CN116868095A

CN116868095A - Resin composition, optical laminate, optical article, lens, and glasses

Info

Publication number: CN116868095A
Application number: CN202280010524.1A
Authority: CN
Inventors: 野口誉夫; 森力宏; 百田润二
Original assignee: Tokuyama Corp
Current assignee: Tokuyama Corp
Priority date: 2021-01-25
Filing date: 2022-01-12
Publication date: 2023-10-10

Abstract

The purpose of the present invention is to provide a resin composition having excellent photochromic properties and mechanical properties. The present invention is a resin composition comprising (i) a urethane resin having a propylene glycol chain in a molecular chain and (ii) a photochromic compound, which is prepared by ¹³ C-PST/MAS NMR measurement of 16ppm of the spectral intensity of carbon atom of methyl group containing propylene glycol chainThe total spectral intensity of the PMI is more than 20ppm _pst Will pass through ¹³ The total spectral intensity of 16ppm to 20ppm of the spectral intensity of carbon atoms of methyl group containing propylene glycol chain as measured by C-CP/MAS NMR is PMI _cp PMI at the time of _pst And PMI _cp Intensity ratio (PMI) _pst /PMI _cp ) 8.0 to 40.0.

Description

Resin composition, optical laminate, optical article, lens, and glasses

Technical Field

The present invention relates to a resin composition, an optical laminate, an optical article, a lens, and glasses.

Background

The photochromic-spectacle lens containing the photochromic compound rapidly colors outdoors where light containing ultraviolet rays such as sunlight is irradiated, functions as sunglasses, and fades indoors where no light is irradiated, and functions as transparent spectacles. In recent years, demand for such photochromic optical articles having photochromic properties has increased.

In order to impart photochromic properties to a lens for spectacles, the following method is generally employed.

(a) A method of directly molding an optical material such as a lens by polymerizing a composition of a polymerizable compound and a photochromic compound (kneading method).

(b) A method (lamination method) of providing 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 cast molding polymerization.

(c) A method of joining 2 optical sheets by using an adhesive in which a photochromic compound is dispersed (adhesive method). The optical plate may be plastic or inorganic glass.

In recent years, the photochromic optical articles are required to have further improved photochromic characteristics. Further, there is a need for photochromic optical articles that have both high photochromic properties and high mechanical properties. Patent document 1 describes a dyed lens obtained by dyeing a urethane resin (molded article) as an article similar to a photochromic optical article. The urethane resin forming the molded article uses thiol as a monomer, and has excellent mechanical strength having a (thio) urethane bond in a molecular chain.

However, when a photochromic compound which is colored/colorless by ring opening/ring closure is compounded instead of dyeing, the urethane resin as a matrix has a (thio) urethane bond, and if the monomer ratio is not particularly adjusted, the ring opening/ring closure of the photochromic compound may be hindered in molecular mobility.

Prior art literature

Patent literature

Patent document 1 wo2012/176439

Patent document 2 WO2015/115648

Patent document 3 WO2016/143910

Disclosure of Invention

Problems to be solved by the invention

In order to improve the photochromic characteristics, a difunctional active hydrogen compound having a polypropylene glycol chain or the like is used in patent document 2, and a monofunctional active hydrogen compound is used in patent document 3. According to these methods, the photochromic property can be improved by forming a space in the urethane matrix using a specific active hydrogen compound.

Solution for solving the problem

The inventors believe that not only the formation of free space, but also the control of molecular mobility in the urethane resin by cross-linking molecules may be required. Further, it has been found that a cured product (a urethane resin in which a photochromic compound is dispersed) satisfying specific molecular mobility parameters can exhibit excellent photochromic properties and mechanical properties, and the present invention has been completed.

The present invention includes the following inventions.

1. A resin composition comprising a urethane resin having a polyoxypropylene chain in a molecular chain and a photochromic compound,

the resin composition is composed of ¹³ Maximum Intensity (PMI) of signal in the range of 16ppm to 20ppm in the 1 st spectrum obtained by C-PST/MAS nuclear magnetic resonance spectroscopy _pst ) And by ¹³ Maximum Intensity (PMI) of signal in the range of 16ppm to 20ppm in the 2 nd spectrum obtained by C-CP/MAS nuclear magnetic resonance spectroscopy _cp ) Ratio (PMI) _pst /PMI _cp ) 8.0 to 40.0.

2. The resin composition according to the above 1, wherein the maximum intensity (AMI) of the signal in the range of 10ppm to 15ppm in the 1 st spectrum _pst ) Maximum Intensity (AMI) of signal in the range of 10ppm to 15ppm in the 2 nd spectrum _cp ) Ratio (AMI) _pst /AMI _cp ) Is 7.0 to 23.0 inclusive.

3. The resin composition according to the above 1 or 2, wherein the maximum intensity (EI) of the signal in the range of 68ppm to 72ppm in the 1 st spectrum _pst ) And the maximum intensity (EI) of the signal in the range of 68ppm to 72ppm in the 2 nd spectrum _cp ) Ratio (EI) _pst /EI _cp ) Is 5.0 to 20.0 inclusive.

4. The resin composition according to any one of the above 1 to 3, wherein the total content of alkali metal ions and alkaline earth metal ions obtained by fluorescent X-ray analysis is 500ppm or less.

5. The resin composition according to any one of the above 1 to 4, wherein the urethane resin is a resin obtained by reacting (A) a polyisocyanate component having 2 or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule with (B) an active hydrogen-containing component having an active hydrogen-containing group,

The total mole number of active hydrogen-containing groups of the active hydrogen-containing component (B) is nB,

when the total mole number of isocyanate groups of the polyisocyanate component (A) is nA,

the ratio (nA/nB) is 1.00 or more and 1.50 or less,

the (B) active hydrogen-containing component comprises:

(B1) A polyfunctional active hydrogen-containing component having 3 or more active hydrogen-containing groups in 1 molecule, and (B2) an active hydrogen-containing component 1 having 1 or 2 active hydrogen-containing groups in 1 molecule,

the active hydrogen-containing component (B2) 1 has a number average molecular weight of 500 or more and a polyoxypropylene chain in the molecule.

6. The resin composition according to the above 5, wherein the average value of the repeating units of oxypropylene groups of the polyoxypropylene chain of the (B2) 1 st active hydrogen-containing component is 2 or more and 25 or less.

7. The resin composition according to the above 5 or 6, wherein the (B2) 1 st active hydrogen-containing component further has at least one of an alkyl group and a polyoxyethylene chain in a molecule.

8. The resin composition according to the above 7, wherein the (B2) 1 st active hydrogen-containing component has the alkyl group and has a carbon number of 5 or more and 20 or less.

9. The resin composition according to the above 7, wherein the active hydrogen-containing component (B2) 1 has the polyoxyethylene chain, and the average value of the repeating units thereof is 5 or more and 25 or less.

10. The resin composition according to any one of the above 5 to 9, wherein the (B1) polyfunctional active hydrogen-containing component comprises a compound having a quaternary carbon atom in the molecule and all groups bonded to the quaternary carbon atom have active hydrogen-containing groups.

11. An optical laminate comprising: an optical substrate; and the resin composition according to any one of 1 to 10 above laminated on at least one main surface of the optical substrate.

12. The optical laminate according to the above 11, further comprising a polarizing film.

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

14. A lens comprising the resin composition according to any one of 1 to 10.

15. An eyeglass comprising the lens of 14 above.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition having excellent photochromic properties and mechanical properties can be obtained. In particular, a resin composition excellent in photochromic characteristics and heat resistance can be obtained.

Drawings

Fig. 1 is a view showing 1 example of the 1 st spectrum of the resin composition according to the embodiment.

Fig. 2 is a view showing 1 example of the 2 nd spectrum of the resin composition according to the embodiment.

FIG. 3 is a schematic view of the polyrotaxane component (B1B) used in the examples.

Fig. 4 is a schematic diagram showing 1 example of a multifunctional active hydrogen-containing component having active hydrogen-containing groups in which all groups bonded to quaternary carbon atoms.

Fig. 5 is a schematic diagram showing 1 example of a multifunctional active hydrogen-containing component having an active hydrogen-containing group in a part of groups bonded to quaternary carbon atoms.

Fig. 6 is a cross-sectional view schematically showing 1 example of the optical laminate according to the embodiment.

Fig. 7 is a perspective view schematically showing 1 example of glasses according to the embodiment.

Detailed Description

< resin composition >

The resin composition comprises:

(i) Urethane resin having polyoxypropylene chain in molecular chain ((i) component), and process for producing the same

(ii) Photochromic compounds ((ii) ingredients).

Further, it has been found that the (i) urethane resin exhibits excellent effects when it is a matrix of a urethane resin having a polyoxypropylene chain in a molecular chain and the molecular mobility of the polyoxypropylene chain satisfies a specific range. Specifically, with solids ¹³ CNMR assay on the polyoxypropylene chainThe motility of the portion containing a carbon atom of a methyl group was evaluated, and the index of the motility satisfied a specific range, thereby obtaining a resin composition having excellent photochromic properties and mechanical properties.

< solids based ¹³ Molecular motility evaluation of CNMR assay

Solid NMR measurement methods of carbon nuclei include pulse saturation transfer/magic angle spinning nuclear magnetic (Pulse Saturation Transfer/Magic Angle Spinning, PST/MAS) method and cross polarization/magic angle spinning nuclear magnetic (Cross Polarization/Magic Angle Spinning, CP/MAS) method.

The PST/MAS method is a method of observing a portion (amorphous site) with high mobility emphasized. The CP/MAS method is a method of observing a portion (crystalline portion) with low motility. Therefore, by comparing the intensities of specific signals in these spectra, the molecular mobility of the components constituting the urethane resin (matrix resin in which the photochromic compound is dispersed) can be evaluated. Solid of resin composition based on PST/MAS method ¹³ CNMR spectra are also referred to as spectrum 1. Solid of resin composition based on CP/MAS method ¹³ CNMR spectra are also referred to as spectrum 2.

That is, the intensity of each peak measured by the PST/MAS method is defined as I _PST The intensity of each peak measured by the CP/MAS method was defined as I _CP When I _PST Divided by I _CP The value I obtained _PST /I _CP As an index of molecular motility, the greater the molecular motility, I _PST /I _CP The greater the value. In order to compare the molecular mobilities between different urethane resin compositions, it is preferable that the peak of the hard segment site which is not easily affected by the surrounding molecular mobilities is taken as a reference (I _PST /I _CP =1). The peak was defined as a peak based on carbon atoms of c=o groups present in the range of 163 to 168 ppm.

(i) The component (a) contains a polyoxypropylene chain as an essential component. And, preferably, comprises alkyl groups and/or oxyethylene chains.

Solid body ¹³ The chemical shift values of the carbon nuclei in the respective units observed in the C-NMR measurement are approximately as follows.

10-15 ppm: a terminal methyl group in the alkyl group,

16-20 ppm: methyl groups in oxypropylene units,

68ppm to 72ppm: ethylene in the oxyethylene unit,

73ppm to 80ppm: ethylene (excluding methyl) in the oxypropylene units.

＜PMI _pst PMI (PMI) _cp Measurement of >

16-20 ppm: the methyl group in the oxypropylene unit may be identified. However, when component (i) contains an alkyl group having 2 or more carbon atoms, the peak of the methylene group beside the terminal methyl group falls within this range.

＜EI _pst EI (electronic equipment) _cp Measurement of >

68-72 ppm; the ethylene group in the oxyethylene unit can be confirmed.

＜AMI _pst AMI (advanced mechanical interface) _cp Measurement of >

10-15 ppm; (i) When the component contains an alkyl group having 2 or more carbon atoms, a methyl group at the terminal of the alkyl group can be confirmed.

< others >

73-80 ppm; the ethylene group (excluding the methyl group) in the oxypropylene unit may be confirmed.

The resin composition or photochromic optical article containing the photochromic compound can be directly analyzed by NMR to determine the I of each carbon core _PST /I _CP Values.

Through intensity ratio (PMI) _pst /PMI _cp ) When the ratio is 8.0 to 40.0, excellent photochromic properties and mechanical properties can be exhibited. PMI (PMI) _pst The maximum intensity of the signal appearing in the range of 16ppm to 20ppm inclusive of the 1 st spectrum is the maximum height. PMI (PMI) _cp The maximum intensity of the signal appearing in the range of 16ppm to 20ppm inclusive of the 2 nd spectrum is the maximum height. As described above, the signals appearing in the range of 16ppm to 20ppm inclusive of the 1 st and 2 nd spectra are signals considered to be methyl groups originating from oxypropylene units.

By making the strength ratio (PMI) of the resin composition _pst /PMI _cp ) For a specific purposeThe reason why the range of (c) can exert excellent effects is not clear, but is estimated as follows. It is considered that when most of the urethane resins constituting the matrix of the resin composition have polyoxypropylene chains in the molecular chain, free space is easily ensured, and thus high photochromic characteristics can be exhibited. That is, since the matrix of the resin composition is soft, the structural change of the photochromic compound is not easily inhibited, and the photochromic property can be exhibited for a long period of time. On the other hand, if the ratio of the polyoxypropylene chain is too high or the length of the introduced chain is too long, the mechanical properties may be lowered. Under such circumstances, the present inventors considered that in order to improve the photochromic properties while maintaining high mechanical properties, it is necessary to evaluate the mobility of the component (i) itself. Further, it was found that when the motility of component (i) was measured by the above-described NMR method, the intensity ratio (PMI _pst /PMI _cp ) An excellent effect can be exhibited when the ratio is 8.0 to 40.0. That is, it is considered that not only the free space is formed, but also the mobility of the component (i) itself is moderate, and therefore the balance between the photochromic property and the mechanical property is excellent.

(i) Intensity ratio of component (PMI) _pst /PMI _cp ) When the content is less than 8.0, the photochromic property is poor, which is not preferable. On the other hand, if it exceeds 40.0, mechanical properties, particularly heat resistance, are deteriorated, which is not preferable.

Namely, the intensity ratio (PMI _pst /PMI _cp ) A value of less than 8.0 may mean that the proportion of the polyoxypropylene chain in the resin composition, which is highly mobile and soft, is too low. In such a resin composition, structural changes of the photochromic compound are difficult to occur, and it is difficult to develop photochromic characteristics such as a fading rate and a color developing concentration of the photochromic compound. Intensity ratio (PMI) _pst /PMI _cp ) Exceeding 40.0 may mean that the proportion of the polyoxypropylene chain having high crystallinity in the resin composition is too low. Such a resin composition tends to have insufficient mechanical properties such as heat resistance.

