JP6579938B2 - Photochromic composition, laminate comprising the composition, and article using the laminate - Google Patents

Description

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

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

  For example, as a method of laminating a functional layer having antiglare properties between two plastic sheets or films, a method of laminating a photochromic layer between two polycarbonate sheets is known (see Patent Document 1). ). Specifically, a photochromic coating solution containing a solvent is applied to one plastic sheet, dried by passing it through a dryer at a specific temperature at a specific speed, and then the other plastic sheet is joined. A method (method of manufacturing a laminated sheet) is shown. According to this method, a laminated sheet having an adhesive layer with excellent smoothness can be produced continuously.

  However, according to the study by the present inventors, the adhesiveness of laminated sheets (adhesiveness between plastic sheets) may not be sufficient even by the method described in Patent Document 1. In particular, when an adhesive resin having a high softening point is used in order to stably perform the secondary processing (thermal bending processing, injection molding) of the laminated sheet, the adhesiveness may be lowered.

  As a method for improving the adhesion between the photochromic layer and the resin sheet or film, a photochromic polyurethane-urea resin formed using a polyurethane urea resin is used as the photochromic adhesive layer, and the photochromic layer and the resin sheet or A method of laminating a film with an adhesive layer has been proposed (see Patent Document 2).

Japanese Patent No. 4661017 JP2013-33131A

A photochromic laminated sheet exhibiting excellent adhesion and photochromic properties can be obtained by the method described in Patent Document 2 above. However, when the photochromic adhesive layer having the same composition is used, the adhesive layer can be used between lots. It has been found that there is a variation in the adhesion between the resin and the resin sheet or film, and the adhesion to polycarbonate may not be sufficient. It has also been found that there is a problem with the heat resistance of the adhesive layer.
Furthermore, photochromic sunglasses may require “sweat resistance” depending on their usage (though sunglasses that do not change their state even when they come into contact with human sweat) may be used, but conventional laminated sheets are used. In sunglasses, peeling of a polycarbonate sheet or the like was observed, and there was no one that could fully meet the requirements.

Therefore, the object of the present invention is, first of all, when used as an adhesive layer when joining a resin sheet or film, it has excellent adhesion, heat resistance, sweat resistance, and excellent photochromic properties. It is to provide a photochromic composition that exhibits.
The second object of the present invention is an optical article comprising a laminated structure in which a resin sheet or film is joined by an adhesive layer having photochromic properties, and has excellent adhesiveness in the laminated structure, as well as excellent It is to provide a laminate having excellent heat resistance and excellent photochromic properties.

  The present inventors have intensively studied to solve the above problems. When using a photochromic adhesive layer of the same composition, paying attention to the fact that there is a variation in the adhesion between the adhesive layer and the resin sheet or optical film, the polyurethane urea resin used in the adhesive layer was analyzed, It was confirmed that this was a mixture of low and high molecular weight polyurethane urea resins. Therefore, it was speculated that the presence of low molecular weight polyurethane urea resin had an influence on the heat resistance of polyurethane urea resin, and as a result of investigation, a polyurethane urea resin containing a large amount of low molecular weight polyurethane urea resin was used. The knowledge that the heat resistance and adhesiveness of the photochromic adhesive layer obtained in this case is low was obtained.

  Based on the above knowledge, as a result of further investigation on the composition of the polyurethane urea resin used in the photochromic adhesive layer, it can be obtained when a polyurethane urea resin whose polydispersity is controlled within a certain range is used for the adhesive layer. The present inventors have found that the laminate has excellent adhesiveness, heat resistance, sweat resistance, photochromic properties, durability thereof, and the like, and completed the present invention.

That is, the present invention provides a photochromic composition comprising (I) a polyurethane urea resin having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4, and (II) a photochromic compound. It is a thing.
Another invention of the present invention is a laminate comprising a laminate structure in which two resin sheets or films facing each other are bonded via an adhesive layer comprising the photochromic composition according to claim 1, and the laminate A light shielding window material, a display material, an agricultural film, a toy, clothes, and an umbrella using a laminate.

  The photochromic composition of the present invention is characterized by using a polyurethane urea resin having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4. When a laminate is produced by joining a resin sheet or film made of a polycarbonate resin or the like with an adhesive layer made of the composition, the obtained laminate shows excellent adhesiveness, particularly excellent adhesiveness at high temperatures, The obtained laminate has high sweat resistance. That is, excellent adhesion is exhibited even after contact with artificial sweat. Although details are unknown as the reason why such an effect is obtained, the present inventors presume as follows. That is, when the polydispersity (weight average molecular weight / number average molecular weight) is in the range of 1.6 to 2.4, the content of low molecular weight polyurethane urea can be reduced, the heat resistance is stable, and the low molecular weight. Degradation of physical intermolecular interaction (entanglement of polymer chains between molecules) due to the influence of polyurethane urea can be suppressed, and destruction within the polyurethane urea layer (cohesive failure) when polyurethane urea resin is used for the adhesive layer It was presumed that the adhesiveness was improved because of being able to be suppressed.

  Furthermore, the laminate of the present invention has a high color density when irradiated with sunlight, a high fading speed when not irradiated with sunlight, and has high repetition durability due to color fading. Accordingly, the laminate of the present invention can be used as a laminate for developing photochromic properties in articles such as light shielding window materials, display materials, agricultural films, toys, clothes, umbrellas, etc., in addition to the above-mentioned plastic sunglasses. it can.

  The photochromic composition of the present invention comprises (I) a polyurethane urea resin (hereinafter also referred to as “I component”) having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4. (II) A photochromic compound (hereinafter also referred to as II component) is included. Hereinafter, these I component and II component are demonstrated.

<I component: Polyurethane urea resin whose polydispersity (weight average molecular weight / number average molecular weight) is in the range of 1.6 to 2.4>
In the photochromic composition of the present invention, a polyurethane urea resin (hereinafter also simply referred to as “polyurethane urea resin”) having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4 is used. It is a feature. The polyurethane urea resin is a polyurethane resin having a urea bond (—R—NH—CO—NH—) in the molecular chain. By having such a narrow range of polydispersity, the polyurethane urea resin of the present invention has good adhesion, heat resistance, and sweat resistance. Note that the lower the polydispersity, that is, the closer the polydispersity is to 1.0, the more the effect of the present invention tends to be exhibited. However, the polyurethane urea resin having a polydispersity of less than 1.6 is industrially It is considered that it is substantially difficult in the production method, and when the polydispersity exceeds 2.4, the softening start temperature becomes low due to the influence of the low molecular weight polyurethane urea resin, so that the polydispersity is narrow. Compared with heat resistance, the adhesiveness under high temperature falls. Further, due to the influence of the high molecular weight polyurethane urea resin, the viscosity when dissolved in an organic solvent is remarkably increased as compared with a resin having a narrow polydispersity, and coating becomes difficult. From the viewpoint of good adhesive strength, heat resistance, and coatability, the polydispersity of the polyurethane urea resin of the present invention is more preferably in the range of 1.8 to 2.2.

  The molecular weight of the polyurethane urea resin of the present invention is not particularly limited as long as the polydispersity (weight average molecular weight / number average molecular weight) satisfies the above range, but the adhesive strength, heat resistance, and From the viewpoint of sweat resistance, the number average molecular weight is 5,000 to 100,000, particularly 8,000 to 50,000, and most preferably 10,000 to 40,000.

  The number average molecular weight and the weight average molecular weight of the polyurethane urea resin are as follows. Column: Shodex KD-806M (manufactured by Showa Denko KK) is used for gel permeation chromatography (GPC) in terms of polyethylene oxide. Two in series, eluent: LiBr (10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, polyurethane urea resin sample solution: 1.0% dimethylformamide (DMF) solution It is a value calculated using the GPC analysis software “Empower Personal GPC Option” manufactured by Japan Waters Corporation. The polydispersity is a value calculated by weight average molecular weight / number average molecular weight, and is a value calculated from the number average molecular weight and the weight average molecular weight determined by the above method.

The component I in the photochromic composition of the present invention is not particularly limited as long as the polydispersity (weight average molecular weight / number average molecular weight) is a polyurethane urea resin satisfying the above range, but the adhesiveness, heat resistance, And from the viewpoint of sweat resistance,
(A) a urethane prepolymer having an isocyanate group at the molecular end;
(B) a polyamine compound having two or more amino groups in the molecule;
Is preferably obtained by reacting
(C) a compound having one group capable of reacting with an isocyanate group in the molecule;
It is preferable that it is obtained by reacting. In such a polyurethane urea resin, a urea bond is introduced into the molecule due to the use of a polyamine compound as the raw material (B) component. Hereinafter, these components will be described.

<Component A: Urethane prepolymer having an isocyanate group at the molecular end>
As the urethane prepolymer (component A) having an isocyanate group at the molecular terminal, which is a constituent component of the polyurethane urea resin, a known urethane prepolymer can be used. Above all,
(A1) at least one polyol compound selected from the group consisting of polyols having at least two or more hydroxyl groups such as polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol;
(A2) a diisocyanate compound having two isocyanate groups in the molecule;
It is preferable that it is obtained by reacting.

<A1 component: at least one polyol compound selected from the group consisting of polyols having at least two hydroxyl groups such as polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol>
As said polyol compound (A1 component), it is preferable that the number of hydroxyl groups contained in a molecule | numerator is 2-6 from the reason that the polyurethane urea resin (I component) to produce | generate does not become a highly crosslinked body, and to an organic solvent. In consideration of solubility, the number of hydroxyl groups contained in the molecule is more preferably 2 to 3. In addition, polyol compounds such as the above-described polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol may be used alone or in combination of two or more, but heat resistance, adhesiveness, From the viewpoints of weather resistance, hydrolysis resistance and the like, it is particularly preferable to use polycarbonate polyol and polycaprolactone polyol. Hereinafter, various compounds used as the A1 component will be described in detail.

