JP5888895B2 - Photochromic laminate and manufacturing method thereof - Google Patents

Description

  The present invention relates to a novel photochromic laminate in which optical sheets or films are bonded to each other through an adhesive layer made of a photochromic composition. Specifically, the present invention relates to a novel photochromic laminate having a second adhesive layer on both surfaces of a first adhesive layer made of a photochromic composition, and an optical sheet or film laminated on the second adhesive layer.

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

  However, processing of plastic photochromic sunglasses is not always easy.

  For example, a method using a photochromic paint in which a photochromic agent is added to an acrylate copolymer is known, but there is room for improvement in the following points. Specifically, as a method of using the paint, a composite film in which a photochromic film made of the paint is formed on the surface of the polycarbonate film is prepared, and the composite film is mounted in a mold and a polycarbonate resin is injection-molded. A method has been proposed (see Patent Document 1). However, with this method, it has been difficult to obtain sunglasses having good photochromic properties.

  Moreover, in the method described in the said patent document 1, it replaces with the said composite film and there exists a method of using "the laminated sheet which joined the polycarbonate sheet | seat by the polyurethane resin contact bonding layer containing a photochromic pigment | dye" (patent document 2 and patent document) 3). However, with this method, the adhesion and heat resistance of the polycarbonate sheet in the laminated sheet were insufficient. For this reason, when an optical article is manufactured by mounting the laminate on a mold and then injection-molding a polycarbonate resin on the mold, the resulting optical article may be peeled off or optical distortion may occur. There was a problem.

JP 61-5910 A Special table 2003-519398 gazette US Patent Application Publication No. 2004-096666

  Therefore, an object of the present invention is a laminate in which an optical sheet or an optical film is bonded by an adhesive layer having photochromic properties, and a laminate having excellent adhesion, excellent heat resistance, and excellent photochromic properties. Is to provide.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the relationship between the structure of the photochromic polyurethane resin adhesive layer and the properties of the obtained optical article. As a result, (1) when a photochromic polyurethane-urea resin adhesive layer (first adhesive layer) formed using a polyurethane-urea resin is used, the heat resistance, photochromic property and durability of the resulting laminate are obtained. The optical sheet or the like without impairing the photochromic properties and durability by providing another adhesive layer (second adhesive layer) on both surfaces of the adhesive layer. It has been found that the adhesive strength of the film can be increased, and the present invention has been completed.

That is, the present invention
Two optical sheets or films facing each other
(A) A first adhesive layer comprising a polyurethane-urea resin having a urea bond in a molecular chain , ( B) a photochromic compound , and a photochromic composition containing an isocyanate compound (D) having two or more isocyanate groups in the molecule. When,
A second adhesive layer made of at least one urethane compound selected from the group consisting of urethane (meth) acrylate, two-component urethane, moisture-curable urethane, and urethane dead polymer formed on both sides of the first adhesive layer; It is the photochromic laminated body joined via.

  The photochromic laminate of the present invention exhibits excellent adhesion and photochromic properties. Furthermore, since the first adhesive layer containing the photochromic compound has high heat resistance, the optical article of the present invention is mounted on a mold, and then a thermoplastic resin such as a polycarbonate resin is injection-molded on the mold, so that the optical Even when an article is manufactured, adhesion and photochromic properties are unlikely to deteriorate and optical distortion hardly occurs.

It is a figure which shows the layer structure of the photochromic laminated body of this invention.

In the photochromic laminate of the present invention, two optical sheets or films facing each other are composed of a photochromic composition comprising (A) a polyurethane-urea resin having a urea bond in a molecular chain, and (B) a photochromic compound. It is joined via one adhesive layer and a second adhesive layer present on both sides of the first adhesive layer. That is, in the laminate of the present invention, the second adhesive layer is formed on both sides of the first adhesive layer, and the optical sheet or film is further laminated on the second adhesive layer.
First, the photochromic composition for forming the first adhesive layer will be described.

Photochromic Composition Forming First Adhesive Layer In the present invention, the photochromic composition comprises (A) a polyurethane-urea resin having a urea bond in the molecular chain (hereinafter also simply referred to as component (A)), and (B). ) A photochromic compound (hereinafter also simply referred to as B component). Hereinafter, the A component and the B component will be described.

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

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

The polyurethane-urea resin used as the component A is not particularly limited as long as it is a polyurethane-urea resin having a urea bond in the molecular chain, but has no isocyanate group at the end of the molecule because of its good photochromic properties. A polyurethane-urea resin is preferred. From the viewpoint of photochromic properties and adhesion,
(A1) at least one polyol compound selected from the group consisting of polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol (hereinafter, also simply referred to as “A1 component”);
(A2) a polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also simply referred to as A2 component),
(A3) An amino group-containing compound having two or more groups capable of reacting with an isocyanate group in the molecule, at least one of which is an amino group (hereinafter also simply referred to as an A3 component).
It is preferable that it is a polyurethane-urea resin obtained by reacting. In such a polyurethane-urea resin, a urea bond is introduced into the molecule due to the use of a compound having an amino group as the A3 component as a raw material. Hereinafter, these components will be described.

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

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

  The compounds having two or more active hydrogen-containing groups in the molecule include water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, tritriol. Examples thereof include polyol compounds such as glycol and glycerin having one or more hydroxyl groups in the molecule such as methylolpropane and hexanetriol, and these may be used alone or in admixture of two or more.

  Moreover, as said alkylene oxide, cyclic ether compounds, such as ethylene oxide, a propylene oxide, and tetrahydrofuran, are mentioned, These may be used individually or may be used in mixture of 2 or more types.

  In the polyether polyol of the A1 component, the number average molecular weight is 400 to 400 from the viewpoint of the heat resistance and photochromic properties (color density, fading speed, weather resistance, etc.) of the resulting polyurethane-urea resin, particularly the weather resistance of the photochromic compound. It is preferably 3000, particularly preferably 400 to 2000, and most preferably 400 to 1500.

  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 (Ciethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and other low-molecular polyols such as polycarbonate polyols obtained by phosgenation or transesterification with ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc. The polycarbonate polyol obtained by the above can be mentioned. In the polycarbonate polyol as the A1 component, for the same reason as in the polyether polyol, the number average molecular weight is preferably 400 to 3000, particularly preferably 400 to 2000, and most preferably 400 to 1500. These polycarbonate polyols are available as reagents or industrially, and examples of those that are commercially available include "Duranol (registered trademark)" series manufactured by Asahi Kasei Chemicals Corporation, "Kuraray polyol (registered trademark)" manufactured by Kuraray Co., Ltd. ) "Series," Placcel (registered trademark) "series manufactured by Daicel Chemical Industries, Ltd.," Nipporan (registered trademark) "series manufactured by Nippon Polyurethane Industry Co., Ltd.," ETERNACOLL (registered trademark) "series manufactured by Ube Industries, Ltd. be able to.

  Polycaprolactone polyol: As the polycaprolactone polyol used as the A1 component, a compound obtained by ring-opening polymerization of ε-caprolactone can be used. In the polycaprolactone polyol as the A1 component, the number average molecular weight is preferably 400 to 3000, particularly preferably 400 to 2000, and most preferably 400 to 1500 for the same reason as in the polyether polyol. Such polycaprolactone polyol is commercially available as a reagent or industrially. Examples of commercially available products include “Placcel (registered trademark)” series manufactured by Daicel Chemical Industries, Ltd.

  Polyester polyol: Examples of the polyester polyol used as the A1 component include a polyester polyol obtained by a condensation reaction of a polyhydric alcohol and a 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-hexane Diol, 3,3′-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. These may be used alone or in combination of two or more. Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more.

