CN117178209A

CN117178209A - Optical article, spectacle lens and spectacles

Info

Publication number: CN117178209A
Application number: CN202280028686.8A
Authority: CN
Inventors: 服部有辉; 森力宏; 百田润二
Original assignee: Tokuyama Corp
Current assignee: Tokuyama Corp
Priority date: 2021-04-21
Filing date: 2022-03-30
Publication date: 2023-12-05

Abstract

The optical article of the present invention is composed of a photochromic compound and a 1 st compound having an absorption peak in a wavelength range of 550 to 600nm, and has a laminated structure in which (A) at least a first functional layer containing the photochromic compound and (B) a lens base material are independent of each other, the light transmittance of the photochromic compound in an uncolored state is 30% or more, the light transmittance of the photochromic compound in a colored state is 25% or less, and the minimum light transmittance of the photochromic compound in a colored state at a wavelength of 550 to 600nm is 0.1 to 20%. According to the present invention, a novel photochromic optical article exhibiting excellent photochromic characteristics, visibility, antiglare properties and high contrast (in which red, green, and blue are clearly recognized, and the outline and the irregularities of an object are clearly recognized) can be provided.

Description

Optical article, spectacle lens and spectacles

Technical Field

The present invention relates to a novel optical article having a laminated structure, an eyeglass lens formed from the optical article, and an eyeglass provided with the eyeglass lens. More specifically, the present invention relates to a novel optical article having a layer having a photochromic property and a lens substrate separately, and having excellent photochromic property, visibility, antiglare property, and high contrast (in which red, green, and blue colors can be clearly recognized, and the outline and unevenness of an object are clear), an eyeglass lens formed from the optical article, and an eyeglass provided with the eyeglass lens.

Background

Photochromic compounds represented by chromene compounds, fulgide compounds, spirooxazine compounds and the like have the following characteristics (photochromism): when light including ultraviolet rays such as sunlight or light of a mercury lamp is irradiated, the color is changed rapidly, and when the irradiation of light is stopped and the light is placed in a dark place, the original color is restored. Further, the present invention makes full use of the characteristics, and is useful for various applications, particularly for optical materials.

For example, a photochromic spectacle lens provided with photochromic properties by using a photochromic compound is rapidly colored outside a room where light including ultraviolet rays such as sunlight is irradiated to function as sunglasses, and is discolored inside a room where such light is not irradiated to function as transparent general spectacles. Such photochromic spectacle lenses have been in increasing demand in recent years (see patent documents 1 to 3).

In addition, in order to further improve antiglare properties, an optical article having both photochromic properties and polarizing properties has been developed (see patent document 4).

Prior art literature

Patent literature

Patent document 1: U.S. Pat. No. 7166357

Patent document 2: japanese patent No. 4672768

Patent document 3: japanese patent No. 5914674

Patent document 4: japanese patent laid-open publication No. 2019-164271

Patent document 5: japanese patent laid-open No. 2018-097173

Patent document 6: international publication No. 2018/062385

Disclosure of Invention

Problems to be solved by the invention

As described above, optical articles having improved photochromic properties and antiglare properties have been developed. In recent years, as lenses with further improved antiglare properties and high contrast, the following optical articles have been developed.

Specifically, an optical article having both photochromic and polarizing properties and containing a dye having a main absorption peak at a wavelength of 565nm to 605nm has been developed (see patent documents 5 and 6)

The optical article described in patent document 5 has the characteristics of the prior art and is particularly excellent in antiglare property. Is an optical article excellent in antiglare property even when used indoors such as in an automobile.

However, in the method described in patent document 5, an optical article having a relatively high absorbance at a wavelength of 420nm is formed in order to exhibit a high antiglare property. Therefore, there is room for improvement in that yellow coloration is observed in a state in which the photochromic compound is not developed (in an unirradiated state/use in a room). The yellow coloration is a color tone that looks like deterioration of a plastic lens, and is sometimes avoided. On the other hand, in the comparative example of patent document 5, a transparent optical article in an unirradiated state is exemplified, but in this example, there is room for improvement in that antiglare property and contrast are required to be further improved.

Further, patent document 6 discloses an optical article comprising a photochromic compound and a tetraazaporphyrin compound and having a specific transmittance curve. The optical article has a high contrast. Patent document 6 describes a method for producing an optical article by injecting a polymerizable composition containing a photochromic compound and a porphyrazine compound between molding dies and forming the polymerizable composition itself.

However, in the method described in patent document 6, only an optical article having a relatively large thickness can be manufactured. In the examples, optical articles having a thickness of 2mm were manufactured. In the case of using such an optical article as, for example, an eyeglass lens, a difference in thickness is generated between the center portion and the end portion in any case. The optical article containing the photochromic compound functions as a sunglass when irradiated with light, and thus is colored. In this case, if there is a difference in thickness between the center portion and the end portion, color unevenness occurs in any case. That is, the invention described in patent document 6 has room for improvement because it includes a photochromic compound.

It is therefore an object of the present invention to provide: an optical article which has excellent antiglare properties, high contrast, excellent visibility even at a time point when sunlight is not irradiated, and little occurrence of color unevenness even in a state where a photochromic compound develops.

Solution for solving the problem

The present inventors have made intensive studies to solve the above problems. Furthermore, it was found that: in order to improve contrast and initial light transmittance and visibility (light transmittance in a state where light irradiation is not performed) while maintaining high antiglare properties, it is effective to use a specific photochromic compound and a compound having an absorption peak in a wavelength range of 550 to 600nm and to have a laminated structure, so that the present invention has been completed.

Namely, the first invention is an optical article,

comprising a photochromic compound and a 1 st compound having an absorption peak in the wavelength range of 550 to 600nm,

the optical article has a laminated structure in which (A) a first functional layer containing at least a photochromic compound and (B) a lens base material are present independently of each other,

the light transmittance of the photochromic compound in the non-developed state is 30% or more,

the light transmittance of the photochromic compound in the developed state is 25% or less,

the minimum transmittance of the photochromic compound in the state of color development at a wavelength of 550 to 600nm is 0.1 to 20%.

The second invention is an ophthalmic lens comprising the optical article as the first invention.

The third invention is an eyeglass comprising an eyeglass lens as the second invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an optical article having high light transmittance and visibility in a state where light irradiation is not performed, that is, in a state where no color development of the photochromic compound is performed, and sufficient antiglare properties and high contrast in a state where light irradiation is performed (use in the presence of sunlight) can be obtained. Further, even in the case of using the lens as a spectacle lens, color unevenness at the time of light irradiation can be reduced.

In addition, by providing the (D) polarizing functional layer, antiglare property can be improved. In the case of providing (laminating) (D) the polarizing functional layer, the (a) first functional layer needs to be disposed closer to the side irradiated with sunlight than the (D) polarizing functional layer.

Drawings

Fig. 1 is a schematic view showing an example of a laminated structure of a photochromic optical article according to the present invention.

Fig. 2 is a schematic diagram showing another example of the laminated structure of the photochromic optical article of the present invention.

Detailed Description

< optical article >)

The optical article of the present invention comprises a photochromic compound and a 1 st compound having an absorption peak in the wavelength range of 550 to 600nm,

First, the respective features of the optical article will be described.

In the present specification, unless otherwise specified, the "x to y" where the values x and y are used means "x or more and y or less". In the above-mentioned label, when only a unit is given to the value y, the unit is also applicable to the value x.

In this specification, the first functional layer refers to a layer containing a photochromic compound. The second functional layer refers to a layer containing the 1 st compound. In addition, there is a case where a single layer contains both the photochromic compound and the 1 st compound, and in this case, the single layer is a first functional layer and also a second functional layer (also sometimes referred to as a first functional layer and also a second functional layer, etc.).

In addition, the optical article of the present invention is also sometimes referred to as a photochromic optical article.

Optical transmittance of optical article

Light transmittance/initial light transmittance when not irradiated >

In the optical article of the present invention, the light transmittance (hereinafter, also simply referred to as "initial light transmittance") of the photochromic compound in the non-colored (non-irradiated) state must be 30% or more. When the initial light transmittance is less than 30%, the transparency is lowered, and the contrast (visibility in a room) is lowered when not irradiated, which is not preferable. In order to improve transparency and contrast (visibility) when not irradiated, the initial light transmittance is preferably 50% or more, more preferably 60% or more, in the case where the polarizing function layer (D) described in detail below is not provided. The higher the initial light transmittance, the more excellent the effect is, but the upper limit of the initial light transmittance is 90% in consideration of industrial production of optical articles. That is, in the case where the polarizing functional layer is not provided, the initial light transmittance of the optical article is preferably 30 to 90%, more preferably 50 to 80%, and even more preferably 60 to 80%.

In order to further improve the antiglare property, when the polarizing function layer (D) is provided, the initial light transmittance is preferably 30% or more, and more preferably 35% or more. Even in the case of providing the (D) polarization functional layer, the upper limit value of the initial light transmittance is 90%. However, in the case of providing the (D) polarizing functional layer, the initial light transmittance is preferably 30 to 70%, more preferably 35 to 60%, and even more preferably 35 to 50%, in view of industrial production.

The initial light transmittance can be adjusted by the material constituting the optical article, for example, the thickness, material, compound compounded in these layers, and the like of (a) the first functional layer containing at least a photochromic compound, and (B) the lens base material, and (C) the second functional layer, which are provided as needed, which are described in detail below. In addition, when the polarizing functional layer (D) is provided as described above, the transmittance and the polarization degree of the polarizing functional layer can be adjusted.

Light transmittance at the time of light irradiation

In the optical article of the present invention, the light transmittance in the state in which the photochromic compound develops color (the state irradiated with light, hereinafter, also sometimes referred to as "light irradiation") must be 25% or less. When the light transmittance at the time of light irradiation exceeds 25%, the function as a sunglass lens is insufficient, and the antiglare property is not good, which is not preferable. In order to have excellent antiglare properties and to sufficiently exert an effect as a function of sunglasses, the light transmittance at the time of light irradiation is preferably 20% or less. In consideration of the light transmittance (good field of view) during light irradiation, the lower limit value of the light transmittance during light irradiation is preferably 8% or more, more preferably 10% or more. That is, the optical article of the present invention preferably has a light transmittance of 8 to 25%, more preferably 10 to 20% when irradiated with light.

In the case where the (D) polarizing functional layer is provided for further improvement of antiglare properties, the light transmittance at the time of light irradiation is preferably 8 to 25%, more preferably 10 to 20%, in order to provide excellent antiglare properties, sufficiently exert the effect as a function of sunglasses, and ensure the transmittance (good field of view) at the time of light irradiation.

The light transmittance upon light irradiation can be adjusted by the material constituting the optical article, for example, the thickness and the material of (a) the first functional layer containing at least a photochromic compound, and (B) the lens base material, and (C) the second functional layer, which are provided as needed, and the compound to be compounded in these layers, which will be described in detail below. In the case of providing the polarizing functional layer (D), the transmittance and the polarization degree of the polarizing functional layer may be adjusted.

(2) minimum transmittance at a wavelength of 550 to 600nm at the time of light irradiation

The optical article of the present invention must have a minimum transmittance of 0.1 to 20% at a wavelength of 550 to 600nm in a state in which the photochromic compound develops color (a state irradiated with light, hereinafter, also sometimes referred to as "light irradiation"). In other words, the transmittance at the maximum absorption wavelength at the wavelength of 550 to 600nm must be 0.1 to 20% at the time of light irradiation. When irradiated with light, the light exhibits a minimum transmittance of 20% or less at a wavelength of 550 to 600nm, thereby increasing the contrast. Therefore, the contrast is high even when the light is irradiated or not irradiated. When irradiated with light, the optical article exhibits photochromic characteristics and has high contrast. In order to exert more excellent effects, the minimum transmittance at a wavelength of 550 to 600nm is preferably 15% or less at the time of light irradiation. In consideration of the production of industrial optical articles, the minimum transmittance lower limit value at a wavelength of 550 to 600nm at the time of light irradiation is 0.1%. In view of industrial production of optical articles, higher contrast, and the like, the minimum transmittance at the time of light irradiation is preferably 1 to 15%.

Since the optical article of the present invention has a high light transmittance when not irradiated, the contrast when not irradiated is also high. The minimum transmittance at a wavelength of 550 to 600nm when not irradiated is preferably 10 to 70%. When the amount is 10% or more, initial coloring (straight color when not irradiated) is small; when the content is 70% or less, an effect of improving visibility can be observed. In order to improve visibility while reducing initial coloring, the minimum transmittance at a wavelength of 550 to 600nm when not irradiated is more preferably 20 to 65%, most preferably 30 to 60%.

In the case of providing the (D) polarizing functional layer for further improving the antiglare property, the minimum transmittance at a wavelength of 550 to 600nm at the time of light irradiation is preferably 0.1 to 20%, more preferably 1 to 15%, in order to increase the contrast.

