JP5762130B2 - Photochromic lens and manufacturing method thereof - 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 in which a photochromic laminate and a synthetic resin are bonded via a specific coating layer having excellent photochromic properties and adhesion.

  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 is 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, a method using a photochromic laminated body has been studied as a method capable of imparting photochromic properties at low cost without impairing the properties of a plastic material as a base material. In this photochromic laminate, first, a photochromic compound is dispersed in an adhesive polyurethane resin to form an adhesive sheet. Next, an optical sheet such as a polycarbonate resin can be laminated on the adhesive sheet.

  As a method for producing a photochromic lens using this photochromic laminate, a method of laminating a thermoplastic resin for lenses on the laminate by injection molding is known. In addition, a method of using a composition (hereinafter, sometimes referred to as “lens-forming monomer composition”) that is polymerized to become a thermosetting resin for a lens in that a functional lens can be easily produced. Is also known. This method is a method for producing a photochromic lens by embedding (immersing) the laminate in a lens-forming monomer composition and polymerizing the lens-forming monomer composition. This method of using a lens-forming monomer composition can produce a photochromic lens at a relatively low temperature. Various functions can be imparted to the lens by changing the type of monomer. For this reason, many studies have been made (for example, see Patent Documents 1 to 3).

  However, these conventional methods have room for improvement in the following points. For example, in the methods described in Patent Documents 1 and 2, the adhesiveness between the thermosetting resin (synthetic resin layer) serving as the base material and the optical sheet, and the adhesiveness between the optical sheet and the photochromic layer (adhesive sheet). There was a case that was not enough. Therefore, each layer may peel off after manufacturing the photochromic lens. Furthermore, depending on the material of the optical sheet used, chemical resistance is not sufficient, so when polymerizing the lens-forming monomer composition into a thermosetting resin (base material: synthetic resin layer), whitening, yellowing, etc. Appearance defects may occur.

  In order to solve such a problem, Patent Document 3 discloses a method of using a photochromic laminate having a coating layer on the surface. In this method, a thermosetting resin (synthetic resin layer) made of a polymerized (cured) body of the lens-forming monomer composition is formed on the coating layer. Patent Document 3 exemplifies a coating layer made of polyurethane (meth) acrylate and polyester (meth) acrylate.

  However, even in a photochromic lens provided with this coating layer, depending on the type of thermosetting resin (synthetic resin layer) or optical sheet, the adhesion between the thermosetting resin (synthetic resin layer) and the optical sheet is sufficient. There were cases where it was not improved. When the adhesiveness is not sufficient, particularly when the end face of the photochromic laminate is on the same plane as the end face of the thermosetting resin (synthetic resin layer), the photochromic lens itself may be peeled off.

  As described above, the conventional method using the photochromic laminate cannot sufficiently solve the problem that any interface of the plurality of formed layers peels off. When used in daily life, the photochromic lens may be left under high humidity or in contact with hot water. Even under such circumstances, the photochromic lens must maintain high adhesion at the interface between the layers. For this reason, it has been desired to develop a photochromic lens that maintains high photochromic properties, for example, has high adhesion between layers and does not have a problem of peeling even after being brought into contact with hot water.

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 synthetic resin layer made of a thermoplastic resin or thermosetting resin as a base material and an optical sheet or optical film. Furthermore, it is providing the photochromic lens excellent in transparency and a photochromic characteristic in addition to the characteristic of the said adhesiveness.

  Another object of the present invention is to provide a photochromic laminate in which the adhesion between the optical sheet or optical film and the polyurethane resin layer containing the photochromic compound is further improved.

  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, it was found that the above problem can be solved by using a coating layer made of a cured product of a curable composition containing a urethane urea resin (b1) having a polymerizable group in the molecule as the coating layer. The present invention has been completed.

That is, the present invention
A photochromic laminate (A) having a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other;
A photochromic lens having a coating layer (B) formed on at least one of the optical sheet or optical film (A2) and a synthetic resin layer (C) formed on the coating layer (B). And
The coating layer (B) is a silanol group or a hydrolyzable to group capable of forming a silanol group, possess (meth) acrylate group, an epoxy group, and a polymerizable group selected from a vinyl group in the molecule, said It is characterized by comprising a cured product of a curable composition containing a urethane urea resin (b1) containing 2 to 30 polymerizable groups in one molecule and 2 to 50 urea bonds in one molecule. It is a photochromic lens.

  The curable composition of the present invention has a polymerizable group having a polymerizable group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. A monomer (b2) can also be included.

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

Another aspect of the present invention is a method for producing the photochromic lens, wherein the polymerizable group is selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. was closed in the molecule, the polymerization of the polymerizable groups 2 to 30 contained in one molecule, and a curable composition containing a urethane urea resin (b1) present 2-50 urea bond per molecule The production of a photochromic lens comprising a step of forming a coating layer (B) comprising a cured product of the curable composition by applying and curing on an optical sheet or an optical film (A2). Is the method.

In another aspect of the invention, at least one of the optical sheets of the photochromic laminate (A) having a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. or on the optical film (A2), a silanol group or a hydrolyzable to group capable of forming a silanol group, have a (meth) acrylate group, a polymerizable group selected from epoxy groups and vinyl groups, polymerizable groups A coating layer (B) comprising a cured product of a curable composition containing a urethane urea resin (b1) containing 2 to 30 per molecule and 2 to 50 urea bonds per molecule It is the laminated body which has.

  The photochromic lens of the present invention is a synthetic resin layer serving as a base material by providing a coating layer (B) made of a cured product of a curable composition containing a urethane urea resin (b1) having a polymerizable group in the molecule. And the adhesiveness with an optical sheet or an optical film (A2) can be improved. Furthermore, by providing the coating layer (B) between the optical sheet or optical film (A2) and the polyurethane adhesive layer (A1) containing the photochromic compound, the adhesion between the two can be further improved. Can do.

  Therefore, the photochromic lens of the present invention has excellent photochromic characteristics and can be used for a long time.

  Furthermore, the photochromic laminate (laminate) having the coating layer is excellent in solvent resistance. Therefore, in the case of producing a photochromic lens by embedding (immersing) a photochromic laminate (laminate) having the coating layer in a lens-forming monomer composition to be a thermosetting resin (base material), It can prevent that an optical sheet or an optical film elutes in the monomer composition for lens formation. As a result, a transparent photochromic lens free from white turbidity can be obtained. In addition, by using a photochromic laminate (laminate) having the coating layer, a photochromic lens can be produced 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 is
A photochromic laminate (A) having a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other;
A photochromic lens having a synthetic resin layer (C) on at least one surface of the optical sheet or optical film (A2),
A coating film comprising a cured product of a curable composition containing a urethane urea resin (b1) having a specific polymerizable group in the molecule between the optical sheet or optical film (A2) and the synthetic resin layer (C). It is a photochromic lens characterized by having a layer (B).

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

Photochromic laminate (A)
The photochromic laminate (A) has a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. 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 adhesive layer. It means both adhesiveness between (A1) and the optical sheet or optical film (A2). First, the polyurethane adhesive layer (A1) constituting the photochromic laminate (A) will be described.

Polyurethane adhesive layer containing photochromic compound (A1)
(Polyurethane resin constituting the polyurethane adhesive layer (A1))
In this invention, the polyurethane resin used for the polyurethane contact bonding 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, there is no particular limitation as long as it is a resin that exists between two optical sheets or optical films (A2) facing each other and can bond both. The polyurethane resin may be a thermosetting polyurethane or a thermoplastic polyurethane.

  The polyurethane resin used for the polyurethane adhesive layer (A1) 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 adhesive 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. Further, the reaction can be carried out in an organic solvent such as tetrahydrofuran (THF) or dimethylformamide (DMF). 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 adhesive layer (A1) containing the photochromic compound. At this time, an organic solvent such as tetrahydrofuran (THF) or propylene glycol monomethyl ether can be used for viscosity adjustment.

(Photochromic compound)
Next, the photochromic compound contained in the polyurethane adhesive 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. Specifically, JP2001-031670, JP2001-011067, JP2001-011066, JP2000-344761, JP2000-327675, JP2000-256347, JP2000. -229976, JP-A-2000-229975, JP-A-2000-229974, JP-A-2000-229993, JP-A-2000-229972, JP-A-2000-219678, JP-A-2000-219686, JP-A-11- No. 322739, JP-A No. 11-286484, JP-A No. 11-279171, JP-A No. 09-218301, JP-A No. 09-124645, JP-A No. 08-295690, JP-A No. 08-176139, JP-A No. 08-157467. No., US Pat. No. 5,645,767, US Pat. No. 5, No. 58501, U.S. Pat. No. 5,961,892, U.S. Pat. No. 6,296,785, Japanese Patent No. 42494981, Japanese Patent No. 4424962, WO2009 / 136668, WO2008 / 023828, Japanese Patent No. 4369754 Gazette, Japanese Patent No. 4301621, Japanese Patent No. 4256985, pamphlet of WO2007 / 086532, JP2009-120536, JP2009-67754, JP2009-67680, JP2009-57300A. No. 4, Japanese Patent No. 4195615, Japanese Patent No. 41588881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent No. 4157227, Japanese Patent No. 41 No. 8458, JP 2008-74832 A, Japanese Patent No. 3982770, Japanese Patent No. 3801386, WO 2005/028465 pamphlet, WO 2003/042203 pamphlet, JP 2005-289812 A, JP 2005-289807 A. , JP 2005-112772, Japanese Patent No. 3522189, WO 2002/090342 pamphlet, Japanese Patent No. 3471703, JP 2003-277181, WO 2001/060811 pamphlet, WO 00/71544 pamphlet, etc. Has been.

  Among these photochromic compounds, one kind of chromene compound having an indenonaft “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 the above.

