Resin compositions, optical laminates, optical articles, lenses, and eyeglasses

Abstract

The purpose of the present invention is to provide a resin composition having excellent photochromic characteristics and mechanical characteristics. The present invention is a resin composition comprising (i) a urethane resin having a propylene glycol chain in the molecular chain thereof and (ii) a photochromic compound, wherein if the total spectral intensity at 16-20 ppm inclusive, including the spectral intensity of the carbon atom of the methyl group of the propylene glycol chain, as measured by 13C-PST / MAS NMR is PMIpst, and the total spectral intensity at 16-20 ppm inclusive, including the spectral intensity of the carbon atom of the methyl group of the propylene glycol chain, as measured by 13C-CP / MAS NMR is PMIcp, then the intensity ratio of PMIpst with respect to the PMIcp (PMIpst / PMIcp) is 8.0-40.0 inclusive.

Description

[Technical Field]

[0001] The present invention relates to resin compositions, optical laminates, optical articles, lenses, and eyeglasses. [Background technology]

[0002] Photochromic eyeglass lenses containing photochromic compounds quickly color in sunlight or other light containing ultraviolet rays outdoors, functioning as sunglasses, and fade in indoor environments where such light is absent, functioning as clear eyeglasses. The demand for photochromic optical articles with such photochromic properties has been increasing in recent years.

[0003] The following methods are generally used to impart photochromic properties to eyeglass lenses.

[0004] (a) A method of directly forming optical materials such as lenses by polymerizing a composition of a polymerizable compound and a photochromic compound (mixing method).

[0005] (b) A method of forming a resin layer in which a photochromic compound is dispersed on the surface of a plastic molded product such as a lens by coating or casting polymerization (lamination method).

[0006] (c) A method of joining two optical plates with an adhesive containing a dispersed photochromic compound (binder method). The optical plates may be made of plastic or inorganic glass.

[0007] In recent years, there has been a demand for further improvements in the photochromic properties of the aforementioned photochromic optical articles. In addition, there is a need for photochromic optical articles that possess both high photochromic properties and high mechanical properties. Patent Document 1 describes a dyed lens made by dyeing a urethane resin (molded body) as something similar to a photochromic optical article. The urethane resin that forms this molded body uses thiol as a monomer and has excellent mechanical strength due to the (thio)urethane bond in the molecular chain.

[0008] However, when a photochromic compound that becomes colored or colorless by ring-opening and ring-closing is incorporated instead of staining, the urethane resin matrix, having (thio)urethane bonds, may inhibit the ring-opening and ring-closing molecular mobility of the photochromic compound unless the monomer composition is specially adjusted. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] WO2012 / 176439 [Patent Document 2] WO2015 / 115648 [Patent Document 3] WO2016 / 143910 [Overview of the project] [Problems that the invention aims to solve]

[0010] To improve photochromic properties, Patent Document 2 uses a bifunctional active hydrogen compound having a polypropylene glycol chain, while Patent Document 3 uses a monofunctional active hydrogen compound. According to these methods, photochromic properties can be improved by forming spaces in the urethane matrix using specific active hydrogen compounds. [Means for solving the problem]

[0011] The inventors considered that it might be necessary to control the molecular mobility within the urethane resin not only by creating free space, but also by using crosslinking molecules. They then discovered that a cured product (urethane resin in which a photochromic compound is dispersed) that satisfies specific molecular mobility parameters can exhibit good photochromicity and mechanical properties, thus completing the present invention.

[0012] This invention encompasses the following inventions. 1. A urethane resin having polyoxypropylene chains in its molecular chain, and a photochromic compound, 13 The maximum signal intensity (PMI) in the range of 16 ppm to 20 ppm in the first spectrum obtained by C-PST / MAS nuclear magnetic resonance spectroscopy. pst )and, 13 The maximum signal intensity (PMI) in the range of 16 ppm to 20 ppm in the second spectrum obtained by C-CP / MAS nuclear magnetic resonance spectroscopy. cp ) ratio (PMI) pst / PMI cp ) is between 8.0 and 40.0 the law of nature, The total content of alkali metal ions and alkaline earth metal ions determined by X-ray fluorescence analysis is 500 ppm or less. A resin composition, The aforementioned urethane resin is (A) A polyiso(thio)cyanate component having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in its molecule, (B) Active hydrogen-containing component having an active hydrogen-containing group, A resin obtained by reacting, Let nB be the total number of moles of active hydrogen-containing groups in the (B) active hydrogen-containing component. When the total number of moles of iso(thio)cyanate groups in the (A) polyiso(thio)cyanate component is nA, The ratio (nA / nB) is between 1.00 and 1.50. The aforementioned (B) active hydrogen-containing component is (B1) A polyfunctional active hydrogen-containing component having three or more active hydrogen-containing groups in one molecule, and (B2) a first active hydrogen-containing component having one or two active hydrogen-containing groups in one molecule, and the (B2) first active hydrogen-containing component has a number average molecular weight of 700 or more Under 3000 and has a polyoxypropylene chain in the molecule, the (B1) polyfunctional active hydrogen-containing component has a quaternary carbon atom in the molecule, and a resin composition containing a compound in which all groups bonded to the quaternary carbon atom have active hydrogen-containing groups. 2. The maximum intensity (AMI pst ) of the signal in the range of 10 ppm or more and 15 ppm or less in the first spectrum, and the maximum intensity (AMI cp ) of the signal in the range of 10 ppm or more and 15 ppm or less in the second spectrum, and the ratio (AMI pst / AMI cp ) is 7.0 or more and 23.0 or less, the resin composition according to item 1 above. 3. The maximum intensity (EI pst ) of the signal in the range of 68 ppm or more and 72 ppm or less in the first spectrum, and the maximum intensity (EI cp ) of the signal in the range of 68 ppm or more and 72 ppm or less in the second spectrum, and the ratio (EI pst / EI cp ) is 5.0 or more and 20.0 or less, the resin composition according to item 1 or 2 above. 4 . The polyoxypropylene chain of the (B2) first active hydrogen-containing component has an average value of 2 or more and 25 or less of repeating units of oxypropylene, the resin composition according to any one of items 1 to 3 above. 5 . The (B2) first active hydrogen-containing component further has at least one of an alkyl group and a polyoxyethylene chain in the molecule, the resin composition according to any one of items 1 to 4 above. 6The (B2) first active hydrogen-containing component has the alkyl group, and its carbon number is 5 or more and 20 or less, as described in the preceding paragraph. 5 The resin composition described above. 7 The (B2) first active hydrogen-containing component has the polyoxyethylene chain, and the average value of its repeating units is 5 or more and 25 or less, as per the preceding paragraph. 5 The resin composition described above. 8 Optical substrate and, The optical substrate is laminated on at least one main surface of the preceding item 1~ 7 A resin composition according to any one of the following items, An optical laminate containing an optical element. 9 The preceding paragraph further includes a polarizing film. 8 The optical laminate described above. 10 . Previous section 1~ 7 An optical article comprising the resin composition described in any one of the following items. 11 . Previous section 1~ 7 A lens comprising the resin composition described in any one of the following items. 12 Previous section 11 Eyeglasses including the lenses described. [Effects of the Invention]

[0013] According to the present invention, a resin composition having excellent photochromic and mechanical properties can be obtained. In particular, a resin composition with excellent photochromic properties and heat resistance can be obtained. [Brief explanation of the drawing]

[0014] [Figure 1] A graph showing an example of the first spectrum of the resin composition according to the embodiment. [Figure 2] A graph showing an example of the second spectrum of the resin composition according to the embodiment. [Figure 3] A schematic diagram of the polyrotaxane component (B1b) used in the examples. [Figure 4]A schematic diagram showing an example of a polyfunctional active hydrogen-containing component in which all groups bonded to a quaternary carbon atom are active hydrogen-containing groups. [Figure 5] A schematic diagram showing an example of a polyfunctional active hydrogen-containing component in which some groups bonded to quaternary carbon atoms are active hydrogen-containing groups. [Figure 6] A schematic cross-sectional view showing an example of an optical laminate according to this embodiment. [Figure 7] A schematic perspective view showing an example of eyeglasses according to this embodiment. [Modes for carrying out the invention]

[0015] <Resin composition> The resin composition is (i) a urethane resin having polyoxypropylene chains in its molecular chain (component (i)), and (ii) Photochromic compound (component (ii)) Includes.

[0016] Furthermore, it was found that the urethane resin (i) exhibits excellent effects when a urethane resin matrix is ​​used in which the molecular mobility of the polyoxypropylene chains satisfies a specific range. Specifically, the mobility of the carbon atom portion of the methyl group of the polyoxypropylene chain is solid 13 By evaluating the properties using CNMR measurement, a resin composition with excellent photochromic and mechanical properties is obtained when the mobility index satisfies a specific range.

[0017] <Solid 13 Molecular mobility evaluation by CNMR measurement > Solid-state NMR methods for measuring carbon nuclei include the Pulse Saturation Transfer / Magic Angle Spinning (PST / MAS) method and the Cross Polarization / Magic Angle Spinning (CP / MAS) method.

[0018] The PST / MAS method is a technique that emphasizes and observes highly mobile regions (amorphous regions). The CP / MAS method is a technique that emphasizes and observes less mobile regions (crystalline regions). Therefore, by comparing the intensity of specific signals in these spectra, the molecular mobility of the components constituting urethane resins (matrix resins in which photochromic compounds are dispersed) can be evaluated. Solid state of resin composition obtained by PST / MAS method 13 The CNMR spectrum is also called the first spectrum. Solid resin composition by CP / MAS method. 13 The CNMR spectrum is also called the second spectrum.

[0019] In other words, the intensity of each peak measured by the PST / MAS method is I PST The intensity of each peak measured by the CP / MAS method is I CP In that case, I PST to I CP The value I obtained by dividing by PST / I CP This serves as an indicator of molecular mobility, and the greater the molecular mobility, the higher the I PST / I CP The value will be larger. Note that, in order to compare molecular mobility between different urethane resin compositions, the peak of the hard segment region, which is less affected by the surrounding molecular mobility, is used as the reference (I PST / I CP It is preferable to set it to =1). The carbon atom of the C=O group appearing in the range of 163 to 168 ppm was used as the reference peak.

[0020] (i) The component must contain a polyoxypropylene chain, and preferably also contains an alkyl group and / or an oxyethylene chain.

[0021] solid 13 The chemical shift values ​​of the carbon nuclei in each unit observed in 1C-NMR measurements are approximately as follows: 10-15 ppm: Terminal methyl group in alkyl group, 16-20 ppm: Methyl group in the oxypropylene unit, 68 ppm~72 ppm: Ethylene group in the oxyethylene unit 73 ppm to 80 ppm: Ethylene groups (excluding methyl groups) in the oxypropylene unit.

[0022] <PMI pst , and PMI cp Measurement > 16-20 ppm: Methyl groups in the oxypropylene unit can be observed. However, if component (i) contains an alkyl group with 2 or more carbon atoms, the peak of the methylene group adjacent to the terminal methyl group will also fall within this range.

[0023] <EI pst , and EI cp Measurement > 68-72 ppm; Ethylene groups can be identified in the oxyethylene unit.

[0024] <AMI pst , and AMI cp Measurement > 10-15 ppm; If component (i) contains an alkyl group with 2 or more carbon atoms, the methyl group at the end of that alkyl group can be identified.

[0025] <Other> 73-80 ppm; Ethylene groups (excluding methyl groups) in the oxypropylene unit can be identified.

[0026] A resin composition containing a photochromic compound, or a photochromic optical article, is analyzed directly by NMR to determine the I of each carbon nucleus. PST / I CP The value can be calculated.

[0027] Intensity ratio (PMI pst / PMI cp By having a PMI between 8.0 and 40.0, excellent photochromic and mechanical properties can be achieved. pst PMI represents the maximum signal intensity, or maximum height, that appears in the range of 16 ppm to 20 ppm in the first spectrum. cpThis represents the maximum intensity, or maximum height, of the signal appearing in the range of 16 ppm to 20 ppm in the second spectrum. As described above, the signals appearing in the range of 16 ppm to 20 ppm in both the first and second spectra are thought to originate from the methyl group of the oxypropylene unit.

[0028] Strength ratio (PMI) of resin composition pst / PMI cp The reason why the (i) component exhibits superior effects when it falls within a specific range is not clear, but it is presumed that the following occurs: When the urethane resin that constitutes the majority of the matrix of the resin composition has polyoxypropylene chains in its molecular chains, it is easier to secure free space, and it is thought that high photochromic properties can be exhibited. In other words, because the matrix of the resin composition becomes flexible, it is less likely to hinder the structural change of the photochromic compound, and photochromic properties can be exhibited over a long period of time. On the other hand, if the proportion of polyoxypropylene chains becomes excessively high, or if the length of the introduced chains becomes too long, the mechanical properties may decrease. Against this backdrop, the inventors considered that in order to improve photochromic properties while maintaining high mechanical properties, it is necessary to evaluate the mobility of component (i) itself. When the mobility of component (i) was measured by the NMR method described above, the intensity ratio (PMI) of component (i) pst / PMI cp We found that by setting the (i) component to between 8.0 and 40.0, excellent effects can be achieved. In other words, not only is free space formed, but the (i) component itself also has a moderate degree of mobility, so it is thought that an excellent balance between photochromic properties and mechanical properties is achieved.

[0029] (i) Intensity ratio of components (PMI) pst / PMI cp If the value is less than 8.0, it is undesirable because the photochromic properties are inferior. On the other hand, if it exceeds 40.0, it is undesirable because the mechanical properties, especially heat resistance, are reduced. In other words, the intensity ratio (PMI) pst / PMI cpA PMI of less than 8.0 may indicate that the proportion of highly mobile and flexible polyoxypropylene chains in the resin composition is too low. In such resin compositions, the structural changes of the photochromic compound are difficult to undergo, and the photochromic properties such as the fading rate and color intensity of the photochromic compound are not easily exhibited. pst / PMI cp A value exceeding 40.0 may indicate that the proportion of highly crystalline polyoxypropylene chains in the resin composition is too low. Such resin compositions tend to have insufficient mechanical properties, such as heat resistance.

[0030] Intensity ratio (PMI pst / PMI cp To exhibit superior characteristics, the value is preferably set to 10.0 to 35.0, more preferably to 10.0 to 15.0, or more preferably to 20.0 to 35.0.

[0031] (i) When using a monofunctional polymerizable monomer that has one reactive group (iso(thio)cyanate group or active hydrogen-containing group) in the molecule as a polymerizable monomer that forms a component, the intensity ratio (PMI) pst / PMI cp It is particularly preferable to set ) to 10.0 to 15.0.