In order to exert more excellent characteristics, the strength ratio (PMI _pst /PMI _cp ) Preferably 10.0 to 35.0, more preferably 10.0 to 15.0 or 20.0 to 35.0.

Among the polymerizable monomers forming component (i), when a monofunctional polymerizable monomer having 1 reactive group (iso (thio) cyanate group or active hydrogen-containing group) in the molecule is used, it is particularly preferable to use the strength ratio (PMI _pst /PMI _cp ) 10.0 to 15.0.

In the case where a polymerizable monomer having 2 or more functions is used and a monofunctional polymerizable monomer is not used, it is particularly preferable to use the strength ratio (PMI _pst /PMI _cp ) 20.0 to 35.0. It is considered that when the monofunctional polymerizable monomer is not used, the degree of crosslinking is increased, and therefore, even if the strength ratio (PMI _pst /PMI _cp ) High and excellent effects can be exerted. When the monofunctional polymerizable monomer is not used, the strength ratio (PMI) is determined in consideration of the balance of physical properties _pst /PMI _cp ) Preferably 23.5 to 35.0, and more preferably 25.5 to 35.0.

However, even in these preferable ranges, the intensity ratio (PMI _pst /PMI _cp ) 10.0 to 15.0. And, most preferably, the monofunctional polymerizable monomer is used. By using monofunctional polymerizable monomers and strength ratio (PMI _pst /PMI _cp ) Satisfying 10.0 to 15.0, a resin composition excellent in photochromic characteristics and mechanical characteristics can be obtained. In order to exert more excellent photochromic characteristics, the intensity ratio (PMI _pst /PMI _cp ) Is 11.0 to 15.0, more preferably 12.5 to 15.0. Further, not only these physical properties are excellent, but also the polymerization moldability of the photochromic curable composition forming the resin composition is improved. Among them, the photochromic curable composition using the monofunctional polymerizable monomer can suppress a rapid increase in viscosity during polymerization.

Intensity PMI _pst Preferably 1.0 to 20.0. Intensity PMI _pst The resin composition in this range tends to have a sufficiently soft polyoxypropylene chain with high molecular mobility. Intensity PMI _pst More preferably 1.1 to 17.5, still more preferably 1.1 to 3.5, or 13.0 to 17.5.

Intensity PMI _cp Preferably from 0.1 to 1.0. Intensity PMI _cp At the positionThe resin composition in the range tends to have a polyoxypropylene chain having a sufficiently high crystallinity. Intensity PMI _cp More preferably from 0.10 to 0.70, still more preferably from 0.15 to 0.30 or more or from 0.50 to 0.70.

(i) The component (a) preferably has an alkyl group in the molecule. The alkyl group is preferably a group having 5 to 20 carbon atoms, and is preferably a linear alkyl group. The alkyl group may constitute a side chain of component (i) or may constitute a main chain. The component (i) having an alkyl group in a molecule can be obtained, for example, by using a polymerizable monomer having an alkyl group as the monofunctional polymerizable monomer. The terminal group located at the position opposite to the reactive group of the monofunctional polymerizable monomer is an alkyl group, and is preferably a linear alkyl group having 5 to 20 carbon atoms.

(i) In the case where the component has an alkyl group in the molecule,

will be composed of ¹³ The spectral intensity of the carbon atom of the methyl group at the end of the alkyl group as measured by C-PST/MAS NMR was regarded as AMI _pst ，

Will be composed of ¹³ The spectral intensity of the carbon atom of the methyl group at the end of the alkyl group as measured by C-CP/MAS NMR was regarded as AMI _cp In the time-course of which the first and second contact surfaces,

AMI _pst and AMI (advanced mechanical systems) _cp Intensity ratio (AMI) _pst /AMI _cp ) Preferably 7.0 to 23.0. Through peak intensity ratio (AMI) _pst /AMI _cp ) The ratio is 7.0 to 23.0, and the photochromic properties and mechanical properties of the obtained resin composition can be improved. Intensity ratio (AMI) _pst /AMI _cp ) More preferably 11.5 to 20.0, and still more preferably 13.5 to 16.0. As described above, the signal of the carbon atom of the methyl group which is considered to originate from the terminal of the alkyl group appears in the range of 10 to 15ppm of the 1 st and 2 nd spectra.

Strength AMI _pst Preferably 1.0 to 5.0. Strength AMI _pst The resin composition in this range tends to have a sufficiently soft alkyl group having high molecular mobility. Strength AMI _pst More preferably 1.10 to 3.00, still more preferably 2.0 to 2.8.

Strength ofAMI _cp Preferably from 0.1 to 0.5. Strength AMI _cp The resin composition in this range tends to have an alkyl group having sufficiently high crystallinity. Strength AMI _cp More preferably from 0.10 to 0.30, still more preferably from 0.15 to 0.20.

Further, it is preferable that the component (i) has an oxyethylene chain in the molecule. The molecular chain is provided with a polyoxyethylene chain,

will be composed of ¹³ The spectral intensity of carbon atoms of the polyethylene oxide chain as determined by C-PST/MAS NMR was set as EI _pst ，

Will be composed of ¹³ The spectral intensity of carbon atoms of the polyethylene oxide chain measured by C-CP/MAS NMR was set as EI _cp In the time-course of which the first and second contact surfaces,

EI _pst and EI _cp Intensity ratio (EI) _pst /EI _cp ) Preferably 5.0 to 20.0. By peak intensity ratio (EI _pst /EI _cp ) The ratio is 5.0 to 20.0, and the photochromic properties and mechanical properties of the obtained resin composition can be improved. Intensity ratio (EI) _pst /EI _cp ) More preferably 6.5 to 12.0. As described above, the signal which is considered to originate from the ethylene in the oxyethylene unit appears in the range of 68ppm to 72ppm of the 1 st and 2 nd spectra.

Strength EI of _pst Preferably 4.0 to 20.0. Strength EI of _pst The resin composition in this range tends to have a sufficiently soft oxyethylene chain with high molecular mobility. Strength EI of _pst More preferably 4.50 to 18.00, still more preferably 9.50 to 18.00.

Strength EI of _cp Preferably from 0.5 to 3.0. Strength EI of _cp The resin composition in this range tends to have a sufficiently high crystalline oxyethylene chain. Strength EI of _cp More preferably from 0.70 to 2.10, still more preferably from 1.30 to 2.00.

The 1 st spectrum of the resin composition can be obtained by ¹³ C-PST/MAS NMR spectroscopy. A disk-shaped resin composition having a diameter of about 2mm and a thickness of 1mm was used as a sample. For measurement, a filler is usedA4 mm zirconia sample tube filled with the sample. As a measurement device, for example, FT-NMR JNM-ECA400II (Japanese electronics Co., ltd.) was used. The measurement conditions are, for example, as follows.

And (3) probe: 4 mm. Phi. CP/MAS probe (Japanese electronics Co., ltd.).

¹³ Number of C-kernel measurement frequencies: 100.53MHz.

The measuring method comprises the following steps: CP/MAS method.

Contact time: 2 milliseconds.

Delay time: 5 seconds.

Cumulative number of times: 5000 times.

Sample amount: about 80mg.

Sample rotation speed: 6000Hz.

Temperature: 25 ℃.

External standard substance: adamantane (29.5 ppm).

Presaturation method: at intervals of 10 milliseconds.

The 2 nd spectrum of the resin composition can be obtained by ¹³ C-CP/MAS NMR spectrum analysis. The 2 nd spectrum was obtained by the same method as the 1 st spectrum except that the presaturation method was not used. For the 1 st and 2 nd spectra thus obtained, the intensity and chemical shift of each signal were calculated using, for example, JEOL Delta v5.0.4 analysis software.

Fig. 1 is a view showing 1 example of the 1 st spectrum of the resin composition according to the embodiment. Fig. 1 shows a spectrum 1 of a resin composition according to example 15 described below. In fig. 1, the horizontal axis represents chemical shift, and the vertical axis represents strength. The 1 st spectrum shown in FIG. 1 contains PMI showing the maximum value in the chemical shift range of 16ppm to 20ppm _pst And a signal showing a maximum value EIpst in a chemical shift range of 68ppm to 72 ppm.

Fig. 2 is a view showing 1 example of the 2 nd spectrum of the resin composition according to the embodiment. Fig. 2 is a graph showing the 2 nd spectrum of the resin composition according to example 15 described later. In fig. 2, the horizontal axis represents chemical shift, and the vertical axis represents intensity. The 2 nd spectrum shown in FIG. 2 shows a chemical shift range of 16ppm to 20ppm inclusiveMaximum PMI _cp Exhibits a maximum value EI in a chemical shift range of 68ppm to 72ppm _cp Is a signal of (a).

As described above, the component (i) has only a polyoxypropylene chain in the molecular chain and the strength ratio (PMI) _pst /PMI _cp ) The content is 8.0 to 40.0, and the production method is not particularly limited. Among them, in order to obtain a resin composition having good polymerization moldability and ease of production, a polymerizable monomer having an oxypropylene chain is preferably used, a polymerizable monomer having an oxypropylene chain and an oxyethylene chain is more preferably used, and 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) is preferably used.

Next, a photochromic compound contained in the resin composition will be described.

(ii) photochromic Compounds

(ii) The photochromic compound (hereinafter also referred to as component (ii)) may be used without particular limitation as long as it is a compound exhibiting photochromic properties, and 1 or 2 or more of them may be used alone or in combination.

As a representative substance of such a photochromic compound, a known photochromic compound such as a chromene compound, a fulgimide compound, a spirooxazine compound, a spiropyran compound and the like can be used without any limitation.

Examples of the fulgimide compound, the spirooxazine compound, the spiropyran compound and the chromene compound include those described in Japanese patent application laid-open No. 2-28154, japanese patent application laid-open No. 62-288830, WO94/22850 and WO 96/14596.

In particular, as a chromene compound, a chromene compound having excellent photochromic properties is known in addition to those described in the above patent documents, and such a chromene compound can be preferably used as the component (ii). As a result of such a chromene compound, japanese patent application laid-open No. 2001-031670, japanese patent application laid-open No. 2001-011067, japanese patent application laid-open No. 2001-011066, japanese patent application laid-open No. 2000-344761, japanese patent application laid-open No. 2000-327675, japanese patent application laid-open No. 2000-256347, japanese patent application laid-open No. 2000-229976, japanese patent application laid-open No. 2000-229975, japanese patent application laid-open No. 2000-229974, japanese patent application laid-open No. 2000-229973, japanese patent application laid-open No. 2000-219678, japanese patent application laid-open No. 2000-219686, japanese patent application laid-open No. 11-322739, japanese patent application laid-open No. 11-286484, japanese patent application laid-open No. 11-279171, japanese patent application laid-open No. 09-218301, japanese patent application laid-open No. 09-124645, japanese patent application laid-open No. 08-295690, japanese patent application laid-open No. 08-176139, japanese patent application laid-open No. 08-157467, U.S. 5645767, U.S. 5658501, U.S. 3795, japanese patent application laid-open No. 3, japanese patent application laid-open No. 37-5, japanese patent application laid-open No. 37-5, and Japanese patent application U.S. patent No. 6296785, japanese patent No. 4424981, japanese patent No. 4424962, WO2009/136668, WO2008/023828, japanese patent No. 4369754, japanese patent No. 4301621, japanese patent No. 4256985, WO2007/086532, japanese patent application No. 2009-120536, japanese patent application No. 2009-67754, japanese patent application No. 2009-676780, japanese patent application No. 2009-57300, japanese patent application No. 4195615, japanese patent application No. 4158881, japanese patent application No. 4157245, japanese patent application No. 4157239, japanese patent application No. 4157227, japanese patent application No. 4118458, japanese patent application No. 2008-74843, japanese patent application No. 4301621, japanese patent application No. 3801386, WO2005/028465, WO2003/042203, japanese patent application No. 2009-57300, japanese patent application No. 4157227, japanese patent application No. 2008-7482, japanese patent application No. 2008, japanese patent application No. applied, japanese patent application laid-open No. 2005-289812, 2005-289807, 2005-112772, 3522189, WO2002/090342, 3471073, 2003-277381, WO2001/060811, WO00/71544, and the like. Fulgide compounds, chromene compounds and spirooxazine compounds have been disclosed in a large number of documents, for example, japanese patent application laid-open No. 2-28154, japanese patent application laid-open No. 62-288830, WO94/22850, WO96/14596 and the like.

Among known photochromic compounds, a chromene compound having an indeno [ 2,1-f ] naphtho [ 1,2-b ] pyran skeleton is preferably used from the viewpoints of photochromic properties such as color development concentration, initial colorability, durability, fading speed, etc.

In addition to the above, a photochromic compound having an oligomer chain group in the molecule is preferably used. As such a photochromic compound having an oligomer chain group, a large number of documents have been disclosed in WO2000/015630 pamphlet, WO 2004/04961 pamphlet, WO2009/146509 pamphlet, WO2012/149599 pamphlet, WO2012/162725 pamphlet, WO2013/078086 pamphlet, WO 2019/013049 pamphlet, WO2019/203205 pamphlet, and the like. Among these photochromic compounds having an oligomer chain group in the molecule, for the purpose of exhibiting excellent photochromic properties and durability, the photochromic compounds having an oligomer chain group described in WO 2019/013049 or WO2019/203205 are preferably used.

< resin composition >

The resin composition comprises the component (i) and the component (ii). In the resin composition, the blending ratio of the component (i) and the component (ii) may be appropriately determined according to the purpose of the target photochromic optical article, etc. Among them, the component (ii) is preferably contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the component (i) in view of the conventional use.

However, since the component (i) forms a crosslinked structure, the component (ii) is preferably produced by the following method in order to uniformly disperse the component (i) as a matrix. That is, as described in detail below, it is preferable to prepare a polymerizable curable composition (photochromic curable composition) containing a photochromic compound and cure the photochromic curable composition to form a resin composition. In this case, the content of the component (i) is the total amount of polymerizable monomer components forming the component (i) in the photochromic curable composition. Specifically, when the component (i) is formed of the component (a) and the component (B) described in detail below, the content of the component (i) is equal to the total amount of the component (a) and the component (B) ((i) component amount= (a) component amount + (B) component amount). Therefore, in order to make the content of the component (ii) contained in the resin composition preferable, the amount of the component (ii) may be appropriately determined with respect to the total amount of the component (a) and the component (B), as will be described in detail below.

In addition to the component (i) and the component (ii), the resin composition may contain known additives.

Specifically, examples of the polymerization regulator include additives such as ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, coloring inhibitors, antistatic agents, fluorescent dyes, pigments, fragrances, and the like, solvents, leveling agents, internal mold release agents, thiols such as t-dodecyl mercaptan, and the like. These additives are preferably compounded in the photochromic curable composition described in detail below.

