JP2005199683A - Laminate, optical element, manufacturing method for them, and coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance an optical property and the like of a photochromic lens and the like by achieving excellent adhesion between a base material and a photochromic layer in the case of manufacturing a photochromic optical element. <P>SOLUTION: There is proposed as a first means to achieve the purpose the formation of a polyurethane-based primer layer between the base material and the photochromic layer. The polyurethane-based primer layer is obtained by applying a liquid containing a moisture-curable polyurethane resin and/or its precursor and a solvent having a boiling point of not lower than 70°C and a solubility parameter of not less than 8, removing the solvent and curing the moisture-curable polyurethane resin and/or its precursor. There is proposed as a second means to achieve the purpose a photochromic coating agent composed of 100 pts.wt. of a radically polymerizable monomer component, 0.01 to 20 pts.wt. of a photochromic compound, and 0.001 to 5 pts.wt. of a silicone-based or fluorine-based surfactant. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is an optical article such as a plastic lens or a photochromic plastic lens or a laminate suitable as a material thereof, a curable composition having photochromic properties, and a curable composition that can be suitably used for producing the photochromic plastic lens, a method for producing the same, In addition, the present invention relates to a coating solution used in the production thereof.

  Photochromic glasses are lenses that quickly color and function as sunglasses when exposed to light containing ultraviolet rays such as sunlight. These glasses function as glasses, and their demand is increasing in recent years.

  As a method for producing a plastic lens having photochromic properties, a method of impregnating a surface of a lens having no photochromic property with a photochromic compound (hereinafter referred to as an impregnation method), or a curable composition having a photochromic property on the surface of a plastic lens. A coating agent (hereinafter also referred to as photochromic coating agent) is applied and then cured to provide a photochromic resin layer (photochromic coating layer) (hereinafter referred to as coating method), or a photochromic compound is dissolved in a monomer. In addition, a method of directly obtaining a photochromic lens by polymerizing it (hereinafter referred to as a kneading method) is known.

  By the way, in the impregnation method, it is necessary to use a soft base material in which the photochromic compound is easily diffused as the base lens, and a special monomer composition is used in order to develop good photochromic properties even in the kneading method. There is a need. On the other hand, the coating method has an advantage that, in principle, photochromic properties can be imparted to any lens substrate.

  In this way, the coating method can be said to be an excellent method for producing photochromic plastic lenses, but it has sufficient adhesion to the base material and, if necessary, the hard coat layer formed on the photochromic coat layer. In addition, a technique for forming a photochromic coat layer that exhibits good photochromic properties has not yet been established.

  Conventionally, as a coating method, (i) a method in which a photochromic compound dissolved in a urethane oligomer is applied to a lens surface and cured (see Patent Document 1), (ii) monofunctional, bifunctional and polyfunctional. A method in which a photochromic compound is dissolved in a polymerizable monomer composition in which a functional radical polymerizable monomer is combined, applied to the lens surface, and cured (see Patent Document 2); (iii) two or more types of 2 (Iv) N-alkoxymethyl (meth) acrylamide, a method of dissolving a photochromic compound in a monomer composition consisting of a combination of only functional (meth) acrylic monomers, applying it to the lens surface, and curing (iv) N-alkoxymethyl (meth) acrylamide, A method of applying a composition comprising a catalyst (preferably an acidic catalyst) and a photochromic compound to the lens surface and thermally curing (see Patent Document 4) ), And the like are known.

International Publication No. 98/37115 Pamphlet US Pat. No. 5,914,174 International Publication No. 01/02449 Pamphlet International Publication No. 00/36047 Pamphlet

  However, in the above method (i), not only the temperature dependency of the photochromic property is increased due to the low crosslinking density of the obtained photochromic coating layer, but also when the hard coating is applied on the photochromic coating layer. There is a problem that the photochromic compound is eluted in the liquid. Further, the methods (ii), (iii) and (iv) have a problem that the adhesion between the spectacle lens substrate and the photochromic coat layer is not sufficient.

  Therefore, the present inventors have intensively studied to solve the above problems. As a result, as a coating agent that gives a coating layer having high adhesion to a substrate, “a radical polymerizable monomer containing a radical polymerizable monomer having a silanol group or a group that generates a silanol group by hydrolysis” Body, amine compound and photochromic compound each containing a specific amount of photochromic coating agent (International Publication No. 03/011967 pamphlet), and further in the adhesive photochromic coating agent In addition, it has succeeded in obtaining stable adhesion by blending a radically polymerizable monomer containing a maleimide group into the coating (Japanese Patent Application No. 2002-372835, hereinafter, these coating agents are collectively referred to as an adhesive photochromic coating agent). Also called). However, as a result of performing a boiling promotion test assuming use under high-temperature and high-humidity conditions for these adhesive photochromic coating agents, depending on the type of the substrate, etc., the adhesion of the film may decrease and the coat layer may peel off. It has been found.

  As a technique for improving adhesion and adhesiveness, it is known to provide a primer layer between adherends using a primer. For example, as a primer for improving the adhesion between the hard coat layer and the lens substrate, a polyurethane resin, an epoxy resin, a polyacetal resin, or the like has been proposed. However, as far as the present inventor knows, there are no examples in which the effect of the primer has been studied for the purpose of improving the adhesion between the plastic lens substrate and the photochromic coating layer as described above.

  Therefore, the present inventors considered that the adhesion between the plastic lens substrate and the photochromic coating layer could be improved by using these primers, and examined the effects of various primers. In the case of such a case, the inventors have found that the adhesion may be improved. However, when a urethane primer that is generally used as a primer for hard coating of plastic lenses is used, the adhesion properties are improved, but the optical properties and photochromic properties of the finally obtained laminate, etc. It became clear that there was a problem in this point.

  That is, as urethane-based primers used for plastic lenses, the following 1) to 3) are known, but it has been clarified that each has the following problems.

  1) Polyurethane is synthesized by reacting a polyisocyanate and an active hydrogen compound in advance, a paint obtained by dissolving the polyurethane in a solvent is applied to a lens substrate, and then the solvent is volatilized to form a primer layer. When this type of primer is used, since the resulting primer layer does not have a cross-linked structure, when the photochromic coating agent is applied, the polyurethane constituting the primer layer elutes into the coating agent, resulting in a photochromic coating. The agent is contaminated, and a problem that a desired photochromic property cannot be obtained occurs. For example, a solution obtained by dissolving a polyurethane resin formed by the reaction of a diol and diisocyanate described in JP-A-63-87223 in a solvent is applied to a lens substrate, and then heated to volatilize the solvent by heat treatment. When a primer layer made of plastic polyurethane is formed and a photochromic coating agent is applied thereon, the photochromic properties of the photochromic coating layer are lowered.

  2) A composition in which a polyisocyanate, an active hydrogen compound, and a curing catalyst are mixed as necessary, and a primer layer is formed by applying heat and curing as necessary. This type of primer uses polyisocyanate that is not protected by a protecting group, so the reaction of active hydrogen compounds is fast, and the storage stability of the mixed solution is poor, so workability and operability when applying the primer ( The applicability is poor, and there is a problem in the reproducibility of the optical properties of the resulting primer layer.

  3) A block type polyisocyanate blocked with a protecting group such as methyl ethyl ketone and an active hydrogen compound, which is inactivated at room temperature, mixed with a curing catalyst as necessary, and heated after coating to protect the protecting group. A primer layer is formed by cross-linking while removing. Although this type of primer has improved storage stability as described above, a high temperature is required to remove the protecting group, and a high temperature of 140 ° C. or higher is required to enhance the adhesion with the photochromic coating layer. Therefore, there arises a problem that the plastic lens base material is thermally deformed or yellowed.

  In addition, as the same urethane-based primer, a primer of a moisture curable polyurethane resin having a relatively high molecular weight and a low isocyanate group content in the molecule (the primer reacts with moisture in the atmosphere as the name suggests. Carbamic acid is produced and decarboxylated to produce an amine, and the amine and the remaining isocyanate groups are crosslinked and cured by forming a urea bond.) It cannot be used in the inside, and it is difficult to form a thin coat film due to its high viscosity. In addition, there is a problem that bubbles remain in the cured film because carbon dioxide is generated during the curing process. Examples used for optical applications such as lens substrates are not known, and are used exclusively for applications such as construction, where such a phenomenon does not cause a problem.

  The inventors of the present invention are effective when using a urethane primer for improving adhesion, and the moisture-curable polyurethane resin primer is a single solution and does not require high temperature for crosslinking and curing. Focusing on the advantage of not causing deformation or discoloration of the base material due to heat, we considered that it could be used as a primer for a lens depending on the device, and further studied.

  As a result, by using a specific solvent and further using a leveling agent as necessary, the applicability is improved, and it becomes possible to form a thin coating film by spin coating and the thickness of the coating film. When the thickness was reduced, bubbles were not left in the cured film, and it was found that the adhesion characteristics of the photochromic coating layer can be improved without deteriorating the optical characteristics and photochromic characteristics, and the present invention has been completed.

  Further, although the photochromic coating agent disclosed in the above-mentioned International Publication No. 03/011967 pamphlet is excellent, when the present inventors have further studied the photochromic coating agent, the material of the base material to be used Or when a urethane primer is used to improve adhesion durability, the wettability when applying the photochromic coating agent is not sufficient, and the photochromic coat layer and the substrate or primer layer It has been found that there is a possibility that appearance defects may occur due to roughness generated at the interface.

  Accordingly, it is possible to provide a laminate that can be suitably used as a photochromic plastic lens, in which a photochromic coating layer having better photochromic properties is firmly and stably adhered to a base material such as a plastic lens, and the applicability and coating film of a photochromic monomer It is desired to provide a photochromic coating agent that provides a photochromic coating layer having further excellent optical properties and high adhesion to a substrate and having excellent photochromic properties.

  The inventors of the present invention have improved wettability (applicability) to the substrate and optical properties of the coating film when a silicone-based or fluorine-based surfactant is added to the radical polymerizable monomer containing the photochromic compound. As a result, the present invention has been completed.