[0032] Furthermore, when using bifunctional or higher polymerizable monomers and not monofunctional polymerizable monomers, the strength ratio (PMI) is used. pst / PMI cp It is particularly preferable that the strength ratio (PMI) be 20.0 to 35.0. If the monofunctional polymerizable monomer is not used, the degree of crosslinking increases, so the strength ratio (PMI) pst / PMI cp Even if the strength ratio (PMI) is high, it is expected to exhibit excellent effects. When monofunctional polymerizable monomers are not used, considering the balance of physical properties, the strength ratio (PMI) is considered to be high. pst / PMI cp The value is preferably 23.5 to 35.0, and more preferably 25.5 to 35.0.

[0033] However, even within these preferred ranges, in particular, the intensity ratio (PMI) pst / PMI cp It is preferable that the strength ratio (PMI) is 10.0 to 15.0. And it is most preferable to use the monofunctional polymerizable monomer. Using the monofunctional polymerizable monomer, the strength ratio (PMI) is pst / PMI cp By satisfying a value of 10.0 to 15.0, a resin composition with excellent photochromic and mechanical properties can be obtained. but Yes, it is possible. In order to achieve superior photochromic properties, the intensity ratio (PMI) is important. pst / PMI cp It is more preferable that the ratio is 11.0 to 15.0, and even more preferable that it is 12.5 to 15.0. Furthermore, not only are these physical properties excellent, but the polymerizability and moldability of the photochromic curable composition forming the resin composition can be improved. In particular, a photochromic curable composition using the monofunctional polymerizable monomer can suppress a rapid increase in viscosity during polymerization. Strength PMI pst It is preferable that the PMI is between 1.0 and 20.0. pst Resin compositions within this range tend to have a sufficient amount of highly mobile and flexible polyoxypropylene chains. pst It is more preferably 1.1 to 17.5, and even more preferably 1.1 to 3.5, or 13.0 to 17.5. Strength PMI cp It is preferable that the PMI is between 0.1 and 1.0. cp Resin compositions within this range tend to have a sufficient amount of highly crystalline polyoxypropylene chains. cp It is more preferable that the value is between 0.10 and 0.70, and even more preferable that it is between 0.15 and 0.30, or between 0.50 and 0.70.

[0034] Component (i) preferably has an alkyl group in its molecule. This alkyl group is preferably a group having 5 to 20 carbon atoms and is preferably a linear alkyl group. This alkyl group may constitute a side chain or a main chain of component (i). Component (i) having an alkyl group in its molecule can be obtained, for example, by using a polymerizable monomer having an alkyl group as the monofunctional polymerizable monomer described above. The terminal group opposite the reactive group of this monofunctional polymerizable monomer is an alkyl group, and is preferably a linear alkyl group having 5 to 20 carbon atoms.

[0035] (i) If the component has an alkyl group in the molecule, 13 The spectral intensity of the carbon atom of the terminal methyl group of the alkyl group, measured by C-PST / MAS NMR, is AMI pst year, 13 The spectral intensity of the carbon atom of the methyl group at the end of the alkyl group, measured by C-CP / MAS NMR, is AMI cp In that case, AMI cp AMI for pst The intensity ratio (AMI) pst / AMI cp It is preferable that the peak intensity ratio (AMI) is between 7.0 and 23.0. pst / AMI cp By having an intensity ratio (AMI) between 7.0 and 23.0, the photochromic and mechanical properties of the resulting resin composition can be improved. pst / AMI cp ) is more preferably 11.5 to 20.0, and more preferably 13.5 to 16.0. As described above, the signal that is thought to originate from the carbon atom of the methyl group at the end of the alkyl group appears in the range of 10 to 15 ppm in the first and second spectra. Strength AMI pst It is preferable that the strength AMI is between 1.0 and 5.0. pstA resin composition within this range tends to have a high molecular mobility and sufficient flexible alkyl groups. Strength AMI pst is more preferably 1.10 or more and 3.00 or less, and even more preferably 2.0 or more and 2.8 or less. Strength AMI cp is preferably 0.1 or more and 0.5 or less. Strength AMI cp A resin composition within this range tends to have sufficient highly crystalline alkyl groups. Strength AMI cp is more preferably 0.10 or more and 0.30 or less, and even more preferably 0.15 or more and 0.20 or less.

[0036] Furthermore, it is preferable that component (i) has an oxyethylene chain in the molecule. Having a polyoxyethylene chain in the molecular chain, 13 Regarding the spectral intensity of the carbon atoms of the polyoxyethylene chain measured by C-PST / MAS NMR as EI pst and 13 Regarding the spectral intensity of the carbon atoms of the polyoxyethylene chain measured by C-CP / MAS NMR as EI cp when EI cp the intensity ratio of EI pst to EI pst (EI cp / EI pst / EI cp ) is preferably 5.0 or more and 20.0 or less. By making the peak intensity ratio (EI pst / EI cp ) 5.0 or more and 20.0 or less, the photochromic properties and mechanical properties of the resulting resin composition can be improved. The intensity ratio (EI pst / EI cp ) is more preferably 6.5 or more and 12.0 or less. As described above, the signal considered to be derived from the ethylene group in the oxyethylene unit appears within the range of 68 ppm to 72 ppm in the first and second spectra. Strength EI pst is preferably 4.0 or more and 20.0 or less. Strength EI pstResin compositions within this range tend to have a sufficient amount of highly mobile and flexible oxyethylene chains. Strength EI pst It is more preferable that the value is between 4.50 and 18.00, and even more preferable that it is between 9.50 and 18.00. Strength EI cp It is preferable that the intensity EI is between 0.5 and 3.0. cp Resin compositions within this range tend to have a sufficient amount of highly crystalline oxyethylene chains. (Strength EI) cp It is more preferably 0.70 or more and 2.10 or less, and even more preferably 1.30 or more and 2.00 or less.

[0037] The first spectrum of the resin composition is: 13 The sample is obtained by C-PST / MAS NMR spectroscopy. A disc-shaped resin composition with a diameter of approximately 2 mm and a thickness of 1 mm is used as the sample. For measurement, a 4 mm zirconia sample tube filled with this sample is used. As the measuring instrument, for example, an FT-NMR JNM-ECA400II (JEOL Ltd.) is used. The measurement conditions are, for example, as follows. Probe: 4mmΦCP / MAS probe (JEOL Ltd.). 13 C nuclear measurement frequency: 100.53MHz. Measurement method: CP / MAS method. Contact time: 2msec. Delay time: 5 seconds. Total number of times: 5000. Sample quantity: Approximately 80 mg. Sample rotation speed: 6000Hz. Temperature: 25℃. External standard: Adamantane (29.5ppm). Pre-saturation method: interval 10msec.

[0038] The second spectrum of the resin composition is: 13The first spectrum is obtained by C-CP / MAS NMR spectroscopy. The second spectrum is obtained in the same manner as the first spectrum, except that the pre-saturation method is not used. The intensity and chemical shift of each signal are calculated from the first and second spectra obtained in this way using analysis software such as JEOL Delta v5.0.4.

[0039] Figure 1 is a graph showing an example of the first spectrum of a resin composition according to an embodiment. The graph shown in Figure 1 is the first spectrum of a resin composition according to Example 15, which will be described later. In Figure 1, the horizontal axis represents chemical shift, and the vertical axis represents intensity. The first spectrum shown in Figure 1 has a maximum value PMI within a chemical shift range of 16 ppm to 20 ppm. pst A signal indicating this, and the maximum value EI within the chemical shift range of 68 ppm to 72 ppm. pst Includes signals indicating this.

[0040] Figure 2 is a graph showing an example of the second spectrum of the resin composition according to the embodiment. The graph shown in Figure 2 is the second spectrum of the resin composition according to Example 15, which will be described later. In Figure 2, the horizontal axis shows the chemical shift, and the vertical axis shows the intensity. The second spectrum shown in Figure 2 has a maximum value PMI within a chemical shift range of 16 ppm to 20 ppm. cp A signal indicating this, and the maximum value EI within the chemical shift range of 68 ppm to 72 ppm. cp Includes signals indicating this.

[0041] (i) The component has polyoxypropylene chains in its molecular chain, as described above, and has an intensity ratio (PMI). pst / PMI cpIf the ratio is between 8.0 and 40.0, the manufacturing method is not particularly limited. In particular, to obtain good polymerizability and to easily manufacture the resin composition, it is preferable to use a polymerizable monomer having an oxypropylene chain, more preferably a polymerizable monomer having both an oxypropylene chain and an oxyethylene chain, and most preferably a polymerizable monomer having an oxypropylene chain, an oxyethylene chain, and an alkyl group having 5 to 20 carbon atoms (particularly preferably a monofunctional polymerizable monomer).

[0042] Next, we will describe the photochromic compounds contained in the resin composition.

[0043] (ii) Photochromic compounds (ii) Photochromic compounds (hereinafter also referred to as component (ii)) can be used without particular restriction as long as they are compounds that exhibit photochromic properties, and these can be used individually or in combination of two or more.

[0044] Typical examples of such photochromic compounds include known photochromic compounds such as chromene compounds, flugimide compounds, spirooxazine compounds, and spiropyran compounds, which can be used without any limitations.

[0045] Examples of the above-mentioned flugimid compounds, spirooxazine compounds, spiropyran compounds, and chromene compounds include those described in Japanese Patent Publication No. 2-28154, Japanese Patent Publication No. 62-288830, WO94 / 22850, WO96 / 14596, and others.

[0046] In particular, in addition to those described in the above-mentioned patent document, other chromene compounds with excellent photochromic properties are known, and such chromene compounds can be suitably used as component (ii).Examples of such chromene compounds include JP 2001-031670, JP 2001-011067, JP 2001-011066, JP 2000-344761, JP 2000-327675, JP 2000-256347, JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229973, JP 2000-229972, JP 2000-219678, JP 2000-219686, JP Hei 11-322739, and JP Hei 11-28 6484, JP-A-11-279171, JP-A-09-218301, JP-A-09-124645, JP-A-08-295690, JP-A-08-176139, JP-A-08-157467, US Patent No. 5645767, US Patent No. 5658501, US Patent No. 5961892, US Patent No. 6296785, Japanese Patent No. 4424981, Japanese Patent No. 4424962, WO2009 / 136668 pamphlet, WO2008 / 023828 pamphlet, Japanese Patent No. 43 Japanese Patent Publication No. 69754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, Pamphlet WO2007 / 086532, JP-A-2009-120536, JP-A-2009-67754, JP-A-2009-67680, JP-A-2009-57300, Japanese Patent Publication No. 4195615, Japanese Patent Publication No. 4158881, Japanese Patent Publication No. 4157245, Japanese Patent Publication No. 4157239, Japanese Patent Publication No. 4157227, Japanese Patent Publication No. 4118458, JP-A-2008-74832, Japan This is disclosed in Japanese Patent Publication No. 3982770, Japanese Patent Publication No. 3801386, Pamphlets WO2005 / 028465, WO2003 / 042203, JP 2005-289812, JP 2005-289807, JP 2005-112772, Japanese Patent Publication No. 3522189, Pamphlet WO2002 / 090342, Japanese Patent Publication No. 3471073, JP 2003-277381, Pamphlets WO2001 / 060811, WO00 / 71544, etc.Fulgide compounds, chromene compounds, and spirooxazine compounds are disclosed in numerous publications, such as Japanese Patent Publication No. 2-28154, Japanese Patent Publication No. 62-288830, and pamphlets WO94 / 22850 and WO96 / 14596.

[0047] Among known photochromic compounds, it is more preferable to use chromene compounds having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton from the viewpoint of photochromic properties such as color intensity, initial coloration, durability, and fading rate.

[0048] In addition to the above, photochromic compounds having oligomeric chain groups within the molecule can also be suitably used. Such photochromic compounds having oligomeric chain groups are disclosed in many publications, including WO2000 / 015630, WO2004 / 041961, WO2009 / 146509, WO2012 / 149599, WO2012 / 162725, WO2013 / 078086, WO2019 / 013249, and WO2019 / 203205. Among these photochromic compounds having oligomeric chain groups within the molecule, it is preferable to use the photochromic compounds having oligomeric chain groups described in WO2019 / 013249 and WO2019 / 203205, as they exhibit superior photochromicity and durability.

[0049] <Resin composition> The resin composition comprises component (i) and component (ii). The blending ratio of component (i) and component (ii) in the resin composition may be appropriately determined depending on the intended use of the photochromic optical article. In particular, considering general applications, It is preferable that the amount of component (ii) is 0.01 to 10 parts by mass per 100 parts by mass of component (i).

[0050] However, since component (i) forms a crosslinked structure, it is preferable to manufacture it by the following method in order for component (ii) to be uniformly dispersed in component (i), which forms the matrix. In other words, it is preferable to prepare a polymerizable composition containing a photochromic compound (photochromic curable composition) as detailed below, and to cure this photochromic curable composition to obtain a resin composition. In this case, the content of component (i) is the total amount of polymerizable monomer components that form component (i) in the photochromic curable composition. Specifically, if component (i) consists of component (A) and component (B) as detailed below, the content of component (i) is equal to the total amount of component (A) and component (B) ((amount of component (i) = amount of component (A) + amount of component (B)). Therefore, in order to obtain a suitable content of component (ii) in the resin composition, as detailed below, the amount of component (ii) should be appropriately determined in relation to the total amount of component (A) and component (B).

[0051] This resin composition may contain known additives in addition to component (i) and component (ii).

[0052] Specifically, these include additives such as UV absorbers, antistatic agents, infrared absorbers, UV stabilizers, antioxidants, color inhibitors, fluorescent dyes, dyes, pigments, and fragrances; solvents, leveling agents, internal release agents; and polymerization regulators such as thiols including t-dodecyl mercaptan. These additives are preferably incorporated into the photochromic curable composition described in detail below.

[0053] The total content of alkali metal ions and alkaline earth metal ions in the resin composition is preferably 500 ppm or less. Resin compositions with low content of alkali metal ions and alkaline earth metal ions are photocatalytically produced. nine Romic compounds exhibit excellent durability. Alkali metal ions and alkaline earth metal ions are not particularly limited. Examples of alkali metal ions include sodium ions, potassium ions, lithium ions, and cesium ions. Examples of alkaline earth metal ions include calcium ions, magnesium ions, barium ions, strontium ions, beryllium ions, and radium ions. Alkali metal ions and alkaline earth metal ions include, for example, at least one ion selected from the group consisting of sodium ions, potassium ions, cesium ions, and magnesium ions.