<Polycarbonate polyol>
Polycarbonate polyols used as the A1 component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 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 and propylene Oxide polyol, bis (β-hydroxyethyl) benzene, xylylene glycol, glycerin, trimethylolpropane, polycarbonate polyol obtained by phosgenation of one or more kinds of low molecular polyols such as pentaerythritol, ethylene carbonate, diethyl The polycarbonate polyol obtained by the transesterification method with carbonate, diphenyl carbonate, etc. can be mentioned. Among these low molecular polyols, low molecular polyols having a linear alkyl chain are more preferable from the viewpoint of adhesion and heat resistance of the finally obtained polyurethane urea resin (component I), and the side chain has an alkyl group. A polycarbonate polyol synthesized from a low-molecular polyol having a group tends to have poor adhesion.

  In the polycarbonate polyol as the A1 component, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 600 from the viewpoint of heat resistance of the finally obtained polyurethane urea resin (component I). 1200.

  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 2000, more preferably 500 to 1500, and most preferably 600 to 1200 for the same reason as in the polycarbonate 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.

<Polyether polyol>
Polyether polyols include polyether polyol compounds obtained by the reaction of a compound having two or more active hydrogen-containing groups in the molecule with an alkylene oxide, and polymer polyols and urethane-modified poly ures that are modified products of the polyether polyol compounds. Examples thereof include ether 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, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200 for the same reason as in the polycarbonate polyol.

  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.

<Polyester polyol>
Examples of the polyester polyol include a polyester polyol obtained by a condensation reaction between 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, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200 for the same reason as in the polycarbonate polyol.

  These polyester polyols are available as reagents or industrially, and examples of commercially available ones include “Polylite (registered trademark)” series manufactured by DIC Corporation, “Nipporan (registered trademark)” manufactured by Nippon Polyurethane Industry Co., Ltd. ) ”Series,“ Maximol (registered trademark) ”series manufactured by Kawasaki Kasei Kogyo Co., Ltd., and the like.

<A2 component: diisocyanate compound having two isocyanate groups in the molecule>
As said diisocyanate compound (A2 component), an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, and a mixture thereof are used. Among these, it is preferable to use an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound from the viewpoint of weather resistance. For the same reason, it is preferable that 30 to 100% by mass, particularly 50 to 100% by mass of the A2 component is an aliphatic diisocyanate compound.

  Examples of diisocyanate compounds that can be suitably used as the A2 component include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane- Aliphatic diisocyanate compounds such as 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, isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate Nate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, 1,9-diisocyanato-5-methylnonane, 1,1-bis (isocyanato Cycloaliphatic diisocyanate compounds such as methyl) cyclohexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] -1-methylcyclohexane, 2- (3-isocyanatopropyl) cyclohexyl isocyanate, norbornane diisocyanate; phenylcyclohexyl Methane 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-diisocyanato Benzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl) ) Methyl] 2-methylbe Zen, aromatic diisocyanate compounds such as 1-isocyanato-3-[(4-isocyanatophenyl) methyl) -2-methylbenzene, 4-[(2-isocyanatophenyl) oxy] phenyl isocyanate, diphenylmethane diisocyanate, etc. be able to.

  Among these, from the viewpoint of the weather resistance of the resulting polyurethane urea resin (component I), as described above, 30 to 100% by mass, particularly 50 to 100% by mass of the diisocyanate compound of component A2 is an aliphatic diisocyanate compound, and It is preferably at least one diisocyanate compound selected from the group consisting of alicyclic diisocyanate 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, norbornane diisocyanate, 4, 4'-methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahi Rofeniren 1,3 diisocyanate are hexahydrophthalate phenylene-1,4-diisocyanate. These isocyanate compounds may be used alone or in combination of two or more.

<(B) Polyamine compound having two or more amino groups in the molecule>
The polyamine compound (component B) having two or more amino groups in the molecule has two or more amino groups (—NH ₂ or —NH (R) in the molecule, where R is an alkyl group, particularly carbon. A polyamine compound having an alkyl group of 1 to 5).
The component B functions as a chain extender when synthesizing a polyurethane urea resin (component I). By using the component B as the chain extender, a urea bond is introduced into the polyurethane resin, and the polyurethane urea It becomes resin.

  The molecular weight of the polyamine compound is preferably 50 to 300 in order to make the resulting polyurethane urea resin (component I) moderately hard and to maintain good adhesion and heat resistance. 250 is more preferable, and 100 to 220 is most preferable.

  As the polyamine compound of component B, at least one compound selected from the group consisting of diamines and triamines can be suitably used. Specific examples of the compound suitably used as the polyamine 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, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4′-diphenylmethane Diamine, N, N'-diethylethylenediamine, N, N'-dimethyl Examples include ruethylenediamine, N, N′-dipropylethylenediamine, N, N′-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) triamine, 1,2,5-pentanetriamine, and the like. it can.

  In the polyamine compound, it is particularly preferable to use a diamine compound from the viewpoints of adhesiveness and heat resistance. This is because when a urethane urea resin (component I) is synthesized, a polyamine compound is used to have a urea bond, resulting in higher molecular rigidity and stronger hydrogen bonds between molecular chains. Therefore, it is estimated that the heat resistance is improved. In addition, 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 (component I), resulting in photooxidative degradation of the polyurethane urea resin. It is presumed that this was due to suppression. Furthermore, it is presumed that the adhesive force 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.

  Among the polyamine compounds, isophoronediamine, bis- (4-aminocyclohexyl) methane, and norbornanediamine are more preferable from the viewpoint of water resistance and stability to sweat resistance tests. Most preferably,-(4-aminocyclohexyl) methane is used.

<(C) Compound having one group capable of reacting with an isocyanate group in the molecule>
When synthesizing the above polyurethane urea resin, it is also possible to use a compound (C component) having a group capable of reacting with one isocyanate group in the molecule. By using this C component, it becomes a polyurethane urea resin in which the end of the molecular chain is capped. Examples of the group capable of reacting with the isocyanate group include an amino group (—NH ₂ group and —NH (R) group), a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), a carboxyl group [ -C (= O) OH group], or acid chloride group [-C (= O) OCl group]. Among the above C components, a functional compound having at least one piperidine structure in the molecule is preferable. The functional compound may have a hindered phenol structure, a triazine structure, or a benzotriazole structure instead of the piperidine structure. However, it is a functional compound having a piperidine structure that exhibits the most excellent effect.

By using such a function-imparting compound, a piperidine structure can be introduced into the polyurethane urea resin (component I). As a result, it is possible to obtain a polyurethane urea resin (I component) excellent in functionality such as light stability performance, antioxidant performance, and ultraviolet absorption performance.
Hereinafter, as various examples of various compounds used as the component C, compounds having a piperidine structure will be described in detail.

<Compound having piperidine structure>
As the compound having a piperidine structure used as the C component in the polyurethane urea resin, a compound having a structure represented by the following general formula (i) in the molecule can be preferably used.

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

  Among the compounds used as component C in the present invention, compounds that can introduce a piperidine structure at the end of the polyurethane urea resin that is component I of the present invention include compounds represented by the following general formula (1) It is preferably mentioned.

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

In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, but all four alkyl groups are preferably methyl groups.
R ⁵ is a C 1-10 alkyl group or a hydrogen atom. Especially, it is preferable that it is a C1-C4 alkyl group or a hydrogen atom from a viewpoint of availability. Since R ¹ to R ⁴ is an alkyl group having 1 to 4 carbon atoms, even R ⁵ is a hydrogen atom, a nitrogen atom and an isocyanate group R ⁵ is attached to the influence of steric hindrance to react There is nothing.
R ⁶ is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. In addition, although a shows the number of R6, when a is 0, it points to what X has couple | bonded with the piperidine ring directly.

X is a group capable of reacting with an isocyanate group, and is preferably an amino group, a hydroxyl group, a carboxyl group, or a thiol group. Among these, an amino group and a hydroxyl group are preferable from the viewpoints of reactivity with an isocyanate group and availability.
Specific examples of the compound represented by the 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-aminomethylpiperidine 1,2,2,6,6-pentamethyl-4-aminobutylpiperidine and the like.

<Other C components>
As said C component, a general amine, alcohol, thiol, and carboxylic acid other than the compound aiming at the improvement of the weather resistance which has the piperidine structure mentioned above can be used. These compounds have one group capable of reacting with an isocyanate group in the molecule, and thus can inactivate the terminal of the polyurethane urea resin as the I component.
Among the other C components used in the present invention, preferred compounds include the following general formulas (2) and (3).

(Where
R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom,
R ⁸ 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 ⁷ is a hydrogen atom is used as the C component, the terminal of the polyurethane urea resin that is the I component is an —NH (R ⁸ ) group, and this —NH (R ⁸ ) group is It does not substantially react with other polymers and isocyanate compounds. Therefore, the —NH (R ⁸ ) group does not correspond to a group that can react with an isocyanate group.

In the general formula (2), R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or a hydrogen atom. Among them, R ⁷ 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 ⁷ 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, a carboxypropyl group, or a hydrogen atom.

R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group. Among these, R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group. The aryl group may have an alkyl group having 1 to 5 carbon atoms or a halogen atom as a substituent.
Examples of suitable R ⁸ 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, or a carboxypropyl group.

  The following general formula (3)

(Where
R ⁹ 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.

In the general formula (3), R ⁹ 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 ⁹ 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 (3) is a group capable of reacting with an isocyanate group, specifically a hydroxyl group, a carboxyl group, or a thiol group, preferably a hydroxyl group.

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

  The above component C may be used alone or in combination of two or more, but from the viewpoint of improving the durability of the polyurethane urea resin, it is preferable to use a compound having a piperidine structure. is there.