The present invention that achieves such an object includes the following gist.
(1) A laminate comprising a laminate structure in which a polyurethane resin layer comprising a cured product of a moisture curable polyurethane resin and / or a precursor thereof is formed on at least one surface of an optical substrate.
(2) The laminate according to (1), wherein the optical substrate has a surface composed of a three-dimensional crosslinked body, and the polyurethane resin layer is formed on the surface.
(3) The laminate according to (1) or (2), wherein the polyurethane resin layer has a thickness of 0.1 to 10 μm, and substantially no bubbles are present in the layer.
(4) A solvent after applying a coating liquid containing a moisture curable polyurethane resin and / or a precursor thereof and a solvent having a boiling point of 70 ° C. or more and a solubility parameter of 8 or more on at least one surface of the optical substrate. The method for producing a laminate according to any one of (1) to (3), wherein the moisture curable polyurethane resin and / or its precursor is cured.
(5) The method according to (4), wherein the moisture curable polyurethane resin and / or precursor solution thereof further contains a leveling agent.
(6) A laminate comprising a laminated structure in which a polyurethane resin layer and a resin layer containing a photochromic compound are laminated in this order on the surface of an optical substrate.
(7) An optical article comprising the laminate according to (1), (2), (3) or (6). (8) A coating solution for an optical substrate comprising a moisture curable polyurethane resin and / or a precursor thereof and a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8 or higher.
(9) A curable composition comprising 100 parts by weight of a radical polymerizable monomer component, 0.001 to 5 parts by weight of a silicone-based or fluorine-based surfactant, and 0.01 to 20 parts by weight of a photochromic compound.
(10) A photochromic cured product obtained by curing the curable composition according to (9).
(11) A photochromic coating agent comprising the curable composition according to (9) above.
(12) A photochromic optical article, wherein at least a part of the surface of the optical substrate is covered with a photochromic coating layer comprising a cured product of the photochromic coating agent according to (11).
(13) The laminate according to (6), wherein the resin layer containing the photochromic compound is formed of a cured product of the photochromic coating agent according to (11).

  According to the laminates (1), (2) and (3) of the present invention, not only the optical properties are not deteriorated by the polyurethane resin layer, but also the impact resistance is greatly improved by the layer. Is not only useful as a plastic lens with high impact resistance, but also has high adhesion (adhesiveness) to the cured film of the adhesive photochromic coating agent and other photochromic coating agents. It is particularly useful as a raw material base material (intermediate material) when producing optical articles such as the above. That is, the laminate of the present invention improves impact resistance while maintaining the high optical properties of the base material, and itself is useful as an optical article such as a spectacle lens. Furthermore, the laminate of the present invention has an excellent effect of being firmly adhered to the photochromic coat layer when the photochromic coat layer is formed on the surface thereof.

  By adopting the production method (4), (5) of the laminate of the present invention and the coating liquid for optical substrate (8) of the present invention, a moisture curable polyurethane resin having a high molecular weight is used. It is possible not only to form a thin and uniform coating film by applying by spin coating, but also to prevent bubbles from remaining in the coating film and to have good optical properties. It becomes possible to manufacture the laminated body of invention. That is, the production method and the coating liquid for an optical substrate of the present invention are made by applying a moisture-curable polyurethane resin primer not conventionally used for optical applications to optical applications, and have been used for optical applications. It solves various problems of conventional urethane primers. Furthermore, the present invention is highly useful in the field of plastic lenses as a method for producing a photochromic plastic lens that can withstand practical use by a coating method capable of imparting photochromic properties regardless of the type of substrate. .

  Another laminate (6) of the present invention is useful as a photochromic plastic lens because it has a feature that the adhesion between the photochromic coat layer and the substrate is good by interposing a polyurethane resin layer, and in particular, polyurethane. A resin layer made of a cured product of optical moisture-curing urethane primer can be manufactured by the coating method having many advantages as described above, and the coating layer is firmly and firmly adhered, and further has photochromic properties. It has the characteristic that the optical characteristic including is favorable. The laminate of the present invention having a photochromic coating layer not only has excellent optical properties and photochromic properties, but also exhibits strong adhesion that prevents the photochromic coating layer from peeling even under severe conditions of high humidity such as boiling. . Therefore, the laminate of the present invention is a highly reliable photochromic optical article (for example, a photochromic plastic lens) without peeling of the coating film even when used for a long time.

  When used as a photochromic coating agent, the curable composition (9) of the present invention has an effect of improving wettability (applicability) to a substrate or the like and optical properties of a coating film. Among the curable compositions of the present invention, (i) radical polymerizable monomer having a L-scale Rockwell hardness of 60 or more of a cured product obtained when the radical polymerizable monomer component is polymerized alone. A component containing a mixture of a component and a radical polymerizable monomer component having an L-scale Rockwell hardness of 40 or less in a homopolymer cured product exhibits the above-described effect of the present invention when used as a photochromic coating agent. In addition, the photochromic coating layer obtained has a characteristic that the photochromic properties are good.

  In addition, (ii) (a) a radical polymerizable monomer having a silanol group or a group capable of generating a silanol group upon hydrolysis (hereinafter also simply referred to as a silyl monomer) and / or a radical polymerizable monomer having an isocyanate group (B) a compound having a silanol group or a group that generates a silanol group by hydrolysis and having no radically polymerizable group is 100 parts by weight of all radical polymer components. The content of 0.5 to 20 parts by weight, particularly 1 to 10 parts by weight with respect to the photochromic coating layer obtained in addition to the above-described effects of the present invention when used as a photochromic coating agent. It has the characteristic that the adhesiveness with respect to a material becomes favorable. And (iii) a polymerizable monomer component having the L scale Rockwell hardness of 60 or more of the curable composition of the above (ii), which is obtained when the radical polymer component is polymerized alone; A homopolymer cured product containing a mixture of polymerizable monomer components having an L-scale Rockwell hardness of 40 or less has the characteristics (i) and (ii) above.

  And when the curable composition of the present invention is used as a photochromic coating agent, it has not only good wettability (applicability) to a substrate and the like, but also the photochromic and optical properties of the resulting photochromic layer are good. And it has the outstanding characteristic that the adhesiveness with respect to a base material is high. Therefore, the composition of the present invention is useful as a photochromic coating agent when a photochromic lens is produced by a coating method.

  The laminate of the present invention is formed on at least one surface of an optical substrate such as a plastic lens substrate (herein, the optical substrate means a substrate having a pair of front and back main surfaces made of an optical material). A polyurethane resin layer composed of a cured product of a moisture curable polyurethane resin and / or a precursor thereof is formed. Here, the optical base material is not particularly limited as long as it is a light-transmitting base material, and examples thereof include known optical base materials such as glass and plastic lenses, house and automobile window glass, and plastic lenses are used. Is particularly preferred.

  Plastic lenses include thermoplastic resin lenses such as (meth) acrylic resins and polycarbonate resins; crosslinkability such as polyfunctional (meth) acrylic resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins. Although known lenses currently used as plastic lenses, such as resin lenses, can be used, when forming a polyurethane resin layer with the coating liquid for optical substrates of the present invention, the selection of the solvent for the coating liquid for optical substrates Since the width increases (in other words, the range of the solvent that does not attack the substrate is wide), the surface to which the coating liquid for optical substrate is applied is preferably composed of a three-dimensional crosslinked body. That is, when the plastic material is a cross-linked resin, it can be used as it is, but when it is made of a thermoplastic resin such as a polycarbonate resin, it is preferable to form a three-dimensional cross-linked layer on the surface. The three-dimensional crosslinked body layer is not particularly limited, but a preferable example is a so-called hard coat layer.

  The laminate of the present invention is a urethane resin comprising a cured body of the optical substrate coating liquid (8) of the present invention (hereinafter also referred to as “optical moisture-curable urethane primer”) on the surface of the optical substrate. The greatest feature is that a layer is formed. By forming the layer, the impact resistance of the optical substrate can be improved, and further to the substrate of the coating layer when the photochromic coating layer is formed by applying the adhesive photochromic coating agent as described above. It becomes possible to increase the adhesiveness (adhesiveness).

  Here, the cured body forming the cured body layer is a polyurethane resin obtained by curing a moisture curable polyurethane resin and / or a precursor thereof, which is a component of the optical moisture curable urethane primer. As described above, it is known that a urethane resin layer is formed on a plastic lens substrate. However, an example using a moisture curable polyurethane resin and / or a precursor thereof as a primer for optical materials is known. Therefore, these urethane resins are cured products (the structure corresponds to the structure of the compound before curing, so the urethane resin is based on a urethane primer used for conventional optical applications) Optical substrates having a layer consisting of

  The moisture-curable polyurethane resin and / or precursor thereof used in the present invention is a decarboxylation after a part of isocyanate groups present in the molecule react with moisture in the atmosphere to generate carbamic acid, for example. An isocyanate group-containing compound or a compound or a combination of compounds that is a precursor of such a compound, which forms an amine and is crosslinked and cured by reacting the amine with the remaining isocyanate group to form a urea bond, for example, molecular weight The number average molecular weight is preferably 300 to 5000, particularly 500 to 3000, and the average content of isocyanate groups present at the end in one molecule is 0.001 mol% to 50 mol%, preferably 0. Polyurethane oligomers or polyurethanes adjusted to 1 mol% to 10 mol%, most preferably 0.5 mol% to 5 mol% “Polyisocyanate oligomer or a derivative thereof” or “a combination of these“ isocyanate compound or a derivative thereof ”and an active hydrogen-containing compound”, which is a precursor of these polyurethane oligomers or polyurethane polymers, can be used. The average isocyanate group content (mol%) in the above is determined by chemically quantifying the number of moles of isocyanate groups present in a specific amount of the compound, and the number of moles of isocyanate groups obtained is determined by the specific amount. The number of moles of isocyanate groups present in one molecule of the compound is obtained by dividing by the number of moles of the compound contained therein (value obtained by dividing the weight of the specific amount by the number average molecular weight), and the mole number is further calculated as the molecular weight of the compound. Means the value divided by (number average molecular weight) expressed in% .These moisture-curable polyurethane resins Beauty / or its precursors are commercially available, for example, as primers for architectural applications, it is available as industrial or reagents.