Method for Forming Polyurethane Adhesive Layer (A1) Containing Photochromic Compound In the present invention, the polyurethane adhesive 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. Therefore, it is preferable that a polyurethane contact bonding layer (A1) contains 1 to 10 mass parts of photochromic compounds per 100 mass parts of polyurethane resins.

  In addition, a known additive can be blended with the photochromic composition in order to improve the durability of the polyurethane adhesive layer (A1) to be formed, to improve the color development speed, to improve the fading speed, and to form a film. . Specific additives include surfactants, hindered amine light stabilizers, hindered phenol antioxidants, phenolic radical scavengers, sulfur antioxidants, phosphorus antioxidants, UV stabilizers, UV absorbers Agents, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers and the like. 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 in the range of 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 polyurethane adhesive layer (A1) and the optical sheet. Specific examples of the adhesive include terpene resins, terpene phenol resins, phenol resins, hydrogenated terpene resins, rosin resins, xylene resins, acrylic adhesives, silicone adhesives, urethane adhesives, and the like.

  In addition, the photochromic composition is blended with inorganic oxide fine particles and organic / inorganic composite materials for the purpose of improving the heat resistance of the polyurethane adhesive layer and reducing the solubility in the monomer composition for lens formation. You can also. Examples of the inorganic oxide fine particles include metal sols such as silica sol and composite oxide sol dispersed in an organic solvent such as methanol, methyl ethyl ketone, and propylene glycol monomethyl ether. Examples of organic / inorganic hybrid materials include silica / melamine hybrid materials, silica / urethane hybrid materials, silica / acrylic hybrid materials, silica / epoxy resin hybrid materials, and the like.

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

  In the present invention, the thickness of the polyurethane adhesive 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 adhesive layer (A1). Next, the optical sheet or optical film (A2) will be described.

Optical sheet or optical film (A2)
The optical sheet or optical film (A2) used in the present invention is a light-transmitting sheet or film. 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. In addition, a polarizing film (for example, a polarizing film made of polyvinyl alcohol sandwiched between triacetyl cellulose resin films) can also be used as an optical film (sheet). 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. A particularly preferable polycarbonate resin is a resin 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 (A2) used in the present invention may be modified by a known method. For example, in order to further improve the adhesion to the polyurethane adhesive layer (A1), a material whose surface has been modified can be used. 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.

  In the present invention, the two optical sheets or optical films (A2) facing each other may be sheets or films made of the same resin, or sheets or films made of different resins. In particular, when the polarizing film is used, the other optical sheet or optical film facing each other is preferably an optical sheet or optical film having other types of transparency.

  The thickness of the optical sheet or optical film (A2) used in the present invention is usually 50 μm to 1 mm, and particularly preferably 0.1 mm to 0.5 mm. When the thickness is less than 50 μm, when the photochromic laminate (A1) is embedded (immersed) in the lens-forming monomer composition and the composition is cured, the optical sheet or film may be distorted. On the other hand, when the thickness of the optical sheet or the optical film (A2) exceeds 1 mm, the resulting photochromic lens becomes thick, which may be unsuitable for glasses use. Moreover, curved surface processing may be difficult.

  In this optical sheet or optical film (A2), the coating layer (B) is laminated on the surface in contact with the synthetic resin layer (C). Moreover, you may laminate | stack a coating-film layer (B) on the surface which the said polyurethane resin layer (A1) touches as needed. Next, the manufacturing method of the photochromic laminated body (A) which has this optical sheet or optical film (A2) is demonstrated.

Production method of photochromic laminate (A) The photochromic laminate (A) used in the present invention is a polyurethane adhesive 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 adhesive layer (A1) may be used. For example, the photochromic composition is directly laminated on the optical sheet or optical film (A2) to form a polyurethane adhesive layer (A1), and another optical layer is formed on the surface of the polyurethane adhesive 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 adhesive 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. First, 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 adhesive layer (A1) is separated from the substrate. Next, the optical sheet or the optical film (A2) is laminated on both surfaces of the obtained polyurethane adhesive layer (A1). In this case, as a smooth base material having high solvent resistance, a film obtained by previously laminating the coating layer (B) on the optical sheet or optical film (A2) in contact with the polyurethane adhesive layer (A1) can also be used. The coating layer (B) described in detail below is excellent in solvent resistance. Therefore, for example, what laminated | stacked the coating-film layer (B) 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 (B) as an optical sheet or an optical film (A2), the production process of the photochromic laminate (A) can be simplified.

  By adopting any of the above methods, the polyurethane adhesive layer (A1) can be formed, and the photochromic laminate (A) can be produced. In the polyurethane adhesive layer (A1), a polyurethane resin as a main component functions as an adhesive. Therefore, the photochromic laminate (A) produced by the above method can be used for production of a photochromic lens as it is. However, after laminating the optical sheet or the optical film (A2) on both surfaces of the polyurethane adhesive 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. or higher and 130 ° C. or lower for 30 minutes or longer and 3 hours or shorter (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 (C) on at least one surface of a photochromic laminate (A) obtained by such a method. And the coating film which consists of a hardening body of the curable composition containing the urethane urea resin (b1) which has a specific polymeric group in a molecule | numerator between this photochromic laminated body (A) and a synthetic resin layer (C). It has a layer (B). Next, the coating layer (B) will be described.

Coating layer (B)
In the photochromic lens of the present invention, the coating layer (B) is necessarily interposed between the optical sheet or optical film (A2) and the synthetic resin layer (C) described in detail below. And this coating-film layer (B) consists of a hardening body of the curable composition containing the urethane urea resin (b1) which has a specific polymeric group in a molecule | numerator.

  In the present invention, the urethane urea resin is an organic polymer having a urea bond in its molecule. The urethane urea resin (b1) used in the present invention is an organic polymer having a urea bond and having a polymerizable group described in detail below. By forming the coating layer (B) from the curable composition containing this urethane urea resin (b1), the adhesion to various optical sheets or optical films (A2) can be improved. Therefore, a photochromic lens having an excellent effect can be obtained.

  Next, the curable composition for forming this coating film layer (B) is demonstrated.

Curable composition The curable composition used by this invention contains the urethane urea resin (b1) which has a specific polymeric group in a molecule | numerator. First, the urethane urea resin (b1) will be described.

Urethane urea resin (b1) having a specific polymerizable group in the molecule
The polymerizable group of the urethane urea resin (b1) used in the present invention is a silanol group or a group that can be hydrolyzed to form a silanol group (a group that undergoes polycondensation), a (meth) acrylate group, an epoxy group, and vinyl. It is a group selected from groups. Hereinafter, these groups may be collectively referred to as “polymerizable group”. The group that can be hydrolyzed to form a silanol group is an alkoxysilyl group or the like. The (meth) acrylate group refers to an acrylate group or a methacrylate group.

  In the prior art, polyurethane (meth) acrylate and polyester (meth) acrylate are coated on an optical sheet and polymerized and cured to form a coating layer. However, the polyurethane (meth) acrylate and polyester (meth) acrylate used in the prior art have room for improvement in terms of solvent resistance and adhesion of the coating layer to be formed.

  On the other hand, in the present invention, a urethane urea resin (b1) having a specific polymerizable group in the molecule and having a urea bond is used. Therefore, it exhibits an excellent effect. The polymerizable group is polymerized to form a crosslinked structure when the coating layer (B) is formed. The urethane urea resin (b1) contains a urea bond having high cohesive strength in the molecule. As a result, the laminate having a coating layer (B) made of a cured product of the curable composition containing the urethane urea resin (b1) has improved solvent resistance and further improved adhesion. Conceivable.

The urethane urea resin (b1) is not particularly limited, but is preferably produced by the following method. Specifically, from the viewpoint of solvent resistance and adhesion,
(B1-1) a polyol compound having two or more hydroxyl groups in the molecule and having a number average molecular weight of 400 to 3,000 (hereinafter also simply referred to as component (b1-1)),
(B1-2) a polyisocyanate compound having two or more isocyanate groups in the molecule (hereinafter also simply referred to as component (b1-2)),
(B1-3) The molecule has a group that reacts with two or more isocyanate groups in the molecule, and at least one of them is an amino group (—NH ₂ group or —NH (R)). An amino group-containing compound having a molecular weight of 50 to 300 (hereinafter also simply referred to as the component (b1-3)),
(B1-4) A compound having a group capable of reacting with one or two isocyanate groups in the molecule and having the polymerizable group in the molecule (hereinafter also simply referred to as component (b1-4). ) Is preferably reacted. By using this component (b1-3), a urethane urea resin having a urea bond in the molecule can be produced. Moreover, the urethane-urea resin (b1) which has a polymeric group in a molecule | numerator can be manufactured by using a (b1-4) component.
Hereinafter, these components will be described.

(B1-1) Component: Polyol Compound The (b1-1) component is a compound having two or more hydroxyl groups in the molecule. The number of hydroxyl groups is preferably 2 to 6 in the molecule, particularly preferably 2. Moreover, it is preferable that the number average molecular weights of (b1-1) component are 400-3000. The component (b1-1) is a polymer, and therefore the molecular weight is represented by a number average molecular weight. From the viewpoint of solvent resistance and adhesion of the obtained b1 component, the number average molecular weight is preferably 400 to 2500, and more preferably 400 to 1500.

  As the component (b1-1), a known polyol compound can be used without any limitation. Specifically, it is preferable to use polyol compounds such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, and polyester polyol. These may be used alone or in combination of two or more. Among these, polycarbonate polyol and polycaprolactone polyol are preferably used from the viewpoints of heat resistance, adhesion, weather resistance, hydrolysis resistance, and the like.