<Use amount of A1, A2, B, and C component in polyurethane urea resin>
The above-mentioned components constituting the polyurethane urea resin (component I) in the photochromic composition of the present invention, that is, the amount ratio of the components A1, A2, B, and C, takes into account the use of the polyurethane urea resin, etc. However, from the viewpoint of balance between the heat resistance and adhesive strength of the resulting polyurethane urea resin, the following quantitative ratio is 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, the total number of amino groups contained in the B component is n3, and included in the C component. N1: n2: n3: n4 = 0.4 to when the total number of moles of the group capable of reacting with the isocyanate group (specifically, amino group, hydroxyl group, mercapto group and / or carboxyl group) is n4 0.8 / 1.0 / 0.19 to 0.59 / 0.01 to 0.2, particularly n1: n2: n3: n4 = 0.45 to 0.75 / 1.0 / 0 It is preferable that the quantity ratio is 23 to 0.53 / 0.02 to 0.15, and n1: n2: n3: n4 = 0.65 to 0.75 / 1.0 / 0.23 to 0. Most preferably, the quantity ratio is 33 / 0.02-0.1. Here, said n1-n4 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.

  The polyurethane urea resin (component I) preferably has no reactive group at the end. In particular, it is preferable to inactivate such that no isocyanate group remains at the terminal. Therefore, at the time of manufacture, it is preferable to manufacture at a blending ratio such that n2 = n1 + n3 + n4. When the total number of moles of n1, n3, and n4 (n1 + n3 + n4) is larger than n2, unreacted A1, B, and C components may be removed by reprecipitation or the like.

  As a method of obtaining the polyurethane urea resin (I component) of the present invention by reacting the above A1 component, A2 component, B component and, if necessary, the C component, polydispersity (weight average molecular weight / number average molecular weight) ) May satisfy the above range, and any one of the so-called one-shot method and prepolymer method can be employed. However, the prepolymer method is preferred from the viewpoint of controlling the polydispersity and obtaining a polyurethane urea resin efficiently. In particular, according to the production method described later, it is possible to easily produce a polyurethane urea resin having a polydispersity (weight average molecular weight / number average molecular weight) satisfying the above range.

<Method for producing polyurethane urea resin>
<Method for producing urethane prepolymer (A)>
The polyurethane urea resin used in the photochromic composition of the present invention can be generally produced by a reaction between a urethane prepolymer and a polyamine such as diamine. The urethane prepolymer (component A) is composed of the polyol compound (component A1) and , By reacting with the diisocyanate compound (component A2) (hereinafter also referred to as “prepolymer reaction”).

  The order of addition when the A1 component and the A2 component are reacted is not particularly limited, and it is possible to add the A1 component and the A2 component as needed during the reaction as needed.

  The reaction between the A1 component and the A2 component may be performed in the presence or absence of an organic solvent, preferably in an inert gas atmosphere such as nitrogen or argon, at a reaction temperature of 70 to 130 ° C. . When the reaction temperature is less than 70 ° C., the reaction is not completed, and when it exceeds 130 ° C., a part of the A1 component is decomposed and a urethane urea resin having desired physical properties cannot be obtained. Although reaction time changes also with preparation ratio of A1 component and A2 component, and reaction temperature, what is necessary is just to make it react in the range of 0.5 to 24 hours.

  Examples of organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF). Organic solvents can be used. These organic solvents can be used in combination of two or more.

  When an organic solvent is used, the amount used is preferably 200 parts by mass or less when the total amount of the A1 component and the A2 component is 100 parts by mass. When the usage-amount of an organic solvent exceeds 200 mass parts, there exists a possibility that reaction time of A1 component and A2 component may become long, and a part of A1 component may decompose | disassemble.

  In the reaction, in order to avoid a reaction between an isocyanate group in the diisocyanate 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 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 A component.

<Method for producing polyurethane urea resin>
A polyurethane urea resin can be generally produced by a reaction between a urethane prepolymer and a polyamine such as diamine, but when the urethane prepolymer (component A) and the polyamine compound (component B) are reacted, The polydispersity (weight average molecular weight / number average molecular weight) is in the range of 1.6 to 2.4 by setting the complete mixing time (θ _M ) with the component B to 30 seconds or less, preferably 15 seconds or less. A polyurethane urea resin can be obtained.

The complete mixing time (θ _M ) is an index representing mixing characteristics in a stirring tank (such as a reaction vessel), and n · θ _M (n is the number of rotations of the stirring blade (1 / second)) and Re (Reynolds number; It is obtained from an “n · θ _M -Re curve” showing the relationship with the index indicating the turbulent state of the liquid. For the complete mixing time (θ _M ) and n · θ _M -Re curve, see, for example, “Sumitomo Heavy Industries Technical Report vol.35 No.104 August 1987 p74-78”, Japanese Patent Application Laid-Open No. 61-200842. JP-A-6-312122 and the like.

Any appropriate method may be adopted as a means for setting the complete mixing time (θ _M ) to 30 seconds or less. However, a baffle plate or the like is installed in a stirring vessel (such as a reaction vessel) to prevent turbulent flow. The method of generating, the method of using arbitrary appropriate stirring blades, etc. are mentioned. Suitable agitation blades include max blend blades, full zone blades, and the like.

  Moreover, when a urethane prepolymer is produced by the above-described method, the polyurethane component may be continuously produced by adding the component B to the reaction solution after the prepolymerization reaction.

  The other reaction conditions in the above polyurethane urea resin production method may be appropriately determined in consideration of production equipment and the like. From the viewpoint of obtaining a polyurethane urea resin having a narrow polydispersity, an organic solvent is used. In an inert gas atmosphere such as nitrogen or argon as necessary in the presence of the reaction temperature in the range of -20 to 40 ° C, more preferably in the range of -10 to 20 ° C. . When the reaction temperature is less than -20 ° C, the viscosity increases in the latter half of the chain extension reaction, resulting in insufficient stirring. When the reaction temperature exceeds 40 ° C, the urea bond formation reaction is fast, and the component A And the B component react immediately after contact, which tends to cause a non-uniform reaction and tends to increase the polydispersity. A reaction time of about 0.5 to 3 hours is sufficient at the reaction temperature.

  As the organic solvent in the production method of the present invention, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) , Tetrahydrofuran (THF), methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mononormal propyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, ethylene glycol mono t-butyl ether, propylene glycol monome Ether, propylene glycol monoethyl ether, propylene glycol mono normal propyl ether, propylene glycol mono-isopropyl, propylene glycol monobutyl n-butyl ether, also alcoholic organic solvents such as propylene glycol monobutyl t- butyl ether may be used. These organic solvents can be used in combination of two or more.

  The amount of the organic solvent used is such that when the total amount of the polyurethane urea resin finally obtained is 100 parts by mass from the viewpoint of performing the reaction efficiently and from the viewpoint of the influence of the remaining organic solvent, etc. The range is preferably 130 to 800 parts by mass, and more preferably 150 to 500 parts by mass.

  In the reaction, in order to avoid a reaction between an isocyanate group in the reaction system and water as an impurity, it is preferable that various reaction reagents and an organic solvent are subjected to dehydration in advance and sufficiently dried. In 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 newly added, or when used in a prepolymer reaction, it may be used as it is without being removed. 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 polyurethane urea resins.

  When synthesizing the polyurethane urea resin (component I) of the present invention, it is also possible to use a compound (component C) having a group capable of reacting with one isocyanate group in the molecule. By using this C component, it becomes a polyurethane urea resin in which the end of the molecular chain is capped.

  The method for obtaining a polyurethane urea resin with the molecular chain end capped (hereinafter also referred to as “terminal modification reaction”) is the polyurethane urea having an isocyanate group at the terminal after the reaction of the above-mentioned component A and component B is completed. A method in which a component C diluted with an organic solvent is added dropwise to the reaction solution in which the resin is dissolved in the organic solvent, if necessary, is preferable. Further, when the alcohol-based organic solvent added at the time of the reaction between the A component and the B component is used as the C component for the terminal modification reaction, it is not necessary to newly add the C component.

  The above terminal modification reaction may be performed in an inert gas atmosphere such as nitrogen or argon as required in the presence of an organic solvent. As for the reaction temperature, when the group capable of reacting with the isocyanate group contained in the C component is an amino group, the reaction may be carried out at a temperature of -20 to 30 ° C. similar to the reaction of the aforementioned A component and B component. . However, when the group capable of reacting with the isocyanate group contained in the component C is other than an amino group, the reaction rate with the isocyanate group is slow, so that the reaction is preferably performed at a temperature higher than 30 ° C. and not higher than 130 ° C.

  The reaction time is about 0.5 to 3 hours when the group capable of reacting with the isocyanate group contained in the C component is an amino group, and when the group capable of reacting with the isocyanate group contained in the C component is other than an amino group Is allowed to react for about 1 to 24 hours.

  As an organic solvent, the organic solvent used for the above-mentioned prepolymer reaction and reaction of A component and B component can be used. Moreover, as a matter of course, the terminal modification reaction may be performed in a state in which the organic solvent used in the above-described prepolymer reaction and the reaction between the A component and the B component is included.

  The amount of the organic solvent used in the terminal modification reaction is preferably in the range of 130 to 800 parts by mass when the total amount of component A finally obtained is 100 parts by mass.

  In the reaction, in order to avoid a reaction between an isocyanate group in the reaction system and water as an impurity, it is preferable that various reaction reagents and an organic solvent are subjected to dehydration in advance and sufficiently dried. In 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 newly added, or when the catalyst is used before the prepolymer reaction, it may be used as it is without being removed. 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 A component.

  Next, the photochromic compound which is the II component of the present invention will be described.

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

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

  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.

  Specific examples of photochromic compounds that can be particularly preferably used in the present invention include the following.