  Examples of moisture curable polyurethane resins and / or precursors thereof that can be suitably used in the present invention include (1) tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and tolidine diisocyanate. , Aromatic isocyanate compounds such as triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate; trimethylhexamethylene diisocyanate, hexamethylene diesocyanate, isophorone diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, water Xylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecantri Aliphatic isocyanate compounds such as socyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and / or (2) activity with these isocyanate compounds A polyisocyanate compound or a polyisocyanate oligomer compound obtained by combining a compound having hydrogen with a charge ratio such that an isocyanate group remains in various ways, (3) a polyisocyanate containing one or more sulfur or halogen groups, and The modified body etc. are mentioned. Examples of the modified body include burette, isocyanurate, allophanate, carbodiimide and the like. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of expressing excellent adhesion at a relatively low temperature, various aliphatic isocyanate compounds and / or various preparation ratios of the aliphatic isocyanate compound and the active hydrogen-containing compound can be used so that the isocyanate group remains. The isocyanate group remains such that the polyisocyanate compound or polyisocyanate oligomer compound bonded by the above method, particularly the cycloaliphatic isocyanate compound and / or the cycloaliphatic isocyanate compound and the compound having active hydrogen from the viewpoint of coating properties. A polyisocyanate compound or a polyisocyanate oligomer compound bonded by various methods at a charging ratio is preferable.

  In addition, from the viewpoint that the resulting polyisocyanate compound or polyisocyanate oligomer compound reacts with moisture in the air and cures quickly, the aromatic isocyanate compound and / or the aromatic isocyanate compound and active hydrogen are present. A polyisocyanate compound or a polyisocyanate oligomer compound obtained by binding a compound with various methods at a charging ratio such that an isocyanate group remains can also be suitably used. In this case, a urea bond is generated as a result of the reaction between moisture and isocyanate, but such a urea bond may be included in the polyurethane resin layer in the present invention.

  Examples of the compound having active hydrogen include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, Alkylene glycols such as diethylene glycol; polyalkylene glycols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol; poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly (neopentylene adipate) Poly (alkylene adipates); poly- [epsilon] -caprolactone, polycaprolactone diol, polycaprolactone toly, and the like; poly (1,4- Tandiene) glycol, polybutadiene glycols such as poly (1,2-butanediene) glycol; poly (alkylene carbonates) such as poly (hexamethylene carbonate); polyester polyols; 1,2,4-butanetriol, 1,2 Polyols containing three or more hydroxy groups, such as 1,6-hexanetriol; silicone polyols and the like, and other known active hydrogen-containing compounds can also be used. Among these, when polyalkylene glycols, polyols containing 3 or more hydroxy groups, polyalkylene adipates, polyalkylene carbonates, polycaprolactones and polyester polyols are used, the heating temperature for curing Can be made lower, and thermal deformation and discoloration of the substrate can be more reliably prevented.

  In addition, the above-mentioned compound having active hydrogen may be used alone or in combination of two or more. In particular, when an aromatic isocyanate compound such as tolylene diisocyanate or 4,4-diphenylmethane diisocyanate is used as a moisture curable polyurethane resin and / or its precursor, the resulting polyisocyanate compound or polyisocyanate oligomer has high crystallinity. In some cases, it is preferable to use a compound having two or more kinds of active hydrogens.

  Further, from the viewpoint of high curing speed, the moisture-curable polyurethane resin and / or precursor thereof in the moisture-curable urethane primer used in the present invention preferably has a relatively high molecular weight. As a technique for increasing the molecular weight, when the above-mentioned isocyanate compound and the compound having active hydrogen are combined by various methods at a charging ratio such that the isocyanate group remains, adjustment is made so as to reduce the remaining amount of the isocyanate group. There is a way. Alternatively, there is a method in which a plurality of isocyanate groups present in the molecule of the moisture curable polyurethane resin and / or its precursor are combined with a chain extender or the like. Here, examples of the chain extender include compounds having active hydrogen as described above and diamine compounds such as ethylenediamine. Among these, from the viewpoint of easy control of the chain extension reaction, 1,3- Alkylene glycols such as butanediol, 1,4-butanediol, propylene glycol and 1,6-hexanediol, and polyalkylene glycols such as polypropylene glycol are preferably used.

  The layer made of a cured product of the moisture-curable urethane primer for optical use may be composed of only the cured product, but generally contains a particulate inorganic material often used for the purpose of improving the surface hardness. Also good. Here, the fine inorganic particles preferably have an average particle shape of about 1 to 300 nm, more preferably about 1 to 200 nm.

  Specific examples of the fine inorganic particles include silicon oxide compounds such as silicon dioxide, aluminum compounds such as aluminum trioxide, titanium oxide compounds such as titanium dioxide, zirconium oxide compounds such as zirconium dioxide, tin oxide compounds such as tin dioxide, And antimony oxide compounds such as antimony oxide and antimony pentoxide.

  Moreover, the thickness of the layer made of the cured product of the moisture-curable urethane primer for optical use is not particularly limited, but good optical properties and adhesion with the photochromic coating layer formed on the layer as necessary ( From the viewpoint of adhesiveness, it is preferably 0.1 to 10 μm, particularly 1 to 7 μm. From the viewpoint of optical properties, it is preferable that bubbles are not substantially present in the layer. Here, “the bubble is not substantially present” means a state where the presence of the bubble is not recognized as a result of visual observation. The urethane resin layer having such characteristics (thickness and absence of bubbles) cannot be obtained when, for example, a moisture-curable polyurethane resin primer commercially available for building materials is used as it is, and the present invention described above. This can be obtained for the first time by adopting this manufacturing method.

  The method for producing the laminate of the present invention is not particularly limited, but the above-described production method of the present invention is adopted, that is, an optical moisture-curable urethane primer is applied on at least one surface of the optical material substrate. It is preferable to manufacture by removing the solvent later and curing the moisture curable polyurethane resin and / or its precursor.

  The optical moisture-curable urethane primer used in the production method of the present invention comprises a moisture-curable polyurethane resin and / or a precursor thereof, and a solvent having a boiling point (normal pressure) of 70 ° C. or higher and a solubility parameter of 8 or higher. If it is a solution containing, it will not specifically limit. Here, the moisture curable polyurethane resin and / or its precursor is as described in the description of the laminate of the present invention.

  The solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8 or higher used in the optical moisture curable urethane primer is a dilution solvent such as a moisture curable polyurethane resin, and such a dilution solvent should be used. Thus, it becomes possible to obtain a cured body layer having the excellent characteristics as described above. Specific examples of the diluting solvent preferably used in the present invention include butyl acetate, acetylacetone, methyl isobutyl ketone, ethylene glycol dimethyl ether, propylene glycol monoethyl ether acetate, xylene, methyl ethyl ketone, methyl acetoacetate, toluene, ethyl acetate. Etc. In the production method of the present invention, it is preferable to use at least one solvent selected from these.

  The content of the moisture curable polyurethane resin and / or its precursor in these solvents is preferably 5 to 80% by weight based on the total weight of the moisture curable polyurethane resin and / or its precursor and the dilution solvent, In order to reduce the trace of carbon dioxide gas while ensuring adhesion, the range of 10 to 50% by weight is more preferable.

  Furthermore, the moisture-curing urethane primer for use in the present invention preferably contains a leveling agent because it improves the smoothness of the coating film. As the leveling agent, known ones can be used without any limitation. Examples of suitable leveling agents include silicone-based, fluorine-based, acrylic-based and vinyl-based agents. The leveling agent is used in an amount of 0.05 to 15% by weight, particularly 0.1 to 10% by weight, based on the total weight of the moisture-curable polyurethane resin and / or its precursor (the weight of the resin component). Preferably there is.

  Furthermore, the optical moisture-curing urethane primer used in the present invention can also contain the particulate inorganic material as described above. The content of the fine inorganic particles is not particularly limited, but is 30% by weight or less, particularly 10% by weight or less, based on the total weight (weight of the resin component) of the moisture-curable polyurethane resin and / or its precursor. Is preferred. Moreover, there is no problem even if various curing agents are included for the purpose of enabling curing acceleration, low-temperature curing, and the like during curing. As a curing agent suitably used, various epoxy resin curing agents or various organosilicon resin curing agents are known. Specific examples of these curing agents include various organic acids and acid anhydrides thereof, nitrogen-containing organic compounds such as tertiary amine compounds, various metal complex compounds such as organic tin compounds and organic zinc compounds, or metal alkoxides, Various salts such as organic carboxylates and carbonates of alkali metals can be mentioned. The amount added is 0.1 to 5% by weight, particularly 0.5 to 2% by weight, based on the total weight of the moisture-curable polyurethane resin and / or its precursor (weight of the resin component). Is preferred.

  The method for applying the moisture-curable urethane primer for optics on the surface of the optical substrate is not particularly limited, and examples thereof include dipping, spin coating, and dip spin coating. It is preferable to employ a spin coating method because it is possible to avoid storage in a state where it comes into contact with moisture containing air (a state where the primer begins to cure). That is, if the moisture-curing urethane primer for optics is placed in a container that can be sealed, and the required amount is taken out and applied to the lens surface when necessary, the above-mentioned curing can be avoided. A coating method by coating is most suitable. Furthermore, by reducing the film thickness of the coating film, the generated carbon dioxide gas is quickly released out of the system, thereby reducing the traces of the carbon dioxide gas that is optically problematic on the coating film. Is possible. The film thickness at this time is preferably in the range of 0.1 to 10 μm, but the range of 1 to 7 μm is particularly preferable in consideration of adhesion and optical characteristics. When the thickness is 10 μm or more, carbon dioxide gas traces remain significantly, which is not preferable. On the other hand, when the thickness is 0.1 μm or less, the uniformity of the film is lowered, so that the adhesion is remarkably lowered.

  In addition, when applying the moisture curable urethane primer for optics to an optical substrate such as a plastic lens substrate, it is preferable to perform a pretreatment of the substrate for the purpose of improving adhesion before the application. As pretreatment, degreasing treatment with an organic solvent, chemical treatment with a basic aqueous solution or an acidic aqueous solution, polishing treatment with an abrasive, plasma treatment using atmospheric pressure plasma or low pressure plasma, corona discharge treatment, flame treatment or UV ozone treatment can be mentioned, but from the viewpoint of adhesion between the plastic lens and the primer layer, a degreasing treatment with an organic solvent, an alkali treatment, a plasma treatment, a corona discharge treatment, or a combination thereof is performed. Is preferred.

