JP5832128B2 - Photochromic lens - Google Patents

Description

  The present invention relates to a novel photochromic lens imparted with a phenomenon that an absorption spectrum reversibly changes by light irradiation, that is, photochromism. Specifically, the present invention relates to a novel photochromic lens excellent in photochromic characteristics and bondability in which a photochromic laminate and a synthetic resin are bonded via a specific coating layer.

  In recent years, for spectacle lenses, the demand for sunglasses having anti-glare properties is rapidly increasing. As a base material of the sunglasses, a plastic lens has come to be used because it is lighter than a glass lens and has high safety in terms of difficulty in breaking. In such plastic sunglasses, a photochromic lens is used in which the photochromic compound can be included to adjust the antiglare property by changing the transmittance according to the ambient brightness.

  Such plastic photochromic lenses are manufactured by various methods. Specifically, a method of applying a coating composition containing a photochromic compound on the surface of a plastic lens, a method of forming a lens by mixing a photochromic compound with the material of the plastic lens itself, and the like can be mentioned.

  In addition, as a method that can impart photochromic properties at a low cost without impairing the properties of the plastic material as a base material, the following methods are also being studied. That is, it is a method using a photochromic laminate in which a photochromic compound is dispersed in an adhesive polyurethane resin to form an adhesive sheet, and an optical sheet such as a polycarbonate resin is laminated on the adhesive sheet. As a method of using this photochromic laminate, a method of manufacturing a photochromic lens by laminating a thermoplastic resin on the laminate by injection molding is known. Further, in terms of easy production of functional lenses, a photochromic lens is obtained by embedding the laminate in a monomer composition that is polymerized to form a thermosetting resin, and polymerizing the monomer composition. Manufacturing methods are known. This method of using a monomer composition can produce a photochromic lens at a relatively low temperature, and various functions can be imparted to the lens by changing the type of monomer. (See Patent Documents 1 to 3).

  However, the conventional method has room for improvement in the following points. For example, in the plastic lens obtained by the method described in Patent Documents 1 and 2, the adhesiveness between the thermosetting resin (synthetic resin) serving as a base material and the optical sheet, and the optical sheet and the photochromic layer (adhesive sheet) In some cases, there is a case where the adhesiveness to the surface is not sufficient, and a problem such as peeling may occur after molding of the photochromic lens. Furthermore, depending on the optical sheet to be used, chemical resistance is not sufficient, so that when the monomer composition is polymerized to form a thermosetting resin (base material), there is a problem that appearance defects such as whitening and yellowing occur. It was.

  In order to solve such a problem, in the method described in Patent Document 3, a coating layer is laminated on the surface of the optical sheet in order to improve chemical resistance (solvent) and adhesion of the optical sheet. Patent Document 3 exemplifies a coating layer made of polyurethane (meth) acrylate and polyester (meth) acrylate as a specific coating layer.

  However, even in a photochromic lens provided with this coating layer, the adhesion between the thermosetting resin (base material) and the optical sheet may not be improved depending on the type of the thermosetting resin (base material) or the optical sheet. There was room for improvement. In such a case, if the end face of the photochromic laminate is on the same plane as the end face of the thermosetting resin (base material), the photochromic lens itself may be peeled off, and there is room for improvement.

  As described above, in the plastic photochromic lens obtained by the conventional methods, there is a case where the problem that peeling occurs at any interface of a plurality of formed layers cannot be solved. When used in daily life, the photochromic lens may come into contact with high humidity or hot water. Even under such circumstances, high adhesion cannot be maintained at the interface between the layers. Don't be. Therefore, it has been desired to develop a photochromic lens that maintains high photochromic characteristics, for example, after being brought into contact with hot water, and has high adhesion between layers and no problem of peeling.

JP-A-61-236521 JP 2005-181426 A JP 2005-215640 A

  Accordingly, an object of the present invention is to provide a photochromic lens having excellent adhesion between a thermoplastic resin as a base material or a synthetic resin that is a thermosetting resin and an optical sheet or an optical film, and further excellent in transparency and photochromic characteristics. Is to provide.

  Furthermore, the other object of this invention is to provide the photochromic laminated body which improved the adhesiveness of an optical sheet or an optical film, and the polyurethane resin layer containing a photochromic compound more.

  The present inventors have intensively studied to solve the above problems. In the photochromic lens, various materials were examined for a coating layer formed on an optical sheet or an optical film and bonded to a synthetic resin as a base material via the optical sheet or optical film. As a result, the coating layer composed of a polymer having a hydrophilic group in the molecule, specifically, a coating comprising a water-dispersible polymer, a crosslinked water-dispersible polymer, or a crosslinked water-soluble polymer. It has been found that the above problems can be solved by using a film layer, and the present invention has been completed.

That is, the present invention
A photochromic laminate (A) having a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other, and at least one of the optical sheets or optical films (A2) A photochromic lens having a synthetic resin layer (B) made of a thermosetting resin or a thermoplastic resin ,
Between the optical sheet or optical film (A2) and the synthetic resin layer (B),
A photochromic lens having a coating layer (C) comprising at least one polymer polymer selected from a water-dispersible polymer, a crosslinked water-dispersible polymer, and a crosslinked water-soluble polymer.

  In this invention, it is preferable that the said coating-film layer (C) consists of a crosslinked body of the water dispersible polymer obtained by making the water dispersible polymer and hydrazide compound which have a carbonyl group react. Moreover, in this invention, it is preferable that the said coating-film layer (C) consists of a crosslinked body of the water-dispersible polymer obtained by making the water-dispersible polymer which has a carboxyl group, and a carbodiimide compound react.

  Furthermore, this invention is a photochromic lens which has the said coating-film layer (C) further between the said polyurethane resin layer (A1) and the said optical sheet or optical film (A2).

Another invention is a laminate for producing a photochromic lens , wherein the coating layer (C) is laminated on at least one surface of the photochromic laminate (A). The laminate may further include the coating layer (C) between the polyurethane resin layer (A1) and the optical sheet or optical film (A2).

  The photochromic lens of the present invention includes a synthetic resin as a base material, an optical sheet, or an optical film by providing a coating layer made of a water-dispersible polymer, a crosslinked water-dispersible polymer, or a crosslinked water-soluble polymer. Adhesiveness can be improved. Furthermore, by providing the coating layer between the optical sheet or optical film and the polyurethane resin layer (adhesive layer) containing the photochromic compound, the adhesion between them can be further improved.

  Therefore, the photochromic lens of the present invention is useful as a plastic lens having excellent photochromic characteristics that can be used for a long period of time.

  Further, in the case where a photochromic laminated body (laminated body) having the coating layer is embedded in a monomer composition that is polymerized to become a thermosetting resin (base material) to produce a photochromic lens, the photochromic laminated body Since the body is excellent in solvent resistance, it is possible to prevent the resin of the optical sheet or optical film from eluting into the monomer composition. Therefore, it is possible to obtain a transparent photochromic lens that does not cause white turbidity. Moreover, since the photochromic laminated body (laminated body) which has this coating film layer is excellent in solvent resistance as above-mentioned, it also becomes possible to manufacture a photochromic lens using an organic solvent.

1 shows one embodiment of a photochromic lens of the present invention. The other aspect of the photochromic lens of this invention is shown.

  The photochromic lens of the present invention includes a photochromic laminate (A) having a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other, and at least one of the photochromic lenses (A2). A photochromic lens having a synthetic resin layer (B) on an optical sheet or optical film (A2), comprising a specific polymer between the optical sheet or optical film (A2) and the synthetic resin layer (B). It is a photochromic lens characterized by having the coating layer (C) which becomes.

  Hereinafter, the photochromic laminate (A), the coating layer (C), and the synthetic resin (B) will be described.

Photochromic laminate (A)
The photochromic laminate of the present invention has a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. Hereinafter, in the present invention, the adhesion in the photochromic laminate (A) is 1) adhesion between the synthetic resin (B) as a base material and the optical sheet or optical film (A2), and 2) polyurethane. It means both the adhesiveness between the resin layer (A1) and the optical sheet or optical film (A2). First, the polyurethane resin layer (A1) constituting the photochromic laminate (A) will be described.

Polyurethane resin layer (A1) containing photochromic compound
(Polyurethane resin constituting the polyurethane resin layer (A1))
In this invention, this polyurethane resin used for the polyurethane resin layer (A1) containing a photochromic compound plays the role of the adhesive agent which can join an optical sheet or an optical film (A2). Therefore, the resin is not particularly limited as long as it is present between the two optical sheets or optical films (A2) facing each other and can join the two, and is a thermosetting polyurethane or a thermoplastic polyurethane. May be.

  The polyurethane resin used in the present invention can be produced by a known method. Among these, a polymer synthesized from a polyisocyanate compound, a polyol compound, and a chain extender is preferable. Hereinafter, each of these components will be described.

(Polyisocyanate compound)
As the polyisocyanate compound used in the polyurethane resin, an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound is preferably used from the viewpoint of weather resistance. Specifically, aliphatic such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate Polyisocyanate compound, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4′-methylenebis (cyclohexyl) Isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-dii Examples thereof include alicyclic polyisocyanate compounds such as socyanate and hexahydrophenylene-1,4-diisocyanate, and it is particularly preferable to use isophorone diisocyanate and norbornene diisocyanate.

(Polyol compound)
As the polyol compound used in the polyurethane resin, polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol can be used. Of these, polycarbonate polyols and polycaprolactone polyols are preferably used from the viewpoints of heat resistance, adhesion, weather resistance, hydrolysis resistance, and the like. The number average molecular weight of the polyol compound is preferably 400 to 3000. Among them, the number average molecular weight is preferably 400 to 2500 from the viewpoint of the heat resistance and photochromic properties (color density, fading speed, weather resistance, etc.) of the obtained polyurethane resin layer, particularly the weather resistance of the photochromic compound. More preferably, it is 1500.

(Chain extender)
The chain extender used in the polyurethane resin is a compound having a molecular weight of 50 to 300 having a functional group capable of reacting with two or more isocyanate groups in the molecule. Specifically, diamine compounds, triamine compounds, amino alcohol compounds, aminocarboxylic acid compounds, aminothiol compounds, diol compounds, and triol compounds can be used. In particular, from the viewpoint of adhesion, heat resistance, and photochromic properties, diamines such as isophoronediamine, ethylenediamine, piperazine, bis- (4-aminocyclohexyl) methane, norbornenediamine, N, N′-diethylethylenediamine, N-ethylethylenediamine Preference is given to using compounds.

(Other components constituting polyurethane resin)
The terminal of the polyurethane resin obtained from the above-mentioned polyisocyanate compound, polyol compound, and chain extender may be an isocyanate group, or the isocyanate group may be capped with a reaction terminator. As the reaction terminator, a group having a structure capable of reacting with one isocyanate group, a group capable of exhibiting various functions, and a structure can be used. Specifically, a compound having a group that reacts with an isocyanate group such as 4-amino-1,2,2,6,6-pentamethylpiperidine can be used as a reaction terminator.

