Moisture-curing polyurethane composition and laminate

Abstract

(A) a moisture-curing polyurethane and (B) an organic solvent are contained in the moisture-curing polyurethane, wherein (A) the moisture-curing polyurethane is obtained by reacting (A1) a polyisocyanate compound having two or more isocyanate groups in its molecule and (A2) a low molecular weight polyol compound having two or more hydroxyl groups in its molecule and a number average molecular weight of 50 to 300, and isocyanate groups at the molecular ends. Additionally, a laminate comprising an optical substrate and a polyurethane resin layer made of the moisture-curing polyurethane composition is provided.

Description

Technology Field

[0001] The present invention relates to a moisture-curing polyurethane composition and a laminate having a layer made of the composition. Background Technology

[0002] Photochromic compounds, represented by chromene compounds, fulgide compounds, and spirooxazine compounds, possess the characteristic (photochromicity) of rapidly changing color when irradiated with light containing ultraviolet rays, such as sunlight or mercury, and returning to their original color when the irradiation is stopped and they are placed in a dark place. Taking advantage of this characteristic, they are used for various applications, particularly as optical materials.

[0003] For example, photochromic eyeglass lenses, which are imparted photochromic properties through the use of photochromic compounds, rapidly tint to function as sunglasses when exposed to light containing ultraviolet rays such as sunlight outside of buildings, and fade to function as transparent ordinary eyeglasses when exposed to light inside buildings where such light is absent; as such, demand for them has been increasing recently.

[0004] Methods for manufacturing photochromic optical articles, such as photochromic eyeglass lenses, are known, for example, a method of directly forming an optical article such as a lens by mixing a polymerizable monomer and a photochromic compound and polymerizing them; a method of coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article such as a plastic lens; and a method of joining two optical articles by an adhesive layer formed by an adhesive resin in which a photochromic compound is dispersed (see Patent Documents 1 to 3). Among these, the method of coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article such as a plastic lens is preferably used.

[0005] The photochromic optical article manufactured by the above method is required to respond rapidly and develop a high concentration of color when irradiated with light containing ultraviolet rays, such as sunlight, and to fade quickly inside a building where such light is absent, thereby requiring the expression of even superior photochromic properties.

[0006] In the method of coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article such as a plastic lens, a method is proposed to have flexibility without hardening the resin layer in which the photochromic compound is dispersed, or to improve photoresponsiveness or fading speed by softening the surface hardness of the resin layer in which the photochromic compound is dispersed (see Patent Document 4).

[0007] Generally, photochromic optical articles, such as photochromic eyeglass lenses, are shipped after being manufactured by wrapping them in a relatively soft material called an inner sheet to prevent scratches on the lens surface, placing them in a pouch, and shipping. Additionally, since photochromic eyeglass lenses are stored and transported in dedicated trays or cleaning racks to ensure a defect-free lens surface during each manufacturing process, storage, and shipment, a protective film is applied to the lens surface. This is done to prevent scratches or dust from adhering to the surface. Furthermore, because photochromic eyeglass lenses are typically transparent, it is difficult to instantly determine whether or not a protective film is attached. Therefore, a colored protective film that allows for easy identification is typically used.

[0008] In the shipping and manufacturing process of the photochromic eyeglass lens described above, there was room for improvement in the case of the photochromic eyeglass lens with softened surface hardness as in Patent Document 4, because the surface hardness of the resin layer in which the photochromic compound is dispersed is insufficient, the lens surface is prone to scratching. In addition, there was room for improvement in the case where, when a colored protective film is attached to the photochromic eyeglass lens, the coloring agent of the colored protective film is transferred to the lens surface, and the initial transparency or color tone of the photochromic eyeglass lens is damaged.

[0009] Meanwhile, when a functional layer having photochromic performance or ultraviolet absorption performance is laminated onto the surface of an optical article such as a plastic lens, the lamination is performed through a primer layer to improve adhesion. For example, methods have been proposed such as using a moisture-curing coating composition as a primer layer when coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article such as a plastic lens, or laminating a moisture-curing coating composition as a primer layer having ultraviolet absorption performance onto the surface of an optical article such as a plastic lens (see Patent Documents 6 and 7).

[0010] However, when using a moisture-curing coating composition as a primer layer, depending on the type of optical substrate such as a plastic lens, there were cases where appearance defects or adhesion defects occurred due to dissolution or penetration by the coating liquid applied to the primer layer, leaving room for improvement. In addition, when performing a pretreatment to laminate another layer after laminating a moisture-curing coating composition as a primer layer on an optical substrate such as a plastic lens, there were problems such as scratches on the primer layer when wiped with a towel or dissolution of the primer layer when immersed in a cleaning solution, leaving room for improvement. Prior art literature

[0011] Patent Document 1: International Publication No. 2012 / 176439 Patent Document 2: International Publication No. 2011 / 125956 Patent Document 3: International Publication No. 2013 / 099640 Patent Document 4: International Publication No. 2008 / 001578 Patent Document 5: International Publication No. 2015 / 054036 Patent Document 6: International Publication No. 2004 / 078476 Patent Document 7: International Publication No. 2018 / 230513 The problem to be solved

[0012] Regarding the problem of damage to the photochromic layer, a method of laminating a layer such as a thermosetting epoxy resin on the surface of a resin layer in which a photochromic compound is dispersed has been proposed (see Patent Document 5). According to this method, since another layer is laminated on the surface of the resin layer in which a photochromic compound is dispersed, the occurrence of scratches can be further suppressed.

[0013] However, according to the inventors' review, even in the case of the method described in Patent Document 5, there was room for improvement in that cracks may occur and appearance defects may occur due to insufficient adhesion during manufacturing.

[0014] Accordingly, the present invention aims to provide a moisture-curing polyurethane composition preferably used to form a protective layer after forming a resin layer (hereinafter also referred to as a "photochromic resin layer") in which a photochromic compound is dispersed on the surface of an optical substrate, or to form a primer layer before forming the photochromic resin layer on the surface of an optical substrate, and a laminate having a polyurethane resin layer formed of said moisture-curing polyurethane composition. means of solving the problem

[0015] Specific means for solving the above problem include the following embodiments.

[0016] <1> (A) containing moisture-curing polyurethane and (B) an organic solvent,

[0017] A moisture-curing polyurethane composition wherein (A) the moisture-curing polyurethane is obtained by reacting (A1) a polyisocyanate compound having two or more isocyanate groups in its molecule and (A2) a low molecular weight polyol compound having two or more hydroxyl groups in its molecule and a number average molecular weight of 50 to 300, and isocyanate groups at the molecular ends.

[0018] <2> The above (A1) polyisocyanate compound having two or more isocyanate groups in the molecule is an aromatic polyisocyanate compound having two or more isocyanate groups in the molecule, <1> Moisture-curing polyurethane composition as described in

[0019] <3> The above (A1) molecule having two or more isocyanate groups is a moisture-curing polyurethane having isocyanate groups at the molecular ends, obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the (A1-1) molecule with a molecular weight of 400 or less and a polyol compound having two or more hydroxyl groups in the (A1-2) molecule with a number average molecular weight of 300 to 5000. <1> Moisture-curing polyurethane composition as described in

[0020] <4> The above (B) organic solvent has a solubility parameter of 8 [(cal / cm²) 3 ) 1 / 2 ] At the same time, an organic solvent that does not have active hydrogen, <1> inside <3> A moisture-curing polyurethane composition as described in any one of the claims.

[0021] <5> The above (A) moisture-curing polyurethane is a moisture-curing polyurethane having isocyanate groups at the molecular ends, obtained by further reacting at least one of (A3) a polyol compound having two or more hydroxyl groups in its molecule and a number average molecular weight of 400 to 2000, and (A4) an amine compound having one or more amino groups in its molecule. <1> inside <4> A moisture-curing polyurethane composition as described in any one of the claims.

[0022] <6> Optical material and, <1> inside <5> A laminate having a polyurethane resin layer made of a moisture-curing polyurethane composition as described in any one of the claims.

[0023] <7> Further comprising a photochromic resin layer, wherein the lamination order is the photochromic resin layer / polyurethane resin layer / optical substrate, <6> The laminate described in

[0024] <8> A photochromic resin layer further provided, wherein the lamination order is polyurethane resin layer / photochromic resin layer / optical substrate, <6> The laminate described in Effects of the invention

[0025] According to the present invention, a moisture-curing polyurethane composition is preferably used to form a protective layer after forming a photochromic resin layer on the surface of an optical substrate, or to form a primer layer before forming a photochromic resin layer on the surface of an optical substrate, and a laminate having a polyurethane resin layer formed from said moisture-curing polyurethane composition can be provided. In particular, by using the moisture-curing polyurethane composition to form a protective layer, a photochromic optical article can be provided that has good photochromic properties, suppresses the transfer of colorants from a colored protective film or surface scratches, and has good adhesion. Furthermore, by using the moisture-curing polyurethane composition to form a primer layer, an optical article with good adhesion can be provided in which a functional layer is laminated on the polyurethane resin layer without causing appearance defects. Specific details for implementing the invention

[0026] Moisture-curing polyurethane composition

[0027] The moisture-curing polyurethane composition according to the present embodiment comprises (A) a moisture-curing polyurethane (hereinafter also referred to as "Component A") and (B) an organic solvent (hereinafter also referred to as "Component B"), wherein (A) the moisture-curing polyurethane is a moisture-curing polyurethane having isocyanate groups at the molecular ends, obtained by reacting (A1) a polyisocyanate compound having two or more isocyanate groups in its molecule and (A2) a low molecular weight polyol compound having two or more hydroxyl groups in its molecule and a number average molecular weight of 50 to 300. Each component is described below.

[0028] <(A) Moisture-curing polyurethane>

[0029] (A) The moisture-curing polyurethane is a moisture-curing polyurethane having isocyanate groups at the molecular ends, obtained by reacting (A1) a polyisocyanate compound having two or more isocyanate groups in its molecule (hereinafter also referred to as “A1 component”) and (A2) a low molecular weight polyol compound having two or more hydroxyl groups in its molecule with a number average molecular weight of 50 to 300 (hereinafter also referred to as “A2 component”).

[0030] (A) In order to suppress the ratio of soft segments and increase the ratio of hard segments in the molecular chain of the polyurethane resin while having isocyanate groups at the molecular ends of the moisture-curing polyurethane, it is preferable to set the number of moles of isocyanate groups in component A1 to n1 and the number of moles of hydroxyl groups in component A2 to n2, so that n1:n2 = 1:0.15~0.70.

[0031] In addition, (A) the moisture-curing polyurethane may be a moisture-curing polyurethane having an isocyanate group at the molecular end, obtained by further reacting at least one of (A3) a polyol compound having two or more hydroxyl groups in its molecule and a number average molecular weight of 400 to 2000 (hereinafter also referred to as "A3 component"), (A4) an amine compound having one or more amino groups in its molecule (hereinafter also referred to as "A4 component"), in addition to the A1 component and the A2 component.

[0032] [(A1) Polyisocyanate compound having two or more isocyanate groups in the molecule]

[0033] The A1 component is a polyisocyanate compound having two or more isocyanate groups within its molecule, and among them, it is preferable that (A1-1) a polyisocyanate compound having two or more isocyanate groups within its molecule with a molecular weight of 400 or less (hereinafter also referred to as "A1-1 component"), and / or (A1-1') a urethane prepolymer having isocyanate groups at the molecular ends (hereinafter also referred to as "A1-1' component") obtained by reacting the A1-1 component with (A1-2) a high molecular weight polyol compound having two or more hydroxyl groups within its molecule with a number average molecular weight of 300 to 5000 (hereinafter also referred to as "A1-2 component").

[0034] ((A1-1) Polyisocyanate compounds having two or more isocyanate groups within the molecule and a molecular weight of 400 or less)

[0035] As for the A1-1 component, it is not particularly limited to polyisocyanate compounds having two or more isocyanate groups in the molecule and a molecular weight of 400 or less. The A1 component may be used as a single type or in combination of two or more types.

[0036] Preferably usable A1-1 component includes aliphatic diisocyanate compounds such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, and 2,2,4-trimethylhexane-1,6-diisocyanate; Isomers of cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, and isophorone diisocyanate, norbornene diisocyanate, and isomers of 4,4'-methylenebis(cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, 1,9-diisocyanate-5-methylnonane, and 1,1-bis(isocyanatemethyl)cyclohexane, Alicyclic diisocyanate compounds such as 2-isocyanate-4-[(4-isocyanate-cyclohexyl)methyl]-1-methylcyclohexane, 2-(3-isocyanate-propyl)cyclohexylisocyanate, and novonandiisocyanate;Phenylcyclohexylmethane diisocyanate, mixture of isomers of 4,4'-methylenebis(phenyl isocyanate), toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1,3-bis(isocyanate-methyl)benzene, m-xylene diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, 1,3-diisocyanate-methylbenzene, 4,4'-diisocyanate-3,3'-dimethoxy(1,1'-biphenyl), 4,4'-diisocyanate-3,3'-dimethylbiphenyl, Aromatic diisocyanate compounds such as 1,2-diisocyanatebenzene, 1,4-bis(isocyanatemethyl)-2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatebenzene, 1-isocyanate-4-[(2-isocyanatecyclohexyl)methyl]2-methylbenzene, 1-isocyanate-3-[(4-isocyanatephenyl)methyl]-2-methylbenzene, 4-[(2-isocyanatephenyl)oxy]phenylisocyanate, diphenylmethanediisocyanate, etc.

