having the piperidine structure, hindered phenol structure, triazine structure, or benzotriazole structure, Typical amines, alcohols, thiols, and carboxylic acids can be used. These compounds have one group capable of reacting with an isocyanate group in the molecule, whereby a nonreactive group can be introduced at the end of the nonreactive polyurethane resin of the component A.

  Among the other reaction terminators used in the present invention, preferred compounds include the following general formulas (5) and (6).

(Where
R ²¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom,
R ²² is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an ester group. )
When a compound in which R ²¹ is a hydrogen atom is used as the A5 component, the terminal of the non-reactive urethane resin is an —NH (R ²² ) group, and this —NH (R ²² ) group is It does not substantially react with the polymer and the isocyanate compound. Therefore, the —NH (R ²² ) group does not correspond to a group that can react with an isocyanate group.

In the general formula (5), R ²¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom. Among them, R ²¹ is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom. The aryl group and aralkyl group may have an alkyl group having 1 to 5 carbon atoms or a halogen atom as a substituent.

Examples of suitable R ²¹ are methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 1,1,3,3. -A tetramethylbutyl group, a phenyl group, a benzyl group, a 1,1-dimethylbenzyl group, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, or a hydrogen atom.

R ²² is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group. Among these, R ²² is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group. The aryl group may have an alkyl group having 1 to 5 carbon atoms or a halogen atom as a substituent.

Examples of suitable R ²² include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 1,1,3,3. -A tetramethylbutyl group, a phenyl group, a benzyl group, a 1,1-dimethylbenzyl group, a carboxymethyl group, a carboxyethyl group, or a carboxypropyl group.

  The following general formula (6)

(Where
R ²³ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group,
Z is a hydroxyl group, a carboxyl group, or a thiol group. )
The compound represented by can also be used suitably as a reaction terminator.

In the general formula (6), R ²³ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group, and an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, Or it is preferable that it is an alkyloxycarbonyl group. This aryl group and aralkyl group may have an alkyl group having 1 to 5 carbon atoms or a halogen atom as a substituent. Preferable groups include alkyl groups having 1 to 5 carbon atoms, phenyl groups, and phenyl groups having a halogen atom. Examples of suitable R ²³ include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 1,1,3,3. -Tetramethylbutyl group, phenyl group, benzyl group, 1,1-dimethylbenzyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group and the like.

  Z in the general formula (6) is a group capable of reacting with an isocyanate group present at the terminal of the reactive polyurethane resin as the A4 component, specifically a hydroxyl group, a carboxyl group, or a thiol group, preferably a hydroxyl group. It is.

  Specific compounds represented by the general formulas (5) and (6) include methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, and 4-heptyl. Amine, octylamine, 1,1-dipropylbutylamine, phenylamine, benzylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, Dioctylamine, methylethylamine, methylbutylamine, methylpentylamine, methylhexylamine, methylheptylamine, methyloctylamine, ethylpropylamine, ethylbutylamine , Amines such as ethylpentylamine, ethylhexylamine, ethylheptylamine, ethyloctylamine, propylbutylamine, isopropylbutylamine, propylpentylamine, propylhexylamine, propylheptylamine, propyloctylamine, methanol, ethanol, propanol, isopropanol, Butanol, 2-butanol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decanol, 2-decanol and other alcohols, methanethiol, ethanethiol, 1-propanethiol, 2-propane Thiol, 1-butanethiol, 2-butanethiol, propanethiol, hexanethiol, heptane All, octanethiol, dodecanethiol, 2-methyl-1-butanethiol, 2-methylpropanethiol, 3-methyl-2-butenethiol, 1,1-dimethylheptanethiol, cyclohexanethiol, cyclopentanethiol, benzenethiol, Examples include thiols such as benzenemethanethiol and 2,6-dimethylbenzenethiol, carboxylic acids such as acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid. It is done.

  The above reaction terminator may be used alone or in combination of two or more, but has a piperidine structure from the viewpoint of improving the durability of the non-reactive polyurethane resin and the photochromic compound. It is preferable to use a reaction terminator or a reaction terminator having a hindered phenol structure.

  Next, a method for synthesizing the component A using the components A1 to A5 will be described.

Method for synthesizing component A When the component A4 is synthesized from the component A1, component A2, and component A3 and then the component A4 and component A5 are reacted to obtain the component A, a so-called one-shot method or prepolymer method is employed. can do. For example, the component A can be suitably obtained by the following method. The A1 component and the A2 component are reacted to obtain a urethane prepolymer, and then the urethane prepolymer and the A3 component are reacted to obtain a reactive polyurethane resin that is the A4 component. The A component of the present invention can be produced by reacting the terminal isocyanate group remaining in the obtained A4 component with the reaction terminator A5 component having a group capable of reacting with one isocyanate group in the molecule.

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

  The reaction between the urethane prepolymer thus obtained and the A3 component is carried out in the presence or absence of a solvent in an inert gas atmosphere such as nitrogen or argon at 25 to 120 ° C. for 0.5 to What is necessary is just to make it react for 24 hours. As the solvent, methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used. By this reaction, an A4 component which is a reactive polyurethane resin having an isocyanate group at the end of the molecular chain is obtained.