[0054] The total content of alkali metal ions and alkaline earth metal ions in a resin composition can be measured by X-ray fluorescence analysis. For the measurement, a circular, flat plate-shaped sample of the resin composition, 40 mm in diameter and 1 mm thick, is used. For the measuring device, for example, a Rigaku Corporation X-ray fluorescence analyzer (ZSX Primus IV) is used. The detection limit of the X-ray fluorescence analyzer is, for example, 1 ppm. The total content of alkali metal ions and alkaline earth metal ions in the resin composition is preferably 200 ppm or less, and more preferably 100 ppm or less. The lower limit of alkali metal ions and alkaline earth metal ions in the resin composition is 0 ppm or the detection limit of the X-ray fluorescence analyzer.

[0055] <Characteristics of the resin composition> A resin composition satisfying a color development density of 0.55 or higher, a fading rate of 200 sec. or less, and a heat resistance (softening temperature) of 45°C or higher can be obtained by measuring using the method described in the examples below. For a better balance between photochromic properties and heat resistance, a color development density of 0.60 or higher, a fading rate of 95 sec. or less, and a heat resistance (softening temperature) of 50°C or higher can be achieved. Furthermore, a color development density of 0.75 or higher, a fading rate of 80 sec. or less, and a heat resistance (softening temperature) of 60°C or higher can also be achieved. In particular, a color development density of 0.85 or higher, a fading rate of 70 sec. or less, and a heat resistance (softening temperature) of 70°C or higher can also be achieved. While there are no particular upper or lower limits for these physical properties, the color development density is generally 1.10 or lower, the fading rate is 40 sec. or higher, and the heat resistance is 90°C or lower.

[0056] <Preferred method for producing resin compositions> As stated above, the method of producing the resin composition is not particularly limited, as long as the urethane resin contained in the resin composition satisfies the requirements. For example, by impregnating component (i) with component (ii) Moyo (i) and (ii) may be mixed. However, in order to efficiently disperse component (ii) in the resin composition, it is preferable to prepare a photochromic curable composition containing a polymerizable monomer that forms a urethane resin and component (ii). Among these, in terms of being able to easily manufacture the photochromic curable composition, (A) A polyiso(thio)cyanate component having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in its molecule, (B) Active hydrogen-containing component having an active hydrogen-containing group, (ii) Components and, It is preferable to prepare a photochromic curable composition containing [a specific ingredient]. Then, it is preferable to produce a resin composition by curing (polymerizing) this photochromic curable composition.

[0057] When preparing a photochromic curable composition, the blending ratio of monomers forming component (i) is not particularly limited, but in order to obtain a stable resin composition, the blending described below is preferable. Next, the photochromic curable composition will be described.

[0058] <Photochromic curable composition> As described above, the photochromic curable composition is (A) Polyiso(thio)cyanate components having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule. (B) Active hydrogen-containing component having an active hydrogen-containing group, (ii) Photochromic compounds, It is preferable that it includes. The following describes each component.

[0059] <(A) Component; a polyiso(thio)cyanate component having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in its molecule> (A) In a polyiso(thio)cyanate component (component (A)) having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule, the number of isocyanate groups is not particularly limited as long as there are two or more. Among these, 2 to 6 is preferred, 2 to 4 is more preferred, and 2 is even more preferred in terms of ease of polymerization control.

[0060] Note that "polyiso(thio)cyanate compound" refers to a group having two or more isocyanate groups and / or isothiocyanate groups.

[0061] The aforementioned component (A) includes aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing heterocyclic isocyanate compounds, sulfur-containing aliphatic isocyanate compounds, aliphatic sulfide isocyanate compounds, aromatic sulfide isocyanate compounds, aliphatic sulfone isocyanate compounds, aromatic sulfone isocyanate compounds, sulfonic acid ester isocyanate compounds, aromatic sulfonic acid amide isocyanate compounds, and the like.

[0062] Furthermore, blocked isocyanate compounds are also obtained in which the isocyanate group of the above-mentioned isocyanate compound is blocked with at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetate ester compounds.

[0063] (Component (A); preferred polyisocyanate compound) Among the polyisocyanate compounds mentioned above, compounds suitable for forming resin compositions with excellent transparency and mechanical strength, and in particular, compounds suitable for producing resin compositions containing photochromic compounds, are those represented by the following formulas (I) to (VIII).

[0064] (Component (A); Aliphatic isocyanate compound) Preferred aliphatic isocyanate compounds include those with the following formula:

[0065] [ka]

[0066] (In the formula, R 100 (This refers to an alkylene group having 1 to 10 carbon atoms, and may be a group in which some of the methylene groups in the alkylene chain are substituted with sulfur atoms.) It is preferable to use the compound shown in [the formula].

[0067] The aforementioned R 100 The alkylene group has 1 to 10 carbon atoms and may be linear or branched. Among these, linear groups such as pentamethylene, hexamethylene, heptamethylene, or octamethylene, or branched groups in which some of the hydrogen atoms of the pentamethylene, hexamethylene, heptamethylene, or octamethylene are substituted with methyl groups are preferred. Furthermore, among alkylene groups in which some of the methylene group is substituted with sulfur atoms, the -CH2CH2SCH2CH2SCH2CH2- group is preferred.

[0068] Specific examples of compounds represented by formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, and 1,2-bis(2-isocyanatoethylthio)ethane. These compounds can be used individually or in combination of two or more compounds.

[0069] (Alicyclic isocyanate compounds, aromatic isocyanate compounds) Preferred aromatic isocyanate compounds and alicyclic isocyanate compounds include those of the following formulas (II) and (III):

[0070] [ka]

[0071] [ka]

[0072] (In the formula, R 101 These are each an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and may be the same group or different groups. R 102 This is an alkyl group having 1 to 4 carbon atoms, and if multiple groups are present, they may be the same group or different groups. a100 is an integer, either 2 or 3, and b 100 c is an integer between 0 and 4, and 100 It is preferable to use the compound represented by formula (II) (where (II) is an integer from 0 to 4). The difference between the compound represented by formula (II) and the compound represented by formula (III) is that the compound has a phenyl group (the compound represented by formula (II)) and the compound has a cyclohexane group (the compound represented by formula (III)).

[0073] The aforementioned R 101 In this, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R 101 It is particularly preferable that R is a hydrogen atom, a methyl group, or an ethyl group. 102 In this, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R 102 It is particularly preferable that the group be a methyl group or an ethyl group.

[0074] Specific examples of compounds represented by formula (II) or formula (III) include isophorone diisocyanate, xylene diisocyanate (o-,m-,p-), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane. These compounds can be used individually or in combination of two or more compounds.

[0075] In addition, preferred aromatic isocyanate compounds and alicyclic isocyanate compounds are those of the following formulas (IV) and (V):

[0076] [ka]

[0077] [ka]

[0078] (In the formula, R 103 Each of these is an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and may be the same group or different groups. 100 It is preferable to use a compound represented by formula (IV) (where is an integer from 0 to 4). The difference between the compound represented by formula (IV) and the compound represented by formula (V) is that the compound has two phenyl groups (the compound represented by formula (IV)) and the compound has two cyclohexane groups (the compound represented by formula (V)).

[0079] The aforementioned R 103 In this, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R 103 It is particularly preferable that the group is a hydrogen atom, a methyl group, or an ethyl group.

[0080] Specific examples of compounds represented by formula (IV) or formula (V) include 4,4'-diphenylmethane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate. These compounds can be used individually or in combination of two or more compounds.

[0081] Furthermore, a preferred alicyclic isocyanate compound is the following:

[0082] [ka]

[0083] (In the formula, R 104 Each of these is an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and may be the same group or different groups, e 100 It is preferable to use the compound represented by ) (where is an integer between 0 and 4).

[0084] The aforementioned R 104 In this, the alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Among them, R104 It is particularly preferable that the group is a hydrogen atom, a methyl group, or an ethyl group.

[0085] Specific examples of compounds represented by formula (VI) include norbornane diisocyanate, 2,5-bis(isocyanate methyl)-bicyclo[2,2,1]-heptane, and 2,6-bis(isocyanate methyl)-bicyclo[2,2,1]-heptane. These compounds can be used individually or in combination of two or more compounds.

[0086] (Component (A): Alicyclic sulfur-containing heterocyclic isocyanate compound) Preferred sulfur-containing heterocyclic isocyanate compounds include those of the following formulas (VII) and (VIII):

[0087] [ka]

[0088] [ka]

[0089] (In the formula, R 105 These are each an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, and may be the same group or different groups. R 106 is a methylene group or a sulfur atom, and R 107 is an alkylene group having 1 to 6 carbon atoms, or a group in which a portion of the methylene group in the chain of the alkylene group having 1 to 6 carbon atoms is replaced by a sulfur atom, f 100 It is preferable to use the compound represented by ) (where is an integer between 0 and 2).

[0090] Specific examples of compounds represented by formula (VII) or formula (VIII) include 2,5-bis(isocyanatomethyl)thiophene, 2,5-bis(isocyanatomethyl)-1,4-dithiane, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, and 4,5-bis(isocyanatomethyl)-1,3-dithiolane. These compounds can be used individually or in combination of two or more compounds.

[0091] Furthermore, halogen-substituted, alkyl-substituted, alkoxy-substituted, and nitro-substituted polyisocyanates, as well as prepolymer-type modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, biuret-modified products, and dimerization or trimmerization reaction products can also be used.

[0092] (Preferred component (A): Polyisothiocyanate compound) Examples of the (A) alicyclic polyisothiocyanate compounds include those in which the isocyanate group is replaced by an isothiocyanate group in the polyisocyanate compounds represented by formulas (I) to (VIII). More specifically, examples include aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, and the like.

[0093] Specific examples of suitable compounds include aliphatic isothiocyanate compounds such as hexamethylene diisothiocyanate, 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, 2,4,4-trimethylhexanemethylene diisothiocyanate, thiobis(3-isothiocyanate propane), thiobis(2-isothiocyanate ethane), and dithiobis(2-isothiocyanate ethane).

[0094] Examples of alicyclic isothiocyanate compounds and aromatic isothiocyanate compounds include p-phenylenediisopropylidene diisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4-diisothiocyanate toluene, isophorone diisothiocyanate, xylene diisothiocyanate (o-,m-,p-), 2,4-toylene diisothiocyanate, 2,6-toylene diisothiocyanate, and cyclohexane diisothiocyanate. Other examples include 1,1'-methylenebis(4-isothiocyanate benzene), 1,1'-methylenebis(4-isothiocyanate 2-methylbenzene), and 1,1'-methylenebis(4-isothiocyanate 3-methylbenzene).

[0095] Furthermore, preferred alicyclic isothiocyanate compounds include 2,4-bis(isothiocyanatomethyl)norbornane, 2,5-bis(isothiocyanatomethyl)norbornane, 2,6-bis(isothiocyanatomethyl)norbornane, 3,5-bis(isothiocyanatomethyl)norbornane, and norbornane diisothiocyanate.

[0096] Preferred sulfur-containing heterocyclic isocyanate compounds include thiophene-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, 2,5-bis(isothiocyanatomethyl)-1,4-dithiane, and 4,5-bis(isothiocyanatomethyl)-1,3-dithiolane.

[0097] (Component (A); a compound having an isocyanate group and an isothiocyanate group) (A) Examples of compounds having both an isocyanate group and an isothiocyanate group as component (A) include the following compounds: For example, compounds in which at least one isocyanate group is an isothiocyanate group in the polyisocyanate compounds specifically exemplified above. Also, compounds in which at least one isothiocyanate group is an isocyanate group in the polyisothiocyanate compounds specifically exemplified above.

[0098] (Component (A); a compound having an isocyanate group blocked with a blocking agent) Compounds having an isocyanate group blocked with a blocking agent (hereinafter also referred to as blocked isocyanate compounds) can be obtained by reacting the isocyanate group of the aforementioned polyiso(thio)cyanate compound with at least one blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds, and acetoacetate ester compounds. The conditions for reacting the isocyanate group with the blocking agent vary depending on the type of blocking agent, and should be determined appropriately according to the selected blocking agent. The protection of the isocyanate group by the blocking agent can be confirmed by Fourier transform infrared spectroscopy (FT-IR).

[0099] By using blocked iso(thio)cyanate compounds, the pot life of photochromic compositions can be further extended.

[0100] (Preferred example of component (A)) Preferred examples of component (A) above include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, norbornane diisocyanate, 2,5-bis(isocyanate methyl)-bicyclo[2,2,1]-heptane, 2,6-bis(isocyanate methyl)-bicyclo[2,2,1]-heptane, 1,2-bis(2-isocyanate-ethylthio)ethane, xylene diisocyanate (o-,m-,p-), 2,4-toylene diisocyanate, 2,6-toylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, which may be used individually or as mixtures thereof.

[0101] <(B) Component; Active hydrogen-containing component having an active hydrogen-containing group> In the above-mentioned (B) active hydrogen-containing component (component (B)), the active hydrogen-containing group is a group that contains active hydrogen. In other words, component (B) is an active hydrogen compound having a group that contains active hydrogen. The above-mentioned active hydrogen-containing group refers to a group that can react with an isocyanate group, and examples include a hydroxyl group, an amino group, a carboxyl group and / or a thiol group.

[0102] Furthermore, component (B) preferably has a polyoxypropylene chain. Moreover, in addition to the polyoxypropylene chain, component (B) preferably has an alkyl group having 5 to 20 carbon atoms and / or a polyoxyethylene chain. By having these chains and groups in component (B), the strength ratio (PMI) is increased. pst / PMI cp A resin composition with a coefficient of 8.0 to 40.0 can be easily manufactured.

[0103] Then, let nB be the total number of moles of active hydrogen-containing groups in component (B). When the total number of moles of iso(thio)cyanate groups in the (A) polyiso(thio)cyanate compound is nA, the ratio (nA / nB) is preferably 1.00 or more and 1.50 or less, more preferably 1.00 or more and 1.20 or less. A nA / nB ratio of 1.00 or more and 1.50 or less results in a high intensity ratio (PMI). pst / PMI cp A resin composition with a coefficient of 8.0 to 40.0 can be easily manufactured. In addition, a resin composition with excellent photochromic properties and heat resistance can be obtained.

[0104] If the nA / nB ratio is less than 1.00 or greater than 1.50, the degree of polymerization will not increase, resulting in low heat resistance.