On the other hand, in the case of providing the (D) polarizing functional layer, the minimum transmittance at a wavelength of 550 to 600nm when not irradiated is preferably 10 to 50%, more preferably 10 to 40%, in order to exert an excellent effect.

The minimum transmittance at a wavelength of 550 to 600nm at the time of irradiation or not of light can be adjusted by the material constituting the optical article, the thickness and material of (a) the first functional layer and (B) the lens base material containing at least the photochromic compound, and (C) the second functional layer, which are provided as needed, and the compound to be compounded in these layers, which will be described in detail below. In the case of providing the polarizing functional layer (D), the transmittance and the polarization degree of the polarizing functional layer may be adjusted. Among them, the type of the 1 st compound having an absorption peak at a wavelength of 550 to 600nm, the compounding amount, the thickness of the (C) second functional layer containing the same, and the like, which will be described in detail below, are preferably mainly adjusted.

(3) other features)

The optical article of the present invention is not particularly limited as long as the above-described features (1) to (2) are satisfied. Among them, in order to exert particularly excellent performance, the following characteristics are preferably satisfied.

(3) -1 a difference between a transmittance at a wavelength of 550nm and a minimum transmittance at a wavelength of 550 to 600nm upon light irradiation

The transmittance at a wavelength of 550nm upon light irradiation is preferably 20% or less. In addition, when light is irradiated, the transmittance at a wavelength of 550nm is preferably higher than the minimum transmittance at a wavelength of 550 to 600 nm. The minimum value of the transmittance at the wavelength of 550nm at the time of light irradiation is not particularly limited, but is preferably 1%.

The optical article of the present invention contains the 1 st compound having an absorption peak in the wavelength range of 550 to 600nm, and the optical article also has an absorption peak in the wavelength range of 550 to 600 nm. The absorption peak of the optical article is preferably present at a wavelength of 550nm, but is preferably present at a wavelength of more than 550nm and 600nm or less, more preferably from 575 to 600nm, and even more preferably from 580 to 595nm. In addition, when light is irradiated, the difference between the transmittance at a wavelength of 550nm and the minimum transmittance at a wavelength of more than 550nm and 600nm or less of the optical article of the present invention is preferably set to 0.1% or more and 19% or less (hereinafter, this difference may be simply referred to as "transmittance difference"). The transmittance difference at the time of light irradiation is set to 0.1% or more, whereby a high contrast can be obtained. On the other hand, when the transmittance difference is 20% or less, the optical article has high transparency and can suppress coloring of blue/violet when not irradiated. In view of higher contrast and non-coloring property when not irradiated, the transmittance difference when irradiated with light is preferably 1% or more and 19% or less, more preferably 3% or more and 15% or less, and still more preferably 4% or more and 10% or less.

On the other hand, in view of non-colorability, the transmittance difference when not irradiated is preferably 5 to 60%, more preferably 15 to 45%.

In the case of providing a polarizing functional layer for further improving antiglare properties, it is preferable to provide the polarizing functional layer in an optical article in which the transmittance difference upon light irradiation satisfies the above range. In the optical article provided with the polarizing functional layer, the transmittance difference at the time of light irradiation is preferably 1 to 19%, more preferably 2 to 10%, for high contrast, high visibility, and the like.

On the other hand, even in the case of an optical article provided with a polarizing functional layer, the transmittance difference when not irradiated is preferably 5 to 50%, more preferably 8 to 30%, in order to improve visibility.

(3) -2 absorbance at 420nm wavelength without irradiation

Optical article with less coloration and high transparency when not irradiated

In the case where the (D) polarizing functional layer is not provided in the optical article of the present invention, the absorbance at 420nm wavelength when not irradiated is preferably 0.25 or less. In patent document 5, the optical article of the example is 0.29 or more, and yellow coloration may be observed even when not irradiated. When the polarizing function layer (D) is not provided, the absorbance at 420nm wavelength at the time of non-irradiation is preferably 0.25 or less. That is, by making the optical article of the present invention not have high absorbance at the wavelength of 420nm when not irradiated, the transparency when not irradiated can be improved. Further, since the absorption in the visible light range is low, an optical article with little coloration can be produced. Further, since the optical article must contain the 1 st compound, it is considered that the antiglare property is excellent.

In order to exert more excellent effects, the absorbance at a wavelength of 420nm is more preferably 0.24 or less, and still more preferably 0.22 or less. The lower limit of absorbance at a wavelength of 420nm is lower, and the transparency is higher, but in consideration of the industrial production of an optical article, the lower limit is 0.05. The absorbance can be determined by directly measuring the optical article.

When the absorbance at the wavelength of 420nm exceeds 0.25 at the time of non-irradiation, coloring of yellow can be suppressed by adding a blue dye or the like to the optical article. However, by adding such a dye, there is a concern that the initial light transmittance is lowered and the visibility is lowered. Therefore, as described above, the absorbance at 420nm which is the wavelength of the non-irradiated light is preferably 0.25 or less.

In the present invention, the light transmittance, the minimum transmittance at a wavelength of 550 to 600nm, and the absorbance at each wavelength can be measured at a measurement temperature of 23℃by using a UV/VIS spectrometer. Details are as described in the examples.

In the case of producing an optical article having little coloring and high transparency when it is not colored, an optical article having a gradation region described in detail below may be produced in order to improve design.

Optical article having polarizing functional layer with less coloration when not irradiated

In the case of providing the polarizing functional layer (D), the absorbance at 420nm wavelength when not irradiated is preferably 0.60 or less, more preferably 0.55 or less. The lower limit of absorbance at 420nm wavelength when the (D) polarizing functional layer was provided was 0.10. This value can be obtained by directly measuring the optical article provided with the (D) polarizing functional layer.

By providing the polarizing functional layer (D), the absorbance at 420nm wavelength at the time of non-irradiation becomes high, and the yellow coloration (less noticeable) becomes invisible. That is, by providing the (D) polarizing functional layer for improving the antiglare property, the (D) polarizing functional layer is provided, and thus the yellow coloration is not observed, and the appearance is improved. Further, it is preferable to further provide (D) a polarizing functional layer to the optical article in which the yellow coloring is not observed. Therefore, in the present invention, it is preferable that: in a state where the (D) polarization functional layer is not included, the (D) polarization functional layer is provided in an optical article having an absorbance at a wavelength of 420nm at the time of non-irradiation of preferably 0.25 or less, more preferably 0.24 or less, and still more preferably 0.22 or less (however, the lower limit value of the absorbance at a wavelength of 420nm at the time of non-irradiation of preferably 0.05). In the state where the (D) polarization functional layer is provided, the absorbance at the wavelength of 420nm when not irradiated is preferably 0.60 or less, more preferably 0.55 or less (however, in this case, the lower limit value of the absorbance at the wavelength of 420nm when not irradiated is preferably 0.10).

In the case of producing such an optical article having a polarizing function layer with little coloring, an optical article having a gradation region described in detail below may be produced in order to improve the design property.

Optical article having polarizing functional layer and colored when not irradiated

On the other hand, as described above, in the case where the (D) polarization functional layer is provided, coloring can be made inconspicuous. Therefore, a dye or a photochromic compound having an absorbance of 0.10 or more at a wavelength of 420nm when not irradiated (the following (b) photochromic compound) may be used. In the optical article of this embodiment, the optical article is a tan optical article when not irradiated, and the optical article can be made gray when irradiated with light.

In this case, in a state where the (D) polarization functional layer is not included, the (D) polarization functional layer is preferably provided in an optical article having an absorbance at a wavelength of 420nm at the time of non-irradiation of preferably 0.28 to 0.60, more preferably 0.32 to 0.58, still more preferably 0.36 to 0.56. In the state where the (D) polarizing functional layer is provided, the absorbance at 420nm, which is the wavelength when not irradiated, is preferably 0.55 to 1.00, more preferably 0.60 to 0.95.

In order to improve the design of such an optical article, an optical article having a gradation region described in detail below may be produced.

In the present invention, the absorbance at a wavelength of 420nm of the optical article when not irradiated is preferably adjusted according to the kind and amount of the photochromic compound, the thickness of the first functional layer, and the like. In particular, in order to produce an optical article with little coloration when not irradiated, the following photochromic compounds are preferably used. Specifically, it is preferable to adjust the amount of the photochromic compound (a) described below) in which the absorbance at a wavelength of 420nm (absorbance at 23 ℃ C. In toluene, 1.0 mmol/l) is less than 0.10 by compounding in a relatively large amount, which will be described in detail below.

On the other hand, in the case of producing an optical article which is colored when not irradiated, it is preferable to adjust the amount of a photochromic compound (the following (b) photochromic compound) having an absorbance at 420nm (absorbance at 23 ℃ C. In toluene, 1.0 mmol/l) of 0.10 or more, which is described in detail below, by relatively more compounding.

In order to adjust the absorbance at 420nm wavelength when the (D) polarizing functional layer is provided and when the layer is not irradiated, the type and amount of the photochromic compound, the thickness of the first functional layer, and the like may be determined assuming that the optical article is not provided with the (D) polarizing functional layer in advance. The optical article having a polarizing function can be checked by the following method. For example, analysis is performed on the material forming the optical article. The photochromic compound was extracted, and the absorbance at the time of color development was confirmed. Then, based on the absorbance of the material and the photochromic compound, the absorbance of the optical article when the (D) polarizing functional layer is not provided can be predicted. It is needless to say that the characteristics (such as polarization degree) and thickness of the polarizing functional layer (D) may be adjusted.

< concerning contrast >

The optical article of the present invention has high contrast. That is, when the photochromic compound is developed outdoors, if the scenery is confirmed by the optical article, the color, the outline of the object, and the irregularities can be clearly confirmed by visual observation. Therefore, the optical article of the present invention preferably satisfies the following requirements.

Specifically, the following optical articles are preferable:

an optical article in a state in which color development occurs by photographing a blue film of 69, a-42, b-34 and a yellow film of 81, a-0, b-85 in hues in CIE1976 (L, a, b) color space through a photochromic compound with a hyperspectral camera,

when the average reflectance at the wavelength of 420 to 519nm at the time of photographing the blue film is R1 and the average reflectance at the wavelength of 580 to 595nm at the time of photographing the yellow film is R2,

the ratio of R1 to R2 (R1/R2) is 0.9 to 2.0.

The method for obtaining the imaging conditions and average reflectance using the hyperspectral camera is described in the following examples.

The hyperspectral camera can split light according to wavelength to shoot. R1 is an average reflectance at a wavelength of 420 to 519nm (precisely, a wavelength of 420.39 to 519.15 nm) when a blue film is imaged, and is a value showing how much blue can be confirmed (in other words, a value indicating an average transmittance in a blue region). Similarly, R2 is an average reflectance at wavelengths of 580 to 595nm (precisely, wavelengths of 580.03 to 594.63 nm) when a yellow film is imaged, and is a value showing how much yellow can be confirmed (in other words, a value indicating average transmittance in a yellow region). The ratio (R1/R2) of both shows an index of how clearly blue can be confirmed based on the visibility of yellow. That is, if R1/R2 becomes high, the contrast is considered to be high.

For the blue thin film and the yellow thin film of the above hue, thin films having L, a, and b values as above may be prepared. As the blue film and the yellow film, commercially available ones can be used. For example, artco, ltd. Neo Cellophane 8-sheet group 63983 is listed.

In the present invention, R1/R2 is more preferably 1.0 or more and 1.9 or less in order to produce an optical article having a higher contrast.

The optical article of the present invention has the above-described characteristics, and in order to exhibit the characteristics, it is necessary to include a photochromic compound and a 1 st compound having an absorption peak in a wavelength range of 550 to 600 nm. These photochromic compounds and the 1 st compound will be described below.

< photochromic Compounds >)

The photochromic compound used in the present invention is not particularly limited as long as it is a compound used so that the optical article satisfies the characteristics of the aforementioned (1) (2) (including the characteristics of (3) if necessary). The photochromic compound is preferably selectively used according to the purpose of use of the resulting optical article. That is, in the case of producing a highly transparent optical article with little coloration when not irradiated, a photochromic compound having an absorbance of less than 0.10 at a wavelength of 420nm (hereinafter, this photochromic compound may be simply referred to as "(a) photochromic compound") is preferably used. On the other hand, in the case of producing an optical article having a polarizing functional layer (D) described in detail below, a photochromic compound having an absorbance of 0.10 or more at a wavelength of 420nm, which also develops color in the visible light region, may be used (hereinafter, the photochromic compound may be simply referred to as a "(b) photochromic compound"). In this case, the colored state is generated when the light is not irradiated, but the antiglare property can be further improved even in a room or the like. These photochromic compounds will be described below.