  In the polyester polyol as the A1 component, for the same reason as in the polyether polyol, the number average molecular weight is preferably 400 to 3000, particularly preferably 400 to 2000, and most preferably 400 to 1500. These polyester polyols are available as reagents or industrially, and examples of commercially available ones include “Polylite (registered trademark)” series manufactured by DIC Corporation, “Nipporan (registered trademark)” manufactured by Nippon Polyurethane Industry Co., Ltd. ) ”Series,“ Maximol (registered trademark) ”series manufactured by Kawasaki Kasei Kogyo Co., Ltd., and the like.

A2 component: polyisocyanate compound As the polyisocyanate compound having two or more isocyanate groups in the molecule used as the A2 component, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, and these A mixture of Among these, it is preferable to use an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound from the viewpoint of weather resistance. For the same reason, it is preferable that 30 to 100% by mass, particularly 50 to 100% by mass of the polyisocyanate compound of the A2 component is an aliphatic polyisocyanate compound. In the A2 component polyisocyanate compound, the number of isocyanate groups contained in the molecule may be two or more, but from the viewpoint of solubility in an organic solvent, the number of isocyanate groups contained in the molecule is 2. It is preferable that

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 Anat -4 - [(4-isocyanatocyclohexyl) methyl] -1-methyl-cyclohexane, 2- (3-isocyanatopropyl) alicyclic polyisocyanate compounds such as cyclohexyl isocyanate,
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-diisocyanatomethylbenzene, 4 , 4′-diisocyanato-3,3′-dimethoxy (1,1′-biphenyl), 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4 Bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl) methyl] 2-methyl And aromatic polyisocyanate compounds such as benzene, 1-isocyanato-3-[(4-isocyanatophenyl) methyl) -2-methylbenzene, 4-[(2-isocyanatophenyl) oxy] phenyl isocyanate. .

  Among these, from the viewpoint of the weather resistance of the resulting polyurethane-urea resin, as described above, 30 to 100% by mass, particularly 50 to 100% by mass of the polyisocyanate compound of component A2 is an aliphatic polyisocyanate compound and an oil. It is preferably at least one polyisocyanate compound selected from cyclic polyisocyanate compounds. Specific examples of suitable compounds include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6- Diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 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: amino group-containing compound The amino group-containing compound used as the A3 component has at least two groups capable of reacting with isocyanate groups in the molecule, and at least half of the groups are amino groups. It is a group-containing compound. The amino group is represented by —NH ₂ or —NH (R), and R is preferably an alkyl group, particularly an alkyl group having 1 to 5 carbon atoms. In addition, reactive groups with isocyanate groups other than amino groups are a hydroxyl group (—OH), a mercapto group (—SH), a carboxyl group [—C (═O) OH], and the like.

  By using this amino group-containing compound, a polyurethane-urea resin can be easily synthesized. The maximum number of amino groups is, of course, the total number of groups that can react with isocyanate groups.

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

  The molecular weight of the amino group-containing compound is preferably 50 to 300 in order to make the resulting polyurethane-urea resin moderately hard and to maintain good heat resistance, adhesion and photochromic properties. More preferably, it is -250, and it is most preferable that it is 55-200.

  As the A3-component amino group-containing compound, at least one compound selected from the group consisting of diamines, triamines, amino alcohols, aminocarboxylic acids, and aminothiols can be suitably used. Specific examples of the compound suitably used as the amino group-containing compound in the present invention include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2- Diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- ( 4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, norbornanediamine, hydrazine, dihydrazine adipate , Phenylenediamine, 4,4'-diphenylmethanedia N, N'-diethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dipropylethylenediamine, N, N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) Examples thereof include triamine and 1,2,5-pentanetriamine.

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

  In the chain extender, it is particularly preferable to use diamine from the viewpoints of heat resistance, adhesion, durability of the photochromic compound, and the like. The reason for this is that when the amino group-containing compound is used when the component A is synthesized, the resulting polyurethane-urea resin has a urea bond, which increases the molecular rigidity and increases the hydrogen between the molecular chains. It is presumed that the heat resistance is improved because the bond becomes stronger. In addition, regarding the improvement of the durability of the photochromic compound, the presence of a 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-urea resin, It is presumed that this is because photooxidation degradation, which is known as a general degradation mechanism of photochromic compounds, 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.

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

  First, the A1 component and the A2 component are reacted to obtain a urethane prepolymer, and then the A component can be produced by reacting the urethane prepolymer with the A3 component.

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

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

The amount ratio of the A1, A2 and A3 components used in the reaction in the above method may be determined as appropriate, but the resulting polyurethane-urea resin has heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance). From the viewpoint of balance such as That is, the total mole number of hydroxyl groups contained in the A1 component is n1, the total mole number of isocyanate groups contained in the A2 component is n2, and a group capable of reacting with the isocyanate group contained in the A3 component (specifically amino group) Group, hydroxyl group, mercapto group and / or carboxyl group) is n3,
n1: n2: n3 = 0.3-0.9: 1: 0.1-0.7 quantitative ratio,
In particular, it is preferable that the quantity ratio is n1: n2: n3 = 0.35-0.85 / 1 / 0.15-0.65,
Most preferably, the ratio is n1: n2: n3 = 0.4 to 0.8 / 1 / 0.2 to 0.6.

  Here, said n1-n3 can be calculated | required as a product of the use mole number of the compound used as each component, and the number of each group which exists in this compound 1 molecule.

  For the polyurethane-urea resin obtained by such a reaction, if necessary, the solvent is distilled off, or the reaction solution is dropped into a poor solvent such as water, and the polyurethane-urea resin is precipitated, filtered and dried. It may be used as the component A after being subjected to post-treatments such as, or may be used as the photochromic composition of the present invention while being dissolved in the reaction solvent.

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

  The number of urea bonds in the polyurethane-urea resin is preferably 0.05 to 4.0 per unit molecular weight (1,000). The number of urea bonds per unit molecular weight can be determined by the ratio of the (A1) component, the (A2) component and the (A3) component of the polyurethane-urea resin, and the number average molecular weight determined by the GPC analysis. The ratio of this urea bond is an average value.

The polyurethane-urea resin as component A was (i) when the photochromic composition of the present invention was used to attach optical sheets or films to form a laminate, or (ii) the obtained laminate was used. From the viewpoint of processability when manufacturing optical articles, and (iii) when forming a hard coat layer on the surface of these laminates or optical articles, processing when applying or curing a hard coat solution From the viewpoint of safety, it is usually preferable to have heat resistance of 60 to 200 ° C., particularly 80 to 150 ° C. In addition, heat resistance here means the softening point measured on the following conditions using the thermomechanical measuring apparatus (The Seiko Instruments company make, TMA120C).
[Measurement Conditions] Temperature rising rate: 10 ° C./min, measurement temperature range: 30 to 200 ° C., probe: needle-inserted probe with a tip diameter of 0.5 mm.

A5 component: Functionality-imparting compound In the present invention, in addition to the above-described components A1 to A3, the molecule has a group capable of reacting with one or two isocyanate groups, and a piperidine structure, hindered in the molecule. It is preferable to use a functional compound having a phenol structure, a triazine structure, or a benzotriazole structure. By using such a function-imparting compound, a piperidine structure, a hindered phenol structure, a triazine structure, or a benzotriazole structure can be imparted to the polyurethane-urea resin, hindered amine light stability performance, antioxidant performance, or A polyurethane-urea resin having excellent functionality such as ultraviolet absorption performance can be obtained.