  The blending amount of the II component in the photochromic composition of the present invention is preferably 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the I component from the viewpoint of photochromic properties. If the amount is too small, there is a tendency that sufficient color density and durability cannot be obtained.If the amount is too large, depending on the type of photochromic compound, the photochromic composition becomes difficult to dissolve, and the composition Not only the uniformity of the object 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 II component added is 0.5 to 100 parts by mass of I component. To 10.0 parts by mass, more preferably 1.0 to 7.0 parts by mass. However, when III component is mix | blended with the photochromic composition of this invention, the addition amount of II component shall be 0.1-20.0 mass parts with respect to 100 mass parts of total amounts of I component and III component. It is preferably 0.5 to 10.0 parts by mass, and more preferably 1.0 to 7.0 parts by mass.

<III component: polyisocyanate compound having at least two isocyanate groups in the molecule>
The photochromic composition of the present invention includes a product obtained by reacting the polyurethane urea resin (component I) with a polyisocyanate compound (component III) having at least two isocyanate groups in the molecule. This is preferable because the adhesion (adhesion) strength of the optical article can be further improved. By having two or more isocyanate groups in the molecule of the III component, it is possible to produce a polyurethane urea resin having a bridge structure by reacting with the I component when the photochromic adhesive layer is formed. By forming this bridge structure in the component I, the heat resistance of the polyurethane urea resin is improved, and cohesive failure is less likely to occur. However, considering the operability, the viscosity of the resulting photochromic composition, storage stability, etc., the number of isocyanate groups is preferably 2 to 3. Among these, it is preferable to use a compound having an isocyanate group bonded to secondary carbon. These may be used alone or in combination of two or more.

  Specific examples of the III component include isomer mixtures of 4,4′-methylenebis (cyclohexyl isocyanate), cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydro Toluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, and trimers of these isocyanate compounds and isophorone diisocyanate (Isocyanurate compound) and the like.

  In the photochromic composition of the present invention, the molecular weight of the III component is not particularly limited, but is preferably less than 1000. When the molecular weight of the III component is 1000 or more, the heat resistance and film strength of the resulting photochromic adhesive layer tend to decrease. This is because when the III component having a large molecular weight is used, the number of bonds between isocyanate groups tends to increase, and even if a bridge structure is formed, the distance between the cross-linking points becomes long and the heat resistance is not improved so much. It is considered that the adhesion is not sufficiently improved. Therefore, the molecular weight of the III component is preferably less than 1000, more preferably 800 or less, and most preferably 500 or less. As described above, the III component is preferably not a polymer. Therefore, the molecular weight of the III component refers to the molecular weight of the III component itself. The lower limit of the molecular weight of the III component is the molecular weight of the simple compound, and is 100, although not particularly limited.

  The compounding quantity of the III component in the photochromic composition of this invention shall be 4.0-20.0 mass parts with respect to 100 mass parts of I components from a viewpoint of adhesiveness, heat resistance, sweat resistance, and a photochromic characteristic. Is preferred. When the blending amount of the III component satisfies this range, the resulting photochromic composition exhibits an excellent effect. When the blending amount is too small, sufficient adhesion and heat resistance cannot be improved. When the blending amount is too large, the cloudiness of the adhesive layer obtained from the photochromic composition, a decrease in adhesiveness, and photochromic are obtained. There is a tendency for the durability of the compound to decrease. In order to improve adhesiveness with an optical substrate such as a plastic film while maintaining photochromic properties such as color density and durability, the amount of the III component is 6.0 to 100 parts by mass of the I component. It is preferable to set it as 17.5 mass parts, especially 7.0-15.0 mass parts. Under the present circumstances, the ratio of the isocyanate group of III component is 1.0-10.0 mass parts with respect to 100 mass parts of I components, More preferably, it is 1.5-6.0 mass parts, Most preferably, it is 2.0- 5.0 parts by mass. Here, the amount of the isocyanate group can be determined from the molecular weight of the III component, the number of isocyanate groups per molecule, and the molecular weight of the isocyanate group.

The reaction product of the I component and the III component is a physical property of a laminate obtained by pasting resin sheets or films using the photochromic composition of the present invention, and bending and injection using the obtained laminate. Applying a hard coat solution in the case of forming a hard coat layer on the surface of the laminated sheet or the molded product, from the viewpoint of processing stability when producing a molded product by molding, and the adhesive property of the laminate. From the viewpoint of workability when it is cured or cured, it preferably has a heat resistance of usually 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.

<Other ingredients>
Furthermore, the photochromic composition used in the present invention includes a solvent capable of dissolving the component I, a surfactant, an oxidation agent for improving the durability of the photochromic compound, improving the color development speed, improving the fading speed, and forming the film. Additives such as inhibitors, radical scavengers, 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, examples of the solvent capable of dissolving the component I include dimethylformamide and dimethyl sulfoxide.

  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 I component.

  Antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenolic radical scavengers, sulfur antioxidants, phosphorus antioxidants, A triazine compound, a benzotriazole compound, a benzophenone compound, or the like can be preferably used. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. Furthermore, when using these additives, surfactants and antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination. The addition amount of these antioxidants, radical scavengers, ultraviolet stabilizers and ultraviolet absorbers is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the I component. However, if these additives are used excessively, the adhesion of the photochromic composition to a resin sheet or film made of polycarbonate resin is lowered, so the amount added is preferably 7 parts by mass or less, more preferably 3 It is 1 part by mass or less, most preferably 1 part by mass or less.

<Method for producing photochromic composition>
The photochromic composition of this invention can be manufactured by mixing the said I component, II component, and another component. The order in which the components are mixed is not particularly limited.

  For example, each component can be melt-kneaded and pelletized into a photochromic composition, or it can be formed into a sheet as it is. When an organic solvent such as dimethylformamide is used, a photochromic composition can be obtained by dissolving each component in the organic solvent.

  The photochromic composition of the present invention thus obtained can be suitably used as a photochromic adhesive, particularly a photochromic adhesive for joining resin sheets or films made of polycarbonate resin. And a laminated body can be obtained by mutually bonding a resin-made sheet | seat or a film through the contact bonding layer which consists of a photochromic composition of this invention.

Among the production methods as described above, the photochromic composition of the present invention contains a component that is not dissolved in a general organic solvent, and thus is preferably produced by the following method.
That is,
(I) Polyurethane urea resin, (II) photochromic compound, and if necessary, (III) polyisocyanate compound, and organic solvent are mixed in a predetermined amount, and then dried to remove the organic solvent, (I) A method for producing a photochromic composition by reacting a polyurethane urea resin with the (III) polyisocyanate compound. In this method, since the photochromic composition of the present invention can be obtained through a step of removing the organic solvent from the composition containing the I component, the II component, the III component, and the organic solvent, hereinafter, the I component, II In some cases, the precursor composition is a composition containing the component, the III component, and the organic solvent. It is also possible to mix the above-mentioned “other components” with the precursor composition.

  In order to produce a photochromic composition from a precursor composition, for example, after applying the precursor composition on a substrate, the organic solvent is removed by drying, and then the I component and the III component are reacted. It is preferable. First, the organic solvent will be described.

<Organic solvent>
By using an organic solvent in the above production method, polyurethane urea resin (component I), polyisocyanate compound (component III), photochromic compound (component II), and other components added as necessary Can be easily mixed, and the uniformity of the precursor composition can be improved. Moreover, the viscosity of a precursor composition can be adjusted moderately, and the operativity at the time of apply | coating a precursor composition to a resin-made sheet | seat or a film, and the uniformity of the coating layer thickness can also be made high. If a resin sheet or film that is easily affected by an organic solvent is used, there may be a problem that the appearance is poor or the photochromic properties are deteriorated. Such a problem can be avoided by adopting a method described later. In the precursor composition, as described later, since various types of solvents can be used, the occurrence of the above problems can be prevented by selecting and using a solvent that does not easily attack the resin sheet or film. can do.

  Examples of organic solvents that can be suitably used include methanol, ethanol, n-propanol, i-propanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, alcohols such as n-butanol, t-butanol, 2-butanol, t-pentyl alcohol 2,2,2-trifluoroethanol; ethylene glycol monomethyl ether, ethylene glycol monoisopropyl 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- Polyhydric alcohol derivatives such as butyl ether and ethylene glycol dimethyl ether; diacetone alcohol; ketones such as methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, methyl isobutyl ketone, diisopropyl ketone and n-butyl methyl ketone; toluene; hexane; heptane Acetates such as ethyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; dimethylformamide (DMF); dimethyl sulfoxide (DMSO); tetrahydrofuran (THF); cyclohexanone; chloroform; dichloromethane and combinations thereof be able to.

  Among these, the precursor composition may contain a polyisocyanate compound (III component), although it may be appropriately selected and used depending on the type of the I component used and the material of the resin sheet or film. It is more preferable to use an organic solvent that does not contain a group that reacts with an isocyanate group. Therefore, more preferable D component is methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, methyl isobutyl ketone, diisopropyl ketone, n-butyl methyl from the viewpoint of solubility of I component and non-reactivity to III component. Examples include ketones such as ketone, acetates such as ethyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; DMF; DMSO; THF; cyclopentanone, cyclohexanone; chloroform;

  Further, in order to coat with good appearance and volatilize the organic solvent in a short time, it is important to increase the solid content concentration and further reduce the viscosity. In order to improve the solubility, it is preferable to use the organic solvent as described above, but in order to reduce the viscosity, it is preferable to use a protic organic solvent such as alcohol. Among these, secondary and tertiary alcohols are preferable, and tertiary alcohols are more preferable in consideration of reactivity with an isocyanate group of a polyisocyanate compound (III component). Suitable secondary alcohols include i-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, propylene glycol monomethyl ether, propylene glycol mono Examples of tertiary alcohols such as ethyl ether and propylene glycol-n-butyl ether include t-butanol and t-pentyl alcohol. These secondary or tertiary alcohols can be used alone or in combination of two or more.