[0105] Furthermore, the mixing ratio of component (A) and component (B) is not particularly limited as long as the nA / nB ratio is within the range of 1.00 to 1.50. In particular, the intensity ratio (PMI) pst / PMI cp Considering the production of a resin composition that satisfies 8.0 to 40.0 and has excellent photochromic properties and heat resistance, when the total mass of component (A) and component (B) is 100 parts by mass, it is preferable that component (B) be 50 to 70 parts by mass, and more preferably that component (B) be 60 to 65 parts by mass.

[0106] Component (B) preferably comprises, considering the photochromic and mechanical properties of the resulting resin composition, a polyfunctional active hydrogen-containing component ((B1) component) having three or more active hydrogen-containing groups in one molecule, and a first active hydrogen-containing component ((B2) component) having one or two active hydrogen-containing groups in one molecule.

[0107] (Component (B1); a polyfunctional active hydrogen-containing component having three or more active hydrogen-containing groups in one molecule) The (B1) component used in the photochromic curable composition is not particularly limited as long as it is a compound having three or more active hydrogen-containing groups in its molecule. In particular, it is preferable that the compound has a total of three or more hydroxyl groups and thiol groups in its molecule. Specifically, it may be a compound having three or more hydroxyl groups in its molecule, a compound having three or more thiol groups in its molecule, or a compound having a total of three or more hydroxyl groups and thiol groups in its molecule. In addition, the number of hydroxyl groups and thiol groups in the (B1) component is not particularly limited as long as there are three or more.

[0108] Specific examples of (B1) components include aliphatic poly(thiol) compounds and aromatic poly(thiol) compounds. More specifically, the following compounds can be listed.

[0109] (Suitable poly(thiol) compounds) Among the (B1) poly(thiol) compounds mentioned above, the following compounds are suitable for forming resin compositions with excellent transparency and heat resistance, and in particular, for producing resin compositions containing photochromic compounds. Specifically, the compounds represented by the following formulas (IX) to (XVII) are examples.

[0110] (Aliphatic poly(thiol) compounds) Preferred aliphatic poly(thiol) compounds include those of the following formula (IX):

[0111] [ka]

[0112] {In the formula, R 108 is a hydrogen atom, or the following formula (X)

[0113] [ka]

[0114] (In the formula, R 111(This refers to an alkylene group with 1 to 6 carbon atoms.) It is a synonymous base, and may be the same or different. R 109 These are, respectively, a hydrogen atom, a methyl group, or an ethyl group, and may be the same or different. R 110 This is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and if there are multiple such atoms, they may be the same or different. o 100 The range is 0 to 2, and p 100 1 to 6, and q 100 r is between 0 and 10, 100 is 2-4, o 100 +r 100 It is 4. It is preferable to use the compound shown in [the formula].

[0115] The aforementioned R 111 R is an alkylene group having 1 to 6 carbon atoms, and may be a linear or branched group. 111 It is particularly preferable that the group is a methylene group, an ethylene group, a trimethylene group, or a propylene group.

[0116] Specific examples of compounds represented by formula (IX) include trimethylolpropane, pentaerythritol, trimethylolpropanetris(3-mercaptopropionate), and pentaerythritoltetrakis(3-mercaptopropionate).

[0117] Among preferred aliphatic poly(thiol) compounds, a polyfunctional poly(thiol) compound having an ether linkage is shown below (XI)

[0118] [ka]

[0119] {In the formula, F 100 Each of these is an alkyl group from 1 to 6, or the following formula (XII)

[0120] [ka]

[0121] (In the formula, R 112 is a hydrogen atom, or a group equivalent to the above formula (X), and may be the same group or a different group. R 113 These are, respectively, a hydrogen atom, a methyl group, or an ethyl group, and may be the same group or different groups. s 100 is 1-6, and t 100 It is between 0 and 10. It is preferable to use the compound shown in [the formula].

[0122] Said F 100 At least two of the groups are represented by formula (XII). Other groups include alkyl groups 1 to 6, which may be linear or branched. Among them, F 100 It is particularly preferable that the group is a methyl group, an ethyl group, a trimethyl group, or a propyl group. Also, F 100 The groups may be the same or different, as long as two or more of them are represented by formula (XII). Specific examples of compounds represented by formula (XI) include ditrimethylolpropane, dipentaerythritol, ditrimethylolpropanetetrakis (3-mercaptopropionate), and dipentaerythritol-lhexakis (3-mercaptopropionate).

[0123] Among preferred aliphatic poly(thiol) compounds, the following polyfunctional polythiol compound is given by formula (XIII):

[0124] [ka]

[0125] (In the formula, R 114R is a hydrogen atom, a C1-C6 alkyl group, or a group in which part of the methylene group of the C1-C6 alkyl group is substituted with a sulfur atom, 114 If multiple groups exist, they may be the same group or different groups. R 115 R is an alkylene group having 1 to 10 carbon atoms, wherein a portion of the methylene groups in the chain of the alkylene group having 1 to 10 carbon atoms is substituted with a sulfur atom, or a portion of the hydrogen atoms in the alkylene group having 1 to 10 carbon atoms is substituted with a thiol group, 115 If multiple groups exist, they may be the same group or different groups. u 100 is an integer between 2 and 4, and v 100 is an integer between 0 and 2, and u 100 +v 100 It is 4. It is preferable to use the compound shown in [the formula].

[0126] The aforementioned R 114 In this, the alkyl group having 1 to 6 carbon atoms may be a linear or branched group, and among them, R 114 The group is preferably a hydrogen atom, a methyl group, or an ethyl group. Specific examples of groups in which a portion of the methylene group in a chain of C1-C6 alkyl groups is substituted with sulfur atoms include -CH2SCH3.

[0127] R 115 In this, the alkylene group having 1 to 10 carbon atoms may be a linear or branched group. Among them, R 115 Methylene groups, ethylene groups, trimethylene groups, and propylene groups are particularly preferred. Specific examples of groups in which a portion of the methylene group in the chain of a C1-C10 alkylene group is substituted with a sulfur atom include -CH2S-, -CH2CH2S-, and -CH2CH2CH2S-. Furthermore, an example of a group in which a portion of the hydrogen atoms of the C1-C6 alkyl group is substituted with a thiol group is a group such as -CH2SCH(SCH2SH)-.

[0128] Specific examples of the compound represented by the formula (XIII) include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,7-bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the like.

[0129] Among the preferred aromatic poly(thio)ol compounds, as the phenyl group-containing polythiol compound, the following formula (XIV)

[0130] [Chemical formula]

[0131] (In the formula, R 116 is an alkylene group having 1 to 6 carbon atoms, or a group in which a part of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom, and w 100 is 3.) It is preferable to use the compound represented by .

[0132] In the above R 116 , the alkylene group having 1 to 6 carbon atoms may be a linear or branched chain group. Among them, R 116 is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. In addition, specific examples of the group in which a part of the methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms is substituted with a sulfur atom include -CH2CH2CH2SCH2-, -CH2CH2SCH2-, -CH2SCH2-, etc. Specific examples of the compound represented by the formula (XIV) include 1,3,5-tris(mercaptopropylthiomethyl)benzene.

[0133] Among the preferred poly(thio)ol compounds other than the above, as the poly(thio)ol compound having a triazine ring, the following formula (XV)

[0134]

Chemical formula

[0135] {In the formula, R 117 each represents an alkyl group having 1 to 6 carbon atoms or the following formula (XVI)

[0136]

Chemical formula

[0137] (In the formula, R 118 and R 119 are alkylene groups having 1 to 6 carbon atoms, R 120 is an oxygen atom or a sulfur atom). is a group represented by, provided that at least two of the said R 117 are groups represented by the said formula (XVI), and the said R 117 may be the same group or different groups.} It is preferable to use the compound represented by

[0138] In the said R 118 and R 119 , the alkylene group having 1 to 6 carbon atoms may be a linear or branched chain group. Among them, it is preferable that R 118 and R 119 are a methylene group, an ethylene group, a trimethylene group, or a propylene group. Specific examples of the compound represented by the said formula (XV) include 2-mercaptomethanol and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate.

[0139] Among the preferred poly(thiol) compounds other than those mentioned above, compounds having a silsesquioxane structure can be used. Compounds having a silsesquioxane structure can take on various molecular structures such as cage-like, ladder-like, and random, and are represented by the following formula (XVII).

[0140] [ka]

[0141] (In the formula, there are multiple R 500 These may be identical or different from each other, and are organic groups containing a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, and at least two or more hydroxyl groups and / or thiol groups in at least one molecule, n 100 (This is an integer between 3 and 100.)

[0142] (Preferred (B1) component) The above-mentioned (B1) component can be used without particular limitation, and multiple combinations can be used, taking into consideration the photochromic and mechanical properties of the resulting photochromic cured product. In particular, in order to produce a resin composition with excellent properties, and for the photochromic curable composition to have excellent moldability and good handling, it is preferable to use a (B1) component that has 3 to 6 active hydrogen-containing groups per molecule. Hereinafter, a polyfunctional active hydrogen-containing component that has 3 to 6 active hydrogen-containing groups per molecule in component (B1) may simply be referred to as component (B1a).

[0143] Among these (B1a) components, the aforementioned intensity ratio (PMI) pst / PMI cpConsidering the production of a resin composition that satisfies the requirement of 8.0 to 40.0 and has excellent photochromic properties and heat resistance, it is preferable that the active hydrogen-containing group is a component with 4 to 6 active hydrogen-containing groups per molecule, and most preferably a component with 6 active hydrogen-containing groups per molecule. Furthermore, considering the increase in viscosity when a photochromic curable composition is prepared, it is preferable that the active hydrogen-containing group is a thiol group.

[0144] The aforementioned component (B1) may consist solely of the aforementioned component (B1a), and may, if necessary, include components with more than six active hydrogen-containing groups per molecule. Hereinafter, this component will also be simply referred to as component (B1b). First, let's explain component (B1a).

[0145] <(B1a) component> Examples of preferred components of component (B1a) above include trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), dipentaerythritolhexakis(3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, and tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate. Among these, it is more preferable to use at least one of trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), and dipentaerythritolhexakis(3-mercaptopropionate).

[0146] Among these, dipentaerythritol hexakis(3-mercaptopropionate) is most preferred because it can improve the photochromic properties and mechanical properties of the resulting photochromic cured product (resin composition). From the viewpoint of photochromic properties, it is preferable to use dipentaerythritol hexakis(3-mercaptopropionate) alone as the (B1a) component. However, dipentaerythritol hexakis(3-mercaptopropionate) has a high viscosity, and when obtaining a photochromic cured product by cast polymerization, other (B1) components can also be mixed and used for viscosity adjustment.

[0147] Other (B1a) components include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), 1,6-hexanediol bis(3-mercaptopropionate), 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 2,2-bis(mercaptomethyl)-1,4-butanedithiol, 2,5-bis(mercaptomethyl)-1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis(mercaptomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, tris-{(3-mercaptopropionyloxy)-ethyl}-isocyanurate, and are preferably used. In particular, when combined with trimethylolpropane tris(3-mercaptopropionate), it is particularly preferred because the handling property can be improved while maintaining excellent photochromic properties.

[0148] (i) Strength ratio of the component (PMI pst / PMI cpIn order for the ratio to satisfy 8.0 to 40.0 and for the resin composition to exhibit particularly excellent effects, it is possible to include components other than the (B1a) component. More specifically, it is preferable to use a component that has a larger number of active hydrogen-containing groups in its molecule than component (B1a). Among these, it is particularly preferable to include a polyrotaxane component (hereinafter sometimes simply referred to as component (B1b)) that has a polyrotaxane structure and has 7 or more active hydrogen-containing groups in its molecule.

[0149] <(B1b) component; polyrotaxane component having more than 6 active hydrogen-containing groups in its molecule> In a photochromic curable composition, it is preferable to further include a polyrotaxane component ((B1b) component) having more than six active hydrogen-containing groups in the molecule. By using the (B1b) component, the photochromic properties of the resulting resin composition can be enhanced by the mobility of the polyrotaxane itself. In addition, by incorporating oxypropylene chains, etc., into the polyrotaxane component, the intensity ratio (PMI) of component (i) can be increased. pst / PMI cp ) can be easily adjusted from 8.0 to 40.0. In other words, because the polyrotaxane component has extremely high mobility, by incorporating an oxypropylene chain into this polyrotaxane component, the strength ratio (PMI) can be easily adjusted. pst / PMI cp This can be easily enhanced. As a result, the resulting resin composition exhibits excellent photochromic properties.

[0150] Component (B1b) is a known compound and has a complex molecular structure formed from a chain-like axial molecule and a cyclic molecule. Specifically, multiple cyclic molecules enclose the chain-like axial molecule, and the axial molecule penetrates the inside of the rings of the cyclic molecules. Therefore, the cyclic molecule can slide freely on the axial molecule, but bulky end groups are formed at both ends of the axial molecule to prevent the cyclic molecule from detaching from the axial molecule.

[0151] The polyrotaxane component (B1b), as shown in Figure 3, has a composite molecular structure formed from a chain-like axial molecule 20 and a cyclic molecule 30. More specifically, multiple cyclic molecules 30 enclose the chain-like axial molecule 20, and the axial molecule 20 penetrates the inside of the rings of the cyclic molecules 30. The cyclic molecules 30 can slide freely on the axial molecule 20, but bulky end groups 40 are formed at both ends of the axial molecule 20, preventing the cyclic molecules 30 from detaching from the axial molecule 20. Thus, because the cyclic molecules 30 of the polyrotaxane 10 can slide on the axial molecule 20, it is thought that the photochromic properties can be improved. In addition, by incorporating an oxypropylene chain into such a polyrotaxane, the strength ratio (PMI) in the resulting resin composition can be improved. pst / PMI cp The ) can be easily adjusted within the range of 8.0 to 40.0, which is thought to improve the photochromic properties. In addition, in the polyrotaxane 10 shown in Figure 3, the side chains 50 that are introduced as needed to the ring of the cyclic molecule 30 are also shown.

[0152] Furthermore, component (B1b) is a known compound and can be synthesized by the method described in International Publication No. 2015 / 068798, etc.

[0153] The axial molecule is not particularly limited as long as it can penetrate the ring of the cyclic molecule, and may be linear or branched. This axial molecule is generally formed from a polymer. Suitable polymers for forming the axial molecule include those exemplified in International Publication No. 2015 / 068798, but polyethylene glycol is particularly preferred. By using polyethylene glycol as the axial molecule, an oxyethylene chain is introduced into the resulting resin composition, resulting in a strength ratio (EI pst / EI cp ) can be easily adjusted within the range of 5.0 to 20.0.