(a) Photochromic compounds

Preferably, the photochromic compound (a) having an absorbance at 420nm of less than 0.10 is used. By using the photochromic compound (a), the absorbance at a wavelength of 420nm can be suppressed to be low even in the case of an optical article. In particular, an optical article satisfying the condition (3) -2 can be easily manufactured. As a result, the transparency, particularly when not irradiated, and the appearance (uncolored state) of the optical article can be improved. That is, in order to produce a highly transparent optical article which is not colored when not irradiated, a photochromic compound having an absorbance of less than 0.10 at a wavelength of 420nm is preferably used. The absorbance of the photochromic compound was measured at 23℃in toluene at a concentration of 1mmol/l (1 mm/l) using a quartz cuvette having a light path length of 10 mm.

Further preferable examples of the photochromic compound include a photochromic compound having an absorbance at a wavelength of 420nm of less than 0.10 and an absorbance at a wavelength of 430nm of less than 0.015. Tone adjustment sometimes uses a variety of photochromic compounds. In this case, in order to produce a highly transparent optical article which is not colored when it is not irradiated, a photochromic compound satisfying the following requirements is preferably used. That is, the absorbance at 420nm is preferably lower than 0.10, and the absorbance at 430nm is preferably lower than 0.015. The lower limit of the absorbance at the wavelength of 420nm of the photochromic compound (a) is preferably 0.001, and the lower limit of the absorbance at the wavelength of 430nm is preferably 0.000.

Representative examples of such photochromic compounds include fulgide compounds, chromene compounds and spirooxazine compounds, and are disclosed in a large number of documents such as Japanese patent application laid-open No. 2-28154, japanese patent application laid-open No. 62-288830, WO94/22850 and WO 96/14596.

In the present invention, from the viewpoints of photochromic properties such as color development concentration, initial coloring property, durability, and fading rate, a known photochromic compound is more preferably used as the chromene compound having an indeno [ 2,1-f ] naphtho [ 1,2-b ] pyran skeleton. In particular, a chromene compound having a molecular weight of 540 or more is particularly excellent in color development concentration and fading speed, and thus can be suitably used. Among them, a chromene compound represented by the following formula (1) is preferable.

＜R ¹⁰ And R is ²⁰ ＞

Wherein R is ¹⁰ And R is ²⁰ Each of which is a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom of a ring member and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group, an arylthio group, or an aryl group.

The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl and the like.

The haloalkyl group is preferably an alkyl group having 1 to 6 carbon atoms which is substituted with a fluorine atom, a chlorine atom or a bromine atom. Examples of suitable haloalkyl groups include trifluoromethyl, tetrafluoroethyl, chloromethyl, 2-chloroethyl, bromomethyl, and the like.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms. Examples of suitable cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.

The amino group is not limited to amino (-NH) ₂ ) Optionally 1 or 2 hydrogen atoms are substituted. Examples of the substituent of the amino group include an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl group having 4 to 14 carbon atoms. As examples of suitable amino groups, ammonia may be mentioned A group, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, diphenylamino, and the like.

Examples of the heterocyclic group containing a nitrogen atom of the ring member and bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring through the nitrogen atom include an aliphatic heterocyclic group such as morpholino, piperidinyl, pyrrolidinyl, piperazinyl, and N-methylpiperazinyl, and an aromatic heterocyclic group such as indolinyl, and the like, as preferable heterocyclic groups. Further, the heterocyclic group may have a substituent. As a preferable substituent, an alkyl group is exemplified. Examples of suitable heterocyclic groups having a substituent include 2, 6-dimethylmorpholinyl, 2, 6-dimethylpiperidinyl, and 2, 6-tetramethylpiperidinyl.

As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms is preferable. Examples of suitable alkylcarbonyl groups include acetyl and ethylcarbonyl groups.

The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms. Examples of suitable alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the aralkyl group, for example, an aralkyl group having 7 to 11 carbon atoms is preferable. Examples of suitable aralkyl groups include benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and the like.

As the above aralkyloxy group, an aralkyloxy group having 7 to 11 carbon atoms is preferable. Examples of suitable aralkyloxy groups include benzyloxy and naphthylmethoxy.

As the above aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of suitable aryloxy groups include phenyloxy and naphthyloxy.

As the above-mentioned arylthio group, an arylthio group having 6 to 12 carbon atoms is preferable. Examples of suitable arylthio groups include phenylthio and naphthylthio.

The aryl group is preferably an aryl group having 6 to 14 carbon atoms. Specific examples of suitable aryl groups include phenyl, 1-naphthyl, 2-naphthyl, and the like.

These aralkyl groups, aralkoxy groups, aryloxy groups, arylthio groups, aryl groups optionally have 1 to 7 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms, of the benzene or naphthalene ring substituted with the aforementioned hydroxyl group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, cyano group, nitro group, halogen atom. In the case where the arylthio group is a phenylthio group, it is preferable that a substituent is present in at least 1 ortho position, and as the substituent, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or an aryl group having 6 to 14 carbon atoms is preferable.

Among them, in the obtained photochromic optical article, R is in order to highly achieve both of easy adjustment of color tone, transmittance and antiglare property ¹⁰ And R is ²⁰ Preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryloxy group, an arylthio group, or an aryl group.

＜R ⁴⁰ And R is ⁵⁰ ＞

R ⁴⁰ And R is ⁵⁰ Preferably aryl, heteroaryl, or alkyl. Among them, in order to exhibit particularly excellent photochromic property fading rate, it is preferable that R is as described above ⁴⁰ And R is ⁵⁰ At least one, preferably both, of which are aryl or heteroaryl. Further, R is ⁴⁰ And R is ⁵⁰ The group of at least one, preferably both, is particularly preferably any of the groups shown in the following (i) to (iii).

(i) Aryl or heteroaryl groups having alkyl or alkoxy groups as substituents.

(ii) Aryl or heteroaryl having amino groups as substituents,

(iii) Aryl or heteroaryl having a nitrogen atom as a ring member heteroatom and having a heterocyclic group bonded to the aryl or heteroaryl through the nitrogen atom as a substituent.

The positions of substituents substituted on the aryl or heteroaryl groups in (i) to (iii) and the total number thereof are not particularly limited, and in order to exhibit excellent photochromic characteristics, when the aryl group is a phenyl group, the substitution position is 3 or 4, and in this case, the number of substituents is preferably 1. Particularly preferred are groups in which an alkyl group, an alkoxy group, an amino group, a heterocyclic group bonded to a benzene ring containing a nitrogen atom of a ring member and bonded thereto via the nitrogen atom, or an aryl group is substituted at the 3-or 4-position of a phenyl group.

In addition, R ⁴⁰ And R is ⁵⁰ Examples of suitable aryl groups include 4-methylphenyl, 4-methoxyphenyl, 3, 4-dimethoxyphenyl, 4-N-propoxyphenyl, 4- (N, N-dimethylamino) phenyl, 4- (N, N-diethylamino) phenyl, 4- (N, N-diphenylamino) phenyl, 4-morpholinophenyl, 4-piperidylphenyl, 3- (N, N-dimethylamino) phenyl, 4- (2, 6-dimethylpiperidinyl) phenyl and the like.

The positions of the substituents for substituting the heteroaryl groups in (i) to (iii) and the total number thereof are not particularly limited, and the number thereof is preferably 1. As the heteroaryl group, there may be mentioned, as suitable specific examples, 4-methoxythienyl, 4- (N, N-dimethylamino) thienyl, 4-methylfuryl, 4- (N, N-diethylamino) furyl, 4- (N, N-diphenylamino) thienyl, 4-morpholinopyrrolinyl, 6-piperidylbenzothienyl, 6- (N, N-dimethylamino) benzofuryl and the like.

Due to R ⁴⁰ And R is ⁵⁰ From the above groups, the chromene compound (photochromic compound) becomes a bimodal compound having 2 absorption peaks. The bimodal compound can be suitably used for reasons such as easy adjustment of color tone and less change of color tone with time due to deterioration. In particular, the compound can be suitably used when mixed with other photochromic compounds to adjust the color tone.

＜R ⁶⁰ And R is ⁷⁰ ＞

In the formula (1), R ⁶⁰ And R is ⁷⁰ Respectively, a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group or an aryl group.

Among the above groups, examples of alkyl, haloalkyl, cycloalkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, halogen atom, aralkyl, aralkoxy, aryloxy and aryl groups include those mentioned above as R ¹⁰ And R is ²⁰ The same groups as those described in the above.

The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 7 carbon atoms. Preferable examples of the group include methoxymethyl, methoxyethyl, methoxy-n-propyl, methoxy-n-butyl, ethoxyethyl and n-propoxypropyl.

In addition, R ⁶⁰ And R is ⁷⁰ Can form together with the carbon atom in position 13 to which they are bound:

an aliphatic ring having 3 to 20 carbon atoms,

Condensed polycyclic rings formed by condensed rings of the aliphatic ring and the aromatic ring or the aromatic heterocyclic ring, heterocyclic rings having 3 to 20 ring members, or

Condensed polycyclic rings formed by condensed rings of the heterocyclic ring and an aromatic ring or an aromatic heterocyclic ring.

Examples of the aliphatic ring include cyclopentane ring, cyclohexane ring, cyclooctane ring, cycloheptane ring, norbornane ring, bicyclononane ring, and adamantane ring.

Examples of the condensed polycyclic ring formed by condensing the aliphatic ring with the aromatic ring or the aromatic heterocyclic ring include phenanthrene rings.

Examples of the heterocycle include a thiophene ring, a furan ring, and a pyridine ring.

Examples of the condensed polycyclic ring formed by condensing the heterocyclic ring with an aromatic ring or an aromatic heterocyclic ring include a phenyl furan ring and a biphenyl thiophene ring.

In the present invention, R is ⁶⁰ And R is ⁷⁰ Suitable substituents of (2) include hydroxyl, alkyl, alkoxy, R ⁶⁰ And R is ⁷⁰ The carbon atoms in the 13-position bonded together form a ring. The alkyl group may be a methyl group, and the alkoxy group may be a methoxy group. Among the above suitable substituents, R is used to maintain high bimodality and to make the fading speed faster ⁶⁰ And R is ⁷⁰ Preferably together with the carbon atom in the 13-position to which they are bound form a ring. Among them, from the viewpoint of particularly rapid fading speed, the formation of the aforementioned fat is further preferredThe aliphatic ring or the condensed polycyclic ring in which the aliphatic ring and the aromatic ring or the aromatic heterocyclic ring are condensed is particularly preferably formed from the viewpoint of reducing initial coloring due to a thermochromic phenomenon.

As R ⁶⁰ And R is ⁷⁰ The aliphatic ring formed is particularly suitably an unsubstituted aliphatic hydrocarbon ring, or an aliphatic hydrocarbon ring having at least 1 substituent selected from the group consisting of an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, an aralkyl group, an aryl group and a halogen atom. As the alkyl group, the haloalkyl group, the cycloalkyl group, the alkoxy group, the amino group, the aralkyl group, the aryl group and the halogen atom as substituents, there may be mentioned the above-mentioned R ¹⁰ And R is ²⁰ The radicals indicated are identical.

Examples of more preferable groups include monocyclic rings such as cyclohexane ring, cyclooctane ring and cycloheptane ring, norbornane ring, bicyclo [3,2,1] octane ring, bicyclo [4,2,0] octane ring, bicyclo [3, 1] nonane ring, bicyclo [4,3,0] nonane ring, bicyclo [6,3,0] undecane ring and tricyclic rings such as adamantane ring, and these rings are substituted with a lower alkyl group having 4 or less carbon atoms such as at least 1 methyl group. Among these, the monocyclic or bicyclic ring exerts a particularly excellent effect from the viewpoint of reducing initial coloring due to a thermochromic phenomenon while maintaining high bimodality and rapid fading speed.

In the present invention, R is ⁶⁰ And R is ⁷⁰ The most suitable representative examples of the monocyclic or bicyclic ring formed by bonding are shown, for example, by the following formulas. In the following formula, the carbon atom attached with 13 is the carbon atom at position 13.

Of the above monocyclic or bicyclic rings, particularly, cyclooctane ring, 3, 5-tetramethyl cyclohexane ring, 4-diethyl cyclohexane ring, 4-dimethyl cyclohexane ring, bicyclo [4,3,0] nonane ring are most suitable.

By using a photochromic compound having such a single ring or double rings, the rate of discoloration can be increased, and the permeability can be improved. In particular, the coloration due to the thermochromic phenomenon can be reduced, and therefore the coloration of the optical article due to the temperature dependency can be reduced. In order to adjust the color tone, a plurality of these photochromic compounds may be used.

Examples of the photochromic compound (a) include the following compounds.

/>

Next, (b) a photochromic compound that can be suitably used when the (D) polarizing functional layer is provided will be described.

(b) Photochromic compounds

In the present invention, when the optical article has (D) a polarizing functional layer, (b) a photochromic compound having an absorbance at a wavelength of 420nm of 0.100 or more and an absorbance at a wavelength of 430nm of 0.015 or more is preferably used in order to further improve antiglare property in a room. When the polarizing functional layer (D) is provided, the film is transparent in a room, but is colored when not irradiated. Therefore, if the light transmittance in the non-irradiated state satisfies 30% or more, the use of (b) the photochromic compound is preferable. By using the (b) photochromic compound, antiglare property can be improved. The upper limit of the absorbance of the photochromic compound (b) at a wavelength of 420nm is 0.800 or less, and the upper limit of the absorbance at a wavelength of 430nm is preferably 0.500. The measurement conditions of absorbance may be the same as those described for the photochromic compound (a) above.