The total content of alkali metal ions and alkaline earth metal ions in the resin composition is preferably 500ppm or less. The photochromic compound of the resin composition having a small content of alkali metal ions and alkaline earth metal ions is excellent in durability.

The alkali metal ion and alkaline earth metal ion are not particularly limited. Examples of the alkali metal ion include sodium ion, potassium ion, lithium ion, cesium ion, and the like. Examples of the alkaline earth metal ion include calcium ion, magnesium ion, barium ion, strontium ion, beryllium ion, and radium ion. The alkali metal ion and alkaline earth metal ion include, for example, at least 1 ion selected from the group consisting of sodium ion, potassium ion, cesium ion, and magnesium ion.

The total content of alkali metal ions and alkaline earth metal ions in the resin composition can be determined by fluorescent X-ray analysis. In the measurement, a circular flat plate-like resin composition having a diameter of 40mm and a thickness of 1mm was used as a sample. As the measurement device, for example, a fluorescence X-ray analyzer (ZSX Primus IV) manufactured by Japanese Kogyo Co., ltd was used. The detection limit of the fluorescent X-ray analyzer is, for example, 1ppm.

The total content of alkali metal ions and alkaline earth metal ions in the resin composition is preferably 200ppm or less, more preferably 100ppm or less. The lower limit of alkali metal ions and alkaline earth metal ions in the resin composition was 0ppm or the detection limit of the fluorescent X-ray analyzer.

< characterization of resin composition >

A resin composition having a color development concentration of 0.55 or more, a fading rate of 200 seconds or less, and a heat resistance (softening temperature) of 45 ℃ or more, as measured by the method described in the following examples, can be obtained. When the composition is a composition having a better balance of photochromic properties and heat resistance, the color development concentration can be 0.60 or more, the fading rate can be 95 seconds or less, and the heat resistance (softening temperature) can be 50 ℃ or more. Further, the color development density may be 0.75 or more, the fading speed may be 80 seconds or less, and the heat resistance (softening temperature) may be 60 ℃ or more. In particular, the color development density may be 0.85 or more, the fading speed may be 70 seconds or less, and the heat resistance (softening temperature) may be 70℃or more. The upper and lower limit values of these physical property values are not particularly limited, but the color development concentration is 1.10 or less, the fading rate is 40 seconds or more, and the heat resistance is 90 ℃ or less.

Suitable method for producing resin composition

As described above, in the resin composition, the method for producing the resin composition is not particularly limited as long as the urethane resin contained therein satisfies the conditions. For example, the component (ii) may be immersed in the component (i), or the component (i) and the component (ii) may be mixed. However, in order to disperse the component (ii) in the resin composition effectively, it is preferable to prepare a photochromic curable composition containing a polymerizable monomer for forming a urethane resin and the component (ii). Among them, from the viewpoint that the photochromic curable composition can be easily produced, it is preferable to prepare a photochromic curable composition comprising:

(A) A polyisocyanate component having 2 or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule,

(B) Active hydrogen-containing component having active hydrogen-containing group, and

(ii) The components are as follows. The resin composition is preferably produced by curing (polymerizing) the photochromic curable composition.

The blending ratio of the monomer forming the component (i) is not particularly limited in preparing the photochromic curable composition, but in order to stably obtain the resin composition, it is preferable to blend it as described later. Next, the photochromic curable composition will be described.

Photochromic curable composition

As described above, the photochromic curable composition preferably comprises:

(ii) Photochromic compounds.

The following describes the respective components.

Component (A): a polyisocyanate component having 2 or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule >

(A) In the polyisocyanate component ((a) component) having 2 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 it is 2 or more. Among them, from the viewpoint of easy control of polymerization, it is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2.

The term "polyiso (thio) cyanate compound" refers to a group having 2 or more isocyanate groups and/or isothiocyanate groups.

The component (a) includes an aliphatic isocyanate compound, a cycloaliphatic isocyanate compound, an aromatic isocyanate compound, a sulfur-containing heterocyclic isocyanate compound, a sulfur-containing aliphatic isocyanate compound, an aliphatic thioether isocyanate compound, an aromatic thioether isocyanate compound, an aliphatic sulfone isocyanate compound, an aromatic sulfone isocyanate compound, a sulfonate isocyanate compound, an aromatic sulfonic acid amide isocyanate compound, and the like.

Further, blocked isocyanate compounds obtained by blocking the isocyanate groups of the isocyanate compounds with at least 1 blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds and acetoacetate compounds are also included.

((A) component: suitable polyisocyanate Compound)

Among the polyisocyanate compounds, compounds represented by the following formulas (I) to (VIII) are preferable as compounds for forming a resin composition excellent in transparency and mechanical strength, particularly preferable as compounds for producing a resin composition containing a photochromic compound.

Component (A) aliphatic isocyanate Compound

As the preferable aliphatic isocyanate compound, a compound represented by the following formula is preferably used.

OCN-R ¹⁰⁰ -NCO (I)

(wherein R is ¹⁰⁰ The alkylene group may be an alkylene group having 1 to 10 carbon atoms, or a group in which a part of methylene groups in the chain of the alkylene group is replaced with a sulfur atom. )

The R is ¹⁰⁰ The alkylene group may be a straight-chain or branched-chain group having 1 to 10 carbon atoms. Among them, a straight chain group of pentamethylene, hexamethylene, heptamethylene or octamethylene or a branched chain group in which a part of hydrogen atoms of pentamethylene, hexamethylene, heptamethylene or octamethylene are substituted with methyl groups is preferable. In addition, alkylene groups in which a part of the methylene groups is replaced by sulfur atoms are preferably-CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ -a radical.

Specific examples of the compound represented by the above formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4, -trimethylhexane methylene diisocyanate, and 1, 2-bis (2-isocyanatoethylthio) ethane. These compounds may be used alone or in combination of 2 or more kinds.

(alicyclic isocyanate Compound, aromatic isocyanate Compound)

As the preferable aromatic isocyanate compound and alicyclic isocyanate compound, a compound represented by the following formula (II) or the following formula (III) is preferably used.

(wherein R is ¹⁰¹ Respectively alkyl with 1-4 carbon atoms or hydrogen atoms, optionally the same groups or different groups,

R ¹⁰² is an alkyl group having 1 to 4 carbon atoms, and when a plurality of groups are present, they are optionally the same group or different groups,

a ¹⁰⁰ is an integer and is 2 or 3, b ¹⁰⁰ Is an integer of 0 to 4, c ¹⁰⁰ Is an integer of 0 to 4. ). The difference between the compound represented by the formula (II) and the compound represented by the formula (III) is the difference between the compound having a phenyl group (the compound represented by the formula (II)) and the compound having a cyclohexyl group (the compound represented by the formula (III)).

The R is ¹⁰¹ The alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Wherein R is ¹⁰¹ Particularly preferred are a hydrogen atom, methyl group and ethyl group. In addition, the R ¹⁰² The alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Wherein R is ¹⁰² Methyl and ethyl are particularly preferred.

Examples of the compound represented by the formula (II) or the formula (III) include isophorone diisocyanate, xylylene diisocyanate (ortho, meta, para), 2, 4-xylylene diisocyanate, 2, 6-xylylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, and 1, 4-bis (isocyanatomethyl) cyclohexane. These compounds may be used alone or in combination of 2 or more kinds.

The aromatic isocyanate compound and the alicyclic isocyanate compound are preferably selected from the compounds represented by the following formulas (IV) and (V).

(wherein R is ¹⁰³ Respectively alkyl with 1-4 carbon atoms or hydrogen atoms, optionally the same group or different groups, d ¹⁰⁰ Is an integer of 0 to 4. ) The difference between the compound represented by the formula (IV) and the compound represented by the formula (V) is the difference between a compound having 2 phenyl groups (the compound represented by the formula (IV)) and a compound having 2 cyclohexane groups (the compound represented by the formula (V)).

The R is ¹⁰³ The alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Wherein R is ¹⁰³ Particularly preferred are a hydrogen atom, methyl group and ethyl group.

The compound represented by the formula (IV) or the formula (V) may be, for example, 4 '-diphenylmethane diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate. These compounds may be used alone or in combination of 2 or more kinds.

In addition, as a preferable alicyclic isocyanate compound, a compound represented by the following formula (VI) is preferably used.

(wherein R is ¹⁰⁴ Respectively alkyl of 1 to 4 carbon atoms or a hydrogen atom, optionally the same group or different groups, e ¹⁰⁰ Is an integer of 0 to 4. )

The R is ¹⁰⁴ The alkyl group having 1 to 4 carbon atoms may be a linear or branched group. Wherein R is ¹⁰⁴ Particularly preferred are a hydrogen atom, methyl group and ethyl group.

Specifically, the compound represented by the formula (VI) may be norbornane diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [ 2,1 ] -heptane, or 2, 6-bis (isocyanatomethyl) -bicyclo [ 2,1 ] -heptane. These compounds may be used alone or in combination of 2 or more kinds.

( (A) The components are as follows: alicyclic sulfur-containing heterocyclic isocyanate compound )

As the preferable sulfur-containing heterocyclic isocyanate compound, a compound represented by the following formula (VII) or the following formula (VIII) is preferably used.

(wherein R is ¹⁰⁵ Respectively alkyl with 1-4 carbon atoms or hydrogen atoms, optionally the same groups or different groups,

R ¹⁰⁶ is methylene or sulfur atom, R ¹⁰⁷ Is a C1-6 alkylene group or a group in which a part of methylene groups in the chain of the C1-6 alkylene group is replaced with sulfur atoms, f ¹⁰⁰ Is an integer of 0 to 2. )

Specific examples of the compound represented by the formula (VII) or the formula (VIII) include 2, 5-bis (isocyanatomethyl) thiophene, 2, 5-bis (isocyanatomethyl) -1, 4-dithiane, 3, 4-bis (isocyanatomethyl) tetrahydrothiophene, 4, 5-bis (isocyanatomethyl) -1, 3-dithiane, and the like. These compounds may be used alone or in combination of 2 or more kinds.

Further, halogen substituents, alkyl substituents, alkoxy substituents, nitro substituents, prepolymer-type modifications with polyols, carbodiimide-modified products, urea-modified products, biuret-modified products, dimerization or trimerization reaction products, and the like of the above polyisocyanates can also be used.

(suitable component (A): polyisothiocyanate Compound)

The alicyclic polyisothiocyanate compound (A) may be a compound in which an isocyanate group is replaced with an isothiocyanate group in the polyisocyanate compounds represented by the formulas (I) to (VIII). More specifically, aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, heterocyclic isothiocyanate-containing compounds, sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, and the like can be cited.

Examples of the aliphatic isothiocyanate compound include hexamethylene diisoisothiocyanate, 1, 2-diisoisothiocyanate ethane, 1, 3-diisoisothiocyanate propane, 1, 4-diisoisothiocyanate butane, 1, 6-diisoisothiocyanate hexane, 2,4, -trimethylhexane methylene diisoisothiocyanate, thiobis (3-isothiocyanate propane), thiobis (2-isothiocyanate ethane) and dithiobis (2-isothiocyanate ethane.

Examples of the alicyclic isothiocyanate compound and the aromatic isothiocyanate compound include p-phenylene diisopropylene diisoisothiocyanate, 1, 2-diisoisothiocyanate benzene, 1, 3-diisoisothiocyanate benzene, 1, 4-diisoisothiocyanate benzene, 2, 4-diisoisothiocyanate toluene, isophorone diisoisothiocyanate, xylylene diisoisothiocyanate (ortho, meta, para), 2, 4-xylylene diisoisothiocyanate, 2, 6-xylylene diisoisothiocyanate, cyclohexane diisoisothiocyanate and the like, and examples thereof include 1,1' -methylenebis (4-isothiocyanate benzene), 1' -methylenebis (4-isothiocyanate 2-methylbenzene), 1' -methylenebis (4-isothiocyanate 3-methylbenzene) and the like.

Further, preferable alicyclic isothiocyanate compounds include 2, 4-bis (isothiocyanato methyl) norbornane, 2, 5-bis (isothiocyanato methyl) norbornane, 2, 6-bis (isothiocyanato methyl) norbornane, 3, 5-bis (isothiocyanato methyl) norbornane, norbornanediisoisothiocyanate and the like.

Preferred examples of the sulfur-containing heterocyclic isocyanate compound include thiophene-2, 5-diisothiocyanate, 1, 4-dithiane-2, 5-diisoisothiocyanate, 2, 5-bis (isothiocyanato methyl) -1, 4-dithiane, and 4, 5-bis (isothiocyanato methyl) -1, 3-dithiane.

( (A) The components are as follows: compounds having isocyanate groups and isothiocyanate groups )

The following compounds are examples of the component (a) having two groups, i.e., an isocyanate group and an isothiocyanate group. For example, the polyisocyanate compounds specifically exemplified above are compounds in which at least one isocyanate group is changed to an isothiocyanate group. In addition, the compound is a compound in which at least one isothiocyanate group in the above specifically exemplified polyisothiocyanate compounds is changed to an isocyanate group.

( (A) The components are as follows: compounds having iso (thio) cyanate groups blocked with blocking agents )

The compound having an isocyanate group blocked with a blocking agent (hereinafter also referred to as blocked isocyanate compound) can be obtained by reacting at least 1 blocking agent selected from the group consisting of alcohols, lactams, phenols, oximes, pyrazoles, thiols, active methylene compounds, malonic acid diester compounds and acetoacetate compounds with the isocyanate group of the polyisocyanate compound. The conditions for reacting the blocking agent with the isocyanate (thio) group may be appropriately determined depending on the type of the blocking agent. Protection of the isocyanate group by the blocking agent can be confirmed by fourier transform infrared spectroscopy (FT-IR).

By using blocked iso (thio) cyanate compounds, the pot life of the photochromic composition can be extended.

((preferred example of component (A))

Preferable examples of the component (A) 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 (isocyanatomethyl) -bicyclo [ 2,1 ] -heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [ 2,1 ] -heptane, 1, 2-bis (2-isocyanatoethylthio) ethane, xylene diisocyanate (o, m, p), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4,4' -diphenylmethane diisocyanate, and they may be used alone or in the form of a mixture thereof.

Component (B): active hydrogen-containing component having active hydrogen-containing group

The active hydrogen-containing group in the active hydrogen-containing component (B) having an active hydrogen-containing group is an active hydrogen-containing group. That is, the component (B) is an active hydrogen compound having a group containing active hydrogen. The active hydrogen-containing group refers to a group that can react with an isocyanate group, and examples thereof include a hydroxyl group, an amino group, a carboxyl group, and/or a thiol group.