[0154] Furthermore, the bulky terminal groups formed at both ends of the axial molecule are not particularly limited as long as they prevent the detachment of the cyclic molecule from the axial molecule. A preferred example is the adamantyl group.

[0155] The mass-average molecular weight (Mw) of the axial molecule is not particularly limited, but is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 80,000, and even more preferably in the range of 10,000 to 50,000. A mass-average molecular weight (Mw) of axial molecule of 1,000 or more tends to improve the mobility of the cyclic molecule. Furthermore, a mass-average molecular weight (Mw) of axial molecule of 100,000 or less tends to improve compatibility with other components. In addition, when polyethylene glycol is used for the axial molecule, the strength ratio (EI) of the resulting resin composition is... pst / EI cp The value can be easily adjusted between 5.0 and 20.0. As a result, the photochromic properties can be improved.

[0156] The cyclic molecule has a ring of a size that can enclose the axial molecule. Examples of such rings include cyclodextrin rings. Cyclodextrin rings include α-isomers (ring inner diameter: 0.45-0.6 nm), β-isomers (ring inner diameter: 0.6-0.8 nm), and γ-isomers (ring inner diameter: 0.8-0.95 nm), with α-cyclodextrin rings being preferred.

[0157] Furthermore, one or more cyclic molecules are enclosed within a single axial molecule. The number of cyclic molecules enclosed within a single axial molecule is generally in the range of 0.001 to 0.6, with a preferred range of 0.002 to 0.5, and a more preferred range of 0.003 to 0.4, when the maximum number of cyclic molecules that can be enclosed within a single axial molecule is set to 1.0.

[0158] The maximum number of cyclic molecules that can be inclusioned into a single axial molecule can be calculated from the length of the axial molecule and the thickness of the ring of the cyclic molecule. For example, if the chain portion of the axial molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α-cyclodextrin ring, the maximum number of inclusions can be calculated as follows: Two repeating units [-CH2-CH2O-] of polyethylene glycol approximate the thickness of one α-cyclodextrin ring. Therefore, the number of repeating units can be calculated from the molecular weight of polyethylene glycol, and half of this number of repeating units can be obtained as the maximum number of cyclic molecules that can be inclusioned. This maximum number of inclusions is set to 1.0, and the number of inclusions of cyclic molecules is adjusted to the range described above.

[0159] Side chains may be introduced into the cyclic molecule. When side chains are introduced in this way, a pseudo-crosslinked structure can be formed in the resulting resin composition (component (i)). This can improve the mechanical properties and photochromic properties of the resin composition.

[0160] The side chain is preferably formed by repeating units of organic groups having 3 to 20 carbon atoms. The mass-average molecular weight (Mw) of the side chain is not particularly limited, but is preferably in the range of 200 to 10000, more preferably in the range of 250 to 8000, even more preferably in the range of 300 to 5000, and particularly preferably in the range of 300 to 1500.

[0161] The aforementioned side chains can be introduced by utilizing the functional groups (e.g., hydroxyl groups) present on the ring of a cyclic molecule and modifying these functional groups. For example, an α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and side chains can be introduced via these hydroxyl groups. That is, up to 18 side chains can be introduced to a single α-cyclodextrin ring. In order to fully exhibit the function of the side chains described above, it is preferable that 6% or more, and especially 30% or more, of the total number of functional groups on the ring are modified by side chains. Note that if side chains are attached to 9 of the 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification is 50%.

[0162] The side chain may be linear or branched. The side chain can be introduced by reacting an appropriate compound with the ring of the cyclic molecule using methods such as ring-opening polymerization, radical polymerization, cationic polymerization, anionic polymerization, and living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, and NMP polymerization, thereby introducing a side chain of an appropriate size. As the cyclic compound, cyclic lactones and cyclic carbonates are preferred, and ε-caprolactone is more preferred.

[0163] Furthermore, when introducing side chains by ring-opening polymerization of cyclic compounds, the functional group attached to the ring (e.g., a hydroxyl group) is poorly reactive, and it may be difficult to directly react larger molecules due to steric hindrance, etc. In such cases, for example, a method can be adopted in which a low molecular weight compound such as propylene oxide is first reacted with the functional group to perform hydroxypropylation, introducing a highly reactive functional group (hydroxyl group), and then introducing the side chain by ring-opening polymerization using the aforementioned cyclic compound. This low molecular weight compound such as propylene oxide can also be considered a side chain. The propylene oxide incorporated into this side chain can be considered an oxypropylene chain. Therefore, especially when introducing a highly reactive hydroxyl group using propylene oxide, the intensity ratio (PMI) can be considered. pst / PMI cp This makes it easier to adjust the value between 8.0 and 40.0.

[0164] It is preferable that a polymerizable functional group selected from a hydroxyl group or a thiol group is introduced at the end of the side chain, and it is most preferable that a polymerizable functional group selected from a hydroxyl group is introduced. When an alkyl group is introduced at the end of the side chain, the strength ratio (AMI) is, of course, the same as that of oxypropylene chains and oxyethylene chains. pst / AMI cp This peak contains the alkyl group.

[0165] The most preferred component (B1b) satisfies the following requirements: Specifically, it has a polyethylene glycol axial molecule bonded to both ends with adamantyl groups, and an α-cyclodextrin ring. to ring The molecule is in a cyclic form, and a hydroxyl group activated by propylene oxide is introduced into the cyclic molecule, and a side chain with a hydroxyl group at its terminus is introduced into the cyclic molecule by the hydroxyl group and polycaprolactone.

[0166] The axial molecule is an oxyethylene chain, the molecular weight of the axial molecule is 8,000 to 30,000, the proportion of α-cyclodextrin rings introduced is in the range of 0.003 to 0.4, and the proportion of α-cyclodextrin ring modification (degree of modification; introduction rate of side chains) is preferably 30% to 70%. Furthermore, the base portion of the side chain is preferably an oxypropylene unit. Furthermore, it is preferable that the α-cyclodextrin ring is fitted with a side chain containing an oxypropylene unit, with an average molecular weight of 400 to 1,500. Furthermore, it is preferable to use a component (B1b) with a weight-average molecular weight of 100,000 to 200,000, and which contains 150 to 350 hydroxyl groups per molecule, although this is an average value.

[0167] <(B1) Preferred arrangement of active hydrogen-containing groups> Component (B1) preferably uses one of the exemplified polyfunctional active hydrogen-containing components. In particular, it is preferable to use a polyfunctional active hydrogen-containing component having the following structure. That is, component (B1) preferably contains a compound having a quaternary carbon atom in its molecule, and all groups bonded to the quaternary carbon atom are active hydrogen-containing groups. By using a compound in which all groups bonded to the quaternary carbon atom are active hydrogen-containing groups, it is believed that when polymerized, a free space in which the photochromic compound can undergo molecular motion can be efficiently formed in the resulting resin.

[0168] The reason for this is not clear, but it can be explained as follows. This will be explained using diagrams. Figure 4 illustrates a compound in which all groups bonded to a quaternary carbon atom are active hydrogen-containing groups (hereinafter sometimes simply referred to as a "total substitution compound"). Figure 4(A) is an example of a "total substitution compound" in which all four groups bonded to a quaternary carbon atom are active hydrogen-containing groups. Figure 5 also illustrates a compound in which some groups bonded to a quaternary carbon atom are active hydrogen-containing groups (hereinafter sometimes simply referred to as a "partial substitution compound"). Figure 5(B) is an example of a "partial substitution compound" in which three groups bonded to a quaternary carbon atom are active hydrogen-containing groups. In Figures 4 and 5, S is a simplified representation of an active hydrogen-containing group. The arrows indicate the direction in which the polymer grows.

[0169] As shown in Figure 4, when a totally substituted compound is used, the groups containing active hydrogen are arranged to form a tetrahedron around the quaternary carbon atom. Then, during polymerization, the polymer is thought to grow three-dimensionally. As a result, free space is effectively formed in the matrix made up of the three-dimensionally grown polymer, and it is thought that the photochromic compound becomes more responsive to molecular motion. Figure 4 shows an example where all the groups bonded to one quaternary carbon atom have active hydrogen-containing groups, but the same can be said for cases where there are four or more active hydrogen-containing groups. For example, dipentaerythritol hexakis (3-mercaptopropionate) is a compound with two quaternary carbon atoms. The groups bonded to these quaternary carbon atoms can be considered as three groups having one thiol group and one group having three thiol groups. Therefore, dipentaerythritol hexakis (3-mercaptopropionate) can be considered a totally substituted compound. In a totally substituted compound, it is sufficient to have at least one quaternary carbon atom in the molecule whose four bonded groups are all active hydrogen-containing groups. Furthermore, considering ease of handling and ease of manufacturing, it is preferable that the number of active hydrogen-containing groups in the totally substituted compound be 4 to 6.

[0170] On the other hand, as shown in Figure 5, when a partially substituted compound is used, the groups containing active hydrogen are not arranged to form a tetrahedron. Therefore, unlike when a fully substituted compound is used, it is presumed that the polymer does not grow three-dimensionally during polymerization, and the space in which the photochromic compound can move is reduced.

[0171] For the reasons stated above, it is preferable to use a component that corresponds to the total substitution compound among the components of (B1).

[0172] <(B2) component; a first active hydrogen-containing component having one or two active hydrogen-containing groups per molecule> In a photochromic curable composition, it is preferable to further include, as component (B2), a first active hydrogen-containing component having one or two active hydrogen-containing groups per molecule, in addition to component (B1). The first active hydrogen-containing component can be a single compound or multiple compounds.

[0173] Specific examples of component (B2) include monoalkyl ether compounds having an oxypropylene chain (primary active hydrogen-containing components having one active hydrogen-containing group per molecule) or glycol compounds having an oxypropylene chain (primary active hydrogen-containing components having two active hydrogen-containing groups per molecule). Among these, polyoxyethylene polyoxypropylene monoalkyl ether compounds or polyoxyethylene polyoxypropylene glycol compounds are particularly noteworthy.

[0174] The aforementioned (B2) component is not particularly limited, but it is important that its number-average molecular weight is 500 or more. pst / PMI cp AMI pst / AMI cp EI pst / EI cpIt is preferable to satisfy the range of ) and improve the photochromic properties of the resulting resin composition. To achieve both excellent photochromic and mechanical properties, the number average molecular weight of component (B2) is preferably 600 or more, and more preferably 700 or more. Also, the intensity ratio (PMI) pst / PMI cp In addition to satisfying the range of ), and considering the optical properties of the resulting resin composition (suppression of turbidity), the upper limit of the molecular weight is preferably 3000.

[0175] If component (B2) has an oxypropylene chain, it is preferable that the average value l of the repeating units of oxypropylene (-CH2CH(CH3)O-) is between 2 and 25. Furthermore, it is preferable that component (B2) contains an oxyethylene chain, and it is preferable that the average value m of the repeating units of oxyethylene (-CH2CH2O-) is between 5 and 25. Furthermore, component (B2) may contain an alkyl group, and it is preferable that the number of carbon atoms in the alkyl group is between 5 and 20.

[0176] By using a photochromic curable composition containing component (B2), the resulting photochromic cured product (resin composition) not only exhibits excellent photochromic properties but also exhibits the following characteristics. For example, when the photochromic curable composition containing component (B2) is cured in a mold made of inorganic glass, the resulting photochromic cured product exhibits improved release properties from the inorganic glass mold. This improved release property effect is particularly pronounced when a compound having one active hydrogen-containing group per molecule is used. Furthermore, when using a photochromic curable composition containing component (B2), the adhesion to other optical substrates can be improved by adjusting the blending ratio of component (A). Examples of other optical substrates include known plastic substrates and inorganic glass substrates. In particular, adhesion to inorganic glass substrates can be improved when the blending ratio of component (A) is relatively high.

[0177] The aforementioned (B2) component to A more detailed explanation will be provided regarding compounds having one active hydrogen-containing group per molecule (hereinafter also simply referred to as component (B21)) or compounds having two active hydrogen-containing groups per molecule (hereinafter also simply referred to as component (B22)).

[0178] <(B21) component> The component (B21) is not particularly limited, but it is preferable to use a compound represented by the following formula (XVIII).

[0179] [ka]

[0180] In the formula, l', m', and n' are integers between 1 and 30.

[0181] In the above formula (XVIII), l' refers to the repeating unit of oxypropylene. This l' is an average value and is an integer between 1 and 30. In particular, the intensity ratio (PMI) pst / PMI cp In order to easily produce a resin composition that satisfies 8.0 to 40.0, preferably in the range of 10.0 to 15, and to have excellent properties, l' is preferably 2 to 25, and more preferably 2 to 5.

[0182] In the above formula (XVIII), m' refers to the repeating unit of oxyethylene. This m' is an average value and is an integer between 1 and 30. In particular, the intensity ratio (EI pst / EI cp In order to easily produce a resin composition that satisfies 5.0 to 20.0 and has excellent properties, m' is preferably 5 to 25, and more preferably 7 to 12.

[0183] In the above formula (XVIII), n' refers to the number of carbon atoms in the alkyl group at the end. This n' is an integer from 1 to 30. In particular, the intensity ratio (AMI pst / AMIcp In order to easily produce a resin composition that satisfies 7.0 to 23.0 and has excellent properties, n' is preferably 5 to 20, and more preferably 10 to 18.

[0184] Suitable specific examples of component (B21) represented by formula (XVIII) include polyoxyethylene polyoxypropylene monolauryl ether (oxyethylene repeating unit m=10, oxypropylene repeating unit l=2, terminal alkyl group has 12 carbon atoms, number average molecular weight 750), polyoxyethylene polyoxypropylene monotridecyl ether (oxyethylene repeating unit m=11, oxypropylene repeating unit l=2, terminal alkyl group has 13 carbon atoms, number average molecular weight 800), and polyoxyethylene polyoxypropylene monostearyl ether (oxyethylene repeating unit m=9, oxypropylene repeating unit l=6, terminal alkyl group has 18 carbon atoms, number average molecular weight 1000).

[0185] In the above formula (XVIII), component (B21) is shown as a block copolymer in the chemical formula, but the polyoxyethylene polyoxypropylene moiety may be a random copolymer. Of course, the moiety may be a block copolymer, but the strength ratio (PMI) pst / PMI cp In order to easily produce a resin composition that satisfies the range of 8.0 to 40.0, preferably 10.0 to 15, and has excellent properties, it is preferable that the polyoxyethylene polyoxypropylene monauryl ether, polyoxyethylene polyoxypropylene monotridecyl ether, and polyoxyethylene polyoxypropylene monostearyl ether also preferably have a random copolymer structure.