  In the production method of the present invention, after applying the moisture-curing urethane primer for optics as described above, the primer layer may be cured after removing the dilution solvent. The optical moisture-curing urethane primer applied with the above-described thickness is considered to be in a state where it can be quickly cured by contact with moisture in the atmosphere (ie, before decarboxylation). Therefore, it can be cured by heating immediately after completion of coating to remove the solvent and to perform decarboxylation and urea bond formation. The heating temperature at this time is not particularly limited, but from the viewpoint of preventing deformation and discoloration of the base material due to heating, it is preferable that the humidity is in the range of 10% to 70%, room temperature to 130 ° C, particularly 80 to 120 ° C. It is. In the method of the present invention, the moisture-curable polyurethane resin and / or its precursor is used, so that it can be sufficiently cured even at such a relatively low temperature. The curing time is not particularly limited, but is usually in the range of 10 minutes to 3 hours.

  The laminate of the present invention thus produced can itself be used as an optical article such as a lens. However, by further laminating a photochromic coat layer on the primer layer, a photochromic lens or the like can be used. It can also be set as an optical optical article.

  As a method for laminating the photochromic coating layer, any known technique described in the section of the prior art can be applied, but from the viewpoint of photochromic characteristics, optical characteristics, solvent resistance of the photochromic layer, scratch resistance, and adhesion, As proposed by the present inventors in the pamphlet of International Publication No. 03/011967 or Japanese Patent Application No. 2002-372835, “a radical containing a radically polymerizable monomer having a silanol group or a group that generates a silanol group by hydrolysis” A photochromic coating agent comprising a curable composition containing a specific amount of a polymerizable monomer, an amine compound and a photochromic compound, or a coating agent comprising a radical polymerizable monomer further containing a maleimide group (adhesiveness) Photochromic coating agent) The method of curing is preferably used.

  The radical polymerizable monomer having a silanol group used in the adhesive photochromic coating agent or a group that generates a silanol group by hydrolysis includes γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltriethoxysilane. , Γ-methacryloyloxypropylmethyldimethoxysilane, (3-acryloyloxypropyl) dimethylmethoxysilane, (3-acryloyloxypropyl) methyldimethoxysilane, (3-acryloyloxypropyl) trimethoxysilane, (methacryloyloxymethyl) dimethylethoxy Silane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxypropyldimethylethoxysilane Down, it can be mentioned methacryloyloxy dimethyl methoxy silane. The amount of the monomer used is not particularly limited, but it is preferably 0.5 to 20% by weight, particularly 1 to 10% by weight based on the total weight of the coating agent.

  Examples of the radical polymerizable monomer containing a maleimide group include 4,4′-diphenylmethane bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2,2-bis [4- (4 -Maleimidophenoxy) phenyl] propane, m-maleimidobenzoyl-N-hydroxysuccinimide ester, succinimidyl-4- (N-maleimidomethyl) cyclohexane-1-carboxylate and the like can be used. The amount of the radically polymerizable monomer used is not particularly limited, but is preferably 0.05 to 15% by weight, particularly 0.1 to 10% by weight based on the total weight of the coating agent.

  In addition, radical polymerizable monomers having a silanol group or a group capable of generating a silanol group by hydrolysis and other radical polymerizable monomers including a maleimide group used as necessary may be used together with other radical polymerizable monomers. As monomers, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, trimethylolpropane triethylene glycol triacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, Urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hex Acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, glycidyl methacrylate, average molecular weight 776 2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane, methyl ether polyethylene glycol methacrylate having an average molecular weight of 475, and the like. The amount of these other radically polymerizable monomers to be used is not particularly limited, but is preferably 20 to 90% by weight, particularly 40 to 80% by weight based on the total weight of the coating agent.

  As the amine compound, triethanolamine, N-methyldiethanolamine, triisopropanolamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate and the like can be used. The amount of the amine compound used is not particularly limited, but is preferably 0.01 to 15% by weight, particularly 0.1 to 10% by weight based on the total weight of the coating agent.

  In addition, when forming a photochromic coating layer on the primer layer which consists of a hardening body of moisture curable polyurethane resin and / or its precursor, an amine compound is not necessarily an essential component. Even a coating agent obtained by removing an amine compound from the adhesive photochromic coating agent can provide sufficient adhesion that can withstand practical use. Although the addition of the amine compound surely improves the adhesion, the usable time for the adhesive photochromic coating solution to give sufficient adhesion is limited, and it may be difficult to use in terms of use.

  However, in the case of using a layer comprising the cured product of the moisture curable polyurethane resin of the present invention and / or its precursor, it is not always necessary to add an amine compound. And economically beneficial.

  Moreover, as a photochromic compound, well-known photochromic compounds, such as a naphthopyran derivative, a chromene derivative, a spirooxazine derivative, a spiropyran derivative, a fulgimide derivative, can be used. The amount of the photochromic compound used is not particularly limited, but is preferably 0.1 to 30% by weight, particularly 1 to 10% by weight based on the total weight of the coating agent.

  When applying a photochromic coating agent such as an adhesive photochromic coating agent on the primer layer of the laminate of the present invention, the coating agent is applied after the pretreatment as described above, if necessary, and cured. You can do it. The application method in this case is not particularly limited, and any known coating method can be applied without any limitation. Specifically, the method of apply | coating this composition by methods, such as spin coating, spray coating, dip coating, dip-spin coating, is illustrated. The thickness of the coating agent layer applied by such a method (corresponding to the thickness of the coating layer after curing) is not particularly limited, but particularly when a photochromic compound is added, even if the photochromic compound concentration is low. Since a sufficient color density can be obtained and the durability of the photochromic property is also good, the thickness is preferably relatively thick. However, on the other hand, the thicker the coating layer, the more the initial yellow color increases. Therefore, it is preferable that the coating layer thickness after curing is 10 to 100 μm, particularly 20 to 50 μm. In order to obtain such a thick coating thickness, the viscosity of the composition at 25 ° C. is preferably 20 to 1000 cP, particularly 50 to 800 cP, and more preferably 70 to 500 cP. Incidentally, since a coating composition such as a hard coat coating agent generally used for plastic lenses contains a solvent in order to obtain a uniform coating film, the viscosity at 25 ° C. is usually 5 cP or less. In addition, the thickness of the coating layer obtained thereby is several μm or less, and the thickness of 10 to 100 μm is very thick as compared with such a thickness.

  As the curing method, a photocuring method or a heat curing method is appropriately employed depending on the type of radical polymerization initiator used. From the viewpoint of physical properties and appearance of the resulting coating film, it is preferable to employ a method in which the photopolymerization initiator is used to cure by light irradiation and then heated to complete the polymerization. At this time, a thermal polymerization initiator may be used in combination. At this time, as a light source used for photocuring, an electrode lamp such as a metal halide lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a sterilization lamp, a xenon lamp, a carbon arc, a tungsten lamp, or an electrodeless A lamp or the like can be used. Further, an electron beam may be used as a light source, and in this case, the coating layer can be cured without adding a photopolymerization initiator. Examples of the thermosetting method include a method in which heat is applied in a polymerization furnace to perform thermal polymerization, or a method in which infrared rays are irradiated in a polymerization furnace for polymerization and hardening.

  The lens material on which the photochromocoat layer formed of the cured product of the composition thus prepared can be used as it is, but more preferably, the surface of the photochromocoat layer is further coated with a hard coat material. It is preferable to coat. By coating with a hard coat layer, the scratch resistance of the optical material can be improved. As the hard coat layer, any known hard coat layer can be used without any limitation, and a hard coat coating agent composed mainly of a silane coupling agent or an oxide sol such as silicon, zirconium, antimony, and aluminum is applied and cured. And those obtained by applying a hard coat coating agent containing an organic polymer as a main component and then curing it. By employing a silyl monomer in the composition, sufficient adhesion can be obtained more firmly and simply.

Further, if necessary, an antireflection treatment, an antistatic treatment, etc. by depositing a thin film made of a metal oxide such as SiO ₂ , TiO ₂ , ZrO _2, or applying a thin film of an organic polymer on the hard coat layer Of course, it is possible to perform the processing and secondary processing.

  By the way, although the photochromic coating agent disclosed in the pamphlet of International Publication No. 03/011967 as described above is excellent, it is urethane-based in order to improve the adhesion durability depending on the material of the applied base material. When a primer is used, the wettability when applying the photochromic coating agent is not sufficient, and there is a possibility that appearance defects may occur due to the roughness generated at the interface between the photochromic coating layer and the substrate or the primer layer. It has been found.

  When such inconvenience arises, this problem can be solved by using the photochromic curable composition of the present invention described below.

  That is, the photochromic curable composition of the present invention comprises 0.001 to 5 parts by weight of a silicon-based (silicone-based) or fluorine-based surfactant and a photochromic compound 0 with respect to 100 parts by weight of the radical polymerizable monomer component. 0.01 to 20 parts by weight.

  The radical polymerizable monomer used in the present invention is not particularly limited. However, when used as a photochromic coating agent, the above-mentioned International Publication No. 03/011967 is used because the resulting photochromic coating layer has good photochromic properties. As in the case of the radically polymerizable monomer used in the photochromic coating agent disclosed in 1), a polymerizable monomer having an L-scale Rockwell hardness of 60 or more when obtained by polymerization alone ( Hereinafter, a high-hardness monomer component and a polymerizable monomer having a L-scale Rockwell hardness of 40 or less (hereinafter also referred to as a low-hardness monomer). It also preferably includes a mixture of components. Furthermore, it is also possible to use a monomer that is neither a high-hardness monomer nor a low-hardness monomer, that is, a monomer that exhibits an L scale Rockwell hardness of more than 40 and less than 60 (hereinafter also referred to as a medium hardness monomer). is there.

  In addition, L scale Rockwell hardness means the hardness measured according to JIS-B7726, and it is easily determined whether or not the above-mentioned hardness condition is satisfied by performing the measurement on the homopolymer of each monomer. Can do. Specifically, as shown in the Examples described later, a monomer is polymerized to obtain a cured body having a thickness of 2 mm, and this is retained in a room at 25 ° C. for 1 day, and then used with a Rockwell hardness meter to measure the L scale. It can be easily confirmed by measuring the Rockwell hardness. However, in the polymer used for the measurement of the L scale Rockwell hardness, 90% or more of the polymerizable group of the charged monomer needs to be polymerized. If 90% or more of the polymerizable groups are polymerized, the L scale Rockwell hardness of the cured product is usually measured as a substantially constant value.

  The high-hardness monomer has the effect of improving the solvent resistance, hardness, heat resistance and the like of the cured product after curing. In order to make these effects more effective, a radical polymerizable monomer having a homopolymer L-scale Rockwell hardness of 65 to 130 is preferable. The low-hardness monomer has the effect of making the cured body tough and improving the fading speed of the photochromic compound.