  Furthermore, the reaction between the obtained A4 component and A5 component is performed in the presence or absence of a solvent in an inert gas atmosphere such as nitrogen or argon at 25 to 120 ° C. for 0.5 to 24 hours. You can do it. As the solvent, methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

The mixing ratio of each component, the characteristics of the A component The amount ratio of the A1, A2, A3, A4, and A5 components used for the reaction in the above method may be determined as appropriate, but the heat resistance of the resulting polyurethane resin From the viewpoint of balance such as adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.), the following ratios are preferred. As described above, the amount ratio of the A1 component, the A2 component, and the A3 component is such that the total number of moles of “functional groups capable of reacting with isocyanate groups” (specifically, hydroxyl groups) contained in the A1 component is n1, The total number of moles of isocyanate groups contained in the A2 component is n2, and the “functional group capable of reacting with an isocyanate group” (specifically, amino group, hydroxyl group, mercapto group and / or carboxyl group) contained in the A3 component. When the total number of moles is n3 and the total number of moles of the group capable of reacting with the isocyanate group contained in the A5 component is n5,
n1: n2: n3: n5 = 0.30-0.89: 1: 0.1-0.69: 0.01-0.20 In order for the obtained photochromic composition (photochromic adhesive) to exhibit excellent adhesion, durability, and photochromic properties, preferably n1: n2: n3: n5 = 0.34-0.83: 1. : 0.15-0.6: 0.02-0.15, more preferably n1: n2: n3: n5 = 0.4-0.78: 1: 0.2-0.5: 0.02 ~ 0.1. Here, the above n1, n2, n3, and n5 can be obtained as the product of the number of moles of the compound used as each component and the number of each group present in one molecule of the compound.

  In addition, as demonstrated in the item of A4 component, A4 component which is a reactive polyurethane resin has an isocyanate group at the terminal. Therefore, the sum (n1 + n3) of n1 and n3 is a value smaller than n2 (n1 + n3 <n2). And in order to make A component into a non-reactive polyurethane resin, n5 must become more than the difference (n2- (n1 + n3)) of the sum total of n2, n1, and n3. When synthesizing the component A, the most preferable blend is when the above-mentioned quantitative ratio is satisfied, and the sum of n2, n1, n3, and n5 is equal (n2 = n1 + n3 + n5).

  In producing the A component which is a non-reactive polyurethane resin, the A5 component can be used in such a blending amount that the sum of n1, n3, and n5 is n2 or more (n2 ≦ n1 + n3 + n5). In this case, the excessively added A5 component may be removed by reprecipitation. In addition, when the excess A5 component is an amount that does not impair the effects of the present invention, the photochromic composition can be formed as it is. In this case, when the photochromic composition is formed, it is considered that the A5 component reacts with the B component and is consumed. Therefore, there is no particular problem as long as the excess A5 component is an amount that does not impair the effects of the present invention. However, since the isocyanate group in the B component that should be originally used for the production of the urea resin is consumed, the most preferred embodiment is to use the A5 component so that n1 + n3 + n5 = n2.

  The non-reactive polyurethane resin (component A) obtained by such a reaction may be used as it is dissolved in the reaction solvent. However, if necessary, the solvent is distilled off or poor water or the like is used. The reaction solution may be dropped into the solvent, and the non-reactive polyurethane resin may be subjected to post-treatment such as precipitation, filtration, and drying, and used as the A component.

  The non-reactive polyurethane resin of component A has a number average molecular weight of 5,000 from the viewpoint of the heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.) of the obtained non-reactive polyurethane resin. Is preferably 150,000 to 150,000, more preferably 8,000 to 100,000, and most preferably 10,000 to 60,000. The number average molecular weight of the polyurethane resin was 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, polyurethane resin sample solution: 0.5% dimethylformamide (DMF) solution.

The non-reactive polyurethane resin as component A preferably has a softening point of 60 to 200 ° C, particularly 80 to 150 ° C. By using a non-reactive polyurethane resin that satisfies the softening point in the above range, the workability when an optical sheet or film is bonded to form a laminate (photochromic laminate) is improved. Moreover, by using the non-reactive polyurethane resin, processability when manufacturing an optical article using the obtained laminate is improved. Furthermore, when a hard coat layer is formed on the surface of these laminates or optical articles, the workability when the hard coat solution is applied or cured is also improved. In addition, a softening point here means the softening point measured on the following conditions using the thermomechanical measuring apparatus (The Seiko Instruments company make, TMA120C).
[Measurement Conditions] Temperature rising rate: 10 ° C./min, measurement temperature range: 30 to 200 ° C., probe: needle-inserted probe with a tip diameter of 0.5 mm.

  Next, the isocyanate compound which has at least 1 isocyanate group in the molecule | numerator which is B component is demonstrated.

Component B: Isocyanate compound having at least one isocyanate group in the molecule As the isocyanate compound having at least one isocyanate group in the molecule of the present invention, a known isocyanate compound can be used without any limitation. These may be used alone or in combination of two or more.

  Although it is not certain about the factor which exhibits the outstanding adhesiveness by adding this B component to the above-mentioned A component, it is considered as follows. A part of the isocyanate group contained in the component B is hydrolyzed by the moisture contained in the photochromic composition of the present invention or humidity in the environment (that is, in the presence of moisture) to produce an amino group. The generated amino group reacts with the isocyanate group remaining in the component B to become a reaction product having a urea bond. The urea group of the reaction product generated here forms a hydrogen bond between the urea bond present in the component A and the urethane bond, so that the cohesive force of the photochromic adhesive layer is improved, and adhesion, In addition, the heat resistance is considered to be improved. In particular, even after contact with hot water, the adhesion (adhesion between the optical sheet and the adhesive layer) can be kept high. This effect is superior to the case where a two-component polyurethane resin is used.