  Examples of the polycarbonate polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, diethylene glycol Propylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene Glycol, glycerin Polycarbonate polyols obtained by phosgenation of one or more low molecular polyols such as trimethylolpropane and pentaerythritol, polycarbonate polyols obtained by transesterification with ethylene carbonate, diethyl carbonate, and diphenyl carbonate, etc. Can do.

  In addition, examples of the polycaprolactone polyol include compounds obtained by ring-opening polymerization of ε-caprolactone.

The polyol compound can be obtained as a reagent or industrially. Examples of commercially available products include polyether polyols such as “EXCENOL (registered trademark)” series, “EMALSTER (registered trademark)” manufactured by Asahi Glass Co., Ltd., and “ADEKA polyether” series manufactured by ADEKA Corporation;
"Duranor (registered trademark)" series manufactured by Asahi Kasei Chemicals Corporation, "Kuraray polyol (registered trademark)" series manufactured by Kuraray Co., Ltd., "Placcel (registered trademark)" series manufactured by Daicel Chemical Industries, Ltd., " Polycarbonate polyols such as “Nipporan (registered trademark)” series and “ETERNACOLL (registered trademark)” series manufactured by Ube Industries, Ltd .;
Polycaprolactone polyols such as “Placcel (registered trademark)” series manufactured by Daicel Chemical Industries, Ltd .;
Examples include polyester polyols such as "Polylite (registered trademark)" series manufactured by DIC Corporation, "Nipporan (registered trademark)" series manufactured by Nippon Polyurethane Industry Co., Ltd., and "Maximol (registered trademark)" series manufactured by Kawasaki Kasei Kogyo Co., Ltd. It is done.

(B1-2) Component: Polyisocyanate Compound The (b1-2) component is a compound having two or more isocyanate groups in the molecule. The number of isocyanate groups is preferably 2-6 in the molecule, and more preferably 2-3. As the “(b1-2) component“ polyisocyanate compound having two or more isocyanate groups in the molecule ”, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, and these A mixture is mentioned. Among these, from the viewpoint of weather resistance, it is preferable to use at least one polyisocyanate compound selected from an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound.

  In the polyisocyanate compound (b1-2) component, the number of isocyanate groups contained in the molecule may be two or more. As the polyisocyanate compound that can be suitably used as the component (b1-2), 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-diisocyanate Isocyanate, alicyclic polyisocyanate compounds such as hexahydroterephthalic phenylene-1,4-diisocyanate can be mentioned, in particular isophorone diisocyanate, are preferably used norbornene diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

  The polyisocyanate compound may be a compound having the following polymerizable group in the molecule. This polymerizable group is a group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. The polymerizable group may be a silanol group, but the silanol group reacts with an isocyanate group and becomes difficult to control. Therefore, a group that can be hydrolyzed to form a silanol group, such as an alkoxysilyl group. It is preferable that

  The polyisocyanate compound having a polymerizable group in the molecule, for example, a diisocyanate compound can be produced by the following method. Taking a diisocyanate compound having a group that can be hydrolyzed to form a silanol group as an example, a method for producing the compound will be described. Specifically, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanate) hexanoate, 1-methyl Benzene-2,4,6-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, etc. A triisocyanate compound having three isocyanate groups in the molecule, and a group capable of reacting with one isocyanate group in the molecule such as a compound represented by the following general formula (1) (amino group, hydroxyl group, carboxyl group, or thiol) Group) and a compound having a group that can be hydrolyzed to form a silanol group. Bayoi.

  In addition, the b1 component which has a polymeric group is compoundable by using the diisocyanate compound which has the above polymerizable groups as a (b1-2) component. Therefore, when the diisocyanate compound having a polymerizable group is used as the component (b1-2), the component (b1-4) (polymerizable group-imparting compound) described in detail below may be used or used. You don't have to.

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

Component (b1-3): Amino group-containing compound The amino group-containing compound has a group that reacts with two or more isocyanate groups in the molecule, and at least one of them has an amino group (-NH2 group, or -NH (R)), which is a compound having a molecular weight of 50 to 300. The number of groups that react with isocyanate groups in the molecule is 2 to 4, and the number of amino groups is preferably 1 to 2, and particularly preferably only 2 amino groups. Since the amino group-containing compound is not a polymer, the molecular weight refers to the molecular weight of the amino group-containing compound itself.

  The component (b1-3) functions as a chain extender when the urethane urea resin (b1) is synthesized. By using the component (b1-3), it is possible to control the molecular weight and urea bond amount of the urethane urea resin (b1). When the molecular weight of the amino group-containing compound is less than 50, the resulting urethane urea resin (b1) tends to be hard and the adhesiveness tends to decrease. On the other hand, when the molecular weight of the amino group-containing compound exceeds 300, the resulting urethane urea resin (b1) tends to be too soft. For this reason, the solvent resistance of the obtained coating layer tends to be lowered. From the above, the molecular weight of the amino group-containing compound is more preferably 50 to 250, and most preferably 55 to 200.

  The component (b1-3) is at least one amino group-containing compound selected from diamine compounds, triamine compounds, amino alcohol compounds, aminocarboxylic acid compounds, and aminothiol compounds. The amino group-containing compound has a group that reacts with at least two isocyanate groups in the molecule, at least one of which is an amino group (—NH 2 group and —NH (R) group, and R is a substituted group. Group) and a reactive group with an isocyanate group other than an amino group is a hydroxyl group (—OH group), a mercapto group (—SH group: thiol group), a carboxyl group [—C (═O) OH group], or It is an acid chloride group [—C (═O) OCl group].

  (B1-3) Examples of compounds suitably used as the amino group-containing compound of the component include diamine compounds and triamine compounds such as isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine , Bis- (4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornenediamine, hydrazine, adipic acid diacid Hydrazine, phenylenediamine, 4,4'-diphenylmethanediamine, N, N ' Diethylethylenediamine, N, N′-dimethylethylenediamine, N, N′-dipropylethylenediamine, N, N′-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis (hexamethylene) triamine, 1,2,5 -A pentanetriamine etc. can be mentioned.

  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.

  The above amino group-containing compounds may be used alone or in combination of two or more.

  By using the amino group-containing compound, a urethane urea resin (b1) having a urea bond can be produced. And as for the coating-film layer (B) which consists of a hardening body of the curable composition containing the obtained urethane urea resin (b1), solvent resistance and adhesiveness improve.

  In addition to the amino group-containing compound, a compound capable of introducing a polymerizable group such as the following general formulas (5), (6), (7), and (8) into the side chain is used as the chain extension of the present invention. It can also be used as an agent. When the compound capable of introducing a polymerizable group described below into the side chain contains an amino group as a group capable of reacting with an isocyanate group, it can be used as the amino group-containing compound as it is or when it does not contain an amino group Is preferably used in combination with the amino group-containing compound. Further, when a chain extender having a polymerizable group as described above is used as the component (b1-3), the component (b1-4) (polymerizable group-imparting compound) described in detail below may be used. Good or not used.

(B1-4) component: a compound having a group capable of reacting with one or two isocyanate groups in the molecule and having a polymerizable group (polymerizable group-providing compound))
This invention improves the crosslink density of the hardening body which hardened the curable composition containing this urethane urea resin (b1) by using the urethane urea resin (b1) which has a polymeric group in a molecule | numerator. Can do. Therefore, while being able to improve the solvent resistance of the coating layer (B) which consists of this hardening body, adhesiveness with an optical sheet (A2) can also be improved.

  The component (b1-4) is a compound having a group capable of reacting with one or two isocyanate groups in the molecule and having a polymerizable group (polymerizable group-imparting compound). Examples of the group capable of reacting with the isocyanate group include an amino group (—NH 2 group), a hydroxyl group (—OH group), a mercapto group (—SH group), a carboxyl group [—C (═O) OH group], and an acid chloride. Selected from the group [—C (═O) OCl group].

The polymerizable group is a group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. The component C1-4 can introduce a polymerizable group into the urethane urea resin (b1) by having at least one polymerizable group in the molecule. Hereinafter, various compounds used as the component (b1-4) will be described in detail.
First, the compound which can introduce | transduce a polymeric group into the terminal of urethane urea resin (b1) is demonstrated.

(Polymerizable group-providing compound capable of introducing a polymerizable group at the terminal (component b1-4))
(Polymerizing compound that introduces a silanol group or a group that can be hydrolyzed to form a silanol group)
Examples of this compound include compounds represented by the following general formula (1).

(Where
R1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R2 is an alkyl group having 1 to 5 carbon atoms,
R3 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms,
T is a group capable of reacting with an isocyanate group,
m is an integer of 1-3. ).

  In the said General formula (1), R1 is a hydrogen atom or a C1-C5 alkyl group. Particularly preferred is a methyl group or an ethyl group.

  R2 is an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group.

  R3 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, and preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms.

  T is a group capable of reacting with an isocyanate group, and is an amino group, a hydroxyl group, a carboxyl group, or a thiol group. Of these, an amino group is preferred from the viewpoints of reactivity with an isocyanate group and availability.

  m is an integer of 1 to 3, and is preferably 2 or 3 because the crosslinking density of the cured product obtained by curing the curable composition containing the urethane urea resin (b1) is improved.

If the compound shown by the said General formula (1) is illustrated,
Aminomethyltrimethoxysilane, aminomethyltriethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxy Aminoalkyltrialkoxysilanes such as silane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane; β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane (Aminoalkyl) alkyl dialkoxysilanes such as γ-aminopropylmethyldiethoxysilane and γ-aminopropylmethyldipropoxysilane and aminoalkyldialkyl corresponding to these (mono Such as alkoxysilanes.