  The contents of the high-hardness monomer, low-hardness monomer and medium-hardness monomer in the radical polymerizable monomer component in the composition of the present invention are not particularly limited, but the cured product such as solvent resistance, hardness, and heat resistance of the cured product. In order to improve the balance of the characteristics, or photochromic properties such as color density and fading speed, the low-hardness monomer is 5 to 70% by weight and the high-hardness monomer is 5 to 95% by weight in all radical polymerizable monomers %, And the balance is preferably a medium hardness monomer. Further, as the high hardness monomer to be blended, it is particularly preferable that a monomer having three or more radical polymerizable groups is blended in the radical polymerizable monomer by at least 5% by weight.

  Further, the radical polymerizable monomer component in the composition of the present invention is a radical polymerizable monomer component because the adhesion to the substrate of the photochromic coating layer obtained when used as a photochromic coating agent is improved. Contains a silyl monomer and / or an isocyanate monomer as a high-hardness monomer, low-hardness monomer or medium-hardness monomer in an amount of 0.5 to 20 parts by weight, particularly 1 to 10 parts by weight, based on 100 parts by weight of all radical polymer components It is preferable to do this.

  Furthermore, the radically polymerizable monomer component in the composition of the present invention further improves the adhesion of the photochromic coating layer obtained when used as a photochromic coating agent to the substrate, and improves the durability of the photochromic compound contained in the layer. From the reason that it can be improved, a radical polymerizable monomer having at least one epoxy group and at least one radical polymerizable group in the molecule (hereinafter, also simply referred to as an epoxy monomer) is converted into a high-hardness monomer, The low-hardness monomer or medium-hardness monomer is preferably contained in an amount of 0.01 to 30% by weight, particularly 0.1 to 20% by weight, based on the weight of all radical polymerizable monomer components.

  The high-hardness monomer, low-hardness monomer, medium-hardness monomer, silyl monomer, isocyanate monomer, and epoxy monomer are recommended for use in the photochromic coating agent disclosed in the International Publication No. 03/011967. It is. As the high hardness monomer, low hardness monomer, medium hardness monomer, silyl monomer, isocyanate monomer and epoxy monomer, the high hardness monomer, low hardness monomer, medium hardness monomer which can be suitably used in the above-mentioned International Publication No. 03/011967 The same silyl monomer, isocyanate monomer and epoxy monomer can be preferably used.

  Specific examples of high-hardness monomers that can be suitably used in the present invention include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane. Tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Methacrylate, di Intererythritol hexaacrylate, urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, etc .; 4 having a molecular weight of 2,500-3,500 Functional polyester oligomer (Daicel UCB, EB80, etc.), tetrafunctional polyester oligomer with molecular weight of 6,000 to 8,000 (Daicel UCB, EB450, etc.), hexafunctional polyester oligomer with molecular weight of 45,000-55,000 ( Daicel UCB, EB1830, etc.), tetrafunctional polyester oligomer with a molecular weight of 10,000 (Daiichi Kogyo) Yakusha, GX8488B, etc.); bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, etc .; Ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,9-nonylene glycol dimethacrylate, neopentylene glycol dimethacrylate, neopentylene glycol diacrylate, etc .; diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, etc .; Examples include Sphenol A diglycidyl methacrylate, ethylene glycol bisglycidyl methacrylate, and glycidyl methacrylate.

  Specific examples of low-hardness monomers that can be suitably used in the present invention include alkylene glycol di (meth) acrylates such as trialkylene glycol diacrylate, tetraalkylene glycol diacrylate, nonyl alkylene glycol diacrylate, and nonyl alkylene glycol dimethacrylate. 2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 776, etc .; polyethylene glycol methacrylate having an average molecular weight of 526, polyethylene glycol methacrylate having an average molecular weight of 360, methyl ether polyethylene glycol meta having an average molecular weight of 475 Acrylate, methyl ether polyethylene glycol methacrylate with an average molecular weight of 1,000, polypropylene with an average molecular weight of 375 Glycol methacrylate, average molecular weight 430 polypropylene methacrylate, average molecular weight 622 polypropylene methacrylate, average molecular weight 620 methyl ether polypropylene glycol methacrylate, average molecular weight 566 polytetramethylene glycol methacrylate, average molecular weight 2,034 octyl Polyalkylene glycol (meth) acrylates such as phenyl ether polyethylene glycol methacrylate, nonyl ether polyethylene glycol methacrylate having an average molecular weight of 610, methyl ether polyethylene thioglycol methacrylate having an average molecular weight of 640, and perfluoroheptylethylene glycol methacrylate having an average molecular weight of 498; , Lauryl metaacryl DOO, ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate. Among these low hardness monomers, methyl ether polyethylene glycol methacrylate with an average molecular weight of 475, methyl ether polyethylene glycol methacrylate with an average molecular weight of 1,000, trialkylene glycol diacrylate, tetraalkylene glycol diacrylate, nonyl alkylene glycol diacrylate, methyl Particularly preferred are acrylate, ethyl acrylate, butyl acrylate, and lauryl acrylate.

  Specific examples of the medium hardness monomer that can be suitably used in the present invention include polytetramethylene glycol dimethacrylate having an average molecular weight of 650, polytetramethylene glycol dimethacrylate having an average molecular weight of 1,400, and bis (2-methacryloyloxy). Bifunctional (meth) acrylates such as ethylthioethyl sulfide; diallyl phthalate, diallyl isophthalate, diallyl tartrate, diallyl succinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, allyl diglycol carbonate Compounds; polyvalent thioacrylic acids such as 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene, and many Thiomethacrylic acid ester compounds; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; acrylics such as methyl methacrylate, butyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, biphenyl methacrylate Acid and methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene and methylstyrene , Vinyl naphthalene, α-methylstyrene dimer, bromostyrene, divinylbenzene, vinyl compounds such as vinylpyrrolidone; Radical polymerizable monofunctional monomers such as (meth) acrylates having 6 to 25 carbon atoms in the hydrocarbon chain having an unsaturated bond in the molecule such as tacrylate, nerol methacrylate, geraniol methacrylate, linalool methacrylate, farnesol methacrylate, etc. Is mentioned.

  Specific examples of silyl monomers that can be suitably used in the present invention include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and (3-acryloyloxypropyl). ) Dimethylmethoxysilane, (3-acryloyloxypropyl) methyldimethoxysilane, (3-acryloyloxypropyl) trimethoxysilane, (methacryloyloxymethyl) dimethylethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, Examples include methacryloyloxypropyldimethylethoxysilane, methacryloyloxypropyldimethylmethoxysilane, and the like.

  Specific examples of the isocyanate monomer that can be suitably used in the present invention include 2-isocyanatoethoxymethacrylate, 4- (2-isocyanatoisopropyl) styrene, and the like.

  Specific examples of epoxy monomers that can be suitably used in the present invention include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl- 2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, average molecular weight And 540 glycidyloxypolyethylene glycol methacrylate. Among these, glycidyl acrylate, glycidyl methacrylate, and glycidyl oxypolyethylene glycol methacrylate having an average molecular weight of 540 are particularly preferable.

  The composition of the present invention contains 0.001 to 5 parts by weight of a silicon-based or fluorine-based surfactant with respect to 100 parts by weight of the radical polymerizable monomer component as described above. Addition of a specific amount of silicon-based or fluorine-based surfactant adversely affects the photochromic properties and substrate adhesion of the cured coating film (photochromic coating layer) when the composition of the present invention is used as a photochromic coating agent. It is possible to improve the wettability with respect to the base material without giving the appearance and to prevent appearance defects. Even when the same surfactant is used as a surfactant other than silicon or fluorine (such as glycerin fatty acid ester or polyoxyethylene alkyl ether), the effect of slightly improving the wettability can be seen, Appearance defects cannot be resolved. In addition, in order to obtain sufficient wettability using such a surfactant, it is necessary to increase the amount of addition, and the substrate adhesion and photochromic performance of the cured film are deteriorated. From the viewpoint of the effect, the content of the silicon-based or fluorine-based surfactant is 0.01 to 2 parts by weight, particularly 0.02 to 1 part by weight based on 100 parts by weight of the radical polymerizable monomer component. Is preferred.

  As the silicon-based surfactant used in the present invention, a known surfactant having a silicone chain (polyalkylsiloxane unit) as a hydrophobic group can be used without any limitation. From the viewpoint of availability, the following formula It is preferable to use what is shown by these.

(In the formula, R is an alkyl group, a, b and x are each independently an integer of 0 to 20, and y is an integer of 1 to 20.)
The fluorine-based surfactant is not particularly limited as long as it is a surfactant having a fluorocarbon chain, and is a perfluoroalkyl group-containing ester oligomer, a perfluoroalkyl group-containing alkylene oxide adduct, or a fluorine-based surfactant. Aliphatic polymer esters can be used.

  Specific examples of silicone surfactants and fluorosurfactants that can be suitably used in the present invention include “L-7001”, “L-7002”, “L-7604”, “FZ-” manufactured by Nippon Unicar Co., Ltd. 2123 ”, Dainippon Ink & Chemicals, Inc.“ Megafac F-470 ”,“ Megafac F-1405 ”,“ Megafac F-479 ”, Sumitomo 3M“ Florad FC-430 ”, etc. Can be mentioned.

  As the photochromic compound used in the curable composition of the present invention, a known photochromic compound can be used without any limitation. For example, photochromic compounds such as fulgimide compounds, spirooxazine compounds, and chromene compounds are well known, and in the present invention, these photochromic compounds can be used without limitation, for example, in the above-mentioned International Publication No. 03/011967. The same photochromic compound that can be suitably used in the disclosed photochromic coating agent can be preferably used.

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

  The photochromic compound is preferably used by appropriately mixing different types of compounds in order to obtain a preferable color tone.

  In the curable composition of the present invention, the amount of the photochromic compound is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 100 parts by weight of the total radical polymerizable monomer. It is the range of 0.1-10 weight part. When the blending amount of the photochromic compound is 0.01 parts by weight or less, the color density may be low. On the other hand, when it is 20 parts by weight or more, it is not sufficiently dissolved in the polymerizable monomer, resulting in nonuniformity and uneven color density. There is.