  The reaction product of component B can be confirmed by comparing the infrared absorption spectra of the photochromic composition of the present invention and the resulting photochromic adhesive (layer). In the photochromic compound and the adhesive layer, the production of the reaction product can be confirmed by confirming the decrease in the absorption of the isocyanate group. Confirmation of this reaction product can be confirmed from the peak intensity ratio of an isocyanate group and a methylene group, for example. In the photochromic composition, absorption derived from an isocyanate group can be confirmed. On the other hand, in the photochromic adhesive layer taken out from the photochromic laminate produced in the presence of moisture, it can be confirmed that the absorption of the isocyanate group decreases with time and eventually disappears. In the adhesive layer, it can also be confirmed that the absorption of urea bonds increases as the absorption of isocyanate groups decreases. From this, it can be confirmed that a reaction product of B component (a reaction product having a urea bond) is present in the adhesive layer.

  As said isocyanate compound, in addition to the isocyanate compound illustrated as above-mentioned A2 component, 1-adamantyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, hexane isocyanate, nonyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate 4-methylcyclohexyl isocyanate, allyl isocyanate, 3-isocyanatopropyltriethoxysilane, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, m-tolyl isocyanate , Phenyl isocyanate, 3,5-di (trifluoromethyl) ) Phenyl isocyanate, 4-fluorophenyl isocyanate, 4- (trifluoromethoxy) phenyl isocyanate, 3- (trifluoromethyl) phenyl isocyanate, 1-isocyanato-2,4-dimethoxybenzene, ethyl isocyanatoacetate, 2-isocyanatobenzoyl Chloride, 3-isocyanato-1,2,4,5-tetramethylbenzene, 4-isocyanato-4-propylpentane, 1-isocyanato-1-propene, 3-bromo-2- (4-isocyanatophenyl) thiophene, Isocyanatopropyldimethylsilylcyclohexyl polyhedral oligomeric silsesquioxane, isocyanatopropyldimethylsilylisobutylpolyoligomeric silsesquioxane, etc. It includes a compound having a group.

  1,3,5-tris (6-isocyanatohexyl) burette, (2,4,6-trioxtriazine-1,3,5 (2H, 4H, 6H) triyl) tris (hexamethylene) isocyanate, 1-methylbenzene-2,4,6-triyltriisocyanate, 4,4 ′, 4 ′ ′-methylidynetris (isocyanatobenzene), methylsilanetriyltrisisocyanate, 2,6-diisocyanatocaproic acid 2 -Isocyanatoethyl, 2,6-bis [(2-isocyanatophenyl) methyl] phenyl isocyanate, tris (3-methyl-6-isocyanatobenzoyl) methane, tris (4-methyl-3-isocyanatobenzoyl) methane , Tris (3-isocyanatophenyl) methane, tris (3-methyl-4-isocyanatobenzo Yl) methane, tris (4-methyl-2-isocyanatobenzoyl) methane, and the like can include compounds having three isocyanate groups in the molecule. Moreover, the isocyanurate compound which has three isocyanate groups can be mentioned.

  Furthermore, compounds having four isocyanate groups in the molecule such as tetraisocyanatosilane and [methylenebis (2,1-phenylene)] bisisocyanate can be exemplified.

  Further, the present invention is an isocyanate compound (B ′) (hereinafter, also simply referred to as B ′ component) obtained by reacting the aforementioned A3 component with an isocyanate compound having two or more isocyanate groups in the molecule. It can also be used as the B component.

When synthesizing the B ′ component, it is preferable that the A2 component, which is a diisocyanate compound, is reacted with an amino alcohol compound or a diol compound among the A3 components. Among them, as the diisocyanate compound,
Aliphatic diisocyanates such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, or Cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, norbornane diisocyanate, 4 , 4'-methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6 Diisocyanate, hexamethylene hydro-phenylene 1,3-diisocyanate, it is preferable to use an alicyclic diisocyanate such as hexahydroterephthalic phenylene-1,4-diisocyanate.

  On the other hand, examples of amino alcohol compounds include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2 -It is preferable to use piperidine ethanol and 4-piperidine ethanol.

  Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-pentane. Diol, 2,4-pentanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2,5-hexanediol, 1 , 6-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-bis (hydroxy Ethyl) - cyclohexane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, it is preferred to use neopentyl glycol.

The B ′ component must have at least one isocyanate group in the molecule. Therefore, when synthesizing the B ′ component, the total number of moles of isocyanate groups of the A2 component must be larger than the total number of moles of groups capable of reacting with the isocyanate group of the A3 component. The isocyanate group contained can also be used in a state protected with a blocking agent. Examples of the blocking agent that can be used include acid amide, lactam, acid imide, imidazole, urea, and oxime compounds. Specific examples include acetanilide, acetic acid amide, ε-caprolactam, succinic imide, maleic imide, dimethylpyrazole, thiourea, acetoaldoxime, acetone oxime, methyl ethyl ketoxime, and the like.

  The number of isocyanate groups contained in the component B (component B ′) may be one, but is preferably two or more. By having two or more isocyanate groups in the molecule of component B, a urea resin having a high molecular weight (reaction product of component B) can be formed when the photochromic adhesive layer is formed. As a result, the cohesive force between the reaction product of the B component and the A component is improved, so that it is considered that the effect of improving the adhesion is enhanced. On the other hand, when there are four or more isocyanate groups in the molecule of the B component, it is formed from a urea resin crosslinked in a network form, so that phase separation is likely to occur between the A component and the present invention. The photochromic adhesive layer tends to become cloudy. For this reason, the component B (including the B ′ component) is preferably a compound having two or three isocyanate groups in the molecule, and particularly preferably a compound having two isocyanate groups.