  Also, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Mercaptoalkyltrialkoxysilanes such as tripropoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane; β-mercaptoethylmethyldimethoxysilane, β-mercaptoethylmethyldiethoxysilane, γ-mercaptopropylmethyl (Mercaptoalkyl) al such as dimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylmethyldipropoxysilane Such distearate alkoxysilane and mercaptoalkyl dialkyl (mono) alkoxysilanes corresponding to these.

(Polymerization-imparting compound (b1-4) component introducing a (meth) acrylate group at the end)
Examples of this compound include compounds represented by the following general formula (2).

(Where
R4 is a hydrogen atom or a methyl group,
R5 is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
Q is a group capable of reacting with an isocyanate group. ).

  In the general formula (2), R4 is a hydrogen atom or a methyl group.

  R5 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms.

Q is a group capable of reacting with an isocyanate group, and examples thereof include an amino group, a hydroxyl group, a carboxyl group, and a thiol group. From the viewpoint of stability of the compound, Q is preferably a hydroxyl group. For example, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol monoacrylate and other acrylic ester monools; 2-hydroxyethyl methacrylate Methacrylic acid ester monools such as 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and 1,6-hexanediol monomethacrylate.

(Polymerizable group-imparting compound (b1-4) component introducing an epoxy group at the end)
Examples of this compound include compounds represented by the following general formula (3).

(Where
R6 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, n is an integer of 0 to 3, and U is a group capable of reacting with an isocyanate group. ).

  In the general formula (3), R6 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. It is a polymethylene group.

  n is an integer of 0 to 3, and is preferably an integer of 0 or 1. In particular, when n is 0, U is directly bonded to the methylene group.

  U is a group capable of reacting with an isocyanate group, and is an amino group, a hydroxyl group, a carboxyl group, or a thiol group, and is preferably a hydroxyl group from the viewpoint of availability.

  The compound represented by the general formula (3) can be synthesized, for example, by a reaction between a divalent alcohol and epichlorohydrin. The synthesis method according to the present invention is not particularly limited, but in any synthesis, 1 mol of epichlorohydrin is bonded to 1 mol of divalent alcohol. In the reaction of a dihydric alcohol and epichlorohydrin, a corresponding by-product is produced, which can be isolated by conventional separation methods.

  Examples of the compound represented by the general formula (3) include glycidol, butanediol monoglycidyl ether, hexanediol monoglycidyl ether, cyclohexanedimethanol glycidyl ether, and the like.

(Polymerization-imparting compound (b1-4) component introducing a vinyl group at the terminal)
Examples of this compound include compounds represented by the following general formula (4).

(Where
R7 is an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
V is a group capable of reacting with an isocyanate group. ).

  In the general formula (4), R7 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. It is a polymethylene group.

  V is a group capable of reacting with an isocyanate group, and is an amino group, a hydroxyl group, a carboxyl group, or a thiol group.

  Examples of the compound represented by the general formula (4) include allyl alcohol.

  Next, the compound which can introduce | transduce a polymeric group into the side chain of urethane urea resin (b1) is demonstrated.

(Polymerization-imparting compound (b1-4) component capable of introducing a polymerizable group into the side chain)
(Silanol group or polymerizable component (b1-4) component that introduces a group capable of forming a silanol group by hydrolysis into a side chain)
As this compound, the compound shown by following General formula (5) or (6) can be mentioned.

(Where
R8 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R9 is an alkyl group having 1 to 5 carbon atoms,
R10 and R11 are each an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms,
p is an integer of 1 to 3. ).

  In the said General formula (5), R8 is a hydrogen atom or a C1-C5 alkyl group. Particularly preferred is a methyl group or an ethyl group.

R9 is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.
R10 and R11 are an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms.

  p is an integer of 1 to 3, and is preferably 2 or 3 because the crosslink density of the coating layer formed from the urethane-urea resin (C1) is improved.

Examples of the compound represented by the general formula (5) include N-β such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane and N-β (aminoethyl) -γ-aminopropyltriethoxysilane. (Aminoalkyl) aminoalkyltrialkoxysilane,
Examples include N- (aminoalkyl) aminoalkylalkyldialkoxysilanes such as N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane.

(Where
R12 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R13 is an alkyl group having 1 to 5 carbon atoms,
R14, R15, R16, and R17 are each an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
q is an integer of 1 to 3, W is —O (C═O) NH—, or —NH (C═O) NH—,
X is a group capable of reacting with isocyanate. ).

  In the said General formula (6), R12 is a hydrogen atom or a C1-C5 alkyl group. Particularly preferred is a methyl group or an ethyl group.

R13 is an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.
R14, R15, R16 and R17 are an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. It is a group.

  q is an integer of 1 to 3, and is preferably 2 or 3 because the crosslink density of the coating layer formed from the urethane-urea resin (C1) is improved.

  W is —O (C═O) NH— or —NH (C═O) NH—, and is formed by the reaction of an isocyanate group with a hydroxyl group or an amino group.

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

  The compound represented by the general formula (6) includes a compound (trivalent alcohol or trivalent amine) having a group capable of reacting with three isocyanate groups in the molecule, and an isocyanate group and hydrolysis in the molecule. And a compound having a group capable of forming a silanol group (an alkoxysilane compound having an isocyanate group). The compound is a compound 1 having an isocyanate group and a silanol group in the molecule or a group capable of forming a silanol group by hydrolysis with respect to 1 mol of the compound having a group capable of reacting with three isocyanate groups in the molecule. It is obtained by reacting moles.

  Compounds having a group capable of reacting with three isocyanate groups in the molecule include trivalent alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol; 2,2 ', 2 "-tri Examples include trivalent amines such as aminotriethylamine and 4-aminomethyloctane-1,8-diamine, etc. Examples of compounds having a group capable of hydrolyzing with an isocyanate group to form a silanol group in the molecule include 3-isocyanate. Examples thereof include propyltriethoxysilane.

(Polymerization-imparting compound (b1-4) component for introducing (meth) acrylate group into side chain)
Examples of this compound include compounds represented by the following general formula (7).

(Wherein R18 is a hydrogen atom or a methyl group,
R19, R20, R21, and R22 are each an alkylene group having 1 to 20 carbon atoms, or a polymethylene group having 3 to 20 carbon atoms,
s is an integer of 0 or 1,
Y is —O (C═O) NH—, or —NH (C═O) NH—,
M is a group capable of reacting with isocyanate. ).

  In the general formula (7), R18 is a hydrogen atom or a methyl group.

  R19, R20, R21, and R22 are each an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, or 3 carbon atoms. To 10 polymethylene groups.

  s is 0 or an integer of 1, and when s is 0, R19 and R20 are directly bonded.

  Y is —O (C═O) NH—, and is formed by a reaction between an isocyanate group and a hydroxyl group.

  M is a group capable of reacting with an isocyanate group, and examples thereof include an amino group, a hydroxyl group, a carboxyl group, and a thiol group. From the viewpoint of stability of the compound, M is preferably a hydroxyl group.

  Examples of the compound represented by the general formula (7) include a reaction product of a trivalent alcohol and (meth) acrylic acid, or a compound having an isocyanate group and a (meth) acrylate group in the molecule. The compound can be obtained by reacting 1 mol of trivalent alcohol with 1 mol of (meth) acrylic acid or a compound having an isocyanate group and a (meth) acrylate group in the molecule.

  Examples of the trivalent alcohol used include glycerin, trimethylolpropane, 1,2,6-hexanetriol and the like. Examples of the compound having an isocyanate group and a (meth) acrylate group in the molecule to be used include 2-methacryloyloxyethyl isocyanate.

(Polymerization compound that introduces an epoxy group into the side chain)
Examples of this compound include compounds represented by the following general formula (8).

(Where
R23, R24, and R25 are each an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms,
Z is a group that reacts with an isocyanate group. )
In the general formula (8),
R23, R24 and R25 are each an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms or a polymethylene group having 3 to 10 carbon atoms. It is a group.

  Z is a group capable of reacting with an isocyanate group, and is an amino group, a hydroxyl group, a carboxyl group, or a thiol group, and is preferably a hydroxyl group from the viewpoint of availability.

  The compound represented by the general formula (8) can be synthesized by a reaction between a trivalent alcohol and epichlorohydrin. The compound can be obtained by reacting 1 mol of epichlorohydrin with 1 mol of a trivalent alcohol. In the reaction of a trivalent alcohol with epichlorohydrin, a corresponding by-product is produced, which can be isolated by a conventional separation method. Examples of the trivalent alcohol used for synthesizing a compound capable of introducing an epoxy group into the urethane polymer side chain include glycerin, trimethylolpropane, 1,2,6-hexanetriol and the like.

  By using the component (b1-4) as described above, a urethane urea resin (b1) having a polymerizable group is obtained. This (b1-4) component is a urethane urea resin (b1) for the purpose of improving the solvent resistance and adhesion of the coating layer (B) comprising a cured product of the curable composition containing the urethane urea resin (b1). ) At both the molecular end and the side chain.

  Next, the production method of the urethane urea resin (b1), the blending ratio of each component, and the characteristics will be described.

(Production method, proportion of each component, characteristics of urethane urea resin (b1))
When the urethane urea resin (b1) is obtained by reacting the component (b1-1), the component (b1-2), the component (b1-3), and the component (b1-4), Similarly, a known one-shot method or a prepolymer method can be employed.