In the present invention, when the polarizing functional layer (D) is provided, various photochromic compounds can be used for color matching. In this case, a photochromic composition formed of only (b) the photochromic compound may be used. However, the composition containing a plurality of photochromic compounds may contain the photochromic compound (a) as long as the composition satisfies that the absorbance at the wavelength of 420nm is 0.100 or more and 0.800 or less and the absorbance at the wavelength of 430nm or more is 0.015 or more and 0.500.

As the specific photochromic compound (b), a chromene compound having an indeno [ 2,1-f ] naphtho [ 1,2-b ] pyran skeleton represented by the following formula (2) is preferably used.

(R ¹ And R is ² )

Here, it is preferably selected from R ¹ And R is ² The following substituent groups.

Namely, R ¹ And R is ² Each hydrogen atom, hydroxyl group, cyano group, nitro group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, heterocyclic group containing a ring member nitrogen atom and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aralkoxy group, aryloxy group, or aryl group. Specific examples of these groups include those described above for R ¹⁰ And R is ²⁰ The same groups as those described in the above. However, in order to form (b) the photochromic compound, R is preferably ¹ And R is ² Both of which are not hydrogen atoms.

(R ³ )

R ³ Is a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom of a ring member and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group, or an aryl group. Alkyl, cycloalkyl, alkoxy, amino, heterocyclic group containing a nitrogen atom of a ring member and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, and alkylExamples of the aminocarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aralkoxy group, aryloxy group or aryl group include those described in the foregoing R ¹⁰ And R is ²⁰ The same groups as those described in the above.

(suitable R) ¹ 、R ² And R is ³ Is a combination of (a) and (b)

In order to increase the wavelength of the absorption end of the photochromic compound (b) and improve the absorbance, the following combination of substituents is preferable. R is R ¹ 、R ² And R is ³ The at least 2 of the above-mentioned alkyl group, cycloalkyl group, alkoxy group, amino group, heterocyclic group containing a nitrogen atom of a ring member and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, aralkyl group, aralkoxy group, aryloxy group, or aryl group is preferable. The remaining 1 group may be any of the groups exemplified above.

More preferably, the process is carried out,

R ¹ is an alkoxy group, an aryloxy group, or an aryl group,

R ² is an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom of a ring member and bonded to an aromatic hydrocarbon ring or an aromatic hetero ring through the nitrogen atom, an aryloxy group, or an aryl group,

R ³ most preferred are alkoxy, amino, aryloxy, or aryl groups.

R is as follows ¹ 、R ² Or R ³ The aryl group in (a) may have a substituent.

It is further preferred that the composition comprises,

R ¹ is any group selected from alkoxy, aryloxy, or aryl,

R ² is alkoxy, amino, aryloxy, or aryl,

R ³ most preferred is an alkoxy group.

(R ⁴ And R is ⁵ )

R ⁴ And R is ⁵ Aryl, heteroaryl or alkyl are each preferred. Specific examples of the group include those other than the above (R ⁴⁰ And R is ⁵⁰ ) The same groups as those described in the above.

(R ⁶ And R is ⁷ )

R ⁶ And R is ⁷ Can be mentioned as R as described above ⁶⁰ And R is ⁷⁰ The same groups as described in the above. In addition, from the viewpoint of fast discoloration, R is the same as ⁶⁰ And R is ⁷⁰ Likewise, it is possible to form, together with the carbon atom in position 13 to which they are bound:

an aliphatic ring having 3 to 20 carbon atoms,

R ⁶ And R is ⁷ Particularly suitable substituents with R ⁶⁰ And R is ⁷⁰ The same applies.

Examples of the photochromic compound (b) include the following compounds.

The above (a) photochromic compound or (b) photochromic compound is preferably selectively used according to the use. In the following, when a plurality of photochromic compounds are used in descriptions such as the blending ratio of the photochromic compounds, the total amount of the photochromic compounds is used as a reference. For example, in the case of using a plurality of (a) photochromic compounds, the total amount of these (a) photochromic compounds is used as a reference. In the same manner, when the photochromic compound (a) and the photochromic compound (b) are used, the blending amount of the photochromic compound (a) and the photochromic compound (b) is based on the total amount of the photochromic compound (a) and the photochromic compound (b).

< Compound (Compound 1) having an absorption peak in the wavelength range of 550 to 600nm >

The compound having an absorption peak in the wavelength range of 550 to 600nm (compound 1) used in the present invention is not particularly limited as long as the compound is used so that the optical article satisfies the characteristics of the above (1) (2) (if necessary, the characteristics of (3)). The 1 st compound may be used alone or in combination of 1 or more than 2.

In view of the antiglare property and the permeability of the obtained optical article, the absorption intensity in the absorption peak of the 1 st compound is preferably 0.1X10 ⁵ ～10.0×10 ⁵ ml/g.cm, more preferably 0.5X10 ⁵ ～5.0×10 ⁵ ml/g.cm, more preferably 1.0X10 ⁵ ～5.0×10 ⁵ ml/g·cm。

In view of the antiglare property and the permeability of the obtained optical article, the half width of the maximum absorption peak of the 1 st compound is preferably 40nm or less. The lower limit of the half-value width is not particularly limited, and is 10nm.

The absorption peak, absorption intensity and half-value width were 1.0X10 in chloroform at 23 ℃ ^-5 g/mL.

The 1 st compound used in the present invention includes a nitro compound, an azo compound, an anthraquinone compound, a reducing compound, a porphyrin compound, a rare earth metal compound, and the like. Among them, porphyrin compounds and rare earth compounds are preferable in terms of both antiglare property and visibility. Further, from the viewpoint of dispersion stability in a plastic material, a porphyrin compound is most preferable.

Examples of the rare earth metal compound include a complex such as hydrated hydroxy (1-phenyl-1, 3-butanedione) neodymium, hydrated hydroxy (benzoylmethylphenyl ketone) neodymium (aquahydroxy (phenacyl phenylketonato) neodymium), hydrated hydroxy (1-phenyl-2-methyl-1, 3-butanedione) neodymium, hydrated hydroxy (1-thiophenyl-1, 3-butanedione) neodymium, hydrated hydroxy (1-phenyl-1, 3-butanedione) erbium, and hydrated hydroxy (1-phenyl-1, 3-butanedione) holmium.

The porphyrin-based compound is a compound optionally having various substituents on the porphyrin skeleton. For example, compounds described in JP-A-5-194616, JP-A-5-195446, JP-A-2003-105218, JP-A-2008-134618, JP-A-2013-61653, JP-A-2015-180942, WO2012/020570, JP-A-5626081, JP-A-5619472, JP-A-5778109 and the like can be suitably used. Among them, a porphyrins compound represented by the following formula (3) is particularly suitable.

(in the formula (3), Y ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ And Y ⁸ Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, a monoalkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkylthio group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and a ring other than an aromatic ring may be formed by the linking group, and a part or all of the hydrogen atoms of the alkyl group, the alkoxy group, or the aryl group may be optionally substituted with halogen.

M is a metal atom of valence 2 or an oxidized metal atom. ).

Wherein,

Y ¹ 、Y ³ 、Y ⁵ and Y ⁷ Is a hydrogen atom, and is preferably a hydrogen atom,

Y ² 、Y ⁴ 、Y ⁶ and Y ⁸ Straight-chain or branched alkyl groups having 1 to 6 carbon atoms are preferable.

Examples of the straight-chain or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1, 2-dimethylpropyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, 2-methylpentyl, 4-methyl-2-pentyl, 1, 2-dimethylbutyl, 2, 3-dimethylbutyl and 2-ethylbutyl.

Examples of the metal atom having a valence of 2 include Cu, zn, fe, co, ni, ru, pd, pt, mn, mg, ti, ba, cd, hg, pd, sn. Examples of the metal oxide atom include VO, mnO, tiO.

Among them, the metal atom (M) is preferably Cu (copper) of valence 2. It is preferable to use a porphyrazine compound having Cu. By using a copper-containing tetrazaporphyrin compound, the photochromic residual ratio described in detail below can be maintained high, and durability can be improved. In particular, when (a) the first functional layer contains the 1 st compound, this effect can be significantly exhibited. That is, in the case where the first functional layer (a) contains the compound 1, a tetrazaporphyrin compound having Cu is preferably used in consideration of the residual rate of photochromic properties. It is presumed that the photochromic compound is decomposed by radical of oxygen source or singlet oxygen generated when the porphyrin compound is photoexcited, but it is considered that the decomposition can be suppressed by using the tetrazaporphyrin compound having Cu.

Further, by using a porphyrazine compound having Cu, the residual ratio of the porphyrin compound itself can be maintained high in the durability evaluation, and a high contrast can be maintained.

The tetrazaporphyrin compound represented by the formula (3) actually represents a mixture of 1 or 2 or more isomers. In describing the structure of such a mixture of a plurality of isomers, in the present invention, for convenience, one structural formula shown in the above formula (3) is also described, for example.

In the optical article of the present invention, 1 kind of the tetrazaporphyrin compound may be used alone or a plurality of kinds may be used in combination. Furthermore, a mixture of 1 or 2 or more isomers may be used. Further, if desired, each isomer may be separated from the mixture, 1 compound among the isomers may be used, and further, a plurality of isomers formed in an arbitrary ratio may be used in combination.

In view of the required characteristics of the optical article of the present invention, among the aforementioned tetrazaporphyrin compounds, the compound having an absorption peak at a wavelength of more than 550nm and 600nm or less is preferable, the compound having an absorption peak at a wavelength of 575 to 600nm is more preferable, and the compound having an absorption peak at a wavelength of 580 to 595nm is further preferable. Particularly preferred are compounds having absorption peaks at wavelengths of 590 to 595 nm.

When the amount of the compound 1 is too large, the antiglare property can be improved, but the compound is likely to be a photochromic optical article having a violet or blue color. Therefore, the following compounding amounts are preferably satisfied.

< compounding ratio of photochromic Compound and Compound 1 >

The blending ratio of the photochromic compound and the 1 st compound in the optical article is not particularly limited as long as the optical article of the present invention satisfies the characteristics of the aforementioned (1) and (2). Further, it is preferable that the ratio of the features of (3) is satisfied in addition to the features of (1) and (2). Among them, the following blending ratio is preferable in order to produce an optical article having more excellent performance and to produce the optical article more easily. That is, when the mass of the first functional layer (a) is set to 100 mass%, the photochromic compound is preferably contained in an amount of 0.1 to 10.0 mass%. In the case where the first functional layer (a) contains the 1 st compound, the first functional layer preferably contains 0.001 to 2.0 mass% of the 1 st compound. Further, in order to produce an optical article exhibiting more excellent performance, when the first functional layer (a) contains the 1 st compound, it is preferable to contain 0.5 to 8.0 mass% of the photochromic compound and 0.003 to 1.0 mass% of the 1 st compound.

The optical article of the present invention is characterized by having a laminated structure. The thickness of each layer varies depending on the method of manufacturing the optical article, the use, and the like, and therefore the amounts of the photochromic compound and the 1 st compound contained in each layer cannot be approximated. For example, if the thickness of the first functional layer (a) is large, the amount of the photochromic compound contained in the first functional layer (a) can be reduced. Thus, the compounding amounts of the photochromic compound and the 1 st compound are exemplified as the amount contained in the optical article to be subject.

In addition, the compounding ratio of the photochromic compound to the 1 st compound preferably satisfies the following range. When the photochromic compound is contained in a plurality of layers, the total amount of the photochromic compound and the total amount of the 1 st compound are used as references. When the amount of the compound 1 is 100 parts by mass, the amount of the compound 1 is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.05 to 10 parts by mass, and even more preferably in the range of 0.05 to 5 parts by mass. The first functional layer (a) may contain both the photochromic compound and the 1 st compound, although the following description will be given. Even in this case, or in the case where (a) the first functional layer and (C) the second functional layer are independently provided, the foregoing compounding ratio is preferably satisfied. That is, the blending ratio of the 1 st compound is preferably in the above range with respect to the total amount of the total photochromic compounds contained in the optical article. In the case of using a plurality of photochromic compounds and a plurality of the 1 st compound, the total amount is taken as a reference.