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

  In addition, the aforementioned piperidine structure, hindered phenol structure, triazine structure, or benzotriazole structure has a light stabilizing effect (piperidine structure), an antioxidant effect (hindered phenol structure), or an ultraviolet absorption effect (triazine structure or benzoid structure). Triazole structure). By using compounds having these structures, the durability (light stability, antioxidant performance, ultraviolet absorption performance) of the polyurethane-urea resin itself as the component A and the photochromic compound can be improved. Especially, in order to improve the durability of a photochromic compound, it is preferable to use the compound which has a piperidine structure. Hereinafter, various compounds used as the A5 component will be described in detail.

Functionality-imparting compound having a piperidine structure As the functionality-imparting compound having a piperidine structure used as the 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. ).

  A compound having a group capable of reacting with an isocyanate group at the nitrogen atom of the piperidine ring or the carbon atom at the 4-position corresponds to a functional compound having a piperidine structure.

  Hereinafter, more specific compounds will be described.

  Among the functional compounds used as the A5 component in the present invention, examples of the compound capable of introducing a piperidine structure at the terminal of the polyurethane-urea resin include compounds represented by the following general formula (1).

(Where
R ¹ , R ² , R ³ , and R ⁴ have the same meaning as in the general formula (i),
R ⁵ is an alkyl group having 1 to 10 carbon atoms 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 an alkyl group having 1 to 10 carbon atoms 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. Incidentally, a is the number of R ^6, when a is 0, refers to those which X is attached directly to the piperidine ring.

  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 functional compound 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- Examples thereof include aminomethylpiperidine, 1,2,2,6,6-pentamethyl-4-aminobutylpiperidine and the like.

  Further, as a compound capable of introducing a piperidine structure at the terminal of the polyurethane-urea resin, the following compound which is a reaction product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol Can also be used.

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

  Among the A5 components used in the present invention, compounds that can introduce a piperidine structure into the main chain of the polyurethane-urea resin include compounds represented by the following general formulas (2), (3), and (4). Is preferably used.

  Following formula (2)

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

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

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

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

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

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

  Following formula (3)

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

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

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

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

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

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

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

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

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

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

Functionality-imparting compound having a hindered phenol structure As the functionality-imparting compound having a hindered phenol structure used as the A5 component in the present invention, a compound having a structure represented by the following general formula (ii) in the molecule is suitable. Can be used for

(Where
R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each an alkyl group having 1 to 18 carbon atoms or a hydrogen atom,
At least one of R ²⁵ and R ²⁶ is an alkyl group having 4 or more carbon atoms. ).

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

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

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

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

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

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

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

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

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

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

Functionality-imparting compound having triazine structure or benzotriazole structure The functionality-imparting compound having triazine structure or benzotriazole structure used as the A5 component in the present invention is represented by the following general formulas (iii) and (iv). A compound having such a structure in the molecule can be preferably used.

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

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

  The following general formula (6)

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

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

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

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

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

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

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

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

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

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

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

  The A5 component can be introduced into any of the terminal, main chain, side chain and the like of the obtained polyurethane-urea resin for the purpose of improving the weather resistance of the polyurethane-urea resin and the photochromic compound. From the viewpoint of not impairing the original heat resistance and mechanical strength (peel strength) of the urethane-urea resin, it is preferably introduced at the end of the polyurethane-urea resin.

Method for synthesizing component A using components A1 to A5 When these components A1, A2, A3 and A5 are reacted to obtain component A, a so-called one-shot method or prepolymer method can be employed. For example, the component A can be suitably obtained by the following method.

Synthesis method 1 (A component having a functional compound at the terminal)
Reaction of A1 component, A2 component, and A3 component can be performed by the method as stated above. The reaction between the obtained urethane polymer and the A5 component can be carried out in the presence or absence of a solvent in an inert gas atmosphere such as nitrogen or argon at 25 to 120 ° C. for 0.5 to 24 hours. That's fine. As the solvent, methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.

Synthesis method 2 (component A having a functionality-imparting compound in the main chain)
A urethane prepolymer having a functional compound is obtained by reacting the A1 component and the A2 component to obtain a urethane prepolymer, and further mixing and reacting the A5 component having a group capable of reacting with two isocyanate groups in the molecule. Next, the A component of the present invention can be produced by reacting the urethane prepolymer with the A3 component.

  In the above method, the reaction between the A1 component and the A2 component, and further the reaction with the A5 component is performed at 25 to 120 ° C. in an inert gas atmosphere such as nitrogen or argon in the presence or absence of a solvent. What is necessary is just to make it react for 5 to 24 hours. As the solvent, organic solvents such as methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the polyisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried. In carrying out the above reaction, dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, 1,4-diazabicyclo [2,2, 2] A catalyst such as octane may be added. As an addition amount at the time of using a catalyst, it is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of this A component.

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

Synthesis method 3 (A component having a functional compound in the side chain)
First, the A5 component having a group capable of reacting with one isocyanate group in the molecule is reacted with a triisocyanate compound having three isocyanate groups to synthesize a diisocyanate compound having a functional structure in the side chain. The A component of the present invention can be produced by reacting the diisocyanate compound with the A1 component and the A2 component to obtain a urethane prepolymer and then reacting with the A3 component.

  In the above method, the reaction between the triisocyanate compound and the 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, organic solvents such as methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the polyisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried.

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

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

The mixing ratio of each component, the characteristics of the A component The amount ratio of the A1, A2, A3, and A5 components used for the reaction in the above method may be determined as appropriate, but the heat resistance of the resulting polyurethane-urea resin, From the viewpoint of balance such as adhesive strength and photochromic properties (color density, fading speed, weather resistance, etc.), the following quantitative ratios are preferable. That is, the total number of moles of hydroxyl groups contained in the A1 component is n1, the total number of isocyanate groups contained in the A2 component is n2, and a group capable of reacting with the isocyanate group contained in the A3 component (specifically an amino group) , A hydroxyl group, a mercapto group and / or a carboxyl group) is n3, and a group (specifically, an amino group, a hydroxyl group, a mercapto group and / or a carboxyl group) which can react with the isocyanate group contained in the component A5. When the total number of moles is n5, n1: n2: n3: n5 = a quantitative ratio of 0.3-0.89 / 1.0 / 0.1-0.69 / 0.01-0.2, In particular, it is preferable that the ratio is n1: n2: n3: n5 = 0.34-0.83 / 1.0 / 0.15-0.60 / 0.02-0.15, and n1: n2: n3: n5 = 0.4-0.78 / 1.0 It is most preferred that the ratio to be 0.2 to 0.5 / 0.02 to 0.1.

  The polyurethane-urea resin 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 the reaction solution in a poor solvent such as water. The polyurethane-urea resin may be used as the component A by subjecting it to a post-treatment such as precipitation, filtration and drying.

A6 component: Reaction terminator When an isocyanate group remains at the end of the polyurethane-urea resin obtained by the above reaction, a reaction terminator having an active hydrogen that reacts with the isocyanate group is added to inactivate the end. Is preferable. When an isocyanate group remains at the terminal, the photochromic property tends to be lowered. Whether or not an isocyanate group remains can be determined by measuring an infrared absorption spectrum.

  Further, when the adhesion strength of the optical article is further improved by using an isocyanate compound having at least one isocyanate group in the molecule as the component (D) described later, the end of the polyurethane-urea resin is non-reactive. It must be stopped by the group. A polyurethane-urea resin terminated with a non-reactive group reacts a polyurethane-urea resin with a terminal isocyanate group with a reaction terminator having a group capable of reacting with one isocyanate group in the molecule. Can be obtained.