  However, depending on the type of polyurethane urea resin (component I) used in the photochromic composition of the present invention, it may be difficult to dissolve in the secondary or tertiary alcohol. Therefore, it is preferable to combine a good solvent such as the aforementioned ketones with a secondary or tertiary alcohol. By using a combination of a good solvent ketone and a secondary or tertiary alcohol, the viscosity of the precursor composition can be lowered while maintaining the solubility of the component I. Moreover, when combining these 2 or more types of organic solvents, it is preferable to combine so that the boiling point of a good solvent may become temperature higher than the boiling point of a secondary or tertiary alcohol.

  The mixing ratio of the secondary or tertiary alcohol in the organic solvent to be used is 0.10 (mass of the secondary or tertiary alcohol) / (mass of the ketone) relative to the ketone of the good solvent. It is preferably ˜1.50, more preferably 0.15 to 1.00, and most preferably 0.20 to 0.70. When a plurality of types of alcohol are used, the above blending ratio is calculated based on the total amount of alcohol. By satisfying the blending ratio of the secondary or tertiary alcohol in the range of 0.10 to 1.50, the solubility of the component I is high, the reaction between the organic solvent and the isocyanate group of the component III is suppressed, and the precursor The viscosity of the composition can be reduced.

  In addition, the organic solvent remains while maintaining the smoothness of the coating layer when the precursor composition is applied on a substrate such as a resin sheet or film, or the photochromic adhesive sheet when the method described later is adopted. For the reason that it is difficult to increase the drying speed, 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. What is necessary is just to determine suitably the mixture ratio of the organic solvent whose boiling point is less than 90 degreeC and 90 degreeC or more according to the other component to be used. Among them, in order to exert an excellent effect, when the total amount of organic solvent is 100% by mass, the organic solvent having a boiling point of less than 90 ° C. is 20 to 80% by mass, and the organic solvent having a boiling point of 90 ° C. or more is 80 to 80%. It is preferable to set it as 20 mass%.

  Moreover, the compounding amount of the organic solvent is preferably 130 to 800 parts by mass, and preferably 150 to 500 parts by mass with respect to 100 parts by mass of the I component, from the viewpoint of the effect obtained by the compounding as described above. More preferred.

In the present invention, it is preferable to produce a photochromic composition from the precursor composition. Therefore, in order to efficiently react the I component and the III component, the precursor composition can be mixed with water.
Next, water will be described.

<Water>
Water can also be mix | blended with the said precursor composition. In particular, when the precursor composition contains a III component that is a polyisocyanate compound, the isocyanate group contained in the III component can be efficiently hydrolyzed (reacted) by blending water. This water can also be incorporated into the precursor composition from the beginning. However, when the storage stability of the precursor composition is taken into consideration, it is preferably blended when the precursor composition is used, that is, when a coating film is formed from the composition and the resin 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 III component proceeds also by contacting the moisture (humidity) in the environment after the precursor composition is coated on a resin 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-fold mole to 5-fold mole, preferably 0.05-fold mole to 3-fold mole, more preferably 0.1-fold mole with respect to the number of moles of isocyanate groups contained in the III component. It is preferable that it is the range of 2 times mole-2 times mole.

  The photochromic composition of the present invention is produced by preparing the precursor composition, applying the precursor composition onto a substrate, removing the organic solvent, and reacting the I component and the III component. be able to.

  The photochromic composition of the present invention obtained by the above method and the method using the precursor composition is a photochromic adhesive, particularly a photochromic adhesive for joining resin sheets or films made of polycarbonate resin. It can be suitably used as an agent. And a laminated body can be obtained by mutually bonding a resin-made sheet | seat or a film through the contact bonding layer which consists of a photochromic composition of this invention. Hereinafter, the laminate and the manufacturing method thereof in the present invention will be described.

<Laminate>
The laminate of the present invention comprises a laminate structure in which two resin sheets or films facing each other are bonded via an adhesive layer made of the photochromic composition of the present invention. As such a laminated body, a laminated sheet or film consisting only of the above laminated structure (hereinafter, also simply referred to as a laminated body of the present invention); when forming the laminated structure, an adhesive layer comprising a photochromic composition is used. A laminated sheet or film formed by joining two resin sheets or films on both sides via separate adhesive layers; an optical sheet or film is further laminated on these laminated sheets or films, a hard coat layer or the like on the surface A composite laminated sheet or film in which a coat layer is formed can be mentioned.

  In the laminate of the present invention, another adhesive layer (hereinafter also referred to as the second adhesive layer) is provided on both sides of the adhesive layer (hereinafter also referred to as the first adhesive layer) made of the photochromic composition as described above. It is also possible to produce a laminated sheet or film obtained by laminating and joining two resin sheets or films via the second adhesive layer.

  By laminating the second adhesive layer, the adhesiveness of the laminate of the present invention can be further improved. By laminating the second adhesive layer, the following two points can be cited as factors for improving the adhesiveness of the laminate of the present invention.

  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 the photochromic compound, etc., which has been decomposed by photooxidation degradation and reduced in molecular weight, migrates to the interface between the adhesive layer and the resin sheet or optical film, thereby reducing the adhesion between them. I guess it will.

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

  Therefore, the second adhesive layer used in the present invention preferably does not contain a photochromic compound, and more preferably is applied directly to a resin sheet or film in the form of a liquid and fluid adhesive. .

  As a component used for the second adhesive layer of the present invention, it is preferable to employ the same polyurethane urea resin as the component I. In particular, by using a polyurethane urea resin whose softening point, polydispersity, etc., which will be described later, are controlled, a stronger adhesion can be obtained with the first adhesive layer having the photochromic compound of the present invention and the resin sheet or film. . The polyurethane urea resin (I ′ component) used for the second adhesive layer will be described below.

<I ′ component: polyurethane urea resin for second adhesive layer>
As the component I ′ of the present invention, it is preferable to use a polyurethane urea resin having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4 as in the case of the component I. By having a polydispersity in such a narrow range, when the I ′ component is used for the second adhesive layer, the first adhesive layer and the strong adhesion to the resin sheet or film, heat resistance, And it becomes possible to have sweat resistance. From the viewpoint of good adhesive strength and heat resistance, the polydispersity of the polyurethane urea resin used for the component I ′ is more preferably in the range of 1.8 to 2.2.

  The I ′ component of the present invention is a polyurethane urea resin similar to the above-mentioned I component, and the A1 component, the A2 component, the B component, and the C component as necessary can be used as constituents of the I component. . Regarding the synthesis method, it can be carried out in the same manner as the above-mentioned I component.

  Suitable A1 components used for the I ′ component are low molecular polyols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. The polycarbonate polyol whose number average molecular weight is 600-1200 used is mentioned.

  As a suitable A2 component used for the I ′ component, an alicyclic diisocyanate compound is preferably used. Specifically, isophorone diisocyanate, norbornane diisocyanate, and 4,4′-methylenebis (cyclohexyl isocyanate) isomers. A mixture is mentioned.

  Suitable B component used for the I ′ component is preferably a diamine compound, and specific examples include isophorone diamine, bis- (4-aminocyclohexyl) methane, norbornane diamine and the like.

  As a suitable C component used for the I ′ component, it is preferable to use the compound represented by the general formula (2), and specifically, an alkylamine such as normal butylamine can be mentioned.

The blending ratio of each component may be determined as appropriate, but the following ratio is preferable from the viewpoint of the balance between the heat resistance of the obtained I ′ component and the adhesive strength. The definitions of n1, n2, n3, and n4 are as described above. The range of a preferable mixture ratio is n1: n2: n3: n4 = 0.30-0.89 / 1 / 0.10-0.69 / 0.00-0.20. Furthermore, in order for the obtained V component to exhibit better adhesion, more preferably, n1: n2: n3: n4 = 0.40-0.80 / 1 / 0.15-0.58 / 0. 0.01 to 0.15, most preferably n1: n2: n3: n4 = 0.51 to 0.68 / 1 / 0.30 to 0.48 / 0.01 to 0.10. Especially, it is preferable to set it as n2 = n1 + n3 + n4, and considering the long-term stability, it is preferable to inactivate the terminal.
The I ′ component can be produced in accordance with the synthesis method of the I component at the blending ratio as described above.

  Further, as other features of the I ′ component, the number average molecular weight of the I ′ component is preferably 10,000 to 120,000, particularly 40,000 to 100,000, from the viewpoints of heat resistance, adhesive strength, and the like. Most preferred. In addition, this molecular weight is the value measured on the same conditions as I component mentioned above.

  In addition, the component I ′ is a physical property of a laminate obtained by attaching resin sheets or films, and a processing stability viewpoint when a molded product is produced by bending or injection molding using the obtained laminate. From the viewpoint of the adhesiveness of these laminated sheets, and also from the viewpoint of workability when applying a hard coat liquid or curing in the case of forming a hard coat layer on the surface of these laminates or molded bodies Usually, it preferably has a heat resistance of 80 to 200 ° C., particularly 100 to 180 ° C. In addition, heat resistance here is the value measured by the method similar to what measured the reaction product obtained from I component and III component in the item of said III component.

<Thickness and formation method of second adhesive layer>
The film thickness of the second adhesive layer is preferably in the range of 2 to 40 μm, more preferably 5 to 15 μm. When the film thickness is less than 2 μm, the adhesion tends to decrease, and when the film thickness exceeds 40 μm, the organic solvent tends to remain. Moreover, it exists in the tendency for the weather resistance (durability) of a photochromic compound to fall.