(Method for producing polyurethane resin)
The polyurethane resin can be produced by a known method using the above components. Specifically, a so-called one-shot method or a prepolymer method can be employed. For example, it is possible to employ a method in which a polyisocyanate compound and a polyol compound are reacted, then a chain extender is reacted, and a reaction terminator is reacted as necessary. Known conditions can be adopted as reaction conditions for these components. As a purification method, a known method can be adopted.

  The polyurethane resin thus obtained is mixed with a photochromic compound described below to form a polyurethane resin layer (A1) containing the photochromic compound. At this time, an organic solvent such as tetrahydrofuran or propylene glycol monomethyl ether can be used to adjust the viscosity.

(Photochromic compound)
Next, the photochromic compound mixed in this polyurethane resin and contained in the polyurethane resin layer (A1) will be described.

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

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

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

  Among these other photochromic compounds, a chromene compound having an indenonaphth “2,1-f” naphtho “2,1-b” pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloration, durability, and fading speed. It is more preferable to use one or more types.

Method for producing polyurethane resin layer (A1) containing photochromic compound In the present invention, the polyurethane resin layer (A1) containing a photochromic compound is formed using a polyurethane resin obtained by the above method and a photochromic composition containing the photochromic compound. it can.

  The photochromic composition is not particularly limited, but preferably contains 1 part by mass or more and 10 parts by mass or less of the photochromic compound per 100 parts by mass of the polyurethane resin.

  In addition, in order to improve the durability of the formed polyurethane resin layer (A1), to improve the color development rate, to improve the fading rate and to form a film, the photochromic composition is added with a surfactant, a hindered amine light stabilizer, a hindered Phenolic antioxidants, phenolic radical scavengers, sulfur antioxidants, phosphorus antioxidants, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments Additives such as fragrances and plasticizers can also be blended. As these additives, known compounds are used without any limitation, and these may be used as a mixture of two or more. The total amount of the additive is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyurethane resin.

  Furthermore, a pressure-sensitive adhesive can be blended with the photochromic composition for the purpose of improving the adhesion between the photochromic adhesive sheet and the optical sheet. Specific examples include terpene resins, terpene phenol resins, phenol resins, hydrogenated terpene resins, rosin resins, xylene resins, acrylic adhesives, silicone adhesives, urethane adhesives, and the like. The photochromic composition can also contain inorganic oxide fine particles and organic / inorganic composite materials for the purpose of improving the heat resistance of the photochromic adhesive sheet and reducing the solubility in the polymerizable monomer. . Inorganic oxide fine particles include metal oxide sols such as silica sol dispersed in organic solvents such as methanol, methyl ethyl ketone, propylene glycol monomethyl ether, etc., and organic / inorganic hybrid materials include silica / melamine hybrid materials, silica / Examples thereof include a urethane hybrid material, a silica / acrylic hybrid material, and a silica / epoxy resin hybrid material.

  The polyurethane resin layer (A1) may be formed from this photochromic composition. The method for forming the polyurethane resin layer (A1) will be described in the following method for producing the photochromic laminate (A).

  In the present invention, the thickness of the polyurethane resin layer (A1) is not particularly limited. However, when the photochromic laminate (A) is used, the color density, weather resistance, adhesive strength, and the like of the photochromic compound are considered. From 5 to 100 μm, particularly 10 to 50 μm is preferable.

  An optical sheet or an optical film (A2) is laminated on both surfaces of the polyurethane resin layer. Next, the optical sheet or optical film (A2) will be described.

(A2): Optical sheet or optical film As the optical sheet or optical film (A2) used in the present invention, a sheet or film having optical transparency is used. The raw materials are polycarbonate resin, polycarbonate alloy resin, polyethylene terephthalate resin, nylon resin, polyolefin resin, polyacrylate resin, allyl resin, polysulfone resin, triacetyl cellulose resin, polyurethane resin, polystyrene resin, epoxy resin, polyvinyl alcohol resin, poly A vinyl chloride resin, a melamine resin, a phenol resin, a urea resin, a polyphenylene oxide resin, etc. are mentioned. A polarizing film (for example, a polarizing film made of polyvinyl alcohol sandwiched by a triacetyl cellulose resin film) can also be used as the optical film of the present invention. A polarizing photochromic lens can be obtained by using the polarizing film.

  Among the raw materials as described above, polycarbonate resin is particularly preferable from the viewpoints of adhesion, optical characteristics, mechanical strength, and the like. As a preferable polycarbonate resin, it is produced by a known method from a bisphenol compound represented by 2,2-bis (4-hydroxyphenyl) alkane or 2,2-bis (4-hydroxy-3,5-dihalogenophenyl) alkane. The polymer which was made is mentioned. In addition, the polymer may have an ester bond containing a structural unit derived from a fatty acid diol. Particularly preferred polycarbonate resins include resins derived from 2,2-bis (4-hydroxyphenyl) propane. The molecular weight of the polycarbonate resin is not particularly limited, but from the viewpoint of formability and mechanical strength, the viscosity average molecular weight is 17,000 to 40,000, more preferably 20,000 to 30,000.

  The optical sheet or optical film used in the present invention may be modified by a known method. For example, in order to further improve the adhesiveness due to the photochromic composition, it is possible to use a modified surface. The modification method is not particularly limited, and examples thereof include plasma discharge treatment, corona treatment, flame treatment, chemical treatment with acid, alkali chemicals, and the like.

  Further, the two optical sheets or films facing each other in the present invention may be sheets or films made of the same resin, or sheets or films made of different resins. When using the said polarizing film especially, it is preferable that the other optical sheet or film which opposes is a sheet | seat or film which has another transparency.

  The thickness of the optical sheet or optical film (A2) used in the present invention is 50 μm to 1 mm, and particularly preferably 0.1 mm to 0.5 mm. When the thickness is less than 50 μm, the optical sheet is cured when the photochromic laminate having the optical sheet or film is embedded in the monomer composition that forms a thermosetting resin by polymerization. Alternatively, the film may be distorted. On the other hand, when the thickness of the optical sheet or film exceeds 1 mm, the resulting photochromic lens becomes thick, which is not preferable for eyeglass use, and curved surface processing may be difficult.

  The surface on which the synthetic resin layer (B) is in contact with the optical sheet or optical film (A2), or the surface on which the synthetic resin layer (B) and the polyurethane resin layer (A1) are in contact (optical sheet or optical film (A2)). The coating layer (C) can be laminated on both sides). Next, the manufacturing method of the photochromic laminated body (A) which has this optical sheet or optical film (A2) is demonstrated.

Method for Producing Photochromic Laminate (A) The photochromic laminate (A) used in the present invention is a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. It has. This photochrome laminate (A) can be produced, for example, according to the following procedures and conditions.

  Specifically, the photochromic composition described in the polyurethane resin layer (A) may be used. For example, the photochromic composition is laminated directly on the optical sheet or optical film (A2) to form a polyurethane resin layer (A1), and another optical fiber is formed on the surface of the polyurethane resin layer (A1). What is necessary is just to laminate | stack a sheet | seat or an optical film (A2).

  When a photochromic composition containing an organic solvent is used, it is applied onto the optical sheet or optical film (A2), and the organic solvent is dried to form the polyurethane resin layer (A1). What is necessary is just to laminate | stack another optical sheet or optical film (A2) on the surface of a layer (A1).

  In addition, when using the optical sheet or optical film (A2) which is easy to melt | dissolve in an organic solvent, for example, a polycarbonate, the following methods are also employable. Specifically, after applying a photochromic composition containing an organic solvent on a smooth substrate having high solvent resistance, the organic solvent is dried and the polyurethane resin layer (A1) is separated from the substrate. In this method, the optical sheet or the optical film (A2) is laminated on both surfaces of the obtained polyurethane resin layer (A1). In this case, as a smooth base material having high solvent resistance, a film layer (C) previously laminated on the surface of the optical sheet or optical film (A2) in contact with the polyurethane resin layer (A1) can be used. The coating layer (C) described in detail below is excellent in solvent resistance. Therefore, for example, what laminated | stacked the coating-film layer (C) on the optical sheet or optical film made from a polycarbonate with low solvent resistance can be used as this base material as it is. By using a polycarbonate optical sheet having a coating layer (C) as an optical sheet or optical film (A2) as the base material, the production process of the photochromic laminate (A) can be simplified.

  By adopting any of the above methods, the polyurethane resin layer (A1) can be formed, and the photochromic laminate (A) can be produced. Since the polyurethane resin as the main component functions as an adhesive, the polyurethane resin layer (A1) can be used as it is after obtained by the above method. However, after laminating the optical sheet or the optical film (A2) on both surfaces of the polyurethane resin layer (A1), it is preferable to stabilize the state by the following method. Specifically, it is preferable to leave the photochromic laminate (A) just joined (laminated) at a temperature of 20 ° C. or higher and 60 ° C. or lower for 12 hours or longer. The upper limit of the standing time is not particularly limited, but 50 hours is sufficient. Furthermore, it is preferable to leave this stationary photochromic laminate (A) at a temperature of 80 ° C. to 130 ° C. for 30 minutes to 3 hours (hereinafter referred to as heat treatment). The laminate obtained by this heat treatment has a very stable state.

  The present invention is a photochromic lens having a synthetic resin layer (B) on at least one surface of a photochromic laminate (A) obtained by such a method, the photochromic laminate (A) and the synthetic resin layer. Between (B), it has the coating-film layer (C) which consists of a specific polymer, It is characterized by the above-mentioned. Next, the coating layer (C) will be described.

Coating layer (C)
In the photochromic lens of the present invention, the coating layer (C) is necessarily interposed between the optical sheet or optical film (A2) and the synthetic resin layer (B) described in detail below. And this coating-film layer (C) consists of at least 1 sort (s) of high molecular polymer chosen from the water-dispersible polymer, the crosslinked body of a water-dispersible polymer, and the crosslinked body of a water-soluble polymer. By using the above polymer for the coating layer (C), a thermoplastic resin (synthetic resin layer (B), optical, compared with a coating layer obtained using an organic solvent-based material. Since it is difficult to dissolve the sheet or the optical film (A2), a photochromic lens having excellent transparency can be obtained.

  Next, the high molecular polymer which forms this coating-film layer (C) is demonstrated. First, the water dispersible polymer will be described.

(Water dispersible polymer)
Specific examples of this water-dispersible polymer include water-dispersed polyurethane resins, water-dispersed polyester resins, water-dispersed acrylic resins, and water-dispersed polyurethane / acrylic resins.

(Water-dispersed polyurethane resin)
As the water-dispersed polyurethane resin, it is preferable to use a polyurethane resin in which at least a polyisocyanate compound and a polyol compound are dispersed in water.