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

  This reaction terminator has only one group in the molecule that can react with an isocyanate group. When two or more groups capable of reacting with an isocyanate group are present in the molecule, the polyurethane-urea resin has a high molecular weight and becomes highly viscous when diluted with an organic solvent, making it difficult to form a coating film, and the resulting photochromic properties. The adhesiveness (adhesiveness with an optical sheet) of an adhesive agent will be reduced. By introducing the reaction terminator at the end of the polyurethane-urea resin, it becomes possible to control the number-average molecular weight of the urethane-urea resin, and the adhesion, heat resistance, and photochromic properties can be easily achieved. Can be adjusted.

  As a reaction terminator, amine, alcohol, thiol, and carboxylic acid can be used. Specific examples include normal butylamine, sec-butylamine, tert-butylamine, dibutylamine, diisopropylamine, methanol, ethanol, isopropanol, normal butanol, sec-butanol, tert-butanol, and acetic acid.

  In addition, by using the above-described function-imparting compound as the A5 component as a reaction terminator, the terminal isocyanate group can be inactivated simultaneously with the introduction of the function-imparting compound into the polyurethane-urea resin. That is, the A5 component can also be used as the A6 component described later.

  The reaction terminator (A6 component) that can be suitably used in the present invention will be described below.

A6 component: Reaction terminator Preferred compounds as the reaction terminator can be represented by the following general formulas (8) and (9).

(Where
R ³⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom,
R ⁴⁰ 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 ³⁹ is a hydrogen atom is used as the A5 component, the end of the polyurethane-urea resin is —NH (R ⁴⁰ ), and this —NH (R ⁴⁰ ) is another polymer, and It does not substantially react with the isocyanate compound. Therefore, —NH (R ⁴⁰ ) does not correspond to a group that can react with an isocyanate group.

In the general formula (8), R ³⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom. Among these, R ³⁹ 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 ³⁹ 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 ⁴⁰ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group. Among them, R ⁴⁰ is an alkyl group having 1 to 10 carbon atoms, an aryl group, or 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 ⁴⁰ 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 (9)

(Where
R ⁴¹ 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 (9), R ⁴¹ 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 ⁴¹ 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. -Tetramethylbutyl group, phenyl group, benzyl group, 1,1-dimethylbenzyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group and the like.

  Z in the general formula (9) is a group capable of reacting with an isocyanate group present at the end of the polyurethane-urea resin, specifically a hydroxyl group, a carboxyl group, or a thiol group, and preferably a hydroxyl group.

  Specific compounds represented by the general formulas (8) and (9) 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, Alcohols such as butanol, 2-butanol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decanol, 2-decanol; 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, 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 terminators may be used alone or in combination of two or more.

Mixing ratio of A6 component, characteristics of A component The A6 component can be introduced into the polyurethane-urea resin by reacting in the same manner as the above-described A5 component.

  The amount ratio of the A1, A2, A3 and A6 components may be determined as appropriate, but the obtained polyurethane-urea resin has heat resistance, adhesive strength, photochromic properties (color density, fading speed, weather resistance, etc.), etc. From the viewpoint of balance, the following quantitative ratio is preferable. As described above, the amount ratio of the A1 component, the A2 component, and the A3 component is such that the total mole number of hydroxyl groups contained in the A1 component is n1, the total mole number of isocyanate groups contained in the A2 component is n2, and the A3 component A group capable of reacting with an isocyanate group contained in the A6 component, wherein the total number of moles of functional groups (specifically, amino group, hydroxyl group, mercapto group and / or carboxyl group) capable of reacting with the isocyanate group contained in n3 is n3 N1: n2: n3: n6 = 0.30-0.89: 1: 0.1-0.69: 0.01-0.20 It is preferable. In order for the obtained photochromic composition (photochromic adhesive) to exhibit excellent adhesion, durability, and photochromic properties, preferably n1: n2: n3: n6 = 0.34-0.83: 1. : 0.15-0.6: 0.02-0.15, more preferably n1: n2: n3: n6 = 0.4-0.78: 1: 0.2-0.5: 0.02 ~ 0.1. Here, n1, n2, n3, and n6 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.

  In addition, A component before A6 component introduction | transduction 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 inactivate the terminal of A component, n6 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 blending is a case where the above-mentioned quantitative ratio is satisfied and the sum of n2, n1, n3, and n6 is equal (n2 = n1 + n3 + n6).

  When inactivating the terminal of the A component, the A6 component can be used in such a blending amount that the sum of n1, n3, and n6 is n2 or more (n2 ≦ n1 + n3 + n6). In this case, the excessively added A6 component may be removed by reprecipitation. In addition, when the excess A6 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 A6 component is consumed by reacting with the B component. Therefore, there is no particular problem as long as the excess A6 component is an amount that does not impair the effects of the present invention. However, since the isocyanate group in the A6 component that should be originally used for the production of the polyurethane-urea resin is consumed, the most preferred embodiment is to use the A6 component so that n1 + n3 + n6 = n2.

  When only the A5 component is used instead of the A6 component, the n6 can be read as n5. Moreover, when A5 component and A6 component are used together as a reaction terminator, said n6 can be read as the sum of n6 and n5 (n6 + n5).

  Further, the polyurethane-urea resin (component (A)) obtained by using a reaction terminator, that is, A5 and A6 components, does not greatly change the molecular weight, heat resistance, and urea bond amount depending on these reaction terminators. . Therefore, the polyurethane-urea resin obtained by using these reaction terminators also has a number average molecular weight in terms of polyethylene oxide of 5,000 to 150,000, particularly 8,000 to 100,000, and 10,000 to 60,000. Most preferably, there are preferably 0.05 to 4.0 urea bonds per unit molecular weight (1,000), and the heat resistance is preferably 60 to 200 ° C, particularly preferably 80 to 150 ° C.

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

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

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

  Among these other photochromic compounds, a chromene compound having an indeno (2,1-f) naphtho (2,1-b) pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloring, 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.

  Such a chromene compound can be represented by the following general formula.

  The chromene compound having the structure represented by the general formula (10) may have a known substituent without any particular limitation on the substituent.

  Among the chromene compounds, as described above, indeno (2,1-f) naphtho (1, 1) represented by the following general formula (11) from the viewpoint of photochromic properties such as color density, initial coloration, durability, and fading speed. 2-b) A chromene compound having a pyran structure is more preferred.

  The chromene compound having the structure represented by the general formula (11) may have a known substituent without any particular limitation on the substituent.

  Examples of photochromic compounds that can be suitably used in the present invention include the following.

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

Optional component In addition to the A component and the B component, the photochromic composition includes (C) an organic solvent (hereinafter also simply referred to as C component), (D) an isocyanate compound having two or more isocyanate groups in the molecule. In addition, other components may be included. Hereinafter, these optional components will be described.

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

  Examples of organic solvents that can be suitably used as component C include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, 2-butanol; ethylene glycol monomethyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n- Polyhydric alcohol derivatives such as butyl ether and ethylene glycol dimethyl ether; diacetone alcohol; methyl ethyl ketone, diethyl ketone, etc. Ketones; toluene; hexane; heptane: ethyl acetate, 2-methoxyethyl, acetate such as 2-ethoxyethyl acetate; DMF; DMSO; THF; cyclohexanone; and combinations thereof can be exemplified.

  What is necessary is just to select suitably from these according to the kind of A component to be used, and the material of an optical sheet or a fill. For example, when an optical sheet or film made of polycarbonate resin is used and the photochromic composition of the present invention is directly applied, it is preferable to use alcohols or polyhydric alcohol derivatives as the solvent.