  Moreover, it is preferable that this B component is an isocyanate compound chosen from an aliphatic isocyanate compound and an alicyclic isocyanate compound from a weather-resistant viewpoint. In the aromatic isocyanate compound, phase separation is likely to occur between the component A and the photochromic adhesive layer of the present invention tends to become cloudy. This is thought to be due to the fact that the aromatic isocyanate compound is faster in reactivity than the aliphatic isocyanate compound and the alicyclic isocyanate compound, and further has a high cohesive force. Also from the viewpoint of cloudiness, the component B is preferably an isocyanate compound selected from an aliphatic isocyanate compound and an alicyclic isocyanate compound.

  In the present invention, the molecular weight of the B component (including the B ′ component) is not particularly limited, but is preferably less than 1000. When the molecular weight of the component B is 1000 or more, the heat resistance and film strength of the resulting photochromic adhesive layer tend to be lowered. It is considered that this is because when a high molecular weight isocyanate compound is blended, the structural part other than the urea bond in the reaction product of the B component affects. In addition, in order to improve the adhesion, when trying to make the number of moles of the isocyanate group more than a certain amount, the isocyanate compound having a large molecular weight increases the blending amount with respect to the component A. As a result, it is considered that the structure part other than the urea bond of the reaction product is likely to be affected. Also from this point, the molecular weight of the component B is preferably less than 1000. From the above, the molecular weight of component B is more preferably 750 or less, and most preferably 600 or less. As a matter of course, the molecular weight of the B ′ component is preferably less than 1000 for the same reason. As described above, the B component (B ′ component) is preferably not a polymer. Therefore, the molecular weight of the B component (B ′ component) refers to the molecular weight of the B component (B ′ component) itself. The lower limit of the molecular weight of the component B is the molecular weight of the simple compound, and is 100, although not particularly limited.

(B component content)
The blending amount of the B component in the photochromic composition of the present invention is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the A component from the viewpoints of adhesion, heat resistance, and photochromic properties. . When the blending amount is too small, sufficient adhesion and heat resistance improvement effect cannot be obtained, and when too large, the cloudiness of the adhesive layer obtained from the photochromic composition, decrease in adhesion, There is a tendency for the durability of photochromic compounds to decrease. In order to improve the adhesion with an optical substrate such as a plastic film while maintaining the photochromic properties such as color density and durability, the blending amount of the B component is 0.1 to 100 parts by mass of the A component. It is preferable to set it as 10 mass parts, especially 0.5-5 mass parts. Under the present circumstances, the ratio of the isocyanate group contained in B component is 0.01-10.0 mass part with respect to 100 mass parts of A component, More preferably, it is 0.02-5.0 mass part, Most preferably, it is 0. .1 to 3.0 parts by mass. Here, the amount of isocyanate groups can be determined from the molecular weight of component B and the number of isocyanate groups per molecule.

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

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

  In particular, chromene compounds having excellent photochromic properties other than those described in the above-mentioned patent documents are known as chromene compounds, and such chromene compounds can be suitably used as the B component. Examples of such chromene compounds include JP2001-031670, JP2001-011067, JP2001-011066, JP2000-344761, JP2000-327675, JP2000-256347, JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229993, JP 2000-229972, JP 2000-219678, JP 2000-219686, Special Kaihei 11-322739, JP 11-286484, JP 11-279171, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139, JP 08-157467, US Pat. No. 56457 No. 7, U.S. Pat. No. 5,658,501, U.S. Pat. No. 5,961,892, U.S. Pat. No. 6,296,785, Japanese Patent No. 4,424,981, Japanese Patent No. 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)
The blending amount of the C component in the photochromic composition of the present invention is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the A component from the viewpoint of photochromic properties. When the amount is too small, sufficient color density and durability tend not to be obtained. When the amount is too large, depending on the type of photochromic compound, the photochromic composition dissolves in the A component. Not only does this tend to be difficult and the uniformity of the composition tends to decrease, but also the adhesive strength (adhesion) tends to decrease. In order to maintain sufficient adhesion to an optical substrate such as a plastic film while maintaining photochromic properties such as color density and durability, the amount of component C added is 0.1% relative to 100 parts by weight of component A. It is more preferable to set it as 5-10 mass parts, especially 1-5 mass parts.

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

Component D: Organic solvent By blending an organic solvent in the photochromic composition of the present invention, a non-reactive polyurethane resin (component A), an isocyanate compound (component B), a photochromic compound (component C), and further, as required The other components added accordingly are easily mixed. As a result, the uniformity of the photochromic composition can be improved. Furthermore, the viscosity of the photochromic composition can be appropriately adjusted by using an organic solvent. And the operativity when apply | coating the photochromic 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 shown as [13] above. In the photochromic 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 organic solvents that can be suitably used as the component D include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, and 2-butanol; ethylene glycol monomethyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n- Polyhydric alcohol derivatives such as butyl ether and ethylene glycol dimethyl ether; diacetone alcohol; methyl ethyl ketone, diethyl ketone, etc. Ketones; toluene; hexane; heptane: ethyl acetate, 2-methoxyethyl, acetate such as 2-ethoxyethyl acetate; DMF; DMSO; THF; cyclohexanone; and combinations thereof can be exemplified. What is necessary is just to select suitably from these, according to the kind of A component to be used, and the material of an optical sheet or a film. For example, when an optical sheet or film made of polycarbonate resin is used and the photochromic composition of the present invention is directly applied, it is preferable to use alcohols or polyhydric alcohol derivatives as the solvent.