Examples of the polyisocyanate compound include conventionally used aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, and mixtures thereof. If the polyisocyanate compound which can be used conveniently as a polyisocyanate compound is illustrated,
Aliphatic polyisocyanates such as diethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate Compound,
Cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4 ′ -Methylenebis (cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate 2,6-bis (isocyanatomethyl) decahydronaphthalene, 1,9-diisocyanato-5-methylnonane, 1,1-bis (isocyanatomethyl) ) Cyclohexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] -1-methylcyclohexane, 2- (3-isocyanatopropyl) cyclohexyl isocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1 , Cycloaliphatic polyisocyanate compounds such as 4-bis (isocyanatomethyl) cyclohexane and bis (isocyanatomethyl) adamantane,
Phenylcyclohexylmethane diisocyanate, 4,4′-methylenebis (phenylisocyanate) isomer mixture, toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3- Diisocyanate, phenylene-1,4-diisocyanate, diphenyl ether diisocyanate, 1,3-bis (isocyanatomethyl) benzene, 1,1′-methylenebis (3-methyl-4-isocyanatobenzene), 1,3-bis (1 -Isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) benzene, xylylene diisocyanate, tetramethyl Xylylene Isocyanate, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, diphenyl ether diisocyanate, 1,3-diisocyanatomethylbenzene, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato -3,3'-dimethoxy (1,1'-biphenyl), 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl) methyl] 2-methylbenzene, 1-isocyanato- 3-[(4-Isocyanatophenyl) methyl) -2-methylbenzene, 4-[(2-iso Cyanatophenyl) oxy] aromatic polyisocyanate compounds such as phenyl isocyanate,
Can be mentioned. These can be used alone or in a mixture of two or more.

The polyol compound has at least two active hydrogen groups reactive with an isocyanate group. Examples of the active hydrogen group reactive with an isocyanate group include a hydroxyl group, an amino group, a mercapto group, and the like. Preferably a hydroxyl group is mentioned. Further, the number of active hydrogen groups contained in the polyol compound is preferably 2 to 6 and particularly preferably 2 to 4 from the viewpoint of maintaining good film properties.
Examples of the polyol compound include polyester polyol, polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, polyurethane polyol or a mixture thereof, and silicone polyol.

Specific examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol. , Neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, and other glycols Polyester polyols obtained by reacting a mixture thereof or a mixture thereof, for example, lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) Polyester polyols obtained by ring-opening polymerization.
Specific examples of polyether polyols include, for example, low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as initiators, and oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Examples include polyether polyols obtained by polymerization.

  Specific examples of the polyether ester polyol include, for example, a reaction between a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or a dialkyl ester thereof or a mixture thereof and the above polyether polyol. Examples include polyether ester polyols obtained.

  As a specific example of the polyesteramide polyol, in the above polyesterification reaction, for example, an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine or the like is added as a raw material to the raw material of the polyesterification reaction product. Can be obtained.

  Specific examples of the acrylic polyol include polymerizable monomers having one or more hydroxyl groups in one molecule, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or their corresponding methacrylic acid derivatives, etc. Examples thereof include those obtained by copolymerizing acrylic acid, methacrylic acid or esters thereof.

  Specific examples of the polycarbonate polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5. -Pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol-A and hydrogenated bisphenol Examples thereof include those obtained by reacting one or more glycols selected from the group consisting of -A with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.

  Specific examples of the polyhydroxyalkane include isoprene, butadiene, or liquid rubber obtained by copolymerizing butadiene and acrylamide.

  Specific examples of the polyurethane polyol include, for example, a polyol having a urethane bond in one molecule, and the polyol is, for example, a polyether polyol, a polyester polyol, a polyether ester polyol or the like having a molecular weight of 200 to 5,000 as described above. Examples thereof include those obtained by reacting an isocyanate group-containing compound having at least two isocyanate groups per molecule with an (NCO group / OH group) molar number of less than 1, preferably 0.9 or less.

  Further, in addition to the polyol compound, a low molecular weight polyol compound may be mixed as a chain extender. Specific examples of these low molecular weight polyol compounds include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9- Nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, glycols used for the production of polyester polyols such as 1,4-cyclohexanedimethanol, glycerin, Examples include trimethylolpropane and pentaerythritol.

  In addition to the low molecular weight polyol compound, a diamine compound, a triamine compound, an amino alcohol compound, an aminocarboxylic acid compound, an aminothiol compound, or the like can also be used as a chain extender.

  Examples of diamine compounds and triamine compounds include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1, 5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- (4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) Methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, phenylenediamine, 4,4′-diphenylmethanediamine, N, N′-diethylethylenediamine, N, N′-dimethylethylenediamine, N , N′-dipropylethylenediamine, N, N′-di Chill ethylenediamine, N- methyl ethylenediamine, N- ethylenediamine, bis (hexamethylene) triamines may be mentioned 1,2,5-pentanetricarboxylic amine.

  Examples of amino alcohol compounds include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-piperidinemethanol, 3-piperidinemethanol, 4-piperidinemethanol, 2 -Piperidine ethanol, 4-piperidine ethanol, etc. can be mentioned.

  Examples of aminocarboxylic acids include glycine, alanine, lysine, and leucine.

  Examples of aminothiol include 1-aminothiol and 2-aminoethanethiol.

  A water-dispersed polyurethane resin in which a polyurethane resin synthesized from the above components is dispersed in water can be used. The number average molecular weight of a suitable water-dispersed polyurethane resin is 2000 to 100,000.

  A commercially available product can be used as the water-dispersed polyurethane resin that satisfies the above requirements. Specifically, “Superflex” series from Daiichi Kogyo Seiyaku Co., Ltd., “Neo Sticker”, “Evaphanol” series from Nikka Chemical Co., Ltd., “Hydran”, “Bondic” series from DIC Corporation, Arakawa Chemical "Yuriano" series manufactured by Kogyo Co., Ltd., "NeoRez" series manufactured by Enomoto Kasei Co., Ltd., "Adekabon titer HUX" series manufactured by ADEKA Co., Ltd., "Takeseal" manufactured by Takebayashi Chemical Industry Co., Ltd. Etc. are exemplified.

(Water-dispersed polyester resin)
Examples of the water-dispersed polyester resin include resins formed by polycondensation of a polybasic acid and a polyhydric alcohol and containing no urethane bond (—NHCOO—) in the molecule.

  The water-dispersed polyester resin is preferably a polyester composed of a copolymer of a hard segment and a soft segment and a polyester elastomer, and a hard segment constituent component is a dicarboxylic acid that is a polybasic acid and a low molecular glycol that is a polyhydric alcohol. used.

  Dicarboxylic acids constituting the hard segment include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, decamethylene dicarboxylic acid, and octadecanedicarboxylic acid. C4-20 linear saturated aliphatic dicarboxylic acid, aliphatic oxycarboxylic acid such as ε-oxycaproic acid, dimer acid (a dibasic polymer obtained by dimerizing an aliphatic monocarboxylic acid having a double bond) Acid) and the like, and ester-forming derivatives thereof.

  On the other hand, examples of low molecular weight glycol include ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol and other aliphatic glycols, 1,6-cyclohexane. Examples include aliphatic glycols such as dimethanol, and ester-forming derivatives thereof.

  As the soft segment constituent component, polyester or polyether is preferably used as described above.

  Examples of the polyester serving as the soft segment include those composed of dicarboxylic acids and long-chain glycol (polyhydric alcohol). As the dicarboxylic acid constituting the soft segment, the same one as in the hard segment can be used. On the other hand, examples of the long-chain glycol include poly (1,2-butadiene glycol), poly (1,4-butadiene glycol), and hydrogenated products thereof. Also, ε-caprolactone, enanthlactone, and caprolylactone are useful as the polyester component.

  The polyether serving as the soft segment includes poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol and the like ( Alkylene oxide) glycols.

  A water-dispersed polyester resin in which a polyester resin synthesized from the above components is dispersed in water can be used. The number average molecular weight of a suitable water-dispersed polyester resin is 2000 to 50,000.

  A commercially available product can be used as the water-dispersed polyester resin that satisfies the above requirements. Specific examples include “Pesresin A” series manufactured by Takamatsu Yushi Co., Ltd., “Vylonal” series manufactured by Toyobo Co., Ltd., “Aronmelt” manufactured by Toagosei Co., Ltd., and the like.

(Water-dispersed acrylic resin)
As the water-dispersed acrylic resin, a resin obtained by emulsion polymerization using an acrylic monomer as shown below is preferably used. As an acrylic monomer used as a raw material for the water-dispersed acrylic resin, preferably, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate , Lauryl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate , (Meth) acrylic acid alkyl ester monomers such as isobornyl methacrylate, carboxyl group-containing acrylic monomers such as acrylic acid and methacrylic acid, 2-hydroxyethyl acrylate Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate Hydroxyl group-containing acrylic monomers such as polytetramethylene glycol monoacrylate and polytetramethylene glycol monomethacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N , N-diethylaminoethyl methacrylate and other tertiary amino group-containing acrylic monomers, 4 Hindered amino group-containing acrylic monomers such as methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, acrylamide, N, N -Dimethylacrylamide, N-isopropylacrylamide, hydroxymethylacrylamide, hydroxyethylacrylamide, N, N-dimethylaminopropylacrylamide, 2-acrylamide-2-methyl-propanesulfonic acid, diacetone acrylamide, N-methoxymethylacrylamide, N- Amide group-containing acrylic monomers such as ethoxymethylacrylamide, N-butoxymethylacrylamide, 4-methacrylamidoethylethyleneurea, 2-methacryloyloxyethyl-ethyleneurea Examples include urea group-containing acrylic monomers such as glycidyl acrylate, methyl glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and vinyl benzyl glycidyl ether. The water-dispersed acrylic resin may be composed of these acrylic monomers alone or a mixture of two or more kinds.

  It is preferable to use a water-dispersed acrylic resin obtained by emulsion polymerization of the above monomers. The number average molecular weight of a suitable water-dispersed acrylic resin is 5,000 to 200,000.

  Commercially available water-dispersed acrylic resins that satisfy the above requirements can be used. Specifically, Etec Co., Ltd. acrylic emulsion, DIC Co., Ltd. “Boncoat”, Takebayashi Chemical Industries Co., Ltd. “Taketac”, Taisei Fine Chemical Co., Ltd. “3MF”, “SE”, “UW”, “RKW” , “AKW” series and the like.

(Water-dispersed polyester / polyurethane resin)
Examples of water-dispersed polyester / polyurethane resins include polyisocyanate compounds and polyol compounds used in the water-dispersed polyurethane resins, and resins obtained using polybasic acids and polyhydric alcohols used in the water-dispersed polyester resins. Gained. A suitable water-dispersed polyester / polyurethane resin has a number average molecular weight of 1,000 to 100,000.

  Commercially available water-dispersed polyester / polyurethane resins that satisfy the above requirements can be used. Specifically, “WAC” series manufactured by Takamatsu Yushi Co., Ltd. and the like are exemplified.