  In addition, the organic solvent hardly remains and increases the drying speed while maintaining the smoothness of the photochromic adhesive sheet when the coating layer when the photochromic composition of the present invention is applied to the optical sheet or film or the method described later is adopted. For this reason, it is preferable to use a mixture of an organic solvent having a boiling point of less than 90 ° C. and an organic solvent having a boiling point of 90 ° C. or more as the C component. 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 addition amount in the case of adding C component is 5-900 mass parts with respect to 100 mass parts of A component especially from 20-750 mass parts from a viewpoint of the effect acquired by above-mentioned C component addition. It is preferable to set it to 40 to 400 parts by mass.

D component: Isocyanate compound having one or more isocyanate groups in the molecule The isocyanate compound having an isocyanate group may be blended with the photochromic composition. By using an isocyanate compound having at least one isocyanate group in the molecule as the D component, the adhesion strength of the optical article described later can be further improved.

  As the isocyanate compound having at least one isocyanate group in the molecule, known isocyanate compounds 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 D component to the above-mentioned A component, it is considered as follows. Some of the isocyanate groups contained in the component D are hydrolyzed by the moisture contained in the photochromic composition of the present invention and the humidity in the environment (that is, in the presence of moisture) to produce amino groups. The generated amino group reacts with the isocyanate group remaining in the component D to become a reaction product having a urea bond. The urea bond 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 D 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 the reaction product of D component (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 (D ′) (hereinafter, also simply referred to as “D ′ 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 D component.

  When synthesizing the D ′ component, it is preferable that the A2 component, which is a diisocyanate compound, is reacted with the amino alcohol compound or diol compound, which is the A3 component. Among them, as the diisocyanate compound, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, etc. Aliphatic 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, isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate), hexahydrotoluene-2,4-di Isocyanate, hexahydroterephthalic toluene-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 D 'component must have at least one isocyanate group in the molecule. Therefore, when synthesizing the D ′ 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 in the component D 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 D component (D ′ component) may be one, but is preferably two or more. By having two or more isocyanate groups in the molecule of the D component, a urea resin having a large molecular weight (a reaction product of the D component) can be formed when the photochromic adhesive layer is formed. As a result, the cohesive force between the reaction product of the D 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 four or more isocyanate groups are present in the molecule of component D, it is formed of a urea resin crosslinked in a network form, so that phase separation is likely to occur between component A and the present invention. The photochromic adhesive layer tends to become cloudy. Therefore, the component D (including the D ′ 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 D 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 D 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 D component (including the D ′ component) is not particularly limited, but is preferably less than 1000. When the molecular weight of the component D is 1000 or more, the heat resistance and film strength of the resulting photochromic adhesive layer tend to be reduced. It is considered that this is because when a high molecular weight isocyanate compound is blended, the structure part other than the urea bond in the reaction product of the D component is affected. 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 D component is preferably less than 1000. From the above, the molecular weight of the D component is more preferably 750 or less, and most preferably 600 or less. Naturally, the molecular weight of the D 'component is preferably less than 1000 for the same reason. As described above, the component D (component D ′) is preferably not a polymer. Therefore, the molecular weight of the D component (D ′ component) refers to the molecular weight of the D component (D ′ component) itself. The lower limit of the molecular weight of component D is the molecular weight of the simple compound, and is 100, although not particularly limited.

Compounding amount of D component The compounding amount of D component in the photochromic composition is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of component A from the viewpoint of adhesion, heat resistance, and photochromic properties. is there. When the blending amount is too small, sufficient adhesion and heat resistance cannot be improved. When the blending amount is too large, cloudiness of the adhesive layer obtained from the photochromic composition, decrease in adhesion, photochromic There is a tendency for the durability of the compound to decrease. In order to improve the adhesion to an optical substrate such as a plastic film while maintaining the photochromic properties such as color density and durability, the amount of component D is 0.1 to 100 parts by mass of component A. 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 of D 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. It is -3.0 mass part. Here, the amount of isocyanate groups can be determined from the molecular weight of component B and the number of isocyanate groups per molecule.

Water Water can also be mix | blended with a photochromic composition. In particular, the isocyanate group contained in the D component of the present invention can be efficiently hydrolyzed by adding water when adding the D component which is an isocyanate compound. 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 D 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 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 mole-5 times mole with respect to the number of moles of the isocyanate group contained in D component, preferably 0.05 times mole-3 times mole, more preferably 0.1 times mole. It is preferable that it is the range of 2 times mole-2 times mole.

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

  For example, as the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in the photochromic composition. Specific examples of nonionic surfactants that can be suitably used include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester , Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensate, a single-chain polyoxyethylene alkyl ethers, and more may be mentioned surfactants of the silicone-based or fluorine.

  In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the polyurethane-urea resin (component A).

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

Method for Producing Photochromic Composition The photochromic composition can be produced by mixing the A component and the B component, and the C component, D component (D ′ component), and other components used as necessary. it can. The order in which the components are mixed is not particularly limited.

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

  The photochromic composition thus obtained can be suitably used as a photochromic adhesive, particularly a photochromic adhesive for joining optical sheets or films made of polycarbonate resin.

  In the present invention, the first adhesive layer is formed from the photochromic composition thus produced. Next, the adhesive composition for forming the second adhesive layer will be described.

Adhesive composition for forming the second adhesive layer The second adhesive layer is laminated on both sides of the first adhesive layer made of the photochromic composition. Then, an optical sheet or film described in detail below is laminated (adhered) on the second adhesive layer. By adhering two opposing optical sheets or films via the adhesive layers laminated in the order of the second adhesive layer / first adhesive layer / second adhesive layer, excellent adhesion can be exhibited. .

  The adhesive composition forming the second adhesive layer is not particularly limited as long as it is in close contact with the optical sheet or film. Especially, it is preferable that this adhesive composition contains the compound (henceforth only a urethane compound) which has a urethane bond or a urea bond. By using the urethane compound, the first adhesive layer made of the photochromic composition and stronger adhesion can be obtained. This is thought to be because an intermolecular force such as a hydrogen bond is generated between the polyurethane-urea resin contained in the first adhesive layer of the present invention and the urethane compound.

  Examples of the urethane compound that can be used as the adhesive composition include urethane (meth) acrylate, two-component urethane, moisture-curing urethane, and urethane dead polymer.

  As the urethane (meth) acrylate, an isocyanate compound obtained by reacting the polyisocyanate compound described in the component (A2) with a polyol compound such as diol or triol described in the component (A1), hydroxyethyl ( The reactive organism of the compound which has a hydroxyl group and a (meth) acrylate group in molecules, such as a (meth) acrylate, can be mentioned.

  As the two-component urethane, a known two-component urethane resin can be used. This can include a mixture of a compound having an isocyanate group at the molecular chain terminal and a compound having a period (specifically, a hydroxyl group, an amino group, etc.) capable of reacting with the isocyanate group at the molecular chain terminal.

  As the moisture curable urethane, a known moisture curable urethane resin can be used. Mention may be made of a urethane prepolymer having an isocyanate group at the terminal obtained by reacting a polyol having two or more hydroxyl groups in the molecule with an excess amount of a polyisocyanate compound. Part of the component (A) can also be used as a moisture curable urethane resin.

  Unlike the urethane compound, the urethane dead polymer does not have a reactive group at the terminal, and the terminal is reacted with a reaction terminator ((A5), (A6)) in the component (A). Mention may be made of urethane compounds.

  In this adhesive composition, an object to be joined is a first adhesive layer made of an optical sheet or film described in detail below and the photochromic composition. Therefore, it is most preferable to use a urethane compound (polyurethane-urea resin) synthesized with the same components as the (A) polyurethane-urea resin used in the photochromic composition. Furthermore, as the other components, the component (C), the component (D), water, and other additive components described in the photochromic composition can be included.