< others; antioxidant >

In the optical article of the present invention, known additives may be compounded. (A) The first functional layer is an important functional layer comprising a photochromic compound. Therefore, in order to prevent the (a) first functional layer itself from oxidative deterioration during the production of an optical article and/or during the long-term use of the optical article, it is preferable to blend an antioxidant in the (a) first functional layer. The antioxidant can also prevent oxidative degradation of the photochromic compound and the 1 st compound. Therefore, it is considered that the effect of improving the durability (photochromic residual rate, contrast durability) of the optical article is also exhibited. Therefore, in the case where the (a) first functional layer contains the aforementioned compound 1, the aforementioned antioxidant may be suitably compounded in the (a) first functional layer. Further, as will be described in detail below, when the first functional layer (a) contains the compound 1, it is preferable to compound both the antioxidant and the stabilizer described in detail below.

It is to be noted that these antioxidants may be contained in layers other than the first functional layer (a).

The antioxidant used in the present invention specifically includes hindered phenol antioxidants, phosphorus antioxidants and sulfur antioxidants. Among them, a hindered phenol-based antioxidant is preferably contained.

In the present invention, commercially available hindered phenol antioxidants can be used. Examples thereof include 2, 6-bis (1, 1-dimethylethyl) -4-methylphenol,

Ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ]

Octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate, tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 4' -butylidenebis (3-methyl-6-tert-butylphenol), tris- (3, 5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 2,4, 6-tris [3, 5-di-tert-butyl-4-hydroxybenzyl ] -1,3, 5-trimethylbenzene, 4- [ [4, 6-bis (octylthio) -1,3, 5-triazin-2-yl ] amino ] -2, 6-bis (1, 1-dimethylethyl) phenol, examples thereof include ADK STAB (registered trademark) AO series (AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, etc.), irganox (registered trademark) series (Irganox 245, irganox1010, irganox1135, etc.), sumiLIZER (registered trademark) GA80, etc. manufactured by Sumitomo chemical Co., ltd., BASF Japan Ltd.

< compounding amount of antioxidant >

In the present invention, the compounding amount of the antioxidant is not particularly limited. Among them, the following blending amount is preferable from the viewpoint of suppressing oxidative degradation and improving durability of the optical article by combining with a stabilizer described in detail below. Specifically, the first functional layer (a) is preferably 20 to 200 parts by mass per 100 parts by mass of the photochromic compound. By satisfying the blending amount, the effect of preventing oxidative deterioration and the effect of maintaining durability can be exerted. In order to further exert these effects, the first functional layer (a) is preferably 50 to 150 parts by mass per 100 parts by mass of the photochromic compound.

The antioxidant may be used alone or in combination of two or more kinds. When a plurality of types are used, the total amount is used as a reference.

Next, a stabilizer required for further improving durability in the optical article of the present invention will be described.

< stabilizer >)

The (a) first functional layer of the optical article of the present invention, which contains at least a photochromic compound, preferably contains at least 1 stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine-based light stabilizer, and a singlet oxygen quencher. By compounding the stabilizer, the photochromic residual ratio can be maintained high, and durability can be improved. In particular, this effect is particularly remarkable in the following cases. That is, in the case where the first functional layer (a) contains the compound 1, the effect of compounding the stabilizer becomes remarkable. The stabilizer may be used alone or in combination of two or more kinds.

The effect is presumed, but the present inventors consider the following. In particular, when the 1 st compound and the photochromic compound coexist in the same layer, the 1 st compound is considered to have an adverse effect on the photochromic compound. Although this is only presumed, it is considered that the photochromic compound is decomposed by radicals or singlet oxygen generated from the 1 st compound in an excited state in which ultraviolet rays are absorbed. As a result, the photochromic residual rate was considered to be reduced. It is considered that if the above-mentioned stabilizer is compounded (present) therein, decomposition of the photochromic compound can be suppressed. As a result, it is considered that the photochromic residual rate can be maintained high and the durability can be improved. In this case, the 1 st compound used is preferably a porphyrazine compound having copper. By using the copper-containing tetrazaporphyrin compound, the effect of suppressing the decomposition of the photochromic compound (the effect of maintaining the photochromic residual rate at a high level) can be further improved. Further, when the first functional layer (a) contains the compound 1, the antioxidant is preferably contained.

Further, the effect of the stabilizer when compounded can be significantly exhibited when (a) the first functional layer is a relatively thin layer. For example, when the thickness of the first functional layer (a) is about 10 to 100 μm, the amount of the photochromic compound and/or the 1 st compound blended increases. In this case, the concentration of the photochromic compound is high, and thus the decomposition inhibition effect by compounding the stabilizer is remarkable.

A stabilizer; ultraviolet absorber >, and

in the present invention, a commercially available product can be used as the ultraviolet absorber. Among them, an ultraviolet absorber having an absorption peak at a wavelength of 320 to 400nm is preferably used. Specifically, benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and benzoate-based compounds can be used. Among them, benzotriazole-based compounds are particularly preferable. Specifically, there may be mentioned:

2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ], 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazol-2-yl) -6-t-butyl-4-methylphenol 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1, 1-dimethylpropyl) phenol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2' -methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, branched/linear alkyl esters of 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy having 7 to 9 carbon atoms,

A mixture of about 50 mass% of the ester compound of beta- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl ] -propionic acid with polyethylene glycol 300, about 38 mass% of the ester compound of bis { beta- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl ] -propionic acid } with polyethylene glycol 300, and about 12 mass% of polyethylene glycol 300. Examples of commercially available products include the ADK STAB (registered trademark) LA series (LA-24, LA-29, LA-31, LA32, LA-36, etc.) manufactured by ADEKA CORPORATION, the SHIPRO KASEI KAISHA, LTD. SEESORB (registered trademark) series (SEESORB 701, SEESORB703, SEESORB704, SEESORB709, etc.), chemipro Kasei Kaisha, ltd, the KEMISORB (registered trademark) series (KEMSORB 74, KEMSORB79, KEMSORB279, etc.), and the BASF Japan Ltd, the TINUVIN (registered trademark) series (TINUVINPS, TINUVIN-2, TINUVIN1130, etc.). These ultraviolet absorbers may be used in an amount of 1 or more.

The ultraviolet absorber is effective to be contained in the first functional layer (a), but may be incorporated in other layers.

A stabilizer; hindered amine light stabilizer

In the present invention, the hindered amine light stabilizer is preferably a hindered amine compound having a 2, 6-tetramethyl-4-piperidinyl skeleton, and commercially available ones can be used. Examples thereof include bis (2, 6-tetramethyl-4-piperidinyl) sebacate, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate, and the like bis (1-octyloxy-2, 6-tetramethyl-4-piperidinyl) sebacate bis (1-octyloxy-2, 6-tetramethyl) -4-piperidinyl) sebacate ester 1,2, 6-pentamethyl-4-piperidinyl acrylic acid methyl ester, 2- [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -2-butylmalonic acid [1,2, 6-pentamethyl-4-piperidinyl ], poly [ {6- (1, 3-tetramethylbutyl) amino-1, 3, 5-triazine-2, 4-diyl } { (2, 6-tetramethyl-4-piperidinyl) imino } hexamethylene{ (2, 6-tetramethyl-4-piperidinyl) imino } ], and methyl 1,2, 6-pentamethyl-4-piperidinyl acrylate and the like. Trade names include ADK STAB (registered trademark) LA series (LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-81, LA-82, etc.) manufactured by ADEKA CORPORATION, TINUVIN (registered trademark) series (TINUVIN 123, TINUVIN171, TINUVIN249, TINUVIN292, TINUVIN765, TINUVIN622SF, etc.) manufactured by BASF Japan Ltd, chimassorb (registered trademark) series (Chimassorb 2020FDL, chimassorb944FDL, etc.), and the like. These hindered amine-based light stabilizers may be 1 kind, or a plurality of kinds may be used.

The hindered amine-based light stabilizer is effective to be contained in the first functional layer (a), but may be compounded in other layers.

A stabilizer; singlet oxygen quencher

In the present invention, the singlet oxygen quencher is not particularly limited as long as it captures singlet oxygen generated by activation of oxygen by energy of light and deactivates the singlet oxygen, and commercially available products can be used. Examples thereof include vinyl, amine, furan, diimmonium salt, and nickel complex. More specifically, there are no particular restrictions, and examples thereof include olefinic compounds such as tetramethylethylene, cyclopentene, cyclohexene, 2, 5-dimethyl-2, 4-hexadiene, 1, 3-cyclopentadiene, α -terpene, and β -carotene,

Amine compounds such as diethylamine, triethylamine, 1, 4-Diazabicyclooctane (DABCO), 2, 6-tetramethylpiperidine, N-ethylimidazole, N, N, N ', N' -tetramethylphenylenediamine, N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N-isopropylcarbazole, N-phenylcarbazole, and furan compounds such as 1, 3-diphenylisobenzofuran,

Naphthalene, dimethylnaphthalene, dimethoxy anthracene, diphenyl anthracene, pyrene,Perylene, coronene, tetracene, pentacene, rubrene, 3, 4-benzofluoranthene, 2, 3-benzofluorene, 1, 12-benzopyrene, 3, 4-benzopyrene, 4, 5-benzopyrene, and polycyclic aromatic compounds such as alkyl substituents thereof,

Aromatic compounds such as 1,2,3, 4-tetraphenyl-1, 3-cyclopentadiene and penta-phenylcyclopentadiene,

Organic nickel compounds such as bis (dithiobenzyl) nickel, nickel p-toluenesulfonate, bis (4-dimethylaminodithiobenzyl) nickel, bis (dithiodiacetyl) nickel, bis (dibutyldithiocarbamate) nickel bis (octylphenyl) sulfide, bis (1, 2-dithiophenol) tetrabutylammonium salt, bis (thioccatechol) tetrabutylammonium salt, tetrabutylphosphonium bis (1, 2-benzenedithio) nickel (III) carboxylate, bis (4, 4 '-di-t-butyl-dithiobenzyl) nickel, bis (4, 4' -diisopropyldithiobenzyl) nickel, and 4-N, N-diethylaminosulfonyl-1, 2-benzenedithiol nickel.

It is to be noted that inclusion of the singlet oxygen quencher in the (a) first functional layer is effective, but may be compounded in other layers.

Suitable compounding amount of stabilizer and combination with antioxidant

In the present invention, the compounding amount of the stabilizer is not particularly limited, and in the case of compounding in the first functional layer (a), the following compounding amount is preferable. (A) The first functional layer preferably contains 1 to 1000 parts by mass of a stabilizer, more preferably 5 to 800 parts by mass, and still more preferably 10 to 400 parts by mass, per 100 parts by mass of the photochromic compound. In the case where the stabilizer is used alone, the compounding amount thereof preferably satisfies the above-described range, and in the case where the stabilizer is used in plural, the total amount thereof preferably satisfies the above-described range.

The optimum value of the stabilizer may be determined within the above-mentioned compounding amount range depending on the effect and compatibility with the resin. Among them, for example, when an ultraviolet absorber is used, it is preferable that the ultraviolet absorber is contained in an amount of 20 to 250 parts by mass based on 100 parts by mass of the photochromic compound. When the hindered amine light stabilizer is used, it is preferable that the hindered amine light stabilizer is contained in an amount of 20 to 250 parts by mass per 100 parts by mass of the photochromic compound. When the singlet oxygen quencher is used, it is preferable to contain 10 to 100 parts by mass of the singlet oxygen quencher per 100 parts by mass of the photochromic compound.

In the case of using the stabilizer, the first functional layer (a) preferably contains the aforementioned compound 1. That is, the (a) first functional layer preferably contains a photochromic compound, a 1 st compound, and a stabilizer. In this case, the stabilizer is preferably in the aforementioned range. The first functional layer (a) preferably contains 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.05 to 5 parts by mass of the 1 st compound per 100 parts by mass of the photochromic compound.

Even when the stabilizer is contained, the first functional layer (a) preferably contains the antioxidant. That is, in the case where the first functional layer (a) contains the photochromic compound and the 1 st compound, it is preferable to contain both the antioxidant and the stabilizer. The antioxidant is preferably the hindered phenol antioxidant. In order to improve the durability of the optical article, the compounding stabilizer is considered to be effective, but it is considered that the inclusion of the antioxidant can exert a higher effect. (A) When the first functional layer contains the photochromic compound and the 1 st compound, the antioxidant is preferably blended in an amount of 20 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the photochromic compound. By satisfying the antioxidant in this range, not only the oxidation degradation of the first functional layer (a) is prevented, but also excellent effects are exhibited and durability is improved. In this case, the compounding amounts of the compound 1 and the stabilizer are as described above.

Further, as described above, when (a) the first functional layer is a thin film facing each other, the effect can be significantly exhibited.

Layer composition of optical article

The optical article of the present invention has a laminated structure in which (a) the first functional layer and (B) the lens substrate are independent of each other. That is, by forming the laminated structure, for example, in the case of forming an eyeglass lens, the difference in thickness between the center portion and the end portion of the colored (a) first functional layer portion at the time of color development is small (almost none), and therefore, color unevenness can be suppressed. That is, by forming the laminated structure, the first functional layer (a) can be made relatively thin, and thus the absolute difference in thickness can be made small. As a result, color unevenness in color development can be suppressed.