(Water-dispersed polyurethane / acrylic resin)
The water-dispersed polyurethane / acrylic resin can be obtained, for example, by the following method. First, a urethane prepolymer having an isocyanate group at the terminal is reacted with an ethylenically unsaturated monomer having a hydroxyl group to obtain a self-emulsifying modified prepolymer having an ethylenically unsaturated bond and an isocyanate group in the molecule. . Next, it can be obtained by emulsion polymerization of an aqueous dispersion of a polymerizable mixture in which this self-emulsifying modified prepolymer and an ethylenically unsaturated monomer mainly composed of an acrylic monomer are mixed.

  In order to obtain a urethane prepolymer having an isocyanate group at the terminal, a polyisocyanate compound, a polyol compound, and a chain extender used in the water-dispersed polyurethane resin can be used.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl acrylate, and acryloyl hydrogen phthalate. Oxyethyl, β-hydroxyethyl-β-acryloyloxyethyl phthalate, 1,4-butylene glycol monoacrylate, N-methylol acrylamide, hydroxystyrene, vinyl alcohol, allyl alcohol, methallyl alcohol, isopropenyl alcohol, 1-Putynyl Alcohol, ethylene glycol monoacrylate, 1,4-butanediol monoacrylate and the like are used.

  The reaction ratio between the urethane prepolymer having an isocyanate group at the terminal and the ethylenically unsaturated monomer having a hydroxyl group is the equivalent ratio of the —NCO group of the prepolymer and the —OH group of the monomer (—OH / —NCO). ) Is 0.3 to 0.6, and in the case of emulsion polymerization using a self-emulsifying modified prepolymer having an ethylenically unsaturated bond in which all of the —NCO groups have reacted with a hydroxyl group, gelation tends to occur. It should be around 5.

  The reaction product of the urethane prepolymer and the ethylenically unsaturated monomer having a hydroxyl group has a free -NCO group, but it is not preferable because it reacts with active hydrogen, so this -NCO group is masked with glycerin, caprolactam or the like. Mask with an agent and ionize with acid or alkali. As the alkali, tertiary amines, ammonia and the like are used, and as the acid, an inorganic acid such as hydrochloric acid and an organic acid such as acetic acid are used.

Furthermore, the main component of the ethylenically unsaturated monomer is an acrylate such as an alkyl acrylate ester or an alkyl methacrylate ester from the viewpoint of weather resistance. In addition, styrene, vinyl acetate, ethylene, acrylonitrile, acrylamide, or the like may be used in combination.

  Specifically, acrolein, diacetone acrylamide, formyl styrol, vinyl alkyl ketone having 4 to 7 carbon atoms, acrylic (or methacrylic) oxyalkyl propanal, acetonitrile acrylate, diacetone acrylate, diacetone methacrylate, 2- Hydroxypropyl acrylate-acetyl acetate, butanediol-1,4-acrylate-acetyl acetate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, normal propyl methacrylate, tert-butyl methacrylate, normal butyl methacrylate, methacrylic acid Isobutyl, 2-butyl methacrylate, ethyl acrylate, propyl acrylate, normal butyl acrylate, 2-ethylhexyl acrylate, acrylic Le acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, acrylonitrile, acrylamide, methacrylamide, styrene, vinyl acetate, alpha-methyl styrene, ethylene, vinyl chloride and the like.

  Examples of the method for obtaining the water-dispersed polyurethane / acrylic resin include emulsion polymerization. As a method for emulsion polymerization, an aqueous dispersion of a modified urethane prepolymer having a self-emulsifying ethylenically unsaturated bond is mixed or emulsified with the ethylenic monomer mixture as it is or with the addition of a surfactant, and then emulsified. The polymerization initiator may be used at a temperature of 40 to 100 ° C., and the self-emulsifying modified urethane prepolymer and the ethylenically unsaturated monomer mixture are added to water containing a surfactant, You may carry out stirring and mixing.

  The number average molecular weight of a suitable water-dispersed polyurethane / acrylic resin is 3000 to 100,000.

  Commercially available water-dispersed polyurethane / acrylic resins that satisfy the above requirements can be used. Specifically, “NeoPac” series manufactured by Enomoto Kasei Co., Ltd., “WEM” series manufactured by Taisei Fine Chemical Co., Ltd. and the like are exemplified.

(Suitable water-dispersible polymer and production method thereof)
In order to obtain a water-dispersible polymer such as the above-mentioned water-dispersed polyurethane resin, water-dispersed polyester resin, and water-dispersed polyurethane / acrylic resin, an ionic or nonionic surfactant having a surface active action (emulsifying action) in the resin structure It must be of a self-emulsifying type having a functional group or an atomic group or forcedly emulsified with an emulsifier. From the viewpoint of the wettability of the synthetic resin layer (B) with respect to the coating layer (C) obtained using the water-dispersible polymer, and the storage stability of the water-dispersible polymer, The molecular component is preferably a self-emulsifying type.

  The group or atomic group having a surface-active action that the self-emulsifying polymer has is a group or atomic group having a high affinity for water, and can be a group or atomic group capable of emulsifying a polymer resin in water. There is no particular limitation. Suitable groups or atomic groups include sulfonyl groups, carboxyl groups, or groups having an anionic surface active activity such as structures (atomic groups) in which they are alkali metal salts, alkylamine salts, or amine salts, or Examples include atomic groups. In addition, cationic groups such as a group having a nonionic surface active activity such as a hydroxyl group or a polyalkylene glycol group, an amino group or an alkylamino group, or a structure (atomic group) in which they are sulfonate or alkylsulfonate And a group or an atomic group having a surface-active action. Among them, the stability of the emulsion is relatively high, for reasons such as adhesion to the optical sheet or optical film (A2) and the synthetic resin layer (B), a group or atomic group having an anionic surface active action, In particular, a water-dispersible polymer containing a self-emulsifying polymer component having an alkylamine salt of carboxylic acid in the polymer resin structure is preferably used.

  When producing a water-dispersible polymer containing a self-emulsifying polymer component, a method for introducing a surface-active group includes hydrophilic groups such as a carboxyl group, a sulfonic acid group, a sulfonate group, an epoxy group, and a polyoxyalkylene group. In general, a method in which a compound having a functional group is incorporated into a polymer resin molecule and neutralized with a neutralizing agent to form a surface-active group or atomic group.

  Examples of the compound having a hydrophilic group include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6- Sulfonic acid-containing compounds such as disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid, or derivatives thereof, or polyester polyols obtained by copolymerization thereof, such as 2,2-dimethylolpropionic acid, 2,2 -Carboxyl group-containing compounds such as dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid or their derivatives, maleic anhydride, phthalic anhydride , Succinic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Carboxyl group-containing compounds by reacting a compound having an active hydrogen group or derivatives thereof and. Further, diacetone acrylamide obtained by addition reaction of dialkanolamine can also be used. In producing the water-dispersible polymer, these compounds having a hydrophilic group can be used alone or in combination of two or more.

  Further, for the purpose of improving the adhesion of the coating layer made of a water-dispersible polymer, the water-dispersible polymer has a silanol group, a group capable of generating a silanol group by hydrolysis, a (meth) acryloyloxy group, (meth) It is also possible to introduce at least one group selected from the group consisting of an acrylamide group and an epoxy group.

  In addition, the dispersion particle size (average particle size) of the resin in the water dispersion medium in which the water-dispersible polymer is dispersed depends on the type of resin, the type of emulsifier used, and the emulsification method as required. I can't do it. However, from the viewpoint of improving the wettability of the coating layer (C) to be formed, it is preferably 30 nm to 1000 nm, and from the viewpoint of optical transparency of the coating layer (C), 40 nm to 500 nm or less. In particular, the thickness is preferably 50 nm to 100 nm or less.

  It is preferable to use a water-dispersible polymer as described above. Such a water-dispersible polymer can be used as it is, but can also be used as a cross-linked product of a water-dispersible polymer in combination with a crosslinking agent. Examples of the crosslinking agent include polyisocyanate compounds, epoxy compounds, aziridine compounds, oxazolidine compounds, hydrazide compounds, and carbodiimide compounds.

  Among these, when the polymer has a carbonyl group, a hydrazide compound is preferably blended as a crosslinking agent and used as a crosslinked product of a water-dispersible polymer. Moreover, when it has a carboxyl group in this polymer, it is preferable to mix | blend a carbodiimide compound as a crosslinking agent and to use as a crosslinked body of a water-dispersible polymer.

(Crosslinked product of water-dispersible polymer: crosslinked product)
(Hydrazide compound)
As the polymer polymer for forming the coating layer (C), a hydrazide compound can be blended as a crosslinking agent in a polymer having a carbonyl group among the water-dispersible polymers, and used as a crosslinked product. By using a cross-linking agent, the cross-linking density of the coating layer (C) can be improved, the resistance to the polymerizable monomer forming the synthetic resin layer (B) before curing, and the synthesis formed Adhesion with the resin layer (B) can be further improved.

  Examples of the crosslinking agent include hydrazide compounds having a hydrazide group that can react with a carbonyl group contained in the water-dispersed polymer emulsion. The hydrazide compound is a compound represented by the following formula:

It is a compound which has group shown by these. Particularly preferred hydrazide compounds are polyhydrazine compounds having at least two groups represented by the above formula in the molecule.

  Specific examples of the polyhydrazide compound include dicarboxylic acid dihydrazide having 2 to 18, preferably 2 to 10 carbon atoms, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, and adipic acid. Examples include dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, and terephthalic acid dihydrazide.

  Examples of the aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms include ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine.

  Furthermore, the following general formula:

(Where
R is a linear or branched divalent aliphatic residue having 2 to 7 carbon atoms or a divalent cyclic residue having 6 to 8 carbon atoms,
and x is an integer of 1 to 5).

  R is a linear or branched divalent aliphatic residue having 2 to 7 carbon atoms, specifically, a linear or branched alkylene group having 2 to 7 carbon atoms. It is preferable. Examples of the divalent cyclic residue having 6 to 8 carbon atoms include an aromatic residue and an aliphatic cyclic group, and preferably an o-, m-, or p-phenylene group, a tolylene group, a cyclohexyl group. Examples include a silene group or a methylcyclohexylene group.

  x is an integer of 1 to 5, preferably an integer of 1 to 3.

  Of these, the following general formula

An aliphatic, alicyclic or aromatic bissemicarbazide represented by the formula can be preferably used. Specific examples of the compound include pyromellitic acid dihydrazide, trihydrazide, and tetrahydrazide, and specific examples of the aliphatic trihydrazide include nitrilotriacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrid. Examples of hydrazide and tetrahydrazide include ethylenediaminetetraacetic acid tetrahydrazide and 1,4,5,8-naphthoic acid tetrahydrazide.