  Moreover, although this adhesive composition is demonstrated in detail in the 2nd contact bonding layer explained in full detail below, it is preferable that a photochromic compound is not included. Although this adhesive composition does not exclude the composition containing a photochromic compound, it is preferable that the photochromic composition is not included in consideration of the adhesion of the resulting laminate.

  Moreover, it is preferable to make the 2nd contact bonding layer formed from this adhesive composition thinner than a 1st contact bonding layer. Therefore, the adhesive composition contains an organic solvent that dissolves the solid content, for example, the alcohols described in the C component, with respect to 100 parts by mass of the solid content (for example, the urethane compound) forming the second adhesive layer. It is preferable to contain 10 to 900 parts by mass of an organic solvent such as a polyhydric alcohol derivative or ketones. Among these, it is preferable to use a polyhydric alcohol derivative.

  The second adhesive layer can be formed using the adhesive composition as described above. Next, the optical sheet or film which comprises the laminated body of this invention is demonstrated.

Optical Sheet or Film In the present invention, as the optical sheet or 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 and easy to process. It is preferable to use a resin-made one from the viewpoints of thickness. Examples of resins suitable as raw materials for optical sheets or films and optical substrates include polycarbonate resins, polyethylene terephthalate resins, nylon resins, triacetyl cellulose resins, acrylic resins, urethane resins, allyl resins, epoxy resins, and polyvinyl alcohol resins. Etc. Among these, polycarbonate resin is particularly preferable because it has good adhesion and high applicability to the injection molding method. A polarizing film (a polyvinyl alcohol polarizing film sandwiched between triacetyl cellulose resin films) can also be used as the optical film of the present invention. Further, the optical sheet or film used in the present invention may be washed and degreased with an organic solvent such as methanol in advance. Furthermore, corona discharge treatment, plasma discharge treatment, UV ozone treatment, or the like can be performed.

  The thickness of the optical sheet or film is not particularly limited, but is 50 μm to 1 mm in view of secondary processability, stability after secondary processing, and ease of manufacturing a laminate. Is preferred.

  Next, the photochromic laminated body which joined this optical sheet or film is demonstrated.

Photochromic Laminate The laminate of the present invention has the configuration shown in FIG. That is, two optical sheets or films 1 that face each other are (A) a polyurethane-urea resin having a urea bond in a molecular chain, and (B) a first adhesive layer 2 made of a photochromic composition containing a photochromic compound; The second adhesive layer 3 is formed on both sides of the first adhesive layer.

  By laminating the second adhesive layer, the adhesion of the laminate of the present invention can be further improved. The following two points can be cited as factors that improve the adhesion of the laminate by laminating the second adhesive layer.

  The first is that a layer having a compound that easily undergoes photo-oxidative degradation such as a photochromic compound is not brought into direct contact with the optical sheet or optical film. The reason for this is not clear, but photochromic compounds that have been decomposed and reduced in molecular weight due to photooxidation degradation, etc., migrate to the interface between the adhesive layer and the optical sheet or optical film, thereby reducing the adhesion between them. I guess.

  The second is particularly effective for an optical sheet or an optical film made of a thermoplastic resin, but a liquid and fluid adhesive such as dissolved in an organic solvent is directly applied to the optical sheet or the optical sheet before curing. By applying to the optical film, the optical sheet or optical film can be penetrated while being eroded with an adhesive, so that it is considered that the adhesion is further improved.

  Therefore, it is preferable that the second adhesive layer does not contain a photochromic compound, and it is more preferable that the second adhesive layer is directly applied to the optical sheet or the optical film in a liquid and fluid adhesive state. The second adhesive layer can be thinned. Therefore, even if the adhesive composition containing an organic solvent is directly applied to the optical sheet or film, the transparency of the optical sheet or film is not greatly reduced.

  In this laminate, the thickness of the first adhesive layer containing the photochromic compound is preferably 5 to 100 μm and more preferably 20 to 60 μm in view of good photochromic properties, adhesion, and the like. The second adhesive layer is thinner than the first adhesive layer in order to exhibit excellent adhesion, and is preferably in the range of 1 to 40 μm, and more preferably 2 to 20 μm.

Production method of photochromic laminate In the present invention, the production method of the laminate is not particularly limited as long as the second adhesive layer is laminated between the first adhesive layer and the optical sheet or optical film. Not limited. Especially, it is preferable to manufacture a 1st contact bonding layer independently.

Method for producing first adhesive layer (step (1))
The first adhesive layer can be obtained by the following method depending on the properties of the photochromic composition to be used. In the case of using a photochromic composition containing an organic solvent, after spreading the photochromic composition on a smooth substrate, the organic solvent is removed by drying, and then the substrate is peeled off. And the 1st contact bonding layer (1st contact bonding sheet: 1st contact bonding layer which consists of a photochromic composition) containing B component disperse | distributed in this A component can be formed.

  As a method for spreading the photochromic composition, known methods such as a spin coating method, a spray coating method, a dip coating method, a dip-spin coating method, and a dry laminating method are used without any limitation.

  As the material for the smooth base material, those which are resistant to the solvent used in the present invention and those in which the polyurethane-urea resin of the present invention is easily peeled are preferable. Specific examples include glass, stainless steel, Teflon. (Registered trademark), polyethylene terephthalate, polypropylene, and a plastic film in which a coating layer that improves the peelability of silicon or fluorine is laminated.

  The application and further drying of the photochromic composition is preferably performed at a temperature of room temperature to 130 ° C. and a humidity of 10 to 100% RH. In particular, when a photochromic composition containing a component D is used, it is preferably operated in the presence of humidity. That is, when the D component is present, by performing coating and drying under these conditions, the hydrolysis reaction of the D component is promoted, and a stronger adhesion can be obtained. By drying under the above humidity (in the presence of moisture), the first adhesive layer (first adhesive sheet) that exhibits excellent performance can be obtained without adding water to the photochromic composition. it can. Moreover, when water is blended, the first adhesive layer can be formed by drying in a temperature range of room temperature to 130 ° C.

  Moreover, when using the photochromic composition which does not contain an organic solvent, it is also possible to produce a 1st contact bonding layer by extrusion molding.

Method for Producing Laminate by Laminating Second Adhesive Layer on Both Sides of First Adhesive Layer A method for producing a laminate using the first adhesive layer obtained by the above method is not particularly limited. The following methods are mentioned. For example,
1) A method of previously laminating a second adhesive layer on an optical sheet or optical film, and sandwiching the first adhesive layer between two optical sheets or optical films having the second adhesive layer,
2) A method in which a second adhesive layer is applied on both sides of the first adhesive layer, and an optical sheet or an optical film is attached to both sides of the first adhesive layer,
3) A method of sequentially laminating a second adhesive layer, a first adhesive layer, a second adhesive layer, and further an optical sheet or optical film on the optical sheet or optical film,
Etc. Of these, it is most preferable to adopt the method 1) from the viewpoint of production efficiency.

More specifically, a suitable manufacturing method will be described.
A step (1) of forming a first adhesive layer comprising a polyurethane-urea resin having a urea bond in the molecular chain and a photochromic composition containing a photochromic compound;
A step (2) of forming a second adhesive layer on two optical sheets or films;
The first adhesive layer obtained in the step (1) and the two laminates having the second adhesive layer on the optical sheet or film obtained in the step (2) are combined with the first adhesive layer and the second adhesive. It is preferable to implement the step (3) of laminating so that the layers are in contact with each other.

  The step (1) is as described in the method for producing the first adhesive layer.

  In the step (2), when the adhesive composition forming the second adhesive layer contains an organic solvent, first, the adhesive composition may be spread on an optical sheet or film and dried. The spreading method and the drying method can be carried out by the same method as that for the first adhesive layer. In the case of using a photopolymerization initiator in combination with the urethane (meth) acrylate adhesive, it is also possible to carry out photocuring. When the adhesive composition does not contain an organic solvent, the second adhesive layer and the optical sheet or film can be laminated by coextrusion molding.