The amount ratio of the (b1-1) component, (b1-2) component, (b1-3) component, and (b1-4) component used for the reaction is such that the resulting urethane urea resin (b1) is a polymerizable group, And the ratio should have a urea bond. Especially, it is preferable to set it as the following quantitative ratios from a viewpoint of the solvent resistance of the coating film layer (B) formed, and adhesiveness. The amount ratio of (b1-1) component, (b1-2) component, (b1-3) component, and (b1-4) component is
The total number of moles of “group capable of reacting with an isocyanate group” (specifically, a hydroxyl group) contained in the component (b1-1) is n1,
The total number of moles of isocyanate groups contained in the component (b1-2) is n2,
The total number of moles of the group capable of reacting with the isocyanate group contained in the component (b1-3) is n3,
When the total number of moles of the group capable of reacting with the isocyanate group contained in the component (b1-4) is n4,
n1: n2: n3: n4 = 0.30-0.85: 1.0: 0.1-0.69: It is preferable to set it as the quantity ratio used as 0.01-0.3. Among them, in order for the coating layer (B) to exhibit excellent solvent resistance and adhesion, preferably n1: n2: n3: n4 = 0.40-0.80: 1.0: 0.15. -0.55: 0.02-0.25, more preferably n1: n2: n3: n4 = 0.45-0.75: 1.0: 0.15-0.4: 0.04-0 .2.

  Here, n1, n2, n3, and n4 can be determined as the product of the number of moles of the compound used as each component and the number of groups present in one molecule of the compound. Considering the storage stability of the urethane urea resin (b1) itself, it is preferable that the amount ratio of each component constituting satisfies n2 = n1 + n3 + n4.

  The urethane urea resin (b1) obtained by the above reaction may be used while dissolved in a reaction solvent (for example, tetrahydrofuran (THF), dimethylformamide (DMF), etc.). Accordingly, the solvent may be distilled off, or the reaction solution may be dropped into a poor solvent such as water, and the urethane urea resin (b1) may be subjected to post-treatment such as precipitation, filtration, and drying.

  The urethane urea resin (b1) preferably has a number average molecular weight of 2,000 to 100,000, more preferably 3,000 to 50,000, from the viewpoint of solvent resistance and adhesion of the coating layer to be formed. In particular, and most preferably from 4,000 to 30,000. In addition, the number average molecular weight of the urethane urea resin (b1) is a column: Shodex KD-805, KD-804 (manufactured by Showa Denko KK) using gel permeation chromatograph (GPC) in terms of polyethylene oxide. ), Eluent: LiBr (10 mmol / L) / DMF solution, flow rate: 1 ml / min, detector: RI detector, urethane polymer sample solution: number average measured by conditions of 0.5% dimethylformamide (DMF) solution Molecular weight.

  The number of polymerizable groups contained in one molecule of the urethane urea resin (b1) is preferably 2-30. The number of this polymerizable group is the ratio of the (b1-1) component, (b1-2) component, (b1-3) component, and (b1-4) component used for the synthesis of the urethane urea resin (b1). Further, it can be determined from the number average molecular weight determined by the GPC analysis. The number of polymerizable groups is an average value. Moreover, when it has the group which can form a silanol group or a silanol group, the number of the hydroxyl groups couple | bonded with a silicon atom corresponds to the number of polymeric groups.

  Moreover, it is preferable that 2-50 urea bonds of this urethane urea resin exist in 1 molecule. The ratio of urea bonds is also the ratio of the components (b1-1), (b1-2), (b1-3), and (b1-4) used in the synthesis of the urethane urea resin (b1), Can be determined from the number average molecular weight determined by the GPC analysis. The ratio of this urea bond is an average value.

  By using the urethane urea resin (b1) satisfying the above several molecular weights, the number of polymerizable groups, and the urea bond ratio, the polymerization yield can be further reduced and the cohesive force can be further increased. As a result, it is possible to obtain a laminate superior in solvent resistance and adhesion.

  In the present invention, it is presumed that the reason why an excellent effect is exhibited by using the curable composition containing the urethane urea resin (b1) is as follows. The urethane urea resin (b1) having a urea bond is considered to have higher molecular rigidity and stronger hydrogen bonds between molecular chains. And when forming a coating-film layer (B), this urethane urea resin (b1) is considered that the polymeric group contained in the molecule | numerator reacts and forms a crosslinked structure. As a result, the coating layer (B) made of a cured product of the curable composition is considered to have improved solvent resistance. Furthermore, regarding the improvement of adhesion, the presence of the urea bond strengthens the hydrogen bond between the molecular chains, and it is also a factor that cohesive failure of the formed cured body (coating layer) is less likely to occur. Conceivable.

  In addition to the urethane urea resin (b1), the curable composition used in the present invention can also contain other polymerizable monomers. Next, the polymerizable monomer (b2) that can be blended in the curable composition will be described.

Polymerizable monomer (b2)
This polymerizable monomer (b2) is a monomer having in the molecule a polymerizable group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. is there. However, as a matter of course, the urethane urea resin (b1) does not correspond to the polymerizable monomer (b2).

  As the polymerizable monomer (b2) used in the present invention, known alkoxysilane compounds, (meth) acrylate monomers, epoxy monomers, and vinyl monomers can be used.

  In the present invention, when the urethane urea resin (b1) having a silanol group or a group capable of forming a silanol group by hydrolysis is used, an alkoxysilane compound is preferably used as the polymerizable monomer (b2). . Examples of the alkoxysilane compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, n-hexyltri Methoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-octadecyltrimethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrime Kishishiran, .gamma.-mercaptopropyltrimethoxysilane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) alkoxysilane compounds such as ethane.

  When the urethane urea resin (b1) having a (meth) acrylate group or a vinyl group is used, a (meth) acrylate monomer and a vinyl monomer may be used as the polymerizable monomer (b2). preferable. Examples of the (meth) acrylate monomer and the vinyl monomer include glycidyl (meth) acrylate, methylene glycidyl (meth) acrylate, ethylene glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolmethane. Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyethylene glycol di (average molecular weight 250-1000) (Meth) acrylate, polytetramethylene glycol di (meth) acrylate having an average molecular weight of 250 to 1000, polypropylene having an average molecular weight of 250 to 1000 Recall di (meth) acrylate, 2,2-bis [4- (meth) acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (meth) acryloxy diethoxy) phenyl] propane, ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, styrene, α-methylstyrene, methylvinylbenzene, Examples thereof include ethyl vinyl benzene, α-chlorostyrene, chloro vinyl benzene, vinyl benzyl chloride, paradivinyl benzene, and metadivinyl benzene.

  Various urethane (meth) acrylate monomers can also be used. Examples of the urethane (meth) acrylate monomer include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, Known compounds such as norbornene diisocyanate or methylcyclohexane diisocyanate and polyalkylene glycol having repeating units of ethylene oxide, propylene oxide, hexamethylene oxide having 2 to 4 carbon atoms, or polyester diol such as polycaprolactone diol, polycarbonate diol, polybutadiene diol, etc. A urethane prepolymer reacted with a diol is converted into 2-hydroxy (meth) a Further reacted with Relate, molecular weight, and the like urethane di (meth) acrylate was adjusted from 1300-10000.

  When the urethane urea resin (b1) having an epoxy group is used, it is preferable to use an epoxy monomer as the polymerizable monomer (b2). Examples of the epoxy monomer include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and nonaethylene glycol diglycidyl ether. , Propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol hydroxyhybalic acid ester Diglycidyl ether, trimethylolpropane jig Cidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, Aliphatics such as pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, etc. Epoxy compound, isophoronediol diglycidyl ester Terpyl, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, alicyclic epoxy compounds, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester And aromatic epoxy compounds such as phenol novolac polyglycidyl ether and cresol novolac polyglycidyl ether.

  In the curable composition used for forming the coating layer (B), the polymerizable monomer (b2) has a molar number of polymerizable groups of 30 mmol or more per 100 g of all components having a polymerizable group. It is preferable to blend within a range satisfying 500 mmol or less. When only the urethane urea resin (b1) satisfies the mole number of the polymerizable group of 30 mmol or more and 500 mmol or less, the polymerizable monomer (b2) may not be blended or has a polymerizable group. It can also mix | blend in the range which the mole number of a polymeric group satisfies 1 to 300 mmol per 100g of all the components.

  The number of moles of the polymerizable group refers to the number of moles of the portion involved in the polymerization. Therefore, for example, when the polymerizable group is a dialkoxysilyl group, if 1 mmol of dialkoxysilyl group is present, the polymerizable group is converted to 2 mmol. This number of moles is the number of moles per 100 g of all components having a polymerizable group contained in the curable composition. The total component is a component obtained by summing the urethane urea resin (b1) and the polymerizable monomer (b2) optionally blended. The number of moles is a value obtained by calculating the number of moles of polymerizable groups contained in each component (urethane urea resin (b1) and polymerizable monomer (b2)) according to the following formula, and then calculating the total number thereof. is there.

  Number of moles of polymerizable group = (number of polymerizable groups contained in one molecule) × {Amount of each component used per 100 g of all components having a polymerizable group (g)} / (molecular weight).

  When the polymerizable monomer (b2) is blended in the curable composition, a preferable range is a urethane urea resin (b1) in which the number of moles of the polymerizable group satisfies the above range and has a polymerizable group in the molecule. It is 1-50 mass parts with respect to 100 mass parts, Preferably it is 5-30 mass parts.

  Moreover, it is preferable that the curable composition used by this invention mix | blends various polymerization initiators according to the polymeric group which urethane urea resin (b1) has other than the said polymerizable monomer (b2). Next, the polymerization initiator will be described.

(Polymerization initiator)
In the present invention, the curable composition used for forming the coating layer (B) is blended with various polymerization initiators in order to efficiently crosslink the polymerizable group of the urethane urea resin (b1). You can also.

(Silanol group or polymerization initiator of a group that can be hydrolyzed to form a silanol group)
When the urethane urea resin (b1) has a group that can be hydrolyzed to form a silanol group, an acid aqueous solution is preferably added. Such acids are not particularly limited, but inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic acids such as acetic acid and propionic acid are typical, particularly from the viewpoint of hydrolyzability. Hydrochloric acid is preferred, and 0.0001 to 0.1 N aqueous hydrochloric acid is preferably used. The acid aqueous solution may be added in an amount of 0.1 to 3 mol times the amount necessary for hydrolysis of all hydrolyzable groups of the group capable of hydrolyzing to form a silanol group. preferable.