In addition, thiocarbohydrazide, N, N′-diaminoguanidine, hydrazine-pyridine derivatives (for example, 2-hydrazinopyridine-5-carboxylic acid hydrazide, 3-chloro-hydrazinopyridine-5-carboxylic acid hydrazide, 6-chloro) -2-hydrazinopyridine-4-carboxylic acid hydrazide, 2,5-dihydrazinopyridine-4-carboxylic acid, etc.), bis-thiosemicarbazide, alkylenebisacrylamide bishydrazine, dihydrazine alkane, aromatic hydrocarbons Dihydrazine (eg, 1,4-dihydrazinobenzol, 1,3-dihydrazinobenzol, 2,3-dihydrazine naphthalene),
Examples thereof include polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate (hydrazine hydride) (see Japanese Patent Publication No. 52-22878). These polyhydrazine compounds may be used alone or in admixture of two or more.

  The polyhydrazide compound has a relatively low molecular weight (approx. 300 or less) having appropriate hydrophilicity, because if the hydrophobicity is too strong, it tends to be difficult to disperse in water and a uniform crosslinked coating film tends not to be obtained. It is preferred to use a compound. One suitable representative example is a dihydrazide compound of a dicarboxylic acid having 4 to 12 carbon atoms such as succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like.

  The compounding quantity of the said hydrazide compound is 0.01-5 molar equivalent with respect to the total number of moles of the carbonyl group in the said water-dispersible polymer, Preferably it is the quantity used as 0.05-3 molar equivalent. In addition, the said compounding quantity is the number-of-moles of a hydrazide group.

(Carbodiimide compound)
Moreover, as another crosslinking agent, a carbodiimide compound having a carbodiimide bond, that is, a bond represented by -N = C = N-, in the molecule may be used. In particular, it is preferable to use a polycarbodiimide compound having two or more carbodiimide bonds in the molecule. When a carbodiimide compound is used as a crosslinking agent, a carbodiimide group contained in the carbodiimide compound reacts with a carboxyl group contained in the water-dispersible polymer to obtain a coating layer in which the water-dispersible polymer is crosslinked. it can.

  As the carbodiimide compound used in the present invention, a commercially available carbodiimide compound can be used. For example, as described in JP-A-59-187029, a polyisocyanate compound or a polyisocyanate compound can be used. It can be prepared by subjecting a monoisocyanate compound to a carbon dioxide removal reaction in the presence of a catalyst.

Examples of the isocyanate compound used in preparing the carbodiimide compound by the above-described method include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, phenyl isocyanate, benzyl isocyanate, β-phenethyl isocyanate or α-naphthyl isocyanate. Monoisocyanate compounds, such as
Tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, hexahydrotolylene-2,4-diisocyanate, hexahydrotolylene-2, Examples thereof include diisocyanate compounds such as 6-diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate or 1,3-diisocyanate methylcyclohexane, or polyisocyanate compounds having an isocyanurate ring obtained by trimerization of the diisocyanate compound. .

  Examples of reaction catalysts that are particularly representative include phosphine compounds, phospholene compounds, phospholene oxide compounds, and phospholene sulfide compounds.

  The carbodiimide compound can be obtained by reacting in the temperature range of 100 to 200 ° C., preferably 130 to 160 ° C., in an organic solvent that is appropriately used, using the aforementioned isocyanate compound.

  Furthermore, examples of commercially available carbodiimide compounds include “Carbodilite” manufactured by Nisshinbo Chemical Co., Ltd.

  The compounding quantity of the said carbodiimide compound is 0.01-5 molar equivalent with respect to the total mole number of the carboxyl group in the said water-dispersible polymer, Preferably it is the quantity used as 0.05-3 molar equivalent. In addition, the said compounding quantity is the number-of-moles of a carbodiimide bond.

  In addition to the water-dispersible polymer and the crosslinked product thereof as described above, a crosslinked product of a water-soluble polymer can also be used for the coating layer (C). Next, the crosslinked body of the water-soluble polymer will be described.

(Crosslinked water-soluble polymer)
As the polymer that forms the coating layer (C), a water-soluble polymer crosslinked product can also be used. Examples of the water-soluble polymer include polymers having a hydroxyl group in the molecule and soluble in water. Among these, a polyvinyl alcohol polymer (PVA) can be preferably used.

  As the PVA, so-called normal PVA produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is generally used. Although there is no restriction | limiting in particular in this PVA, the polymerization degree is 100-10000 normally, Preferably it is 150-8000, More preferably, it is 200-6000. Moreover, the number average molecular weight of suitable PVA is 4000-450,000, Preferably it is 6000-350,000, More preferably, it is 8000-250,000. On the other hand, the degree of saponification may be appropriately selected depending on the situation, but is usually 70 to 99.99 mol%, preferably 80 to 99.95 mol%, more preferably 90 to 99.9 mol%. It is.

  In addition to these normal PVA, modified polyvinyl alcohol copolymerized with less than about 15 mol% with unsaturated carboxylic acid or derivative thereof, unsaturated sulfonic acid or derivative thereof, α-olefin having 2 to 30 carbon atoms, etc. , Polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, etc., ethylene-vinyl alcohol copolymer (EVOH) with ethylene unit content of 5 mol% or more, urethanization, etherification, grafting, phosphate ester of polyvinyl alcohol Modified polyvinyl alcohol, and acetoacetate group-containing polyvinyl alcohol (polyvinyl alcohol is reacted with polyvinyl alcohol and acetoacetate to react with polyvinyl alcohol, Those were introduced acetoacetate group Le) and the like can also be used.

  A silyl group may be introduced into the terminal or side chain of the PVA, and the chemical resistance of the coating layer can be improved by introducing the silyl group.

  Examples of commercially available water-soluble polymers include “GOHSENOL”, “SOANOL”, “GOHSEPIMAR” manufactured by Nippon Synthetic Chemical Industry, “Kuraray Poval”, “Exeval” manufactured by Kuraray Co., Ltd., and the like.

  In the present invention, a crosslinked product obtained by crosslinking the water-soluble polymer with a crosslinking agent can also be used. Next, this crosslinking agent will be described.

(Water-soluble polymer crosslinking agent)
In order to obtain a crosslinked product of a water-soluble polymer, a crosslinking agent that acts on a group in the molecule, for example, a group such as a hydroxyl group, to bond the molecules together may be blended. Examples of such crosslinking agents include organic titanium compounds, organic zirconium compounds, organic aluminum compounds, organic silicon compounds, carbodiimide compounds, and polyisocyanate compounds used for the A1 component. By mixing these cross-linking agents with a water-soluble polymer, the cross-linking density of the water-soluble polymer can be improved, the resistance to the polymerizable monomer forming the synthetic resin layer (B), and the formed synthetic resin Adhesion with the layer (B) can be further improved.

Various compounds can be used as the organic titanium compound. Specific examples include tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, and tetrakis (2-ethylhexyloxy). Titanium alkoxides such as titanium, butyl titanate dimer, tetra (2-ethylhexyl) titanate;
Diisopropoxybis (acetylacetonato) titanium, diisopropoxy (2-ethyl-1,3-hexanediolato) titanium, di (2-ethylhexoxy) bis (2-ethyl-1,3-hexanediolato) titanium , Di-n-butoxybis (triethanolaminato) titanium, diisopropoxybis (triethanolaminato) titanium, tetrakis (acetylacetonato) titanium, dioctyloxybis (octylene glycolate) titanium, diisopropoxybis (Ethyl acetoacetate) titanium, tetrakis (N-aminoethyl-aminoethyl) titanate, tetrakis (bis (N-aminoethyl) -aminoethyl) titanate, titanium tetrakis (N-hydroxyethyl-aminoethyl) titanate, titanium tetrakis ( Screw (N-Hi Roxyethyl) -aminoethyl) titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate, isopropyl tris (bis (N-aminoethyl) -aminoethyl) titanate, isopropyl tris (N-hydroxyethyl-aminoethyl) titanate, Isopropyltris (bis (N-hydroxyethyl) -aminoethyl) titanate, n-butyltris (N-aminoethyl-aminoethyl) titanate, n-butylisopropyltris (bis (N-aminoethyl) -aminoethyl) titanate, n -Butyl isopropyl tris (N-hydroxyethyl-aminoethyl) titanate, n-butyl isopropyl tris (bis (N-hydroxyethyl) -aminoethyl) titanate, titanium lactate or titanium lactate Titanium chelates such as over preparative ammonium salts or titanium chelate ammonium salt;
Titanium acylates such as isopropyl isostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl isostearoyl acrylic titanate, polyhydroxy titanium stearate;
Etc.

  Among these organic titanium compounds, water-soluble ones are preferable. Specifically, titanium lactate, titanium lactate ammonium salt, diisopropoxybis (triethanolaminato) titanium, di-n-butoxybis (triethanolaminato) titanium. Is mentioned. These organotitanium compounds do not necessarily need to be used alone, and may be used as a mixture of two or more as required.

  Further, in addition to the titanium compound, one of hydroxycarboxylic acid or a salt thereof (such as lactic acid, malic acid, tartaric acid, salicylic acid or a salt thereof), β-diketone (such as acetylacetone), amino alcohol (such as triethanolamine) Examples include, but are not limited to, those comprising a ligand capable of coordinating with bidentate or higher polydentate by a covalent bond or hydrogen bond to a titanium atom. .

  Various organic zirconium compounds can also be used, and examples include various zirconyl alkoxides, zirconyl chelates, zirconyl chelate ammonium salts, and zirconyl acylates. Among them, zirconium carbonate or zirconium carbonate ammonium salt. Are preferred, and zirconium carbonate ammonium salt is particularly preferred.

  Specific examples of the organic zirconium compound include zirconium normal propyrate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium monoethylacetoacetate, zirconium acetylacetonate bisethyl. Organic zirconium compounds such as acetoacetonate, zirconium acetate, zirconium tributoxy systemate, zirconium halides such as zirconium oxychloride, hydroxy zirconium chloride, zirconium tetrachloride, zirconium bromide, zirconium sulfate, basic zirconium sulfate, zirconium nitrate, etc. Zirconium salt of mineral acid, zirconium formate, zirconium acetate, propionic acid Zirconium salts of organic acids such as ruthenium, zirconium caprylate, and zirconium stearate, zirconium complex salts such as ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, sodium zirconium citrate, and zirconium ammonium citrate .

  Examples of the organoaluminum compound include aluminum triethoxide, aluminum triisopropylate, aluminum tributyrate, aluminum acetylacetonate, and aluminum organic chelate.

  Examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetraisopropyl silicate, tetranormal butyl silicate, butyl silicate dimer, tetra (2-ethylhexyl) silicate, tetramethyl silicate, silicon acetylacetonate, silicon ethyl acetoacetate, silicon Octanediolate, silicon lactate, silicon triethanolamate, polyhydroxysilicon stearate, silicon normal propyrate, silicon monoacetylacetonate, silicon bisacetylacetonate, silicon monoethylacetoacetate, silicon bisethylacetonate, silicon acetate And silicon tributoxy systemate.

  The amount of the crosslinking agent to be added is not particularly limited, but from the viewpoint of dissolution resistance of the obtained coating layer and adhesion to the synthetic resin layer (B), hydrogen bonds such as hydroxyl groups in the water-soluble polymer are removed. The number of moles of the crosslinking agent is 0.0001 to 5 mole equivalents, preferably 0.001 to 2 mole equivalents relative to the total number of moles of groups that can be formed.