The component (B) preferably has a polyoxypropylene chain. Further, the component (B) preferably has an alkyl group having 5 to 20 carbon atoms and/or a polyoxyethylene chain in addition to the polyoxypropylene chain. By having these chains and groups in the component (B), a resin composition having a strength ratio (PMIpst/PMICP) of 8.0 to 40.0 can be easily produced.

The ratio (nA/nB) of the total number of moles of active hydrogen-containing groups in the component (B) to the total number of moles of isocyanate groups in the polyisocyanate compound (a) to nA is preferably 1.00 to 1.50, more preferably 1.00 to 1.20. The nA/nB is 1.00 to 1.50, whereby the strength ratio (PMI) can be easily produced _pst /PMI _cp ) A resin composition of 8.0 to 40.0 inclusive. Further, a resin composition having excellent photochromic characteristics and heat resistance can be obtained.

When the nA/nB ratio is less than 1.00 or more than 1.50, the polymerization degree is not improved, and thus the heat resistance is lowered.

The blending ratio of the component (a) and the component (B) is not particularly limited as long as the nA/nB ratio is in the range of 1.00 to 1.50. Wherein the intensity ratio (PMI) is made in consideration of _pst /PMI _cp ) The resin composition satisfying 8.0 to 40.0 and having excellent photochromic properties and heat resistance is preferably 50 to 70 parts by mass, more preferably 60 to 65 parts by mass, based on 100 parts by mass of the total mass of the component (A) and the component (B).

(B) Among the components, the component (B) preferably contains (B1) a multifunctional active hydrogen-containing component having 3 or more active hydrogen-containing groups in the molecule (component (B1)) and (B2) a 1 st active hydrogen-containing component having 1 or 2 active hydrogen-containing groups in the molecule (component (B2)) in view of the photochromic characteristics and mechanical characteristics of the resulting resin composition.

( (B1) The components are as follows: 1 multifunctional active hydrogen-containing component having 3 or more active hydrogen-containing groups in the molecule )

The component (B1) used in the photochromic curable composition is not particularly limited as long as it is a compound having 3 or more active hydrogen-containing groups in the molecule. Among them, compounds having a total of 3 or more hydroxyl groups and thiol groups in the molecule are preferable. Specifically, the compound may be any one of a compound having 3 or more hydroxyl groups in the molecule, a compound having 3 or more thiol groups in the molecule, or a compound having 3 or more total hydroxyl groups and thiol groups in the molecule. In the component (B1), the number of hydroxyl groups and thiol groups is not particularly limited as long as it is 3 or more.

Specific examples of the component (B1) include aliphatic polyhydric (thio) alcohol compounds and aromatic polyhydric (thio) alcohol compounds. More specifically, the following compounds are exemplified.

(suitable polyhydric (thio) alcohol compounds)

Among the above (B1) polyol compounds, the following compounds are exemplified as compounds suitable for forming a transparent/heat-resistant resin composition, in particular, compounds suitable for producing a resin composition containing a photochromic compound. Specifically, compounds represented by the following formulas (IX) to (XVII) are exemplified.

(aliphatic polyhydric (thio) alcohol Compound)

As a preferable aliphatic polyhydric (thio) alcohol compound, a compound represented by the following formula (IX) is preferably used.

{ in formula (IX), R ¹⁰⁸ Is a hydrogen atom or a group synonymous with the following formula (X), optionally the same or different.

(in the formula (X), R ¹¹¹ Is an alkylene group having 1 to 6 carbon atoms. )

R ¹⁰⁹ Respectively a hydrogen atom, a methyl group or an ethyl group, optionally identical or different,

R ¹¹⁰ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when a plurality of the alkyl groups are present, they are optionally the same or different,

o ¹⁰⁰ 0 to 2, p ¹⁰⁰ Is 1 to 6, q ¹⁰⁰ 0 to 10, R ¹⁰⁰ Is 2 to 4 o ¹⁰⁰ +R ¹⁰⁰ 4.

The R is ¹¹¹ The alkylene group may be a straight-chain or branched-chain group having 1 to 6 carbon atoms. Wherein R is ¹¹¹ Particularly preferred are methylene, ethylene, trimethylene and propylene.

Specific examples of the compound represented by the formula (IX) include trimethylolpropane, pentaerythritol, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and the like.

Among the preferred aliphatic polyhydric (thio) alcohol compounds, as the polyfunctional polyhydric (thio) alcohol compound having an ether bond, a compound represented by the following formula (XI) is preferably used.

{ in F ¹⁰⁰ Alkyl groups of 1 to 6 or the following formula (XII), respectively.

(wherein R is ¹¹² Is a hydrogen atom or a radical synonymous with the formula (X), optionally the same or different,

R ¹¹³ each hydrogen atom, methyl or ethyl, optionally the same group or different groups,

s ¹⁰⁰ is 1 to 6, t ¹⁰⁰ 0 to 10. ) }

The F is ¹⁰⁰ Is at least 2 of the groups of formula (XII). The other groups may be alkyl groups of 1 to 6, or chain or branched groups. Wherein F is ¹⁰⁰ Particularly preferred are methyl, ethyl, trimethyl and propyl. In addition, F ¹⁰⁰ As long as 2 or more groups represented by the above formula (XII) are present, they may be the same groups or may be different groups. Specific examples of the compound represented by the formula (XI) include di (trimethylol) propane, dipentaerythritol, di (trimethylol) propane tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and the like.

Among the preferred aliphatic polyhydric (thio) alcohol compounds, as the polyfunctional polythiol compound, a compound represented by the following formula (XIII) is preferably used.

(wherein R is ¹¹⁴ A group which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a group in which a part of methylene group of the alkyl group having 1 to 6 carbon atoms is replaced with a sulfur atom, R ¹¹⁴ Where there are a plurality, optionally the same group or different groups,

R ¹¹⁵ is an alkylene group having 1 to 10 carbon atoms, a group in which a part of methylene groups in the chain of the alkylene group having 1 to 10 carbon atoms is replaced with a sulfur atom or a group in which a part of hydrogen atoms in the alkylene group having 1 to 10 carbon atoms is replaced with a thiol group, R ¹¹⁵ Where there are a plurality, optionally the same group or different groups,

u ¹⁰⁰ v is an integer of 2 to 4 ¹⁰⁰ Is an integer of 0 to 2, u ¹⁰⁰ +v ¹⁰⁰ 4. )

The R is ¹¹⁴ Wherein the alkyl group having 1 to 6 carbon atoms may be a linear or branched group, wherein R ¹¹⁴ Preferably a hydrogen atom, methyl group, ethyl group. In addition, a specific group in which a part of methylene groups in the chain as an alkyl group having 1 to 6 carbon atoms is replaced with a sulfur atomThe group may be-CH ₂ SCH ₃ Etc.

R ¹¹⁵ The alkylene group having 1 to 10 carbon atoms may be a linear or branched group. Wherein R is ¹¹⁵ Particularly preferred are methylene, vinyl, trimethylene and propylene. In addition, specific groups in which a part of methylene groups in the chain of the alkylene group having 1 to 10 carbon atoms is replaced with sulfur atoms include-CH ₂ S-、-CH ₂ CH ₂ S-、-CH ₂ CH ₂ CH ₂ S-, etc. Further, examples of the group in which a part of hydrogen atoms of the alkyl group having 1 to 6 carbon atoms is substituted with a thiol group include-CH ₂ SCH(SCH ₂ SH) -such groups.

Specifically, when the compound represented by the formula (XIII) is mentioned, examples thereof include 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 1-tetrakis (mercaptomethyl) methane 1, 3-tetra (mercaptomethylthio) propane, 1, 2-tetra (mercaptomethylthio) ethane 4, 7-dimercaptomethyl-3, 6, 9-trithio-1, 11-undecanedithiol, 5, 7-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercaptomethyl-3, 6, 9-trithioundecane, and the like.

Among the preferred aromatic poly (thio) alcohol compounds, as the phenyl-group-containing polythiol compound, a compound represented by the following formula (XIV) is preferably used.

(wherein R is ¹¹⁶ Is an alkylene group having 1 to 6 carbon atoms or a group in which a part of methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms is replaced with a sulfur atom, w ¹⁰⁰ 3. )

The R is ¹¹⁶ The alkylene group having 1 to 6 carbon atoms may be a linear or branched group. Wherein R is ¹¹⁶ Preferably a methylene group, an ethylene group, a trimethylene group, and a propylene group. Further, the group in which a part of methylene groups in the chain of the alkylene group having 1 to 6 carbon atoms is replaced with a sulfur atom is specifically exemplified by-CH ₂ CH ₂ CH ₂ SCH ₂ -、-CH ₂ CH ₂ SCH ₂ -、-CH ₂ SCH ₂ -and the like. Specifically, the compound represented by the formula (XIV) is 1,3, 5-tris (mercaptopropylthiomethyl) benzene.

Among the polyhydric (thio) alcohol compounds other than the above, a compound represented by the following formula (XV) is preferably used as the polyhydric (thio) alcohol compound having a triazine ring.

{ in which R ¹¹⁷ An alkyl group having 1 to 6 carbon atoms or a group represented by the following formula (XVI).

(wherein R is ¹¹⁸ R is R ¹¹⁹ Is alkylene of 1 to 6 carbon atoms, R ¹²⁰ Is an oxygen atom or a sulfur atom. ) Wherein the R is ¹¹⁷ At least 2 of the groups of the formula (XVI), R ¹¹⁷ The groups may be the same or different. }

The R is ¹¹⁸ R is R ¹¹⁹ The alkylene group having 1 to 6 carbon atoms may be a linear or branched group. Wherein R is ¹¹⁸ R is R ¹¹⁹ Preferably a methylene group, an ethylene group, a trimethylene group, and a propylene group. Specifically, the compound represented by the formula (XV) is exemplified by 2-mercaptomethanol and tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate.

Among preferred poly (thio) alcohol compounds other than the above, compounds having a silsesquioxane structure may be used. The compound having a silsesquioxane structure has various molecular structures such as cage-like, ladder-like and random, and is a compound represented by the following formula (XVII).

(wherein, a plurality of R ⁵⁰⁰ Optionally identical to or different from each other, are hydrogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, phenyl groups, and at least 1 organic group containing more than 2 hydroxyl and/or thiol groups in the molecule, n ¹⁰⁰ Is an integer of 3 to 100. )

(suitable (B1) component)

The component (B1) may be used without particular limitation, and may be used in combination of various kinds in view of photochromic characteristics and mechanical characteristics of the resulting photochromic cured product. Among them, in order to produce a resin composition having excellent properties and a photochromic curable composition having excellent moldability and good handleability, it is preferable to use a component (B1) having 3 to 6 active hydrogen-containing groups in 1 molecule. Hereinafter, the polyfunctional active hydrogen-containing component having 3 to 6 active hydrogen-containing groups in 1 molecule in the component (B1) may be referred to simply as the component (B1 a).

In the component (B1 a), the strength ratio (PMI) is produced _pst /PMI _cp ) The resin composition satisfying 8.0 to 40.0 and having excellent photochromic properties and heat resistance is preferably a component having 4 to 6 active hydrogen-containing groups in 1 molecule, and most preferably a component having 6 active hydrogen-containing groups in 1 molecule. In addition, the active hydrogen-containing group is preferably a thiol group in view of an increase in viscosity at the time of preparing the photochromic curable composition.

The component (B1) may be composed of only the component (B1 a), but may contain more than 6 active hydrogen-containing groups in 1 molecule, if necessary. Hereinafter, this component will also be referred to simply as the (B1B) component.

First, the component (B1 a) will be described.

Component (B1 a)

When component (B1 a) is used as a suitable component for component (B1), at least 1 of trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, and tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate is preferable, and among these, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and dipentaerythritol hexa (3-mercaptopropionate) is more preferable.

Among them, dipentaerythritol hexa (3-mercaptopropionate) is most preferable because it can improve the photochromic properties and mechanical properties of the resulting photochromic cured product (resin composition). From the standpoint of photochromic properties, it is preferable to use dipentaerythritol hexa (3-mercaptopropionate) alone as the component (B1 a), but when the dipentaerythritol hexa (3-mercaptopropionate) has a high viscosity and a photochromic cured product is obtained by cast polymerization, other components (B1) may be used in combination for adjusting the viscosity.

As the other component (B1 a), preferably trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1, 6-hexanediol bis (3-mercaptopropionate), 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 2-bis (mercaptomethyl) -1, 4-butanedithiol, 2, 5-bis (mercaptomethyl) -1, 4-dithiane 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 1-tetrakis (mercaptomethyl) methane, 1, 3-tetrakis (mercaptomethylthio) propane, 1, 2-tetrakis (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane, tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate, in particular, when trimethylolpropane tris (3-mercaptopropionate) is used in combination, the handleability can be improved while maintaining excellent photochromic properties, and is particularly preferable.

In order to make the intensity ratio (PMI) of the component (i) _pst /PM _Icp ) The resin composition satisfies 8.0 to 40.0 and exhibits particularly excellent effects, and may contain a component (B1) other than the component (B1 a). More specifically, it is preferable to use a component having a larger number of active hydrogen-containing groups contained in the molecule than the component (B1 a). Among them, a polyrotaxane component having a polyrotaxane structure and having 7 or more active hydrogen-containing groups in the molecule (hereinafter, also referred to simply as a (B1B) component) is particularly preferable.

Component (B1B): polyrotaxane composition having more than 6 active hydrogen-containing groups in its molecule

The photochromic curable composition preferably further contains a polyrotaxane component ((B1B) component) having an active hydrogen-containing group in an amount of more than 6 in a molecule. By using the component (B1B), the photochromic properties of the obtained resin composition can be improved by utilizing the mobility of the polyrotaxane itself. Further, by incorporating an oxypropylene chain or the like into the polyrotaxane component, the strength ratio (PMI) of the component (i) can be easily determined _pst /PMI _cp ) Adjusting the temperature to 8.0-40.0. That is, since the mobility of the polyrotaxane component is extremely high, the incorporation of the oxypropylene chain into the polyrotaxane component can easily improve the strength ratio (PMI _pst /PMI _cp ). As a result, the obtained resin composition exhibits excellent photochromic properties.

The component (B1B) is a known compound and has a complex molecular structure composed of a chain-like axial molecule and a cyclic molecule. That is, a plurality of cyclic molecules are bound to a chain-like shaft molecule, and the shaft molecule penetrates the inside of a ring of the cyclic molecule. Therefore, the cyclic molecule can freely slide on the shaft molecule, but a bulky terminal group is formed at both ends of the shaft molecule, thereby preventing the cyclic molecule from falling off from the shaft molecule.