In the optical article of the present invention, the method for forming the laminated structure having (a) the first functional layer and (B) the lens substrate is not particularly limited, and the following method can be used.

There may be mentioned: a method in which a pair of optical sheets are bonded with (a) a first functional layer having adhesiveness to obtain a laminate, and then (B) a lens base material is formed on the surface of the optical sheet on one side of the obtained laminate, for example, by injection molding. Hereinafter, this method may be simply referred to as "adhesive method".

There may be mentioned: preparing (B) a lens substrate, and forming (a) a first functional layer thereon by a coating method or a casting polymerization method. Hereinafter, when a laminated structure is formed by a coating method, it may be simply referred to as a "coating method". In the case of forming a laminated structure by a casting polymerization method, it is sometimes simply referred to as "casting polymerization method".

In these "binder method", "coating method" and "casting polymerization method", the 1 st compound may be blended in the (a) first functional layer. In this case, (a) the first functional layer becomes a second functional layer which also contains (C) the 1 st compound.

In the above method, the 1 st compound may be blended into the (B) lens substrate, or the 1 st compound may be blended into a layer other than the (a) first functional layer and the (B) lens substrate. (B) When the 1 st compound is blended in the lens substrate, (B) the lens substrate can be regarded as (C) the second functional layer. When the 1 st compound is blended in a layer other than the (a) first functional layer and the (B) lens base material, the (C) second functional layer is independently present.

In the present invention, the (a) first functional layer containing at least a photochromic compound is present independently of the (B) lens base material, and the thickness thereof is preferably 10 to 1000 μm, more preferably 20 to 900 μm. By satisfying this range, the photochromic characteristics can be fully exhibited, and a photochromic optical article with less color unevenness can be produced. The first functional layer (a) may be formed to have a different thickness suitable for the use of the aforementioned "adhesive method", "coating method" or "cast polymerization method". These will be described in detail below. The "casting polymerization method" can be used, but when the first functional layer (a) is formed to a thickness of about 10 to 100 μm, the "adhesive method" or the "coating method" is advantageous.

Of course, when the compound 1 is compounded, the above-described means may be combined and compounded.

Lens substrate (B)

The (optical) substrate to be used is not particularly limited, and any substrate used in a usual optical substrate may be used. Specifically, plastic lenses and inorganic glass can be used as the substrate. The plastic lens may be a thermosetting resin or a thermoplastic resin. The lens base material may also include a polarizing functional layer (D) described in detail below. The surface on which the first functional layer and/or the second functional layer are formed may be subjected to chemical treatment with an alkali solution, an acid solution, or the like, or physical treatment with corona discharge, plasma discharge, polishing, or the like. In the case of using a coating method described in detail below, an adhesive resin layer (i.e., an undercoat layer) may be provided in advance. The thickness of the lens substrate (B) is not particularly limited, but is preferably 0.5 to 30mm.

(A) first functional layer and/or (C) second functional layer >

Substrate for forming (A) first functional layer and/or (C) second functional layer

Among the above-mentioned "adhesive method", "coating method" and "casting polymerization method", an adhesive composition or a curable composition in which an adhesive resin or a polymerizable monomer and a photochromic compound and a 1 st compound are combined is preferably used. These compositions are preferably used to form (a) a first functional layer and/or (C) a second functional layer.

Examples of the resin constituting the adhesive resin include acrylic resins (such as poly (meth) acrylic acid, polymethyl methacrylate, polymethyl acrylate, and butyronitrile-methyl acrylate copolymer resins), epoxy resins, episulfide resins, thietanyl resins, allyl resins, vinyl resins, poly (thio) urethane-urea resins, polyvinyl alcohols, polyvinyl pyrrolidones, cellulose resins (such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose), polyacrylamides, polyethylene oxides, polyethylene glycols, polypropylene glycols, casein, gelatin proteins, starches, olefin resins (such as polyethylene and polypropylene), polyesters, polyvinyl chloride, styrene resins (such as polystyrene, and butyronitrile-styrene copolymer resins), polycarbonates, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral, polyisobutylene, polytetrahydrofuran, polyaniline, and butyronitrile-butadiene-styrene copolymer (such as ABS resins), polyamides (such as nylon), polyimides, polydienes (such as polyisoprene, polybutadiene), polysiloxanes (such as polydimethylsiloxane), polysulfones, polyethylene anhydrides, polydienes, and polydienes. These resins may be copolymerized as appropriate, or modified.

As the polymerizable monomer, a monomer component constituting the resin is preferably used, and examples thereof include urethane monomers containing a polyisocyanate component (polyisocyanate compound and/or polythiourethane compound) and a poly (thio) polyol component (polyol compound and/or polythiol compound). Further, a radically polymerizable monomer component containing a vinyl monomer and a (meth) acrylic monomer may be mentioned.

In the present invention, as described above, a photochromic compound is preferably used in which a part of the molecule is cleaved to develop a color and the site of the cleavage is recombined to fade. In the case of using such a photochromic compound, it is preferable to use a combination of polymerizable monomers or a resin which forms a matrix in which a free space which does not interfere with molecular movement at the time of occurrence of the cleavage and recombination is sufficiently present.

The resin to be the matrix may be mixed with known additives.

In the case where the (a) first functional layer contains the photochromic compound and the 1 st compound, the (C) second functional layer may not be provided independently, but the (C) second functional layer may be provided even in such a case as long as the effect is exerted. However, in the case where the (a) first functional layer contains the photochromic compound and the 1 st compound, as described above, the (a) first functional layer preferably contains a stabilizer.

Further, as a result of studies by the present inventors, it has been found that when the optical article includes (a) the first functional layer (excluding the 1 st compound) and (C) the second functional layer independently of each other, the photochromic residual rate can be maintained at a high level. In the case where the first functional layer (a) (not including the 1 st compound) is not directly bonded to the second functional layer (C), specifically, bonded via another layer, the photochromic residual ratio can be maintained high. For example, if the laminate is formed by the first functional layer (a) excluding the 1 st compound)/(D) polarizing functional layer, or the other adhesive layer/(C) second functional layer in this order, the photochromic residual ratio can be maintained high even if the stabilizer is not blended. However, even in this case, the stabilizer can be compounded in each layer.

In the case where the second functional layer (C) is provided independently, it may be appropriately determined according to various compounds used and the like. Among them, it is preferable to dispose (a) the first functional layer on the sunlight-irradiated side and (C) the second functional layer behind it. Namely, (C) the second functional layer is disposed on the sunlight irradiation side. There is light absorbed by the (C) second functional layer. As a result, (a) the photochromic compound in the first functional layer may not develop color sufficiently. Therefore, the first functional layer (a) is preferably disposed on the sunlight-irradiated side.

Next, a method of manufacturing the optical article of the present invention will be described.

< formation of laminated Structure based on adhesive method >

(A) formation of first functional layer based on adhesive method >)

The binder method comprises the following steps: a first functional layer (A) having adhesiveness is prepared, and an optical sheet is bonded to at least one surface thereof. The optical sheet may be provided with a polarizing function layer (D) described in detail below. Fig. 1 shows an example of a laminated structure when an adhesive method is used. Fig. 1 is an example of a case where the first functional layer contains a photochromic compound and a 1 st compound. Fig. 1 shows an example of an optical article in which an optical sheet 1, a pre-adhesive layer 2, and a first functional layer 3 (in this example, the first functional layer 3 is a layer having a second functional layer) are laminated in this order of the pre-adhesive layer 2 '/the optical sheet 1'/(B) a lens substrate 7. In this example, it is preferable that: after manufacturing the photochromic laminate 6 formed of the optical sheet 1/the pre-adhesive layer 2/the first functional layer 3 (in this example, the first functional layer 3 is a layer having a second functional layer) and/or the pre-adhesive layer 2 '/the optical sheet 1, the lens substrate 7 is formed (B) on the optical sheet 1' of the photochromic laminate 6, and the optical article 8 is manufactured.

In the case of producing the first functional layer (a) by the adhesive method, a functional layer sheet is produced using an adhesive composition containing a polymerizable monomer, an adhesive resin, and a photochromic compound, and the functional layer sheet is sandwiched between 2 transparent sheets (optical sheets), so that a laminate having the first functional layer (functional layer sheet) having adhesion is produced. In this case, in the production of the functional layer sheet, it is preferable that: the functional layer sheet is obtained by coating with a coating liquid using an organic solvent in the adhesive composition. The polymerizable monomer or the adhesive resin is preferably a urethane monomer or a urethane resin adhesive. In this case, the adhesive composition can further contain the 1 st compound, whereby the first functional layer (a) can be formed into a layer containing the photochromic compound and the 1 st compound.

The optical sheet may be any sheet that can be applied to an optical article having light transmittance without limitation. Wherein the laminate obtained by the adhesive method can be subjected to bending processing. Further, 2 times of processing such as lamination of a resin layer on the back surface of the laminate by injection molding becomes possible. Therefore, the optical sheet preferably uses a thermoplastic resin. Examples of suitable thermoplastic resins include polycarbonate resins, acrylic resins, polyacetal resins, polyamide resins, polyethylene resins, polypropylene resins, polyethylene terephthalate resins, polystyrene resins, polyphenylene sulfide resins, and polyvinyl chloride resins. Among them, polyamide resins or polycarbonate resins are particularly preferable for the reason of good adhesion and high versatility.

The optical sheet may also contain the 1 st compound. When the optical sheet contains the compound 1, the optical sheet can be regarded as (C) the second functional layer. The optical sheet may be formed of the (D) polarizing functional layer itself described in detail below. Alternatively, an optical sheet may be integrated with the polarizing functional layer (D).

The thickness of the optical sheet is preferably 30 to 1000. Mu.m, more preferably 50 to 400. Mu.m. In addition, these optical sheets may be used in combination with different thicknesses.

In addition, a lens substrate (B) is laminated on at least one surface of the optical sheet. The (B) lens substrate may include a 1 st compound. (B) In the case where the lens substrate includes the 1 st compound, (B) the lens substrate may be regarded as (C) the second functional layer.

The thickness of the first functional layer (A) in the adhesive method is preferably 10 to 100. Mu.m. In the adhesive composition containing the photochromic compound, the blending amount of the photochromic compound is not particularly limited as long as the optical article satisfies the characteristics of the above (1) (2) (if necessary, the characteristics of (3)). Among them, in view of productivity, the adhesive composition forming the first functional layer (a) preferably contains 0.5 to 5.0 parts by mass of the photochromic compound, assuming that 100 parts by mass of the polymerizable monomer or the adhesive resin (the component forming the matrix) is used. In the endurance test by the method described in examples, the following blending ratio is preferable in order to maintain a high residual rate of the photochromic compound. Specifically, when the polarizing functional layer is not included, the polymerizable monomer or the adhesive resin (component forming the matrix) is preferably included in an amount of 1.0 to 5.0 parts by mass, more preferably 1.5 to 5.0 parts by mass, and even more preferably 2.0 to 5.0 parts by mass, based on 100 parts by mass of the composition. When the polarizing functional layer is included, the photochromic compound is preferably included in an amount of 0.8 to 4.0 parts by mass, more preferably 1.0 to 4.0 parts by mass, and even more preferably 1.2 to 4.0 parts by mass, based on 100 parts by mass of the polymerizable monomer or the adhesive resin (the component forming the matrix).

The case of using the adhesive method will be described in detail. Specifically, a functional layer sheet (final (a) first functional layer) formed of an adhesive composition containing a polymerizable monomer or an adhesive resin, a photochromic compound, and if necessary, a 1 st compound and an organic solvent is produced. A functional sheet having adhesiveness was disposed between 2 optical sheets, and 2 optical sheets were bonded via the functional sheet. In this case, a layer (pre-adhesive layer) made of a pre-adhesive resin may be laminated on the surface of the optical sheet bonded to the functional sheet. By providing the pre-adhesive layer, a laminate having high bonding strength can be formed. In this case, the 1 st compound may be blended in the pre-adhesive layer. The pre-adhesive layer compounded with the 1 st compound corresponds to the (C) second functional layer.

By using the above method, a photochromic laminate having the following layer structure can be produced.

Optical sheet/(A) first functional layer/optical sheet,

Optical sheet/pre-adhesive layer/(A) first functional layer/optical sheet

Optical sheet/pre-adhesive layer/(a) first functional layer/pre-adhesive layer/optical sheet.

The 1 st compound is blended in at least 1 layer selected from the group consisting of the optical sheet, (a) the first functional layer and the pre-adhesive layer, and the layer may be formed into (C) the second functional layer. Alternatively, the 1 st compound may be disposed on the (B) lens substrate formed on the surface of one optical sheet. When the pre-adhesive layer is used, the thickness thereof is preferably 0.5 to 50. Mu.m. However, in the case of providing the (D) polarizing functional layer described in detail below, it is preferable to provide the (D) polarizing functional layer between the pre-adhesive layer of 20 to 50 μm and the first functional layer (a) in order to further improve the adhesion. In this case, a pre-adhesive layer of 0.5 to 20 μm is preferably provided on the optical sheet. The 1 st compound may be blended in any of the pre-adhesive layers.