(Formation method of coating layer (C))
In the present invention, the coating layer (C) is formed on the optical sheet or the optical film (A2). Therefore, before manufacturing a photochromic laminated body (A), you may form a coating film layer (C) previously on an optical sheet or an optical film (A2). Moreover, after forming a photochromic laminated body (A), a coating-film layer (C) can also be formed on the surface which forms the synthetic resin layer (B) of this photochromic laminated body (A). Hereinafter, the example in the case of forming a coating film layer (C) on an optical sheet or an optical film (A2) is demonstrated.

  A well-known method can be employ | adopted for the method of forming a coating-film layer (C). For example, an aqueous dispersion in which the water-dispersible polymer is dispersed in water is applied to one side or both sides of the optical sheet or optical film (A2) and dried to form a coating layer (C ) Can be formed.

  As a method for applying the aqueous dispersion, known methods such as spin coating, spray coating, dip coating, dip-spin coating, dry laminating, flow coating, and bar coater are used without any limitation. (Heating) drying of the aqueous dispersion is preferably carried out at a temperature of 30 to 130 ° C. for 1 minute to 120 minutes, and the temperature may be varied by combining heating and cooling. . The aqueous dispersion has a solid content (water-dispersible polymer) concentration of 1 to 40% by mass, preferably 5 to 20% by mass.

  Moreover, when using the crosslinked body of a water-dispersible polymer or the crosslinked body of a water-soluble polymer, the following method is employable. On one side or both sides of the optical sheet or optical film (A2), an aqueous dispersion in which a water-dispersible polymer is dispersed in water or an aqueous solution in which a water-soluble polymer is dissolved in water, and a crosslinking agent that crosslinks these polymers are mixed. Thereafter, the obtained mixture is applied on the optical sheet or optical film (A2), dried and further cured to form a coating layer (C) comprising a crosslinked water-dispersible polymer or a crosslinked water-soluble polymer. Can be formed. The method for applying the mixture can be the same as the method for applying the aqueous dispersion. Furthermore, the heating (drying) of the mixture may be performed in the same manner as in the above method. If it dries on the said conditions, the coating-film layer (C) which consists of a crosslinked body of a water-dispersible polymer or a crosslinked body of a water-soluble polymer can be formed. In this case as well, the solid content concentration in the mixture is 1 to 40% by mass, and preferably 5 to 20% by mass.

  An aqueous dispersion in which the water-dispersible polymer is dispersed in water, or an aqueous solution in which the aqueous dispersion or water-soluble polymer is dissolved in water, and a crosslinking agent, which are coated on the optical sheet or optical film (A2), are mixed. When making a mixture into a composition for coating-film layer formation, as above-mentioned, it is preferable that the solid content (polymer polymer) density | concentration of this composition shall be 1-40 mass%, and shall be 5-20 mass%. Is more preferable. The composition for forming a coating film layer contains water as a main component except for the solid content, but can also contain a water-soluble organic solvent. Examples of water-soluble organic solvents that can be used include alcohols such as methanol, ethanol, and isopropyl alcohol; glycols such as ethylene glycol, propylene glycol, and butyl glycol; ethers thereof; N-methylpyrrolidone; dimethyl sulfoxide; Can be used. The content of these organic solvents is usually 1 part by mass to 50 parts by mass with respect to 100 parts by mass of water, but 3 parts by mass to 30 parts by mass in order to maintain adhesion and appearance. preferable.

  The film thickness of the coating layer (C) formed by the above method is the solubility resistance to the polymerizable monomer constituting the synthetic resin layer (B), and further the synthetic resin layer (B) or the polyurethane resin layer (A1). ) (When the coating layer (C) is laminated on both sides of the optical sheet or optical film (A2)) From the viewpoint of adhesion, 0.1 to 20 μm is preferable, and more preferably 0.2 to 10 μm. Most preferably, the thickness is 0.3 to 5 μm.

  In addition, as above-mentioned, this coating-film layer (C) can also be previously provided in the surface of an optical sheet or an optical film (A2), or after manufacturing a photochromic laminated body (A), on the surface of this laminated body. It can also be provided. When interposing between the polyurethane resin layer (A1) and the optical sheet or optical film (A2), it is preferable to form a coating layer (C) on both surfaces of the optical sheet or optical film in advance. .

  Next, the synthetic resin layer (B) formed on the coating layer (C) will be described.

((B) Synthetic resin layer)
The synthetic resin layer (B) can be formed from a thermoplastic resin that is a normal plastic lens material, or a thermosetting resin obtained by curing a composition of a polymerizable monomer. Among them, the effect of forming the coating layer (C) is more remarkably exhibited when the synthetic resin layer (B) is formed from a thermosetting resin obtained by curing the polymerizable monomer composition. . Specific examples of the polymerizable monomer composition include thermosetting such as a (meth) acrylate monomer composition, an allyl monomer composition, a thiourethane monomer composition, a urethane monomer composition, and a thioepoxy monomer composition. A polymerizable monomer composition capable of forming a polymerizable resin can be mentioned.

(Polymerizable monomer composition)
(Meth) acrylate monomer composition The (meth) acrylate monomer composition is a composition comprising a (meth) acrylate monomer as exemplified below, and further, other (meth) acrylate monomers, Other polymerizable monomers may be mixed. Examples of specific (meth) acrylate monomers include glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, trimethylolpropane triethylene glycol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, urethane oligomer tetra (meth) acrylate, urethane oligomer hexa (meth) acrylate, polyester oligomer hexa (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethylene glycol phenyl) having an average molecular weight of 776 And (meth) acrylate monomers having at least one (meth) acrylate group in the molecule, such as propane, methyl ether polyethylene glycol (meth) acrylate having an average molecular weight of 475, and methyl methacrylate.

(Allyl monomer composition)
Examples of the allylic monomer composition include a composition comprising an allyl monomer having an allyl group, such as diethylene glycol bisallyl carbonate, diallyl isophthalate, diallyl terephthalate.

(Thiourethane monomer composition)
The thiourethane monomer composition is composed of a mixture of a polyisocyanate compound and a polythiol compound. Specific examples of the polyisocyanate compound include 2,5-diisocyanatomethyl-1,4-dithiane and 2,5-bis (4-isocyanate-) in addition to the diisocyanate compound used in the water-dispersed polyurethane resin. 2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanatomethyl-4-isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanate- 2-thiapropyl) -1,4-dithiane, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris (isocyanatomethyl) cyclohexane, bis (isocyanatomethylthio) methane, 1,5-diisocyanate-2 -Isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatoethylthio) pro Bread, 1,2,3-tris (isocyanatomethylthio) propane, 1,1,6,6-tetrakis (isocyanatomethyl) -2,5-dithiahexane, 1,1,5,5-tetrakis (isocyanatomethyl) -2 1,4-dithiapentane, 1,2-bis (isocyanatomethylthio) ethane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane, etc. Polyisocyanates, dimers of these polyisocyanates by burette-type reaction, cyclized trimers of these polyisocyanates, adducts of these polyisocyanates and alcohols or thiols, and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

Specific examples of the polythiol compound include 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, bis (2,3-dimercaptopropyl) sulfide, 1,2-bis (2-mercaptoethylthio) ethane 1,5-dimercapto-3-oxapentane, 1,8-dimercapto-3,6-dioxaoctane, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2- Dithiol, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3, 6-dithiaoctane, 2,4-bis (mercaptomethyl) -1,5-dimercapto-3-thiapentane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithiaundecane, 5,7-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-trithia Undecane, 1,2,7-trimercapto-4,6-dithiaheptane, 1,2,9-trimercapto-4,6,8-trithianonane, 1,2,8,9 Tetramercapto-4,6-dithianonane, 1,2,10,11-tetramercapto-4,6,8-trithiaundecane, 1,2,12,13-tetramercapto-4,6,8,10-tetra Thiatridecane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, tetrakis (4-mercapto-2-thiabutyl) methane, tetrakis (7-mercapto-2,5-dithiaheptyl) methane, Ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate) ), Trimethylolpropane tris (2-mercaptoacetate) ), Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptocetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,1-dimercaptocyclohexane, 1,4- Dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,2-dimercaptocyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) ) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (2-mercaptoethyl) ) -1-thian, 1,4-bis (mercaptomethyl) be , 1,3-bis (mercaptomethyl) benzene, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) ether, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4-mercapto) Phenyl) propane, bis (4-mercaptomethylphenyl) sulfide, bis (4-mercaptomethylphenyl) ether, 2,2-bis (4-mercaptomethylphenyl) propane, 2,5-dimercapto-1,3,4 Thiadiazole, 3,4-thiophenedithiol, 1,2-dimercapto-3-propanol, 1,3-dimercapto-2-propanol, glyceryl dithioglycolate, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1 , 1,3,3-Tetrakis (mercaptomethi Thio) propane, 3-mercaptomethyl-1,5-dimercapto-2,4-polythiols such as Jichiapentan can be mentioned. These may be used alone or in combination of two or more.

(Urethane monomer composition)
As the urethane monomer composition, a mixture comprising a diisocyanate compound, a polyol compound, and a diamine curing agent can be suitably used.

  As the diisocyanate compound, a diisocyanate compound used for the water-dispersed polyurethane resin can be used for the urethane resin composition.

  As the polyol compound, a polyol compound used for the water-dispersed polyurethane resin can be used for the urethane resin composition.

  Examples of the diamine compound include 2,4-diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene and mixtures thereof, 4,4′-methylenebis (3-chloro-2, 6-diethylaniline), paraphenylenediamine, metaphenylenediamine, 4,4′-diaminodiphenyl ether, diaminodiphenylmethane, bis-4- (4-aminophenoxy) phenylsulfone, bis-4- (3-aminophenoxy) phenylsulfone 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenoxy) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl , And Lonza Ltd. as a commercial product. In addition to the diamine compound used in the water-dispersed polyurethane resin, commercially available products such as “JEFFAMINE” series manufactured by Huntsman can be used.

(Thioepoxy monomer composition)
Examples of the thioepoxy monomer composition include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, , 2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropylthio) ) Butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β- Epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β − (Pithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- Chain organic compounds such as (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethane; tetrakis (β-epithiopropylthiomethyl) methane 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, , 5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,2-bis (β -Epithio Propylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (β-epi Thiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β-epithiopropylthiomethyl) 3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β- Epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,5-bis (β -Epithiopropyl Omethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyl) Thio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-[(2- β-epithiopropylthioethyl) Methyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithia Branched organic compounds such as undecane and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, etc .; 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1 , 3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) ) Cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthiomethyl) -1, -At least one of the cycloaliphatic organic compounds such as dithiane and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane and the episulfide group of these compounds is substituted with a methyl group 1,3 and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β- Epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- ( Aromatic organic compounds such as β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl, and epis of these compounds Examples thereof include compounds in which at least one hydrogen of the rufido group is substituted with a methyl group, and these may be used alone or in combination of two or more.