[0186] By using component (B21), the polymerizability of the photochromic curable composition can be further improved. In other words, because component (B21) is monofunctional, it can suppress a rapid increase in the viscosity of the photochromic curable composition. Normally, the photochromic curable composition is stored with components (A) and (B) separately. When manufacturing the resin composition, components (A), (B), essential components, and optional components added as needed are mixed to first prepare the photochromic curable composition. If a rapid increase in viscosity occurs during this mixing, it may become difficult to obtain a uniform resin composition. Therefore, it is preferable that the viscosity of the photochromic curable composition does not change until the conditions for starting polymerization (e.g., temperature) are met. By using component (B21), this temperature increase can be suppressed. For the reasons above, although both components (B21) and (B22) can be used simultaneously as component (B2), it is preferable to use only component (B21).

[0187] <(B22) component> The component (B22) is not particularly limited, but it is preferable to use the compound represented by the following formula (XIX).

[0188] [ka]

[0189] In the formula, l'' and m'''+m'' are integers between 1 and 30.

[0190] In the above formula (XIX), l'' refers to the repeating unit of oxypropylene. This l'' is an average value and is an integer between 1 and 30. In particular, the intensity ratio (PMI) pst / PMI cp In order to easily produce a resin composition that satisfies 8.0 to 40.0, preferably in the range of 20.0 to 35.0, and that has excellent properties, l'' is preferably 2 to 25, and more preferably 12 to 20.

[0191] In the above formula (XIX), m'' and m''' refer to the repeating units of oxyethylene. These m'' and m''' are average values, and m'' + m''' is an integer between 1 and 30. In particular, the intensity ratio (EI pst / EI cp In order to easily produce a resin composition that satisfies 5.0 to 20.0 and has excellent properties, it is preferable that m'' + m''' be 5 to 25, and more preferably 10 to 20.

[0192] The aforementioned intensity ratio (PMI) pst / PMI cp EI pst / EI cp Satisfying the range of ), and further considering the photochromic properties of the resulting resin composition, the (B22) component represented by formula (XIX) is a block copolymer type polyoxyethylene polyoxypropylene glycol represented by formula (XIX).

[0193] Specifically, examples include polyoxyethylene polyoxypropylene glycol with a number average molecular weight of 1600 (l''=16, m''+m'''=14), polyoxyethylene polyoxypropylene glycol with a number average molecular weight of 1900 (l''=16, m''+m'''=22), and polyoxyethylene polyoxypropylene glycol with a number average molecular weight of 2000 (l''=21, m''+m'''=18).

[0194] (Photochromic curable composition; preferred blending ratio of component (A), component (B1), and component (B2)) The photochromic curable composition preferably has a blending ratio of component (A) and component B (component (B1) and component (B2)) within the following ranges. Specifically, when nA is the total number of moles of iso(thia)cyanate groups in component (A) and nB is the total number of moles of active hydrogen-containing groups in components (B1) and (B2), it is preferable that nA / nB = 1.00 or more and 1.50 or less, more preferably 1.00 or more and 1.20 or less, even more preferably 1.02 or more and 1.15 or less, and most preferably 1.04 or more and 1.10 or less. Satisfying the range of nA / nB = 1.00 or more and 1.50 or less allows the PMI to be achieved. pst / PMI cp AMI pst / AMI cp EI pst / EI cp A photochromic cured body can be obtained that satisfies the preferred range and possesses excellent photochromicity, durability, and heat resistance.

[0195] Within the above range, when curing a photochromic curable composition in an inorganic glass mold, it is particularly preferable that the nA / nB ratio be 1.00 or higher and 1.09 or lower in order to improve the release properties between the resulting photochromic cured product and the mold. However, even if the nA / nB ratio exceeds 1.09, the release properties can be improved by incorporating the release agent described in detail below into the photochromic curable composition.

[0196] Furthermore, within the above range, when improving adhesion to an optical substrate made of inorganic glass, the nA / nB ratio is preferably 1.10 or more and 1.50 or less, and preferably 1.10 or more and 1.40 or less.

[0197] Furthermore, when manufacturing a laminate using a photochromic curable composition, if the optical substrate to be laminated is plastic, sufficient adhesion to the optical substrate is possible if the nA / nB ratio is 1.00 or more and 1.50 or less. In particular, to obtain a laminate with excellent adhesion, photochromic properties, and mechanical properties, it is preferable that the nA / nB ratio be 1.05 or more and 1.20 or less.

[0198] However, when using the photochromic curable composition to bond a polarizing film based on polyvinyl alcohol to another substrate (for example, an optical substrate made of a plastic other than polyvinyl alcohol or inorganic glass), it is preferable that the nA / nB be within the following range. Specifically, when a polyvinyl alcohol-based polarizing film is present in the object to be laminated, it is preferable that the nA / nB be 1.10 or more and 1.50 or less, and more preferably 1.20 or more and 1.40 or less.

[0199] Furthermore, in order to create a photochromic cured material that possesses excellent photochromicity, durability, and heat resistance, When the total number of moles of active hydrogen-containing groups in component (B1) and component (B2) are nB1 and nB2, respectively, it is preferable that nB1 / nB2 = 10.0 to 30.0, more preferably 12.0 to 25.0, and most preferably 12.0 to 22.0. If component (B1) contains component (B1b), the number of moles of active hydrogen-containing groups in component (B1b) is calculated, for example, from the hydroxyl value.

[0200] The photochromic curable composition preferably satisfies the above range in terms of the number of moles of each component, but it is preferable that it satisfies the following range when expressed as a mass ratio.

[0201] The mixing ratio of components (A), (B1), and (B2) by mass is not particularly limited, but in order to obtain excellent photochromic properties, durability, and heat resistance of the photochromic cured product, it is preferable to satisfy the following ranges. For a total of 100 parts by mass of components (A), (B1), and (B2), it is preferable that component (A) is in the range of 20 to 74 parts by mass, component (B1) is in the range of 20 to 75 parts by mass, and component (B2) is in the range of 5 to 40 parts by mass. Furthermore, it is preferable that the following mixing amounts are satisfied. It is preferable that, with respect to 100 parts by mass of the total of components (A), (B1), and (B2), the amounts of component (A) be in the range of 25 to 71 parts by mass, component (B1) be in the range of 23 to 67 parts by mass, and component (B2) be in the range of 6 to 30 parts by mass; more preferably, the amounts of component (A) be in the range of 25 to 69 parts by mass, component (B1) be in the range of 23 to 67 parts by mass, and component (B2) be in the range of 6 to 30 parts by mass; even more preferably, the amounts of component (A) be in the range of 30 to 63 parts by mass, component (B1) be in the range of 30 to 60 parts by mass, and component (B2) be in the range of 7 to 20 parts by mass; and most preferably, the amounts of component (A) be in the range of 30 to 57 parts by mass, component (B1) be in the range of 35 to 60 parts by mass, and component (B2) be in the range of 8 to 20 parts by mass.

[0202] Among these, in order to exhibit particularly excellent effects, it is more preferable to use component (B21) as component (B2), and the mass ratio of the mass of component (B21) to the mass of component (B1) ((B21) / (B1)) is 0.35 or more and 0.65 or less, and even more preferable to be 0.40 or more and 0.55 or less.

[0203] <Other additives; (C) Polymerization and curing accelerators> Depending on the type of component described above, the photochromic curable composition may further contain various (C) polymerization curing accelerators (hereinafter also referred to as (C) component) to rapidly promote its polymerization curing.

[0204] Reaction catalysts and condensing agents for urethanes or ureas used in the reaction between hydroxyl groups and thiol groups and isocyanate groups and isothiocyanate groups are used as polymerization curing accelerators.

[0205] These urethane or urea reaction catalysts are used in the formation of poly(thio)urethane bonds through the reaction of polyiso(thio)cyanates with polyols or polythiols. Examples of these urethane or urea reaction catalysts include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. Specific examples are listed below. Furthermore, if the catalytic activity is too high depending on the type of compound selected, it is possible to suppress the catalytic activity by using a mixture of tertiary amines and Lewis acids. Tertiary amines; triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N,N-dimethyloctylamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, 4,4'-trimethylenebis(1-methylpiperidine), 1,8-diazabicyclo-(5,4,0)-7-undecene. Phosphines; trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, trimenzylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(dimethylphosphino)ethane. Quaternary ammonium salts; tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide. Quaternary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide. Lewis acids; triphenylaluminum, dimethyltin dichloride, dimethyltinbis(isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltin maleate polymer, dibutyltin diricinoleate, dibutyltinbis(dodecyl mercaptide), dibutyltinbis(isooctylthioglycolate), dioctyltin dichloride, dioctyltin maleate, dioctyltin maleate polymer, dioctyltinbis(butyl maleate), dioctyltin dilaurate, dioctyltin diricinoleate, dioctyltin dioleate, dioctyltin di(6-hydroxy)caproate, dioctyltinbis(isooctylthioglycolate), didodecyltin diricinoleate. Organic sulfonic acids; methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

[0206] (A polymerization initiator, which is a condensing agent) Specific examples of the aforementioned condensing agent include the following: Inorganic acids; such as hydrogen chloride, hydrogen bromide, sulfuric acid, and phosphoric acid. Organic acids; such as p-toluenesulfonic acid and camphor-sulfonic acid. Acid ion exchange resins; Amberite, Amberist, etc. Carbodiimide; dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopyrrolyl)-carbodiimide.

[0207] Each of the above-mentioned (C) components can be used individually or in combination of two or more, but the amount used should be a so-called catalytic amount. For example, a small amount of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, is sufficient for 100 parts by mass of the total of components (A) and (B).

[0208] <Other additives> The photochromic curable composition may, as needed, contain various additives known on their own, such as ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, color inhibitors, fluorescent dyes, dyes, pigments, fragrances, solvents, leveling agents, internal release agents, and polymerization regulators such as thiols including t-dodecyl mercaptan, provided that these additives do not impair the effects.

[0209] In particular, considering the need to improve the durability of photochromic compounds, the use of UV stabilizers is preferable. Known UV stabilizers include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants. Particularly suitable UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 2,6-di-t-butyl-4-methylphenol, and ethylenebis(oxyethylene)bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate]. Commercially available examples include Adekastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 from Asahi Denka Kogyo Co., Ltd., and IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, and 565 from Ciba Specialty Chemicals.

[0210] Furthermore, considering the improvement of the durability and photochromicity of photochromic compounds, it is preferable to use ultraviolet absorbers. Examples of such ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, and malonic acid ester-based ultraviolet absorbers and cinnamic acid ester-based ultraviolet absorbers.

[0211] Among these, cyanoacrylate-based UV absorbers, diphenyl acrylate-based UV absorbers, phenol-based UV absorbers, oxanilide-based UV absorbers, malonic acid ester-based UV absorbers, and cinnamic acid ester-based UV absorbers are preferred. In particular, cinnamic acid ester-based UV absorbers are preferred because they improve durability without impairing photochromicity (especially color intensity) compared to when no UV absorber is used.

[0212] Furthermore, if the mold release properties of the resin composition are poor, an internal mold release agent can be used. Any internal mold release agent that has a mold release effect and does not impair the physical properties of the resin, such as transparency, can be used, but surfactants are preferably used. Among these, phosphate ester surfactants are preferred. The internal mold release agents referred to here include those catalysts that exhibit a mold release effect, as mentioned above, and may also include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal mold release agents are appropriately selected based on their combination with monomers, polymerization conditions, economy, and ease of handling. Specific examples of phosphate ester internal mold release agents are as follows.

[0213] Alkyl acid phosphates; mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, mono-n-octyl phosphate, mono-n-butyl phosphate, bis(2-ethylhexyl) phosphate, di(2-ethylhexyl) phosphate, di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate (mono-, di-mixture), ethyl acid phosphate (mono-, di-mixture), butoxyethyl acid phosphate (mono-, di-mixture), 2-ethylhexyl acid phosphate (mono-, di-mixture), isotrid Sil Acid phosphates (mono- and di-mixtures), tetracosyl acid phosphates (mono- and di-mixtures), stearyl acid phosphates (mono- and di-mixtures) Other phosphate esters include oleyl acid phosphate (mono- and di-mixtures), dibutyl pyrophosphate, ethylene glycol acid phosphate (mono- and di-mixtures), and butoxyethyl acid phosphate (mono- and di-mixtures), among others.

[0214] Each of the above-mentioned other compounding agents can be used individually or in combination of two or more, but only in small amounts. For example, it can be used in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the total of components (A) and (B).

[0215] <Alkali metal ions, alkaline earth metal ions> In a photochromic curable composition, the total amount of alkali metal ions and alkaline earth metal ions is preferably 500 ppm or less. When the amount of alkali metal ions and alkaline earth metal ions in the photochromic curable composition is 500 ppm or less, a cured product with excellent color development durability of the photochromic compound can be achieved, that is, a cured product in which the photochromic compound can maintain its color over a long period of time can be realized. The reason for this is thought to be as follows.

[0216] First, the components of photochromic curable compositions, such as active hydrogen compounds, may use alkali metal salts or alkaline earth metal salts during their synthesis, or these metal salts may be generated. These metal salts may remain as trace impurities in the synthesized active hydrogen compounds. Counteranions contained in alkali metal salts, particularly carboxylate ions, can react with the isocyanate groups of polyiso(thio)cyanate compounds to produce cyclic polyiso(thio)cyanurate compounds with bonded isocyanate groups. In other words, when alkali metal salts are included in a photochromic curable composition, the isocyanate component is excessively consumed, and polyiso(thio)cyanurate compounds may be produced as by-products. This excessive consumption of the isocyanate component results in a surplus of active hydrogen compounds in the photochromic curable composition. In the cured product of a photochromic composition with a surplus of active hydrogen compounds, for example, active hydrogen groups such as thiol groups become surplus. These excess active hydrogen groups can generate radicals when exposed to ultraviolet light, which can cause the cured material to deteriorate. From the above, it can be concluded that the deterioration of the cured product can be suppressed by reducing the amount of alkali metal salts and alkaline earth metal salts in the photochromic curable composition. The amount of alkali metal salts and alkaline earth metal salts in the photochromic curable composition can be estimated from the amount of alkali metal ions and alkaline earth metal ions in the photochromic composition.