  Further, when the urethane urea resin (b1) has a silanol group or a group that can be hydrolyzed to form a silanol group, an acetylacetonate complex, a perchlorate, an organic metal salt, various Lewiss can be used as a polymerization initiator. It is preferable to use a curing catalyst such as an acid.

  As the acetylacetonate complex, aluminum acetylacetonate, lithium acetylacetonate, indium acetylacetonate, chromium acetylacetonate, nickel acetylacetonate, titanium acetylacetonate, iron acetylacetonate, zinc acetylacetonate, cobalt acetylacetonate Nart, copper acetylacetonate, zirconium acetylacetonate and the like can be mentioned. Among these, aluminum acetylacetonate and titanium acetylacetonate are preferable.

  Examples of the perchlorate include magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate.

  Examples of the organic metal salt include sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate and the like.

  Examples of the Lewis acid include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, and antimony chloride.

  In the present invention, an acetylacetonate complex is particularly suitable from the viewpoint of crosslinking in a short time even at a relatively low temperature.

  The amount of these curing catalysts used is not particularly limited as long as the urethane urea resin (b1) and the polymerizable monomer (b2) blended as necessary are sufficiently reacted. Specifically, it is preferable to use in the range of 0.001 to 3 parts by mass with respect to 100 parts by mass of the urethane urea resin (b1). The curing catalyst may be used alone or in combination.

((Meth) acrylate group or vinyl group polymerization initiator)
When the urethane urea resin (b1) has a (meth) acrylate group or a vinyl group, it is preferable to blend a thermal polymerization initiator or a photopolymerization initiator as a polymerization initiator.

  Examples of the thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl oxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; t-butylperoxy-2-ethylhexanoate, t -Peroxyesters such as butyl peroxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate Percarbonates such as 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) 1,1′-azobis (cyclohexane-1-carbonitrile), etc. A The compounds can be used.

  Although the usage-amount of these thermal-polymerization initiators changes with polymerization conditions, the kind of initiator, the kind and content of a polymeric group, it is 0.001-1 mass part with respect to 100 mass parts of urethane urea resins (b1). It is suitable to use in the range. The thermal polymerization initiators may be used alone or in combination.

  Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Benzyl methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxanthone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2-benzi 2-dimethylamino-1- (4-morpholinophenyl) - can be used butanone.

  Although the usage-amount of these photoinitiators changes with polymerization conditions, the kind of initiator, the kind and content of a polymeric group, it is 0.001-0.5 with respect to 100 mass parts of urethane urea resins (b1). It is suitable to use in the range of parts by mass. The photopolymerization initiators may be used alone or in combination.

  When a photopolymerization initiator is blended, it is preferable that the curable composition is applied on the optical sheet (A2) and then irradiated with light to promote polymerization. Specifically, a curable composition containing a photopolymerization initiator using a metal halide lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, an electroded lamp such as a medium-pressure mercury lamp, a xenon lamp, or an electrodeless lamp as a light source. In contrast, light irradiation may be performed. The atmosphere for light irradiation may be in the presence of oxygen, but it may be replaced with an inert gas such as nitrogen. Further, heat treatment or the like may be performed after the light irradiation.

(Epoxy group polymerization initiator)
When the urethane urea resin (b1) has an epoxy group, a curing agent used for polymerization of a conventional epoxy compound can be used without limitation as a polymerization initiator. Examples of the curing agent include a phenol resin curing agent, a polyamine curing agent, a polycarboxylic acid curing agent, and an imidazole curing agent. Specifically, phenol novolak resins, cresol novolac resins, poly p-vinylphenol, etc. are listed as phenol resin-based ones, and polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, Polyamidoamine (polyamide resin), melamine resin, ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, dicyandiamide and the like, and polycarboxylic acid-based curing agents include phthalic anhydride, tetrahydro Examples include phthalic acid, methyltetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, methyl-3,6-endomethylenetetrahydrophthalic anhydride, and imidazole curing agents. As 2-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate and the like. .

  Moreover, a photocation generator can also be used as an epoxy group polymerization initiator. As the photocation generator, an onium salt such as a diazonium salt, a sulfonium salt or an iodonium salt can be used, and an aromatic onium salt is particularly preferable. In addition, iron-arene complexes such as ferrocene derivatives, arylsilanol-aluminum complexes, and the like can be preferably used.

  Specific examples of the photocation generator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4 -Chlorphenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenyl-sulfonio) phenyl] sulfide-bis-hexafluorophosphate, bis [4-diphenyl-sulfonio) phenyl] sulfide -Bis-hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methyl Chill) benzene] -Fe- hexafluorophosphate and the like. Examples of commercially available products include “SP-150” and “SP-170” manufactured by ADEKA Corporation; “Irgacure 261” and “Irgacure 264” manufactured by Ciba-Geigy Corporation; “UVR-6974” and “UVR-” manufactured by Union Carbide Corporation. 6990 ";" Syracure UVI-6970 "," Syracure UVI-6974 "," Syracure UVI-6990 "manufactured by Dow Chemical Co., USA;" CI-2481 "," CI-2624 "manufactured by Nippon Soda it can.

  The amount of these curing agents used is preferably in the range of 0.001 to 1.0 parts by mass with respect to 100 parts by mass of the urethane urea resin (b1). The said hardening | curing agent may be used independently and may be used in mixture of multiple.

(Other ingredients)
An organic solvent can also be mix | blended with the curable composition used by this invention as needed. By mix | blending an organic solvent, it becomes easy to mix a urethane urea resin (b1), the polymerizable monomer (b2) mix | blended as needed, and another component. As a result, the viscosity of the curable composition that forms the coating layer can be appropriately adjusted. And the operativity when apply | coating this curable composition to an optical sheet or an optical film (A2), and the uniformity of the thickness of a coating film can also be made high.

  Examples of organic solvents that can be suitably used in the present invention include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, and 2-butanol; ethylene glycol monomethyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n Polyhydric alcohol derivatives such as butyl ether; diacetone alcohol; methyl ethyl ketone; toluene; hexane; heptane; ethyl acetate; Bromide (DMF); dimethyl sulfoxide (DMSO); tetrahydrofuran (THF); cyclohexanone; and combinations thereof can be exemplified. From these, the urethane urea resin (b1) to be used and the material of the optical sheet or optical film (A2) may be appropriately selected and used. For example, when an optical sheet or an optical film (A2) made of polycarbonate resin is used and the curable composition of the present invention is directly applied, an alcohol or a polyhydric alcohol derivative is used as the solvent. It is preferable.

  The curable composition can also contain the organic solvent as described above. However, the curable composition can also be used without blending an organic solvent.

  In the present invention, it is preferable to use a curable composition containing the above components. The curable composition is not particularly limited, but it is preferable that the viscosity at 25 ° C. is prepared in the range of 50 to 10,000 cP, more preferably 100 to 7,000 cP.

  Next, a method for forming the coating layer (B) using the curable composition will be described.

(Formation method of coating layer (B))
In the present invention, the coating layer (B) 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 (B) on an optical sheet or an optical film (A2) previously. Moreover, after forming a photochromic laminated body (A), a coating-film layer (B) can also be formed on the surface which arrange | positions the synthetic resin layer (C) of this photochromic laminated body (A). Hereinafter, the example in the case of forming a coating film layer (B) 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 (B). For example, by applying and curing a curable composition containing the urethane urea resin (b1) on one side or both sides of an optical sheet or optical film (A2), a coating comprising a cured product of the curable composition is formed. A film layer (B) can be formed.

  As the method for applying the curable composition, 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. It is done. Curing of the curable composition can be performed by heat or light. This condition may be appropriately selected depending on the polymerizable group of the component contained in the curable composition and the types of various polymerization initiators to be blended. Moreover, thermosetting and photocuring can also be used together. To describe a specific curing method, when heating is performed, it is preferable to hold the sheet coated with the curable composition at a temperature of 40 ° C. or higher and 130 ° C. or lower. The heating may be performed in a convection oven or the like, and may be performed for a time during which the polymerizable group of the urethane urea resin (b1) sufficiently reacts, for example, 0.5 to 5 hours.

  In the case of performing light irradiation, light irradiation may be performed using a light source such as a metal halide, a high-pressure mercury lamp, or an electrodeless lamp in an inert gas or air. Further, heating or the like can be performed after the light irradiation.

  When an organic solvent is added to the curable composition for viscosity adjustment or the like, the organic solvent is first heated and dried in an oven or the like, and then the above heat treatment or light irradiation may be performed.

  The film thickness of the coating layer (B) formed by the above method is the resistance to dissolution for the lens-forming monomer composition constituting the synthetic resin layer (C), and further the synthetic resin layer (C) or polyurethane adhesive From the viewpoint of adhesion with the layer (A1) (when the coating layer (B) is laminated on both sides of the optical sheet or optical film (A2)), 0.1 to 20 μm is preferable, and more preferably 0.2 to 0.2 μm. 10 μm, most preferably 0.3 to 5 μm.

  In addition, as above-mentioned, this coating-film layer (B) 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 adhesive layer (A1) and the optical sheet or optical film (A2), the coating layer (B) is formed on both surfaces of the optical sheet or optical film (A2) in advance. It is preferable.