  An appropriate amount of a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator may be added to the polymerizable monomer composition as described above, if necessary.

(Lamination method of synthetic resin layer (B) (production method of photochromic lens))
Examples of the method for laminating the synthetic resin layer (B) on the optical sheet of the photochromic laminate (A) or the coating layer (C) of the optical film include the following methods. Specifically, the photochromic laminate (A) having the coating layer (C) on the outermost surface is placed in a glass mold or a mold used for manufacturing a plastic lens, and the synthetic resin layer is provided there. This is a method of filling the polymerizable monomer composition forming (B).

  When the above-mentioned thermosetting resin is employed as the synthetic resin layer (B), a commonly used glass mold is used, and the glass mold is filled with the polymerizable monomer composition and then thermoset (Note). By performing type polymerization, a photochromic lens can be molded. Furthermore, the polymerization can be carried out in combination with heat curing or by light irradiation alone. The polymerization time may be determined as appropriate.

  In the specific operation for carrying out the casting polymerization as described above, for example, a polymerizable monomer composition is filled in one of the glass molds, and a coating layer (C) is formed on the surface thereof. It is also possible to employ a method in which the photochromic laminate (A) is floated, the other glass mold is set via a gasket or tape, and then the polymerizable monomer composition is further injected into the glass mold for polymerization. . In addition, the photochromic laminate (A) is supported in the glass mold by a gasket, tape or other means fixing the glass mold, and the polymerizable monomer composition is filled in the glass mold for polymerization. It is also possible to adopt a method of Furthermore, the photochromic laminate (A) is adhered to one side of the glass mold, and a method of polymerizing the polymerizable monomer composition on the opposite coated film layer (C) is utilized. be able to.

  Moreover, in this invention, a synthetic resin layer (B) can also be comprised from a thermoplastic resin other than using the said polymerizable monomer composition. When a thermoplastic resin is employed as the synthetic resin, an injection molding method can be employed. Specifically, the photochromic laminate (A) having the coating layer (C) on the outermost surface is in close contact with one inner wall of the mold or is fixed in the vicinity of the middle of the mold and then thermoplastic. By injecting the resin into the mold, the photochromic lens of the present invention can be obtained.

  When manufacturing a photochromic lens, the magnitude | size and shape of a photochromic laminated body (A) which have a coating-film layer (C) can be determined suitably as needed. That is, it may have a shape over the entire photochromic lens finally obtained, or may cover a part of the lens. Among these, the elution of the photochromic compound or the polyurethane resin itself from the polyurethane resin layer (A1) is suppressed by installing the side surface of the photochromic laminate (A) so as to protrude outside the glass mold or the mold. It becomes possible.

  In addition, the thickness of the synthetic resin layer (B) is not particularly limited, and may be appropriately determined according to the use of the obtained photochromic lens, the method of laminating the synthetic resin layer (B), and the like. Usually, the thickness of the synthetic resin layer (B) is 0.5 mm or more and 10.0 mm or less.

  A photochromic lens can be manufactured by the method as described above. FIG. 1 and FIG. 2 show configuration examples of the photochromic lens of the present invention. The photochromic lens 1 is a photochromic laminate (A) 4 having an optical sheet or an optical film (A2) 3 on both surfaces of a polyurethane resin layer (A1) 2 containing a photochromic compound. And it has the coating-film layer (C) 5 on this optical sheet or optical film (A2) 3, and also laminated | stacked the synthetic resin layer (B) 6 on this coating-film layer (C) 5. This is the photochromic lens 1 (FIG. 1).

  Moreover, the photochromic lens 1 of this invention can also form the coating film layer 5 between the polyurethane resin layer 2 and the optical sheet or the optical film 3, as shown in FIG. By forming this coating film layer 5, productivity and the adhesiveness of the photochromic laminated body 4 itself can be improved.

  In addition, although the form which has the coating film layer 5 on both surfaces of the photochromic laminated body 4 was shown in FIG. 1, 2, you may have the coating film layer 5 only on one surface.

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

(High molecular polymer for forming the coating layer (C))
(Water dispersible polymer)
E1: Water-dispersed polyester resin having a carbonyl group and a carboxyl group (self-emulsifying type: “Vylonal MD-1930” manufactured by Toyobo Co., Ltd., resin solid content concentration 31 wt%).
E2: Water-dispersed polyester / polyurethane resin having a carbonyl group and a carboxyl group (self-emulsifying type: “WAC-15X” manufactured by Takamatsu Yushi Co., Ltd., resin solid concentration 20 wt%).
E3: Water-dispersed urethane resin having a carbonyl group and a carboxyl group (self-emulsifying type: “Evaphanol HA-107C” manufactured by Nikka Chemical Co., Ltd., resin solid content concentration 40 wt%).
E4: Water-dispersed urethane resin having a carbonyl group and a carboxyl group (self-emulsifying type: “Superflex 210” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., resin solid concentration 35 wt%).
E5: Water-dispersed urethane resin having a carboxyl group (self-emulsifying type: “Hydran CP-7050” manufactured by DIC Corporation, resin solid content concentration 25 wt%).
E6: Water-dispersed urethane resin having a carboxyl group (self-emulsifying type: “Ulliano W600” manufactured by Arakawa Chemical Industries, Ltd., resin solid content concentration 35 wt%).
E7: Water-dispersed acrylic resin having a carbonyl group and a carboxyl group (self-emulsifying type: “SE-953A-2” manufactured by Taisei Fine Chemical, resin solid content concentration: 39 wt%).

(Water-soluble polymer)
E8: Polyvinyl alcohol (saponification degree: 99.6%, polymerization degree 1700).
E9: Polyvinyl alcohol (saponification degree: 99.2%, polymerization degree 1000).

(Crosslinking agent)
F1: hydrazide compound (adipic acid dihydrazide).
F2: Carbodiimide compound (“Carbodilite V-02” manufactured by Nisshinbo Chemical Co., Ltd.).
F3; diisopropoxybis (acetylacetonato) titanium.
F4: Titanium lactate ammonium salt.

Preparation method of polyurethane resin layer (A1) forming composition (photochromic composition) Polycarbonate diol (1,5-pentane) having a number average molecular weight of 800 in a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube Polycarbonate diol using diol and hexanediol as raw materials) 252 g and isophorone diisocyanate 100 g were charged and reacted in a nitrogen atmosphere at 70 ° C. for 6 hours to obtain a prepolymer. Thereafter, 1000 ml of THF was added, 19 g of isophoronediamine was added dropwise under a nitrogen atmosphere, and the mixture was reacted at 25 ° C. for 1 hour after the completion of the dropwise addition.

  Next, 8 g of 4-amino-1,2,2,6,6-pentamethylpiperidine was added to the above solution under a nitrogen atmosphere, and a polyurethane resin was obtained by reacting at 25 ° C. for 1 hour.

  A photochromic composition was obtained by mixing and dissolving 18.5 g of the photochromic compound (PC1) shown below in the above solution.

Optical sheet or optical film (A2)
POLYCA: Polycarbonate sheet (thickness 0.4 mm).
PET: Polyethylene terephthalate sheet (thickness 0.3 mm).
-TAC: Triacetylcellulose sheet (thickness 0.3 mm).

Composition for forming synthetic resin layer (B) (polymerizable monomer) and method for producing photochromic lens using the same A photochromic laminate (A) having a coating layer (C), each having a circular shape with a diameter of 65 mm And placed in a glass mold having a gasket (set to 0.00D, lens diameter 70 mm, wall thickness 3.0 mm). A polymerizable monomer composition described below was poured into the glass mold, and was cured under the following conditions. Then, the outer periphery was polished with a ball grinder to obtain a photochromic lens having a diameter of 60 mm. In addition, Comparative Examples 1-3 used the photochromic laminated body (A) which does not have a coating-film layer (C).

[Allyl monomer composition and method for producing photochromic lens using the same]
As a polymerizable monomer composition, 3 parts by mass of diisopropyl peroxydicarbonate (polymerization initiator) and 100 parts by mass of diethylene glycol bisallyl carbonate were prepared.

  Next, the polymerizable monomer composition is injected above and below the photochromic laminate (A) having the coating layer (C) placed in the glass mold, and it takes 20 hours from 30 to 90 ° C. in an air furnace. The temperature was gradually raised and polymerization was carried out by maintaining at 90 ° C. for 1 hour. After the polymerization was completed, the gasket and the mold were removed, followed by heat treatment at 120 ° C. for 2 hours.

[Acrylic monomer composition and method for producing photochromic lens using the same]
A mixture of 20 parts by mass of trimethylolpropane trimethacrylate, which is a radically polymerizable monomer, 40 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 522, and 40 parts by mass of urethane acrylate (EBECRYL4858 manufactured by Daicel Chemical Industries) was prepared.

  Furthermore, with respect to 100 parts by mass of the radical polymerizable monomer, 1.0 part by mass of t-butyl peroxyneodecanate as a polymerization initiator was stirred and mixed to obtain a polymerizable monomer composition.

  Next, the polymerizable monomer composition is injected above and below the photochromic laminate (A) having the coating layer (C) installed in the glass mold, and polymerization is performed from 33 ° C. to 90 ° C. using an air furnace. After gradually raising the temperature over 17 hours, the temperature was maintained at 90 ° C. for 2 hours. After completion of the polymerization, the gasket and the mold were removed, and then placed in an oven and heated at 110 ° C. for 3 hours.

[Thiourethane monomer composition and method for producing photochromic lens using the same]
As a polymerizable monomer composition, 43.5 parts by mass of dicyclohexylmethane-4,4′-diisocyanate, 43.5 parts by mass of isophorone diisocyanate, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane 63 A mixture of 0.0 part by mass and 0.1 part by mass of dibutyltin dilaurate as a polymerization initiator was prepared.

  Next, the synthetic resin composition is injected on the top and bottom of the photochromic laminate having the coating layer (C) placed in the glass mold, and polymerization is carried out from 35 ° C. to 130 ° C. over 12 hours using an air furnace. After gradually raising the temperature, the temperature was maintained at 130 ° C. for 0.5 hour. After completion of the polymerization, the gasket and the mold were removed, and then placed in an oven and heated at 130 ° C. for 3 hours.

[Thioepoxy monomer composition and method for producing photochromic lens using the same]
As a polymerizable monomer composition, 95 parts by mass of bis (β-epithiopropylthio) ethane, 5 parts by mass of 2-mercaptoethanol, and tetrabutylammonium bromide 0. 1 part by weight of the mixture was prepared.

  Next, the synthetic resin composition is injected above and below the photochromic laminate having the coating layer (C) installed in the glass mold, and polymerization is performed using an air furnace for 20 hours from 20 ° C. to 90 ° C. After gradually raising the temperature, the temperature was maintained at 90 ° C. for 1 hour. After the polymerization was completed, the gasket and the mold were removed, and then placed in an oven and heated at 90 ° C. for 1 hour.