As shown in fig. 3, the polyrotaxane component (B1B) has a composite molecular structure formed of chain-like axial molecules 20 and cyclic molecules 30. More specifically, the structure is as follows: the plurality of cyclic molecules 30 includes chain-shaped shaft molecules 20, and the shaft molecules 20 penetrate the inside of the ring of the cyclic molecules 30. The cyclic molecule 30 can freely slide on the shaft molecule 20, but the terminal groups 40 having a large volume are formed at both ends of the shaft molecule 20, thereby preventing the cyclic molecule 30 from falling off the shaft molecule 20. Thus, it is considered that the cyclic molecule 30 of the polyrotaxane 10 can slide on the axial molecule 20, and thus the photochromic property can be improved. Further, it is considered that by incorporating an oxypropylene chain into such a polyrotaxane, the strength ratio (PMI) can be easily controlled in the obtained resin composition _pst /PMI _cp ) The photochromic characteristics can be improved by adjusting the content to a range of 8.0 to 40.0. In the polyrotaxane 10 shown in fig. 3, a side chain 50 to be introduced into a ring of the cyclic molecule 30 is also shown as needed.

The component (B1B) is a known compound, and can be synthesized by a method described in International publication No. 2015/068798 or the like.

The shaft molecule is not particularly limited as long as it can penetrate the ring of the cyclic molecule, and may be linear or branched. The axial molecules are typically formed from polymers. Suitable polymers for forming the shaft molecule include those listed in International publication No. 2015/068798, and among these, polyethylene glycol is preferably used. By using polyethylene glycol as an axial molecule, an oxyethylene chain is introduced into the obtained resin composition, and the strength ratio (EI _pst /EI _cp ) Is adjusted to a range of 5.0 to 20.0.

The bulky terminal groups formed at both ends of the shaft molecule are not particularly limited as long as they are groups for preventing the cyclic molecule from being detached from the shaft molecule. Specifically, adamantyl is preferable.

The mass average molecular weight (Mw) of the axial molecule is not particularly limited, and is preferably in the range of 1000 to 100000, more preferably in the range of 5000 to 80000, and even more preferably in the range of 10000 to 50000. When the mass average molecular weight (Mw) of the axial molecule is 1000 or more, the fluidity of the cyclic molecule tends to be improved. In addition, when the mass average molecular weight (Mw) of the axial molecule is 100000 or less, compatibility with other components tends to be improved. In addition, when polyethylene glycol is used as the axial molecule, the strength ratio (EI _pst /EI _cp ) Is adjusted to 5.0 to 20.0. As a result, the photochromic characteristics can be improved.

The cyclic molecule has a ring of a size that can encapsulate the shaft molecule. Examples of such a ring include cyclodextrin rings. The cyclodextrin ring has an alpha body (ring inner diameter: 0.45 to 0.6 nm), a beta body (ring inner diameter: 0.6 to 0.8 nm) and a gamma body (ring inner diameter: 0.8 to 0.95 nm), and is preferably an alpha-cyclodextrin ring.

In addition, more than 1 cyclic molecule is wrapped on one shaft molecule. When the maximum number of cyclic molecules that can be bonded to each 1 axial molecule is 1.0, the number of cyclic molecules bonded is usually in the range of 0.001 to 0.6, preferably in the range of 0.002 to 0.5, and more preferably in the range of 0.003 to 0.4.

The maximum number of the cyclic molecules to be bound to 1 axial molecule can be calculated from the length of the axial molecule and the thickness of the ring of the cyclic molecule. For example, taking the case where the chain portion of the shaft molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α -cyclodextrin ring as an example, the maximum number of bonds can be calculated as follows. Namely, 2 repeating units of polyethylene glycol [ -CH ₂ -CH ₂ O-]Approximately 1 a-cyclodextrin ring thickness. Therefore, the number of repeating units is calculated from the molecular weight of the polyethylene glycol, and 1/2 of the number of repeating units is obtained as the maximum number of cyclic molecules. The maximum number of packets was set to 1.0, and the number of packets of the cyclic molecule was adjusted to the above range.

The cyclic molecule may have a side chain introduced therein. When side chains are introduced in this manner, a pseudo-crosslinked structure can be formed in the obtained resin composition ((i) component). This can improve the mechanical properties of the resin composition and improve the photochromic properties.

The side chain is preferably formed of a repeating unit of an organic group 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, still more preferably in the range of 300 to 5000, and particularly preferably in the range of 300 to 1500.

The side chain may be introduced by modifying a functional group (for example, a hydroxyl group) of a ring of the cyclic molecule with the functional group. For example, in the α -cyclodextrin ring, 18 hydroxyl groups are present as functional groups, and a side chain can be introduced through the hydroxyl groups. That is, a maximum of 18 side chains can be introduced with respect to 1 α -cyclodextrin ring. In order to fully exert the functions of the side chains, it is preferable that 6% or more, particularly 30% or more of the total functional groups of the ring be modified with the side chains. The degree of modification of the α -cyclodextrin ring was 50% when 9 of the 18 hydroxyl groups of the ring were bonded with side chains.

The side chain may be linear or branched. For the side chain, by using ring-opening polymerization; free radical polymerization; cationic polymerization; anionic polymerization; living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, etc.; and the like, a side chain of an appropriate size can be introduced by reacting an appropriate compound with a ring of a cyclic molecule. The cyclic compound is preferably a cyclic lactone or a cyclic carbonate, and more preferably epsilon-caprolactone.

When a side chain is introduced by reacting a cyclic compound by ring opening polymerization, there is a case where it is difficult to directly react a large molecule due to lack of reactivity of a functional group (for example, a hydroxyl group) bonded to a ring, steric hindrance, or the like. In this case, for example, the following method can be adopted: a low molecular compound such as propylene oxide is first reacted with a functional group to undergo hydroxypropylation, and a functional group (hydroxyl group) having high reactivity is introduced, and then a side chain is introduced by ring-opening polymerization using the above-mentioned cyclic compound. The low molecular weight compound such as propylene oxide may be regarded as a side chain. The propylene oxide incorporated in the side chain can be regarded as an oxypropylene chain. Therefore, particularly when propylene oxide is used to introduce a hydroxyl group having a high reactivity, the strength ratio (PMI) _pst /PMI _cp ) Adjusting the temperature to 8.0-40.0.

Preferably, a polymerizable functional group selected from a hydroxyl group and a thiol group is introduced into the terminal of the side chain, and particularly, most preferably, a polymerizable functional group selected from a hydroxyl group is introduced. When an alkyl group is introduced into the terminal of the side chain, the strength ratio (AMI) is, of course, similar to that of the oxypropylene chain and the oxyethylene chain _pst /AMI _cp ) Comprising the peak of the alkyl group.

The most preferably used component (B1B) satisfies the following conditions. Specifically, polyethylene glycol having adamantyl groups bonded to both ends is used as an axial molecule, a cyclic molecule having an α -cyclodextrin ring is used as a cyclic molecule, an activated hydroxyl group is introduced into the cyclic molecule through propylene oxide, and a side chain having a hydroxyl group at the end is introduced into the cyclic molecule through the hydroxyl group and polycaprolactone.

The ratio of modification of the α -cyclodextrin ring (degree of modification; rate of introduction of side chain) is preferably 30% to 70% inclusive, with the oxyethylene chain as an axial molecule having a molecular weight of 8000 to 30000 and an introduction ratio of the α -cyclodextrin ring in the range of 0.003 to 0.4. The root of the side chain is preferably an oxypropylene unit. Further, it is preferable that a side chain having an average molecular weight of 400 to 1500 containing an oxypropylene unit is introduced into the α -cyclodextrin ring. The component (B1B) preferably has a weight average molecular weight of 10 to 20 ten thousand and contains 150 to 350 hydroxyl groups per 1 molecule although it is an average value.

Configuration of suitable active Hydrogen-containing groups in component (B1)

(B1) The components preferably used are the polyfunctional active hydrogen-containing components listed above. Among them, a polyfunctional active hydrogen-containing component having the following structure is preferably used. That is, the component (B1) preferably contains a compound having a quaternary carbon atom in the molecule and all groups bonded to the quaternary carbon atom have active hydrogen-containing groups. It is considered that by using a compound having active hydrogen-containing groups in all groups bonded to quaternary carbon atoms, free space in which a photochromic compound can perform molecular movement can be efficiently formed in the resulting resin upon polymerization.

The reason for this is not clear, but is considered as follows. The description will be made with reference to the drawings. In fig. 4, compounds in which all groups bonded to quaternary carbon atoms have active hydrogen-containing groups (hereinafter, also referred to simply as "fully substituted compounds") are exemplified. Fig. 4 (a) shows an example of a "fully substituted compound" in which all of the 4 groups bonded to the quaternary carbon atom have active hydrogen-containing groups. In fig. 5, a compound having an active hydrogen-containing group as a partial group bonded to a quaternary carbon atom (hereinafter, also referred to as "partially substituted compound") is exemplified. Fig. 5 (B) shows an example of a "partially substituted compound" in which 3 groups bonded to quaternary carbon atoms have active hydrogen-containing groups. In fig. 4 and 5, S is a schematic representation of an active hydrogen-containing group. Arrows indicate the direction of polymer growth.

As shown in fig. 4, when the fully substituted compound is used, the groups having active hydrogen-containing groups are arranged so as to form tetrahedra around quaternary carbon atoms. And, it is considered that the polymer grows three-dimensionally upon polymerization. As a result, it is considered that a free space is effectively formed in a matrix formed of a polymer grown in three dimensions, and a photochromic compound easily undergoes molecular movement. An example of the case where all groups bonded to 1 quaternary carbon atom have active hydrogen-containing groups is shown in fig. 4, but it can be said that the same is true of the case where there are 4 or more active hydrogen-containing groups. Dipentaerythritol hexa (3-mercaptopropionate), for example, is a compound having 2 quaternary carbon atoms. And, the group bonded to the quaternary carbon atom can be regarded as 3 groups having 1 thiol group, 1 group having 3 thiol groups. Thus, dipentaerythritol hexa (3-mercaptopropionate) can be considered a fully substituted compound. In the fully substituted compound, at least 1 quaternary carbon atom having a group containing active hydrogen is present in the molecule in each of the 4 groups bonded thereto. In addition, the number of active hydrogen-containing groups of the total substituted compound is preferably 4 to 6 in view of ease of handling and ease of manufacturing itself.

On the other hand, as shown in fig. 5, when a partially substituted compound is used, the group having an active hydrogen-containing group is not arranged so as to form a 4-face body. It is therefore presumed that, unlike when a fully substituted compound is used, the polymer does not grow three-dimensionally during polymerization, and the space in which the photochromic compound can undergo molecular motion is reduced.

Based on the above, among the components (B1), the component belonging to the total substituted compound is particularly preferably used.

Component (B2): 1 st active hydrogen-containing component having 1 or 2 active hydrogen-containing groups in the molecule >, 1

In addition to the component (B1), the photochromic curable composition preferably further contains, as the component (B2), a 1 st active hydrogen-containing component having 1 or 2 active hydrogen-containing groups in 1 molecule. The active hydrogen-containing component 1 may be used alone or in combination of 1 or more.

Specific examples of the component (B2) include a monoalkyl ether compound having an oxypropylene chain (active hydrogen-containing component 1 having 1 active hydrogen-containing group in the molecule) and a diol compound having an oxypropylene chain (active hydrogen-containing component 1 having 2 active hydrogen-containing groups in the molecule). Among them, polyoxyethylene polyoxypropylene monoalkyl ether compounds or polyoxyethylene polyoxypropylene glycol compounds can be mentioned.

The component (B2) is not particularly limited, but is a component satisfying the peak intensity ratio (PMI) of the NMR _pst /PMI _cp 、AMI _pst /AMI _cp 、EI _pst /EI _cp ) The number average molecular weight is preferably 500 or more, and the photochromic properties of the resulting resin composition can be improved. In order to achieve both excellent photochromic properties and mechanical properties, the number average molecular weight of the component (B2) is preferably 600 or more, more preferably 700 or more. In addition, in order to satisfy the intensity ratio (PMI _pst /PMI _cp ) The upper limit of the molecular weight is preferably 3000 in view of the optical characteristics (suppression of white turbidity) of the resulting resin composition.

When the component (B2) has an oxypropylene chain, the component (B) is a repeating unit (-CH) of an oxypropylene group ₂ CH(CH ₃ L of the average value of O-) is preferably 2 or more and 25 or less. In addition, the component (B2) preferably contains an oxyethylene chain as a repeating unit (-CH) of an oxyethylene group ₂ CH ₂ M, the average value of O-) is preferably 5 to 25. The component (B2) may contain an alkyl group having preferably 5 to 20 carbon atoms.

By using the photochromic curable composition containing the component (B2), the obtained photochromic cured product (resin composition) can exhibit not only excellent photochromic characteristics but also the following features. For example, when the photochromic curable composition containing the component (B2) is cured in a mold made of inorganic glass, the releasability of the obtained photochromic cured product from the inorganic glass mold is improved. When a compound having 1 active hydrogen-containing group in 1 molecule is used, the release property improving effect can be remarkably exhibited.

Further, when the photochromic curable composition containing the component (B2) is used, the adhesion to other optical substrates can be improved by adjusting the blending ratio of the component (a). Examples of the other optical substrate include a known plastic substrate and an inorganic glass substrate. In particular, when the blending ratio of the component (a) is large, the adhesion to the inorganic glass substrate can be improved.

The compound having 1 active hydrogen-containing group in 1 molecule (hereinafter also simply referred to as component (B21)) or the compound having 2 active hydrogen-containing groups in 1 molecule (hereinafter also simply referred to as component (B22)) in the component (B2) will be described in more detail.

Component (B21)

(B21) The component (A) is not particularly limited, but a compound represented by the following formula (XVIII) is preferably used.

Wherein l ', m ' and n ' are integers of 1 to 30, respectively.

In the formula (XVIII), l' means a repeating unit of oxypropylene group. And l' is an average value and is an integer of 1 to 30. Wherein, in order to easily manufacture the intensity ratio (PMI _pst /PMI _cp ) The resin composition satisfying the range of 8.0 to 40.0, preferably 10.0 to 15, and having excellent properties is preferably 2 to 25, more preferably 2 to 5.

M' in the formula (XVIII) means a repeating unit of an oxyethylene group. And m' is an average value and is an integer of 1 to 30. Wherein, in order to easily manufacture the strength ratio (EI _pst /EI _cp ) The resin composition satisfying 5.0 to 20.0 and having excellent properties is preferably 5 to 25, more preferably 7 to 12.