  The adhesive (the composition containing the I ′ component) that forms the second adhesive layer may contain an organic solvent as used in the first adhesive layer (the photochromic composition) as necessary. However, when a thermoplastic resin such as polycarbonate is used as a resin sheet or film, the organic solvent used for the adhesive forming the second adhesive layer may have a low solubility in the thermoplastic resin. preferable. If the solubility in the thermoplastic resin is high, the thermoplastic resin may be excessively dissolved, which may cause poor appearance (white turbidity), reduced adhesiveness, and reduced photochromic properties when the first adhesive layer is laminated. is there. On the other hand, if the solubility in the thermoplastic resin is too low, the resin sheet or film is not dissolved and the adhesiveness with the second adhesive layer is not sufficiently exhibited. From the above, as the organic solvent used for the second adhesive layer, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, 2-butanol; ethylene glycol monomethyl ether, Ethylene glycol monoisopropyl 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 -Polyhydric alcohol derivatives such as n-butyl ether and ethylene glycol dimethyl ether; diacetone alcohol is preferably used as the main solvent.

Furthermore, in order to further improve the adhesion (adhesion) strength of the laminate, the III component used for the first adhesive layer may be included. Moreover, in order to improve film forming property and weather resistance, a surfactant, an antioxidant, a radical scavenger, an ultraviolet stabilizer, an ultraviolet absorber, a dye, and the like used for the first adhesive layer may be included. .
Next, the material or member which comprises the laminated body of this invention is demonstrated.

<Resin sheet or film>
In the present invention, as the resin sheet or film, a light-transmitting sheet or film can be used without particular limitation, but a resin-made sheet or film should be used from the viewpoints of availability and ease of processing. Is preferred. Examples of resins suitable as raw materials for resin sheets or films include polycarbonate resins, polyethylene terephthalate resins, nylon resins, triacetyl cellulose resins, acrylic resins, urethane resins, allyl resins, epoxy resins, polyvinyl alcohol resins, and the like. . Among these, polycarbonate resin is particularly preferable because it has good adhesiveness and high applicability to the injection molding method. In addition, a polarizing film (a polyvinyl alcohol polarizing film sandwiched between triacetyl cellulose resin films), a polarizing sheet (a polyvinyl alcohol polarizing film sandwiched between polycarbonate sheets), a dyed film, and a dyed sheet are also included in the resin of the present invention. It can be used as a sheet or film. In the case of using a dyed resin sheet or film, it is possible to use an originally dyed sheet, or after producing the laminated sheet of the present invention, dye the surface resin sheet or film. May be.

  When an optical article is obtained using the polarizing film, polarizing sheet, dyeing film, and dyeing sheet, the first adhesive layer is on the upper side (the side irradiated with sunlight or ultraviolet rays) than the polarizing film or the like. It is preferable that they are laminated.

  As suitable thickness of the resin-made sheet | seat or film used in this invention, 100-1500 micrometers is preferable and 200-1000 micrometers is more preferable. In addition, these resin sheets or films can be used in combination with different thicknesses.

  Moreover, the following coating layers may be formed on the surfaces (upper surface and lower surface) of the resin sheet and film of the present invention. The coating layer comprises a water-dispersible polymer such as water-dispersed polyurethane resin, water-dispersed polyester resin, water-dispersed acrylic resin, water-dispersed polyurethane / acrylic resin; among the water-dispersible polymers, a polymer having a carbonyl group and a hydrazide compound A crosslinked product of a water-soluble polymer such as polyvinyl alcohol; a polymerizable monomer having a (meth) acrylic group and / or an epoxy group, a (meth) acrylic group, a vinyl group, an amino group, and a mercapto group. Of a hydrolyzable organosilicon compound having a group capable of forming a silanol group or a urethane having a polymerizable group selected from a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group Composition of urea resin; propenyl ether group-containing compound, polyene compound and Ene / thiol compositions comprising ol compound, such as light-curable composition comprising an oxetane compound, a resin, crosslinked, may be formed from the composition. By forming the coating layer on the outermost surface (the side where no photochromic adhesive sheet is present), a (meth) acrylate-based monomer composition, an allyl-based monomer composition, a thiourethane-based monomer composition, a urethane-based monomer composition The laminate of the present invention can be embedded in a monomer composition that forms a thermosetting resin (optical substrate) such as a thioepoxy monomer composition. As a result, it is possible to obtain an optical article in which the laminate is embedded in the thermosetting resin (optical substrate) having good adhesion between the thermosetting resin (optical substrate) and the laminated sheet. .

<The manufacturing method of the laminated body of this invention>
The laminate of the present invention is produced by joining two resin sheets or films facing each other via an adhesive layer made of the photochromic composition of the present invention. The thickness of the first adhesive layer is preferably 5 to 100 μm, particularly 10 to 50 μm, from the viewpoint of the color density of the photochromic compound, weather resistance, adhesive strength, and the like. Moreover, when using a 2nd contact bonding layer, it is preferable that the film thickness is the range of 2-40 micrometers as above-mentioned, and it is more preferable that it is 5-15 micrometers. The thickness of the obtained optical article is preferably 500 to 3000 μm from the viewpoint of ease of manufacturing the optical article and the workability of processing described later.

  The said 1st contact bonding layer can be obtained with the following methods according to the property of the photochromic composition to be used. That is, when the photochromic composition (or precursor composition) of the present invention is adjusted to an appropriate viscosity by blending a solvent or the like, the photochromic composition of the present invention is formed on one resin sheet or film. Is applied and (heated) drying is performed as necessary, and then another resin sheet or film may be (heated) pressed. The suitable kinematic viscosity of the photochromic composition (or precursor composition) of the present invention is 2,000 to 50,000 cSt at 25 ° C., more preferably 5,000 to 40,000 cSt, still more preferably. Is 8,000 to 30,000 cSt. When the photochromic composition (or precursor composition) is 2,000 to 60,000 cSt, the smoothness of the photochromic adhesive sheet is increased, and roll-to-roll coating allows the appearance of vertical and horizontal stripes. The occurrence of defects can be suppressed.

  At this time, as a coating method of the photochromic composition (or precursor composition), a known method such as a spin coating method, a spray coating method, a dip coating method, a dip-spin coating method, or a dry laminating method is used without any limitation. It is done. The resin 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. Moreover, as a coating machine used for coating, general coating machines, such as a knife coater, a die coater, a gravure coater, a reverse roll coater, and a bar coater, can be used without any limitation. Among these, a knife coater and a die coater having a relatively wide allowable range of coating solution viscosity are preferably used.

  Further, when the photochromic composition (or precursor composition) of the present invention containing an organic solvent is used, after the photochromic composition (or precursor composition) of the present invention is spread on a smooth substrate. The organic solvent is removed by drying, then the substrate is peeled off, and the component I (or component I and component III) and the component II dispersed in component I (or component I and component III) are mixed. A photochromic adhesive sheet is prepared. Next, the laminate of the present invention can also be produced by joining the two resin sheets or films with the photochromic adhesive sheet interposed between the two resin sheets or films facing each other. . When the precursor composition is used, a photochromic composition (photochromic adhesive sheet: first adhesive layer) is formed in the course of manufacturing this laminate.

  As the material for the smooth substrate, a material that is resistant to the solvent used in the present invention and a material that can easily be peeled off from the photochromic composition (or precursor composition) are preferable. Examples thereof include stainless steel, Teflon (registered trademark), polyethylene terephthalate, polypropylene, and a plastic film on which a coating layer that improves peelability such as silicon or fluorine is laminated.

  When such a method is employed, it is possible to eliminate adverse effects caused by the use of the solvent regardless of the type of solvent and the type of resin sheet or film.

  The application and further drying of the photochromic composition (or precursor composition) are preferably performed at a temperature of room temperature to 130 ° C. and a humidity of 10 to 100% RH. The organic solvent may adversely affect the photochromic properties by remaining in the photochromic adhesive sheet after drying, and the mass of the organic solvent after drying is 0.1% or less with respect to the photochromic adhesive sheet. It is preferable. Moreover, when using a precursor composition, since an isocyanate compound is blended as the III component in the precursor composition, by performing operations such as coating and drying in the presence of humidity, The hydrolysis reaction of the III component is promoted, and a stronger adhesion can be obtained. By drying under the above humidity (in the presence of moisture), a photochromic adhesive sheet that exhibits excellent performance can be obtained without adding water to the precursor composition. When water is added, the sheet can be formed under dry conditions.

  The laminate obtained in the step of joining the resin sheet or film can be used as it is, but the state can be stabilized and used by the following method. Specifically, it is preferable to leave the laminated body just joined at a temperature of 20 ° C. or higher and 60 ° C. or lower for 4 hours or longer to deaerate. The upper limit of the standing time is not particularly limited, but 50 hours is sufficient. In addition, when standing, it can be left at normal pressure or left under vacuum. Furthermore, it is preferable to leave this standing laminate at a temperature of 60 ° C. to 130 ° C. for 30 minutes to 3 hours (hereinafter referred to as heat treatment). By performing this heat treatment, it is considered that a part of the isocyanate group of the III component is subjected to the reaction. As a result, it is considered that this isocyanate group is bonded to the urethane bond or urea bond of the I component to form an allophanate bond or a burette bond. And the laminated sheet obtained by this heat treatment has a very stable state.

  Moreover, when the precursor composition which mix | blended III component is used, it is preferable to humidify under the temperature of room temperature-100 degreeC, and the humidity of 30-100% RH. By carrying out this humidification treatment, the bridge structure between the I components by the III component can be completed, and the isocyanate group derived from the III component present in the laminated sheet can be completely eliminated, and the photochromic properties and adhesion It is possible to further stabilize the property.

  Furthermore, after the humidification treatment, excess moisture present in the laminate can be removed by standing at 40 to 130 ° C. under normal pressure or under vacuum. Therefore, after preparing the photochromic laminate from the precursor composition, it is preferable to perform post-treatment in the order of 1) deaeration, 2) heat treatment, 3) humidification treatment, and 4) moisture removal. It is preferable to react the I component and the III component in the adhesive layer.