(C) formation of second functional layer by adhesive method >)

As previously described, the 1 st compound may be compounded into the optical sheet, (a) the first functional layer, the pre-adhesive layer, and/or (B) the lens substrate. The compounding amount of the 1 st compound is not particularly limited as long as the optical article satisfies the characteristics of the aforementioned (1) (2) (including the characteristics of (3) if necessary). In view of productivity, the compound 1 is preferably contained in an amount of 0.01 to 1.0 parts by mass based on 100 parts by mass of the matrix-forming component such as the resin component. The 1 st compound can improve the productivity of the optical article itself by being compounded in the (a) first functional layer. In addition, when the adhesive is blended with the optical sheet, the pre-adhesive layer, and/or the lens substrate (B), the second functional layer (C) is present independently of the first functional layer (a). In this case, since the (a) first functional layer and the (B) second functional layer are present independently, the influence of the 1 st compound and the photochromic compound on each other can be reduced. As a result, each layer exhibits its own characteristics, and becomes a high-performance optical article.

In the case where the 1 st compound is blended with the optical sheet, the pre-adhesive layer, or (B) the lens base material, the thickness of the (C) second functional layer is the thickness of the optical sheet, the pre-adhesive layer, or (B) the lens base material.

Suitable (B) lens substrates by the adhesive method

In the laminate of the above layers, it is preferable that the (B) lens base material is integrated by injection molding a thermoplastic resin formed of the same material as the optical sheet on the optical sheet existing in the outermost layer. The method of integration includes: and a method of mounting the laminate of the layers in a mold and injection molding a thermoplastic resin for constituting an optical substrate such as a polycarbonate resin. The laminate having the first functional layer (a) obtained by the adhesive method can be processed into a spherical lens shape by bending before injection molding. Examples of the method of bending include hot press working, and vacuum suction working. The thickness of the lens substrate (B) is not particularly limited, and is 1.0 to 5.0mm.

< formation of laminated Structure based on coating method >

(A) formation of first functional layer based on coating method >)

In the case of producing a laminated structure by a coating method, the following method is preferably employed. First, a curable composition containing at least a polymerizable monomer, a photochromic compound, and if necessary, a 1 st compound is applied to a (B) lens substrate by spin coating, dipping, or the like. In the case of using the coating method, the polymerizable monomer is preferably a (meth) acrylic monomer. By using the (meth) acrylic monomer, the (a) first functional layer can be formed smoothly with less unevenness. When the curable composition has a high viscosity, it is preferable to prepare a curable composition diluted with an organic solvent, apply the composition, and then dry the composition to remove the organic solvent.

Subsequently, according to the polymerizable monomer used, the first functional layer (a) can be formed on the lens substrate (B) by thermal polymerization and/or photopolymerization. If the 1 st compound is previously blended in the curable composition, the (a) first functional layer can be regarded as having both (C) second functional layer. In addition, the 1 st compound may be blended into the (B) lens base material. In this case, (B) the lens substrate may be regarded as (C) the second functional layer.

In the case of using the coating method, there is no particular limitation, and the thickness of the first functional layer (a) is preferably 10 to 100 μm in view of productivity. In the curable composition containing the photochromic compound, the compounding amount of the photochromic compound is not particularly limited as long as the optical article satisfies the characteristics of the above (1) (2) (if necessary, the characteristics of (3)). Among them, in view of productivity, the adhesive composition for forming the first functional layer (a) preferably contains 0.5 to 5.0 parts by mass of a photochromic compound, based on 100 parts by mass of a polymerizable monomer or an adhesive resin (a component for forming a matrix).

Suitable (B) lens substrates for coating methods

The lens substrate (B) used in the coating method may be any of those described above. The thickness of the lens substrate (B) is not particularly limited, but is preferably 0.5 to 30mm.

In the case of using the coating method, it is effective to have an undercoat layer on the surface of the (B) lens substrate on which the (a) first functional layer is formed. The primer layer may be formed using a known adhesive resin. Primer compositions containing, for example, moisture-curable polyurethane-based, polyisocyanate-polyester-based two-component, polyisocyanate-polyether-based two-component, polyisocyanate-polyacrylic-based two-component, polyisocyanate-polyurethane elastomer-based two-component, epoxy-based, epoxy-polyurethane-based two-component, polyester-based, polyurethaneurea-based one-component, water-dispersible polyurethane-based, and the like are preferably used. The primer composition is applied to (B) a lens substrate, and then cured, whereby a primer layer can be formed. In the present invention, the 1 st compound may be blended in the undercoat layer. In this case, the undercoat layer may be regarded as (C) the second functional layer. In the case of forming the undercoat layer, the thickness is preferably 0.5 to 10. Mu.m.

Further, by using (B) a lens substrate having (D) a polarizing functional layer, a laminate in which (a) a first functional layer and (D) a polarizing functional layer are disposed can be produced. In this case, the (D) polarizing functional layer may be formed on the surface of the (B) lens substrate, or may be buried in the (B) lens substrate. By using a base material having (D) a polarizing functional layer, a laminate having a structure of (a) a first functional layer/(D) a polarizing functional layer can be produced. However, the first functional layer (a) may be formed on a substrate having no polarizing functional layer (D), and then the polarizing functional layer (D) may be laminated.

(C) formation of the second functional layer by coating method >

In the present invention, as described above, the (C) second functional layer may be formed by being disposed in the (a) first functional layer, the primer layer, and/or the (B) lens base material. The compounding amount of the 1 st compound to be compounded in the (C) second functional layer is not particularly limited as long as the optical article satisfies the characteristics of the aforementioned (1) (2) (including the characteristics of (3) if necessary). In view of productivity, the compound 1 is preferably contained in an amount of 0.01 to 1.0 parts by mass based on 100 parts by mass of the matrix-forming component such as the resin component. The 1 st compound can improve the productivity of the optical article itself by being compounded in the (a) first functional layer. In addition, when the primer layer and/or (B) the lens substrate are/is blended, the (C) second functional layer exists independently of the (a) first functional layer. This effect exhibits the same effects as those described in the adhesive method.

In the case where the 1 st compound is blended in the primer layer or the (B) lens substrate, the thickness of the (C) second functional layer is the thickness of the primer layer or the thickness of the (B) lens substrate.

< formation of laminated Structure based on cast polymerization >

(A) formation of the first functional layer based on cast polymerization method >)

In the present invention, when a casting polymerization method is used, the following method is preferably used. First, a lens substrate (B) is disposed between the molds. At this time, a gap for forming the first functional layer (a) is provided between at least one mold and the base material in advance. Next, in the gap, a polymerizable monomer, a photochromic compound, and a curable composition containing the 1 st compound as needed are injected between the substrate and the mold. Further, by curing the injected curable composition, the first functional layer (a) can be formed on the substrate. By this method, (a) the first functional layer can be formed relatively thicker than that by the coating method. For example, this method is suitable for the case of forming 100 to 1000 μm of the (A) first functional layer, and more suitable for the case of forming 200 to 900 μm of the (A) first functional layer.

In the case of using the cast polymerization method, the polymerizable monomer contained in the curable composition may be any of a (meth) acrylic monomer and a urethane monomer. In the case of using the casting method, the compounding amount of the photochromic compound in the curable composition containing the photochromic compound is not particularly limited as long as the compounding amount is such that the optical article satisfies the characteristics of the aforementioned (1) (2) (including the characteristics of (3) if necessary). Among them, in view of productivity, the curable composition (adhesive composition) for forming the first functional layer (a) preferably contains 0.05 to 1.0 part by mass of the photochromic compound, assuming that 100 parts by mass of the polymerizable monomer or adhesive resin (component for forming the matrix) is used.

When the compound 1 is blended in the curable composition in forming such a laminated structure, the first functional layer (a) also serves as the second functional layer (C). When the (B) lens substrate containing the 1 st compound is used, the (B) lens substrate can be regarded as the (C) second functional layer.

Suitable (B) lens substrate and (C) formation of the second functional layer by cast polymerization

The lens substrate (B) used in the casting method may be any of those described above. The thickness of the lens substrate (B) is not particularly limited, but is preferably 0.5 to 30mm.

The polarizing functional layer (D) described in detail below may be embedded in the lens substrate (B) in advance, or may be laminated on the surface of the lens substrate (B). In the case of lamination, the lamination may be bonded by an adhesive.

In the case of using the casting method, an inorganic glass can be suitably used as the (B) lens substrate. As a particularly preferred method, the following is mentioned. As a substitute for the mold, inorganic glass was prepared. Then, a laminate formed of the inorganic glass (lens substrate)/(a) first functional layer/inorganic glass (lens substrate) can be produced by injecting a curable composition between the inorganic glass and curing the composition by polymerization using a pair of inorganic glasses as a mold. In this case, in order to improve the adhesion to inorganic glass, a urethane monomer is preferably used as the curable composition for forming the first functional layer (a). In addition, the 1 st compound may be compounded in a curable composition containing a photochromic compound. When the compound 1 is blended in the curable composition, the first functional layer (a) functions as a second functional layer (C).

Further, an inorganic glass having (C) a second functional layer may be used in which a curable composition containing the compound 1 is applied to the surface of the inorganic glass to be bonded to the first functional layer (a) and/or the surface opposite thereto and cured.

In the case of providing the polarizing functional layer (D) described in detail below, if the second functional layer (C) is independently present, it is preferable to have a laminated structure of inorganic glass/(a) first functional layer/(D) polarizing functional layer/(C) second functional layer/inorganic glass. In this case, in order to exhibit excellent adhesion, the polymerizable monomer forming the (a) first functional layer and the (C) second functional layer is preferably a urethane monomer. However, the present invention is not limited to this, and for example, a layer structure of inorganic glass/(a) first functional layer/(D) polarizing functional layer/adhesive layer/inorganic glass may be formed. In this case, the adhesive layer may be a photocurable acrylic adhesive or a urethane monomer. The 1 st compound may be blended in the (a) first functional layer and/or the adhesive layer. Although the above-described examples of the inorganic glass are shown, at least one of the inorganic glasses may be modified into a plastic lens (base material).

In the case where the (C) second functional layer is independently formed, it is preferable that: preparing a curable composition containing the compound 1, and forming (C) a second functional layer on (B) the lens substrate by a coating method or a casting polymerization method. In this case, the thickness of the second functional layer (C) is preferably 5 to 1000. Mu.m.

The amount of the 1 st compound to be blended in the (a) first functional layer, the (C) second functional layer, and/or the (B) lens substrate, which are independently present, is not particularly limited as long as the amount is an amount such that the optical article satisfies the characteristics of the above (1) (2) (including the characteristics of (3) if necessary). In view of productivity, the compound 1 is preferably contained in an amount of 0.01 to 1.0 parts by mass based on 100 parts by mass of the matrix-forming component such as the resin component.

< suitable laminate structure, thickness/curvature of optical article >

By the above method, a laminated structure including at least (a) the first functional layer and (B) the lens base material can be formed. When the laminated structure is formed by the adhesive method, the coating method, or the cast polymerization method, the productivity is good, and the following laminated structure is given as an example of a mode for exerting an excellent effect.

As a suitable laminated structure in the adhesive method, the following laminated structure can be exemplified.

Optical sheet/(A) first functional layer (also having (C) second functional layer)/optical sheet/(B) lens base material,

(C) a second functional layer/an optical sheet/(B) a lens substrate formed of an optical sheet/(A) a first functional layer/a pre-adhesive layer,

A second functional layer formed of (C) an optical sheet/pre-adhesive layer/(A) a first functional layer/pre-adhesive layer/(B) a lens base material,

Optical sheet/pre-adhesive layer/(a) first functional layer/(C) second functional layer/pre-adhesive layer/optical sheet/(B) lens substrate.

As described above, the 1 st compound may be blended in the (a) first functional layer may also have the (C) second functional layer. In this case, the 1 st compound used is preferably a tetrazaporphyrin compound having a copper atom. Further, a stabilizer is preferably further compounded. The compounding amount of the stabilizer, compound 1, is as described in < suitable compounding amount of the stabilizer >.

In addition, as described above, when the photochromic compound and the 1 st compound are simultaneously present in the first functional layer (a), the photochromic residue rate may be reduced. Therefore, a correspondence relationship in which the (C) second functional layer containing the 1 st compound exists independently is also suitable. (C) In the case where the second functional layer is independently present, the 1 st compound may be blended into the optical sheet or the (B) lens substrate as described above. In the case of blending the 1 st compound into the optical sheet, it is preferable to blend the compound into the optical sheet disposed behind the side where light is irradiated.

In addition, the following modes can be produced.

Optical sheet/pre-adhesive layer/(A) first functional layer/pre-adhesive layer (or other protective layer)/second functional layer (C) formed of pre-adhesive layer/optical sheet/(B) lens substrate,

Optical sheet/pre-adhesive layer/(a) first functional layer/pre-adhesive layer (or other protective layer)/(C) second functional layer/pre-adhesive layer/optical sheet/(B) lens substrate.