[Urethane monomer composition and method for producing photochromic lens using the same]
As a polymerizable monomer composition, 100 parts by mass of a polyester polyol having a number average molecular weight of 1000 consisting of adipic acid and 1,6-hexanediol, 78 parts by mass of an isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate), and aromatic As a diamine curing agent, 17 parts by mass of 2,4-diamino-3,5-diethyl-toluene / 2,6-diamino-3,5-diethyl-toluene was prepared.

  First, a mixture of the polyester polyol and an isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate) was heated at 140 ° C. for 10 minutes under dry nitrogen to produce a prepolymer. The prepolymer was cooled to 70 ° C. and left for 24 hours. Here, an aromatic diamine curing agent was mixed, poured into the top and bottom of the photochromic laminate (A) having the coating layer (C) placed in the glass mold, and cured at 120 ° C. for 10 hours. After the polymerization was completed, the gasket and the mold were removed and then placed in an oven and heated at 110 ° C. for 1 hour.

Example 1
(Formation of coating layer (C))
300 g of water-dispersed polyester resin (Toyobo Co., Ltd. “Vylonal MD-1930”), 60 g of methanol, 250 g of water, and 1 g of FZ-2104 (surfactant manufactured by Toray Dow Corning Co., Ltd.) are mixed and stirred. A film layer forming composition (A1-1) was obtained. This composition for forming a coating layer (A1-1) was applied to one surface of a polycarbonate sheet (optical sheet or optical film (A2): POLYCA) having a thickness of 0.4 mm and dried at 110 ° C. for 30 minutes. By curing, an optical sheet having a coating layer with a thickness of 5 μm was obtained.

Production of Photochromic Laminate (A) The photochromic composition obtained by the preparation method of the composition for forming the polyurethane resin layer (A1) is made of a PET film (Purex film manufactured by Teijin DuPont Films Ltd., with a silicon coating). And dried at 50 ° C. for 30 minutes to obtain a polyurethane resin layer (A1) having a thickness of about 40 μm. Subsequently, the obtained polyurethane resin layer (A1) was sandwiched between two POLYCA sheets (polycarbonate sheets) on which the coating layer (C) was formed by the above-described method, and left at 40 ° C. for 24 hours. Heat treatment was performed at 110 ° C. for 60 minutes. And the photochromic laminated body (A: (S1)) which has the target photochromic characteristic was obtained. The obtained photochromic laminate (A: (S1)) had the coating layer (C) only on the surface not in contact with the polyurethane resin layer (A1).

Production of Photochromic Lens A photochromic lens was produced according to the above method using the above-mentioned allylic monomer composition.

  When the obtained photochromic lens was evaluated, the color density as a photochromic characteristic was 1.1, the fading speed was 40 seconds, and the durability was 98%. In addition, peeling between each layer of the photochromic lens and color tone were evaluated by visual observation, but defects were seen in the initial stage, after the weather resistance test, after 1 hour after the boiling test, after 2 hours, and after 3 hours. There wasn't. These evaluations were performed as follows.

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

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

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

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

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

Visual evaluation Visual evaluation was performed from the following two viewpoints.

[Hagare]
The obtained photochromic lens had a plurality of interfaces, and the adhesion evaluation between the respective layers was performed visually. This adhesion evaluation was carried out after 1) initial stage, 2) the above-described deterioration promotion test (48 hours), and 3) boiling test with distilled water (1 hour, 2 hours, and 3 hours). The evaluation criteria are as follows.
0: No peeling is observed between the layers.
1; peeling is seen at least partially between the coating layer and the synthetic resin layer.
2; peeling is observed at least partially between the optical sheet and the polyurethane resin layer.

[Color tone]
The color tone of the obtained photochromic lens was implemented by visual evaluation using a condenser. The evaluation criteria are as follows.
0: No color defects such as white turbidity or yellowing are observed, and the transparency is high.
1: By applying a light collector, it is possible to confirm a slight color defect such as white turbidity, but there is no practical problem.
2; It is possible to confirm poor color tone such as cloudiness without applying a light collector.

Examples 2-24
Formation of coating layer (C) The coating layer forming composition shown in Table 1 (A1-1 to A1-9) and the optical sheet (A2) were used except that the method described in Example 1 was used. The coating layer (C) was formed on the surface (one side or both sides) of the optical sheet (A2). In the column of the laminated surface of the coating layer of Table 1, what was described as one side refers to what provided the coating layer only on the surface on which the synthetic resin layer of the optical sheet is laminated. Moreover, what was described as both surfaces refers to what provided the coating layer on both surfaces of the optical sheet.

Production of photochromic laminate (A) A polyurethane resin layer (A1) was produced in the same manner as in Example 1, and then the optical sheet having the coating layer (C) obtained above was used in Example 1. The photochromic laminated body (A: (S2)-(S20)) was obtained by the method similar to.

Production of Photochromic Lens A photochromic lens was produced in the same manner as in Example 1 except that the photochromic laminate (A) having the coating layer (C) shown in Table 2 and the synthetic resin layer (B) were used. The evaluation results of the obtained photochromic lens are shown in Table 2.

  In addition, regarding the curing conditions for obtaining each synthetic resin layer, it was carried out according to the above-mentioned `` Synthetic resin layer (B) formation (polymerizable monomer) composition and photochromic lens production method using the same '' did.

Comparative Examples 1-3
Production of photochromic laminate (A) A polyurethane resin layer (A1) was produced in the same manner as in Example 1, and the photochromic laminate (A) was prepared in the same manner as in Example 1 except that the optical sheet shown in Table 1 was used. : (S21) to (S23)). The obtained photochromic laminate (A: (S21) to (S23)) does not have the coating layer (C).

Production of Photochromic Lens A photochromic lens was produced in the same manner as in Example 1 except that the photochromic laminate (A) and the synthetic resin layer (B) shown in Table 2 were used. The evaluation results of the obtained photochromic lens are shown in Table 2.

  In addition, regarding the curing conditions for obtaining each synthetic resin layer, it was carried out according to the above-mentioned `` Synthetic resin layer (B) formation (polymerizable monomer) composition and photochromic lens production method using the same '' did.

Comparative Example 4
Formation of coating layer (C) 50 g of triethylene glycol dimethacrylate, 50 g of urethane oligomer hexaacrylate, and Irgacure 1870 (1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl) A coating layer forming composition (A1-10) was obtained by mixing and stirring 0.3 g of a mixture of phosphine oxide (weight ratio 3: 7) and Ciba Specialty Chemicals.

  This composition for forming a coating layer (A1-10) was applied to one surface of a 0.3 mm thick polyethylene terephthalate sheet (optical sheet or optical film (A2): PET), and manufactured by Fusion UV Systems. An optical sheet having a coating layer (C) with a film thickness of 6 μm was obtained by photocuring with F3000SQ (D bulb) for 1 minute.

Production of photochromic laminate (A) A polyurethane resin layer (A1) was produced in the same manner as in Example 1, and then the optical sheet having the coating layer (C) obtained above was used in Example 1. A photochromic laminate (A: (S24)) was obtained in the same manner as above. The obtained photochromic laminate (A: (S24)) had the coating layer (C) only on the surface not in contact with the polyurethane resin layer (A1) of the optical sheet (A2).

Production of Photochromic Lens A photochromic lens was produced in the same manner as in Example 1 except that the photochromic laminate (A) having the coating layer (C) shown in Table 2 and the synthetic resin layer (B) were used. The evaluation results of the obtained photochromic lens are shown in Table 2.

  In addition, regarding the curing conditions for obtaining each synthetic resin layer, it was carried out according to the above-mentioned `` Synthetic resin layer (B) formation (polymerizable monomer) composition and photochromic lens production method using the same '' did.

  As is clear from Examples 1 to 24, according to the present invention, a photochromic laminate obtained by sandwiching a polyurethane resin layer containing a photochromic compound using two optical sheets having a coating layer, It can be seen that by embedding in a transparent synthetic resin, a photochromic lens having excellent photochromic properties and adhesion can be obtained.

  On the other hand, when an optical sheet having no coating layer was used as in Comparative Examples 1 to 3, the photochromic characteristics were not problematic, but the adhesion was insufficient. Moreover, also in the comparative example 4, when a (meth) acrylic-type composition was used for the coating layer, although there was no problem in a photochromic characteristic, adhesiveness was inadequate.

DESCRIPTION OF SYMBOLS 1 Photochromic lens 2 Polyurethane resin layer (A1) containing a photochromic compound
3 Optical sheet or optical film (A2)
4 Photochromic laminate (A)
5 Coating layer (C)
6 Synthetic resin layer (B)

Claims (8)

A photochromic laminate (A) having a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other, and at least one of the optical sheets or optical films (A2) ) On which a synthetic resin layer (B) made of a thermosetting resin or a thermoplastic resin is formed ,
Between the optical sheet or optical film (A2) and the synthetic resin layer (B),
A photochromic lens comprising a coating layer (C) comprising at least one polymer polymer selected from a water-dispersible polymer, a cross-linked product of a water-dispersible polymer, and a cross-linked product of a water-soluble polymer.   2. The photochromic lens according to claim 1, wherein the coating layer (C) is a crosslinked product of a water-dispersible polymer obtained by reacting a water-dispersible polymer having a carbonyl group with a hydrazide compound.   2. The photochromic lens according to claim 1, wherein the coating layer (C) comprises a crosslinked body of a water-dispersible polymer obtained by reacting a water-dispersible polymer having a carboxyl group with a carbodiimide compound.   The photochromic lens according to claim 1, further comprising the coating layer (C) between the polyurethane resin layer (A1) and the optical sheet or optical film (A2). A method for producing the photochromic lens according to claim 1, comprising:
Including a step of forming a coating layer (C) made of a water-dispersible polymer by applying an aqueous dispersion in which the water-dispersed polymer is dispersed in water onto the optical sheet or optical film (A2) and drying. A method for producing a photochromic lens. A method for producing the photochromic lens according to claim 1, comprising:
After mixing an aqueous dispersion in which the water-dispersed polymer is dispersed in water or an aqueous solution in which the water-soluble polymer is dissolved in water, and a crosslinking agent that crosslinks these polymers, the resulting mixture is placed on the optical sheet or optical film (A2). A method for producing a photochromic lens, comprising a step of forming a coating layer (C) composed of a crosslinked product of a water-dispersible polymer or a crosslinked product of a water-soluble polymer by applying to a substrate and drying. A laminate for producing a photochromic lens,
At least one optical sheet or optical film (A2) of the photochromic laminate (A) having a polyurethane resin layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. on top of,
A laminate obtained by laminating a coating layer (C) made of at least one polymer selected from a water-dispersible polymer, a crosslinked water-dispersible polymer, and a crosslinked water-soluble polymer.   The laminate according to claim 7, further comprising the coating layer (C) between the optical sheet or optical film (A2) and the polyurethane resin layer (A1).

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