[0217] The total amount of alkali metal ions and alkaline earth metal ions in a photochromic curable composition can be measured by inductively coupled plasma (ICP) emission spectrometry. For example, 10 g of the photochromic curable composition is first dissolved in 20 g of chloroform to obtain 30 g of solution. 20 g of 1% HNO3-containing ultrapure water is added to this solution, and the supernatant is extracted. The extracted supernatant is used as the sample. For example, an ICP emission spectrometer (iCAP6500DUO) manufactured by Thermo Fisher Scientific is used as the measuring instrument. The detection limit for ICP emission spectrometry is, for example, 1 ppb. A calibration curve method is used to calculate the concentrations of alkali metal ions, etc. The total content of alkali metal ions and alkaline earth metal ions in the photochromic curable composition is preferably 200 ppm or less, and more preferably 100 ppm or less. The lower limit of alkali metal ions and alkaline earth metal ions in the photochromic composition is 0 ppm or the detection limit of the ICP emission spectrometer.

[0218] The content of alkali metal salts, alkaline earth metal salts, alkali metal ions, alkaline earth metal ions, and their counter anions in a photochromic curable composition can be reduced, for example, by water washing, contact with various adsorbents and ion exchange resins, etc. The amount of alkali metal salts, etc. can be further reduced by increasing the water washing time of the photochromic curable composition, increasing the amount of adsorbents and ion exchange resins, or increasing the contact time with these. Alternatively, instead of reducing alkali metal ions in the photochromic curable composition, the photochromic curable composition may be prepared using components such as active hydrogen compounds that have undergone the above reduction treatment as raw materials.

[0219] <Method for producing a photochromic curable composition> The photochromic curable composition can be prepared by mixing the aforementioned (ii) photochromic compound, component (A), component (B), and other components in a known and not particularly limited manner. For example, a photochromic curable composition can be obtained by dissolving component (ii) in component (A), and then adding component (B) and stirring. The stirring temperature can be adjusted as appropriate within the range of 0 to 100°C, and the stirring time within the range of 0.1 to 48 hours. By using component (B21), the viscosity increase during the manufacturing of this photochromic curable composition can also be suppressed.

[0220] Furthermore, since component (A) contains an iso(thio)cyanate group in its molecule, it is preferable to manufacture it under an inert gas atmosphere such as argon or nitrogen in order to suppress the inclusion of moisture.

[0221] <Photochromic optical articles> Photochromic optical articles can be obtained by polymerizing a photochromic curable composition to form a photochromic cured body. Polymerization is usually carried out by thermal polymerization. This cured body is a resin composition, and a photochromic optical article can be made from this resin composition.

[0222] When thermally polymerizing the aforementioned photochromic curable composition, the temperature, in particular, affects the properties of the resulting photochromic cured product. While this temperature condition cannot be generalized as it is influenced by the type and amount of the thermal polymerization initiator and the type of compound, it is generally preferable to start polymerization at a relatively low temperature and slowly increase the temperature. Polymerization time also varies depending on various factors, similar to temperature, so it is preferable to determine the optimal time in advance according to these conditions. Generally, it is preferable to select conditions such that polymerization is completed in 2 to 48 hours. When obtaining a photochromic laminated sheet, it is preferable to polymerize at a temperature at which the reaction between polymerizable functional groups proceeds, and to determine the optimal temperature and time to achieve the desired molecular weight.

[0223] Furthermore, there are no particular limitations on the form in which a photochromic curable composition is polymerized to obtain a photochromic optical article. For example, when obtaining a photochromic lens, which is a type of optical article, the known methods described below can be employed.

[0224] When manufacturing the photochromic lens by the compounding method, Lastma - By injecting the above-mentioned photochromic composition between inorganic glass molds held together by gaskets or spacers, and after thorough degassing, a photochromic cured body (photochromic optical article) molded into the form of an optical material such as a lens can be obtained by casting polymerization in an air furnace or by heating in water.

[0225] Furthermore, a photochromic lens (a laminate of photochromic optical articles) can also be obtained by casting polymerization using an inner mold, in which an optical substrate such as a lens substrate is arranged so as to form predetermined voids, a photochromic curable composition is injected into these voids, and polymerization is carried out by heating in this state (manufacturing of a laminate by casting polymerization). The optical substrate is not particularly limited, and optical substrates made of known plastics can be used. Specifically, examples include plastic materials such as (meth)acrylic resin, polycarbonate resin, allyl resin, thiourethane resin, urethane resin, and thioepoxy resin.

[0226] When forming a photochromic layer on the surface of an optical substrate using the casting polymerization method described above, the adhesion between the photochromic layer and the optical substrate can be improved by pre-treating the surface of the optical substrate with chemical treatments such as alkaline solutions or acid solutions, or with physical treatments such as corona discharge, plasma discharge, or polishing. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical substrate.

[0227] Alternatively, a required amount of photochromic curable composition can be applied to one optical substrate, such as inorganic glass, on which a spacer is placed. Then, the other optical substrate, such as glass, is placed on top of it, and the applied photochromic curable composition is cured to bond the pair of optical substrates, such as inorganic glass optical materials. A photochromic lens (a laminate of laminated photochromic optical materials) can be obtained by bonding a pair of optical substrates, such as glass optical articles (glass bonding method).

[0228] Furthermore, when manufacturing photochromic lenses using the binder method, a photochromic sheet made of a photochromic curable composition is first prepared. The obtained photochromic sheet is sandwiched between two transparent sheets (optical sheets), and the polymerization described above is carried out to obtain a photochromic laminate with the photochromic layer as the adhesive layer.

[0229] In this case, the photochromic sheet can also be prepared by coating it using a coating solution in which a photochromic curable composition is dissolved in an organic solvent.

[0230] The photochromic laminate thus fabricated can be, for example, placed in a mold, and then a thermoplastic resin (such as polycarbonate) for optical substrates such as lenses can be injection molded to obtain a photochromic lens of a predetermined shape in which the photochromic laminates are stacked. Alternatively, this photochromic laminate can be bonded to the surface of an optical substrate using an adhesive, thereby also obtaining a photochromic lens.

[0231] Furthermore, when producing a photochromic laminate as described above, it is preferable to use a urethane or urea-based polymerizable compound, particularly a urethane-based polymerizable compound, as the polymerizable compound, in order to ensure high adhesion to the optical substrate, and to prepare the laminate so that polyurethane is formed.

[0232] The resulting photochromic cured / laminated material exhibits excellent photochromic properties in terms of color intensity and fading rate, and can be effectively used in the production of photochromic optical substrates, such as photochromic lenses (photochromic optical articles).

[0233] Furthermore, the photochromic cured body can be laminated with other functional layers or dyed using disperse dyes, etc., depending on its application, as long as the effect is not impaired. A hard coat film can also be fabricated on it using a silane coupling agent or a hard coat agent mainly composed of silicon, zirconium, antimony, aluminum, tin, tungsten, etc. In addition, thin films can be fabricated by depositing metal oxides such as SiO2, TiO2, and ZrO2. Anti-reflective treatment can be applied as a thin film by coating with an organic polymer. Antistatic treatment can also be applied.

[0234] Furthermore, as a lamination with the other functional layers mentioned above, a polarizing film may be laminated to the resulting photochromic cured body in order to impart polarizing properties. The position of the polarizing film is not particularly limited and may be laminated on the outside of the photochromic cured body, between the photochromic cured body and other layers, or within the adhesive layer if an adhesive layer is used. However, from the viewpoint of adhesion, it is preferable to embed it within the adhesive layer when an adhesive layer is used.

[0235] The method for laminating the polarizing film is not particularly limited, and any known method may be used. For example, in the case of the casting polymerization method described above, when injecting the photochromic curable composition into a glass mold, a polarizing film is placed between the front or rear mold and the photochromic curable composition, or within the photochromic composition, and then the photochromic curable composition is polymerized to laminate the films.

[0236] Furthermore, in the case of the glass bonding method described above, it is preferable to pre-laminate a polarizing film on one side of the optical substrate made of inorganic glass. When using the laminated product, a known thermosetting adhesive or ultraviolet (UV) curing adhesive can be used to bond the optical substrate made of inorganic glass and the polarizing film.

[0237] The polarizing film is not particularly limited, and commercially available polarizing films can be used.

[0238] The polarizing film can preferably have a thickness of 20 to 100 μm. The polarizing film is made by stretching polyvinyl alcohol that has been dyed with a dichroic substance such as iodine or a dichroic dye.

[0239] Any commercially available dichroic dye can be used without restriction as the dichroic dye contained in the polarizing film. Examples include azo dyes and anthraquinone dyes. Specifically, examples include Chloranthine Fast Red (CI28160), Congo Red (CI22120), Brilliant Blue B (CI24410), Benzopurprine (CI23500), Chlorazole Black BH (CI22590), Direct Blue 2B (CI22610), Diamine Green (CI30295), Chrysophenine (CI24895), Sirius Yellow (CI29000), Direct Fast Red (CI23630), Acid Black (CI20470), Direct Sky Blue (CI24400), Sorophenyl Blue 4GL (CI34200), Direct Copper Blue 2B (CI24185), Nippon Brilliant Violet BKconc (CI27885), and others. Two or more pigments can be selected from these dichroic dyes depending on the purpose. The Colour Index No. shown in parentheses is from "New Edition Dye Handbook" compiled by the Society of Organic Synthesis (Maruzen Co., Ltd., 1970).

[0240] By using the photochromic curable composition described above, even polarizing films with a luminous transmittance of 10-60% and a polarization degree of 70.0-99.9, which are normally difficult to bond, can be firmly bonded.

[0241] The polarizing film may have cellulose triacetate films laminated on both sides to enhance its functionality and adhesion. The thickness of the cellulose triacetate film is preferably 20 to 200 μm, and more preferably 20 to 100 μm.

[0242] Furthermore, to adjust the moisture content of the polarizing film and ensure its dimensional stability, the polarizing film may be subjected to a heat treatment at 40-100°C for 5 seconds to 30 minutes before manufacturing the photochromic cured product. The optical laminate according to the embodiment includes an optical substrate and a resin composition according to the embodiment laminated on at least one main surface of the optical substrate. Figure 6 is a schematic cross-sectional view showing an example of an optical laminate according to an embodiment. The optical laminate 1 shown in Figure 6 comprises an optical substrate 2, a primer layer 3 provided on one main surface of the optical substrate 2, and a resin composition 4 provided on the primer layer 3. The optical substrate 2 has an uneven surface. The primer layer 3 and the resin composition 4 cover the convex side of the optical substrate 2. The primer layer 3 includes an adhesive, for example, a polyurethane resin. The primer layer 3 may be omitted. The eyeglasses according to this embodiment include lenses according to this embodiment. Figure 7 is a schematic perspective view showing an example of eyeglasses according to the embodiment. The eyeglasses 110 shown in Figure 7 comprises two lenses 111 and a frame 112 that fixes these lenses 111. At least one of the two lenses 111 is a lens containing the resin composition according to the embodiment. [Examples]

[0243] The present invention will be described in detail below using examples, but the present invention is not limited to these examples. In the examples, the evaluation methods for each of the above components and resin compositions are as follows.

[0244] <Photochromic curable composition> <(ii) Components> PC1: A photochromic compound represented by the following formula.

[0245] [ka]

[0246] <(A) component> NBDI: Norbornane diisocyanate. IPDI: Isophorone diisocyanate. 1,3-H6XDI:1,3-bis(isocyanatomethyl)cyclohexane. 1,4-H6XDI:1,4-bis(isocyanatomethyl)cyclohexane.

[0247] <(B1) component> <(B1a) component> TMMP: Trimethylolpropanetris (3-mercaptopropionate), which has three thiol groups in one molecule. PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), which has four thiol groups in its molecule. DPMP: Dipentaerythritol-hexakis(3-mercaptopropionate), which has six thiol groups in its molecule.

[0248] <(B1b) component> RX-1: Polyrotaxane This is a polyrotaxane synthesized by the method described in International Publication No. 2015 / 068798. The axial molecule is formed of polyethylene glycol with a molecular weight of 11,000, with bulky groups at both ends being adamantyl groups, and the cyclic molecule is α-cyclodextrin, with an average of 3.5 molecules of ε-caprolactone undergoing ring-opening polymerization via oxypropylene groups. The characteristics of the RX-1 are as follows: Inclusion amount of α-cyclodextrin: 0.25. Side chain modification degree: 0.5. Side chain molecular weight: approximately 450 on average. Weight average molecular weight: 180000. Hydroxyl value: 85 mg KOH / g. Based on the above figures, the average number of hydroxyl groups in one molecule is 270.

[0249] <(B2) component> <(B21) component> WS-140: Polyoxyethylene polyoxypropylene lauryl ether (oxyethylene repeating units m'=10 (average value), oxypropylene chain repeating units l'=2 (average value), number-average molecular weight 750). It has a hydroxyl group at one end and a C12 alkyl group at the other end. The repeating oxyethylene and oxypropylene portions are random copolymers. MPEG750: Methoxypolyethylene glycol (average molecular weight 750)

[0250] <(B22) component> L-34: Polyoxyethylene polyoxypropylene glycol (oxyethylene repeating units m''+m'''=14 (average value), oxypropylene chain repeating units l''=16 (average value), number-average molecular weight 1600). It has hydroxyl groups at both ends of the molecule (it has two hydroxyl groups). The repeating portions of oxyethylene and oxypropylene form a block copolymer.

[0251] <(C) component; polymerization curing accelerator> C1: Dimethyl tin dichloride.

[0252] <Other ingredients> Ir245: Ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]. <Alkali metal ions> potassium acetate sodium acetate

[0253] <Example 1> Photochromic curable compositions were prepared by mixing each component according to the formulations shown in Tables 1 and 3.

[0254] The alkali metal ions or alkaline earth metal ions in the photochromic curable composition were measured using an ICP emission spectrometer (iCAP6500DUO) manufactured by Thermo Fisher Scientific. For the measurement of these metal ions, the sample used was an extraction of 10 g of the photochromic composition dissolved in 30 g of chloroform solution into 20 g of ultrapure water (containing 1% HNO3).

[0255] Next, the prepared photochromic curable composition was thoroughly degassed and then injected into an inorganic glass mold with a 2 mm gap. The photochromic curable composition was polymerized by casting polymerization. Polymerization was carried out in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured body was removed from the inorganic glass mold to obtain a 2 mm thick photochromic cured body (resin composition). The obtained photochromic cured material was evaluated by the method described below.