  In the curable composition of the present invention, in order to improve the adhesion of the photochromic coating layer obtained when used as a photochromic coating agent to the substrate, in place of the silyl monomer and / or isocyanate monomer described above or A compound other than the silyl monomer in combination with these mono-compounds, which has a silanol group or a group that generates a silanol group by hydrolysis, can be further contained. Such compounds include γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl And methyldiethoxysilane. Although the usage-amount of this silane coupling agent is not specifically limited, It is suitable that it is 0.5-20 weight part with respect to 100 weight part of all the radically polymerizable monomers, Especially 1-10 weight part.

  The curable composition of the present invention further includes an antioxidant, a radical scavenger, a UV stabilizer, for improving the durability of the photochromic compound, improving the color development rate, improving the fading rate and improving the moldability. Additives such as ultraviolet absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers may be added. It is also very preferable to add a polymerization initiator described later in order to cure the curable composition. As these additives to be added, known compounds are used without any limitation.

  Such antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, and benzotriazole compounds. Benzophenone compounds and the like can be preferably used. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. The addition amount of these antioxidants, radical scavengers, UV stabilizers and UV absorbers is preferably in the range of 0.001 to 20 parts by weight with respect to 100 parts by weight of the total polymerizable monomer.

  The method for obtaining the photochromic cured product by curing the curable composition of the present invention is not particularly limited, and a known polymerization method according to the type of the radical polymerizable monomer to be used can be employed. The polymerization initiating means can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, or irradiating with ultraviolet rays, α rays, β rays, γ rays or the like or using both in combination.

  The radical polymerization initiator is not particularly limited and known ones can be used. Typical examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide. Diacyl peroxides such as oxides; Peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxy Percarbonates such as dicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-dimethylvaleronitrile) ) 2,2'-azobis (2-methylbutyronitrile), azo compounds such as 1,1'-azobis (cyclohexane-1-carbonitrile) and the like. The amount of these radical polymerization initiators used varies depending on the polymerization conditions, the type of initiator, the type and composition of the radical polymerizable monomer, and cannot be limited in general. It is suitable to use in the range of 0.01 to 10 parts by weight with respect to parts.

  The above radical polymerization initiators may be used alone or in combination.

  In the case of polymerization by irradiation with light such as ultraviolet rays, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl are used as photopolymerization initiators. -1-phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxane, Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiph Cycloalkenyl - phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - be used butanone -1 or the like. These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of all radical polymerizable monomer components.

  A particularly preferable polymerization method is a method in which the curable composition of the present invention containing the photopolymerization initiator is irradiated with ultraviolet rays and cured, and then further heated to complete the polymerization.

  The curable composition of the present invention can be cured by using the above polymerization initiator and the like, and can be used alone as a photochromic material, but as a coating agent for coating optical materials such as spectacle lenses. It is particularly preferred to use it. In particular, the curable composition of the present invention has excellent wettability and can form a photochromic layer having high adhesion to the urethane primer layer formed on the optical substrate as described above.

  The optical material is not particularly limited, and examples thereof include known optical materials such as spectacle lenses, houses and automobile window glass.

  As spectacle lenses, (meth) acrylic resin-based, polycarbonate-based resins, allyl-based resins, thiourethane-based resins, urethane-based resins and thioepoxy-based resin-based spectacle lenses, glass-based spectacle lenses are known, When the curable composition of the present invention is used as a coating material for spectacle lenses, it can be used for any spectacle lens without any particular limitation. However, it is more preferable to use it as a coating material for plastic spectacle lenses. Preferably, it is more preferably used as a coating material for spectacle lenses such as (meth) acrylic resin, polycarbonate resin, allyl resin, thiourethane resin, urethane resin, and thioepoxy resin.

  When used as a coating material for optical materials such as eyeglass lenses, the curable composition of the present invention is applied to the optical material by spin coating, dipping, etc., and then cured by irradiation with light, or heat cured. A method is preferred, and more preferred is a method of completing the polymerization by further heating after curing by light irradiation.

  The thickness of such a coating layer is not particularly limited, but a sufficient color density can be obtained even when the photochromic compound concentration is low, and the durability of the photochromic property is also good. Therefore, the thickness is preferably relatively thick. . However, on the other hand, the thicker the coating layer, the higher the initial yellowness, so the thickness of the coating layer is preferably 10 to 100 μm, more preferably 20 to 50 μm.

  Moreover, you may form the laminated body which has a primer layer between the coating film of the curable composition of this invention, and the above base materials. At this time, it is very preferable from the viewpoint of adhesion that the primer layer is a layer made of a cured product of the moisture curable polyurethane resin and / or its precursor according to the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example are hung up and this invention is demonstrated, this invention is not limited to these Examples.

Example 1
CR39 (allyl resin plastic lens; refractive index = 1.50) was used as a lens substrate. This lens substrate is thoroughly degreased with acetone, and a moisture-curing primer “Takenate M-605N” manufactured by Mitsui Takeda Chemical Co., Ltd. and butyl acetate are mixed at a weight ratio of 1: 1 as a primer. Stir well until uniform. The isocyanate group content of this primer determined by the amine equivalent method was 2.4 mol%. This was spin-coated using a spin coater 1H-DX2 manufactured by MIKASA. This was cured at 110 ° C. for 1 hour using a thermostat to prepare a lens substrate having a primer layer. In order to prepare a photochromic cured film, the surface was treated using a corona treatment device multidyne manufactured by Navitas as a pretreatment of the lens substrate. The photochromic polymerizable composition includes a radical polymerizable monomer 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer. Hexaacrylate (Daicel UCB, EB-1830) / glycidyl methacrylate was blended at a blending ratio of 50 parts by weight / 15 parts by weight / 15 parts by weight / 10 parts by weight / 10 parts by weight, respectively. The following formula is used for 100 parts by weight of the radical polymerizable monomer mixture.

2.35 parts by weight of a photochromic compound having the structure

0.6 part by weight of a photochromic compound having a structure represented by

After adding 0.4 parts by weight of a photochromic compound having a structure represented by the following formula and thoroughly mixing, CGI1800 {1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4, which are polymerization initiators 4-trimethyl-pentylphosphine oxide mixture (weight ratio 3: 1)} and 0.5 parts of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer. 7 parts by weight of γ-methacryloyloxypropyltrimethoxysilane which is a silane coupling agent and 3 parts by weight of N-methyldiethanolamine were added and mixed thoroughly.

Subsequently, about 2 g of the mixed solution obtained by the above method was spin-coated on the surface of the lens substrate using a spin coater 1H-DX2 manufactured by MIKASA. The surface-coated lens is irradiated with a metal halide lamp with an output of 120 mW / cm ^{2 in} a nitrogen gas atmosphere for 3 minutes to cure the coating film, and then heat-treated with a 120 ° C. incubator. A photochromic cured thin film was obtained. The film thickness of the obtained thin film can be adjusted by the conditions of spin coating. In the present invention, the film thickness of the photochromic cured thin film was adjusted to 40 ± 1 μm. Evaluation of the appearance of the lens substrate having the photochromic cured film thus prepared was performed by irradiating the lens substrate having the cured film with a projector and observing and evaluating the projection surface. The evaluation criteria are shown below.

A: Flat and unevenness is not seen at all B: Very slight unevenness is seen C: Unevenness is partially visible D: Unevenness is seen uniformly or the substrate is affected The evaluation of the appearance of the lens substrate was A.

  Subsequently, the adhesion was evaluated. As an evaluation method, a lens substrate having a photochromic cured film was immersed in boiling water at 100 ° C. for 1 hour, then cooled to room temperature, and a cross-hatch test was performed within 30 minutes. The evaluation criteria are shown below.

A: No peeling B: Peeling less than 5% C: Peeling of 5% or more and less than 15% D: Peeling of 15% or more The adhesion of the lens substrate prepared by the above-described method was A.

Example 2
A photochromic cured film was prepared in the same manner as in Example 1 except that a moisture curing type primer “Takenate M-402P” manufactured by Takeda Chemical Co., Ltd. was used as a primer, and the appearance and adhesion were evaluated. The isocyanate group content of this primer was 2.6 mol%. The results are summarized in Table 1.

Example 3
Moisture-curing primer “Takenate M-631N” manufactured by Mitsui Takeda Chemical Co., Ltd. is used as a primer component, and this is mixed with butyl acetate at a weight ratio of 1: 2, and stirred thoroughly until uniform in a nitrogen atmosphere. Then, 1 part by weight of a silicone leveling agent “L-7001” manufactured by Nippon Unicar Co., Ltd. was added as a leveling agent, and the mixture was sufficiently stirred until uniform in a nitrogen atmosphere. Otherwise, a photochromic cured film was prepared in the same manner as in Example 1, and the appearance and adhesion were evaluated. The isocyanate group content of this primer was 4.2 mol%. The results are summarized in Table 1.

Example 4
Use the moisture curing type primer “Takeseal No.400 Primer” manufactured by Takebayashi Chemical Co., Ltd. as a primer component, and mix it with xylene at a weight ratio of 1: 3, enough until uniform in a nitrogen atmosphere A photochromic cured film was prepared in the same manner as in Example 1 except that it was used after stirring, and the appearance and adhesion were evaluated. The isocyanate group content of this primer was 3.6 mol%. The results are summarized in Table 1.

Example 5
Using moisture curing type primer “Primer PFR” manufactured by Takebayashi Chemical Co., Ltd. as a primer component, this is mixed with butyl acetate at a weight ratio of 2: 1, and stirred thoroughly until uniform in a nitrogen atmosphere. What was done was used. Further, 1 part by weight of a leveling agent “Furorad FC-470” manufactured by Sumitomo 3M Co., Ltd. was added as a leveling agent, and the mixture was sufficiently stirred until it became uniform in a nitrogen atmosphere. Otherwise, a photochromic cured film was prepared in the same manner as in Example 1, and the appearance and adhesion were evaluated. The isocyanate group content of this primer was 2.4 mol%. The results are summarized in Table 1.

Example 6
A photochromic cured film was prepared in the same manner as in Example 1 except that the moisture curing type primer “Urethane Primer 06” manufactured by Alps Chemical Co., Ltd. was used as a primer component, and the appearance and adhesion were evaluated. The isocyanate group content of this primer was 0.8 mol%. The results are summarized in Table 1.