  The smoothness of the coating layer when the photochromic 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 shown in [13] is adopted. In consideration of the above, it is preferable to use a mixture of an organic solvent having a boiling point of less than 90 ° C. and an organic solvent having a boiling point of 90 ° C. or more. By using such a combination of organic solvents, in addition to the above 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 100 mass parts of A component especially from 100-750 mass parts from the viewpoint of the effect acquired by D component addition as mentioned above. It is preferable to set it to 200 to 600 parts by mass.

Water can also be incorporated into the photochromic composition of the water present invention. By blending water, the isocyanate group contained in the component B of the present invention can be efficiently hydrolyzed. This water can also be blended into the photochromic composition of the present invention from the beginning. However, in consideration of the storage stability of the photochromic composition, it is preferably blended when the photochromic composition is used, that is, when a coating film is formed from the composition and the optical sheets are laminated. Further, this water will be described in detail below, but when forming a photochromic adhesive sheet, moisture existing in the atmosphere can be substituted. Hydrolysis of the isocyanate group contained in the component B also proceeds by contacting the moisture (humidity) in the environment after the photochromic composition is coated on the optical sheet to form a coating film.

  The blending amount of the water is not particularly limited, and can be handled by moisture under the environment described in detail below. If a preferable compounding quantity is described, it is 0.01 times mol-5 times mol, preferably 0.05 times mol-3 times mol, more preferably 0.1 times the number of moles of the isocyanate group contained in B component. It is preferable that it is the range of 2 times mole-2 times mole.

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

  For example, as the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in the photochromic composition. Specific examples of nonionic surfactants that can be suitably used include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensate, a single-chain polyoxyethylene alkyl ethers, and more may be mentioned surfactants of the silicone-based or fluorine. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.001 to 1 part by mass with respect to 100 parts by mass of the non-reactive polyurethane resin (component A).

  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 preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the non-reactive polyurethane resin (component A). However, if these additives are used excessively, the adhesiveness of the photochromic composition to an optical sheet or film made of polycarbonate resin is lowered, so the addition amount is preferably 7 parts by mass or less, more preferably 3 masses. Part or less, most preferably 1 part by weight or less.

Production Method of Photochromic Composition The photochromic composition of the present invention can be produced by mixing the A component, the B component and the C component, and the D component and other components used as necessary. 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 composition and pelletized. It is also possible to form the sheet as it is. Moreover, when using an organic solvent, a photochromic composition can be obtained by dissolving each main component in an organic solvent.

  The photochromic composition of the present invention thus obtained can be suitably used as a photochromic adhesive, particularly a photochromic adhesive for joining optical sheets or films made of polycarbonate resin. The optical article of the present invention indicated as [11] can be obtained by bonding the optical sheet or the optical film to each other via the adhesive layer made of the photochromic composition of the present invention. Hereinafter, the optical article of the present invention and the method for producing the optical article will be described.

  In addition, although mentioned in full detail below, when joining with an optical sheet or an optical film with the photochromic composition of this invention, joining in presence of moisture (in presence of moisture) is preferable.

Optical Article of the Present Invention The optical article of the present invention comprises a laminated structure in which two optical sheets or optical films facing each other are bonded via an adhesive layer made of the photochromic composition of the present invention. As such an optical article,
A photochromic laminated sheet or film comprising only the above 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;
Optical articles in which these laminates and composite laminates are integrated with an optical substrate such as a plastic lens body;
And so on. 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. Examples thereof include 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. In addition, after immersing the laminate (which may be a composite laminate) in a polymerizable monomer capable of forming an optical substrate, the polymerizable monomer is cured to thereby form the laminate in the optical substrate. It can also be embedded and integrated. Therefore, the optical article may be one obtained by laminating the above laminate (may be a composite laminate) on a plastic optical substrate made of a thermoplastic resin or a thermosetting resin, The above-mentioned laminated body (may be a composite laminated body) may be embedded in a plastic optical substrate. Hereinafter, these materials or members constituting the optical article of the present invention will be described.

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

  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.

Production method of laminate of the present invention 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 composition of the present invention. . The thickness of the adhesive layer is preferably 5 to 100 μm, particularly 10 to 50 μm, from the viewpoint of the color density of the photochromic compound, weather resistance, adhesive strength, and the like.

  The said adhesive layer can be obtained with the following methods according to the property of the photochromic composition to be used. That is, when the photochromic composition of the present invention is prepared to have an appropriate viscosity by blending an organic solvent, etc., the photochromic composition of the present invention is applied on one optical sheet or optical film, if necessary. (Heated) after drying, another optical sheet or optical film may be (heated) pressure bonded. At this time, as a method for applying the photochromic composition, a known method such as a spin coating method, a spray coating method, a dip coating method, a dip-spin coating method, or a dry laminating method is used without any limitation. The photochromic 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. In particular, by carrying out drying under these conditions, the hydrolysis reaction of the component B is promoted, and a stronger adhesion can be obtained. By drying under the above humidity (in the presence of moisture), a photochromic adhesive layer (sheet) that exhibits excellent performance can be obtained without adding water to the photochromic composition. When water is added, the sheet can be formed under dry conditions.