[0256] (Evaluation method) [Photochromic properties] All values ​​used were measured using a spectrophotometer (instantaneous multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Industry Co., Ltd. [1] Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development. [2] Color density: The difference between the absorbance {A(300)} after light irradiation at 23°C for 300 seconds at the maximum absorption wavelength and the absorbance A(0) when light is not irradiated. [3] Fading half-life [t 1 / 2(sec)]: This is the time required for the absorbance of the sample at the maximum absorption wavelength to decrease to half of {A(300)-A(0)} after light irradiation is stopped following 300 seconds of light irradiation at 23°C. [Durability] [1] Survival rate (%) = [(A 96 ) / (A0)×100]: Accelerated degradation was performed for 96 hours using a Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd. The color intensity was evaluated before and after the accelerated degradation test, and the color intensity before the test (A0) and the color intensity after the test (A 96 ) ratio (A 96 The survival rate ( / A0) was used as an indicator of color durability. A higher survival rate indicates greater color durability. [2] Degree of yellowing (ΔYI): Degree of yellowing (YI) after accelerated degradation for 96 hours using the xenon weather meter X25 described above. 96 This is the difference between the yellowness level (YI0) and the yellowness level before the test. The yellowness level used was measured using a touch-panel type SM color computer SM-T manufactured by Suga Test Instruments Co., Ltd. [Heat resistance] The softening temperature of the obtained photochromic cured material was measured using a thermomechanical analyzer TMA8311 manufactured by Rigaku Corporation (three-point bending method, heating rate: 10°C / min).

[0257] 〔solid 13 [CNMR measurement] The resulting photochromic cured body 13 The CNMR measurement was performed as follows: For the measurement, a photochromic hardened material with a thickness of approximately 1 mm was cut into a disc shape with a diameter of approximately 2 mm and packed into a 4 mm zirconia sample tube. Equipment: FT-NMR JNM-ECA400II (JEOL Ltd.). Probe: 4mmΦCP / MAS probe (JEOL Ltd.). 13 C nuclear measurement frequency: 100.53MHz. Measurement method: CP / MAS method. Contact time: 2msec. Delay time: 5 seconds. Total number of times: 5000. Sample quantity: Approximately 80 mg. Sample rotation speed: 6000Hz. Temperature: 25℃. External standard: Adamantane (29.5ppm). In addition, the PST / MAS measurement was performed using the pre-saturation method with an interval of 10 msec under the aforementioned conditions.

[0258] [Viscosity increase (Δν 3h )] Kinematic viscosity (ν) of the photochromic curable composition after 3 hours of preparation. 3h This is the difference between the initial kinematic viscosity (ν0) and the initial kinematic viscosity (ν0). The kinematic viscosity used was measured using a Cannon-Fenske system.

[0259] [Alkali metal ions or alkaline earth metal ions] The alkali metal ion or alkaline earth metal ion concentrations in the obtained photochromic cured material were measured using a Rigaku Corporation ZSX Primus IV X-ray fluorescence analyzer on a circular plate measuring Φ40 mm and 1 mm in thickness. The detection limit for this measurement was 1 ppm. The evaluation results for the photochromic cured material are shown in Table 5.

[0260] <Examples 2-24, Comparative Examples 1-3> Photochromic cured materials were prepared and evaluated using the formulations shown in Tables 1-4 above, in the same manner as in Example 1. The evaluation results are shown in Tables 5-6, as in Example 1. Note: Example 13 Examples 22, 23 and 24 This will be treated as a comparative example.

[0261] [Table 1]

[0262] [Table 2]

[0263] [Table 3]

[0264] [Table 4]

[0265] [Table 5]

[0266] [Table 6]

[0267] <Examples 25-48, Comparative Examples 4-6> (ii) Photochromic curable compositions were prepared according to the formulations shown in Tables 1 to 4 above, except that 0.2 parts by mass of component PC1 was used. Corresponding examples and comparative examples are shown in Tables 7 and 8. In addition, a mold consisting of an inorganic glass plate and a thiourethane-based plastic lens with a refractive index of 1.60 was prepared separately. The gap between the inorganic glass plate and the thiourethane-based plastic lens was set to 1 mm. After thoroughly degassing the prepared photochromic curable composition, it was injected into the mold with a 1 mm gap and polymerized. Polymerization was carried out in an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. After polymerization, the cured body was removed from the inorganic glass plate, and a laminated type was obtained in which a 1 mm thick layer of photochromic cured material was laminated on the surface of a thiourethane-based plastic lens with a refractive index of 1.60. The obtained laminates were evaluated for photochromicity and durability using the same method as in Example 1, and the evaluation results are shown in Tables 7-8. Note that heat resistance was not evaluated because it would be affected by the thiourethane-based plastic lens. Furthermore, the mobility of component (i) was the same as in the corresponding examples and comparative examples, so it was omitted from the description. Examples 37, 46, 47, and 48 will be treated as comparative examples.

[0268] [Table 7]

[0269] [Table 8]

[0270] <Examples 49-72, Comparative Examples 7-9> The photochromic curable compositions described in Tables 9-12 below were prepared. The prepared photochromic curable composition was used as an adhesive. In other words, a laminate was manufactured by joining a pair of inorganic glass substrates (plates) for optical articles with this adhesive. First, the photochromic curable composition was applied to one of the inorganic glass plates for optical articles, which had a 0.1 mm thick spacer placed at its edge. Then, the other inorganic glass plate for optical articles was placed on top of the applied photochromic curable composition. After that, the photochromic curable composition was polymerized. Polymerization was carried out using an air furnace, and curing was performed over 18 hours while gradually increasing the temperature from 27°C to 120°C. This resulted in obtaining a laminate in which a pair of inorganic glass plates for optical articles were joined with this adhesive. In other words, a glass-bonded type photochromic laminate with a 0.1 mm thick photochromic cured layer was obtained.

[0271] The photochromic properties and durability of the obtained photochromic laminates were evaluated using the same method as in Example 1, and the evaluation results are shown in Tables 13-14. Note that the mobility of component (i) was measured by curing a photochromic curable composition separately under the same conditions as described above, and measuring the resulting cured material. Heat resistance was not evaluated due to the influence of the inorganic glass plate. Note: Example 61 Examples 70, 71, and 72 This will be treated as a comparative example.

[0272] [Table 9]

[0273] [Table 10]

[0274] [Table 11]

[0275] [Table 12]

[0276] [Table 13]

[0277] [Table 14]

[0278] <Examples 73-96, Comparative Examples 10-12> Photochromic curable compositions were prepared as described in Tables 15-18 below. The prepared photochromic curable composition was used as an adhesive. Specifically, a laminate was manufactured by joining two optical substrates (plates) made of inorganic glass for optical articles, one of which had a polarizing film on its surface, with the other plate using the adhesive. First, an acrylic adhesive was applied to one side of a plate made of inorganic glass for optical articles by spin coating, and a polarizing film (thickness 27 μm, visible transmittance 42.5%, polarization degree 99.2%, gray color, polyvinyl alcohol base) was placed on top of it. Then, by irradiating the plate with UV light, an optical substrate in which the polarizing film and the plate were laminated was prepared. Next, a photochromic curable composition was applied to a plate made of inorganic glass for optical articles, with 0.1 mm thick spacers placed at its edges. The optical substrate, on which a polarizing film was laminated, was then positioned so that the polarizing film surface was in contact with the photochromic curable composition.

[0279] Subsequently, the photochromic curable composition was polymerized. Polymerization was carried out using an air furnace, gradually increasing the temperature from 27°C to 120°C over 18 hours. By joining a pair of plates for optical articles, a glass-laminated photochromic laminate comprising a polarizing film layer and a 0.1 mm thick photochromic layer was obtained. The photochromic properties and durability of the obtained photochromic laminates were evaluated using the same method as in Example 1, and the evaluation results are shown in Tables 19-20. Note that the mobility of component (i) was measured by curing a photochromic curable composition separately under the same conditions as described above, and measuring the resulting cured material. Heat resistance was not evaluated due to the influence of the inorganic glass plate. Note: Example 85 Examples 94, 95, and 96 This will be treated as a comparative example.

[0280] [Table 15]

[0281] [Table 16]

[0282] [Table 17]

[0283] [Table 18]

[0284] [Table 19]

[0285] [Table 20]

[0286] Intensity ratio (PMI pst / PMI cp Resin compositions with a molecular mobility of 8.0 to 40.0 demonstrate that excellent photochromic and mechanical properties can be achieved through control of molecular mobility by crosslinking. In particular, resin compositions with excellent photochromic properties and heat resistance can be obtained.

[0287] (B1) By using a component having six thiol groups in its molecule, a resin composition exhibiting excellent effects can be obtained. By using a component having six thiol groups in its molecule, the strength ratio (PMI) of the resulting resin composition can be improved. pst / PMI cp ) can be set to a relatively high value.

[0288] Furthermore, the resin composition according to this embodiment has excellent photochromic properties and, in particular, excellent heat resistance. Therefore, the intensity ratio (PMI) used to evaluate molecular mobility is... pst / PMI cp It is clear that the photochromic properties can be evaluated from this. In addition, the effect of using a component with six thiol groups in the molecule to improve heat resistance is thought to be due to the increased number of hydrogen bonds per bridging point, resulting in improved heat resistance through the effect of multivalent interaction (multi-point hydrogen bonding).

[0289] Among these, by combining a component having six thiol groups in its molecule with component (B21), the intensity ratio (PMI) is achieved. pst / PMI cpThe viscosity can be set to 10.0 or more and 15.0 or less, more preferably 11.0 to 15.0, and even more preferably 12.5 to 15.0. In this case, the increase in viscosity of the photochromic curable composition can also be kept low.

[0290] Furthermore, the following trends were observed in the comparison of the examples. Component (B1), PEMP (a component with 4 thiol groups in its molecule) and DPMP (a component with 6 thiol groups in its molecule), are total substitution compounds. On the other hand, TMMP (a component with 3 thiol groups in its molecule) is a partial substitution compound. Comparing these examples, it was found that using PEMP and DPMP, which are total substitution compounds, exhibited particularly superior photochromic properties compared to using TMMP, which is a partial substitution compound. From this, it is considered that when a total substitution compound is used as component (B1), a free space for molecular motion of the photochromic compound is effectively formed.

[0291] Furthermore, the durability can be improved by adjusting the content of alkali metal ions and alkaline earth metal ions in the photochromic composition of the present invention. The reason for this is thought to be as follows: When the content of alkali metal salts and alkaline earth metal salts in the photochromic composition is high, side reactions such as isocyanuration occur during the preparation or polymerization of the photochromic composition, resulting in an increase in the number of residual thiol groups in the cured product. Thiol groups generate radicals when exposed to ultraviolet light, which is thought to accelerate the degradation of the photochromic compound and reduce its durability. In the present invention, it is thought that side reactions are suppressed and durability is improved by adjusting the content of alkali metal ions and alkaline earth metal ions to a suitable level. [Explanation of symbols]

[0292] 10: Polyrotaxane 20: Axial molecule 30: Cyclic molecules 40: Bulky terminal groups 50: Side chain 1: Optical laminate 2: Optical substrate 3: Primer layer 4: Resin composition 110: Glasses 111: Lens 112: Frame

Claims

1. The urethane resin having polyoxypropylene chains in its molecular chain, and the photochromic compound are included. １３ The maximum signal intensity (PMI) in the range of 16 ppm to 20 ppm in the first spectrum obtained by C-PST / MAS nuclear magnetic resonance spectroscopy. ｐｓｔ )and, １３ The maximum signal intensity (PMI) in the range of 16 ppm to 20 ppm in the second spectrum obtained by C-CP / MAS nuclear magnetic resonance spectroscopy. ｃｐ ) ratio (PMI ｐｓｔ / PMI ｃｐ ) is between 8.0 and 40.0, A resin composition in which the total content of alkali metal ions and alkaline earth metal ions determined by X-ray fluorescence analysis is 500 ppm or less, The aforementioned urethane resin is (A) A polyiso(thio)cyanate component having two or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in its molecule, (B) Active hydrogen-containing component having an active hydrogen-containing group, A resin obtained by reacting, Let nB be the total number of moles of active hydrogen-containing groups in the (B) active hydrogen-containing component. When the total number of moles of iso(thio)cyanate groups in the polyiso(thio)cyanate component (A) is nA, The ratio (nA / nB) is between 1.00 and 1.

50. The aforementioned (B) active hydrogen-containing component is (B1) A polyfunctional active hydrogen-containing component having three or more active hydrogen-containing groups in one molecule, (B2) A first active hydrogen-containing component having one or two active hydrogen-containing groups in one molecule, The (B2) first active hydrogen-containing component has a number average molecular weight of 700 or more and 3000 or less, and contains a polyoxypropylene chain in its molecule. The aforementioned (B1) polyfunctional active hydrogen-containing component is A resin composition comprising a compound having a quaternary carbon atom in its molecule, wherein all groups bonded to the quaternary carbon atom are active hydrogen-containing groups.

2. The maximum signal intensity (AMI) in the range of 10 ppm to 15 ppm in the first spectrum. ｐｓｔ )and, The maximum intensity (AMI ｃｐ of the signal within the range of 10 ppm or more and 15 ppm or less in the second spectrum) and the ratio (AMI ｐｓｔ / AMI ｃｐ ) is 7.0 or more and 23.0 or less. The resin composition according to claim 1.

3. The maximum signal intensity (EI) in the range of 68 ppm to 72 ppm in the first spectrum. ｐｓｔ )and, The maximum signal intensity (EI) in the range of 68 ppm to 72 ppm in the second spectrum. ｃｐ ) ratio (EI ｐｓｔ / EI ｃｐ The resin composition according to claim 1 or 2, wherein the ratio is 5.0 or more and 20.0 or less.

4. The resin composition according to any one of claims 1 to 3, wherein the polyoxypropylene chain of the (B2) first active hydrogen-containing component has an average value of 2 or more and 25 or less of repeating oxypropylene units.

5. The resin composition according to any one of claims 1 to 4, wherein the (B2) first active hydrogen-containing component further has at least one of an alkyl group and a polyoxyethylene chain in its molecule.

6. The resin composition according to claim 5, wherein the (B2) first active hydrogen-containing component has the alkyl group and the number of carbon atoms is 5 or more and 20 or less.

7. The resin composition according to claim 5, wherein the (B2) first active hydrogen-containing component has the polyoxyethylene chain, and the average value of its repeating units is 5 or more and 25 or less.

8. Optical substrate and A resin composition according to any one of claims 1 to 7 is laminated on at least one main surface of the optical substrate, An optical laminate containing an optical element.

9. The optical laminate according to claim 8, further comprising a polarizing film.

10. An optical article comprising the resin composition according to any one of claims 1 to 7.

11. A lens comprising the resin composition according to any one of claims 1 to 7.

12. Eyeglasses including the lens described in claim 11.

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