In the formula (XVIII), n' represents the number of carbons of the alkyl group at the terminal. And n' is an integer of 1 to 30. Wherein, in order to easily manufacture the intensity ratio (AMI _pst /AMI _cp ) The resin composition satisfying 7.0 to 23.0 and having excellent properties is preferably 5 to 20, more preferably 10 to 18.

As preferable specific examples of the component (B21) represented by the above formula (XVIII), polyoxyethylene polyoxypropylene monolauryl ether (recurring unit of oxyethylene group m=10, recurring unit of oxypropylene group l=2, carbon number of terminal alkyl group is 12, number average molecular weight 750), polyoxyethylene polyoxypropylene monolridecyl ether (recurring unit of oxyethylene group m=11, recurring unit of oxypropylene group l=2, carbon number of terminal alkyl group is 13, number average molecular weight 800), polyoxyethylene polyoxypropylene monolearyl ether (recurring unit of oxyethylene group m=9, recurring unit of oxypropylene group l=6, carbon number of terminal alkyl group is 18, number average molecular weight 1000) can be cited.

Regarding the component (B21) represented by the above formula (XVIII), the polyoxyethylene polyoxypropylene site is represented as a block copolymer in the chemical formula, but the site may be a random copolymer. Of course, although this site may be a block copolymer, in order to easily produce the strength ratio (PMI _pst /PMI _cp ) The resin composition satisfying the range of 8.0 to 40.0, preferably 10.0 to 15 is preferably a random copolymer, which has excellent properties. That is, in the polyoxyethylene polyoxypropylene monolauryl ether, polyoxyethylene polyoxypropylene monolridecyl ether, polyoxyethylene polyoxypropylene monolearyl ether, and polyoxyethylene polyoxypropylene sites are also preferably random copolymers.

By using the component (B21), the polymerization moldability of the photochromic curable composition can be further improved. That is, since the component (B21) is monofunctional, a rapid increase in viscosity of the photochromic curable composition can be suppressed. In general, the photochromic curable composition is prepared by storing the component (A) and the component (B) separately. In the production of the resin composition, the component (a), the component (B), and optional components to be blended as needed are mixed, and the photochromic curable composition is prepared. If a rapid increase in viscosity occurs during mixing, it may be difficult to obtain a uniform resin composition. Therefore, it is preferable that the viscosity of the photochromic curable composition is not changed until the conditions (e.g., temperature) for initiating the polymerization are reached. By using the component (B21), this temperature increase can be suppressed. For the above reasons, as the component (B2), both the component (B21) and the component (B22) may be used at the same time, but it is preferable to use only the component (B21).

Component (B22)

(B22) The component (c) is not particularly limited, but a compound represented by the following formula (XIX) is preferably used.

Wherein l "and m'" +m "are integers of 1 to 30, respectively.

In the formula (XIX), l "means a repeating unit of oxypropylene group. And, l' is an average value, and is an integer of 1 to 30. Wherein, in order to easily manufacture the intensity ratio (PMI _pst /PMI _cp ) The resin composition satisfying the range of 8.0 to 40.0, preferably satisfying the range of 20.0 to 35.0 is excellent in characteristics, and l' is preferably 2 to 25, more preferably 12 to 20.

M ", m'" in the formula (XIX) means a repeating unit of an oxyethylene group. And m ', m ' is an average value, m "+m '" is an integer from 1 to 30. Wherein, in order to easily manufacture the strength ratio (EI _pst /EI _cp ) The resin composition satisfying 5.0 to 20.0 and having excellent properties is preferably 5 to 25, more preferably 10 to 20, m "+m'".

To satisfy the intensity ratio (PMI _pst /PMI _cp 、EI _pst /EI _cp ) In consideration of the photochromic characteristics of the resulting resin composition, the component (B22) represented by the formula (XIX) may be a block copolymer type polyoxyethylene polyoxypropylene glycol represented by the formula (XIX).

Specifically, polyoxyethylene polyoxypropylene glycol having a number average molecular weight of 1600 (l "=16, m" +m ' "=14), polyoxyethylene polyoxypropylene glycol having a number average molecular weight of 1900 (l" =16, m "+m '" =22), and polyoxyethylene polyoxypropylene glycol having a number average molecular weight of 2000 (l "=21, m" +m ' "=18) may be mentioned.

( A photochromic curable composition; (A) Preferable blending ratio of component (B1) and component (B2) )

In the photochromic curable composition, the blending ratio of the component (a) and the component (B) (component (B1) and component (B2)) is preferably in the following range. Specifically, when the total mole number of isocyanate groups in the component (a) is nA and the total mole number of active hydrogen-containing groups in the component (B1) and the component (B2) is nB, nA/nb=1.00 or more and 1.50 or less, more preferably 1.00 or more and 1.20 or less, still more preferably 1.02 or more and 1.15 or less, and most preferably 1.04 or more and 1.10 or less. The PMI can be satisfied by satisfying nA/nB in a range of 1.00 to 1.50 inclusive _pst /PMI _cp 、AMI _pst /AMI _cp 、EI _pst /EI _cp A photochromic cured product having excellent photochromic properties, durability and heat resistance.

In the above range, in curing the photochromic curable composition in an inorganic glass mold, nA/nB is particularly preferably 1.00 to 1.09 in order to improve releasability between the obtained photochromic cured product and the mold. However, even when nA/nB exceeds 1.09, releasability can be improved by compounding a release agent described in detail below in the photochromic curable composition.

In the above range, nA/nB is preferably 1.10 or more and 1.50 or less, and preferably 1.10 or more and 1.40 or less, when the adhesion (bonding) property with an optical substrate made of inorganic glass is improved.

When a laminate is produced using the photochromic curable composition, when the optical substrate on the object side to be laminated is plastic, nA/nB is 1.00 or more and 1.50 or less, the laminate can be sufficiently bonded to the optical substrate. Among them, nA/nB is preferably 1.05 to 1.20 in order to produce a laminate excellent in adhesiveness, photochromic properties, and mechanical properties.

However, when the photochromic curable composition is used in the case of joining a polarizing film comprising a polyvinyl alcohol-based resin to another substrate (for example, an optical substrate made of plastic or inorganic glass other than the polyvinyl alcohol), nA/nB is preferably in the following range. Specifically, when a polyvinyl alcohol-based polarizing film is present on a laminated object, nA/nB is preferably 1.10 or more and 1.50 or less, and more preferably 1.20 or more and 1.40 or less.

In order to produce a photochromic cured product having excellent photochromic properties, durability and heat resistance, it is preferable that nB1/nB 2=10.0 to 30.0, more preferably 12.0 to 25.0, and most preferably 12.0 to 22.0, when the total mole number of active hydrogen-containing groups in the component (B1) and the component (B2) is nB1 and nB2, respectively. When the component (B1) contains the component (B1B), the number of moles of the active hydrogen-containing group in the component (B1B) is calculated from, for example, the hydroxyl value.

The photochromic curable composition preferably satisfies the ranges described above in terms of the respective mole numbers, but preferably satisfies the following ranges when expressed in terms of mass ratio.

(A) The blending ratio of the mass of the component (B1) and the mass of the component (B2) are not particularly limited, but the following ranges are preferably satisfied in order to obtain excellent photochromic characteristics, durability and heat resistance of the photochromic cured product. The amount of the component (A) is preferably 20 to 74 parts by mass, the amount of the component (B1) is preferably 20 to 75 parts by mass, and the amount of the component (B2) is preferably 5 to 40 parts by mass, based on 100 parts by mass of the total of the components (A), (B1) and (B2). Further, it is preferable that the following compounding amount is satisfied. The total amount of the component (a), the component (B1) and the component (B2) is preferably 25 to 71 parts by mass, the component (B1) is 23 to 67 parts by mass, the component (B2) is 6 to 30 parts by mass, the component (a) is more preferably 25 to 69 parts by mass, the component (B1) is 23 to 67 parts by mass, the component (B2) is 6 to 30 parts by mass, the component (a) is more preferably 30 to 63 parts by mass, the component (B1) is 30 to 60 parts by mass, the component (B2) is 7 to 20 parts by mass, and the component (a) is most preferably 30 to 57 parts by mass, the component (B1) is 35 to 60 parts by mass, and the component (B2) is 8 to 20 parts by mass.

Among them, in order to exert particularly excellent effects, the mass ratio ((B21)/(B1)) of the mass of the (B21) component to the mass of the (B1) component is more preferably 0.35 or more and 0.65 or less, and still more preferably 0.40 or more and 0.55 or less, in order to use the (B21) component as the (B2) component.

< other additives; (C) Polymerization curing accelerator >

Depending on the types of the above components, the photochromic curable composition may contain various (C) polymerization curing accelerators (hereinafter also referred to as (C) components) in order to accelerate the polymerization curing.

A reaction catalyst for urethane or urea used in the reaction of the hydroxyl group and thiol group with the isocyanate group and isothiocyanate group, and a condensing agent can be used as a polymerization curing accelerator.

The reaction catalyst for urethane or urea is used for forming a poly (thio) urethane bond by the reaction of a poly (iso (thio) cyanate with a polyol or polythiol. Examples of the reaction catalyst for carbamates and ureas include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, lewis acids, and organic sulfonic acids. Specific examples thereof include the following. In addition, if the catalytic activity is too high, the catalytic activity can be suppressed by using a tertiary amine and a lewis acid in combination, depending on the kind of the above-mentioned compound selected.

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' -trimethylenebis (1-methylpiperidine), 1, 8-diazabicyclo- (5, 4, 0) -7-undecene.

Phosphines: trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (dimethylphosphino) ethane.

Quaternary ammonium salts: tetramethyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide.

Quaternary phosphonium salts: tetramethyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide.

Lewis acid: triphenylaluminum, dimethyltin dichloride, dimethyltin bis (isooctylthioacetic acid), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate polymer, dibutyltin dittanoleate, dibutyltin bis (dodecylmercaptan), dibutyltin bis (isooctylthioacetic acid), dioctyltin dichloride, dioctyltin maleate polymer, dioctyltin bis (butylmaleic acid), dioctyltin dilaurate, dioctyltin ditricinoleate, dioctyltin dioleate, dioctyltin di (6-hydroxy) hexanoate, dioctyltin bis (isooctylthioacetic acid) and didodecyl ditricinoleate.

Organic sulfonic acid: methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid.

(polymerization initiator as condensing agent)

Specific examples of the condensing agent include the following.

Inorganic acid: hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, and the like.

Organic acid: p-toluenesulfonic acid, camphorsulfonic acid, and the like.

Acidic ion exchange resin: amberlite, amberlyst, etc.

Carbodiimide: dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide.

The amount of each of the above-mentioned components (C) may be 1 alone or 2 or more, and is preferably a so-called catalyst amount, for example, a small amount in the range of 0.001 to 10 parts by mass, particularly 0.01 to 5 parts by mass, based on 100 parts by mass of the total of the above-mentioned components (A) and (B).

< other additives >)

The photochromic curable composition may be blended with various additives known per se, for example, an ultraviolet absorber, an antistatic agent, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a colorant, an antistatic agent, a fluorescent dye, a pigment, a perfume, and other additives, a solvent, a leveling agent, an internal mold release agent, and a thiol type polymerization regulator such as t-dodecyl mercaptan, as required, within a range that does not impair the effect.

Among them, in view of improving the durability of the photochromic compound, an ultraviolet stabilizer is preferably used. As such ultraviolet stabilizers, hindered amine light stabilizers, hindered phenol antioxidants, sulfur antioxidants, and the like are known. Particularly preferred ultraviolet stabilizers include bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, 2, 6-di-t-butyl-4-methylphenol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ], and the like, and commercially available products include ADEKA STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87, ciba Specialty Chemicals Inc. IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, and the like.

In addition, in view of improving the durability and photochromic property of the photochromic compound, an ultraviolet absorber is preferably used. 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, malonate-based ultraviolet absorbers, and cinnamate-based ultraviolet absorbers.

Among them, cyanoacrylate-based ultraviolet absorbers, diphenylacrylate-based ultraviolet absorbers, phenol-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, malonate-based ultraviolet absorbers, and cinnamate-based ultraviolet absorbers are preferably used, and particularly from the viewpoint of improving durability without impairing photochromic properties (particularly color development concentration) as compared with when no ultraviolet absorber is used, cinnamate-based ultraviolet absorbers are particularly preferably used.

In addition, when the releasability of the resin composition is poor, an internal release agent may be used. The internal mold release agent may be any one that has an effect of releasability and does not impair physical properties such as transparency of the resin, and a surfactant is preferably used. Among them, a phosphate-based surfactant is preferable. Here, the internal mold release agent also includes a substance exhibiting a mold release effect among the above-mentioned various catalysts, and for example, quaternary ammonium salts and quaternary phosphonium salts may be included. These internal mold release agents are appropriately selected depending on the combination with the monomer, polymerization conditions, economy, and ease of handling. Specific examples of the internal mold release agent for phosphate esters are described below.

There may be mentioned: acid alkyl phosphate: mono-n-butyl phosphate, mono-2-ethylhexyl phosphate, shan Zhengxin phosphate, mono-n-butyl phosphate, bis (2-ethylhexyl) phosphate, di-n-octyl phosphate, di-n-butyl phosphate, butyl acid phosphate (mixture of monoesters, diesters), ethyl acid phosphate (mixture of monoesters, diesters), butoxyethyl acid phosphate (mixture of monoesters, diesters), 2-ethylhexyl acid phosphate (mixture of monoesters, diesters), isotridecyl acid phosphate (mixture of monoesters, diesters), ditetradecyl acid phosphate (mixture of monoesters, diesters), stearyl acid phosphate (mixture of monoesters, diesters)

Other phosphates: acid oil phosphates (mixture of monoesters and diesters), dibutyl pyrophosphate, glycol acid phosphates (mixture of monoesters and diesters), acid butoxyethyl phosphates (mixture of monoesters and diesters), and the like.

The other compounding agents may be used alone or in combination of 1 or 2 or more, and the amount thereof is preferably small, for example, 0.001 to 10 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

Alkali metal ion, alkaline earth metal ion >

The total amount of alkali metal ions and alkaline earth metal ions in the photochromic curable composition is preferably 500ppm or less. When the amount of the alkali metal ion and the alkaline earth metal ion in the photochromic curable composition is 500ppm or less, the photochromic compound has excellent color development durability, that is, a cured product in which the photochromic compound can develop color for a long period of time can be realized. The reason is considered as follows.