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

(Synthetic resin layer (C))
The synthetic resin layer (C) can be formed from a thermoplastic resin that is a normal plastic lens material or a thermosetting resin obtained by curing a lens-forming monomer composition. Among them, the effect of forming the coating layer (B) is more remarkably exhibited when the synthetic resin layer (C) is formed from a thermosetting resin obtained by curing the monomer composition for lens formation. is there. Specific examples of the lens-forming monomer composition include (meth) acrylate-based monomer compositions, allyl-based monomer compositions, thiourethane-based monomer compositions, urethane-based monomer compositions, and thioepoxy-based monomer compositions. Mention may be made of a lens-forming monomer composition capable of forming a curable resin.

(Monomer composition for lens formation)
(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. As the polyisocyanate compound, in addition to the isocyanate compounds exemplified as the polyisocyanate compound of the urethane-urea resin (C1), 2,5-diisocyanatomethyl-1,4-dithiane, 2,5-bis (4- Isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3-isocyanatomethyl-4-isocyanato-2-thiabutyl) -1,4-dithiane, 2,5-bis (3- Isocyanato-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 (isocyanate Ethethylthio) propane, 1,2,3-tris (isocyanatemethylthio) propane, 1,1,6,6-tetrakis (isocyanatemethyl) -2,5-dithiahexane, 1,1,5,5-tetrakis (isocyanatemethyl) -2,4-dithiapentane, 1,2-bis (isocyanatomethylthio) ethane, 1,5-diisocyanate-3-isocyanatomethyl-2,4-dithiapentane, 1,5-diisocyanate-3-isocyanatomethyl-2,4- Examples thereof include polyisocyanates such as dithiapentane, dimers obtained by burette-type reaction of these polyisocyanates, cyclized trimers of these polyisocyanates, and adducts of these polyisocyanates with alcohols or thiols. 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 polyisocyanate compound, a polyol compound, and a diamine curing agent can be suitably used.

  As a polyisocyanate compound, the isocyanate compound illustrated by the polyisocyanate compound of the said urethane urea resin (b1) can be used.

  As a polyol compound, the polyol compound illustrated with the polyol compound of the said urethane-urea resin (b1) can be used.

  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. Aromatic diamine compounds such as “Lonzacure” series manufactured by Co., Ltd .; in addition to the diamine compounds exemplified as the chain extender of the urethane-urea resin (C1), “JEFFAMINE” series manufactured by Huntsman can be listed as commercial products. .

(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 lens forming monomer composition as described above, if necessary.

(Method for forming synthetic resin layer (C) (method for producing photochromic lens))
Examples of the method for forming (laminating) the synthetic resin layer (C) on the coating layer (B) of the optical sheet or the optical film in the photochromic laminate (A) include the following methods. Specifically, the photochromic laminate (A) having the coating layer (B) 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. (C) is a method of filling a lens forming monomer composition.

  When the above-mentioned thermosetting resin is employed as the synthetic resin layer (C), a commonly used glass mold is used, and after the lens-forming monomer composition is filled in the glass mold, thermosetting ( A photochromic lens can be molded by casting polymerization). 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.

  Specific operations for carrying out the casting polymerization as described above are as follows. For example, one of the glass molds is filled with a lens-forming monomer composition, and a photochromic laminate (A) having a coating layer (B) on the surface is floated thereon. Next, after setting the other glass mold via a gasket or a tape, the monomer composition for lens formation is further injected into the glass mold for polymerization. Further, the photochromic laminate (A) is supported in the glass mold by a gasket, tape or other means fixing the glass mold, and the monomer composition for lens formation is filled in the glass mold for polymerization. A method is also mentioned. Furthermore, the photochromic laminated body (A) is made to contact | adhere to one side of a glass mold, and the monomer composition for lens formation is filled and superposed | polymerized on the coating film layer (B) of the contact | adhered side is also mentioned. .

  Moreover, in this invention, a synthetic resin layer (C) can be comprised from a thermoplastic resin other than using the said monomer composition for lens formation. 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 (B) on the outermost surface is closely attached to 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 (B) can be suitably determined 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 them, it is preferable to use a photochromic laminate (A) having such a size that the side surface of the photochromic laminate (A) protrudes outside the glass mold or mold. By doing so, elution of the photochromic compound from the polyurethane adhesive layer (A1) or the polyurethane resin itself can be suppressed.

  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 adhesive layer (A1) 2 containing a photochromic compound. And it has the coating-film layer (B) 5 on this optical sheet or optical film (A2) 3, and also laminated | stacked the synthetic resin layer (C) 6 on this coating-film layer (B) 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 contact bonding 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.

(Components for forming the coating layer (B) (components used in the curable composition))
(Raw material used for the synthesis of urethane urea resin (b1) having a polymerizable group in the molecule)
(Polyol compound: component (b1-1))
PL1: Duranol (polycarbonate diol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 800) manufactured by Asahi Kasei Chemicals Corporation.

(Polyisocyanate compound: (b1-2) component)
NCO1: isophorone diisocyanate.

(Amino group-containing compound: component (b1-3))
CE1: 4,4′-methylenebis (cyclohexylamine).

(Polymerization imparting compound: component (b1-4))
RC1: aminopropyltrimethoxysilane.
RC2: 2-hydroxyethyl acrylate.
RC3: butanediol monoglycidyl ether.
RC4: Allyl alcohol.
RC5: N-β (aminoethyl) -γ-aminopropyltrimethoxysilane.
RC6: Compound 2- (hydroxymethyl) -3-hydroxypropyl acrylate represented by the following formula

RC7: Compound 2- (hydroxymethyl) -3-hydroxypropyl glycidyl ether represented by the following formula

(Synthesis of urethane urea resin (b1) having a polymerizable group in the molecule)
(B1): Synthesis of urethane urea resin (U1) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 234 g of polycarbonate polyol (PL1: (b1-1) component) having a number average molecular weight of 800, 100 g of isophorone diisocyanate (NCO1: (b1-2) component) was charged and reacted at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a prepolymer. Thereafter, 1500 ml of tetrahydrofuran (THF) was added, and then 18.9 g of 4,4′-methylenebis (cyclohexylamine) (CE1: (b1-3) component) was added dropwise under a nitrogen atmosphere. For 1 hour. Then, a urethane urea resin having an isocyanate group at the end of the molecular chain was synthesized.

  Next, 24.2 g of aminopropyltrimethoxysilane (RC1: (b1-4) component) was added to the solution under a nitrogen atmosphere and reacted at 25 ° C. for 1 hour. Thereafter, the solvent was distilled off under reduced pressure to obtain a urethane urea resin (U1: (b1)) having a trimethoxysilyl group (polymerizable group) at the end of the urethane urea resin. The number average molecular weight of the urethane urea resin (U1) having a polymerizable group in the molecule was 5,000 (theoretical value: 5,000) in terms of polyoxyethylene. Here, the theoretical value of the number average molecular weight means that the (b-1) component, (b-2) component, (b-3) component, and (b-4) component used in the raw material are not crosslinked. The molecular weight when a urethane urea resin is theoretically produced in a linear shape. In addition, the average number of urea bonds was 4.7 per molecule, and the average number of polymerizable groups per molecule was 6. These results are summarized in Table 2.

(B1): Synthesis of urethane urea resin (U5) In a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube, 234 g of a polycarbonate polyol (PL1: (b1-1) component) having a number average molecular weight of 800, 100 g of isophorone diisocyanate (NCO1: (b1-2) component) was charged and reacted at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a prepolymer. Thereafter, 1500 ml of THF was added, and 15 g of N-β (aminoethyl) -γ-aminopropyltriethoxysilane (RC5: (b1-4) component) was added dropwise under a nitrogen atmosphere. The reaction was performed for 2 hours. Further, 14.2 g of 4,4′-methylenebis (cyclohexylamine) (CE1: (b1-3) component) was added dropwise, and the mixture was reacted at 25 ° C. for 1 hour after the completion of the dropwise addition. Thereafter, 8.0 g of aminopropyltrimethoxysilane (RC1: (b1-4) component) was added and reacted at 25 ° C. for 1 hour. And the urethane urea resin (U5) which has a trimethoxysilyl group in the side chain and terminal of a urethane urea resin was obtained by depressurizingly distilling a solvent. The number average molecular weight of the obtained urethane urea resin (U5) was 17,000 (theoretical value: 16,000) in terms of polyoxyethylene. Further, the average number of urea bonds was 24 per molecule, and the average number of polymerizable groups per molecule was 14. These results are summarized in Table 2.

(B1): Synthesis of urethane urea resins (U2 to U4 and U6 to U8) (b-1) component, (b-2) component, (b-3) component, (b-4) component shown in Table 1 , And a reaction solvent, except that the reaction conditions shown in Table 1 were used, and the urethane urea resins (U2) to (U4) and (U6) to (U6)-( The synthesis of U8) was performed. The synthesis conditions for the urethane urea resin are also shown in Table 1.

  Moreover, the blending ratio of each component used for the synthesis of the obtained urethane urea resins (U1) to (U9), the number average molecular weight, the number of polymerizable groups per molecule, and the number of urea bonds per molecule. The results are summarized in Table 2.

Other components blended in the curable composition (polymerizable monomer (b2))
M1: γ-glycidoxypropyltrimethoxysilane.
M2: ethylene glycol diacrylate.
M3: 1,6-hexanediol diglycidyl ether.

(Organic solvent)
D1: Propylene glycol monomethyl ether (polymerization initiator)
P1: 0.001N hydrochloric acid aqueous solution.
P2: Diethylenetriamine.
P3: Diisopropyl peroxydicarbonate.
P4: Irgacure 1800 {mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (weight ratio 3: 1)}.
P5: Tris (2,4-pentanedionato) aluminum (III)
Preparation Method of Polyurethane Adhesive Layer (A1) Composition (Photochromic Composition) Polycarbonate diol (1,5-pentanediol) 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 And polycarbonate diol using hexanediol as raw materials) and 100 g of isophorone diisocyanate were charged and reacted in a nitrogen atmosphere at 70 ° C. for 6 hours to obtain a prepolymer. Thereafter, 1000 ml of tetrahydrofuran (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 synthesized by reacting at 25 ° C. for 1 hour. The photochromic compound (PC1) 18.5g shown below was mixed and melt | dissolved in the solution containing this polyurethane resin, and the photochromic composition was obtained.