  Moreover, as a method of manufacturing the laminated sheet having the above-mentioned second adhesive layer, if the second adhesive layer is laminated between the first adhesive layer and the resin sheet or the optical film, the manufacturing thereof is possible. The method is not particularly limited.

As a manufacturing method,
1) A method of previously laminating a second adhesive layer on a resin sheet or film and sandwiching the first adhesive layer between two resin sheets or films having the second adhesive layer,
2) A method in which the second adhesive layer is applied on both surfaces of the first adhesive layer, and a resin sheet or film is pasted on both surfaces,
3) A method of sequentially laminating the first adhesive layer, the second adhesive layer, the first adhesive layer, and further the resin sheet or film on the resin sheet or film,
However, it is most preferable to adopt the method 1) from the viewpoint of production efficiency.

  The application method and the drying method of the second adhesive layer of the present invention can be carried out by the same method as the first adhesive layer.

  Furthermore, when a solvent is not included, the mixture of the precursor composition and the polyisocyanate compound (III component) can be processed into a laminate by coextrusion molding or the like.

<Articles using laminates>
In the photochromic composition of the present invention, the obtained laminate exhibits excellent adhesiveness, particularly excellent adhesiveness at high temperatures, and the obtained laminate has high sweat resistance. That is, excellent adhesion is exhibited even after contact with artificial sweat. Furthermore, the laminate of the present invention has a high color density when irradiated with sunlight, a high fading speed when not irradiated with sunlight, and has high repetition durability due to color fading. Accordingly, the laminate of the present invention can be used as a laminate for developing photochromic properties in articles such as light shielding window materials, display materials, agricultural films, toys, clothes, umbrellas, etc., in addition to the above-mentioned plastic sunglasses. it can.

  In the present invention, a polycarbonate resin is preferable as the optical substrate when the laminate is integrated with an optical substrate such as a plastic lens. Examples of the integration method include a method in which the laminate is mounted in a mold and a thermoplastic resin such as a polycarbonate resin is formed by injection molding. In addition, the laminated body of the present invention can be processed into a lens-shaped spherical shape by performing bending before being integrated with the optical substrate. Examples of the method for bending the laminated sheet include hot press processing, pressure processing, and vacuum suction processing. The temperature at the time of bending may be appropriately determined depending on the type of the resin sheet or film used in the laminated sheet, but it is preferably performed at 120 to 200 ° C. Moreover, it can be set as a light shielding window material or an agricultural film by integrating with other resin-made sheets or glass. Moreover, it can be set as a display material by combining with displays, such as a liquid crystal display panel, a field emission display, an electroluminescent display, and a plasma display. Furthermore, by combining with members such as metal, glass, wood, paper, and fabrics such as cotton, hemp, and silk, photochromic toys, clothes, umbrellas, and the like can be obtained.

  Specifically, a molded body useful as a light shielding window material can be obtained by laminating silicate glass on both surfaces of the laminate of the present invention. Such a molded body can be expected as a window material with high adhesion of the laminated body and excellent durability. Moreover, the display material excellent in the contrast outdoors can be obtained by bonding the laminated body of this invention on the back surface of a liquid crystal panel. This display material can be easily processed into various shapes, and is particularly useful as a head-up display. Alternatively, since the laminate of the present invention can provide a large laminate having high adhesion, a display material excellent in contrast outdoors can be obtained by bonding the laminate of the present invention to the back surface of the plasma display panel. In particular, a molded product that can withstand long-term use as an outdoor display can be obtained.

  Furthermore, since the laminate of the present invention can be easily processed into various shapes, a molded body that can withstand long-term use as an agricultural film can be obtained by laminating a polypropylene film on one side. Further, instead of polypropylene film, fabric (cotton, hemp, etc.), resin material, metal, etc., can be used as materials for toys, clothes, etc. that can withstand long-term use by bonding to the laminate of the present invention. .

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

The abbreviations of the compounds used as the respective components in the examples and comparative examples are summarized below.
A1 component; polyol compound PL1: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 800).
PL2: Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 1000).
A2 component; diisocyanate compound NCO1: isophorone diisocyanate.
NCO2: Isomeric mixture of 4,4′-methylenebis (cyclohexyl isocyanate).
B component; polyamine compound CE1: isophoronediamine.

CE2: bis- (4-aminocyclohexyl) methane.
Component C: Compound having a group capable of reacting with one isocyanate group in the molecule HA1: 1,2,2,6,6-pentamethyl-4-aminopiperidine.
HA2: normal butylamine.
Organic solvent D1: Isopropyl alcohol.
D2: Propylene glycol monomethyl ether.
D3: Toluene.
D4: Diethyl ketone.
D5: t-butyl alcohol.
II component; photochromic compound PC1: Compound represented by the following formula

  PC2: Compound represented by the following formula

  PC3: Compound represented by the following formula

III component: polyisocyanate compound CA1: isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate) (molecular weight 262)
Other components L1: Ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by Ciba Specialty Chemicals).
L2: DOW CORNING TORAY L-7001 (manufactured by Toray Dow Corning Co., Ltd., surfactant).

Production Example 1 (Production of polyurethane urea resin)
(Manufacture of urethane prepolymer)
A cooling tube, a thermometer, and a nitrogen gas introduction tube were connected to a reaction vessel having a blade diameter of 135 mm, a Max Blend blade, an inner diameter of 260 mm equipped with baffle plates, a height of 280 mm, and a charged amount of 10 L. The Max Blend blade was agitated at 100 rpm.
Into this reaction vessel, 1770 g of polycarbonate diol having a number average molecular weight of 800, 700 g of isophorone diisocyanate and 500 g of toluene were charged and reacted at 100 ° C. for 7 hours in a nitrogen atmosphere to synthesize a urethane prepolymer having an isocyanate group at the terminal. The end point of the reaction was confirmed by an isocyanate group back titration method.

(Manufacture of polyurethane urea resin (U1))
After completion of the urethane prepolymer reaction, the reaction solution was cooled to around 0 ° C., dissolved in 1430 g of isopropyl alcohol and 2670 g of diethyl ketone, and the solution temperature was kept at 0 ° C. Next, a mixed solution of 171 g of chain extender bis- (4-aminocyclohexyl) methane and 145 g of diethyl ketone was added dropwise within 30 minutes and reacted at 0 ° C. for 1 hour. Thereafter, 42 g of 1,2,2,6,6-pentamethyl-4-aminopiperidine was further added dropwise and reacted at 0 ° C. for 1 hour to obtain a diethyl ketone solution of polyurethane urea resin. The resulting polyurethane urea resin has a number average molecular weight of 19,000, a weight average molecular weight of 41,000, a polydispersity of 2.16, and a softening point of 105 ° C. (softening start temperature; about 80 ° C) and the kinematic viscosity was 15,000 cSt.
The viscosity of the reaction liquid at the start of dropping of the polyamine compound bis- (4-aminocyclohexyl) methane is 0.06 kg / m · s, the density is 900 kg / m ³ , and the rotation speed of the Max Blend blade is 100 rpm. , The Reynolds number (Re) is 456, and the mixing time number (n · θ _M ) is 14 from the n · θ _M -Re curve in the Max blend blade, so the complete mixing time (θ _M ) is 8 seconds. there were.

<Evaluation method>
The number average molecular weight, weight average molecular weight, polydispersity, softening point, and kinematic viscosity of the urethane urea resin were measured by the following methods.

(Number average molecular weight, weight average molecular weight, and polydispersity)
Regarding the number average molecular weight, weight average molecular weight, and polydispersity, the analysis was carried out by the method described in the text.
That is, using gel permeation chromatograph (GPC) in terms of polyethylene oxide, two columns: Shodex KD-806M (manufactured by Showa Denko KK) connected in series, eluent: LiBr (10 mmol / L) / Measured under the conditions of DMF solution, flow rate: 1 ml / min, detector: RI detector, polyurethane urea resin sample solution: 1.0% dimethylformamide (DMF) solution, GPC analysis software “Empower Personal” manufactured by Japan Waters Co., Ltd. It was calculated using “GPC Option”. The polydispersity is a value calculated by weight average molecular weight / number average molecular weight, and was calculated from the number average molecular weight and the weight average molecular weight determined by the above method.

(Softening point)
A polyurethane urea resin solution was poured into a stainless steel container, and dried at 40 ° C. for 10 hours, 60 ° C. for 10 hours, and further dried at 60 ° C. for 12 hours in a vacuum dryer to prepare a test piece having a thickness of 1 mm. The obtained test piece was measured using a thermomechanical measurement device (Seiko Instruments, TMA120C), with a temperature increase rate of 10 ° C./min, a measurement temperature range of 30 to 200 ° C., and a probe with a tip diameter of 0.5 mm. The softening point was measured under the conditions of the needle probe.

(Kinematic viscosity)
About 10 g of the polyurethane resin solution was put into a Canon Fenceke viscometer (# 600), and this Canon Fenceke viscometer (manufactured by Shibata Kagaku Co., Ltd.) was immersed in a constant temperature water bath controlled at 25 ° C. ± 0.1 ° C. for 15 minutes. Thereafter, the kinematic viscosity was measured.

Production Examples 2 to 17
Using a polyol compound (A1 component), a diisocyanate compound (A2 component), a polyamine compound (B component), a compound having a group capable of reacting with one isocyanate group (C component) and an organic solvent shown in Table 1, Except for using the reaction conditions shown in Table 1 and Table 2, polyurethane urea resins of U2 to 17 were synthesized in the same manner as the synthesis method of U1. The evaluation results are shown in Table 2. The complete mixing time (θ _M ) is determined from the Reynolds number (Re) based on the viscosity and density of the reaction liquid of the urethane prepolymer (component A) at the start of dropping of the polyamine compound (component B) and the rotation speed of the Max blend blade. ) was calculated, and then calculated from the n · θ _M which is Dasa led from the n · θ _M -Re curve in Max blend wing.