Example 7
Taken Mitsui Takeda as a primer component, using a lens lens base material coated with Nippon Seika Co., Ltd. thermosetting hard coating agent “NSC1274” with a film thickness of 2 μm and cured at 110 ° C. for 1 hour. A photochromic cured film was prepared in the same manner as in Example 1 except that the moisture curing primer “Takenate M-402P” manufactured by Chemical Co. was used, and the appearance and adhesion were evaluated. The results are summarized in Table 1.

Example 8
As a lens substrate, a photocurable hard coating agent “UVHC1105” manufactured by GE Toshiba Silicone Co., Ltd. is applied to the surface of a polycarbonate lens substrate with a film thickness of 2 μm, and then cured by irradiation with a 120 W metal halide lamp in a nitrogen atmosphere for 2 minutes. A photochromic cured film was prepared in the same manner as in Example 1 except that a moisture curing type primer “Urethane Primer 06” manufactured by Alps Chemical Industries, Ltd. was used as a primer component, and the appearance and adhesion were evaluated. Went. The results are summarized in Table 1.

Example 9
In Example 1, it carried out similarly to Example 1 except having remove | excluded N-methyldiethanolamine from the photochromic polymerizable composition, and having made the hardening time of the primer into 120 degreeC 2 hours. The results are summarized in Table 1.

Example 10
In Example 9, Example 9 except that 1.5 parts by weight of 4,4′-diphenylmethane bismaleimide was added as a maleimide compound to the photochromic polymerizable composition and the primer curing time was 110 ° C. for 2 hours. As well as. The results are summarized in Table 1.

Example 11
550 g of polycaprolactan triol (product name: Plaxel 305 (manufactured by Daicel Chemical)) was reacted with 524 g of hydrogenated 4,4-diphenylmethane diisocyanate to obtain a polyisocyanate compound. This polyisocyanate compound was used as a primer component of a moisture curable urethane resin, and the same procedure as in Example 1 was performed except that 0.3 part by weight of a leveling agent “FZ2123” manufactured by Nihon Unicar Co., Ltd. was added as a leveling agent. It was. The isocyanate group content of this primer was 1.6 mol%. The results are summarized in Table 1.

Example 12
134 g of 1,2,6-hexanetriol was reacted with 524 g of hydrogenated 4,4-diphenylmethane diisocyanate to obtain a polyisocyanate compound. This polyisocyanate compound was used as a primer component of a moisture curable urethane resin, and the same procedure as in Example 1 was performed except that 0.3 part by weight of a leveling agent “FZ2123” manufactured by Nihon Unicar Co., Ltd. was added as a leveling agent. It was. The isocyanate group content of this primer was 2.0 mol%. The results are summarized in Table 1.

Example 13
In Example 1, except that N-methyldiethanolamine was removed from the photochromic polymerizable composition and 0.1 part by weight of a leveling agent “L-7001” manufactured by Nihon Unicar Co., Ltd. was used as the photochromic polymerizable composition. , Using moisture-curing primer “Takenate M-402P” manufactured by Mitsui Takeda Chemical Co., Ltd. as a primer component, and blending it with ethyl acetate to a weight ratio of 1: 1, and Dainippon Ink and Chemicals as a leveling agent A leveling agent “Megafac F-479” manufactured by Co., Ltd. was added in an amount of 0.5 parts by weight and stirred under a nitrogen atmosphere until uniform. This primer was cured in the same manner as in Example 1 except that the curing time of the primer was 10 minutes in an environment of 25 ° C. and humidity of 40%, and the pretreatment of the lens substrate was omitted. The isocyanate group content of this primer was 2.4 mol%. The results are summarized in Table 1.

Example 14
A moisture curing primer “Bernock DM652” manufactured by Dainippon Ink and Chemicals, Inc. was used as a primer component, and this was mixed with ethyl acetate at a weight ratio of 3: 1. Furthermore, Nihon Unicar Co., Ltd. was used as a leveling agent. The same procedure as in Example 13 was performed, except that 0.5 part by weight of the leveling agent “L-7001” was added and the mixture was sufficiently stirred until uniform in a nitrogen atmosphere. The isocyanate group content of this primer was 3.6 mol%. The results are summarized in Table 1.

Example 15
134 g of 1,2,6-hexanetriol was reacted with 287 g of an 80:20 mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI80) to obtain a polyisocyanate compound. This was mixed with ethyl acetate so that the weight ratio would be 1: 2, and 0.5 parts by weight of leveling agent “L7001” manufactured by Nihon Unicar Co., Ltd. was added as a leveling agent until it became uniform in a nitrogen atmosphere. The same procedure as in Example 13 was performed, except that the polyisocyanate compound obtained by stirring was used as a primer component of a moisture-curable urethane resin. The isocyanate group content of this primer was 1.5 mol%. The results are summarized in Table 1.

Example 16
281 g of polytetramethylene ether diol having an average molecular weight of 1000, 67 g of 1,2,6-hexanetriol, 195 g of a 80:20 mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI80) are reacted, A polyisocyanate compound was obtained. This was mixed with ethyl acetate so that the weight ratio would be 1: 2, and 0.5 parts by weight of leveling agent “L7001” manufactured by Nihon Unicar Co., Ltd. was added as a leveling agent until it became uniform in a nitrogen atmosphere. The same procedure as in Example 13 was performed, except that what was obtained by stirring was used as a primer component of a moisture-curable urethane resin. The isocyanate group content of this primer was 2.4 mol%. The results are summarized in Table 1.

Example 17
60 g of butyl acetate and 0.5 g of 1,4-butanediol were added to 40 g of the polyisocyanate compound of Example 16, and this was reacted at 80 ° C. for 5 hours. As a leveling agent, 0.5 parts by weight of a leveling agent “L7001” manufactured by Nihon Unicar Co., Ltd. was added and thoroughly stirred until uniform in a nitrogen atmosphere as a primer component of a moisture curable urethane resin. The same operation as in Example 13 was carried out except that it was used. The isocyanate group content of this primer was 0.9 mol%. The results are summarized in Table 1.

Example 18
To 40 g of the polyisocyanate compound of Example 16, 30 g of toluene and 0.5 g of propylene glycol were added and reacted at 80 ° C. for 5 hours. As a leveling agent, 0.5 parts by weight of a leveling agent “L7001” manufactured by Nihon Unicar Co., Ltd. was added and thoroughly stirred until uniform in a nitrogen atmosphere as a primer component of a moisture curable urethane resin. The same operation as in Example 13 was carried out except that it was used. The isocyanate group content of this primer was 1.6 mol%. The results are summarized in Table 1.

Comparative Example 1
Block type polyisocyanate “Bernock D-500” manufactured by Dainippon Ink as a primer component {This primer component is shown in the “Background Art” column (the isocyanate group of polyisocyanate is blocked with a protecting group such as methyl ethyl ketone and is not A primer corresponding to an activated block type polyisocyanate, an active hydrogen compound, and a curing catalyst, if necessary, and heating after coating to form a primer layer by removing the protective group and crosslinking. is there. } And butyl acetate were prepared so as to have a weight ratio of 1: 1, and the mixture was sufficiently stirred until uniform in a nitrogen atmosphere, except that the primer curing temperature was 130 ° C. A photochromic cured film was prepared in the same manner as in Example 1, and the appearance and adhesion were evaluated. The results are summarized in Table 2.

Comparative Example 2
As a primer component, block type polyisocyanate “Takenate B-883BS” manufactured by Mitsui Takeda Chemical Co., Ltd. {This primer component is shown in the column of “Means for Solving the Problems”. Block type polyisocyanate blocked and inactivated at room temperature, active hydrogen compound, and curing catalyst if necessary, then heated after coating to form a primer layer by crosslinking while removing protecting groups) It is a primer corresponding to. } And xylene were mixed at a weight ratio of 1: 1, and stirred thoroughly until uniform in a nitrogen atmosphere, except that the primer curing temperature was 130 ° C. A photochromic cured film was prepared in the same manner as in No. 1, and the appearance and adhesion were evaluated. The results are summarized in Table 2.

Comparative Example 3
The same procedure as in Example 1 was performed except that the primer dilution solvent was acetone (boiling point 56 ° C., SP value 9.8). The results are summarized in Table 2.

Comparative Example 4
In Example 1, it carried out like Example 1 except having made the dilution solvent of the primer into diethyl ether (boiling point 35 degreeC, SP value 7.3). The results are summarized in Table 2.

Comparative Example 5
In Example 1, it carried out like Example 1 except having made the dilution solvent of the primer into n-octane (boiling point 126 degreeC, SP value 7.7). The results are summarized in Table 2.

  The photochromic coating agent was prepared and evaluated as follows.

  The abbreviations and names of the compounds used are shown below. As for the radical polymerizable monomer, each compound (monomer) is cast-polymerized as “homo-HL” in parentheses (the temperature is raised from 30 ° C. to 90 ° C. over 20 hours, and further polymerized at 120 ° C. for 2 hours. The Rockwell hardness on the L scale of the cured product obtained by homopolymerization was described. The hardness was measured using a Akashi Rockwell hardness meter (type: AR-10) after holding the cured body in a room at 25 ° C. for 1 day. Glycidyl methacrylate is an epoxy monomer.

(1) Radical polymerizable monomer High hardness monomer TMPT: Trimethylolpropane trimethacrylate (homo-HL = 122)
DPEHA: Dipentaerythritol hexaacrylate (homo-HL = 100)
U6A: Urethane oligomer hexaacrylate (homo-HL = 100) (Shin Nakamura Chemical Co., Ltd .: U-6HA)
EB6A: Polyester oligomer hexaacrylate (homo-HL = 100) (Daicel UCB: EB1830)
GMA: Glycidyl methacrylate (homo-HL = 80)
BPE: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (homo-HL = 110)
Low hardness monomer 9GDA: polyethylene glycol diacrylate having an average molecular weight of 532 (homo-HL <20)
MePEGMA (475): methyl ether polyethylene glycol methacrylate having an average molecular weight of 1000 (homo-HL <20)
BPE oligo: 2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane with an average molecular weight of 776 (homo-HL <40).