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).

(Lens forming monomer composition and photochromic lens manufacturing method using the same)
Each of the produced photochromic laminates (A) having the coating layer (B) is cut into a circle having a diameter of 65 mm, and set in a glass mold having a gasket (0.00D, lens diameter 70 mm, wall thickness 3.0 mm). ). The lens forming monomer composition described below was injected into the glass mold and cured under the following conditions. Thereafter, 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 (B).

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

  Next, the lens-forming monomer composition is injected above and below the photochromic laminate (A) having the coating layer (B) placed in the glass mold, and it takes 20 hours to 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 lens-forming monomer composition.

  Next, the monomer composition for lens formation is injected above and below the photochromic laminate (A) having the coating layer (B) placed in the glass mold, and polymerization is performed at 33 ° C. to 90 ° C. using an air furnace. The temperature was gradually raised to 17 hours and then 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 lens-forming 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 A mixture of 63.0 parts by mass and 0.1 parts by mass of dibutyltin dilaurate as a polymerization initiator was prepared.

  Next, the synthetic resin composition is injected above and below the photochromic laminate having the coating layer (B) placed in the glass mold, and polymerization is carried out using an air furnace for 12 hours from 35 ° C. to 130 ° C. 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 lens-forming 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 (B) 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 monomer composition for forming a lens, 100 parts by mass of a polyester polyol having a number average molecular weight of 1000 consisting of adipic acid and 1,6-hexanediol, and 78 parts by mass of an isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate), and an aromatic 17 parts by mass of 2,4-diamino-3,5-diethyl-toluene / 2,6-diamino-3,5-diethyl-toluene as an aromatic diamine curing agent 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 (B) 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 (B))
100 g of (U1) as urethane urea resin (b1) having a polymerizable group in the molecule, 100 g of propylene glycol monomethyl ether, 2.0 g of 0.001N hydrochloric acid aqueous solution (P1) as a polymerization initiator, and tris (2,4-pentane Diato) 0.5 g of aluminum (III) (P5) was mixed by stirring to obtain a curable composition for forming the coating layer (B). This curable composition was applied to one surface of a polycarbonate sheet (optical sheet or optical film (A2): POLYCA) having a thickness of 0.4 mm, dried at 50 ° C. for 30 minutes, and then heated at 110 ° C. for 2 hours. -The optical sheet which has a coating-film layer (B) with a film thickness of 5 micrometers was obtained by hardening.

Production of Photochromic Laminate (A) The photochromic composition obtained by the above preparation method of the composition for the polyurethane adhesive layer (A1) is applied to a PET film (Purex film manufactured by Teijin DuPont Films Ltd., with a silicon coating film). It was applied and dried at 50 ° C. for 30 minutes. Thereafter, the PET film was separated to obtain a polyurethane adhesive layer (A1) having a thickness of about 40 μm. Next, after sandwiching the obtained polyurethane adhesive layer (A1) between the two POLYCA sheets (polycarbonate sheet: optical sheet) on which the coating layer (B) was formed by the above method, the mixture was allowed to stand at 40 ° C. for 24 hours. Further, heat treatment was performed at 110 ° C. for 1 hour. 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 (B) only on the surface not in contact with the polyurethane adhesive layer (A1). The structure of this laminate is shown in Table 1.

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 at all between the layers.
1; peeling is observed in at least a part between the coating layer and the synthetic resin layer.
2: peeling is observed in at least part of the optical sheet and the polyurethane adhesive 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.

  The above results are shown in Table 4.

Examples 2-16
Formation of coating layer (B) and preparation of photochromic laminate (A) (laminates (S1) to (S12) having a coating layer) The curable composition and optical sheet (A2) shown in Table 3 A coating layer (B) was formed on the surface (one side or both sides) of the optical sheet (A2) in the same manner as in Example 1 except that it was used. In the column of the laminated surface of the coating film layer of Table 3, what was described as one surface refers to what provided the coating film 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.

  In addition, when Irgacure 1800 (P4) was used as a polymerization initiator, a photochromic laminate was produced according to the following procedure.

Formation of coating layer (B) when using photopolymerization initiator Polycarbonate sheet (optical sheet or optical film (A2): POLYCA) having a thickness of 0.4 mm is used as the curable composition for forming the coating layer. The optical sheet having a coating layer thickness of 5 μm was obtained by applying to one surface of the film and photocuring for 1 minute under a nitrogen flow using F3000SQ (D bulb) manufactured by Fusion UV Systems.

Preparation of photochromic laminate (A) (laminate having a coating layer)
A photochromic laminate was produced in the same manner as in Example 1 except that the polyurethane adhesive layer (A1) was produced in the same manner as in Example 1 and then the optical sheet having the coating layer (B) obtained above was used. (A: (S2) to (S12)) were obtained. Table 3 shows the results.

Production of Photochromic Lens Photochromic laminate (A: (S1) to (S12)) having a coating layer (B) shown in Table 4 and a synthetic resin layer (C) were used, and the same as in Example 1 A photochromic lens was produced by this method. Table 4 shows the evaluation results of the obtained photochromic lens.

  The curing conditions for obtaining each synthetic resin layer were carried out in accordance with the above-mentioned “lens forming monomer composition and method for producing photochromic lens using the same”.

Comparative Examples 1-3
Production of photochromic laminate (A) A polyurethane adhesive 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 3 was used. : (S13) to (S15)). The obtained photochromic laminated body (A: (S13)-(S15)) does not have a coating-film layer (B). Table 3 shows the results.

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 (C) shown in Table 4 were used. In addition, Table 5 shows the evaluation results of the obtained photochromic lens.

  The curing conditions for obtaining each synthetic resin layer were carried out in accordance with the above-mentioned “lens forming monomer composition and method for producing photochromic lens using the same”.

Comparative Example 4
Formation of coating layer (B) and production of photochromic laminate (A) (laminate having coating layer (S16)) Except for using the curable composition and optical sheet (A2) shown in Table 3. In the same manner as in the method described in Example 1, the coating layer (B) was formed on the surface (one side) of the optical sheet (A2).

Production of photochromic laminate (A) A polyurethane adhesive 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 2 was used. : (S16)). The obtained photochromic laminate (A: (S16)) had the coating layer (B) only on the surface not in contact with the polyurethane adhesive layer (A1) of the optical sheet (A2). Table 3 shows the results.

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 (C) shown in Table 5 were used. In addition, Table 5 shows the evaluation results of the obtained photochromic lens.

  The curing conditions for obtaining each synthetic resin layer were carried out in accordance with the above-mentioned “lens forming monomer composition and method for producing photochromic lens using the same”.

  As is clear from Examples 1 to 16, it can be seen that the photochromic lens having the coating layer of the present invention provides a photochromic lens having excellent photochromic properties and adhesion.

  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. Further, as is clear from Comparative Example 4, a photochromic lens having a coating layer made of a cured product that does not use a urethane urea resin having a polymerizable group in the molecule has no problem in photochromic properties but has poor adhesion. It was enough.

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

Claims (7)

A photochromic laminate (A) having a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other;
A coating layer (B) formed on at least one of the optical sheet or optical film (A2);
A photochromic lens having a synthetic resin layer (C) formed on the coating layer (B),
The coating layer (B) is a silanol group or a hydrolyzable to group capable of forming a silanol group, have a polymerizable group selected from (meth) acrylate group, an epoxy group and a vinyl group, the polymerizable group A cured product of a curable composition containing a urethane urea resin (b1) containing 2 to 30 per molecule and 2 to 50 urea bonds per molecule .   The curable composition further comprises a polymerizable monomer (b2) having a polymerizable group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. The photochromic lens according to claim 1, comprising:   The photochromic lens according to claim 1, further comprising the coating layer (B) between the polyurethane adhesive layer (A1) and the optical sheet or optical film (A2). A method for producing the photochromic lens according to claim 1, comprising:
Silanol groups or hydrolyzable to group capable of forming a silanol group, have a (meth) acrylate group, a polymerizable group selected from an epoxy group and a vinyl group, from 2 to 30 pieces of polymerizable groups in one molecule By applying a curable composition containing a urethane urea resin (b1) containing 2 to 50 urea bonds in one molecule on an optical sheet or optical film (A2) and curing the composition. The manufacturing method of the photochromic lens characterized by including the process of forming the coating-film layer (B) which consists of a hardening body of a curable composition. On at least one optical sheet or optical film (A2) of the photochromic laminate (A) having a polyurethane adhesive layer (A1) containing a photochromic compound between two optical sheets or optical films (A2) facing each other. In addition,
Silanol groups or hydrolyzable to group capable of forming a silanol group, have a (meth) acrylate group, a polymerizable group selected from an epoxy group and a vinyl group, from 2 to 30 pieces of polymerizable groups in one molecule A laminate having a coating layer (B) comprising a cured product of a curable composition containing a urethane urea resin (b1) containing 2 to 50 urea bonds in one molecule .   The curable composition further comprises a polymerizable monomer (b2) having a polymerizable group selected from a silanol group or a group that can be hydrolyzed to form a silanol group, a (meth) acrylate group, an epoxy group, and a vinyl group. The laminate according to claim 5, comprising:   The laminate according to claim 5, further comprising the coating layer (B) between the optical sheet or optical film (A2) and the polyurethane adhesive layer (A1).

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