[0037] When using tolylene diisocyanate, it is preferable to use a mixture of tolylene-2,4-diisocyanate (50-90 mass%) and tolylene-2,6-diisocyanate (10-50 mass%) from the perspective of ease of obtaining raw materials.

[0038] Among these, in terms of forming a rigid hard segment within the molecular chain of the polyurethane resin, it is preferable that an aromatic diisocyanate compound be included as the A1-1 component, and it is more preferable that at least one selected from tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, and m-xylene diisocyanate be included. According to this composition, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, transfer of the coloring agent from the colored protective film or scratches on the surface tend to be further suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion with the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0039] ((A1-2) High molecular weight polyol compound having two or more hydroxyl groups within the molecule and a number average molecular weight of 300 to 5000)

[0040] As the A1-2 component, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols are preferably used. The A1-2 component may be used as a single type or in combination of two or more types.

[0041] The number average molecular weight of the A1-2 component needs to be 300 to 5000 in terms of adhesion and durability. In particular, in terms of suppressing the amount of soft segments included in the molecular chains of the polyurethane resin, the number average molecular weight of the A1-2 component is preferably 300 to 1000, and more preferably 300 to 600. According to this composition, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, the transfer of the coloring agent from the colored protective film and scratches on the surface tend to be further suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion with the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0042] In addition, from the perspective that the polyurethane resin layer obtained by polymerization is highly interchangeable and appearance defects such as cracks do not occur easily, it is preferable that the number of hydroxyl groups included in the molecule of the A2 component be 2 to 6, and considering solubility in organic solvents, it is more preferable that the number of hydroxyl groups included in the molecule be 2 to 3.

[0043] Below, various compounds used as A1-2 components are described in detail.

[0044] (Polyetherpolyol)

[0045] Examples of polyether polyols used as A1-2 components include polyether polyol compounds obtained by the reaction of a compound having two or more active hydrogen-containing groups in its molecule with an alkylene oxide, or polymer polyols, urethane-modified polyether polyols, polyether ester copolymer polyols, etc., which are modified versions of the said polyether polyol compounds.

[0046] Examples of compounds having two or more active hydrogen-containing groups in the molecule include water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythritol, trimethylolpropane, and hexanetriol. One of these may be used alone, or two or more may be used in combination.

[0047] Examples of alkylene oxides include cyclic ether compounds such as ethylene oxide, propylene oxide, and tetrahydrofuran. One type may be used alone, or two or more types may be used in combination.

[0048] Polyether polyols are available as reagents or industrially. Commercially available polyether polyols include the "excenol" (registered trademark) series and "Emulstar" (registered trademark) series from AGC Co., Ltd.; and the "ADEKA polyether" series from ADEKA Co., Ltd.

[0049] (Polyester polyol)

[0050] Polyester polyols used as A1-2 components include polyester polyols obtained by the condensation reaction of polyhydric alcohols and polybasic acids.

[0051] Examples of polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, etc. One of these may be used alone, or two or more may be used in combination.

[0052] Examples of polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. One of these may be used alone, or two or more may be used in combination.

[0053] Polyester polyols are available as reagents or industrially, and commercially available polyester polyols include the “Polylite” (registered trademark) series from DIC Co., Ltd., the “Nipporan” (registered trademark) series from Toso Co., Ltd., the “MAXIMOL” (registered trademark) series from Kawasaki Kasei Kogyo Co., Ltd., and the “Gurare Polyol” (registered trademark) series from Gurare Co., Ltd.

[0054] (Polycarbonate polyol)

[0055] The polycarbonate polyols used as A1-2 components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimersandiol, ethylene oxide or propylene oxide adducts of bisphenol A, bis(β-hydroxyethyl)benzene, Examples include polycarbonate polyols obtained from the phosgenation of one or more low molecular weight polyols such as xylene glycol, glycerin, trimethylolpropane, and pentaerythritol; polycarbonate polyols obtained by an ester exchange method using ethylene carbonate, diethyl carbonate, diphenyl carbonate, etc.

[0056] Polycarbonate polyols are available as reagents or industrially. Commercially available polycarbonate polyols include the "DURANOL" (registered trademark) series from Asahi Kasei Co., Ltd., the "Kurare Polyol" (registered trademark) series from Kurare Co., Ltd., the "PLACCEL" (registered trademark) series from Daicel Co., Ltd., the "Nipporan" (registered trademark) series from Tosho Co., Ltd., and the "ETERNACOLL" (registered trademark) series from Ube Kosan Co., Ltd.

[0057] (Polycaprolactone polyol)

[0058] Polycaprolactone polyols used as A1-2 components include compounds obtained by ring-opening polymerization such as ε-caprolactone.

[0059] Polycaprolactone polyols are available as reagents or industrially. Commercially available polycaprolactone polyols include the "Fraxel" (registered trademark) series from Daicel Co., Ltd.

[0060] Among the above A1-2 components, polyester polyols and polycarbonate polyols containing aromatic rings are preferred from the perspective of improving the intermolecular forces between molecular chains of the moisture-curing urethane resin. According to this composition, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, the transfer of coloring agents from a colored protective film or scratches on the surface tend to be further suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion with the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0061] ((A1-1') Urethane Prepolymer)

[0062] The A1-1' component is a urethane prepolymer having isocyanate groups at the molecular ends, obtained by reacting the A1-1 component with the A1-2 component.

[0063] For the A1-1' component, in order to have the molecular ends as isocyanate groups, it is preferable to set the molar ratio (n3:n4) of the number of moles of isocyanate groups (n3) in the A1-1 component and the number of moles of hydroxyl groups (n4) in the A1-2 component to n3:n4 = 1:0.01 to 0.7, and more preferable to set n3:n4 = 1:0.3 to 0.6.

[0064] The method for manufacturing the A1-1' component is not particularly limited, and known methods may be employed. For example, a method may be employed in which the A1-1 component and the A1-2 component are reacted in the presence or absence of an organic solvent, preferably in an inert gas atmosphere such as nitrogen or argon, at a reaction temperature of room temperature (23°C) to 130°C. By keeping the reaction temperature at 130°C or lower, the decomposition of the A1-2 component can be suppressed, thereby obtaining the desired urethane prepolymer. The reaction time varies depending on the input ratio of the A1-1 component and the A1-2 component and the reaction temperature, but typically, the reaction should be carried out in the range of 0.5 to 24 hours. The order of addition when reacting the A1-1 component and the A1-2 component is not particularly limited, and it is also possible to add the A1-1 component and the A1-2 component appropriately during the reaction as needed.

[0065] As for the organic solvent, any organic solvent used in the prepolymer reaction is not particularly limited and examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, dioxane, toluene, hexane, heptane, ethyl acetate, butyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), etc. These organic solvents may be used in a mixture of two or more types. Among them, it is preferable to use the organic solvent described as component B below. In this case, the organic solvent used may be part of component B.

[0066] It is preferable that the amount of organic solvent used be 300 parts by mass or less per 100 parts by mass of the total amount of A1-1 and A1-2 components. By reducing the amount of organic solvent used to 300 parts by mass or less, an appropriate reaction time is achieved, and the decomposition of A1-2 components can be suppressed.

[0067] When preparing component A1-1', a catalyst for a prepolymer reaction such as dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, and 1,4-diazabicyclo[2,2,2]octane may be used. When using the catalyst, the amount used is preferably 0.001 to 3 parts by mass per 100 parts by mass of the total amount of component A1-1 and component A1-2.

[0068] In addition, when preparing component A1-1', it is desirable to perform dehydration treatment on component A1-2, the organic solvent, and the catalyst in advance and dry them sufficiently to avoid the reaction between the isocyanate groups in component A1-1 and water as an impurity.

[0069] [(A2) A low molecular weight polyol compound having two or more hydroxyl groups within the molecule and a number average molecular weight of 50 to 300]

[0070] As for the A2 component, it is not particularly limited to a low molecular weight polyol compound having a number average molecular weight of 50 to 300 and having two or more hydroxyl groups in the molecule. The A2 component may be used as a single type or in combination of two or more types.

[0071] Among these, in order to suppress the proportion of soft segments included in the molecular chain of the moisture-curing polyurethane and increase the proportion of hard segments, it is preferable that the A2 component be a low molecular weight polyol compound having two hydroxyl groups in the molecule and a number average molecular weight of 50 to 300. Furthermore, the number average molecular weight of the A2 component is preferably 50 to 200, and more preferably 50 to 100. According to this configuration, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, the transfer of the coloring agent from the colored protective film or scratches on the surface tend to be further suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion with the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0072] Examples of A2 components that can be preferably used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1,2,4-butanetriol, 1,2,6-hexanetriol, etc. Among these, it is preferable that at least one selected from 1,2-propanediol and 1,3-butanediol be included as the A2 component.

[0073] [(A3) Polyol compounds having two or more hydroxyl groups within the molecule and a number average molecular weight of 400 to 2000]

[0074] As for the A3 component, among the A1-2 components described above, one having a number average molecular weight of 400 to 2000 may be appropriate. The A3 component may be used as a single type or two or more types may be used in combination.

[0075] [(A4) Amine compound having at least one amino group]

[0076] As the A4 component, monoamines, diamines, and triamines are preferably used. The A4 component may be used as a single type or in combination of two or more types.

[0077] Preferably usable A4 components include normal butylamine, sec-butylamine, tert-butylamine, dibutylamine, diisopropylamine, 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,2,6,6-tetramethyl-4-aminopiperidine, 1,2,2,6,6-pentamethyl-4-aminomethylpiperidine, 1,2,2,6,6-pentamethyl-4-aminobutylpiperidine, isophoronediamine, ethylenediamine, 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)piperidine, Examples include bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylcyclohexyl)methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, novonandiamine, hydrazine, adipic acid dihydrazine, 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-pentanetriamine, etc.

[0078] [Usage of Ingredient A1, Ingredient A2, and Ingredients A3 and A4 added as needed]

[0079] (A) The ratio of the amounts of each of the above components constituting the moisture-curing polyurethane can be appropriately determined by taking into account the application of the moisture-curing polyurethane, but from the perspective of the balance of hardness, heat resistance, adhesion, etc. of the resulting moisture-curing polyurethane, it is desirable to have the following ratios.

[0080] That is, when the number of moles of isocyanate groups included in component A1 is n1 and the number of moles of hydroxyl groups included in component A2 is n2, it is preferable to have a molar ratio n1:n2 = 1:0.15 to 0.70, more preferable to have it = 0.25 to 0.65, and even more preferable to have it = 0.30 to 0.60. Here, n1 and n2 can be obtained by multiplying the number of moles of the compound used as each component by the number of each group present in one molecule of the compound.

[0081] And, if component A1 is component A1-1 as is, the number of moles of isocyanate groups contained in component A1-1 should be set to n1. Also, if component A1 is component A1-1' obtained by reacting component A1-1 with component A1-2, the number of moles of isocyanate groups contained in component A1-1' should be set to n1.

[0082] In addition, when the number of moles of hydroxyl groups included in the A3 component used as needed is set to n5 and the number of moles of amino groups included in the A4 component is set to n6, it is preferable to have the following ratios. That is, it is preferable to have n1:n2:(n5+n6)=1:0.15~0.70:0.01~0.7, more preferable to have n1:n2:(n5+n6)=1:0.25~0.65:0.01~0.4, and even more preferable to have n1:n2:(n5+n6)=1:0.30~0.60:0.01~0.25. Here, the above n1, n2, n5, and n6 can be obtained by multiplying the number of moles of the compound used as each component by the number of each group present in one molecule of the compound.

[0083] [(A) Isocyanate group content in moisture-curing polyurethane]

[0084] (A) The isocyanate content included in the moisture-curing polyurethane is preferably 1.0 to 15.0 mass%, more preferably 2.0 to 10.0 mass%, and more preferably 3.5 to 7.0 mass%, in terms of adhesion to an optical substrate, a photochromic resin layer, etc.

[0085] And, (A) the isocyanate group content in the moisture-curing polyurethane is determined by the back titration method of the isocyanate group.

[0086] [(A) Number average molecular weight of moisture-curing polyurethane]

[0087] (A) The number average molecular weight of the moisture-curing polyurethane is preferably 500 to 10,000, more preferably 1,000 to 3,000, and more preferably 1,000 to 2,500, in order to improve the intermolecular forces between the molecular chains of the moisture-curing polyurethane. By having such a number average molecular weight, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, the transfer of the coloring agent from the colored protective film or damage to the surface tends to be more suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion of the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0088] In addition, the number average molecular weight of (A) moisture-curing polyurethane is to be measured by gel permeation chromatography (GPC measurement) under the following conditions. Specifically, a liquid chromatograph (manufactured by Nihon Waters Co., Ltd.) is used as the apparatus. A Shodex GPC KD-806 M (exclusion limit molecular weight: 200000000) manufactured by Showa Denko Co., Ltd. is used as the column. In addition, dimethylformamide (DMF) is used as the developing solvent, and the measurement is performed under conditions of a flow rate of 1 mL / min and a temperature of 40°C. Then, polyethylene glycol is used as a standard sample, and the number average molecular weight is determined by comparative conversion. A differential refractive index meter is used as the detector. Furthermore, the measurement of (A) moisture-curing polyurethane is performed after inactivating the isocyanate groups by treating them with butylamine beforehand.

[0089] [(A) Number of urethane bonds contained in moisture-curing polyurethane]

[0090] (A) Regarding the number of urethane bonds included in the moisture-curing polyurethane, it is preferable to have 0.100 to 0.700 mol / 100 g, more preferable to have 0.200 to 600 mmol / g, and more preferable to have 0.300 to 0.500 mmol / g, in order to improve the intermolecular forces between the molecular chains of the moisture-curing polyurethane. By having such a number of urethane bonds, when a protective layer is formed using the moisture-curing urethane composition according to the present embodiment, the transfer of the coloring agent from the colored protective film or damage to the surface tends to be more suppressed. In addition, when a primer layer is formed using the moisture-curing urethane composition according to the present embodiment, the adhesion with the functional layer laminated on the primer layer is improved, and furthermore, appearance defects such as dissolution or penetration by the coating liquid forming the functional layer tend to be suppressed.

[0091] In addition, the number of urethane bonds contained in (A) moisture-curing polyurethane is calculated by determining the number of urethane bonds contained in one molecule from the molar ratio of each component used in the manufacture when theoretically reacted, and converting that number into the number of moles contained in 100 g of the moisture-curing polyurethane. When urea bonds are introduced into the molecular chain using component A4 when manufacturing (A) moisture-curing polyurethane, these urea bonds are also included in the calculation of the number of urethane bonds.

[0092] [(A) Method for manufacturing moisture-curing polyurethane]

[0093] (A) The method for manufacturing a moisture-curing polyurethane is not particularly limited and may employ known methods. For example, a method may be employed in which the A1 component and the A2 component, and the A3 component and the A4 component added as needed, are reacted in the presence or absence of an organic solvent, preferably in an inert gas atmosphere such as nitrogen or argon, at a reaction temperature of room temperature (23°C) to 130°C. By keeping the reaction temperature at 130°C or lower, the decomposition of the reactants can be suppressed, and the desired (A) moisture-curing polyurethane can be obtained. The reaction time may vary depending on the input ratio of each component and the reaction temperature, but may be carried out in the range of 0.5 to 96 hours. Additionally, if necessary, the organic solvent and / or catalyst described in the method for manufacturing the A1-1' component may be used.

[0094] The total content of component A is preferably 10 to 50 mass% with respect to the total amount of the moisture-curing polyurethane composition according to the present embodiment, and more preferably 15 to 35 mass%.

[0095] <(B) Organic Solvent>

[0096] As for the organic solvent of component B, any known organic solvent may be used without any restriction. One type of organic solvent may be used alone, or two or more types may be used in combination.

[0097] In particular, in terms of the solubility of component A, the applicability of the moisture-curing polyurethane composition to optical articles such as plastic lenses, and the storage stability of the moisture-curing polyurethane composition, the solubility parameter is 8 [(cal / cm²) 3 ) 1 / 2An organic solvent that is ] above and does not have active hydrogen is preferred. Examples of such organic solvents include toluene (8.8), ethyl acetate (9.0), xylene (8.8), acetone (10.0), tetrahydrofuran (9.4), dichloromethane (9.7), chloroform (9.3), cyclopentylmethyl ether (8.4), methyl ethyl ketone (9.3), methyl isobutyl ketone (9.6), diethyl ketone (8.7), etc., and toluene, ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, and diethyl ketone are preferred. Also, the numbers in parentheses represent solubility parameters. Solubility parameters are also referred to as Hildebrand parameters, SP values, etc.

[0098] The content of component B is preferably 100 to 1000 parts by mass and more preferably 150 to 700 parts by mass with respect to 100 parts by mass of component A, from the perspective of reaction efficiency or the influence of residual organic solvent.

[0099] <(C) Other ingredients>

[0100] The moisture-curing polyurethane composition according to the present embodiment may contain the (E) photochromic compound described below or various compounding agents known in itself, to the extent that it does not impair the effects of the present invention. Examples of compounding agents include compounds that absorb specific wavelengths, such as ultraviolet absorbers and infrared absorbers; ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, dyes, pigments, fragrances, leveling agents, silane coupling agents, glycidyl compounds, etc.

[0101] The total content of other components is preferably 0.001 to 20 parts by mass per 100 parts by mass of component A.

[0102] In particular, the moisture-curing polyurethane composition according to the present embodiment preferably contains a leveling agent to improve the smoothness of the polyurethane resin layer. Examples of leveling agents include surfactants such as silicone surfactants and fluorine-containing surfactants. Specific examples of silicone surfactants and fluorine-containing surfactants include "L-7001," "L-7002," "L-7604," "FZ-2123," and "FZ-2104" from Toray Dow Corning Co., Ltd.; "MegaFace F-470," "MegaFace F-1405," and "MegaFace F-479" from DIC Co., Ltd.; and "Fluorad FC-430" from 3M Japan Co., Ltd. The surfactants may be used in a mixture of two or more types.

[0103] The content of the leveling agent is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 0.001 to 1 part by mass and more preferably 0.01 to 0.5 parts by mass per 100 parts by mass of component A.

[0104] In addition, the moisture-curing polyurethane composition according to the present embodiment preferably contains a silane coupling agent and / or a glycidyl compound to improve adhesion.

[0105] As for the silane coupling agent, there are no particular limitations, and known compounds may be used. Among them, compounds having an alkoxy group as a hydrolytic group are preferred, and compounds having two or more alkoxy groups bonded to a silicon atom are more preferred.

[0106] Preferred silane coupling agents include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane tetramer, tetraethoxysilane penmer, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. Cyclohexylmethyldimethoxysilane, 1,2-Bis(trimethoxysilyl)ethane, 1,2-Bis(triethoxysilyl)ethane, 1,3-Bis(trimethoxysilyl)propane, 1,3-Bis(triethoxysilyl)propane, 1,6-Bis(trimethoxysilyl)hexane, 1,6-Bis(triethoxysilyl)hexane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, 3-ureidopropyltriethoxysilane, bis[3-(diethoxymethylsilyl)propyl]carbonate, trifluoropropyltrimethoxysilane, Perfluorooctylethyltriethoxysilane, γ-chloropropyltrimethoxysilane, vinyltri(β-methoxy-ethoxy)silane, allyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethoxymethylsilane, γ-mercaptopropyltrialkoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, p-styryltrimethoxysilane, 3-isocyanatepropyltriethoxysilane,Examples include those in which some or all of the hydrolyzable groups among the above organosilicon compounds have been hydrolyzed or partially condensed. A silane coupling agent may be used as a single type or in combination of two or more types.

[0107] Among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc. are preferably used as silane coupling agents that further improve adhesion.

[0108] The amount of silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 0.001 to 20 parts by mass and more preferably 0.01 to 10 parts by mass per 100 parts by mass of component A.

[0109] As for the glycidyl compound, there are no particular limitations, and known glycidyl compounds can be used. Preferred glycidyl compounds include, for example, glycidyl methacrylate.

[0110] The content of the glycidyl compound is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably 0.001 to 20 parts by mass and more preferably 0.01 to 10 parts by mass per 100 parts by mass of component A.

[0111] In addition, the moisture-curing polyurethane composition according to the present embodiment preferably contains at least one selected from the group consisting of a compound that absorbs a specific wavelength, (C1) a compound having a maximum absorption wavelength in the range of greater than 400 nm and less than or equal to 450 nm (hereinafter also referred to as "C1 component"), (C2) an ultraviolet absorber (hereinafter also referred to as "C2 component"), and (C3) a pigment having an absorption peak in the range of 550 to 600 nm (hereinafter also referred to as "C3 component").

[0112] As for the C1 component, commercially available compounds may be used without particular limitation as long as the maximum absorption wavelength is in the range of greater than 400 nm and less than or equal to 450 nm. In terms of dispersibility in the moisture-curing polyurethane composition according to the present embodiment, perylene-based compounds, porphyrin compounds, carotenoid compounds, cyanine-based compounds, etc. are preferred as the C1 component.

[0113] Examples of carotenoid compounds include carotenes such as zetacarotene. Zetacarotene can be synthesized by known methods.

[0114] Commercially available cyanine compounds may be used. Examples of commercially available products include cyanine compounds and merocyanine compounds sold by Tokyo Kasei Kogyo Co., Ltd., etc.; and Yamada Kagaku Kogyo Co., Ltd.'s product name FDB-009; etc.

[0115] Among these C1 components, it is preferable to use porphyrin compounds. Furthermore, among porphyrin compounds, it is preferable to use porphyrin metal complexes containing metals such as copper, magnesium, zinc, cobalt, titanium, tin, iron, lead, and vanadium as the central metal. Additionally, as porphyrin compounds, compounds described in International Publication No. 2018 / 230513, etc., may be preferably used.

[0116] As the above porphyrin metal complex, commercially available products may be used. Examples of commercially available products include those sold by Tokyo Kasei Kogyo Co., Ltd., and products such as FDB-001 and FDB-002 from Yamada Kagaku Kogyo Co., Ltd.

[0117] The content of the C1 component is not particularly limited and can be appropriately determined according to the intended use, etc. Among these, it is preferable that the content be 0.01 to 20 parts by mass per 100 parts by mass of component A, more preferable that it be 0.01 to 10 parts by mass, and even more preferable that it be 0.02 to 3 parts by mass.

[0118] As the C2 component, commercially available triazine compounds, benzotriazole compounds, benzophenone compounds, etc., may be used. Among these, it is desirable to have high durability while effectively absorbing long-wavelength ultraviolet light or blue light, and an ultraviolet absorber having a maximum absorption wavelength in the range of 320 to 400 nm, such as described in International Publication No. 2018 / 230513, etc., may be preferably used.

[0119] The content of component C2 is not particularly limited, but is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of component A, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 20 parts by mass.

[0120] C3 components are useful in terms of improving antifouling properties. Examples of C3 components include nitro compounds, azo compounds, anthraquinone compounds, threne compounds, porphyrin compounds, and rare earth metal compounds. Among these, porphyrin compounds and rare earth metal compounds are preferred in terms of the balance between antifouling properties and visibility, and porphyrin compounds are more preferred in terms of dispersion stability in a moisture-curing polyurethane composition. Furthermore, the porphyrin compounds of the C3 components are different from the porphyrin compounds of the C1 components.

[0121] Examples of rare earth metal compounds include complexes such as aquahydroxy(1-phenyl-1,3-butanedioneto)neodymium, aquahydroxy(phenacylphenylketonato)neodymium, aquahydroxy(1-phenyl-2-methyl-1,3-butanedioneto)neodymium, aquahydroxy(1-thiophenyl-1,3-butanedioneto)neodymium, aquahydroxy(1-phenyl-1,3-butanedioneto)erbium, and aquahydroxy(1-phenyl-1,3-butanedioneto)holonium.

[0122] Porphyrin compounds are compounds that may have various substituents on a porphyrin backbone, and, for example, compounds described in Japanese Patent Publication No. H05-194616, Japanese Patent Publication No. H05-195446, Japanese Patent Publication No. 2003-105218, Japanese Patent Publication No. 2008-134618, Japanese Patent Publication No. 2013-61653, Japanese Patent Publication No. 2015-180942, International Patent Publication No. 2012 / 020570, Japanese Patent Publication No. 5626081, Japanese Patent Publication No. 5619472, Japanese Patent Publication No. 5778109, etc. may be preferably used.

[0123] The content of the C3 component is not particularly limited and can be appropriately determined according to the intended use, etc. Among these, it is preferable that it be 0.001 to 10 parts by mass per 100 parts by mass of component A.

[0124] In addition, it is desirable to incorporate a UV stabilizer into the moisture-curing polyurethane composition according to the present embodiment, as this can improve the durability of the polyurethane resin layer. Known UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, which are products of ADEKA Co., Ltd.; 2,6-di-t-butyl-4-methyl-phenol, ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate]; Examples include BASF products such as IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, etc.

[0125] The content of the UV stabilizer is not particularly limited, but is preferably 0.001 to 10 parts by mass and more preferably 0.01 to 5 parts by mass per 100 parts by mass of component A.

[0126] To prepare component A, a catalyst such as dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, or 1,4-diazabicyclo[2,2,2]octane, or a catalyst to promote the dissociation of block isocyanates, may be added separately. In addition, when using a urethane prepolymer obtained by a prepolymer reaction, the catalyst used in the prepolymer reaction may be used as is without removing it. When using a catalyst, the amount added is preferably 0.001 to 1 part by mass per 100 parts by mass of component A.

[0127] Method for manufacturing a moisture-curing polyurethane composition

[0128] The moisture-curing polyurethane composition according to the present embodiment can be prepared by a known method. For example, a moisture-curing polyurethane composition can be obtained by mixing (A) a moisture-curing polyurethane with (B) an organic solvent and, if necessary, (C) other components and stirring. The stirring temperature can be appropriately adjusted within the range of 0 to 100°C, and the stirring time within the range of 0.1 to 48 hours. Furthermore, since isocyanate groups are present at the ends of (A) the moisture-curing polyurethane, it is preferable to prepare the composition under an inert gas atmosphere, such as argon or nitrogen, to suppress the incorporation of moisture.

[0129] <<Laminated>>

[0130] The laminate according to the present embodiment comprises an optical substrate and a polyurethane resin layer composed of the moisture-curing polyurethane composition described above. The laminate according to the present embodiment may further comprise a photochromic resin layer. When the laminate according to the present embodiment comprises a photochromic resin layer, the lamination order may be the order of photochromic resin layer / polyurethane resin layer / optical substrate, or the order of polyurethane resin layer / photochromic resin layer / optical substrate.

[0131] <Photochromic resin layer>

[0132] The photochromic resin layer is not particularly limited as long as it is composed of a resin containing a photochromic compound. As the resin, (meth)acrylate resin, polyurethane resin, polyurethaneurea resin, epoxy resin, polycarbonate resin, allyl resin, etc., may be used. Among these, (meth)acrylate resin, polyurethane resin, and polyurethaneurea resin are preferred in terms of photochromic properties (particularly, fading rate), and (meth)acrylate resin is more preferred in terms of good photochromic properties and hardness. Furthermore, the term "(meth)acrylate" refers to both "acrylate" and "methacrylate." The same applies to other terms such as "(meth)acryloyl group."

[0133] [(D) (Met)Acrylate Resin]

[0134] (D) As for the (meth)acrylate resin, it is not particularly limited, but from the view that it has good photochromic properties, a resin obtained by polymerizing (D1) a polymerizable monomer represented by the following formula (1) (hereinafter also referred to as "D1 component") and (D2) a polymerizable monomer other than the D1 component (hereinafter also referred to as "D2 component") is preferred.

[0135] ((D1) Polymerizable monomer represented by the following formula (1))

[0136] [Chemical Formula 1]

[0137]

[0138] During the meal, R 1 and R 2 Each represents a hydrogen atom or a methyl group independently, and a and b each represent an integer greater than or equal to 0 independently, and a + b is an integer greater than or equal to 2. Furthermore, the polymerizable monomer represented by the above formula (1) is often obtained as a mixture during manufacturing. Therefore, a + b is a number greater than or equal to 2 as an average value, and preferably a number between 2 and 50 as an average value.

[0139] Specific examples of the polymerizable monomer represented by the above formula (1) include, for example, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, dimethacrylate composed of a mixture of polypropylene glycol and polyethylene glycol (having two repeating units of polyethylene and two repeating units of polypropylene), polyethylene glycol dimethacrylate (particularly, a=4, b=0, average molecular weight: 330), polyethylene glycol dimethacrylate (particularly, a=9, b=0, average molecular weight: 536), polyethylene glycol dimethacrylate (particularly, a=14, Examples include b=0, average molecular weight: 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (particularly, a=0, b=7, average molecular weight: 536), polyethylene glycol diacrylate (particularly, average molecular weight: 258), polyethylene glycol diacrylate (particularly, a=4, b=0, average molecular weight: 308), polyethylene glycol diacrylate (particularly, a=9, b=0, average molecular weight: 508), polyethylene glycol diacrylate (particularly, a=14, b=0, average molecular weight: 708), polyethylene glycol methacrylate acrylate (particularly, a=9, b=0, average molecular weight: 522), etc.

[0140] ((D2) Polymerizable monomers other than D1 component)

[0141] As for the D2 component, any polymerizable monomer capable of polymerizing with the D1 component is not particularly limited and known monomers may be used. Among these, it is preferable to include a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups in the molecule, and it is more preferable to include a (D2-1) difunctional (meth)acrylate having two (meth)acryloyl groups in the molecule (hereinafter also referred to as "D2-1 component") and a (D2-2) polyfunctional (meth)acrylate having three or more (meth)acryloyl groups in the molecule (hereinafter also referred to as "D2-2 component"). Additionally, it may include a (D2-3) monofunctional (meth)acrylate having one (meth)acryloyl group in the molecule (hereinafter also referred to as "D2-3 component").

[0142] ((D2-1) 2-functional (meth)acrylate)

[0143] As for the D2 component, it is preferable to include (D2-1) a difunctional (meth)acrylate, and among them, a difunctional (meth)acrylate represented by the following formula (2) or (3), a difunctional (meth)acrylate having a urethane bond, and a difunctional (meth)acrylate not corresponding to the above are preferably used.

[0144] ((D2-1-1) A difunctional (meth)acrylate represented by the following formula (2))

[0145] [Chemical Formula 2]

[0146]

[0147] During the meal, R 3 and R 4 Each independently represents a hydrogen atom or a methyl group, and R 5 and R 6 Each independently represents a hydrogen atom or a methyl group, and R 7Silver represents a hydrogen atom or a halogen atom, and A represents -O-, -S-, -(SO2)-, -CO-, -CH2-, -CH=CH-, -C(CH3)2-, or -C(CH3)(C6H5)-. c and d each independently represent an integer greater than or equal to 1, and c+d is an average value of 2 to 30. Furthermore, the difunctional (meth)acrylate expressed by the above formula (2) can typically be obtained in the form of a mixture of molecules with different molecular weights. Therefore, c+d is expressed as an average value.

[0148] Specific examples of the difunctional (meth)acrylates represented by the above formula (2) include, for example, 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane (c+d=2, average molecular weight: 452), 2,2-bis[4-(methacryloyloxydiethoxy)phenyl]propane (c+d=4, average molecular weight: 540), 2,2-bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=7, average molecular weight: 672), 2,2-bis[3,5-dibromo-4-(methacryloyloxyethoxy)phenyl]propane (c+d=2, average molecular weight: 768), and 2,2-bis(4-(methacryloyloxydipropoxy)phenyl)propane (c+d=4, average molecular weight: 596). 2,2-Bis[4-(acryloyloxydiethoxy)phenyl]propane (c+d=4, average molecular weight: 512), 2,2-Bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=3, average molecular weight: 466), 2,2-Bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=7, average molecular weight: 642), 2,2-Bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight: 804), 2,2-Bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=17, average molecular weight: 1116), 2,2-Bis[4-(methacryloyloxypolyethoxy)phenyl]propane (c+d=30, average Examples include 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=10, average molecular weight: 776), 2,2-bis[4-(acryloyloxypolyethoxy)phenyl]propane (c+d=20, average molecular weight: 1216), etc.

[0149] ((D2-1-2) A difunctional (meth)acrylate represented by the following formula (3))

[0150] [Chemical Formula 3]

[0151]

[0152] During the meal, R 8 and R 9Each represents independently a hydrogen atom or a methyl group, e represents a number from 1 to 20 as an average value, and B and B' each represent independently a straight-chain or branched-chain alkylene group having 2 to 15 carbon atoms. If multiple B are present, the multiple B may each be the same group or different groups.

[0153] The difunctional (meth)acrylate represented by the above formula (3) can be prepared by reacting polycarbonate diol with (meth)acrylic acid.

[0154] Specific examples of polycarbonate diols include, for example, polycarbonate diol obtained by the phosgenation of trimethylene glycol (average molecular weight: 500–2000), polycarbonate diol obtained by the phosgenation of tetramethylene glycol (average molecular weight: 500–2000), polycarbonate diol obtained by the phosgenation of pentamethylene glycol (average molecular weight: 500–2000), polycarbonate diol obtained by the phosgenation of hexamethylene glycol (average molecular weight: 500–2000), polycarbonate diol obtained by the phosgenation of octamethylene glycol (average molecular weight: 500–2000), polycarbonate diol obtained by the phosgenation of nonamethylene glycol (average molecular weight: 500–2000), and polycarbonate diol obtained by the phosgenation of triethylene glycol and tetramethylene glycol (average Examples include polycarbonate diol obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol (average molecular weight: 500~2000), polycarbonediol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (average molecular weight: 500~2000), polycarbonediol obtained by phosgenation of tetramethylene glycol and octamethylene glycol (average molecular weight: 500~2000), polycarbonate diol obtained by phosgenation of hexamethylene glycol and octamethylene glycol (average molecular weight: 500~2000), and polycarbonate diol obtained by phosgenation of 1-methyltrimethylene glycol (average molecular weight: 500~2000).

[0155] ((D2-1-3) Difunctional (meth)acrylate having urethane bonds)

[0156] As for the difunctional (meth)acrylate having urethane bonds, it is preferable to obtain it by reacting a polyisocyanate compound having two or more isocyanate groups in the (A1-1) molecule described above, a polyol compound having two or more hydroxyl groups in the (A1-2) molecule, and a hydroxyl group-containing (meth)acrylate.

[0157] Specific examples of polyisocyanate compounds having two or more isocyanate groups within the molecule include, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl isocyanate, dicyclohexyl methane diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate, etc.

[0158] Specific examples of polyol compounds having two or more hydroxyl groups within the molecule include, for example, polyalkyleneglucol having repeating units of ethylene oxide, propylene oxide, or hexamethylene oxide; polyester diols such as polycaprolactone diol; polycarbonate diol, polybutadiene diol, pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane; etc.

[0159] In addition, as a difunctional (meth)acrylate having urethane bonds, a reaction mixture obtained by reacting a urethane prepolymer having isocyanate groups at the molecular ends, which is obtained by reacting the polyisocyanate compound and the polyol compound, with 2-hydroxy(meth)acrylate, or a urethane(meth)acrylate obtained by directly reacting the A1-1 component with 2-hydroxy(meth)acrylate, etc., may also be used.

[0160] Specific examples of hydroxyl group-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.

[0161] Commercially available products may be used as difunctional (meth)acrylates having urethane bonds. Examples of commercially available products include U-2 PPA (molecular weight: 482), UA-122 P (molecular weight: 1100), U-122 P (molecular weight: 1100) manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd., and EB4858 (molecular weight: 454) manufactured by Daicel Allnex Co., Ltd.

[0162] ((D2-1-4) Difunctional (meth)acrylates not corresponding to the above)

[0163] (D2-1-4) Examples of difunctional (meth)acrylates not corresponding to the above include compounds having (meth)acrylate groups at both ends of an alkylene group that may have a substituent. Among these, it is preferable to have an alkylene group having 6 to 20 carbon atoms. Specifically, examples include 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, etc.

[0164] In addition, difunctional (meth)acrylates that do not fall under the above may include difunctional (meth)acrylates containing sulfur atoms. It is preferable that the sulfur atom forms part of the molecular chain as a sulfide group. Specifically, examples include bis(2-methacryloyloxyethylthioethyl)sulfide, bis(methacryloyloxyethyl)sulfide, bis(acryloyloxyethyl)sulfide, 1,2-bis(methacryloyloxyethylthio)ethane, 1,2-bis(acryloyloxyethyl)ethane, bis(2-methacryloyloxyethylthioethyl)sulfide, bis(2-acryloyloxyethylthioethyl)sulfide, 1,2-bis(methacryloyloxyethylthioethylthio)ethane, 1,2-bis(acryloyloxyethylthioethylthio)ethane, 1,2-bis(methacryloyloxyisopropylthioisopropyl)sulfide, 1,2-bis(acryloyloxyisopropylthioisopropyl)sulfide, etc.

[0165] For each of the above D2-1 components, one type may be used alone or two or more types may be used in combination. Additionally, the components described individually may be used in combination with each other. When using a combination of multiple types of D2-1 components, the mass that serves as the standard for the B2-1 component is the sum of these amounts.

[0166] ((D2-2) Polyfunctional (meth)acrylate)

[0167] As for the D2-2 component, a polyfunctional (meth)acrylate represented by the following formula (4), a polyfunctional (meth)acrylate having urethane bonds, a polyrotaxane having (meth)acryloyl groups, and a polyfunctional (meth)acrylate not corresponding to the above are preferably used.

[0168] ((D2-2-1) Polyfunctional (meth)acrylate represented by the following formula (4))

[0169] [Chemical Formula 4]

[0170]

[0171] During the meal, R 10Representing silver, a hydrogen atom, or a methyl group, R 11 Representing silver, a hydrogen atom, or an alkyl group having 1 to 2 carbon atoms, R 12 represents a 3 to 6-valent organic group having 1 to 10 carbon atoms, f represents a number from 0 to 3 as an average value, and g represents an integer from 3 to 6. R 11 As for the alkyl group having 1 to 2 carbon atoms represented by, a methyl group is preferred. R 12 Examples of organic groups represented by [the name] include groups derived from polyols, 3 to 6-valent hydrocarbon groups, and organic groups including 3 to 6-valent urethane bonds.

[0172] Specific examples of the polyfunctional (meth)acrylate expressed by the above formula (4) include, for example, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, etc.

[0173] ((D2-2-2) Polyfunctional (meth)acrylate having urethane bonds)

[0174] (D2-2-2) A polyfunctional (meth)acrylate having urethane bonds is obtained by reacting the above-described A1-1 component with the A1-2 component and / or A2 component, and further reacting a hydroxyl group-containing (meth)acrylate, and among these, it is preferable to have three or more (meth)acryloyl groups in the molecule.

[0175] Commercially available products may be used as polyfunctional (meth)acrylates having urethane bonds. Examples of commercially available products include U-4 HA (molecular weight: 596, number of functional groups: 4), U-6 HA (molecular weight: 1019, number of functional groups: 6), U-6 LPA (molecular weight: 818, number of functional groups: 6), and U-15 HA (molecular weight: 2300, number of functional groups: 15), manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.

[0176] ((D2-2-3) Polyrotaxane having (meth)acryloyl groups)

[0177] (D2-2-3) A polyrotaxane having a (meth)acryloyl group has a complex molecular structure comprising a axial molecule and a plurality of cyclic molecules that enclose the axial molecule, and a polyrotaxane in which a side chain having a hydroxyl group is introduced into the cyclic molecule, wherein the hydroxyl group of the side chain is modified by 1 mol% or more and less than 100 mol% with a compound having a (meth)acryloyl group. In addition, in this specification, the reaction of reacting the hydroxyl group of the side chain with another compound to introduce a structure derived from the other compound is also referred to as "modification."

[0178] Polyrotaxanes having (meth)acryloyl groups can be manufactured according to known methods described in International Publication No. 2018 / 030275, etc.

[0179] ((D2-2-4) Polyfunctional (meth)acrylates not corresponding to the above)

[0180] (D2-2-4) Polyfunctional (meth)acrylates not corresponding to the above may include, for example, compounds in which the terminals of a polyester compound are modified with (meth)acryloyl groups. Various polyester (meth)acrylate compounds are commercially available depending on the molecular weight of the raw polyester compound or the amount of modification of the (meth)acryloyl groups, and these commercially available products may be used. Specific examples of polyester (meth)acrylate compounds include, for example, tetrafunctional polyester oligomers (molecular weight: 2500–3500, manufactured by Daicel All Nex Co., Ltd., EB80, etc.), hexafunctional polyester oligomers (molecular weight: 6000–8000, manufactured by Daicel All Nex Co., Ltd., EB450, etc.), hexafunctional polyester oligomers (molecular weight: 45000–55000, manufactured by Daicel All Nex Co., Ltd., EB1830, etc.), tetrafunctional polyester oligomers (molecular weight: 10000, manufactured by Daiichi Kokyose Iyaku Co., Ltd., GX8488B, etc.).

[0181] By using the D2-2 component exemplified above, the crosslinking density can be improved by polymerization as needed while maintaining photochromic properties.

[0182] For each of the above D2-2 components, one type may be used alone or two or more types may be used in combination. Additionally, the components described individually may be used in combination with each other. When using a combination of multiple types of D2-1 components, the mass that serves as the standard for the D2-2 components is the sum of these amounts.

[0183] ((D2-3) Monofunctional (meth)acrylate)

[0184] (D2-3) As a monofunctional (meth)acrylate, an example is a monofunctional (meth)acrylate represented by the following formula (5).

[0185] [Chemical Formula 5]

[0186]

[0187] During the meal, R 13 Representing silver, a hydrogen atom, or a methyl group, R 14 represents a hydrogen atom, a methyl dimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group, h represents an integer from 0 to 10, and i represents an integer from 0 to 20.

[0188] Specific examples of monofunctional (meth)acrylates represented by the above formula (5) include, for example, methoxypolyethylene glycol methacrylate (particularly, average molecular weight: 293), methoxypolyethylene glycol methacrylate (particularly, average molecular weight: 468), methoxypolyethylene glycol acrylate (particularly, average molecular weight: 218), methoxypolyethylene glycol acrylate (particularly, average molecular weight: 454), stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, etc.

[0189] [(E) Photochromic Compounds]

[0190] (E) As photochromic compounds (hereinafter also referred to as “E component”), examples include fulgide compounds, chromene compounds, spirooxazine compounds, etc., and in the present embodiment, these photochromic compounds may be used without any limitation. One type may be used alone, or two or more types may be used in combination. Examples of fulgide compounds, chromene compounds, and spirooxazine compounds include compounds described in Japanese Patent Publication No. H02-28154, Japanese Patent Publication No. S62-288830, International Patent Publication No. 94 / 22850, International Patent Publication No. 96 / 14596, etc.

[0191] In addition, compounds newly discovered by the inventors as compounds having excellent photochromic properties, for example, Japanese Patent Publication No. 2001-114775, Japanese Patent Publication No. 2001-031670, Japanese Patent Publication No. 2001-011067, Japanese Patent Publication No. 2001-011066, Japanese Patent Publication No. 2000-347346, Japanese Patent Publication No. 2000-344762, Japanese Patent Publication No. 2000-344761, Japanese Patent Publication No. 2000-327676, Japanese Patent Publication No. 2000-327675, Japanese Patent Publication No. 2000-256347, Japanese Patent Publication No. 2000-229976, Japanese Patent Publication No. 2000-229975, Japanese Published Patent Application No. 2000-229974, Japanese Published Patent Application No. 2000-229973, Japanese Published Patent Application No. 2000-229972, Japanese Published Patent Application No. 2000-219687, Japanese Published Patent Application No. 2000-219686, Japanese Published Patent Application No. 2000-219685, Japanese Published Patent Application No. H11-322739, Japanese Published Patent Application No. H11-286484, Japanese Published Patent Application No. H11-279171, Japanese Published Patent Application No. H10-298176, Japanese Published Patent Application No. H09-218301, Japanese Published Patent Application No. H09-124645, Japan Korean Patent Publication No. H08-295690, Japanese Patent Publication No. H08-176139, Japanese Patent Publication No. H08-157467, U.S. Patent Specification No. 5645767, U.S. Patent Specification No. 5658501, U.S. Patent Specification No. 5961892, U.S. Patent Specification No. 6296785, Japanese Patent Publication No. 4424981, Japanese Patent Publication No. 4424962, International Publication No. 2009 / 136668, International Publication No. 2008 / 023828, Japanese Patent Publication No. 4369754, Japanese Patent Publication No. 4301621, Japanese Patent Publication No. 4256985, International Publication No. Japanese Patent Publication No. 2007 / 086532, Japanese Patent Publication No. 2009-120536, Japanese Patent Publication No. 2009-67754,Japanese Published Patent Application No. 2009-67680, Japanese Published Patent Application No. 2009-57300, Japanese Patent Publication No. 4195615, Japanese Patent Publication No. 4158881, Japanese Patent Publication No. 4157245, Japanese Patent Publication No. 4157239, Japanese Patent Publication No. 4157227, Japanese Patent Publication No. 4118458, Japanese Published Patent Application No. 2008-74832, Japanese Patent Publication No. 3982770, Japanese Patent Publication No. 3801386, International Published Patent No. 2005 / 028465, International Published Patent No. 2003 / 042203, Japanese Published Patent Application No. 2005-289812, Japanese Published Patent Application No. 2005-289870, Japanese Patent Publication No. 2005-112772, Japanese Patent Publication No. 3522189, International Publication No. 2002 / 090342, Japanese Patent Publication No. 3471073, Japanese Patent Publication No. 2003-277381, International Publication No. 2001 / 060811, International Publication No. 2000 / 071544, International Publication No. 2005 / 028465, International Publication No. 2011 / 16582, International Publication No. 2011 / 034202, International Publication No. 2012 / 121414, International Publication No. 2013 / 042800, Japanese Patent Publication No. Compounds disclosed in Japanese Patent Application No. 6031035, Japanese Patent Application No. 2019-120178, Japanese Patent Application No. 2019-190604, Japanese Patent Application No. 2020-025057, Japanese Patent Application No. 2020-031674, Japanese Patent Application No. 2020-033969, etc. may also be preferably used.

[0192] Among these E components, it is more preferable to use one or more chromene compounds having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton in terms of photochromic properties such as color intensity, initial color, durability, and fading speed. In addition, among these chromene compounds, compounds with a molecular weight of 540 or more are preferred because their color intensity and fading speed are particularly excellent.

[0193] In addition, as component E, any compound having a long chain group with a molecular weight of 300 or more as a substituent, particularly a polysiloxane chain, a polyoxyalkylene chain, a polyester chain, or a polyester-polyether chain, may be appropriately selected and used. Since a molecular chain with a molecular weight of 300 or more is a high molecular weight, when preparing a photochromic compound, there may be cases where multiple types of molecular chains are present rather than just one type. In such cases, the molecular weight of the above molecular chains is such that the average value (number average molecular weight) of the multiple types falls within the range specified above. This molecular weight can be determined by the type of raw material used during the preparation of the photochromic compound, or it can be determined from the product by known means such as NMR, IR, or mass spectrometry.

[0194] It can be assumed that a higher level of photochromicity can be exhibited even within a photochromic resin layer by having a molecular chain with a molecular weight of 300 or more. Considering the photochromicity, the amount of the photochromic compound, and the productivity of the photochromic compound itself, the molecular weight of the above molecular chain is preferably 300 to 25000, more preferably 400 to 20000, even more preferably 440 to 15000, and particularly preferably 500 to 10000.

[0195] When a photochromic compound has molecular chains with a molecular weight of 300 or more, it is preferable that the number of said molecular chains be 0.5 or more per molecule of the photochromic compound. That is, even when the number of said molecular chains is at its smallest, it is preferable to have a structure such as combining two photochromic compounds with said molecular chains. Considering the balance with the molecular weight of the molecular chains and photochromic properties, the upper limit of the number of said molecular chains is preferably 4 or fewer, more preferably 2 or fewer, and even more preferably 1.

[0196] In addition, for component E, it is desirable that the molecular structure exhibiting photochromic properties causes a portion of the molecule to cleave upon light irradiation to develop color, and that the cleavage portion recombines to fade. Therefore, for a photochromic compound to reversibly repeat color development and fading, it is important that there is a free space (molecular degrees of freedom) that does not hinder the movement of the molecule when cleavage and recombination occur. In the case of a compound having such a molecular structure, it can be considered that the effect of the above molecular chain is particularly exerted.

[0197] Examples of such photochromic compounds include, for example, International Publication No. 2000 / 015630, International Publication No. 2004 / 041961, International Publication No. 2005 / 105874, International Publication No. 2005 / 105875, International Publication No. 2006 / 022825, International Publication No. 2009 / 146509, International Publication No. 2010 / 20770, International Publication No. 2012 / 121414, International Publication No. 2012 / 149599, International Publication No. 2012 / 162725, International Publication No. 2012 / 176918, International Publication No. 2013 / 078086, International Publication No. Examples of compounds described in Patent Publication No. 2019 / 013249, International Publication No. 2019 / 203205, International Publication No. 2020 / 017610, International Publication No. 2019 / 203205, Japanese Patent Publication No. 2019-182866, etc.

[0198] The content of component E is preferably 0.01 to 20 parts by mass per 100 parts by mass of the photochromic resin layer, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass.

[0199] [Mixing ratio of each component in the photochromic resin layer]

[0200] Considering photochromic properties such as the color intensity and fading speed of the resulting photochromic resin layer, the mixing ratio of the above-described D1 component and D2 component is preferably such that when the total amount of the D1 component and D2 component is 100 parts by mass, the D1 component is 40 to 95 parts by mass and the D2 component is 5 to 60 parts by mass.

[0201] In addition, it is preferable that the D2 component includes the D2-2 component and, if necessary, the D2-1 component and the D2-3 component. More specifically, when the total amount of the D2 component is 100 parts by mass, it is preferable to have the D2-1 component in an amount of 0 to 30 parts by mass, the D2-2 component in an amount of 50 to 100 parts by mass, and the D2-3 component in an amount of 0 to 50 parts by mass.

[0202] In addition, considering photochromic properties such as the color intensity and fading speed of the resulting photochromic resin layer, the mixing ratio of the photochromic compound is preferably 0.1 to 10 parts by mass when the total amount of component D1 and component D2 is 100 parts by mass, and more preferably 2 to 10 parts by mass.

[0203] [Other ingredients]

[0204] The photochromic resin layer may contain a polymerization initiator, such as a thermal polymerization initiator or a photopolymerization initiator.

[0205] Examples of thermal polymerization initiators include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; peroxyesters such as t-butyl peroxy-2-ethylhexanate, t-butyl peroxyneodecanate, cumyl peroxyneodecanate, and t-butyl peroxybenzoate; percarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; and azo compounds such as azobisisobutyronitrile.

[0206] Examples of photopolymerization initiators include acetophenone compounds such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; and acylphosphine oxide compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide.

[0207] In addition, when using a photopolymerization initiator, known polymerization curing accelerators such as tertiary amines may be used in combination.

[0208] In addition, the photochromic resin layer may contain various additives that are known in themselves, in addition to the components described above, to the extent that they do not impair the effects of the present invention. Examples of additives include ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, dyes, pigments, fragrances, solvents, leveling agents, etc.

[0209] Among these, the use of UV stabilizers is desirable because it can improve the durability of photochromic compounds. Known UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly preferred UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; Adecastav LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, which are products of ADEKA Co., Ltd.; 2,6-di-t-butyl-4-methyl-phenol; and ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate]. Examples include BASF products such as IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, 254; etc.

[0210] The amount of UV stabilizer incorporated is not particularly limited as long as it does not impair the effects of the present invention, but typically, it is preferably 0.001 to 10 parts by mass and 0.01 to 3 parts by mass with respect to 100 parts by mass of the total amount of component D1 and component D2. In particular, when using a hindered amine light stabilizer, in order to prevent color separation of the adjusted color tone from occurring as a result of differences in the durability improvement effect depending on the type of photochromic compound, it is preferable to have 0.5 to 30 moles per mole of photochromic compound, more preferable to have 1 to 20 moles, and even more preferable to have 2 to 15 moles.

[0211] Optical Materials

[0212] Examples of optical substrates include plastic lens substrates. Examples of plastic lens substrates include thermoplastic resin lenses such as (meth)acrylic resin and polycarbonate resin; crosslinkable resin lenses such as multifunctional (meth)acrylic resin, allyl resin, thiourethane resin, urethane resin, and thioepoxy resin; etc. Furthermore, it is also applicable to plastic lens substrates in which a hard coating layer, etc., is laminated thereon.

[0213] The optical substrate may be subjected to chemical treatment with an alkaline solution, an acidic solution, etc., or physical treatment with corona discharge, plasma discharge, polishing, etc., to improve adhesion with a photochromic resin layer, etc.

[0214] In addition, when the moisture-curing polyurethane composition described above is laminated onto a photochromic resin layer of an optical article to be used as a protective layer, another layer may be laminated between the optical substrate and the photochromic resin layer, or between the photochromic resin layer and the protective layer made of the moisture-curing polyurethane composition, to the extent that the effects of the present invention are not impaired. For example, before forming a photochromic resin layer on the surface of the optical substrate, it is possible to provide a primer layer such as a polyurethane-based, polyester-based, polyvinyl acetal-based, or epoxy-based layer on the surface of the optical substrate. Of course, the moisture-curing polyurethane composition described above may also be used to form the primer layer.

[0215] As for the primer layer, it is possible to use a known polyurethane resin. Among these, from the perspective of adhesion, a primer layer composed of a moisture-curing polyurethane resin or its precursor as described in Japanese Patent Publication No. 4405833, or a water-dispersible urethane emulsion as described in Japanese Patent Publication No. 5016266 or Japanese Patent Publication No. 5084727 is preferred.

[0216] Method for forming a photochromic resin layer on an optical substrate

[0217] (D) The photochromic resin layer is preferably formed by preparing a photochromic monomer composition by mixing, for example, each monomer component described above, a photochromic compound, and other components as needed, and polymerizing this on an optical substrate.

[0218] Polymerization for producing a photochromic resin layer is carried out by irradiation with active energy rays (ultraviolet rays, α rays, β rays, γ rays, LED light, etc.), heating, or a combination of both. That is, depending on the type of polymerizable monomer or polymerization curing accelerator used and the shape of the photochromic resin layer to be formed, an appropriate polymerization means may be employed. When forming a photochromic resin layer by the coating method described later, it is preferable to employ photopolymerization for the reason that a uniform film thickness is obtained.

[0219] When photopolymerizing a photochromic monomer composition, the light intensity conditions, in particular among the polymerization conditions, affect the properties and state of the resulting photochromic resin layer. Since these light intensity conditions are influenced by the type and amount of the photopolymerization initiator and the type of polymerizable monomer, they cannot be limited to a single value; however, generally, they are 10 to 500 mW / cm² at a wavelength of 365 nm. 2 It is preferable to select conditions to irradiate with UV light for 0.1 to 5 minutes.

[0220] When forming a photochromic resin layer by the coating method described above, a photochromic monomer composition is used as a coating solution, and the coating solution is applied to the surface of an optical substrate, such as a lens substrate, by spin coating, dipping, etc., and then polymerization is performed by UV irradiation or heating in an inert gas such as nitrogen, thereby forming a photochromic resin layer on the surface of the optical substrate.

[0221] When forming a photochromic resin layer on the surface of an optical substrate by the coating method described above, the adhesion between the photochromic resin layer and the optical substrate can be enhanced by performing chemical treatments such as using an alkaline solution or an acidic solution, or physical treatments such as corona discharge, plasma discharge, or polishing on the surface of the optical substrate in advance. Of course, it is also possible to separately provide a transparent adhesive resin layer on the surface of the optical substrate.

[0222] The aforementioned photochromic resin layer can exhibit excellent photochromic properties, such as color intensity and, in particular, fading speed, and is effectively used in the production of optical substrates endowed with photochromic properties, such as photochromic lenses. Furthermore, although a coating method was described as a method for forming the photochromic resin layer, the photochromic resin layer may also be formed by other methods, such as mold polymerization.

[0223] Method for forming a polyurethane resin layer on an optical substrate and / or a photochromic resin layer

[0224] A method for forming a polyurethane resin layer composed of a moisture-curing polyurethane composition is not particularly limited, but, for example, it is preferable to prepare a moisture-curing polyurethane composition containing (A) a moisture-curing polyurethane and (B) an organic solvent, apply this to an optical substrate and / or a photochromic resin layer formed on an optical substrate, and form a polyurethane resin layer by curing it by drying in the presence of moisture (i.e., moisture in the air). If necessary, additional heating is also possible.

[0225] The method of applying a moisture-curing polyurethane composition onto an optical substrate and / or a photochromic resin layer is not particularly limited, and methods such as dip coating, spin coating, dip-spin coating, dip-and-spin coating, and flow coating may be employed. Among these, spin coating is preferred in terms of reacting with moisture (i.e., moisture in the air).

[0226] In addition, the above curing may be achieved simply by drying in the presence of moisture (i.e., moisture in the air) after applying the moisture-curing polyurethane composition, but heat treatment and / or heated humidification treatment may also be performed to accelerate drying within a range that does not affect the heat resistance of the optical substrate or resin.

[0227] Specifically, the temperature for accelerating drying is preferably in the range of room temperature (23°C) to 130°C. In addition, the humidity for speeding up drying is preferably in the range of 45%RH to 95%RH. Within this range, deformation or discoloration of the optical substrate due to heating can be suppressed. The heating time is not particularly limited, but is typically in the range of 1 minute to 6 hours, and the heating and humidification time is not particularly limited, but is typically in the range of 5 minutes to 48 hours.

[0228] The thickness of the moisture-curing polyurethane resin layer is not particularly limited, but considering the appearance, adhesion, hardness of the UV lens and the smoothness of the moisture-curing polyurethane resin layer formed, it is preferable to have a thickness of 0.1 to 10 μm, more preferable to have a thickness of 0.1 to 8 μm, and more preferable to have a thickness of 0.5 to 5 μm.

[0229] In addition, depending on the application, the laminate according to the present embodiment may be subjected to post-processing such as dyeing using a dye such as a disperse dye; making a hard coating film using a hard coating agent mainly composed of a silane coupling agent or a colloidal solution of silicon, zirconium, antimony, aluminum, tin, tungsten; forming a thin film by depositing a metal oxide such as SiO2, TiO2, ZrO2; or anti-reflective treatment, antistatic treatment, mirror coating treatment, water-repellent treatment, hydrophilization treatment, antifogging treatment, anti-fouling treatment, or (near)infrared cutting treatment by forming a thin film coated with an organic polymer.

[0230] Examples

[0231] Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. Each of the above components and evaluation methods, etc., are as follows.

[0232] Moisture-curing polyurethane composition

[0233] [A1-1 component]

[0234] TDI: A mixture of tolylene-2,4-diisocyanate (80 mass%) and tolylene-2,6-diisocyanate (20 mass%) (molecular weight: 174)

[0235] MDI: 4,4-Diphenylmethane diisocyanate (Molecular weight: 250)

[0236] XDI: m-xylene diisocyanate (molecular weight: 188)

[0237] IPDI: Isophorone diisocyanate (mixture of isomers) (Molecular weight: 222)

[0238] [A1-2 Components and A3 Components]

[0239] PL1: Product of Asahi Kasei Co., Ltd., Duranol (polycarbonate diol derived from 1,5-pentanediol and hexanediol, number average molecular weight: 500)

[0240] PL2: Polypropylene glycol (Number average molecular weight: 400)

[0241] PL3: Product of Asahi Kasei Co., Ltd., Duranol (polycarbonate diol derived from 1,5-pentanediol and hexanediol, number average molecular weight: 1000)

[0242] PL4: Product of Asahi Kasei Co., Ltd., Duranol (polycarbonate diol derived from 1,5-pentanediol and hexanediol, number average molecular weight: 2000)

[0243] PL5: Polyester polyol derived from adipic acid and 3-methyl-1,5-pentanediol (Number average molecular weight: 500)

[0244] PL6: Polyester polyol made from isophthalic acid and 3-methyl-1,5-pentanediol (number average molecular weight: 500)

[0245] PL7: Daicel Co., Ltd. product, Fraxel (polycaprolactone diol, number average molecular weight: 500)

[0246] [A2 Component]

[0247] EG: Ethylene glycol (Molecular weight: 62)

[0248] PG1: 1,2-propanediol (molecular weight: 76)

[0249] PG2: 1,3-propanediol (molecular weight: 76)

[0250] BG: 1,3-butanediol (molecular weight: 90)

[0251] HG: 1,6-Hexanediol (Molecular weight: 118)

[0252] TMP: Trimethylolpropane (Molecular weight: 134)

[0253] [A4 Ingredients]

[0254] IPDA: Isophoronediamine (mixture of isomers)

[0255] [Component B (solubility parameters in parentheses)]

[0256] B1: Diethyl ketone (8.7)

[0257] B2: Toluene (8.8)

[0258] B3: Ethyl acetate (9.0)

[0259] [Other ingredients]

[0260] L7001: Product of Toray Dow Corning Co., Ltd., Product name; L7001 (Leveling agent)

[0261] <Photochromic Monomer Composition>

[0262] [D1 Component]

[0263] 14G: Polyethylene glycol dimethacrylate (Average ethylene glycol chain length: 14, Average molecular weight: 736)

[0264] A-400: Polyethylene glycol diacrylate (Average chain length of ethylene glycol: 9, Average molecular weight: 508)

[0265] [D2 component]

[0266] TMPT: Trimethylolpropane trimethacrylate

[0267] D-TMP: Ditrimethylolpropane tetraacrylate

[0268] SI-1: γ-methacryloyloxypropyltrimethoxysilane

[0269] GMA: Glycidyl methacrylate

[0270] RX-1: Polyrotaxane having (meth)acryloyl groups

[0271] In addition, RX-1 was synthesized according to the method described in International Publication No. 2018 / 030275. The characteristics of RX-1 are as follows.

[0272] Mass average molecular weight (Mw) measured by GPC: 880,000

[0273] Acryloyl modification ratio: 85 mol%

[0274] Percentage of hydroxyl groups remaining in the side chain: 15 mol%

[0275] Axis molecule; linear polyethylene glycol (PEG) with a molecular weight of 20,000

[0276] Inclusion ring; α-cyclodextrin (α-CD) (Introduction ratio: 0.25)

[0277] Terminal of the axial molecule; encapsulation with adamantane

[0278] Side chain introduced into the inclusion ring: The (average) molecular weight of the side chain is approximately 600

[0279] [Photochromic Compound]

[0280] PC1: A compound represented by the following formula

[0281] [Chemical Formula 6]

[0282]

[0283] [Other ingredients]

[0284] CGI: Phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (Trade name: Omnirad 819, IGM product) (Polymer initiator)

[0285] HALS: Bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (Molecular weight: 508) (UV stabilizer)

[0286] HP: Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate](BASF product, Irganox 245)(UV stabilizer)

[0287] L7001: Product of Toray Dow Corning Co., Ltd., L7001 (Leveling agent)

[0288] <Preparation Example 1: Preparation of Moisture-Curing Polyurethane Composition (PU1)>

[0289] TDI (90 g), which is component A1-1, PL1 (130 g), which is component A1-2, and toluene (235 g), which is an organic solvent (hereinafter referred to as one component of component B), were added to a reaction vessel equipped with a stirrer chip, a cooling tube, a thermometer, a nitrogen gas inlet tube, and a stirrer, and mixed uniformly. A prepolymer reaction was carried out on this mixture under a nitrogen atmosphere at 90°C to obtain a urethane prepolymer solution.

[0290] In addition, PG1 (9.8 g), which is component A2, and ethyl acetate (125 g), which is component B, were added to the urethane prepolymer solution obtained by the above method, adjusted to 75°C, and the reaction was carried out.

[0291] To the above reaction solution, ethyl acetate (360 g), which is component B, and L7001 (1.0 g), which is another component, were additionally added and stirred under a nitrogen atmosphere until homogeneous to obtain a moisture-curing polyurethane composition (PU1). The composition of the moisture-curing polyurethane composition (PU1) is shown in Table 1.

[0292] (Measurement of number average molecular weight of moisture-curing polyurethane)

[0293] The number average molecular weight of the moisture-curing polyurethane obtained in Preparation Example 1 was measured by gel permeation chromatography (GPC measurement) under the following conditions. A liquid chromatograph (manufactured by Nihon Waters Co., Ltd.) was used as the apparatus. A Shodex GPC KD-806 M (exclusion limit molecular weight: 200000000) manufactured by Showa Denko Co., Ltd. was used as the column. Additionally, the measurement was performed using dimethylformamide (DMF) as the developing solvent under conditions of a flow rate of 1 mL / min and a temperature of 40°C. The number average molecular weight was determined by comparative conversion using polyethylene glycol as a standard sample. A differential refractive index meter was used as the detector. The measurement of the moisture-curing polyurethane was performed after inactivating the isocyanate groups by prior treatment with butylamine. The number average molecular weight of the moisture-curing polyurethane obtained by this method was 1800.

[0294] (Measurement of isocyanate group content in moisture-curing polyurethane)

[0295] The isocyanate group content in the moisture-curing polyurethane was determined by the back titration method of isocyanate groups. The back titration of isocyanate groups was performed in the following order.

[0296] 1) 12.5 g of n-butylamine was added to 500 mL of dehydrated dioxane and stirred until homogeneous to prepare an n-butylamine / dioxane solution.

[0297] 2) 10 mL of the n-butylamine / dioxane solution was taken into a 110 mL screw tube using a volumetric pipette, and approximately 20 mL of THF and 3 drops of bromocresol blue 1% ethanol solution were added. The solution was titrated with 0.1 mol / L aqueous sulfuric acid solution while stirring, with the endpoint set as the point where the color changed from blue to yellowish-green or yellow. A 50 mL burette was used for the titration. Two measurements were performed, and a blank value was calculated from the average (unit: mL).

[0298] 3) About 1 g of a moisture-curing polyurethane composition was weighed into a 110 mL screw tube to the nearest 0.01 g, about 20 mL of THF was added, followed by the addition of 10 mL of the butylamine / dioxane solution using a volumetric pipette, and the mixture was homogenized by stirring. After confirming that it was homogenized, the mixture was titrated with a 0.1 mol / L aqueous sulfuric acid solution while stirring.

[0299] 4) The isocyanate group content (NCO amount) was calculated by the following formula.

[0300] [Mathematical Formula 1]

[0301]

[0302] In the formula, f is the titer of the 0.1 mol / L aqueous sulfuric acid solution used for titration, and is 1 in this titration. The solid content was determined using the results measured by the method described below. The isocyanate group content of the moisture-curing polyurethane obtained in Preparation Example 1, obtained by this method, was 4.7 mass%.

[0303] (Calculation of the number of urethane bonds contained in moisture-curing polyurethane)

[0304] The number of urethane bonds contained in the moisture-curing polyurethane was determined by calculating the number of urethane bonds contained in one molecule from the molar ratio of each component when each component used in the preparation theoretically reacts, and converting that number into the number of moles contained in 100 g of the moisture-curing polyurethane. The number of urethane bonds in the moisture-curing polyurethane obtained in Preparation Example 1, calculated by this method, was 0.333 mol / 100 g.

[0305] (Measurement of solid content of moisture-curing polyurethane composition)

[0306] The solid content of the moisture-curing polyurethane composition was measured in the following order. First, a convection oven was set to 120°C.

[0307] 1) The weight of the empty container (aluminum cup) was measured to the nearest 0.0001 g (Weight 1).

[0308] 2) About 2 g of moisture-curing polyurethane composition was placed in a container (aluminum cup) and weighed to the nearest 0.0001 g (weight 2).

[0309] 3) It was dried for 3 hours in a convection oven set to 120℃.

[0310] 4) The moisture-curing polyurethane composition after drying was weighed to the nearest 0.0001 g per container (weight 3), and the solid content concentration was calculated using the following formula.

[0311] [Mathematical Formula 2]

[0312]

[0313] The solid content of the moisture-curing polyurethane composition obtained in Preparation Example 1, obtained by this method, was 24.2 mass%.

[0314] (Viscosity measurement of moisture-curing polyurethane compositions)

[0315] The viscosity of the moisture-curing polyurethane composition was measured using a Canon Penske clay system. Specifically, 10 mL of the moisture-curing polyurethane composition was weighed into the Canon Penske clay system using a volumetric pipette, and the Canon Penske clay system was placed in a constant temperature water bath (25 ± 0.1°C) set to 25°C and left for 15 minutes, after which the kinematic viscosity was measured. In addition, the specific gravity was measured using a buoyancy scale, and the viscosity was calculated by multiplying the kinematic viscosity by the specific gravity. The viscosity of the moisture-curing polyurethane composition obtained in Preparation Example 1, calculated by this method, was 5.2 mPa·s.

[0316] <Preparation Example 2: Preparation of Moisture-Curing Polyurethane Composition (PU2)>

[0317] TDI (90 g), which is component A1-1, PL2 (103 g), which is component A1-2, and toluene (193 g), which is an organic solvent (hereinafter referred to as one component of component B), were added to a reaction vessel equipped with a stirring chip, a cooling tube, a thermometer, a nitrogen gas inlet tube, and a stirrer, and mixed uniformly. A prepolymer reaction was carried out on this mixture under a nitrogen atmosphere at 90°C to obtain a urethane prepolymer solution.

[0318] In addition, PG1 (9.8 g), which is component A2, was added to the urethane prepolymer solution obtained by the above method, the temperature was adjusted to 75°C, and the reaction was carried out.

[0319] To the above reaction solution, ethyl acetate (396 g), which is component B, and L7001 (0.8 g), which is another component, were additionally added and stirred under a nitrogen atmosphere until homogeneous, thereby obtaining a moisture-curing polyurethane composition (PU2). The composition of the moisture-curing polyurethane composition (PU2) is shown in Table 1.

[0320] <Preparation Example 3: Preparation of Moisture-Curing Polyurethane Composition (PU3)>

[0321] TDI (90 g), which is component A1-1, PL2 (103 g), which is component A1-2, and toluene (193 g), which is an organic solvent (hereinafter referred to as one component of component B), were added to a reaction vessel equipped with a stirrer tip, a cooling tube, a thermometer, a nitrogen gas inlet tube, and a stirrer, and mixed uniformly. The temperature of this mixture was adjusted to 90°C to perform a prepolymer reaction, thereby obtaining a urethane prepolymer solution.

[0322] In addition, PG1 (4.9 g), which is component A2, was added to the urethane prepolymer solution obtained by the above method, the temperature was adjusted to 75°C, and the reaction was carried out. Then, TMP (8.7 g), which is component A2, and ethyl acetate (117 g), which is component B, were added, and the reaction was carried out at 75°C.

[0323] To the above reaction solution, ethyl acetate (517 g), which is component B, and L7001 (1.1 g), which is another component, were additionally added and stirred under a nitrogen atmosphere until homogeneous, thereby obtaining a moisture-curing polyurethane composition (PU3). The composition of the moisture-curing polyurethane composition (PU3) is shown in Table 1.

[0324] [Table 1]

[0325]

[0326] <Preparation Examples 4–24: Preparation of Moisture-Curing Polyurethane Compositions (PU4–PU24)>

[0327] Moisture-curing polyurethane compositions (PU4 to PU24) were prepared in the same manner as in Preparation Example 1 using each component shown in Tables 2 to 4. The compositions of the moisture-curing polyurethane compositions (PU4 to PU24) are shown in Tables 2 to 4.

[0328] [Table 2]

[0329]

[0330] [Table 3]

[0331]

[0332] [Table 4]

[0333]

[0334] <Preparation Example 25: Preparation of Moisture-Curing Polyurethane Composition (PU25)>

[0335] To a moisture-curing polyurethane composition (PU1) (300 parts by weight), a porphyrin compound (FDB-002 manufactured by Yamada Chemical Co., Ltd., maximum absorption wavelength: 431 nm, absorption coefficient: 380 L / mol·cm, half-width: 18 nm) (0.03 parts by weight), a benzotriazole-based UV absorber (SEESORB 703 manufactured by Cyprocasey Co., Ltd., maximum absorption wavelength: 345 nm, absorption coefficient: 50 L / g·cm, half-width: 90 nm) (7 parts by weight), and Mitsubishi Chemical Co., Ltd.'s "Dia Resin Blue J" (maximum absorption wavelength: 590 nm, absorption coefficient: 35 L / g·cm, half-width: 110 nm) (0.04 parts by weight) are added, and the mixture is sufficiently stirred and mixed under a nitrogen atmosphere until homogeneous, thereby providing a composition having UV absorption capability. A moisture-curing urethane composition (PU25) was obtained.

[0336] <Preparation Example 26: Preparation of Photochromic Composition (1)>

[0337] Polyethylene glycol dimethacrylate (14 G) (average chain length of ethylene glycol: 14, average molecular weight: 736) (40 parts by mass), polyethylene glycol diacrylate (A-400) (average chain length of ethylene glycol: 9, average molecular weight: 508) (21 parts by mass), trimethylolpropane trimethacrylate (TMPT) (30 parts by mass), RX-1 (3 parts by mass), SI-1 (3 parts by mass), glycidyl methacrylate (GMA) (1 part by mass), photochromic compound PC1 (2 parts by mass), CGI (0.3 parts by mass), HALS (3 parts by mass), HP (1 part by mass), and L7001 (0.1 parts by mass) were added and stirred and mixed at 70°C for 15 minutes to obtain a photochromic composition (1) used in a coating method. The composition of the photochromic composition (1) is shown in Table 5.

[0338] <Preparation Example 27: Preparation of Photochromic Composition (2)>

[0339] A photochromic curable composition (2) was prepared in the same manner as in Preparation Example 26, except that the materials shown in Table 3 were used. The composition of the photochromic composition (1) is shown in Table 5.

[0340] [Table 5]

[0341]

[0342] <Example 1>

[0343] [Formation of Photochromic Resin Layer]

[0344] First, a thiourethane-based plastic lens with a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. Then, the thiourethane-based plastic lens was subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and subsequently, thoroughly cleaned with distilled water.

[0345] Next, using a spin coater (1 H-DX2, manufactured by Mikasa Bushiki Kaisha), a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Kabushiki Kaisha) was coated on the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds, followed by 1000 rpm for 10 seconds.

[0346] After that, a photochromic composition (1) (2 g) was spin-coated onto a moisture-curing primer layer of an optical substrate at a rotation speed of 100 rpm for 30 seconds, followed by at 800 rpm for 10 to 20 seconds, until the film thickness became 40 μm.

[0347] Thereafter, the lens having the above composition coated on its surface is placed in a nitrogen gas atmosphere at an output of 200 mW / cm² 2 The composition was polymerized by irradiating light for 80 seconds using a metal halide lamp. Afterwards, the composition was further heated at 110°C for 1 hour to form a photochromic resin layer with a thickness of 40 μm on an optical substrate, the resin obtained by polymerizing the photochromic composition (1).

[0348] [Formation of Polyurethane Resin Layer]

[0349] First, the optical substrate having the above-mentioned photochromic resin layer formed thereon was subjected to alkaline etching at 50°C for 5 minutes using a 10% sodium hydroxide aqueous solution, and then thoroughly washed with distilled water.

[0350] Next, the moisture-curing polyurethane composition (PU1) prepared in Preparation Example 1 was spin-coated onto the surface of a photochromic resin layer of an optical substrate using a spin coater (1 H-DX2, manufactured by Mikasa Bushiki Kaisha) and dried for 10 minutes under conditions of 25°C and 50% RH. At this time, the film thickness of the polyurethane resin layer was set to 2 to 3 μm.

[0351] [Evaluation of Photochromic Optical Products]

[0352] For the photochromic optical articles obtained above, each of the evaluations shown below was performed. The evaluation results are shown in Table 6.

[0353] (Photochromic)

[0354] A obtained photochromic optical article was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was applied to it through an aeromass filter (manufactured by Corning) at 20±1℃, with a beam intensity at the surface of the photochromic optical article of 365 nm = 2.4 mW / cm² 2 , 245 nm = 24 μW / cm² 2 Color development was induced by irradiation for 120 seconds, and photochromic properties were measured.

[0355] · Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development, obtained using a spectrophotometer (Instantaneous Multi-Channel Photodetector - MCPD1000) manufactured by Otsuka Denshi Kogyo Co., Ltd. This maximum absorption wavelength is related to the hue at the time of color development.

[0356] · Color intensity {ε(120)-ε(0)}: The difference between the absorbance {ε(120)} after irradiating for 120 seconds at the maximum absorption wavelength and the absorbance ε(0) before irradiation. The higher this value, the better the photochromic properties can be said to be.

[0357] · Fading rate [t1 / 2(sec.)]: The time required for the absorbance at the maximum absorption wavelength of a sample to decrease to 1 / 2 of {ε(120)-ε(0)} when light irradiation is stopped after 120 seconds of light irradiation. The shorter this time, the better the photochromic properties.

[0358] (Exterior, etc.)

[0359] · Appearance (cracks, cloudiness) evaluation

[0360] The obtained photochromic optical articles were observed and evaluated using an optical microscope. The evaluation criteria are shown below.

[0361] A: It is uniform and no appearance defects are visible.

[0362] B: Very slight, minute external defects can be seen.

[0363] C: Partial appearance defects are visible.

[0364] D: Overall, there are visible exterior defects.

[0365] · ΔYI evaluation

[0366] YI was measured using the SM-4 colorimeter manufactured by Sugashi Kengi Co., Ltd., and ΔYI was evaluated by the following equation. When a blue protective film is transferred to a photochromic optical article, ΔYI changes.

[0367] ΔYI=YI 24 -YI0

[0368] (during the meal, YI 24 YI is the value after attaching a blue protective film to the obtained photochromic optical article and removing the film after 24 hours, and YI0 is the value before attaching the blue protective film.

[0369] · Adhesion

[0370] Adhesion was evaluated by a cross-cut tape test in accordance with JIS D-0202. Specifically, using a cutter knife, cuts were made at 1 mm intervals on the surface of the obtained photochromic optical article to form 100 compartments. Cellophane adhesive tape (Cello Tape (registered trademark) manufactured by Nichiban Co., Ltd.) was strongly attached over them, and then peeled off by pulling it in one go at a 90° direction from the surface, after which the compartments remaining of the photochromic optical article were evaluated.

[0371] <Examples 2, 3>

[0372] A photochromic optical article was prepared in the same manner as in Example 1, except that the photochromic composition and moisture-curing polyurethane composition shown in Table 6 were used. The evaluation results of the obtained photochromic optical article are shown in Table 6.

[0373] <Example 4>

[0374] A photochromic optical article was produced in the same manner as in Example 1, except that the moisture-curing polyurethane composition (PU1) prepared in Preparation Example 1 was spin-coated onto the surface of a photochromic resin layer of an optical substrate, dried for 10 minutes under conditions of 25°C and 50%RH, and then additionally heated at 90°C for 3 hours. The evaluation results of the obtained photochromic optical article are shown in Table 6.

[0375] <Comparative Example 1>

[0376] A photochromic optical article was prepared in the same manner as in Example 1, except that a moisture-curing polyurethane resin layer was not formed. The evaluation results of the obtained photochromic optical article are shown in Table 6.

[0377] [Table 6]

[0378]

[0379] As is evident from Table 6, the photochromic optical articles of Examples 1 to 4, in which a protective layer was formed using a moisture-curing polyurethane composition, not only exhibited excellent photochromic properties but also had excellent appearance, adhesion, and weather resistance. On the other hand, the photochromic optical article of Comparative Example 1, which did not use a moisture-curing polyurethane composition, had insufficient appearance and weather resistance, and thus could not obtain sufficient physical properties.

[0380] <Example 5>

[0381] [Formation of Polyurethane Resin Layer]

[0382] Two sheets each of CR, TRB, MRA, MRB, TEA, TEB, and PC, with a center thickness of approximately 2 mm as described below, were prepared as optical substrates. These optical substrates were previously subjected to alkaline etching using a 10% aqueous sodium hydroxide solution at 50°C for 5 minutes, and subsequently thoroughly washed with distilled water. The optical substrates used are as follows.

[0383] CR: Allyl resin plastic lens, refractive index = 1.50

[0384] TRB: Urethane resin plastic lens, refractive index = 1.53

[0385] MRA: Thiourethane resin plastic lens, refractive index = 1.60

[0386] MRB: Thiourethane resin plastic lens, refractive index = 1.67

[0387] TEA: Thioepoxy resin plastic lens, refractive index = 1.71

[0388] TEB: Thioepoxy resin plastic lens, refractive index = 1.74

[0389] PC: Polycarbonate lens with photocurable hard coating layer, refractive index 1.58

[0390] Next, using a spin coater (1 H-DX2, manufactured by Mikasa Co., Ltd.), a moisture-curing polyurethane composition (PU1) was coated onto the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds, followed by 900 rpm for 10 seconds, to form a polyurethane resin layer with a thickness of approximately 7 μm. Additionally, a moisture-curing polyurethane resin layer with a thickness of approximately 5 μm was formed by coating at a rotation speed of 70 rpm for 15 seconds, followed by 1100 rpm for 10 seconds. That is, one optical substrate with a polyurethane resin layer with a thickness of approximately 7 μm and one optical substrate with a polyurethane resin layer with a thickness of approximately 5 μm were each produced.

[0391] [Formation of Photochromic Resin Layer]

[0392] On the polyurethane resin layer of the optical substrate obtained by the above method, a pre-prepared photochromic composition (1) (2 g) was spin-coated by spreading the photochromic composition (1) from the center of the optical substrate outwardly to the outer periphery using a PET film cut into a short strip, at a rotation speed of 100 rpm for 30 seconds and then at 800 rpm for 10 to 20 seconds, so that the film thickness becomes 40 μm.

[0393] Thereafter, the lens having the above composition coated on its surface is placed in a nitrogen gas atmosphere at an output of 200 mW / cm² 2 The composition was polymerized by irradiating light for 80 seconds using a metal halide lamp. After that, it was heated again at 110°C for 1 hour to form a photochromic resin layer with a thickness of 40 μm on a polyurethane resin layer, the resin obtained by polymerizing the photochromic composition (1).

[0394] [Evaluation of Photochromic Optical Products]

[0395] For the photochromic optical article obtained above, photochromic properties were evaluated using the same method as above, and appearance and boiling adhesion were evaluated using the following method. The evaluation results are shown in Tables 7 to 9.

[0396] (Appearance evaluation)

[0397] Light from a high-pressure mercury lamp was irradiated onto a photochromic optical article, and the projected surface was projected onto a blank sheet of paper to observe and evaluate the entire projected surface of the photochromic optical article. The photochromic optical article was placed at a distance of approximately 70 cm from the high-pressure mercury lamp and approximately 20 cm from the blank sheet of paper. The evaluation criteria are shown below.

[0398] 0: No growth ring defects are observed when the photochromic composition spreads from the center of the optical substrate toward the outer periphery, or there are fewer than 5 growth ring defects.

[0399] 1: Five or more to less than 10 growth ring defects are observed as the photochromic composition spreads from the center of the optical substrate toward the outer periphery.

[0400] 2: When the photochromic composition spreads from the center of the optical substrate toward the outer periphery, 10 or more to less than 20 growth-ring defects are observed on the entire surface.

[0401] 3: At least 20 growth-ring defects are observed on the entire surface as the photochromic composition spreads from the center of the optical substrate toward the outer periphery.

[0402] (Compassionate closeness)

[0403] A photochromic optical article was placed in boiling distilled water, and the adhesion between the photochromic resin layer and the lens was evaluated every hour by a cross-cut tape test in accordance with JISD-0202. Specifically, using a cutter knife, cuts were made in the photochromic resin layer at intervals of approximately 1 mm to form 100 compartments. Cellophane adhesive tape (Cello Tape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached over them, and then peeled off by pulling it in a single motion at a 90˚ angle from the surface. Afterward, the number of compartments remaining in the photochromic resin layer was measured. The evaluation results indicated the test time at which the number of remaining compartments was 90 or more. For example, if it was indicated as 3 hours, it meant that the number of remaining compartments in the cross-cut tape test after 3 hours of acceleration was 90 or more, and after 4 hours of acceleration, it became less than 90. Furthermore, for photochromic optical articles in which 90 or more compartments remained, the evaluation was continued up to 5 hours of acceleration.

[0404] <Examples 6–28>

[0405] Photochromic optical articles were fabricated in the same manner as in Example 5, except that the moisture-curing urethane compositions shown in Tables 7 to 9 were used. However, conditions such as the rotation speed of the spin coater were appropriately adjusted to adjust the film thickness of the polyurethane resin layer to approximately 7 μm and approximately 5 μm. The evaluation results of the obtained photochromic optical articles are shown in Tables 7 to 9.

[0406] [Table 7]

[0407]

[0408] [Table 8]

[0409]

[0410] [Table 9]

[0411]

[0412] As is evident from Tables 7 to 9, the photochromic optical articles of Examples 5 to 28 (particularly the photochromic optical articles of Examples 5 to 27) formed with a primer layer using a moisture-curing polyurethane composition not only had excellent photochromic properties but also excellent appearance and adhesion.

[0413] <Example 29>

[0414] [Formation of polyurethane resin layer; manufacture of first laminate]

[0415] A CR-39 (allyl resin plastic lens; refractive index = 1.50) with a thickness of 2.0 mm was used as an optical substrate. This optical substrate was thoroughly degreased with acetone, immersed in a 10 mass% sodium hydroxide aqueous solution at 50°C for 10 minutes, thoroughly washed with hot water, and dried in a dryer at 70°C for 30 minutes. A moisture-curing polyurethane composition (PU25) was spin-coated onto this optical substrate (plastic lens) using a Mikasa Co., Ltd. spin coater 1 H-DX2, and dried for 1 hour under conditions of 25°C and 50% RH to produce a first laminate in which a polyurethane layer was formed on the plastic lens. At this time, the thickness of the polyurethane resin layer was set to 5 to 7 μm.

[0416] The appearance of the obtained first laminate was A, the adhesion was 100, the light transmittance at a wavelength of 400 nm was 1%, and the light transmittance at a wavelength of 420 nm was 64%. In addition, the appearance and adhesion were evaluated in the same manner as in Example 1, and the ultraviolet absorption characteristics and blue light absorption characteristics were evaluated in the following manner.

[0417] (Ultraviolet absorption characteristics, Blue light absorption characteristics)

[0418] The ultraviolet absorption characteristics and blue light absorption characteristics were evaluated by measuring the UV-vis spectrum of the obtained first laminate. The light transmittance (T%) at wavelengths of 400 nm and 420 nm of the first laminate fabricated by the method described above was measured and used as the ultraviolet absorption characteristics and blue light absorption characteristics.

[0419] [Formation of a hard coating layer; manufacture of a second laminate]

[0420] t-butanol (12.2 g), ethylene glycol monobutyl ether (7.0 g), acetylacetone (3.7 g), methyltriethoxysilane (0.41 g), γ-glycidoxypropyltrimethoxysilane (18.9 g), and silicone surfactant (Toray Dow Corning Co., Ltd., trade name L-7001) (0.06 g) were mixed and stirred at room temperature for 30 minutes. Additionally, 9.0 g of 0.05 N hydrochloric acid was added and stirred for 1 hour. Subsequently, a methanol solution (3.2 g) of 0.1 N trimethylammonium chloride was added and stirred at room temperature for 1 hour. Next, a methanol silica colloid solution (solid content: 30 mass%) (44.3 g) and aluminum acetylacetonate (0.51 g) were added, and the mixture was aged for one full day to obtain a hard coating composition.

[0421] The first laminate was immersed in the hard coating composition above and pulled up at a pulling speed of 30 cm / min to apply the hard coating composition to both surfaces of the first laminate. After application, it was dried at 80°C for 20 minutes, then maintained at 120°C for 4 hours to perform curing, thereby forming a hard coating layer. The obtained hard coating layer was a colorless transparent film with a thickness of about 2 μm. The appearance of the obtained second laminate was A, the adhesion was 100, the light transmittance at a wavelength of 400 nm was 1%, and the light transmittance at a wavelength of 420 nm was 64%.

[0422] <Preparation Examples 28~30: Preparation of moisture-curing polyurethane compositions (PU26~PU28)>

[0423] Moisture-curing polyurethane compositions (PU26~PU28) were prepared in the same manner as in Preparation Example 1 using each component shown in Table 10. The compositions of the moisture-curing polyurethane compositions (PU26~PU28) are shown in Table 10.

[0424] [Table 10]

[0425]

[0426] <Examples 30~32>

[0427] Photochromic optical articles were fabricated in the same manner as in Example 5, except that the moisture-curing urethane compositions shown in Tables 11 to 13 were used. However, conditions such as the rotation speed of the spin coater were appropriately adjusted to adjust the film thickness of the polyurethane resin layer to approximately 7 μm and approximately 5 μm. The evaluation results of the obtained photochromic optical articles are shown in Tables 11 to 13.

[0428] [Table 11]

[0429]

[0430] [Table 12]

[0431]

[0432] [Table 13]

[0433]

[0434] As is evident from Tables 11 to 13, the photochromic optical articles of Examples 30 to 32, in which a primer layer was formed using a moisture-curing polyurethane composition, not only had excellent photochromic properties but also excellent appearance and adhesion.

[0435] <Example 33>

[0436] (1) Production of a polycarbonate sheet with a laminated urethane resin layer

[0437] A urethane resin made from isophorone diisocyanate, polycarbonate diol (molecular weight: 1000), and isophorone diamine was dissolved in propylene glycol monomethyl ether, an organic solvent, to a solid content concentration of 15 mass%. The obtained urethane resin solution was applied to a polycarbonate sheet with a thickness of 300 μm to a thickness of 10 μm, and then dried at 110°C for 5 minutes to produce a laminated sheet.

[0438] (2) Formation of a resin layer made of a moisture-curing polyurethane composition

[0439] A moisture-curing polyurethane composition (PU7) was applied to a PET separator film to a thickness of 7 μm and dried at 100°C for 5 minutes to form a resin layer.

[0440] (3) Fabrication of laminated sheets

[0441] The urethane resin layer of the laminated sheet obtained in (1) was heat-pressed at 0.1 MPa and 100°C onto the resin layer made of the moisture-curing urethane composition obtained in (2) above. Then, the PET separator film was peeled off, and the urethane resin layer of the laminated sheet obtained in (1) was heat-pressed at 0.1 MPa and 100°C onto the resin layer on the other side to produce a laminated sheet.

[0442] (4) Measurement of peel strength

[0443] The laminated sheet obtained in (3) above was made into a test specimen having an adhesive portion of 25×100 mm, mounted on a tensile testing machine (Autograph AGS-500 NX, manufactured by Shimadzu Seisakusho Co., Ltd.), and a tensile test was performed at a crosshead speed of 100 mm / min to measure the peel strength. The measurement results are shown in Table 14.

[0444] <Examples 34~36>

[0445] The peel strength was measured in the same manner as in Example 33, except that the moisture-curing polyurethane composition shown in Table 14 was used. The measurement results are shown in Table 14.

[0446] [Table 14]

[0447]

Claims

Claim 1 A laminate comprising an optical substrate, a polyurethane resin layer composed of a moisture-curing polyurethane composition, and a photochromic resin layer, wherein the lamination order is the order of polyurethane resin layer / photochromic resin layer / optical substrate, and wherein the moisture-curing polyurethane composition contains (A) a moisture-curing polyurethane and (B) an organic solvent, and wherein (A) the moisture-curing polyurethane is a moisture-curing polyurethane having isocyanate groups at the molecular ends, obtained by reacting (A1) a polyisocyanate compound having two or more isocyanate groups in a molecule and (A2) a low molecular weight polyol compound having two or more hydroxyl groups in a molecule and a number average molecular weight of 50 to 300. Claim 2 A laminate according to claim 1, wherein the polyisocyanate compound having two or more isocyanate groups in the (A1) molecule is an aromatic polyisocyanate compound having two or more isocyanate groups in the molecule. Claim 3 A laminate according to claim 1, wherein the polyisocyanate compound having two or more isocyanate groups in the (A1) molecule is a urethane prepolymer having isocyanate groups at the molecular ends, obtained by reacting a polyisocyanate compound having two or more isocyanate groups in the (A1-1) molecule with a molecular weight of 400 or less and a polyol compound having two or more hydroxyl groups in the (A1-2) molecule with a number average molecular weight of 300 to 5000. Claim 4 In any one of claims 1 to 3, the organic solvent (B) has a solubility parameter of 8 [(cal / cm²) 3 ) 1 / 2 A laminate that is ] and at the same time is an organic solvent that does not have active hydrogen. Claim 5 A laminate according to any one of claims 1 to 3, wherein (A) the moisture-curing polyurethane is a moisture-curing polyurethane having an isocyanate group at the molecular end, obtained by further reacting at least one of (A3) a polyol compound having two or more hydroxyl groups in the molecule and a number average molecular weight of 400 to 2000, and (A4) an amine compound having one or more amino groups in the molecule. Claim 6 delete Claim 7 delete Claim 8 delete

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