In addition, when using the photochromic composition of the present invention containing an organic solvent,
After spreading the photochromic composition of the present invention on a smooth substrate, the organic solvent (D) is removed by drying, and a non-reactive polyurethane resin (A), an isocyanate compound (B), a photochromic compound ( C) and a step of preparing a photochromic adhesive sheet, and the two sheets in the presence of moisture (humidity) by interposing the photochromic adhesive sheet between two optical sheets or optical films facing each other. The laminated body of this invention can also be manufactured by implementing the process of joining the optical sheet or optical film. When the step of preparing the photochromic adhesive sheet is performed in the presence of moisture (in the presence of moisture), at least a part of the isocyanate compound (B) contained in the photochromic adhesive sheet is a reaction product. It has become. In these steps, the reaction product of the isocyanate compound (B) can be confirmed by analyzing with an infrared absorption spectrum as described above.

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

  The obtained photochromic adhesive sheet is interposed between two optical sheets or optical films facing each other. And both are joined in presence of water. The photochromic laminate obtained in the step of joining the optical sheet or the optical film can be used as it is, but the state can be stabilized and used by the following method. Specifically, it is preferable to leave the laminated body just joined at a temperature of 20 ° C. or higher and 60 ° C. or lower for 4 hours or longer. The upper limit of the standing time is not particularly limited, but 50 hours is sufficient. In addition, when standing, it can be left at normal pressure or left under vacuum. Furthermore, it is preferable to leave this standing laminate at a temperature of 80 ° C. to 130 ° C. for 30 minutes to 3 hours (hereinafter referred to as heat treatment). The laminate obtained by this heat treatment has a very stable state. The heat-treated laminate is preferably humidified at a temperature of room temperature to 100 ° C. and a humidity of 30 to 100% RH. By performing this humidification treatment, the isocyanate group derived from the B component present in the laminated sheet can be eliminated, and the photochromic characteristics and adhesion can be further stabilized. Furthermore, after moisture treatment, excess moisture present in the laminated sheet can be removed by standing at 40 to 130 ° C. under normal pressure or under vacuum.

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

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

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

A1 component; polyol compound PL1: Exenol (polypropylene glycol, number average molecular weight 400) manufactured by Asahi Glass Co., Ltd.
PL2: Exenol (polypropylene glycol, number average molecular weight 1000) manufactured by Asahi Glass Co., Ltd.
PL3: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 500).
PL4: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 800).
PL5: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 1000).
PL6: DURANOL manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 3000).
PL7: Plaxel (polycaprolactone diol, number average molecular weight 500) manufactured by Daicel Chemical Industries, Ltd.
PL8: Polylite manufactured by DIC Corporation (polyester diol composed of adipic acid and 1,4-butanediol, number average molecular weight 1000).
PL9: ETERNACOLL manufactured by Ube Industries, Ltd. (polycarbonate diol using 1,4-cyclohexanedimethanol as a raw material, number average molecular weight 1000).

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

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

A5 component; reaction terminator S1; 1,2,2,6,6-pentamethyl-4-hydroxypiperidine.
S2; 1,2,2,6,6-pentamethyl-4-aminopiperidine.
S3: normal butylamine.
B component; Isocyanate compound B1: Isophorone diisocyanate (molecular weight 222).
B2: 4,4′-methylenebis (cyclohexyl isocyanate) (molecular weight 262).
B3: Hexamethylene-1,6-diisocyanate (molecular weight 168).
B4: Xylylene diisocyanate (molecular weight 188).

Synthesis of isocyanate compound (B5) (B 'component)
Ethylene glycol 31 g and isophorone diisocyanate 222 g were charged into a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere to obtain an isocyanate compound (B5).
B5: Reaction product (molecular weight 506) of isophorone diisocyanate (2 mol) and ethylene glycol (1 mol).

Synthesis of isocyanate compound (B6) (B 'component)
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 41.3 g of ethylene glycol and 222 g of isophorone diisocyanate and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere to obtain an isocyanate compound (B6). It was.
B6: Reaction product (molecular weight 790) of isophorone diisocyanate (3 mol) and ethylene glycol (2 mol).

Synthesis of isocyanate compound (B7) (B 'component)
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 533 g of polycarbonate diol having an average molecular weight of 800 and 222 g of isophorone diisocyanate, and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere to obtain an isocyanate compound (B7). Got.
B7: Reaction product (number average molecular weight 2266) of isophorone diisocyanate (3 mol) and polycarbonate diol (2 mol) having a number average molecular weight of 800.

Component C: photochromic compound PC1: a compound represented by the following formula.

D component: Organic solvent D1: Isopropyl alcohol.
D2: Propylene glycol-mono-methyl ether.
D3: Toluene.
D4: Ethyl acetate.
D5: Cyclohexanone.
D6: THF (tetrahydrofuran).
D7: Diethyl ketone.

Other components Irganox 245: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], manufactured by Ciba Specialty Chemicals
Synthesis of non-reactive polyurethane resin (U1) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 90 g of polypropylene glycol (PL1: polyether diol) having a number average molecular weight of 400, isophorone diisocyanate (NCO1) 100 g was charged and reacted at 70 ° C. for 6 hours under a nitrogen atmosphere to obtain a prepolymer. Thereafter, 800 ml of DMF was added, and 34 g of isophoronediamine (CE1) was added dropwise under a nitrogen atmosphere. After completion of the dropping, the mixture was reacted at 25 ° C. for 1 hour, and a reactive polyurethane resin having an isocyanate group at the end of the molecular chain (A4 ) Was synthesized.