(2) Photochromic compound chromene 1

Chrome 2

Chrome 3

Chrome 4

(3) Surfactant SiL1: Silicone surfactant “L7001” (manufactured by Nihon Unicar)
SiL2: Silicone surfactant “FZ2123” (manufactured by Nihon Unicar)
FL1: Fluorosurfactant "Megafac F-470" (Dainippon Ink Chemical Co., Ltd.)
FL2: Fluorosurfactant “Florad FC-430” (manufactured by Sumitomo 3M)
Re1: Fatty acid ester surfactant “Adekaestol S” (Asahi Denka Kogyo Co., Ltd.) Re2: Polyglycerin ester surfactant “Adecanol OPG” (Asahi Denka Kogyo Co., Ltd.)
(4) Optical material CR39 (allyl resin plastic lens; refractive index = 1.50)
MR (thiourethane resin plastic lens; refractive index = 1.60)
TE (thioepoxy resin plastic lens; refractive index = 1.71)
SPL (methacrylic resin plastic lens; refractive index = 1.54)
(5) Polymerization initiator CGI1800: mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (weight ratio 3: 1)
Example 19
CR39 (allyl resin plastic lens; refractive index = 1.50) was used as a lens substrate. This lens base material is thoroughly degreased with acetone, and as a primer, a moisture-curing primer “Takenate M-402P” manufactured by Mitsui Takeda Chemical Co., Ltd. and butyl acetate are mixed at a weight ratio of 1: 1, and further used as a leveling agent. Add 1 part by weight of “L-7001” (Nihon Unicar Co., Ltd.) to the above solution and stir well until uniform in a nitrogen atmosphere, using a spin coater 1H-DX2 made by MIKASA. Spin coated. This was cured at 110 ° C. for 1 hour using a thermostat to prepare a lens substrate having a primer layer. In order to prepare a photochromic cured film, the surface was treated using a corona treatment device multidyne manufactured by Navitas as a pretreatment of the lens substrate.

  As a photochromic polymerizable composition, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane (average molecular weight 776) / trimethylolpropane trimethacrylate / polyester which is a radical polymerizable monomer and a high hardness monomer 50 parts by weight / 15 parts by weight / 10 parts by weight / 10 parts by weight of oligomeric hexaacrylate (Daicel UCB, EB-1830) / glycidyl methacrylate / polyethylene glycol diacrylate (average molecular weight 532) and low-hardness monomer Blended at a blending ratio of / 15 parts by weight /. 3 parts by weight of chromene 1 was added to 100 parts by weight of the radical polymerizable monomer mixture and mixed thoroughly. Furthermore, 0.1 part of “L-7001” (manufactured by Nippon Unicar Co., Ltd.) which is a silicon-based surfactant is added, 0.5 part of CGI 1800 is used as a polymerization initiator, and bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate and 7 parts γ-methacryloyloxypropyltrimethoxysilane as a silyl monomer were added and mixed well to obtain a photochromic compound-containing curable composition.

  Subsequently, about 2 g of the mixed solution obtained by the above method was spin-coated on the surface of the lens substrate using a spin coater 1H-DX2 manufactured by MIKASA. This surface-coated lens is irradiated with a metal halide lamp with an output of 120 / cm in a nitrogen gas atmosphere for 3 minutes to cure the coating film, and then heat-treat with a 110 ° C incubator. A photochromic cured thin film was obtained. The film thickness of the obtained thin film can be adjusted by the conditions of spin coating. In the present invention, the film thickness of the photochromic cured thin film was adjusted to 40 ± 1 μm.

  The appearance of the optical properties of the photochromic cured film thus prepared was evaluated by observing and evaluating the lens substrate having the photochromic cured film with a reflection CCD microscope. The evaluation criteria are shown below.

A: Uniform and no appearance defects are observed B: Very slight appearance defects are observed C: Some appearance defects are visible D: All appearance defects are visible or the substrate is affected The evaluation of the appearance of the lens base material prepared by the method described above was A.

  The applicability which becomes a problem when applying the photochromic curable composition to various substrates was evaluated by the wettability of the composition to the substrate. The evaluation criteria are shown below.

A: The wettability is good and the composition can be uniformly applied to the substrate. B: The wettability is slightly poor, but the composition can be uniformly applied to the substrate. C: The wettability is poor and the composition is based on the composition. There is repellency at the edge of the material.

    D: The wettability is poor and the composition is repelled at the center of the substrate.

  The applicability evaluation for the base material of the photochromic curable composition prepared by the above-described method was A.

  Further, as an evaluation of the photochromic characteristics of the lens substrate having the photochromic cured film, the color density was measured by the following method.

Xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics was applied to the lens having the photochromic coating layer obtained at 20 ° C. ± 1 ° C. through an aeromass filter (manufactured by Corning) on the polymer surface. Irradiation was performed for 120 seconds at beam intensities of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² , and the maximum absorption wavelength at this time was measured using a spectrophotometer (instant multi-channel photodetector manufactured by Otsuka Electronics Co., Ltd.). MCPD1000). The difference {ε (120) −ε (0)} between the absorbance {ε (120)} at the maximum absorption wavelength and the absorbance {ε (0)} at the wavelength of the cured body not irradiated with light. This was determined as the color density. It can be said that the higher this value, the better the photochromic properties.

  The color density of the lens substrate having the photochromic cured film prepared by the above-described method was 0.85 at the maximum absorption wavelength of 610 nm, and showed good photochromic characteristics.

  Subsequently, the adhesion was evaluated. As an evaluation method, a lens substrate having a photochromic cured film was immersed in boiling water at 100 ° C. for 1 hour, then cooled to room temperature, and a cross hatch test was performed within 30 minutes. The evaluation criteria are shown below.

A: No peeling B: Peeling of less than 5% C: Peeling of 5% or more and less than 15% D: Peeling of 15% or more The adhesion of the lens substrate prepared by the method described above was A.

Examples 20-25
Use the radically polymerizable monomer composition, surfactant, and photochromic compound of the composition shown in Table 3, and adjust the photochromic polymerizable composition using other additives similar to those in Example 19, A lens having the photochromic coating layer of the present invention was produced in the same manner as in Example 19. The evaluation results are shown in Table 4. In addition, the compounding quantity (part) of surfactant and a photochromic compound in Table 3 is a compounding quantity (part) with respect to 100 weight part of all radical polymerizable monomers.

Reference Examples 1-6
For comparison, a lens having a photochromic coating layer was prepared in the same manner as in Example 19 using a radical polymerizable monomer composition, a surfactant, and a photochromic compound as shown in Table 5. The evaluation results are shown in Table 6.

  As is apparent from Tables 3 and 4 above, the photochromic curable composition containing a silicone surfactant or a fluorosurfactant has good applicability and optical properties, and has good adhesion and photochromic properties. It was good.

  On the other hand, as in Reference Examples 1 and 5 shown in Tables 5 and 6, when a photochromic curable composition containing no silicone surfactant or no fluorosurfactant is used, the applicability and optical properties are improved. It was extremely bad. Further, in Reference Example 2 using a fatty acid ester surfactant and Reference Example 3 using a polyglycerin surfactant, applicability and optical properties were not improved, and adhesion was also poor. Moreover, in the reference example 6 which does not contain a low-hardness monomer as a radical polymerizable monomer composition, good photochromic characteristics were not obtained.

  Furthermore, the impact resistance of the optical base material including the laminated structure in which the moisture-curable polyurethane resin layer of the present invention was formed was prepared and evaluated as follows.

CR39 (allyl resin plastic lens; refractive index = 1.50) was used as an optical substrate. As a primer, a moisture-curing primer “Takenate M-605N” manufactured by Mitsui Takeda Chemical Co., Ltd. and butyl acetate were mixed at a weight ratio of 1: 1, and the mixture was sufficiently stirred until it became uniform in a nitrogen atmosphere. . This was spin-coated on an optical base material using a spin coater 1H-DX2 manufactured by MIKASA, and cured at 110 ° C. for 1 hour using a thermostatic chamber to prepare an optical base material having a polyurethane resin layer. The impact resistance was evaluated by the weight of the steel ball when the steel plate was spontaneously dropped from a height of 127 cm onto a test plate having a thickness of 2 mm and a diameter of 65 mm and the sample plate was damaged. The evaluation criteria are “1” when the weight of the steel ball is 20 g or less, “2” when the weight is 20 to 40 g, “3” when the weight is 40 to 60 g, and “3” when the weight is 60 to 80 g. 4 ”, 80 g or more was designated as“ 5 ”. The evaluation result of impact resistance of CR39 having no polyurethane resin layer was “3”, and the evaluation result of impact resistance of CR39 having the polyurethane resin layer produced as described above was “5”. From this, it can be seen that the impact resistance was improved by forming a laminated structure of polyurethane resin layers.

Claims (13)

A laminate comprising a laminate structure in which a polyurethane resin layer comprising a cured product of a moisture curable polyurethane resin and / or a precursor thereof is formed on at least one surface of an optical substrate. The laminate according to claim 1, wherein the optical substrate has a surface composed of a three-dimensional crosslinked body, and the polyurethane resin layer is formed on the surface. The laminate according to claim 1 or 2, wherein the polyurethane resin layer has a thickness of 0.1 to 10 µm, and air bubbles are not substantially present in the layer. On the surface of at least one of the optical substrates, after applying a coating liquid containing a moisture curable polyurethane resin and / or its precursor and a solvent having a boiling point of 70 ° C. or more and a solubility parameter of 8 or more, the solvent is removed. Then, moisture-curable polyurethane resin and / or its precursor are hardened, The manufacturing method of the laminated body in any one of Claims 1-3 characterized by the above-mentioned. The manufacturing method according to claim 4, wherein the moisture curable polyurethane resin and / or a precursor solution thereof further contains a leveling agent. A laminate comprising a laminated structure in which a polyurethane resin layer and a resin layer containing a photochromic compound are laminated in this order on the surface of an optical substrate. An optical article comprising the laminate according to claim 1, claim 2, claim 3 or claim 6. A coating liquid for an optical substrate comprising a moisture curable polyurethane resin and / or a precursor thereof and a solvent having a boiling point of 70 ° C. or higher and a solubility parameter of 8 or higher. A curable composition comprising 100 parts by weight of a radically polymerizable monomer component, 0.001 to 5 parts by weight of a silicone-based or fluorine-based surfactant, and 0.01 to 20 parts by weight of a photochromic compound. A photochromic cured product obtained by curing the curable composition according to claim 9. A photochromic coating agent comprising the curable composition according to claim 9. A photochromic optical article, wherein at least a part of the surface of the optical substrate is covered with a photochromic coating layer comprising a cured product of the photochromic coating agent according to claim 11. The laminate according to claim 6, wherein the resin layer containing the photochromic compound comprises a cured product of the photochromic coating agent according to claim 11.