  In the step (3), the first adhesive layer obtained in the step (1) is laminated on the second adhesive layer of the one laminate obtained in the step (2), and further, the step (2) What is necessary is just to arrange | position so that the 2nd contact bonding layer of this other laminated body and this 1st contact bonding layer may join. As a matter of course, the first adhesive layer may be sandwiched between the two laminates obtained in the step (2).

  A photochromic laminated body can be manufactured by implementing a process (3). The obtained photochromic laminate can be used as it is, but it can also be used with its state stabilized by the following method. Specifically, it is preferable to leave the photochromic laminate that has just been subjected to the step (3) 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 stationary photochromic laminate at a temperature of 80 ° C. to 130 ° C. for 30 minutes to 3 hours (hereinafter referred to as heat treatment). The photochromic laminate obtained by this heat treatment has a very stable state. Moreover, when the photochromic composition which mix | blended D component is used, it is preferable to humidify at the temperature of room temperature-100 degreeC, and the humidity of 30-100% RH. By performing this humidification treatment, the isocyanate group derived from the D component present in the photochromic laminate can be eliminated, and the photochromic properties and adhesion can be further stabilized. Furthermore, after the humidification treatment, excess moisture present in the photochromic laminate can be removed by standing at 40 to 130 ° C. under normal pressure or under vacuum.

Use of photochromic laminate The photochromic laminate of the present invention can be produced by the method as described above. The obtained photochromic laminate can be used as it is, but it can also be applied to optical articles such as spectacle lenses by further providing a synthetic resin layer on an optical sheet or film.

  As a method of laminating the synthetic resin layer on the optical sheet or film of the photochromic laminate, a known method can be adopted. For example, after mounting the photochromic laminate of the present invention in a mold, a method for injection molding a thermoplastic resin for constituting an optical base material (for example, a lens body: synthetic resin layer) such as a polycarbonate resin (hereinafter simply referred to as “molding”). Also referred to as an injection molding method.). Moreover, the method of sticking the said photochromic laminated body of this invention to the surface of an optical base material (synthetic resin layer) with an adhesive agent etc. can be mentioned. Moreover, after immersing the photochromic laminate in a polymerizable monomer capable of forming an optical substrate (synthetic resin layer), the photochromic laminate is cured in the optical substrate (synthetic resin layer) by curing the polymerizable monomer. The body can be embedded and integrated. Therefore, the optical article may be obtained by laminating the photochromic laminate on a plastic optical substrate (synthetic resin layer) made of a thermoplastic resin or a thermosetting resin, or the plastic optical substrate. In the (synthetic resin layer), the photochromic laminate may be embedded.

  Note that, in any method of injection molding and immersion in a polymerizable monomer, the photochromic laminate can be used as it is, or an optical sheet or optical film laminated with a functional film is used. You can also.

  Moreover, the optical article which laminated | stacked the synthetic resin layer can perform the secondary process according to the use. For example, when used for spectacle lens applications, a hard coat layer, an antireflection film layer, an antifouling layer, a water repellent layer, and the like can be laminated on the synthetic resin layer.

  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.

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

A2 component; polyisocyanate compound NCO1: isophorone diisocyanate. (Molecular weight 222)
A3 component; amino group-containing compound (chain extender)
CE1: Isophorone diamine.

A5 component; Functionality-imparting compound HA1; 1,2,2,6,6-pentamethyl-4-hydroxypiperidine.
HA2; 1,2,2,6,6-pentamethyl-4-aminopiperidine.

A6 component: Reaction terminator HA3; normal butylamine.

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

Component C: organic solvent C6: THF (tetrahydrofuran).
C7: Diethyl ketone D component; Isocyanate compound D1: Isophorone diisocyanate (molecular weight 222).
D2: 4,4′-methylenebis (cyclohexyl isocyanate) (molecular weight 262).

(A) Synthesis of polyurethane-urea resin (U1) A three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 252 g of polycarbonate diol having a number average molecular weight of 800 and 100 g of isophorone diisocyanate, and a nitrogen atmosphere. Then, the mixture was reacted at 90 ° C. for 7 hours, then cooled to 25 ° C., and dissolved by adding 1,200 ml of THF. To this, 18.9 g of isophoronediamine as a chain extender was dropped and reacted at 25 ° C. for 1 hour. Then, 8 g of 1,2,2,6,6-pentamethyl-4-aminopiperidine was added, and the reaction was performed at 25 ° C. The reaction was carried out for 1 hour. Subsequently, the solvent was distilled off under reduced pressure to obtain a polyurethane-urea resin (U1). When an infrared absorption spectrum of the obtained polyurethane-urea resin was measured, absorption derived from an isocyanate group was not confirmed at the molecular terminal, and it was confirmed that no isocyanate group remained at the molecular terminal. The molecular weight of the obtained polyurethane-urea resin was 22,000 (theoretical value; 18,000) in terms of polyoxyethylene, and the heat resistance was 100 ° 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-urea resin without cross-linking. That's it.

Synthesis of polyurethane-urea resin (U2) to (U12) Polyol compound (A1 component), polyisocyanate compound (A2 component), amino group-containing compound (A3 component) shown in Table 1, functional compound (A5 component), The synthesis of U2 to U12 was carried out 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 terminator (component A6) and the reaction solvent.

  The results of the blending ratio, number average molecular weight, and heat resistance of the A1, A2, A3, A5, and A6 components of the polyurethane-urea resins U1 to U12 are summarized in Table 2.

Preparation of Adhesive Composition (Adhesive Composition Forming Second Adhesive Layer) Adhesive Composition 1; Urethane (meth) acrylate Adhesive Urethane Oligomer Tetraacrylate (Shin Nakamura Chemical Co., Ltd. U-4HA, 4-functional) 50 parts by mass, 40 parts by mass of triethylene glycol dimethacrylate (bifunctional), 10 parts by mass of γ-glycidoxypropyl methacrylate (bifunctional), and 1-hydroxycyclohexyl phenyl ketone and bis (2 , 6-Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 3: 7 mixture (Irgacure 1870, manufactured by Ciba Specialty Chemicals Co., Ltd.) Obtained.

Adhesive composition 2; 2-pack urethane adhesive 38 parts by mass of urethane prepolymer having 200 mol parts of a hydroxyl group terminated with a hydroxyl group obtained by reacting isophorone diisocyanate with polycarbonate polyol having a number average molecular weight of 800 in a molar ratio of 3: 4 Was added, and 5 parts by mass of isocyanurate-modified hexamethylene diisocyanate having an isocyanate group at the end was added thereto to obtain an adhesive composition 2.

Adhesive composition 3; moisture-curing urethane-based adhesive In a nitrogen atmosphere, 18.0 parts by weight of a polycarbonate diol having a number average molecular weight of 800, 10.0 parts by weight of isophorone diisocyanate, and 100 parts by weight of DMF are charged under a nitrogen atmosphere. Then, 1.2 parts by mass of 1,4-butanediol, which is a chain extender, is dropped, and the reaction is continued at 100 ° C. for 5 hours. A resin was obtained. To 10 g of the obtained polyurethane resin, 50 g of THF as an organic solvent was added and dissolved with stirring at room temperature to obtain an adhesive composition 3.

Adhesive composition 4; Urethane dead polymer adhesive 50 g of propylene glycol monomethyl ether as an organic solvent was added to 10 g of polyurethane-urea resin (U5) and dissolved at room temperature with stirring to obtain an adhesive composition 4 .