First, in the synthesis of the constituent components of the photochromic curable composition such as an active hydrogen compound, alkali metal salts or alkaline earth metal salts may be used or these metal salts may be formed. In the synthesized active hydrogen compound or the like, these metal salts may remain in a trace amount as impurities. Among counter anions contained in the alkali metal salt or the like, carboxylate ions act on the iso (thio) cyanate group of the poly (thio) cyanate compound, whereby the poly (thio) cyanurate compound in which isocyanate groups are bonded to form a cyclic form can be produced. That is, when an alkali metal salt or the like is contained in the photochromic curable composition, the isocyanate (thio) component is excessively consumed, and a polyisocyanate compound or the like may be by-produced. The active hydrogen compound in the photochromic curable composition is excessive due to excessive consumption of the iso (thio) cyanate component. In the cured product of the photochromic composition in which the active hydrogen compound is present in excess, for example, the active hydrogen group such as a thiol group is present in excess. These excessive active hydrogen groups can generate radicals by ultraviolet rays, and thus can become a cause of deterioration of the cured product.

Based on the above, by reducing the amounts of the alkali metal salt and the alkaline earth metal salt in the photochromic curable composition, deterioration of the cured product can be suppressed. The amounts of the alkali metal salt and the alkaline earth metal salt in the photochromic curable composition can be estimated from the amounts of the alkali metal ion and the alkaline earth metal ion in the photochromic composition.

The total amount of alkali metal ions and alkaline earth metal ions in the photochromic curable composition can be determined by inductively coupled plasma (Inductively Coupled Plasma:ICP) emission spectrometry. In the measurement, for example, 10g of the photochromic curable composition was dissolved in 20g of chloroform to obtain 30g of a solution. To this solution 20g of 1% HNO were added ₃ Extracting the supernatant. The extracted supernatant was used as a measurement sample. As the measurement device, for example, an ICP emission spectrometry device (iCAP 6500 DUO) manufactured by Thermo Fisher Scientific corporation is used. The detection limit value of the ICP emission spectrometry is, for example, 1ppb. The concentration of alkali metal ions and the like is calculated by a standard curve method.

The total content of alkali metal ions and alkaline earth metal ions in the photochromic curable composition is preferably 200ppm or less, more preferably 100ppm or less. The lower limit of alkali metal ions and alkaline earth metal ions in the photochromic composition was 0ppm or the detection limit of the ICP emission spectrum analyzer.

The content of the alkali metal salt, alkaline earth metal salt, alkali metal ion, alkaline earth metal ion, and their counter anions in the photochromic curable composition can be reduced by, for example, water washing treatment or treatment of contact with various adsorbents, ion exchange resins, and the like. The amount of alkali metal salt or the like can be further reduced by allowing the photochromic curable composition to have a long water washing time, or by increasing the amount of the adsorbent and the ion exchange resin, or by allowing the composition to be in contact with them for a long time. Instead of the alkali metal ion reduction treatment of the photochromic curable composition, the photochromic curable composition may be prepared using the constituent components such as the active hydrogen compound subjected to the above reduction treatment as a raw material.

Process for producing photochromic curable composition

The photochromic curable composition may be prepared by mixing the above-mentioned (ii) photochromic compound, (a) component, (B) component and other compounding components by a known method, and is not particularly limited. For example, the component (ii) is dissolved in the component (a), and then the component (B) is further added thereto and stirred, thereby obtaining the photochromic curable composition. The stirring temperature is 0-100 ℃, and the stirring time is properly adjusted within the range of 0.1-48 hours.

By using the component (B21), an increase in viscosity at the time of producing the photochromic curable composition can be suppressed.

Since the isocyanate (thio) group is present in the molecule of the component (a), it is preferable to manufacture the component (a) under an inert gas atmosphere such as argon or nitrogen in order to suppress the mixing of moisture.

Photochromic optical article

The photochromic optical article can be obtained by polymerizing a photochromic curable composition to form a photochromic cured product. The polymerization is generally carried out by thermal polymerization. The cured product is a resin composition, and a photochromic optical article formed from the resin composition can be produced.

When the photochromic curable composition is thermally polymerized, particularly, the temperature affects the properties of the resulting photochromic cured product. The temperature conditions are affected by the kind and amount of the polymerization initiator and the kind of the compound, and therefore cannot be defined in any way, but a method of initiating polymerization at a relatively low temperature and slowly increasing the temperature is generally preferred. The polymerization time varies depending on various factors, like the temperature, and therefore, it is preferable to determine the optimum time in advance according to these conditions, but it is generally preferable to select the conditions so that the polymerization ends within 2 to 48 hours. When the photochromic laminate is obtained, polymerization is carried out at a temperature at which the reaction between the polymerizable functional groups proceeds, and in this case, the optimum temperature and time are preferably determined so as to be the target molecular weight.

The method for polymerizing the photochromic curable composition to obtain a photochromic optical article is not particularly limited, and for example, a known method described below can be used when a photochromic lens which is one type of optical article is produced.

In the production of the photochromic lens by the kneading method, the photochromic composition is injected between inorganic glass molds held by an elastomer gasket or a spacer, and after sufficient deaeration, the photochromic composition is polymerized by casting under heating in an air oven or in water, whereby a photochromic cured product (photochromic optical article) molded into the form of an optical material such as a lens can be obtained.

In addition, an optical substrate such as a lens substrate is disposed so as to form a predetermined gap, and a photochromic curable composition is injected into the gap, and in this state, a photochromic lens (a laminate of photochromic optical articles) in which a photochromic layer is formed on the surface of the optical substrate is obtained by cast polymerization using an in-mold polymerization by heating polymerization (a laminate is produced by cast polymerization). The optical substrate is not particularly limited, and an optical substrate formed of a known plastic may be used. Specifically, plastic materials such as (meth) acrylic resins, polycarbonate resins, acrylic resins, thiocarbamate resins, urethane resins, and thiocpoxy resins can be used.

When the photochromic layer is formed on the surface of the optical substrate by the above-described cast polymerization method, the adhesion between the photochromic layer and the optical substrate can be improved by subjecting the surface of the optical substrate to a chemical treatment with an alkali solution, an acid solution or the like, a physical treatment with corona discharge, plasma discharge, polishing or the like in advance. Of course, a transparent adhesive resin layer may be provided on the surface of the optical substrate in advance.

Further, a necessary amount of the photochromic curable composition may be applied to an optical substrate such as one inorganic glass on which a spacer is disposed, and after another optical substrate such as glass is disposed thereon, the applied photochromic curable composition may be cured to join a pair of optical substrates such as inorganic glass optical objects. A photochromic lens (a laminate of photochromic optical articles) obtained by joining a pair of optical substrates such as glass optical articles (glass bonding method) can be obtained.

In addition, when a photochromic lens is manufactured by an adhesive method, first, a photochromic sheet formed from a photochromic curable composition is manufactured. The obtained photochromic sheet was sandwiched between 2 transparent sheets (optical sheets) and the polymerization was performed as described above, whereby a photochromic laminate having a photochromic layer as an adhesive layer was obtained.

In this case, a method of coating with a coating liquid obtained by dissolving the photochromic curable composition in an organic solvent may be used for the production of the photochromic sheet.

The photochromic laminate thus produced is, for example, mounted in a mold, and then an optical substrate such as a lens is injection molded with a thermoplastic resin (for example, polycarbonate) to obtain a photochromic lens having a predetermined shape, in which the photochromic laminate is laminated. The photochromic laminate may be bonded to the surface of the optical base material by an adhesive or the like, thereby obtaining a photochromic lens.

In the case of producing a photochromic laminate as described above, it is preferable to use a urethane or urea polymerizable compound, particularly a urethane polymerizable compound, as the polymerizable compound, in order to form polyurethane, particularly from the viewpoint of high adhesion to an optical substrate.

The obtained photochromic cured product/laminate can exhibit excellent photochromic properties such as color development concentration and fading speed, and can be effectively used for producing an optical substrate to which photochromic properties are imparted, for example, a photochromic lens (photochromic optical article).

The photochromic cured product may be laminated with other functional layers and dyed with a dye such as a disperse dye, in a range that does not impair the effect, depending on the application. In addition, a hard coat film may be produced using a hard coat agent containing a sol of a silane coupling agent, silicon, zirconium, antimony, aluminum, tin, tungsten or the like as a main component. In addition to this, siO can be used ₂ 、TiO ₂ 、ZrO ₂ And vapor deposition of metal oxide to prepare film. The antireflection treatment may be performed using a thin film coated with an organic polymer. Antistatic treatment or the like may be performed.

Further, as the lamination with the other functional layers, there may be mentioned lamination of a polarizing film on the obtained photochromic cured product for the purpose of imparting polarizing characteristics. The position of the polarizing film is not particularly limited, and any of the outside of the photochromic cured product, between the photochromic cured product and other layers, and in the adhesive layer in the case of using the adhesive layer may be laminated, and from the viewpoint of adhesion, a method of embedding in the adhesive layer in the case of using the adhesive layer is preferable.

The method of laminating the polarizing film is not particularly limited, and a known method may be used. For example, in the case of the cast polymerization method, when the photochromic curable composition is injected into a glass mold, a polarizing film is disposed between the front or rear mold and the photochromic curable composition or in the photochromic composition, and then the photochromic curable composition is polymerized to laminate the polarizing film.

In the case of the glass bonding method, it is preferable that a polarizing film is laminated on one surface of an optical substrate made of inorganic glass. When the laminate is used, a laminate obtained by bonding an optical substrate made of inorganic glass to a polarizing film using a known thermosetting adhesive or Ultraviolet (UV) curable adhesive can be used.

The polarizing film is not particularly limited, and a commercially available polarizing film can be used.

As the thickness of the polarizing film, a polarizing film of 20 to 100 μm is preferably used. The polarizing film is formed by stretching polyvinyl alcohol dyed with a dichroic substance such as iodine or a dichroic dye.

As the dichroic dye contained in the polarizing film, a commercially available dichroic dye can be used without limitation. For example, azo dyes, anthraquinone dyes, and the like can be used. Specifically, chloranil fast red (c.i.28160), congo red (c.i.22120), brilliant blue B (c.i.24410), benzored violet (c.i.23500), chlorazol black BH (c.i.22590), direct blue 2B (c.i.22610), diamine green (c.i.30295), direct chrysanthemum yellow (c.i.24895), siraitia yellow (c.i.29000), direct fast red (c.i.23630), acid black (c.i.20470), direct cyan (c.i.24400), sha Lafei denier blue 4GL (c.i.34200), direct copper blue 2B (c.i.24185), nippon Brilliant Violet BKconc (c.i.27885), and the like can be cited. Pigments of 2 or more colors may be selected from these dichroic dyes according to the purpose. The color Index (color Index No.) described in "new dye handbook" (pill good, 1970) by the organic synthesis society is shown in parentheses.

When the photochromic curable composition is used, the composition can be firmly bonded even to a polarizing film having a visible light transmittance of 10 to 60% and a polarization degree of 70.0 to 99.9, which is generally difficult to bond.

For the function and adhesiveness of the polarizing film, a cellulose triacetate film may be laminated on both surfaces. The thickness of the cellulose triacetate film is preferably 20 to 200. Mu.m, more preferably 20 to 100. Mu.m.

In order to adjust the amount of water contained in the polarizing film and to stabilize the size of the polarizing film, the polarizing film may be subjected to a heat treatment at 40 to 100 ℃ for about 5 seconds to 30 minutes before the photochromic cured product is produced.

An optical laminate according to an embodiment includes an optical substrate and a resin composition according to an embodiment laminated on at least one main surface of the optical substrate.

Fig. 6 is a cross-sectional view schematically showing 1 example of the optical laminate according to the embodiment. The optical laminate 1 shown in fig. 6 includes an optical substrate 2, a primer layer 3 provided on one principal surface of the optical substrate 2, and a resin composition 4 provided on the primer layer 3. The optical base material 2 has a concave-convex shape. The primer layer 3 and the resin composition 4 cover the convex side of the optical substrate 2. The primer layer 3 contains, for example, an adhesive containing a polyurethane resin or the like. The primer layer 3 may be omitted.

The glasses according to the embodiment include the lenses according to the embodiment.

Fig. 7 is a perspective view schematically showing 1 example of glasses according to the embodiment. The glasses 110 shown in fig. 7 include 2 lenses 111 and a frame 112 for fixing the lenses 111. At least one of the 2 lenses 111 is a lens including the resin composition according to the embodiment.

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the examples, the evaluation methods and the like of the respective components and the resin composition are as follows.

Photochromic curable composition

Component (ii)

PC1: photochromic compounds represented by the following formula

Component (A)

NBDI: norbornane diisocyanate.

IPDI: isophorone diisocyanate.

1,3-H6XDI:1, 3-bis (isocyanatomethyl) cyclohexane.

1,4-H6XDI:1, 4-bis (isocyanatomethyl) cyclohexane.

Component (B1)

Component (B1 a)

TMMP: trimethylolpropane tris (3-mercaptopropionate), having 3 thiol groups within 1 molecule.

PEMP: pentaerythritol tetrakis (3-mercaptopropionate) having 4 thiol groups in the molecule.

DPMP: dipentaerythritol hexa (3-mercaptopropionate) having 6 thiol groups in the molecule.

Component (B1B)

RX-1: polyrotaxane

Is polyrotaxane synthesized by the method described in International publication No. 2015/068798. The shaft molecule is formed by polyethylene glycol with molecular weight of 11000, the two ends of the shaft molecule are large-volume groups which are adamantyl, the cyclic molecule is alpha cyclodextrin, and the average 3.5 molecules epsilon caprolactone is subjected to ring opening polymerization through oxypropylene.

The characteristics of RX-1 are shown below.

Inclusion amount of alpha cyclodextrin: 0.25.

degree of modification of side chain: 0.5.

molecular weight of side chain: average about 450.

Weight average molecular weight: 180000.

hydroxyl number: 85mgKOH/g.

According to the above values, the number of hydroxyl groups in 1 molecule is on average 270.

Component (B2)

Component (B21)

WS-140: polyoxyethylene polyoxypropylene lauryl ether (recurring units of oxyethylene m '=10 (average), chain recurring units of oxypropylene l' =2 (average), number average molecular weight 750). One terminal has a hydroxyl group and the other terminal has an alkyl group having 12 carbon atoms. The repeating portion of the oxyethylene group and the repeating portion of the oxypropylene group are random copolymers.

MPEG750: methoxy polyethylene glycol (average molecular weight 750)

Component (B22)

L-34: polyoxyethylene polyoxypropylene glycol (recurring units of oxyethylene m "+m'" =14 (average), chain recurring units of oxypropylene l "=16 (average), number average molecular weight 1600).

The two ends of the molecule have hydroxyl groups (having 2 hydroxyl groups).

The repeating part of the oxyethylene group and the repeating part of the oxypropylene group are block copolymers.