  Next, 8 g of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine was added to the above solution under a nitrogen atmosphere and reacted at 110 ° C. for 5 hours, and then the solvent was distilled off under reduced pressure. A non-reactive polyurethane resin (A5: U1) having a piperidine ring at the end of the urethane resin was obtained. The number average molecular weight of the obtained non-reactive polyurethane resin was 10,000 (theoretical value; 10,000) in terms of polyoxyethylene, and the heat resistance was 120 ° C. The theoretical value of the number average molecular weight here refers to the molecular weight when the A1 component, A2 component, A3 component, and A5 component used as raw materials are theoretically purified from a polyurethane resin without crosslinking. It is.

Synthesis of non-reactive polyurethane resins (U2) to (U33) Polyol compound (A1 component), polyisocyanate compound (A2 component), chain extender (A3 component), reaction terminator (A5 component) shown in Table 1, and U2 to U33 were synthesized in the same manner as the synthesis method of U1 described above except that the reaction conditions shown in Table 1 were used using a reaction solvent. The synthesis conditions of the obtained non-reactive polyurethane resin are also shown in Table 1. U30 is a reactive polyurethane resin that does not use a reaction terminator (component A5) and has an isocyanate group at the terminal.

  The results of the blending ratio, number average molecular weight, and heat resistance of the A1, A2, A3, and A5 components of the non-reactive polyurethane resins U1 to U33 are summarized in Table 2.

Example 1
Preparation of photochromic composition 20 g of isopropyl alcohol as an organic solvent was added to 5 g of non-reactive polyurethane resin (U1) and dissolved by ultrasonic wave while stirring at 80 ° C. After confirming that the non-reactive polyurethane resin was dissolved, the mixture was cooled to room temperature, 0.15 g of isophorone diisocyanate (component B) and 0.25 g of the photochromic compound (PC1) were added, and the mixture was stirred to obtain a photochromic composition.

Preparation of photochromic laminate The obtained photochromic composition was applied to a PET film (Purex film, Teijin DuPont Films Co., Ltd., with silicon coating), and experimented in the presence of moisture (23 ° C, humidity 50%). After drying in a chamber at 50 ° C. for 30 minutes, the PET film was peeled off to obtain a photochromic adhesive sheet having a thickness of about 40 μm. Next, the obtained photochromic adhesive sheet was sandwiched between two polycarbonate sheets having a thickness of 400 μm, and allowed to stand at 40 ° C. for 24 hours in a laboratory in the presence of moisture (23 ° C., humidity 50%). Furthermore, the laminated body which has the target photochromic characteristic was obtained by heat-processing at 110 degreeC for 60 minute (s). In addition, when the infrared absorption spectrum of the photochromic adhesive sheet and the photochromic composition taken out from the laminate was confirmed, the peak of isocyanate groups in the photochromic adhesive sheet was reduced, and isophorone diisocyanate was a reaction product. I was able to confirm. It was also confirmed that the isocyanate group peak in the photochromic adhesive sheet decreased with time.

  When the obtained photochromic laminate was evaluated, the color density as a photochromic property was 1.0, the fading speed was 90 seconds, and the durability was 94%. Further, the heat resistance of the photochromic laminate was 130 ° C., and the peel strength was 80 N / 25 mm in the initial stage and 70 N / 25 mm after the boiling test. These evaluations were performed as follows.

A laminate obtained with photochromic properties was used as a sample, and a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was used at 23 ° C. via an aeromass filter (manufactured by Corning). The surface 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 laminate were measured.

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

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

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

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

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

  The above results are summarized in Table 3.

Examples 2-45
A photochromic composition was prepared in the same manner as in Example 1 except that the nonreactive polyurethane resin, isocyanate compound, and organic solvent shown in Tables 3 and 4 were used. As a matter of course, as in Example 1, the photochromic compound (PC1) was blended so as to be 5 parts by mass (actual use amount 0.25 g) with respect to the non-reactive polyurethane resin (component A). Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic composition.

  The evaluation results of the various photochromic laminates obtained are shown in Tables 3 and 4. In these examples, when the infrared absorption spectrum of the photochromic adhesive sheet was confirmed, the peak of the isocyanate group decreased in any sheet, and it was confirmed that the various isocyanate compounds used were reaction products. .

Comparative Examples 1 and 2
A photochromic composition was prepared in the same manner as in Example 1 except that the non-reactive polyurethane resin, isocyanate compound, and organic solvent shown in Table 5 were used. As a matter of course, as in Example 1, the photochromic compound (PC1) was blended so as to be 5 parts by mass (actual use amount 0.25 g) with respect to the non-reactive polyurethane resin (component A). Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic composition.

  Table 5 shows the evaluation results of the obtained various photochromic laminates.

Comparative Example 3
By the following method, a polyurethane resin (I) having an isocyanate group at the end of the molecular chain and a polyurethane resin (II) having a hydroxyl group at the end of the molecular chain were synthesized.

(Synthesis of polyurethane resin (I))
In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 100 g of polycaprolactone polyol (Placcel manufactured by Daicel Chemical Industries, Ltd.) having a number average molecular weight of 1000, 39.5 g of 4,4′-methylenebis (cyclohexyl isocyanate). Was reacted at 90 ° C. for 6 hours under a nitrogen atmosphere to obtain a prepolymer having an isocyanate group at the terminal (polyurethane resin (I)). The number average molecular weight of the obtained prepolymer (polyurethane resin (I)) was 2500 (theoretical value: 2800) in terms of polyoxyethylene.