Example 1
(Preparation of precursor composition)
43 g of polyurethane urea resin (U1) solution, 12.1 g of photochromic compound (PC1 / PC2 / PC3 = 8.7 / 2.0 / 1.4 g), isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate) 43 .2 g, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant, 3.6 g, DOW CORNING TORAY L-7001 as a surfactant 0.5 g was added and stirred and mixed at room temperature to obtain a precursor composition.

(Adjustment of second adhesive layer adhesive)
To 1000 g of the polyurethane urea resin (U4) solution, 0.7 g of DOW CORNING TORAY L-7001 as a surfactant was added, and stirred and mixed at room temperature to obtain an adhesive for the second adhesive layer.

(Production of laminated sheet)
A laminated sheet was prepared using a coater (manufactured by Tester Sangyo). The second adhesive layer having a thickness of 8 μm is formed by applying the adhesive for the second adhesive layer onto a polycarbonate sheet having a thickness of 300 μm at a coating speed of 0.5 m / min and drying at a drying temperature of 110 ° C. for 3 minutes. A polycarbonate sheet was obtained.

The precursor composition is applied on a PET film (Purex film manufactured by Teijin DuPont Films Ltd., with silicon coating) at a coating speed of 0.3 m / min, and dried at a drying temperature of 100 ° C. for 5 minutes. Thus, a photochromic adhesive layer having a thickness of about 40 μm was obtained, and the polycarbonate sheet having the second adhesive layer was laminated with a pressure of 0.1 MPa.
Next, the PET film of the laminate obtained by laminating the PET film coated with the precursor composition and the polycarbonate sheet having the second adhesive layer is peeled, and the polycarbonate sheet having the peeled surface and the second adhesive layer is reduced to 0.00. Lamination was performed with a pressure of 1 MPa to obtain a laminated sheet. The laminated sheet has a second adhesive layer on both surfaces of the first adhesive layer which is a photochromic adhesive layer, and a polycarbonate sheet is laminated on the outer surface of the second adhesive layer (the surface on which the first adhesive layer is not laminated). It was a configuration. The obtained laminated sheet was allowed to stand at 40 ° C. under vacuum for 24 hours, and then heat-treated at 110 ° C. for 60 minutes, and then humidified at 60 ° C. and 100% RH for 24 hours. The laminated sheet which has the target photochromic characteristic was obtained by leaving still for 24 hours under. The amount of residual solvent was measured and found to be 0.01%. In addition, when the photochromic adhesive sheet finally obtained was peeled from the polycarbonate sheet and the infrared absorption spectrum was confirmed, the peak of isocyanate group was not detected in the photochromic adhesive sheet.

The resulting laminated sheet had a color density of 1.0 as a photochromic property, a fading speed of 45 seconds, and a durability of 93%. The peel strength is 200 N / 25 mm in the initial stage, the peel strength in a 70 ° C. atmosphere is 140 N / 25 mm, and the peel strength in a 150 ° C. atmosphere is 40 N / 25 mm. The adhesion stabilization time in the sweat resistance test is 1200 hours. Met.
These evaluations were performed as follows.

[Photochromic characteristics]
The obtained laminated sheet was used as a sample, and a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was applied to the laminated sheet surface through an aeromass filter (manufactured by Corning). 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 laminated sheet 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 (%) = [(A96 / A0) × 100]: In order to evaluate the durability of color development by light irradiation, the following deterioration acceleration test was conducted. That is, the obtained laminated sheet was accelerated and deteriorated for 96 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 (A0) before the test and the color density (A96) after the test were measured, and the value of [(A96) / 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 laminated sheet is used as a test piece having an adhesive portion of 25 × 100 mm, and is mounted on a testing machine (Autograph AGS-500NX, manufactured by Shimadzu Corp.) equipped with a thermostatic bath capable of setting a test atmosphere temperature. A tensile test was performed at a speed of 100 mm / min, and the peel strengths 1) to 3) below were measured.

1) The initial peel strength was tested as described above.
2) The peel strength in a 70 ° C. atmosphere was measured as described above after heating a test piece cut out to the above size for 10 minutes in a thermostat set at 70 ° C.
3) The peel strength in an atmosphere at 150 ° C. was measured as described above after the test piece cut out in size was heated for 10 minutes in a thermostat set at 150 ° C.

[Sweat resistance test]
The obtained laminated sheet was cut into a circle having a diameter of 50 mm, and the outer periphery of the test piece was clamped with a ring-shaped stainless steel jig. Separately, artificial sweat (distilled water added with 10% sodium chloride and 5% lactic acid) was prepared in a plastic container with a lid, and the test piece was immersed in the artificial sweat. This test piece and a plastic container containing artificial sweat were stored at 70 ° C., and the presence or absence of peeling at the end of the test piece was visually evaluated every 24 hours. The numerical value of the evaluation result is a time (time until immediately before peeling occurs) showing stable adhesiveness.

Example 2
(Preparation of precursor composition)
The precursor composition was obtained in the same manner as in Example 1.

(Production of laminated sheet)
A laminated sheet was prepared using a coater (manufactured by Tester Sangyo). The precursor composition is applied on a PET film (Purex film manufactured by Teijin DuPont Films Ltd., with silicon coating) at a coating speed of 0.3 m / min, and dried at a drying temperature of 100 ° C. for 5 minutes. Thus, a photochromic adhesive layer having a thickness of about 40 μm was obtained, and the polycarbonate sheet was laminated with a pressure of 0.1 MPa.

  Next, the PET film of the laminate obtained by laminating the PET film coated with the precursor composition and the polycarbonate sheet was peeled off, and the peeled surface and the polycarbonate sheet were stuck together at a pressure of 0.1 MPa to obtain a laminated sheet. The laminated sheet had a configuration in which polycarbonate sheets were laminated on both surfaces of the first adhesive layer which is a photochromic adhesive layer. The obtained laminated sheet was allowed to stand at 40 ° C. under vacuum for 24 hours, and then heat-treated at 110 ° C. for 60 minutes, and then humidified at 60 ° C. and 100% RH for 24 hours. The laminated sheet which has the target photochromic characteristic was obtained by leaving still for 24 hours under. The amount of residual solvent was measured and found to be 0.01%. In addition, when the photochromic adhesive sheet finally obtained was peeled from the polycarbonate sheet and the infrared absorption spectrum was confirmed, the peak of isocyanate group was not detected in the photochromic adhesive sheet.

The resulting laminated sheet had a color density of 1.0 as a photochromic property, a fading speed of 47 seconds, and a durability of 92%. The peel strength is initially 150 N / 25 mm, the peel strength in a 70 ° C. atmosphere is 100 N / 25 mm, the peel strength in a 150 ° C. atmosphere is 20 N / 25 mm, and the adhesion stabilization time in the sweat resistance test is 400 hours. Met.
These evaluations were performed by the same method as in Example 1.

Examples 3-9, 11-16, Comparative Example 1
The same method as in Example 1 except that the polyurethane urea resin (I component), photochromic compound (II component), polyisocyanate compound (III component), organic solvent, other components, and second adhesive layer shown in Table 3 were used. A laminated sheet was obtained. Table 4 shows the evaluation results of the obtained various laminated sheets.

Example 10 and Comparative Example 2
A laminated sheet was prepared in the same manner as in Example 2 except that the polyurethane urea resin (I component), photochromic compound (II component), polyisocyanate compound (III component), organic solvent, and other components shown in Table 3 were used. Obtained. Table 4 shows the evaluation results of the obtained various laminated sheets.

  As is clear from Examples 1 to 16, the laminated sheet of the present invention using a urethane urea resin having a narrow polydispersity has good adhesion. In particular, it has excellent adhesion at high temperatures.

  On the other hand, as shown in Comparative Examples 1 and 2, a laminated sheet using a urethane urea resin having a wide polydispersity could not obtain sufficient adhesion.

Claims (14)

(I) A photochromic composition comprising a polyurethane urea resin having a polydispersity (weight average molecular weight / number average molecular weight) in the range of 1.6 to 2.4, and (II) a photochromic compound. The photochromic composition according to claim 1, wherein the photochromic composition further comprises (III) a polyisocyanate compound having at least two isocyanate groups in the molecule.   2. The photochromic composition according to claim 1, wherein the content of the (II) photochromic compound is 0.1 to 20 parts by mass with respect to 100 parts by mass of the (I) polyurethane urea resin. The polyurethane urea resin is
(A) a urethane prepolymer having an isocyanate group at the molecular end;
(B) a polyamine compound having two or more amino groups in the molecule;
The photochromic composition according to claim 1, wherein the photochromic composition is a resin obtained by reaction. Further, the polyurethane urea resin is
(C) a compound having one group capable of reacting with an isocyanate group in the molecule;
The photochromic composition according to claim 4, which is a resin obtained by reacting the above. The urethane prepolymer is
(A1) a polyether polyol, a polyester polyol, polycarbonate polyol, and at least one polyol selected from the group consisting of a polyol having at least two or more hydroxyl groups of the polycaprolactone polyol Lumpur compound,
(A2) a diisocyanate compound having two isocyanate groups in the molecule;
The photochromic composition according to claim 4, wherein the photochromic composition is a urethane prepolymer obtained by reaction.   A laminate in which two resin sheets or films facing each other are bonded via an adhesive layer made of the photochromic composition according to claim 1.   Two resin sheets or films facing each other are bonded together via a first adhesive layer made of the photochromic composition according to claim 1 and second adhesive layers present on both sides of the first adhesive layer. The laminate according to claim 7, comprising a laminated structure.   The light shielding window material using the laminated body of Claim 7 or 8.   A display material using the laminate according to claim 7 or 8.   The agricultural film using the laminated body of Claim 7 or 8.   A toy using the laminate according to claim 7 or 8.   A garment using the laminate according to claim 7 or 8.   An umbrella using the laminate according to claim 7 or 8.