Adhesive composition 5: Urethane dead polymer adhesive 50 g of propylene glycol monomethyl ether as an organic solvent was added to 10 g of polyurethane-urea resin (U12) and dissolved at room temperature with stirring to obtain an adhesive composition 5 .

Adhesive Composition 6: Urethane Dead Polymer Adhesive To 10 g of polyurethane-urea resin (U3), 50 g of propylene glycol monomethyl ether as an organic solvent was added and dissolved while stirring at room temperature to obtain an adhesive composition 6 .

Adhesive composition 7: Urethane dead polymer adhesive 50 g of propylene glycol monomethyl ether as an organic solvent was added to 10 g of polyurethane-urea resin (U4) and dissolved at room temperature with stirring to obtain an adhesive composition 7 .

Example 1
Preparation of photochromic composition To 5 g of polyurethane-urea resin (U1) and 0.25 g of photochromic compound (PC1), 8 g of THF as an organic solvent, 12 g of diethyl ketone, and 0.15 g of isophorone diisocyanate were added and stirred at 80 ° C. It melt | dissolved by the ultrasonic wave and the photochromic composition was obtained.

Production of Photochromic Laminate Step (1) Production of First Adhesive Layer The photochromic composition is applied to a PET film (Purex film, Teijin DuPont Films Co., Ltd., with silicon coating) in the presence of moisture (23 In a laboratory at 50 ° C. and a humidity of 50%, after drying at 50 ° C. for 30 minutes, the PET film was peeled off to obtain a first adhesive layer having a thickness of about 40 μm.

Step (2) Production of Optical Sheet or Film Having Second Adhesive Layer Adhesive composition 1 was applied on a polycarbonate sheet having a thickness of 400 μm, and F3000SQ (D bulb) manufactured by Fusion UV Systems was used under nitrogen flow. Two polycarbonate sheets having a second adhesive layer having a thickness of 5 μm were obtained by photocuring for 5 minutes.

Step (3)
Next, the first adhesive layer obtained in the step (1) is sandwiched between two polycarbonate sheets having the second adhesive layer obtained in the step (2), and left to stand at 40 ° C. under reduced pressure for 12 hours. The mixture was heat-treated at 110 ° C. for 1 hour, then allowed to stand at 40 ° C. under 80% RH for 6 hours, and further under reduced pressure at 40 ° C. for 12 hours to obtain a photochromic laminate having the desired photochromic properties.

  When the obtained photochromic laminate was evaluated, the color density as a photochromic characteristic was 1.1, the fading speed was 43 seconds, and the durability was 98%. The peel strength was 150 N / 25 mm at the initial stage and 130 N / 25 mm after the boiling test. These evaluations were performed as follows.

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

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

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

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

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

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

Examples 2-22
A photochromic composition was prepared in the same manner as in Example 1 except that the polyurethane-urea resin, isocyanate compound, organic solvent, and other components shown in Table 3 and Table 4 were used. Moreover, the photochromic compound (PC1) was mix | blended so that it might become 5 mass parts (actual usage-amount 0.25g) with respect to a polyurethane-urea resin (A component) like Example 1. FIG. Using the obtained photochromic composition and the adhesive compositions shown in Table 3 and Table 4, a photochromic laminate was produced in the same manner as in Example 1 (steps (1) to (3)).

  However, according to each adhesive composition, step (2) was dried and cured by the following methods to produce two polycarbonates having a second adhesive layer. Thereafter, using the obtained two polycarbonates having the second adhesive layer, the same operation as in step (3) of Example 1 was performed to produce a photochromic laminate.

  The evaluation results of the obtained various photochromic laminates are shown in Table 3 and Table 4.

Step (2)
Use of the adhesive composition 1 (drying and curing method); the same method as in Example 1.

  Use of adhesive composition 2 (drying and curing method); a second adhesive layer having a thickness of 5 μm by applying adhesive composition 2 on a polycarbonate sheet having a thickness of 400 μm, and drying and curing at 110 ° C. for 2 hours. Two polycarbonate sheets having the above were obtained.

  Use of Adhesive Composition 3 (Drying and Curing Method): The adhesive composition 3 was applied on a polycarbonate sheet having a thickness of 400 μm, dried at 110 ° C. for 5 minutes, and then humidified (40 ° C., 80% RH). Were allowed to stand for 1 hour to obtain two polycarbonate sheets having a second adhesive layer having a thickness of 5 μm.

  Use of Adhesive Compositions 4-7 (Drying and Curing Method); Adhesive Compositions 4-7 are coated on a polycarbonate sheet having a thickness of 400 μm and dried at 110 ° C. for 10 minutes, whereby an adhesive layer having a film thickness of 5 μm Two polycarbonate sheets having the above were obtained.

Comparative Examples 1-12
A photochromic composition was prepared in the same manner as in Example 1 except that the polyurethane-urea resin, isocyanate compound, organic solvent, and other components 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 usage amount 0.25 g) with respect to the polyurethane-urea resin (component A). Moreover, the photochromic laminated body was produced by the method similar to Example 1 except not having provided the 2nd contact bonding layer using the obtained photochromic composition. That is, the step (2) of Example 1 is not performed, and in the step (3), the first adhesive layer and the polycarbonate film not having the second adhesive layer are adhered by the same operation, and the photochromic laminate is obtained. Manufactured. Table 5 shows the evaluation results of the obtained various photochromic laminates.

  As is clear from Examples 1-22, according to the present invention, the second adhesive layer is formed on both sides of the first adhesive layer comprising the polyurethane-urea resin (component A) and the photochromic compound (component B), It can be seen that by producing a photochromic laminate in which two optical sheets or films are bonded via this second adhesive layer, it has excellent photochromic properties and peel strength (adhesion).

  On the other hand, as in Comparative Examples 1 to 12, when a photochromic laminate in which the first adhesive layer and two optical sheets or films are joined without using the second adhesive layer, the photochromic characteristics are good. However, the peel strength was lower than that of the example.

DESCRIPTION OF SYMBOLS 1 Optical sheet or film 2 1st contact bonding layer 3 2nd contact bonding layer 4 Photochromic laminated body

Claims (6)

Two optical sheets or films facing each other
(A) A first adhesive layer comprising a polyurethane-urea resin having a urea bond in a molecular chain, (B) a photochromic compound, and a photochromic composition containing an isocyanate compound (D) having two or more isocyanate groups in the molecule. When,
A second adhesive layer made of at least one urethane compound selected from the group consisting of urethane (meth) acrylate, two-component urethane, moisture-curable urethane, and urethane dead polymer formed on both sides of the first adhesive layer; A photochromic laminate formed by bonding via the two.   The photochromic laminate according to claim 1, wherein the second adhesive layer is made of an adhesive composition that does not contain a photochromic compound.   The photochromic laminate according to claim 1, wherein the second adhesive layer is made of an adhesive composition containing a compound having a urethane bond or a urea bond in the molecule.   The photochromic laminate according to claim 1, wherein the optical sheet or film is made of a polycarbonate resin. A step (1) of forming a first adhesive layer comprising a polyurethane-urea resin having a urea bond in the molecular chain and a photochromic composition containing a photochromic compound;
A step (2) of forming a second adhesive layer on two optical sheets or films;
The first adhesive layer obtained in the step (1) and the two laminates having the second adhesive layer on the optical sheet or film obtained in the step (2) are combined with the first adhesive layer and the second adhesive. The manufacturing method of the photochromic laminated body of Claim 1 which has a process (3) laminated | stacked so that a layer may contact | connect.   An optical article having a synthetic resin layer on the optical sheet or optical film of the photochromic laminate according to claim 1.

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