Component (C): polymerization curing accelerator >

C1: dimethyl tin dichloride.

< other compounding ingredients >

Ir245: ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ].

< alkali Metal ion >)

Potassium acetate

Acetic acid sodium salt

Example 1 >

Photochromic curable compositions were prepared by mixing the respective components according to the formulations shown in tables 1 and 3.

The content of the alkali metal ion or alkaline earth metal ion in the photochromic curable composition was measured by an ICP emission spectrometry device (iCAP 6500 DUO) manufactured by Thermo Fisher Scientific. In the measurement of the metal ions, 20g of ultrapure water (containing 1% HNO) was extracted from 30g of chloroform solution in which 10g of the photochromic composition was dissolved ₃ ) The obtained substance was used as a measurement sample.

Then, the prepared photochromic curable composition was sufficiently defoamed, and then poured into an inorganic glass mold having a gap of 2mm, and the photochromic curable composition was polymerized by injection polymerization. The polymerization was carried out using an air oven and allowed to cure for 18 hours while slowly heating from 27℃to 120 ℃. After the polymerization, the cured product was taken out of the inorganic glass mold to obtain a photochromic cured product (resin composition) having a thickness of 2 mm.

The photochromic cured product obtained was evaluated by the following method.

(evaluation method)

[ photochromic Properties ]

All of the values were measured by a spectrophotometer (instantaneous multichannel photodetector MCPD 3000) manufactured by tsuka electronics corporation.

[1] Maximum absorption wavelength (λmax): the absorption wavelength after color development is extremely large.

[2] Color development concentration: the maximum absorption wavelength is the difference between the absorbance { A (300) } after light irradiation at 23 ℃ for 300 seconds and the absorbance A (0) when light is not irradiated.

[3]Fade half-life [ t ] _1/2 (seconds): when the light irradiation was stopped after 300 seconds of light irradiation at 23 ℃, the absorbance at the maximum absorption wavelength of the sample was reduced to 1/2 of { A (300) -A (0) }.

[ durability ]

[1]Residual ratio (%) = [ solution (a) ₉₆ )/(A ₀ ) X 100 ]: the deterioration was accelerated for 96 hours by using a xenon arc lamp weatherometer X25 manufactured by Suga tester Co. The color development concentration before and after the degradation acceleration test was evaluated, and the color development concentration before the test (A ₀ ) Color development concentration after test (A) ₉₆ ) Ratio (A) ₉₆ /A ₀ ) As a residual ratio, as an index of color development durability. The higher the residual ratio, the higher the color development durability.

[2]Degree of yellowing (Δyi): for the Yellowness (YI) after 96 hours of accelerated deterioration by the xenon arc weather meter X25 ₉₆ ) With the yellowness before the test (YI ₀ ) Is a difference between (a) and (b). The yellowness was measured by a touch panel type SM colorimeter SM-T manufactured by Suga testing machine Co.

[ Heat resistance ]

The softening temperature of the obtained photochromic cured product was measured by a thermo-mechanical analyzer TMA8311 (three-point bending method, heating rate: 10 ℃ C./min) manufactured by Japanese Kabushiki Kaisha.

[ solid body ] ¹³ CNMR assay

The photochromic cured product obtained was obtained as follows ¹³ CNMR assay. In the measurement, a sample obtained by cutting a photochromic cured product having a thickness of about 1mm into a disk shape having a diameter of about 2mm and loading the disk shape into a 4mm zirconia sample tube was used.

The device comprises: FT-NMR JNM-ECA400II (Japanese electronics Co., ltd.).

And (3) probe: 4 mm. Phi. CP/MAS probe (Japanese electronics Co., ltd.).

¹³ C nuclear measurement frequency: 100.53MHz.

Assay: CP/MAS method.

Contact time: 2 milliseconds.

Delay time: 5 seconds.

Cumulative number of times: 5000 times.

Sample amount: about 80mg.

Sample rotation speed: 6000Hz.

Temperature: 25 ℃.

External standard substance: adamantane (29.5 ppm).

In the PST/MAS assay, the presaturation method was performed under the conditions described below: at 10 millisecond intervals.

[ viscosity increasing (. DELTA.v) _3h )]

Kinematic viscosity (. Nu.) of the photochromic curable composition after 3 hours _3h ) With the initial kinematic viscosity (v) ₀ ) Is a difference between (a) and (b). The kinematic viscosity was determined using a Canon Finsco viscometer.

[ alkali metal ion or alkaline earth metal ion ]

For the concentration of alkali metal ions or alkaline earth metal ions in the obtained photochromic cured product, a circular flat plate having a thickness of 1mm and a diameter of Φ40mm was prepared, and the value measured by a fluorescence X-ray analyzer (ZSX Primus IV) manufactured by Japanese Kogyo Co., ltd was used. The lower limit of detection in the present measurement was 1ppm.

The evaluation results of the photochromic cured product are shown in Table 5.

Examples 2 to 24 and comparative examples 1 to 3 >, respectively

Photochromic cured products were prepared and evaluated in the same manner as in example 1, according to the formulations shown in tables 1 to 4. The evaluation results are shown in tables 5 to 6 in the same manner as in example 1.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

Examples 25 to 48 and comparative examples 4 to 6 >, respectively

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 (ii) PC1 was used. The corresponding examples and comparative examples are shown in tables 7 and 8.

In addition, a mold composed of an inorganic glass plate and a thiourethane plastic lens having a refractive index of 1.60 was separately prepared. The gap between the inorganic glass plate and the thiocarbamate plastic lens was 1mm.

After the prepared photochromic curable composition was sufficiently defoamed, the photochromic curable composition was injected into the mold having a gap of 1mm, and polymerized. The polymerization was carried out using an air oven, and the mixture was cured for 18 hours while gradually increasing the temperature from 27℃to 120 ℃. After polymerization, the cured product was taken out of the inorganic glass plate to obtain a laminated laminate in which a photochromic cured product having a thickness of 1mm was laminated on the surface of a thiourethane plastic lens having a refractive index of 1.60.

The obtained laminate was evaluated for photochromic properties and durability in the same manner as in example 1, and the evaluation results are shown in tables 7 to 8. In the evaluation of heat resistance, the thiourethane plastic lens was not evaluated because it has an influence. The mobility of the component (i) is the same as that of the corresponding examples and comparative examples, and therefore description thereof is omitted.

TABLE 7

TABLE 8

Examples 49 to 72 and comparative examples 7 to 9 >, respectively

Photochromic curable compositions described in tables 9 to 12 below were prepared.

The prepared photochromic curable composition was used as an adhesive. That is, a pair of optical substrates (plates) made of inorganic glass for optical articles are bonded with the adhesive, thereby producing a laminate. First, a photochromic curable composition was applied to a plate made of inorganic glass for optical articles, the plate being provided with a spacer having a thickness of 0.1mm at the end. Next, another plate formed of inorganic glass for optical articles was disposed on the coated photochromic curable composition. Then, the photochromic curable composition is polymerized. The polymerization was carried out using an air oven, and the mixture was cured for 18 hours while gradually increasing the temperature from 27℃to 120 ℃. Thus, a laminate obtained by bonding a pair of plates made of inorganic glass for optical articles with the adhesive was obtained. Namely, a glass-bonded photochromic laminate having a photochromic cured product of 0.1mm thickness was obtained.

The photochromic laminate obtained was evaluated for photochromic properties and durability in the same manner as in example 1, and the evaluation results are shown in tables 13 to 14. The mobility of the component (i) was measured by curing the photochromic curable composition under the same conditions as those of the above method, and the resultant cured product was measured. With respect to heat resistance, no evaluation was made because of the influence of the plate formed of inorganic glass.

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

Examples 73 to 96 and comparative examples 10 to 12 >

Photochromic curable compositions described in tables 15 to 18 below were prepared.

The prepared photochromic curable composition was used as an adhesive. That is, in a pair of optical substrates (plates) formed of inorganic glass for optical articles, one of the plates having a polarizing film on the surface thereof is bonded to the other plate with the adhesive, thereby producing a laminate.

First, an acrylic adhesive was applied to one surface of a plate made of an inorganic glass for optical articles by spin coating, and a polarizing film (thickness 27 μm, visible light transmittance 42.5%, polarization degree 99.2%, gray, based on polyvinyl alcohol) was disposed thereon. Then, UV irradiation was performed from the plate side to prepare a polarizing film/an optical substrate laminated with the polarizing film/the plate.

Next, a photochromic curable composition was applied to a sheet made of inorganic glass for optical articles, on which spacers of 0.1mm thickness were disposed at the ends, and the optical substrate on which the polarizing film was laminated was disposed so that the polarizing film surface was in contact with the photochromic curable composition.

Then, the photochromic curable composition is polymerized. An air oven was used for polymerization, and the resultant was cured for 18 hours while gradually increasing the temperature from 27℃to 120℃to join a pair of optical article plates, thereby obtaining a glass-bonded photochromic laminate comprising a polarizing film layer and a photochromic layer having a thickness of 0.1 mm.

The photochromic laminate obtained was evaluated for photochromic properties and durability in the same manner as in example 1, and the evaluation results are shown in tables 19 to 20. The mobility of the component (i) was measured by curing the photochromic curable composition under the same conditions as those of the above method, and the resultant cured product was measured. With respect to heat resistance, no evaluation was made because of the influence of the plate formed of inorganic glass.

TABLE 15

TABLE 16

TABLE 17

TABLE 18

TABLE 19

TABLE 20

Knowing the intensity ratio (PMI) _pst /PMI _cp ) The resin composition having a molecular mobility control by a crosslinked structure of 8.0 to 40.0 realizes excellent photochromic properties and mechanical properties. In particular, a resin composition excellent in photochromic characteristics and heat resistance can be obtained.

(B1) Among the components, a resin composition exhibiting excellent effects can be obtained by using a component having 6 thiol groups in the molecule. By using a component having 6 thiol groups in the molecule, the strength ratio (PMI) of the resulting resin composition can be made _pst /PMI _cp ) Is a higher value.

Further, the resin composition according to the embodiment has excellent photochromic characteristics and particularly excellent heat resistance. From this, it was found that the molecular motility was evaluated based on the intensity ratio (PMI _pst /PMI _cp ) The photochromic properties can be evaluated. In addition, the use of a component having 6 thiol groups in the molecule improves heat resistanceThe effect based on Multivalent Interaction (multipoint hydrogen bonding) improves heat resistance as the number of hydrogen bonds per crosslinking point increases.

Wherein the intensity ratio (PMI) can be obtained by combining a component having 6 thiol groups in the molecule with the (B21) component _pst /PMI _cp ) It is preferably from 10.0 to 15.0, more preferably from 11.0 to 15.0, and still more preferably from 12.5 to 15.0. In this case, the increase in viscosity of the photochromic curable composition can be suppressed to a low level.

In addition, the following tendency was confirmed in the comparison of examples. (B1) PEMP (component having 4 thiol groups in the molecule) and DPMP (component having 6 thiol groups in the molecule) are all substituted compounds. On the other hand, TMMP (a component having 3 thiol groups in the molecule) belongs to a partially substituted compound. Comparing these examples, it is evident that particularly excellent photochromic properties can be exhibited when PEMP and DPMP, which are fully substituted compounds, are used, as compared to when TMMP, which is a partially substituted compound, is used. Thus, it is considered that when the fully substituted compound is used as the component (B1), a free space in which the photochromic compound moves in a molecule is effectively formed.

Further, by adjusting the contents of the alkali metal ions and alkaline earth metal ions contained in the photochromic composition of the present invention, durability can be improved. The reason is considered as follows. That is, when the content of the alkali metal salt and the alkaline earth metal salt contained in the photochromic composition is large, side reactions such as isocyanuration occur during the preparation or polymerization of the photochromic composition, and as a result, the residual thiol groups in the cured product increase. The thiol group generates a radical by ultraviolet rays, which promotes degradation of the photochromic compound, reducing durability. In the present invention, by setting the content of the alkali metal ion and the alkaline earth metal ion to be appropriate, side reactions are suppressed, and durability is improved.

Description of the reference numerals

10: polyrotaxane

20: axis 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 with glasses

111: lens

112: frame (B)

Claims

2. The resin composition according to claim 1, wherein the maximum intensity (AMI) of the signal in the range of 10ppm to 15ppm in the 1 st spectrum _pst ) Maximum Intensity (AMI) of signal in the range of 10ppm to 15ppm in the 2 nd spectrum _cp ) Ratio (AMI) _pst /AMI _cp ) Is 7.0 to 23.0 inclusive.

3. The resin composition according to claim 1 or 2, wherein the maximum intensity (EI _pst ) And the maximum intensity (EI) of the signal in the range of 68ppm to 72ppm in the 2 nd spectrum _cp ) Ratio (EI) _pst /EI _cp ) Is 5.0 to 20.0 inclusive.

4. The resin composition according to any one of claims 1 to 3, wherein the total content of alkali metal ions and alkaline earth metal ions obtained by fluorescent X-ray analysis is 500ppm or less.

5. The resin composition according to any one of claims 1 to 4, wherein the urethane resin is a resin obtained by reacting (A) a polyisocyanate component having 2 or more isocyanate groups selected from the group consisting of isocyanate groups and isothiocyanate groups in the molecule with (B) an active hydrogen-containing component having an active hydrogen-containing group,

the ratio (nA/nB) is 1.00 or more and 1.50 or less,

the (B) active hydrogen-containing component comprises:

6. The resin composition according to claim 5, wherein the average value of the repeating units of oxypropylene groups of the polyoxypropylene chain of the 1 st active hydrogen-containing component (B2) is 2 or more and 25 or less.

7. The resin composition according to claim 5 or 6, wherein the (B2) 1 st active hydrogen-containing component further has at least one of an alkyl group and a polyoxyethylene chain in a molecule.

8. The resin composition according to claim 7, wherein the (B2) 1 st active hydrogen-containing component has the alkyl group and has a carbon number of 5 or more and 20 or less.

9. The resin composition according to claim 7, wherein the (B2) 1 st active hydrogen-containing component has the polyoxyethylene chain, and an average value of repeating units thereof is 5 or more and 25 or less.

10. The resin composition according to any one of claims 5 to 9, wherein the (B1) polyfunctional active hydrogen-containing ingredient comprises a compound having a quaternary carbon atom in the molecule and all groups bonded to the quaternary carbon atom have active hydrogen-containing groups.

11. An optical laminate comprising: an optical substrate; and the resin composition according to any one of claims 1 to 10 laminated on at least one main surface of the optical substrate.

12. The optical stack of claim 11, further comprising a polarizing film.

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

14. A lens comprising the resin composition of any one of claims 1 to 10.

15. An eyewear comprising the lens of claim 14.