(Synthesis of polyurethane resin (II))
A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 100 g of polycaprolactone polyol (Placcel manufactured by Daicel Chemical Co., Ltd.) having a number average molecular weight of 1000 and 61.3 g of hydrogenated diphenylmethane diisocyanate under a nitrogen atmosphere. The mixture was reacted at 90 ° C. for 6 hours to obtain a prepolymer having an isocyanate group at the terminal. Thereafter, 200 ml of DMF was added, and 12.7 g of 1,4-butanediol was added dropwise under a nitrogen atmosphere. After completion of the dropping, the mixture was reacted at 90 ° C. for 24 hours, and a polyurethane resin having a hydroxyl group at the end of the molecular chain (II ) Was synthesized. The number average molecular weight of the obtained polyurethane resin (II) was 20,000 (theoretical value: 18,000) in terms of polyoxyethylene.

  Using the polyurethane resin (I) and polyurethane resin (II) obtained as described above, THF (D6) as the organic solvent in the amount shown in Table 6, and using 0.25 g of the photochromic compound (PC1), Examples 1 was used to prepare a photochromic composition. Moreover, the photochromic laminated body was produced by the method similar to Example 1 using the obtained photochromic composition.

  Table 6 shows the evaluation results of the obtained various photochromic laminates.

  As is clear from Examples 1 to 45 above, in the photochromic composition in which the non-reactive polyurethane resin (component A) and the isocyanate compound (component B) are mixed according to the present invention, excellent photochromic properties and peel strength (adhesion) ) And heat resistance.

  On the other hand, as in Comparative Example 1, when the isocyanate compound (component B) was not added, the photochromic characteristics were good, but the peel strength was low, and in particular, the peel strength decreased after the boiling test. In Comparative Example 2, since the reactive urethane resin having an isocyanate group at the terminal was used as the component A instead of the non-reactive polyurethane resin, the durability of the photochromic characteristics was lowered and the peel strength was not sufficient. Moreover, in the comparative example 3, the urethane resin composition which mixes the prepolymer which has an isocyanate group at the terminal, and the polyurethane resin which has a hydroxyl group at the terminal, and makes high molecular weight after a coating film is employ | adopted. However, in this case, the durability of the photochromic characteristics and the peel strength were not sufficient.

Claims (13)

Non-reactive polyurethane resin (A),
Isocyanate compound (B) having at least one isocyanate group in the molecule, and photochromic compound (C)
And a photochromic composition comprising: The non-reactive polyurethane resin (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, and two or more polyol compounds in the molecule A reactive polyurethane resin (A4) having an isocyanate group at the end of the molecular chain, obtained by reacting with a chain extender (A3) having a molecular weight of 50 to 300 having a group capable of reacting with an isocyanate group;
Reaction stopper having a group capable of reacting with one isocyanate group in the molecule (A5)
The photochromic composition according to claim 1, which is a non-reactive urethane resin obtained by reacting with. The amount ratio of the (A1) component, the (A2) component, the (A3) component, and the (A5) component used for obtaining the non-reactive polyurethane resin (A) is the total number of hydroxyl groups contained in the (A1) component. The number of moles is n1, the total number of isocyanate groups contained in the component (A2) is n2, the total number of isocyanate group-reactive groups contained in the component (A3) is n3, and the above (A5) When the total number of moles of the group capable of reacting with the isocyanate group contained in the component is n5,
The photochromic composition according to claim 2, wherein the ratio is n1: n2: n3: n5 = 0.30-0.89: 1: 0.1-0.69: 0.01-0.20.   The photochromic composition according to claim 1, wherein the molecular weight of the isocyanate compound (B) is less than 1000.   The photochromic composition according to claim 1, wherein the polyol compound (A1) is at least one polyol compound selected from polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester diol.   The photochromic composition according to claim 1, wherein 30% by mass or more of the polyisocyanate compound (A2) is at least one polyisocyanate compound selected from an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound.   The photochromic composition according to claim 1, wherein the chain extender (A3) is at least one chain extender selected from a diamine compound, an amino alcohol compound, an aminocarboxylic acid compound, an aminothiol compound, and a diol compound.   The photochromic composition according to claim 1, wherein the reaction terminator (A5) is a compound having a piperidine structure, a hindered phenol structure, a triazine structure, a benzotriazole structure, or an alkyl chain in the molecule. For 100 parts by mass of the non-reactive polyurethane resin (A),
0.01 to 20 parts by mass of the isocyanate compound (B),
The photochromic composition of Claim 1 containing 0.1-20 mass parts of said photochromic compounds (C).   The photochromic composition according to claim 9, further comprising 5 to 900 parts by mass of an organic solvent (D) with respect to 100 parts by mass of the non-reactive polyurethane resin (A).   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 composition according to claim 1.   The optical article according to claim 11, 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 12, comprising:
After spreading the photochromic composition according to claim 10 on a smooth substrate, drying to remove the organic solvent (D), non-reactive polyurethane resin (A), isocyanate compound (B), A step of preparing a photochromic adhesive sheet containing the photochromic compound (C), and the photochromic adhesive sheet interposed between two optical sheets or optical films facing each other, and at least in the presence of moisture A step of producing the laminated structure by bonding a single optical sheet or optical film;
A method comprising the steps of: