Optical member and method for manufacturing optical member

Abstract

Disclosed is an optical member (100) which comprises: a sulfur atom-containing resin base material (11); and a photochromic layer (21) that is superposed on a surface of the sulfur atom-containing resin base material (11). In order to improve adhesion between layers, the maximum point stress measured by the following procedure x is 138 N / mm2 to 177 N / mm2 inclusive. Procedure x: the optical member (100) is subjected to a three-point bending test that is performed at 25°C in accordance with JIS K7171, and the maximum point stress (N / mm2) is measured at the time when the test is performed under a condition that the distance between supporting points is 34 mm, the speed is 10 mm / minute, and the radius R2 of the support base is 2 mm.

Description

Optical member and method for manufacturing the same

[0001] The present invention relates to an optical member and a method for manufacturing an optical member.

[0002] It has been known that photochromic compounds have the property of being able to reversibly color / decolorize depending on the presence or absence of light, such as sunlight. For example, by using plastic lenses with photochromic properties in eyeglasses, the eyeglasses function as normal clear eyeglasses indoors, but when outdoors, the lenses can be colored gray, brown, or the like in response to sunlight (ultraviolet rays), thereby providing eye protection from glare. Furthermore, unlike sunglasses, such eyeglasses do not require changing glasses depending on whether they are worn indoors or outdoors, making them convenient to use both indoors and outdoors.

[0003] Methods for manufacturing photochromic lenses include a kneading method, a coating method, and a lamination method (cast polymerization method).

[0004] For example, Patent Document 1 (WO 2012 / 141306) discloses a kneading method for producing a photochromic lens using a photochromic polymerizable composition in which a photochromic compound is dissolved in a monomer mixture containing a (meth)acrylic acid ester of a specific structure and divinylbenzene.

[0005] Furthermore, Patent Document 2 (WO 2011 / 125956) discloses a coating method for producing a photochromic lens by coating a plastic lens substrate to which no photochromic compound has been added with a coating liquid containing a photochromic compound.

[0006] Furthermore, Patent Document 3 (WO 2003 / 011967) discloses a cast polymerization method in which a plastic lens and a glass mold are placed in a mold so as to secure a gap between them, and a photochromic composition is poured into the gap and polymerized and cured to form a photochromic layer on the surface of the plastic lens.

[0007] Furthermore, plastic lenses are required to have high refractive index, high Abbe number, and physical properties such as high heat resistance, high impact resistance, low specific gravity, etc. Polythiourethane resins and episulfide resins, which are resins into which sulfur atoms have been introduced, are known as materials that satisfy these requirements.

[0008] International Publication No. WO 2012 / 141306 International Publication No. WO 2011 / 125956 International Publication No. WO 2003 / 011967

[0009] However, when a photochromic compound is directly mixed into the material that constitutes the lens substrate, as in the kneading method, the mechanical strength of the material that constitutes the lens substrate itself is important in order to obtain the strength of the lens itself. However, the lens substrate that uses a monomer mixture containing a (meth)acrylic acid ester of a specific structure and divinylbenzene, as disclosed in Patent Document 1, does not have sufficient mechanical strength.

[0010] Furthermore, in the coating method and lamination method, a primer or adhesive is used to bond the lens substrate layer and the photochromic layer, but if no primer or adhesive is used, peeling may occur between the lens substrate layer and the photochromic layer. Therefore, the techniques disclosed in Patent Documents 2 and 3 leave room for improvement in terms of adhesion between the layers.

[0011]

[0003] In recent years, with the increasing demand for photochromic lenses, lenses are sometimes subjected to various processes to enhance their design and functionality. Therefore, lenses are required to have higher adhesion, suppressing delamination during processing, while retaining their photochromic function. The present inventors have therefore focused on photochromic lenses that use a lens substrate layer containing sulfur atoms in the resin, and have conducted extensive research to improve the adhesion between the sulfur-atom-containing resin substrate and the photochromic layer. As a result, they have found that the adhesion between the lens substrate layer and the photochromic layer required for optical components can be improved by manufacturing the optical component so that it satisfies a predetermined maximum point stress, thereby completing the present invention.

[0012] According to the present invention, the following optical member and method for manufacturing the optical member are provided.

[0013] 1. An optical element comprising a sulfur atom-containing resin substrate and a photochromic layer laminated on a surface of the sulfur atom-containing resin substrate, wherein the maximum point stress measured by the following procedure x is 138 N / mm ２ More than 177N / mm ２ An optical element having the following characteristics. Step x: A three-point bending test is performed at 25°C in accordance with JIS K7171 using the optical element, and the maximum point stress (N / mm) when the test is performed under the conditions of a support distance of 34 mm, a speed of 10 mm / min, and a support radius R2 of 2 mm. ２ 2. The optical member according to 1., wherein the photochromic layer is a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). 3. The optical member according to 1. or 2., wherein the sulfur atom-containing resin substrate is a poly(thio)urethane resin substrate or an episulfide-based resin substrate. 4. The optical member according to 3., wherein the surface of the episulfide-based resin substrate is analyzed with a Fourier transform infrared spectrophotometer (FTIR) by the attenuated total reflection method (ATR method), and a wavelength of 2900 to 2970 cm is measured. －１ The absorbance of the maximum absorption peak observed at T1 is 2550-2700 cm －１5. An optical element according to any one of items 3. to 5., wherein the ratio (%) of T0 to T1 is in the range of 4 to 10%, where T0 is the absorbance of the maximum absorption peak observed at 1000 nm, and the photochromic layer is a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). 5. An optical element according to item 3. or 4., wherein the episulfide-based resin substrate is a cured product of a second polymerizable composition containing a difunctional or higher thiol compound (e) and a difunctional or higher episulfide compound (f). 6. An optical element according to any one of items 3. to 5., wherein the equivalent ratio of thiol groups to episulfide groups in the episulfide-based resin substrate is 1:99 to 30:70. 7. 3. 8. The optical member according to 3. or 7., wherein the episulfide compound (f) contained in the episulfide-based resin substrate is either bis(2,3-epithiopropyl) sulfide or bis(2,3-epithiopropyl) disulfide. 9. The optical member according to 3. or 7., wherein the surface of the poly(thio)urethane resin substrate is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method), and a peak intensity of 2900 to 2970 cm －１ The absorbance of the maximum absorption peak observed at A1 is 2250-2260 cm －１An optical element according to any one of 9.3, 7., and 8., wherein the poly(thio)urethane resin substrate is a cured product of a second polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a) and a difunctional or higher thiol compound (e), and wherein the photochromic layer is a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). 10.3, 7., and 9. to 9. 11. The optical member according to any one of the above, wherein the equivalent ratio (SH:NCO) of thiol groups to isocyanato groups in the poly(thio)urethane resin substrate is 40:60 to 60:40. 11. The optical member according to any one of the above, wherein the ratio of the thickness (mm) of the sulfur atom-containing resin substrate to the thickness (mm) of the photochromic layer (sulfur atom-containing resin substrate thickness / photochromic layer thickness) is 0.5 to 20. 12. The optical member according to any one of the above, wherein the thickness (mm) of the sulfur atom-containing resin substrate is 0.5 to 20 mm. 13. The optical member according to any one of the above, wherein the thickness (mm) of the photochromic layer is 0.1 to 5 mm. 14. The optical member according to any one of the above, wherein the thickness (mm) of the photochromic layer is 0.1 to 5 mm. 14. The optical member according to any one of the above, wherein the thickness (mm) of the photochromic layer is 0.1 to 5 mm. The optical member according to any one of the above, wherein the bifunctional or higher iso(thio)cyanate compound (a) contained in the photochromic layer includes one or more compounds selected from the group consisting of xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and phenylene diisocyanate.15. The optical element according to any one of 1. to 14., wherein the bifunctional or higher active hydrogen compound (c) contained in the photochromic layer has one or more functional groups selected from a hydroxy group, a mercapto group, an amino group, and a carboxyl group. 16. The optical element according to any one of 1. to 15., wherein at least one surface is curved, and the radius of curvature is greater than 0 and not greater than 400 mm. 17. An optical lens comprising the optical element according to any one of 1. to 16.. 18. A method for manufacturing an optical element, comprising a lamination step of laminating a photochromic layer on a surface of a sulfur atom-containing resin substrate, wherein the optical element has a maximum point stress of 138 N / mm as measured by procedure x. ２ More than 177N / mm ２ A method for manufacturing an optical element configured as follows: Step x: A three-point bending test is performed at 25°C in accordance with JIS K7171 using the optical element, and the maximum point stress (N / mm) when the test is performed under the conditions of a support distance of 34 mm, a speed of 10 mm / min, and a support radius R2 of 2 mm. ２ ) is measured. 19. The method for producing an optical member according to 18., wherein the photochromic layer is a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). 20. The method for producing an optical member according to 18. or 19., wherein the sulfur atom-containing resin substrate is a poly(thio)urethane resin substrate or an episulfide-based resin substrate. 21. The method for producing an optical member according to 20., wherein in the laminating step, the surface of the episulfide-based resin substrate on which the photochromic layer is laminated is analyzed with a Fourier transform infrared spectrophotometer (FTIR) by an attenuated total reflection method (ATR method), and a wavelength of 2900 to 2970 cm －１ The absorbance of the absorption peak observed at T1, 2550-2700 cm －１22. A method for producing an optical member according to 20. or 21., wherein, when the absorbance of the absorption peak observed at 2000 to 29000 cm is taken as T0, the ratio (%) of T0 to T1 is in the range of 4 to 10%. 23. A method for producing an optical member according to 20., wherein, in the laminating step, the episulfide-based resin substrate is obtained by curing a second polymerizable composition containing a difunctional or higher functional thiol compound (e) and a difunctional or higher functional episulfide compound (f), and has not been subjected to an annealing treatment after being obtained. 24. A method for producing an optical member according to 20., wherein, in the laminating step, the surface of the poly(thio)urethane resin substrate on which the photochromic layer is laminated is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method), and a photochromic layer having a wavelength of 2900 to 2970 cm is obtained. －１ The absorbance of the absorption peak observed at A1 is 2250-2260 cm －１ 24. A method for producing an optical element according to item 20. or 23., wherein, when the absorbance of the absorption peak observed at 1000 nm is defined as A0, the ratio (%) of A0 to A1 is in the range of 30 to 99%. 25. A method for producing an optical element according to any one of items 18. to 24., wherein, in the laminating step, the poly(thio)urethane resin substrate is obtained by curing a second polymerizable composition containing a difunctional or higher functional iso(thio)cyanate compound (a) and a difunctional or higher functional thiol compound (e), and has not been subjected to an annealing treatment after being obtained. 26. A method for producing an optical element according to any one of items 18. to 25., wherein, in the laminating step, the photochromic layer is laminated by curing the first polymerizable composition on a surface of the sulfur atom-containing resin substrate.

[0014] The present invention can provide an optical member that maintains photochromic function while improving adhesion, and a method for manufacturing an optical member.

[0015] 1A to 1C are cross-sectional views schematically showing an optical member of the present embodiment, and FIG. 1B is a cross-sectional view schematically showing an example of a manufacturing process of the optical member of the present embodiment.

[0016] In this specification, the notation "a to b" in the description of a numerical range means from a to b, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% to 5 mass%." Furthermore, the lower limit and upper limit of a numerical range can be arbitrarily combined with the lower limit and upper limit of another numerical range.

[0017] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more.

[0018] In this specification, the term "(meth)acrylic" represents a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0019] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. To avoid complexity, when multiple identical components appear in the same drawing, only one of the components may be labeled with a reference symbol, and not all of the components may be labeled with a reference symbol. All drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual objects.

[0020] <Optical Member> Fig. 1 is a cross-sectional view schematically illustrating an optical member according to the present embodiment. The optical member 100 includes a sulfur-containing resin substrate 11 and a photochromic layer 21 laminated on a surface 11a of the sulfur-containing resin substrate 11. The photochromic layer 21 is composed of a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). Furthermore, the surface 11b of the sulfur-containing resin substrate 11 serves as the eye-facing surface when the optical member 100 is used as an optical lens for eyewear, as described below.

[0021] In this embodiment, the optical member 100 has the photochromic layer 21 laminated on the surface 11 a of the sulfur atom-containing resin substrate 11. In other words, the sulfur atom-containing resin substrate 11 and the photochromic layer 21 are in direct contact with each other, without an adhesive layer or primer layer interposed therebetween. This eliminates the need for forming an adhesive layer or primer, simplifies the manufacturing process, and prevents poor appearance due to the adhesive or primer.

[0022] In addition, in this embodiment, an example is described in which the photochromic layer 21 is laminated on the surface (surface 11a) of the sulfur atom-containing resin substrate 11, but the photochromic layer 21 may also be provided on the surface (surface 11b) side of the sulfur atom-containing resin substrate 11.

[0023] In a plan view of the optical member 100 , the photochromic layer 21 may be included in a region surrounded by the outer edge of the sulfur atom-containing resin substrate 11 .

[0024] The optical element 100 has at least one curved surface, with a radius of curvature of preferably 50 mm to 400 mm, more preferably 45 mm to 350 mm, and even more preferably 50 mm to 300 mm. The radius of curvature of one surface of the optical element 100 and the radius of curvature of the opposite surface are preferably the same.

[0025] The thickness of the optical element 100 is preferably 0.5 to 25 mm, more preferably 1 to 12 mm, in order to facilitate improved adhesion. When the optical element 100 has a curved surface, the thickness is the thickness at the geometric center.

[0026] The optical element 100 of this embodiment has a maximum point stress of 138 N / mm2 measured by procedure x. ３ More than 177N / mm ３ The following is the result.

[0027] Step x: A test piece of 65 mm x 25 mm size is prepared using the optical element 100, and a three-point bending test is performed at 25°C in accordance with JIS K7171. The test force at break (N), maximum point displacement (mm), and maximum point stress (N / mm) are measured under the conditions of a support distance of 34 mm, a speed of 10 mm / min, and a support base radius R2 of 2 mm. ２ ) is measured. ２ ) = Breaking point test force (N) ÷ (thickness of test piece mm × width of test piece mm)

[0028] This improves the adhesion between the sulfur-atom-containing resin substrate 11 and the photochromic layer 21 while maintaining the photochromic function. While the details of the reason for this are unclear, it is speculated as follows: Because the optical element 100 often has a curved surface as a lens element, stress is likely to be applied to the interlayer portions of the optical element 100 during lens framing, and after the lens is placed in the frame after processing, a state in which stress is constantly applied to the interlayer portions is maintained, which is thought to make the lens more susceptible to delamination over long-term use. Therefore, it is speculated that by applying a load between the layers using a three-point bending test and controlling the stress to a level that breaks the lens, it is possible to more highly control the adhesion between the sulfur-atom-containing resin substrate 11 and the photochromic layer 21 of the optical element 100.

[0029] In this embodiment, the sulfur atom-containing resin substrate 11 is preferably an episulfide resin substrate (i) or a poly(thio)urethane resin substrate (ii), which allows for stable high adhesion between the sulfur atom-containing resin substrate 11 and the photochromic layer 21 of the optical member 100.

[0030] When an episulfide-based resin substrate (i) is used, the maximum point stress measured by procedure x is preferably 140 N / mm ３ 150N / mm or more ３Furthermore, when the episulfide-based resin substrate (i) is used, the test force at break measured by the above procedure x is preferably 24 N or less, more preferably 2 N or more and 20 N or less, and even more preferably 5 N or more and 10 N or less. This makes it possible to more stably improve the adhesion between the sulfur atom-containing resin substrate 11 and the photochromic layer 21 while maintaining the photochromic function.

[0031] When a poly(thio)urethane resin substrate (ii) is used, the maximum point stress measured by procedure x is preferably 160 N / mm ３ More than 176N / mm ３ Furthermore, when a poly(thio)urethane resin substrate (ii) is used, the test force at break measured by the above procedure x is preferably 24 N or less, and more preferably 10 N or more and 24 N or less. This makes it possible to more stably improve the adhesion between the sulfur atom-containing resin substrate 11 and the photochromic layer 21 while maintaining the photochromic function.

[0032] An optical member 100 having the above-described maximum point stress and test force at break can be realized by controlling the composition of the first polymerizable composition constituting the photochromic layer 21, the composition of the second polymerizable composition constituting the sulfur atom-containing resin substrate 11, the method for producing the sulfur atom-containing resin substrate 11, and the method for producing an optical member, which will be described later. Specifically, when the sulfur atom-containing resin substrate 11 is an episulfide-based resin substrate (i), it is thought that thiol groups contained in the episulfide-based resin substrate (i) chemically bond with isocyanato groups contained in the photochromic layer 21, thereby contributing to adhesion. Therefore, one example of a method is to polymerize and cure the second polymerizable composition to obtain an episulfide-based resin substrate (i), and then not perform a heat treatment, thereby allowing more thiol groups to remain. Specifically, when the sulfur atom-containing resin substrate 11 is a poly(thio)urethane resin substrate (ii), it is thought that the isocyanato groups contained in the poly(thio)urethane resin substrate (ii) chemically bond with the thiol groups contained in the photochromic layer 21, thereby contributing to adhesion. Therefore, a method can be used in which the second polymerizable composition is polymerized and cured to obtain the poly(thio)urethane resin substrate (ii), and then heat treatment is not performed, thereby allowing more of the isocyanato groups to remain.

[0033] In addition, in the optical member 100 of this embodiment, the surface 11a and / or surface 11b of the sulfur atom-containing resin substrate 11 was analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method), and a wavelength of 2900 to 2970 cm －１ The absorbance of the maximum absorption peak observed at T1 is 2550-2700 cm －１ When the absorbance of the maximum absorption peak observed in the sample is taken as T0, the ratio (%) of T0 to T1 is preferably in the range of 4 to 10%.

[0034] The ratio (%) of T0 to T1 is preferably 5% or more, more preferably 6% or more. This makes it suitable for use as a spectacle lens and improves adhesion. On the other hand, the ratio (%) of T0 to T1 is preferably 95% or less, more preferably 90% or less. This allows it to be used as a spectacle lens while maintaining high adhesion.

[0035] By controlling the ratio (%) of T0 to T1, the optical member 100 can improve the adhesion between the sulfur atom-containing resin substrate 11 and the photochromic layer 21 while maintaining excellent lens function. The details of the reason for this are not clear, but it is presumed as follows. First, it is thought that the thiol group contained in the sulfur atom-containing resin substrate 11 chemically bonds with the isocyanato group contained in the photochromic layer 21, contributing to the adhesion. In addition, the thiol group contained in the sulfur atom-containing resin substrate 11 chemically bonds with the isocyanato group contained in the photochromic layer 21. －１ The maximum absorption peak observed at 2550-2700 cm represents O-H absorption. －１ The absorbance of the maximum absorption peak observed at 2900 to 2970 cm is thought to represent the absorption due to the stretching vibration of the thiol group (-SH). －１ The absorbance of the maximum absorption peak observed at T1 is 2550-2700 cm －１ The absorbance of the maximum absorption peak observed in the lens is defined as T0, and by setting the ratio (%) of T0 to T1 within a specific range, it is believed that it is possible to highly control the chemical bonding by the thiol group, thereby improving adhesion while maintaining excellent lens function. Furthermore, T1 may be derived from an ultraviolet absorber.

[0036] The ratio (%) of T0 to T1 in the optical member 100 of this embodiment can be achieved by controlling the composition of the first polymerizable composition constituting the photochromic layer 21, the composition of the second polymerizable composition constituting the sulfur atom-containing resin substrate 11, the method for producing the sulfur atom-containing resin substrate 11, and the method for producing the optical member, as described below. Specifically, examples include a method in which the amount of thiol groups in the sulfur atom-containing resin substrate is controlled, or a method in which the ratio (%) of T0 to T1 in the sulfur atom-containing resin substrate 11 is reduced by heat treatment, in which the second polymerizable composition is polymerized and cured to obtain the sulfur atom-containing resin substrate 11 and then heat treatment is not performed.

[0037] In addition, in the optical member 100 of this embodiment, the surface 11a and / or surface 11b of the sulfur atom-containing resin substrate 11 was analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method), and a wavelength of 2900 to 2970 cm －１The absorbance of the maximum absorption peak observed at A1 is 2250-2260 cm －１ When the absorbance of the maximum absorption peak observed in the above is taken as A0, the ratio (%) of A0 to A1 is preferably in the range of 30 to 99%.

[0038] The ratio (%) of A0 to A1 is preferably 35% or more, more preferably 40% or more. This allows for improved adhesion while maintaining photochromic function. On the other hand, the ratio (%) of A0 to A1 is preferably 95% or less, more preferably 90% or less. This allows for stable and excellent photochromic function while maintaining high adhesion.

[0039] By controlling the ratio (%) of A0 to A1, the optical member 100 can improve the adhesion between the sulfur atom-containing resin substrate 11 and the photochromic layer 21 while maintaining the photochromic function. The details of the reason for this are not clear, but it is presumed as follows. First, it is thought that the isocyanato groups contained in the sulfur atom-containing resin substrate 11 chemically bond with the thiol groups contained in the photochromic layer 21, contributing to the adhesion. On the other hand, it is presumed that if the thiol groups in the photochromic layer 21 bond too much with the isocyanato groups on the sulfur atom-containing resin substrate 11 side, the photochromic function is likely to be reduced. In addition, －１ The maximum absorption peak observed at 2250-2260 cm represents C—H absorption. －１ The absorbance of the maximum absorption peak observed at 2900 to 2970 cm is thought to represent the absorption due to the stretching vibration of NCO. －１ The absorbance of the maximum absorption peak observed at A1 is 2250-2260 cm －１ The absorbance of the maximum absorption peak observed in the photosensitive resin composition is defined as A0, and by setting the ratio (%) of A0 to A1 within a specific range, it is believed that it is possible to highly control the chemical bonding by the isocyanato group, thereby improving adhesion while maintaining photochromic function. Furthermore, A1 may be derived from an ultraviolet absorber.

[0040] The ratio (%) of A0 to A1 in optical member 100 of this embodiment can be achieved by controlling the composition of the first polymerizable composition constituting photochromic layer 21, the composition of the second polymerizable composition constituting poly(thio)urethane resin substrate 11, the method for producing poly(thio)urethane resin substrate 11, and the method for producing the optical member. Specifically, examples include controlling the equivalent ratio of thiol groups to isocyanato groups in the poly(thio)urethane resin substrate, or a method in which the ratio (%) of A0 to A1 in poly(thio)urethane resin substrate 11 is thought to be reduced by heat treatment, in which the second polymerizable composition is polymerized and cured to obtain poly(thio)urethane resin substrate 11 and then heat treatment is not performed.

[0041] Each component of the optical member 100 will be described below.

[0042] [Sulfur Atom-Containing Resin Substrate 11 ] The sulfur atom-containing resin substrate 11 serves as the base of the optical member 100 and defines the outer shape of the optical member 100 .

[0043] The thickness of the sulfur atom-containing resin substrate 11 is preferably 0.5 to 20 mm, more preferably 1.0 to 17 mm, and even more preferably 2.0 to 15 mm.

[0044] The ratio of the thickness (mm) of the sulfur atom-containing resin substrate 11 to the thickness (mm) of the photochromic layer 21 (thickness of sulfur atom-containing resin substrate 11 / thickness of photochromic layer 21) is preferably 0.5 to 10, more preferably 1 to 7, and even more preferably 2 to 5.

[0045] When the sulfur-containing resin substrate 11 and the photochromic layer 21 have a curved surface, the thickness is the thickness at the geometric center. The thickness can be measured using a dial thickness gauge SM130 manufactured by TECLOCK Corporation.

[0046] The sulfur atom-containing resin substrate 11 may have a flat or curved surface depending on the purpose of the optical lens. Furthermore, the sulfur atom-containing resin substrate 11 has a curved surface on at least one side, with a radius of curvature preferably greater than 0 and less than 400 mm, more preferably 5 mm or more and less than 380 mm, more preferably 30 mm or more and less than 360 mm, more preferably 45 mm or more and less than 350 mm, and even more preferably 50 mm or more and less than 300 mm. Furthermore, the radius of curvature of one side of the sulfur atom-containing resin substrate 11 and the radius of curvature of the opposite side are preferably the same.

[0047] The sulfur atom-containing resin substrate 11 is formed by curing the second polymerizable composition, thereby effectively improving adhesion to the photochromic layer 21. When the sulfur atom-containing resin substrate 11 is an episulfide-based resin substrate (i), the second polymerizable composition preferably contains a difunctional or higher functional thiol compound (e) and a difunctional or higher functional episulfide compound (f), and when the sulfur atom-containing resin substrate 11 is a poly(thio)urethane resin substrate (ii), the second polymerizable composition preferably contains a difunctional or higher functional iso(thio)cyanate compound (a) and a difunctional or higher functional thiol compound (e).

[0048] Furthermore, when the episulfide-based resin substrate (i) is used, the equivalent ratio of thiol groups to episulfide groups in the sulfur atom-containing resin substrate 11 is preferably 1:99 to 30:70, more preferably 2:98 to 20:80, and even more preferably 3:97 to 10:90.

[0049] The equivalent ratio of thiol groups to isocyanato groups in the poly(thio)urethane resin substrate (ii) is preferably 40:60 to 60:40, more preferably 45:55 to 55:45, and even more preferably 48:52 to 52:48.

[0050] Each component will be described below.

[0051] (Bifunctional or higher thiol compound (e)) Examples of the bifunctional or higher thiol compound (e) include polythiol compounds having two or more mercapto groups, and these compounds are used alone or in combination. Examples of these thiol compounds include the compounds exemplified in WO 2016 / 125736.

[0052] Examples of the bifunctional or higher functional thiol compound (e) include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptomethyl-1,11-dimercaptomethyl-3,6,9-trithiaundecane, and 2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane.

[0053] The content of the difunctional or higher functional thiol compound (e) is preferably 2 to 80 mass %, more preferably 5 to 70 mass %, and even more preferably 8 to 60 mass %, based on the total amount of the sulfur atom-containing resin substrate 11.

[0054] When a difunctional or higher functional episulfide compound (f) is contained, the content of the difunctional or higher functional thiol compound (e) is preferably 2 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 8 to 12 parts by mass, relative to 100 parts by mass of the episulfide compound (f). When a difunctional or higher functional iso(thio)cyanate compound (a) is contained, the content of the difunctional or higher functional thiol compound (e) is preferably 60 to 150 parts by mass, more preferably 80 to 120 parts by mass, and even more preferably 90 to 110 parts by mass, relative to 100 parts by mass of the iso(thio)cyanate compound (a).

[0055] (Episulfide Compound (f)) The episulfide compound (f) is a compound having two or more episulfide groups in one molecule, and is preferably an episulfide compound represented by formula (1).

[0056]

[0057] Specific examples of the episulfide compound (f) include bis(β-epithiopropyl) sulfide, bis(β-epithiopropyl) disulfide, bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,2-bis(β-epithiopropylthio)propane, 1,3-bis(β-epithiopropylthio)propane, 1,3-bis(β-epithiopropylthio)-2-methylpropane, 1,4-bis(β-epithiopropylthio)butane, 1,4-bis(β-epithiopropylthio)-2-methylbutane, 1,3-bis(β-epithiopropylthio)-2-methylbutane, 1,4-bis(β-epithiopropylthio)-2-methylbutane, 1,3-bis(β-epithiopropylthio)-2-methylpropane, 1,4 ... Bis(β-epithiopropylthio)butane, 1,5-bis(β-epithiopropylthio)pentane, 1,5-bis(β-epithiopropylthio)-2-methylpentane, 1,5-bis(β-epithiopropylthio)-3-thiapentane, 1,6-bis(β-epithiopropylthio)hexane, 1,6-bis(β-epithiopropylthio)-2-methylhexane, 3,8-bis(β-epithiopropylthio)-3,6-dithiaoctane, 1,2,3-tris(β-epithiopropylthio)propane, 2,2-bis(β-epithiopropylthio)-1,3-bis(β-epithiopropylthio) Bis(β-epithiopropylthiomethyl)propane, 2,2-bis(β-epithiopropylthiomethyl)-1-(β-epithiopropylthio)butane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1,5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β-epithiopropylthiomethyl)-4-thiahexane, 1,8-bis(β-epithiopropylthio)-4-(β- epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-Dithiaoctane, 1,1,1-tris[{2-(β-epithiopropylthio)ethyl}thiomethyl]-2-(β-epithiopropylthio)ethane, 1,1,2,2-tetrakis[{2-(β-epithiopropylthio)ethyl}thiomethyl]ethane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(β-epithiopropylthio)-4,7-bis(β-epithiopropylthiomethyl)- aliphatic β-epithiopropylthio compounds such as 1,11-bis(β-epithiopropylthiomethyl)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane, and 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithiaundecane; and aliphatic β-epithiopropylthio compounds such as 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis(β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1, cycloaliphatic β-epithiopropylthio compounds such as 4-bis(β-epithiopropylthiomethyl)cyclohexane, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, and 2,5-bis[{2-(β-epithiopropylthio)ethyl}thiomethyl]-1,4-dithiane; 1,3-bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, and 1,3-bis(β-epithiopropylthiomethyl)benzene; Examples of aromatic β-epithiopropylthio compounds include 1,4-bis(β-epithiopropylthiomethyl)benzene, bis{4-(β-epithiopropylthio)phenyl}methane, 2,2-bis{4-(β-epithiopropylthio)phenyl}propane, bis{4-(β-epithiopropylthio)phenyl}sulfide, bis{4-(β-epithiopropylthio)phenyl}sulfone, and 4,4'-bis(β-epithiopropylthio)biphenyl. These compounds may be used alone or in combination of two or more.

[0058] Furthermore, polysulfide oligomers such as dimers, trimers, and tetramers of the episulfide compound (f), episulfide resins having a mercapto group that are produced when epihalohydrin is insufficient during the synthesis of the episulfide compound (f), and further organic and inorganic compounds such as inorganic acids, organic acids, solvents, unreacted raw materials, other by-products, and impurities used during the synthesis of the episulfide may also be contained within ranges that do not cause problems.

[0059] In this embodiment, a lens can be produced by polymerization, either in the presence or absence of a curing catalyst, by heating or leaving at room temperature, but in the absence of a curing catalyst, the polymerization may not proceed well, resulting in poor polymerization or no polymerization at all. As the curing catalyst, amines, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts, etc. are usually used.

[0060] The content of the episulfide compound (f) is preferably 80 to 99% by mass, more preferably 85 to 95% by mass, and even more preferably 88 to 92% by mass, based on the total amount of the sulfur atom-containing resin substrate 11.

[0061] (Difunctional or higher functional iso(thio)cyanate compound (a)) The difunctional or higher functional iso(thio)cyanate compound (a) is an iso(thio)cyanate compound having two or more iso(thio)cyanato groups, and the iso(thio)cyanate compound here means an isocyanate compound or an isothiocyanate compound.

[0062] Examples of the iso(thio)cyanate compound (a) of the present embodiment include alicyclic polyiso(thio)cyanate compounds, aromatic polyiso(thio)cyanate compounds, and modified products thereof.

[0063] More specifically, the isocyanate compound includes isophorone diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, alicyclic polyisocyanate compounds such as bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, and 4,9-bis(isocyanatomethyl)tricyclodecane; and aromatic polyisocyanate compounds such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and diphenyl sulfide-4,4'-diisocyanate.

[0064] Examples of the isothiocyanate compound include isophorone diisothiocyanate, bis(isothiocyanatomethyl)cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, 3,8-bis(isothiocyanatomethyl)bicyclo-[2.2.1]-heptane, alicyclic polyisothiocyanate compounds such as 3,9-bis(isothiocyanatomethyl)tricyclodecane, 3,9-bis(isothiocyanatomethyl)tricyclodecane, 4,8-bis(isothiocyanatomethyl)tricyclodecane, and 4,9-bis(isothiocyanatomethyl)tricyclodecane; and aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, and diphenyl disulfide-4,4'-diisothiocyanate.

[0065] The iso(thio)cyanate compound (a) may also be a halogen-substituted compound such as a chlorine-substituted compound or a bromine-substituted compound, an alkyl-substituted compound, an alkoxy-substituted compound, a nitro-substituted compound, a prepolymer-type modified compound with a polyhydric alcohol, a carbodiimide-modified compound, a urea-modified compound, a biuret-modified compound, a dimerization or trimerization reaction product, etc. The iso(thio)cyanate compound (a) may be used alone or in combination of two or more selected from these.

[0066] Among these, it is preferable that the difunctional or higher iso(thio)cyanate compound (a) is one or more selected from xylylene diisocyanate or a hydrogenated product thereof, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and phenylene diisocyanate.

[0067] The content of the difunctional or higher iso(thio)cyanate compound (a) is preferably 40 to 60 mass %, more preferably 45 to 55 mass %, and even more preferably 48 to 52 mass %, based on the total amount of the sulfur atom-containing resin substrate 11.

[0068] (Others) The second polymerizable composition may further contain additives such as an ultraviolet absorber, a catalyst, an internal mold release agent, a resin modifier, a light stabilizer, an antioxidant, and a color inhibitor, depending on the properties desired for the application to which it is applied.

[0069] Examples of the ultraviolet absorber include benzophenone compounds, triazine compounds, and benzotriazole compounds.

[0070] Examples of the benzophenone-based ultraviolet absorber include 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone.

[0071] Examples of triazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(1-octyloxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine, and the like.

[0072] Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5-t-octylphenyl)-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]. These ultraviolet absorbents may be used alone or in combination of two or more.

[0073] The catalyst may be, for example, one or more selected from Lewis acids, tertiary amines, organic acids, and amine-organic acid salts, etc. Among these, Lewis acids, amines, and amine-organic acid salts are preferred, and dimethyltin chloride, dibutyltin dichloride, and dibutyltin laurate are more preferred.

[0074] An internal mold release agent may be contained for the purpose of improving releasability from the mold after molding. An acidic phosphate ester can be used as the internal mold release agent. Examples of acidic phosphate esters include monophosphate esters and diphosphate esters, each of which can be used alone or in combination of two or more. Examples of commercially available internal mold release agents include ZelecUN manufactured by STEPAN Corporation, MR internal mold release agents manufactured by Mitsui Chemicals, Inc., the JP series manufactured by Johoku Chemical Industry Co., Ltd., the Phosphanol series manufactured by Toho Chemical Industry Co., Ltd., and the AP and DP series manufactured by Daihachi Chemical Industry Co., Ltd.

[0075] A resin modifier may be contained for the purpose of adjusting various physical properties such as optical properties, impact resistance, specific gravity, etc., and adjusting viscosity and pot life. Examples of the resin modifier include episulfide compounds, alcohol compounds other than the above-mentioned polyol compounds, amine compounds other than the above-mentioned amine compounds, epoxy compounds, organic acids and anhydrides thereof, and olefin compounds including (meth)acrylate compounds.

[0076] The light stabilizer may be a hindered amine compound having a 2,2,6,6-tetramethylpiperidine skeleton or a 1,2,2,6,6-pentamethylpiperidine skeleton. Commercially available hindered amine compounds include Lowilite 76 and Lowilite 92 manufactured by Chemtura Corporation, Tinuvin 144, Tinuvin 292, and Tinuvin 765 manufactured by BASF, Adekastab LA-52 and LA-72 manufactured by ADEKA Corporation, JF-95 manufactured by Johoku Chemical Industry Co., Ltd., and Hostavin PR-25 manufactured by Clariant Chemicals.

[0077] [Photochromic Layer 21] The photochromic layer 21 is a layer for imparting photochromic functionality to the optical member 100. The photochromic layer 21 is provided so as to be in contact with at least one surface of the sulfur atom-containing resin substrate 11.

[0078] The thickness of the photochromic layer 21 is preferably 0.1 to 5 mm, more preferably 0.2 to 3 mm, and even more preferably 0.4 to 2 mm.

[0079] The photochromic layer 21 has at least one curved surface, with a radius of curvature of preferably 30 mm to 400 mm, more preferably 45 mm to 350 mm, and even more preferably 50 mm to 300 mm. The radius of curvature of one surface of the photochromic layer 21 and the radius of curvature of the opposite surface are preferably the same.

[0080] (First Polymerizable Composition) The photochromic layer 21 is a cured product of a first polymerizable composition containing a difunctional or higher iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a difunctional or higher active hydrogen compound (c), and a photochromic compound (d). This effectively improves adhesion to the sulfur atom-containing resin substrate 11. Each component will be described below.

[0081] (Difunctional or higher functional iso(thio)cyanate compound (a)) The difunctional or higher functional iso(thio)cyanate compound (a) may be the same as that described for the second polymerizable composition. The iso(thio)cyanate compound (a) in the second polymerizable composition may be the same as or different from the iso(thio)cyanate compound (a) in the first polymerizable composition.

[0082] The content of the difunctional or higher iso(thio)cyanate compound (a) is preferably 30 to 70% by mass, more preferably 35 to 60% by mass, and even more preferably 40 to 55% by mass, based on the total amount of the photochromic layer 21.

[0083] (Hydroxyl Group-Containing Polyether Compound (b)) The hydroxyl group-containing polyether compound (b) of this embodiment is a polyether compound containing at least one hydroxyl group and includes at least one polyether segment. The hydroxyl group-containing polyether compound (b) of this embodiment is preferably a block copolymer that may be combined with at least one segment of polyester, polycarbonate, poly(meth)acrylate, polyamide, polyethyleneimine, polysiloxane, polysulfide, polyolefin, or polystyrene, in addition to polyether.

[0084] Another embodiment of the hydroxyl group-containing polyether compound (b) of this embodiment is a linear polyether block copolymer having at least two different segments, such as a segment structure having a divalent organic group derived from ethylene glycolate, propylene glycolate, butylene glycolate, or the like, or a segment structure having a divalent organic group derived from ethanedithiol, propanedithiol, or the like.

[0085] The polyether is not particularly limited, but examples thereof include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

[0086] The polyesters include, but are not limited to, those obtained by condensation of dicarboxylic acids and diols.

[0087] The dicarboxylic acid may include adipic acid, succinic acid, or a combination thereof.

[0088] Examples of the diol include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, pentane-1,5-diol, heptane-1,7-diol, and the like, or combinations thereof.

[0089] The polyester may also include polycaprolactone, polybutyrolactone, polyvalerolactone, polylactic acid, polyglycolic acid, or combinations thereof.

[0090] The polycarbonate is not particularly limited, but examples thereof include those obtained by condensation of carbonate and diol.

[0091] Examples of the diol include ethylene-1,2-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol, 3-methylpentane-1,5-diol, 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, pentane-1,5-diol, heptane-1,7-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like, or combinations thereof.

[0092] The poly(meth)acrylate is not particularly limited, but examples thereof include methyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, and the like, or combinations thereof.

[0093] The polyamide is not particularly limited, but examples thereof include those obtained by condensation of dicarboxylic acid and diamine.

[0094] Examples of the dicarboxylic acid include adipic acid, succinic acid, and the like, and a combination thereof. Examples of the diamine include hexamethylenediamine.

[0095] The polyamides may also include lactams such as polycaprolactam.

[0096] The polyethyleneimine may be a polyethyleneimine chain, which is a polymer chain, such as a polyethyleneimine chain, a polypropionylaziridine chain, a polyacetylaziridine chain, or a polyformylaziridine chain.

[0097] The polysiloxane may be a polysiloxane chain, which is a polymer chain, such as a polydimethylsiloxane chain or a polymethylphenylsiloxane chain.

[0098] The polysulfide may contain a polyethylene sulfide chain or the like.

[0099] The polyolefin may include polyethylene, polypropylene, and the like, or a combination thereof.

[0100] The polystyrene may include polystyrene, polystyrene sulfonate, and the like, or a combination thereof.

[0101] The hydroxyl group-containing polyether compound (b) of this embodiment forms a domain structure. Specifically, it preferably forms micelles by microphase separation, which can provide uniformly dispersed nano-sized structures. The micellar structure can effectively disperse functional compounds such as photochromic dyes in the optical element 100 of this embodiment while maintaining the mechanical and optical properties.

[0102] The number of hydroxyl groups per molecule of the hydroxyl group-containing polyether compound (b) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. By setting the number of hydroxyl groups per molecule of the hydroxyl group-containing polyether compound (b) within the above numerical range, the compound can more easily exhibit its functions, and performance such as the color development density and color development / decolorization speed of the photochromic compound can be improved.

[0103] The number-average molecular weight of the hydroxyl group-containing polyether compound (b) is preferably 500 to 50,000, more preferably 1,000 to 30,000, and even more preferably 2,000 to 20,000. By setting the number-average molecular weight of the hydroxyl group-containing polyether compound (b) to the above-mentioned lower limit or more, the photochromic performance is easily improved. On the other hand, by setting the number-average molecular weight of the hydroxyl group-containing polyether compound (b) to the above-mentioned upper limit or less, the photochromic performance can be maintained well while opacification of the optical element 100 can be suppressed.

[0104] The content of the hydroxyl group-containing polyether compound (b) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 18% by mass, based on the total amount of the photochromic layer 21.

[0105] (Difunctional or Higher Functional Active Hydrogen Compound (c)) The active hydrogen compound (c) of this embodiment has two or more functional groups. Examples of the functional groups include a hydroxy group, a mercapto group, an amino group, and a carboxyl group.

[0106] Examples of the active hydrogen compound (c) include poly(thio)ol compounds having two or more hydroxyl groups or mercapto groups, polyamine compounds having two or more primary amino groups or secondary amino groups, and polycarboxylic acid compounds having two or more carboxyl groups. Also included are compounds having two or more active hydrogen groups selected from hydroxyl groups, mercapto groups, primary amino groups, secondary amino groups, and carboxyl groups in one molecule. The two or more active hydrogen groups may be the same or different. Examples of the bifunctional or more active hydrogen compound (c) having a mercapto group include the same compounds as the bifunctional or more thiol compound (e).

[0107] For example, bifunctional or higher active hydrogen compounds having a hydroxy group, such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, polyglycerin, and thioglycerin; trithioglycerin, pentaerythritol tetrakis(thioglycolate), trimethylolpropane(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol, 4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-1 difunctional or higher active hydrogen compounds having a mercapto group, such as 1,11-dithiol, 4,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis(mercaptomethyl)-3,6,9-trithiaundecane-1,11-dithiol, 1,1,3,3-tetrakis(mercaptomethyl)-2-thiapropane, 1,4-dithiane-2,5-dithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, and xylylenedithiol; Examples include bifunctional or higher active hydrogen compounds having an amino group, such as xylylenediamine, α,α,α',α'-tetramethyl-xylylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, diaminopolypropylene, diaminopolyethylene, isophoronediamine, bis(aminocyclohexyl)methane, bis(aminomethyl)cyclohexane, and bis(aminomethyl)norbornane.

[0108] The content of the difunctional or higher active hydrogen compound (c) is preferably 25 to 55% by mass, more preferably 30 to 50% by mass, and even more preferably 35 to 45% by mass, based on the total amount of the photochromic layer 21.

[0109] (Photochromic Compound (d)) Examples of the photochromic compound (d) include compounds whose absorption characteristics (absorption spectrum) change with respect to light of a specific wavelength.

[0110] As the photochromic compound (d) of this embodiment, known compounds can be used, and can be obtained by the methods described in, for example, WO 2009 / 146509, WO 2010 / 20770, WO 2012 / 149599, and WO 2012 / 162725. Specific examples include spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, and bisimidazole compounds. Among these, naphthopyran compounds and spiropyran compounds are preferred, and naphthopyran compounds having no active hydrogen are more preferred.

[0111] The content of the photochromic compound (d) is preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, and even more preferably 0.3 to 1% by mass, based on the total amount of the photochromic layer 21.

[0112] (Others) The first polymerizable composition may further contain known additives such as a resin modifier, a light stabilizer, an antioxidant, and a color inhibitor, depending on the properties desired for the application.

[0113] The viscosity of the first polymerizable composition used in this embodiment is preferably 5 to 1000 mPa·s, and more preferably 10 to 500 mPa·s, in order to facilitate application to the production method described below.

[0114] <Method for Manufacturing Optical Member 100> Next, an example of a method for manufacturing the optical member 100 of this embodiment will be described.

[0115] The method for producing the optical member 100 of this embodiment includes a step of laminating the photochromic layer 21 on the surface 11 a of the sulfur atom-containing resin substrate 11. That is, the photochromic layer 21 is disposed so as to be in direct contact with the surface 11 a of the sulfur atom-containing resin substrate 11. Details will be described below.

[0116] First, a second polymerizable composition is prepared and cured by a known method to obtain a sulfur-atom-containing resin substrate 11. The curing conditions can be, for example, thermal polymerization within 48 hours at a temperature range of 20°C to 150°C. The cured sulfur-atom-containing resin substrate 11 is laminated directly to the photochromic layer 21 described below without being annealed. The annealing treatment is a heat treatment at 50°C to 150°C, and from the viewpoint of further improving the appearance, a heat treatment at 50°C to 130°C is preferred. In other words, after the second polymerizable composition is cured to obtain the sulfur-atom-containing resin substrate 11, the sulfur-atom-containing resin substrate 11 is not subjected to a heat treatment at 50°C to 150°C. This results in a sulfur-atom-containing resin substrate 11 that retains thiol groups on its surface, and an optical element 100 with good adhesion is obtained.

[0117] Before the photochromic layer 21 was laminated, the surface of the sulfur-containing resin substrate 11 was analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method). －１ The absorbance of the absorption peak observed at T1, 2550-2700 cm －１ When the absorbance of the absorption peak observed at T0 is defined as T0, the ratio (%) of T0 to T1 is preferably in the range of 4 to 10%. In particular, it is preferable to perform FTIR analysis on the surface of the sulfur atom-containing resin substrate 11 immediately after polymerization and curing. In other words, it is preferable to prevent the absorption peak from changing over time after polymerization and curing.

[0118] Before the photochromic layer 21 is laminated, the surface of the sulfur atom-containing resin substrate 11 is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method). －１ The absorbance of the absorption peak observed at A1 is 2250-2260 cm －１When the absorbance of the absorption peak observed at 1000 nm is defined as A0, the ratio (%) of A0 to A1 is preferably in the range of 30 to 99%. In particular, it is preferable to perform FTIR analysis on the surface of the sulfur atom-containing resin substrate 11 immediately after polymerization and curing. In other words, it is preferable to prevent the absorption peak from changing over time after polymerization and curing.

[0119] Next, the photochromic layer 21 is laminated on at least one surface of the obtained sulfur atom-containing resin substrate 11. The lamination method is not particularly limited, and any known method can be used.

[0120] For example, examples include (i) a method in which a photochromic layer 21 in the form of a film or sheet is attached to at least one surface of the sulfur atom-containing resin substrate 11, and (ii) a method in which the sulfur atom-containing resin substrate 11 is placed along the inner wall of a cavity of a molding mold held by a gasket or tape, and then a first polymerizable composition is injected into the cavity and cured.

[0121] The film- or sheet-shaped photochromic layer 21 used in the above method (i) is not particularly limited, but can be obtained by molding a first polymerizable composition obtained by melt-kneading, impregnation, or the like using various conventionally known methods, specifically, for example, injection molding, profile extrusion molding, pipe molding, tube molding, heterogeneous molded body coating molding, injection blow molding, direct blow molding, T-die sheet or film molding, inflation film molding, press molding, etc. Known methods can be used to attach the film- or sheet-shaped photochromic layer 21 to the surface of the sulfur atom-containing resin substrate 11.

[0122] The cast polymerization in the above method (ii) can be carried out, for example, using a known casting molding apparatus according to the following procedure x. Fig. 2 is a cross-sectional view schematically illustrating an example of a manufacturing process for the optical element 100 of this embodiment. Fig. 2 shows the casting molding apparatus including a sulfur-atom-containing resin substrate 11, a substrate 30 arranged to face the surface 11a of the sulfur-atom-containing resin substrate 11, a fixing member 31 for fixing the peripheral edge of the sulfur-atom-containing resin substrate 11 and the peripheral edge of the substrate 30, and a casting part provided on the fixing member 31.

[0123] The second polymerizable composition is injected into the gap 20 from the injection portion and polymerized and cured, thereby forming a photochromic layer 21 on the surface 11 a of the sulfur atom-containing resin substrate 11 .

[0124] The sulfur atom-containing resin substrate 11 and the substrate 30 may have curved surfaces and may be substantially circular in plan view. The gap 20 is formed by being sandwiched between the sulfur atom-containing resin substrate 11 and the substrate 30, and therefore the shape, thickness, etc. of the gap 20 are adjusted according to the shapes of the sulfur atom-containing resin substrate 11 and the substrate 30. The photochromic layer 21 is also designed according to the shape, thickness, etc. of the gap 20.

[0125] The material constituting the substrate 30 is not particularly limited, and may be glass, metal, resin, etc. The substrate 30 can be later peeled off to obtain a laminate of the substrate 30 and the photochromic layer 21 that will be formed later in the gap 20. Alternatively, the substrate 30 can be used as is to form a laminate of the sulfur atom-containing resin substrate 11, a thin film-like molded product, and the substrate 30.

[0126] The polymerization conditions for the second polymerizable composition to form the photochromic layer 21 are not limited because they vary depending on the composition and amount of the first polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., but are generally carried out at a temperature of approximately −50 to 150° C. for 1 to 50 hours.

[0127] In this manner, the optical member 100 of this embodiment can be manufactured.

[0128] <Applications, Optical Lens> Applications of the optical member 100 of this embodiment include plastic lenses, camera lenses, light-emitting diode lenses, light-emitting diode lens cases, prisms, optical fibers, information recording substrates, filters, etc. In particular, it is suitable as an optical material or optical element for plastic lenses, camera lenses, light-emitting diode lenses, light-emitting diode lens cases, etc. Among these, it is suitable as an optical lens having a photochromic function.

[0129] An optical lens including the optical member 100 of this embodiment may be used as a laminated plastic lens by applying a coating layer to one or both sides of the lens substrate made of the optical member 100, as needed. Examples of coating layers include a primer layer, a hard coat layer, an anti-reflection film layer, an anti-fogging coating film layer, an anti-fouling layer, and a water-repellent layer. These coating layers may be used alone or in combination with multiple coating layers. When coating layers are applied to both sides, the same coating layer or different coating layers may be applied to each side.

[0130] These coating layers may each contain an infrared absorber to protect the eyes from infrared rays, a light stabilizer, an antioxidant, an antistatic agent to improve the weather resistance of the lens, or other known additives to enhance lens performance. A coating layer such as a hard coat layer or an antireflection coat, or a primer layer may also be provided.

[0131] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted.

[0132] Next, the present invention will be described in detail using examples, but the content of the present invention is not limited to these examples. The term "mainly composed" means that the content of component X (when component X consists of two or more compounds, the total content of the two or more compounds) is 50% or more of the total amount of the composition. The term "mainly composed" refers to the ratio (area %) of the total area of ​​all peaks of component X to the total area of ​​all peaks of the composition, as determined by high-performance liquid chromatography.

[0133] Experiment A: In the case where an episulfide-based resin substrate was used (1) Preparation of an episulfide-based resin substrate <Raw materials for episulfide-based resin substrate> (Bifunctional or higher thiol compound (e)) Thiol composition containing as a main component a mixture of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (episulfide compound (f)) Episulfide compound containing as a main component bis(2,3-epithiopropyl)disulfide (ultraviolet absorber) 2-(5'-t-butyl-2-hydroxyphenyl)-benzotriazole ("Tinuvin PS" manufactured by BASF Japan Ltd.)

[0134] An episulfide-based resin substrate was prepared by the following method. Example 1A: 1.1 parts by mass of an ultraviolet absorber was added to 100 parts by mass of an episulfide compound (f) mainly composed of bis(2,3-epithiopropyl)disulfide, and the mixture was stirred for 30 minutes to dissolve. To this solution, 9.0 parts by mass of a thiol composition (e) was added. 0.1 parts by mass of N,N-dicyclohexylmethylamine was added and the mixture was stirred for 10 minutes to dissolve. Furthermore, to this solution, a solution prepared in advance by dissolving 1 part by mass of the thiol composition (e) in 0.02 parts by mass of N,N-dimethylcyclohexylamine was added and stirred for 10 minutes to obtain a polymerizable composition. The polymerizable composition was then stirred and degassed for 30 minutes at a temperature between 10°C and 20°C under a reduced pressure of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter. The resulting polymerizable composition was poured into the space enclosed between glass molds and then heated from 30°C to 120°C over 23 hours. The resulting composition was then cooled to room temperature and removed from the glass molds to obtain an episulfide-based resin substrate. The resulting substrate was used in the subsequent photochromic layer formation step without being annealed.

[0135] <Comparative Example 1A> An episulfide-based resin substrate was obtained in the same manner as in Example 1A, except that the episulfide-based resin substrate removed from the glass mold was further subjected to an annealing treatment under conditions of 120°C / 10 minutes and then used in the subsequent photochromic layer formation step.

[0136] <Comparative Example 2A> A sulfur atom-containing resin substrate was obtained in the same manner as in Example 1A, except that the episulfide-based resin substrate removed from the glass mold was further subjected to annealing treatment under conditions of 120°C / 1 hour and then used in the subsequent photochromic layer formation step.

[0137] (2) Preparation of First Polymerizable Composition for Photochromic Layer <Raw Materials for Photochromic Layer> Iso(thio)cyanate Compounds (a) (a2): An isocyanate composition mainly composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Hydroxyl Group-Containing Polyether Compounds (b) Polyethylene Glycol Polypropylene Glycol Polyethylene Glycol (Pluronic L64, manufactured by BASF) Active Hydrogen Compounds (c) (c2): A thiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

[0138] A master liquid was prepared in advance by dissolving 0.305 parts by mass of Reversacol Wembley Grey and 0.30 parts by mass of Reversacol Heath Green in 19.395 parts by mass of an isocyanate composition containing as a main component a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane. 20 parts by mass of the resulting master solution was added to 22.16 parts by mass of an isocyanate composition primarily composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, and the mixture was stirred. 15 parts by mass of polyethylene glycol polypropylene glycol polyethylene glycol (Pluronic L64, manufactured by BASF) and 0.3 parts by mass of acidic phosphate ester (JP-506H, manufactured by Johoku Chemical Industry Co., Ltd.) were then added, and the mixture was stirred at 15°C to 20°C for 30 minutes. 0.1 parts by mass of dimethyltin dichloride was added to 37.3 parts by mass of a thiol composition primarily composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and the mixture was uniformly dissolved to prepare a solution. The resulting mixture was added to this solution and stirred for 15 minutes at 15°C to 20°C, yielding a first polymerizable composition. Thereafter, the first polymerizable composition was stirred and degassed for 1 hour and 30 minutes at 15°C to 20°C in a reduced pressure environment of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter.

[0139] (3) Production of Photochromic Lens Using an injection molding device such as that shown in Fig. 2, the episulfide-based resin substrate prepared in (1) above was set in a mold, and the first polymerizable composition obtained in (2) above was poured into the space surrounded by the glass mold and the sulfur atom-containing resin substrate, followed by heating from 10°C to 130°C over 24 hours. Thereafter, the mixture was cooled to room temperature, the glass mold was removed, and a photochromic lens in which a photochromic functional layer and an episulfide-based resin substrate were laminated was obtained.

[0140] (4) Measurement of Thiol Group Content Using the episulfide resin substrate prepared in (1) above, Fourier transform infrared spectrophotometer (FTIR) analysis was carried out by the attenuated total reflection method (ATR method) under the following conditions. The episulfide resin substrate was polymerized and cured, removed from the glass mold, and then allowed to stand at 23°C and 50% RH for 1 hour. From the obtained curve, a peak at 2900 to 2970 cm －１ The absorbance of the maximum absorption peak (T1) observed at 2550-2700 cm －１ The absorbance (T0) of the maximum absorption peak observed at each point was determined, and the ratio (%) of T0 to T1 was calculated. －１ <Conditions> Fourier transform infrared spectrophotometer (FTIR): JASCO FT / IR 6100 Method: ATR method (total reflection method) Number of accumulations: 100 Wavelength range: 4000 to 400 cm －１ , resolution: 4cm －１ Prism material: Diamond (φ1.8mm)

[0141] (5) Three-Point Bending Test A test piece measuring 65 mm x 25 mm was cut out from the obtained photochromic lens so that the geometric center was located in the central portion. Using the test piece, a three-point bending test was carried out at 25°C in accordance with JIS K7171, and the breaking test force (N) and maximum point displacement (mm) were measured. The maximum point stress (N / mm) was calculated using the following formula: ２ The results are shown in Table 1. Maximum stress (N / mm ２) = Breaking point test force (N) ÷ (thickness (mm) x width (mm) of test piece) <Test conditions> Test equipment: Tabletop precision universal testing machine Autograph AGS-X series (manufactured by Shimadzu Corporation) Distance between supports: 34 mm Crosshead speed: 10 mm / min Radius of support base R2: 2 mm

[0142] (6) Appearance of Test Pieces After Measurement The appearance of the fracture surface of each test piece after the three-point bending test in (5) above was visually observed and evaluated according to the following criteria: Criteria OK: No peeling was observed at the interlayer surface NG: Peeling was observed at the interlayer surface

[0143] (7) Evaluation of Adhesion The blade of a steel wedge (model number: W-S-1.5, blade length 70.5 mm, total length 230 mm) was placed between the episulfide resin substrate and the photochromic functional layer of the obtained photochromic lens, and the steel wedge was hammered in by hand using a metal hammer until the photochromic lens was broken. OK: The wedge was difficult to penetrate at the point where the wedge was driven in, and only a small amount of the interlayer surface was exposed. NG: The wedge penetrated far at the point where the wedge was driven in, and a large amount of the interlayer surface was exposed.

[0144] (8) Evaluation of Photochromic Function It was confirmed that the photochromic lens of Example 1A exhibited better color development performance more quickly than the photochromic lenses of Comparative Examples 1A to 2A when placed under sunlight, and that the photochromic lens quickly returned to its transparent state when returned indoors.

[0145]

[0146] Experiment B: Using a poly(thio)urethane resin substrate (1) Preparation of a poly(thio)urethane resin substrate <Raw materials for poly(thio)urethane resin substrate> Iso(thio)cyanate compounds (a) (a1): m-xylylene diisocyanate (a2): an isocyanate composition mainly composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Bifunctional or higher thiol compounds (e) (e1): a thiol composition mainly composed of pentaerythritol tetrakis(3-mercaptopropionate) (e2): a thiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (e3): A thiol composition containing as its main component a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0147] A poly(thio)urethane resin substrate was prepared according to the following procedure. Examples 1B, 3B, and 4B: To 50.6 parts by weight of an isocyanate composition primarily composed of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 0.05 parts by weight of 2-(2'-hydroxy-5-t-octylphenyl)benzotriazole (Kyodo Chemical Co., Ltd.: Viosorb 583) as an ultraviolet absorber and 0.125 parts by weight of Zelec-UN (Mitsui Chemicals, Inc.) as an MR internal mold release agent were added, and the mixture was stirred for 5 minutes to dissolve. To this solution, 23.9 parts by weight of a thiol composition primarily composed of pentaerythritol tetrakis(3-mercaptopropionate) was added. Furthermore, a solution was prepared by adding 0.02 parts by weight of dimethyltin chloride to 25.5 parts by weight of a thiol composition primarily composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and stirring for 15 minutes to obtain a polymerizable composition. The polymerizable composition was then stirred and degassed for 30 minutes at 10°C to 20°C under a reduced pressure of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter. The resulting polymerizable composition was poured into the space enclosed between glass molds and heated from 10°C to 130°C over 32 hours. The resulting mixture was then cooled to room temperature and removed from the glass mold to obtain a poly(thio)urethane resin substrate. The resulting substrate was used in the subsequent photochromic layer formation process without annealing.

[0148] Example 2B To 40.7 parts by weight of m-xylylene diisocyanate, 1.5 parts by weight of 2-(2'-hydroxy-5-t-octylphenyl)-benzotriazole (Viosorb 583, manufactured by Kyodo Chemical Industry Co., Ltd.) as an ultraviolet absorber and 0.1 parts by weight of Zelec-UN (manufactured by Mitsui Chemicals, Inc.) as an MR internal mold release agent were added, and the mixture was stirred at 10°C to 15°C for 10 minutes to dissolve. To this solution was added 49.3 parts by weight of a thiol composition containing as a main component a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and further added a solution previously prepared by dissolving 0.005 parts by weight of dimethyltin chloride in 10 parts by weight of m-xylylene diisocyanate, followed by stirring at 10°C to 15°C for 15 minutes to obtain a polymerizable composition. The polymerizable composition was then stirred and degassed for 30 minutes at 10 to 20°C under a reduced pressure of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter. The resulting polymerizable composition was poured into the space enclosed between glass molds and heated from 10 to 130°C over 32 hours. The resulting composition was then cooled to room temperature and removed from the glass molds to obtain a poly(thio)urethane resin substrate. The resulting substrate was used in the subsequent photochromic layer formation process without annealing.

[0149] Comparative Examples 1B and 3B: To 50.6 parts by weight of an isocyanate composition primarily composed of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 0.05 parts by weight of 2-(2'-hydroxy-5-t-octylphenyl)-benzotriazole (Kyodo Chemical: Viosorb 583) as an ultraviolet absorber and 0.125 parts by weight of Zelec-UN (Mitsui Chemicals, Inc.) as an MR internal mold release agent were added and dissolved by stirring for 5 minutes. To this solution was added 23.9 parts by weight of a thiol composition containing pentaerythritol tetrakis(3-mercaptopropionate). Furthermore, a solution was prepared by adding 0.02 parts by weight of dimethyltin chloride to 25.5 parts by weight of a thiol composition primarily composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and stirring for 15 minutes to obtain a polymerizable composition. The polymerizable composition was then stirred and degassed for 30 minutes at 10°C to 20°C under a reduced pressure of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter. The resulting polymerizable composition was poured into the space enclosed between glass molds and heated from 10°C to 130°C over 32 hours. The resulting mixture was then cooled to room temperature and removed from the glass mold to obtain a poly(thio)urethane resin substrate. The resulting substrate was annealed at 120°C for 2 hours and used in the subsequent photochromic layer formation process.

[0150] Comparative Example 2B To 40.7 parts by weight of m-xylylene diisocyanate, 1.5 parts by weight of 2-(2'-hydroxy-5-t-octylphenyl)-benzotriazole (Viosorb 583, manufactured by Kyodo Chemical Industry Co., Ltd.) as an ultraviolet absorber and 0.1 parts by weight of Zelec-UN (manufactured by Mitsui Chemicals, Inc.) as an MR internal mold release agent were added, and the mixture was stirred at 10°C to 15°C for 10 minutes to dissolve. To this solution was added 49.3 parts by weight of a thiol composition containing as a main component a mixture of 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and further added a solution previously prepared by dissolving 0.005 parts by weight of dimethyltin chloride in 10 parts by weight of m-xylylene diisocyanate, followed by stirring at 10°C to 15°C for 15 minutes to obtain a polymerizable composition. The polymerizable composition was then stirred and degassed for 30 minutes at 10°C to 20°C under a reduced pressure of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter. The resulting polymerizable composition was poured into the space enclosed by the glass mold and heated from 10°C to 130°C over 32 hours. The resulting composition was then cooled to room temperature and removed from the glass mold to obtain a poly(thio)urethane resin substrate. The resulting poly(thio)urethane resin substrate was annealed at 120°C for 2 hours and used in the subsequent photochromic layer formation process.

[0151] (2) Preparation of First Polymerizable Composition for Photochromic Layer <Raw Materials for Photochromic Layer> Iso(thio)cyanate Compounds (a) (a2): An isocyanate composition mainly composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane Hydroxyl Group-Containing Polyether Compounds (b) Polyethylene Glycol Polypropylene Glycol Polyethylene Glycol (Pluronic L64, manufactured by BASF) Active Hydrogen Compounds (c) (c2): A thiol composition mainly composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane

[0152] A master liquid was prepared in advance by dissolving 0.305 parts by weight of Reversacol Wembley Grey and 0.30 parts by weight of Reversacol Heath Green in 19.395 parts by weight of an isocyanate composition containing as a main component a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane. To 22.16 parts by weight of an isocyanate composition primarily composed of a mixture of 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 20 parts by weight of the resulting master solution was added and stirred. To this was added 15 parts by weight of polyethylene glycol polypropylene glycol polyethylene glycol (Pluronic L64, manufactured by BASF) and 0.3 parts by weight of acidic phosphate ester (JP-506H, manufactured by Johoku Chemical Industry Co., Ltd.), and the mixture was stirred at 15°C to 20°C for 30 minutes. A solution was prepared by adding 0.1 parts by weight of dimethyltin dichloride to 37.3 parts by weight of a thiol composition primarily composed of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and dissolving the mixture uniformly. The resulting mixture was added to this solution and stirred for 15 minutes at 15°C to 20°C, yielding a first polymerizable composition. Thereafter, the first polymerizable composition was stirred and degassed for 1 hour and 30 minutes at 15°C to 20°C in a reduced pressure environment of 400 Pa or less, and then filtered using a 1.0 μm PTFE filter.

[0153] (3) Production of Photochromic Lens Using an injection molding device such as that shown in Figure 2, the poly(thio)urethane resin substrate prepared in (1) above was set in a mold, and the first polymerizable composition obtained in (2) above was poured into the space surrounded by the glass mold and the poly(thio)urethane resin substrate, followed by heating from 10°C to 130°C over 24 hours. Thereafter, the mixture was cooled to room temperature, and the glass mold was removed to obtain a photochromic lens in which a photochromic functional layer and a poly(thio)urethane resin substrate were laminated.

[0154] (4) Measurement of Isocyanato Group Content Using the poly(thio)urethane resin substrate prepared in (1) above, Fourier transform infrared spectrophotometer (FTIR) analysis was carried out by the attenuated total reflection method (ATR method) under the following conditions. The poly(thio)urethane resin substrate was previously left to stand at 23°C and 50% RH for 1 hour. From the obtained curve, a peak was observed in the range of 2900 to 2970 cm. －１ The absorbance of the maximum absorption peak (A1) observed at 2250-2260 cm －１ The absorbance (A0) of the maximum absorption peak observed at each point was determined, and the ratio (%) of A0 to A1 was calculated. <Conditions> Fourier transform infrared spectrophotometer (FTIR): JASCO FT / IR 6100 Method: ATR method (total reflection method) Number of accumulations: 100 Wavelength range: 4000 to 400 cm －１ , resolution: 4cm －１ Prism material: Diamond (φ1.8mm)

[0155] (5) Three-Point Bending Test A test piece measuring 65 mm x 25 mm was cut out from the obtained photochromic lens so that the geometric center was located in the central portion. Using the test piece, a three-point bending test was carried out at 25°C in accordance with JIS K7171, and the breaking test force (N) and maximum point displacement (mm) were measured. The maximum point stress (N / mm) was calculated using the following formula: ２ The results are shown in Table 2. Maximum stress (N / mm ２ ) = Breaking point test force (N) ÷ (thickness (mm) x width (mm) of test piece) <Test conditions> Test equipment: Tabletop precision universal testing machine Autograph AGS-X series (manufactured by Shimadzu Corporation) Distance between supports: 34 mm Crosshead speed: 10 mm / min Radius of support base R2: 2 mm

[0156] (6) Appearance of Test Pieces After Measurement The appearance of the fracture surface of each test piece after the three-point bending test in (5) above was visually observed and evaluated according to the following criteria: Criteria OK: No peeling was observed at the interlayer surface NG: Peeling was observed at the interlayer surface

[0157] (7) Evaluation of Adhesion The blade of a steel wedge (model number: W-S-1.5, blade length 70.5 mm, total length 230 mm) was placed between the poly(thio)urethane resin substrate and the photochromic functional layer of the obtained photochromic lens, and the steel wedge was hammered in by hand using a metal hammer until the photochromic lens was broken. OK: The wedge was difficult to penetrate at the point where the wedge was driven in, and only a small amount of the interlayer surface was exposed. NG: The wedge penetrated far at the point where the wedge was driven in, and a large amount of the interlayer surface was exposed.

[0158] (8) Evaluation of Photochromic Function It was confirmed that the photochromic lenses of Examples 1B to 4B exhibited better color development performance more quickly than the photochromic lenses of Comparative Examples 1B to 2B when placed under sunlight, and quickly returned to a transparent state when returned indoors.

[0159]

[0160] This application claims priority based on Japanese Patent Application No. 2023-196633 filed on November 20, 2023, and Japanese Patent Application No. 2024-161960 filed on September 19, 2024, the disclosures of which are incorporated herein in their entireties.

[0161] REFERENCE SIGNS LIST 11 Sulfur atom-containing resin substrate 11a surface 11b surface 20 Gap 21 Photochromic layer 30 Substrate 31 Fixing member 100 Optical member

Claims

1. An optical member comprising a sulfur-containing resin substrate and a photochromic layer laminated on a surface of the sulfur-containing resin substrate, the maximum point stress measured by the following procedure x being 138 N / mm ２ More than 177N / mm ２ An optical member having the following characteristics. Step x: A three-point bending test is performed at 25° C. in accordance with JIS K7171 using the optical member, and the maximum point stress (N / mm ２ ) is measured.

2. An optical component according to claim 1, wherein the photochromic layer is a cured product of a first polymerizable composition containing (a) an iso(thio)cyanate compound having two or more functionalities, (b) a hydroxyl group-containing polyether compound, (c) an active hydrogen compound having two or more functionalities, and (d) a photochromic compound.

3. The optical member according to claim 1 or 2, wherein the sulfur atom-containing resin substrate is a poly(thio)urethane resin substrate or an episulfide-based resin substrate.

4. The optical member according to claim 3, wherein the surface of the episulfide-based resin substrate is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method) to find a wavelength of 2900 to 2970 cm －１ The absorbance of the maximum absorption peak observed at T1, 2550-2700 cm －１ the ratio (%) of T0 to T1, where T0 is the absorbance of the maximum absorption peak observed at the photochromic layer, is in the range of 4 to 10%, and the photochromic layer is a cured product of a first polymerizable composition containing (a) a difunctional or higher iso(thio)cyanate compound, (b) a hydroxyl group-containing polyether compound, (c) a difunctional or higher active hydrogen compound, and (d) a photochromic compound.

5. An optical member according to claim 3 or 4, wherein the episulfide-based resin substrate is a cured product of a second polymerizable composition containing a di- or higher functional thiol compound (e) and a di- or higher functional episulfide compound (f).

6. The optical member according to any one of claims 3 to 5, wherein the equivalent ratio of thiol groups to episulfide groups in the episulfide resin substrate is 1:99 to 30:

70.

7. The optical member according to claim 3, wherein the episulfide compound (f) contained in the episulfide resin substrate is either bis(2,3-epithiopropyl)sulfide or bis(2,3-epithiopropyl)disulfide.

8. The optical member according to claim 3 or 7, wherein the surface of the poly(thio)urethane resin substrate is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method) to determine a wavelength of 2900 to 2970 cm －１ The absorbance of the maximum absorption peak observed at 2250-2260 cm is A1, －１ the ratio (%) of A0 to A1 is in the range of 30 to 99%, where A0 is the absorbance of the maximum absorption peak observed at the photochromic layer; and the photochromic layer is a cured product of a first polymerizable composition comprising (a) a difunctional or higher iso(thio)cyanate compound, (b) a hydroxyl group-containing polyether compound, (c) a difunctional or higher active hydrogen compound, and (d) a photochromic compound.

9. An optical element according to any one of claims 3, 7 and 8, wherein the poly(thio)urethane resin substrate is a cured product of a second polymerizable composition containing (a) an iso(thio)cyanate compound having two or more functionalities and (e) a thiol compound having two or more functionalities.

10. The optical element according to any one of claims 3 and 7 to 9, wherein the equivalent ratio (SH:NCO) of thiol groups to isocyanato groups in the poly(thio)urethane resin substrate is 40:60 to 60:

40.

11. An optical element according to any one of claims 1 to 10, wherein the ratio of the thickness (mm) of the sulfur-atom-containing resin substrate to the thickness (mm) of the photochromic layer (thickness of sulfur-atom-containing resin substrate / thickness of photochromic layer) is 0.5 to 20.

12. The optical element according to any one of claims 1 to 11, wherein the thickness (mm) of the sulfur atom-containing resin substrate is 0.5 to 20 mm.

13. An optical element according to any one of claims 1 to 12, wherein the photochromic layer has a thickness (mm) of 0.1 to 5 mm.

14. An optical member according to any one of claims 1 to 13, wherein the difunctional or higher iso(thio)cyanate compound (a) contained in the photochromic layer comprises one or more compounds selected from the group consisting of xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, and phenylene diisocyanate.

15. An optical element according to any one of claims 1 to 14, wherein the bifunctional or higher active hydrogen compound (c) contained in the photochromic layer has one or more functional groups selected from a hydroxyl group, a mercapto group, an amino group, and a carboxyl group.

16. An optical element according to any one of claims 1 to 15, wherein at least one surface is curved and the radius of curvature is greater than 0 and less than or equal to 400 mm.

17. An optical lens comprising an optical member according to any one of claims 1 to 16.

18. A method for producing an optical member, comprising a lamination step of laminating a photochromic layer on a surface of a sulfur-containing resin substrate, wherein the optical member has a maximum point stress of 138 N / mm2 as measured by a procedure x. ２ More than 177N / mm ２ A method for manufacturing an optical member configured as follows: Step x: A three-point bending test is performed at 25° C. in accordance with JIS K7171 using the optical member, and the maximum point stress (N / mm ２ ) is measured.

19. A method for producing an optical component according to claim 18, wherein the photochromic layer is a cured product of a first polymerizable composition containing a di- or higher functional iso(thio)cyanate compound (a), a hydroxyl group-containing polyether compound (b), a di- or higher functional active hydrogen compound (c), and a photochromic compound (d).

20. A method for producing an optical member according to claim 18 or 19, wherein the sulfur atom-containing resin substrate is a poly(thio)urethane resin substrate or an episulfide-based resin substrate.

21. The method for producing an optical member according to claim 20, wherein in the lamination step, the surface of the episulfide-based resin substrate on which the photochromic layer is laminated is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method), and a wavelength of 2900 to 2970 cm is obtained. －１ The absorbance of the absorption peak observed at T1, 2550 to 2700 cm －１ When the absorbance of the absorption peak observed at is taken as T0, the ratio (%) of T0 to T1 is in the range of 4 to 10%.

22. A method for producing an optical member according to claim 20 or 21, wherein in the lamination step, the episulfide-based resin substrate is obtained by curing a second polymerizable composition containing a di- or higher functional thiol compound (e) and a di- or higher functional episulfide compound (f), and is not subjected to an annealing treatment thereafter.

23. The method for producing an optical member according to claim 20, wherein in the lamination step, the surface of the poly(thio)urethane resin substrate on which the photochromic layer is laminated is analyzed by a Fourier transform infrared spectrophotometer (FTIR) using an attenuated total reflection method (ATR method) to determine whether the photochromic layer has a wavelength of 2900 to 2970 cm －１ The absorbance of the absorption peak observed at A1 is 2250-2260 cm －１ When the absorbance of the absorption peak observed at is taken as A0, the ratio (%) of A0 to A1 is in the range of 30 to 99%.

24. A method for producing an optical component according to claim 20 or 23, wherein in the lamination step, the poly(thio)urethane resin substrate is obtained by curing a second polymerizable composition containing an iso(thio)cyanate compound (a) having two or more functionalities and a thiol compound (e) having two or more functionalities, and has not been subjected to an annealing treatment thereafter.

25. A method for producing an optical member according to any one of claims 18 to 24, wherein the annealing treatment is a heat treatment at 50°C or higher and 150°C or lower.

26. A method for producing an optical member according to any one of claims 18 to 25, wherein in the lamination step, the photochromic layer is laminated by curing the first polymerizable composition on the surface of the sulfur atom-containing resin substrate.

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