As described above, it is preferable to provide another protective layer (or a pre-adhesive layer) between the (a) first functional layer and the (C) second functional layer. It is considered that the provision of the other protective layer (pre-adhesive layer) has an effect of suppressing diffusion and transfer of the 1 st compound from the (C) second functional layer to the (a) first functional layer. Therefore, the protective layer (pre-adhesive layer) preferably has good adhesion to other layers, and can suppress transfer of the 1 st compound. Specifically, a crosslinked resin layer is preferable. The thickness of the protective layer (pre-adhesive layer) is preferably 10 to 100. Mu.m.

In these layer structures, (a) the first functional layer functions to join sheets or layers disposed on both sides. In the above example, (B) a lens substrate is described separately from the optical sheet, but the optical sheet/(B) a portion of the lens substrate may be regarded as 1 optical sheet. However, as described above, it is preferable to form the (B) lens base material made of the same material on the optical sheet by injection molding.

As a suitable laminate structure in the coating method and the casting polymerization method, the following laminate structure can be exemplified.

(A) first functional layer (also having (C) second functional layer)/(B) lens substrate.

(A) first functional layer/second functional layer formed of primer layer/(B) lens substrate

(A) first functional layer/independent (C) second functional layer/(B) lens substrate.

In a suitable laminate structure in the coating method and the casting polymerization method, in the case where the (a) first functional layer contains the 1 st compound, the 1 st compound is suitably a tetrazaporphyrin compound having a copper atom, and the (a) first functional layer is preferably further compounded with a stabilizer. These compounding amounts are preferably the same as those described in the suitable laminate structure in the binder method.

In addition, the second functional layer (C) is preferably independently present, and the 1 st compound may be blended into the lens base material (B) as in the above configuration. Further, a protective layer (adhesive layer) is preferably provided in the same manner as in the adhesive method. For the same reason as described in the adhesive method, the thickness of the protective layer (adhesive layer) in this case is preferably 10 to 100 μm, and a crosslinked resin layer is preferable.

Suitable shape of the resulting optical article

The optical article of the present invention is not particularly limited, and the thickness of all layers including (a) the first functional layer and (B) the lens substrate is preferably 1 to 30mm. In addition, the thickness of the center and the thickness of the peripheral portion may be different. Specifically, the thickness of the center is preferably 1 to 30mm, and the thickness of the peripheral edge (edge) is preferably 1 to 30mm. In this case, the curvature of the optical article is preferably 0.5 to 10.0 for the convex surface, and 0.5 to 10.0 for the base arc of the concave surface. In the present invention, even such an optical article can be manufactured into a high-quality optical article free from color unevenness.

Optical article having (D) polarizing functional layer

The optical article of the present invention is not particularly limited as long as it has the aforementioned laminated structure. Further, (D) a polarizing functional layer having a polarizing function may be provided. In the case of providing the (D) polarizing functional layer, the first functional layer (a) needs to be disposed on the sunlight-irradiated side of the (D) polarizing functional layer so as not to hinder the photochromic property. (D) If the polarizing functional layer is present on the side where sunlight is irradiated, the effect of the photochromic compound cannot be exhibited.

In the present invention, the polarizing functional layer (D) is provided for adjusting the polarization degree of the optical article. Further, by forming an optical article having a specific polarization degree, antiglare properties can be improved, and light transmittance when not irradiated can be improved. In addition, since the light transmittance when not irradiated can be improved, the contrast can be improved.

(D) The polarizing functional layer may be formed by applying a composition containing a dichroic dye to the surface of the base material. In this case, for example, the composition may be applied to a substrate constituting an optical article to form a (D) polarizing functional layer, and a (a) first functional layer and optionally a (C) second functional layer may be formed on the (D) polarizing functional layer.

The polarizing functional layer (a) may be a polarizing film (hereinafter, sometimes simply referred to as a polarizing film) obtained by dyeing a stretched polyvinyl alcohol (PVA) film with a dichroic dye. In the case of using a polarizing film, for example, the polarizing film may be disposed (buried) on the surface of (B) the lens substrate or in (B) the lens substrate. Then, the first functional layer (a) and, if necessary, the second functional layer (C) may be formed on the polarizing film of the lens substrate (B) or on the lens substrate (B) in which the polarizing film is embedded.

When a polarizing film is used, resin sheets such as triacetylcellulose, polycarbonate, and polyamide may be bonded to both surfaces of the polarizing film with an acrylic or urethane adhesive. Further, an acrylic-based or silane-based coating layer may be formed on the surface of the resin sheet. The polarizing film may be formed into a shape having the same curvature as that of the optical article to be finally obtained.

As the dichroic dye forming the (D) polarizing functional layer, a commercially available dichroic dye can be used without limitation. Examples thereof include pigments such as azo pigments and anthraquinone pigments. Specifically, chloranil fast red (c.i.28160), congo red (c.i.22120), brilliant blue B (c.i.24410), benalacin (c.i.23500), karazole 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 red (c.i.23630), acid black (c.i.20470), direct azure (c.i.24400), sha Lafei denier blue 4GL (c.i.34200), direct copper blue 2B (c.i.24185), japanese brilliant violet BKconc (c.i.27885), and the like can be cited. The color of at least 2 colors may be selected from these dichroic colors according to the purpose. Note that color Index No. described in "New dye View" (Wan Shang Co., ltd., 1970) by the organic Synthesis Association is shown in parentheses.

The (D) polarizing functional layer constituted as above was prepared. The polarization functional layer (D) preferably has a polarization degree of 10 to 99.9%, more preferably 30 to 99.5%, and still more preferably 50 to 99.5% of the optical article obtained.

The polarization degree of the (D) polarization functional layer is preferably 10 to 99.5%, more preferably 20 to 99.0% from the viewpoint of making the initial light transmittance of the optical article equal to or higher than a certain level.

When a polarizing film is used as the polarizing functional layer (D), the degree of polarization of the polarizing film is first examined. Then, the degree of polarization of the finally obtained optical article was measured, and it was confirmed that the degree of polarization of the optical article was in the range of 10 to 99.9%. When the (D) polarizing functional layer is formed using the composition containing the dichroic dye, first, the relationship between the production conditions of the (D) polarizing functional layer and the polarization degree of the obtained optical article is examined. Then, the degree of polarization of the obtained optical article may be adjusted to 10 to 99.9%. The degree of polarization of the optical article is mainly dependent on the (D) polarization functional layer. Therefore, it is considered that the polarization degree of the (D) polarization functional layer formed from the composition containing the dichroic dye is the same as the polarization degree of the optical article.

(D) The thickness of the polarizing functional layer may be appropriately determined according to the light transmittance or the like of the obtained optical article when irradiated/not irradiated. Specifically, it is preferably 10 to 100. Mu.m.

Suitable laminated structures when the (D) polarization functional layer is provided are as follows.

Optical sheet/(A) first functional layer (also having (C) second functional layer)/(D) polarizing functional layer/pre-adhesive layer/optical sheet/(B) lens base material,

Optical sheet/(A) first functional layer/(D) polarizing functional layer/second functional layer formed of pre-adhesive layer/optical sheet/(B) lens base material,

Optical sheet/pre-adhesive layer/(A) first functional layer/(D) polarizing functional layer/second functional layer formed of pre-adhesive layer/(C) optical sheet/(B) lens base material,

Optical sheet/pre-adhesive layer/(a) first functional layer/(D) polarizing functional layer/pre-adhesive layer/second functional layer formed of pre-adhesive layer/optical sheet/(B) lens substrate.

Optical sheet/pre-adhesive layer/(a) first functional layer/(D) polarizing functional layer/second functional layer formed of pre-adhesive layer/optical sheet/(B) lens substrate.

In these layer structures, (a) the first functional layer functions to join sheets or layers disposed on both sides. In the above example, (B) the lens substrate and the optical sheet are described independently, but the optical sheet/(B) the portion of the lens substrate may be regarded as 1 optical sheet. However, as described above, it is preferable to form the (B) lens base material made of the same material on the optical sheet by injection molding.

In the above configuration, the laminated structure shown in fig. 2 is preferable. That is, a photochromic laminate 6' having a polarizing function layer, which is constituted by the optical sheet 1/the pre-adhesive layer 2/(a) the first function layer 3/(D) the polarizing function layer 4/the (C) second function layer 5 formed of the pre-adhesive layer/the pre-adhesive layer 2 '/the optical sheet 1', was prepared. Next, by forming (B) the lens substrate 7 on the optical sheet 1' of the photochromic laminate 6', an optical article 8' having a polarizing function can be obtained. The thicknesses of the (C) second functional layer 5 formed of the pre-adhesive layer and the pre-adhesive layer 2' may be different or the same.

In the case where the (D) polarizing functional layer is provided and the (a) first functional layer is provided with the (C) second functional layer, the (a) first functional layer is preferably a tetrazaporphyrin compound having the copper atom, and further a stabilizer is preferably blended, as in the case where the (D) polarizing functional layer is not provided. These blending amounts are also preferably the same as those described in the example in which the (D) polarization functional layer is not provided.

In addition, therefore, a correspondence relationship in which the (C) second functional layer containing the 1 st compound exists independently is also suitable. (C) In the case where the second functional layer is independently present, the 1 st compound may be blended into the optical sheet or the (B) lens substrate as described above. In the case of blending the 1 st compound into the optical sheet, it is preferable to blend the compound into the optical sheet disposed behind the side where light is irradiated.

In addition, it is also preferable to join the (a) first functional layer and the (C) second functional layer by a protective layer (pre-adhesive layer) or the like in the same manner as described above. In the case where the (D) polarizing functional layer is provided, the (a) first functional layer and the (C) second functional layer are preferably bonded to each other by the (D) polarizing functional layer. That is, in consideration of productivity of the optical article itself, it is preferable that (a) the first functional layer/(D) the polarizing functional layer/(C) the second functional layer be arranged in this order. Of course, a pre-adhesive layer may also be present between the layers. In addition, in consideration of the photochromic property, it is preferable to arrange (a) the first functional layer/(D) the polarizing functional layer/(C) the second functional layer in this order from the side where sunlight is irradiated.

(A) first functional layer (also having (C) second functional layer)/(D) polarizing functional layer/bonding layer formed of adhesive/(B) lens substrate,

First functional layer/(D) polarizing functional layer/second functional layer (C) formed of a bonding layer/primer layer as required/(B) lens substrate,

(A) first functional layer/(D) polarizing functional layer/bonding layer/second bonding layer formed of primer layer/(B) lens substrate,

(A) a first functional layer (also having (C) a second functional layer)/(B) a lens substrate (including a polarizing function),

(A) first functional layer/independent (C) second functional layer/(B) lens substrate (including polarizing function).

In the coating method and the cast polymerization method, even when (D) the polarizing functional layer is provided, and the 1 st compound is contained in the (a) first functional layer, the 1 st compound is suitably a tetrazaporphyrin compound having a copper atom, and the (a) first functional layer is preferably further compounded with a stabilizer. These compounding amounts are preferably the same as those described in the suitable laminate structure in the binder method.

In addition, the second functional layer (C) is preferably independently present, and as in the above-described configuration, (B) the 1 st compound may be blended in the lens base material. Further, a protective layer (adhesive layer) is preferably provided in the same manner as in the adhesive method. For the same reason as described in the adhesive method, the thickness of the protective layer (adhesive layer) in this case is preferably 10 to 100 μm, and a crosslinked resin layer is preferable. Further, in the case where the above-described structure of (D) the polarizing functional layer is provided, it is preferable that the (a) first functional layer and the (C) second functional layer are bonded to each other by the (D) polarizing functional layer, as described in the adhesive method. The first functional layer (a) is preferably disposed on the sunlight-irradiated side.

The laminated structure may be formed as described above. However, even when the polarizing functional layer (D) is provided, the optical article of the present invention satisfies the characteristics (including the characteristics (3) as needed) of the above-described (1) (2).

In the optical article of the present invention, even when the polarizing functional layer (D) is provided, the thickness of the entire layer is preferably 1 to 30mm. In addition, the thickness of the center and the thickness of the peripheral portion may be different. Specifically, the thickness of the center is preferably 1 to 30mm, and the thickness of the peripheral edge (edge) is preferably 1 to 30mm. In this case, the curvature of the optical article is preferably 0.5 to 10.0 for the convex surface, and 0.5 to 10.0 for the base arc of the concave surface. In the present invention, even such an optical article can be manufactured into a high-quality optical article free from color unevenness.

< improvement of antiglare property; improvement of antiglare property when (D) polarizing functional layer is provided

In the case where the (D) polarization functional layer is provided, the optical article of the present invention may be provided in the following manner in addition to satisfying the above-described features. That is, the photochromic compound (b) described above may be used. In addition, dyes may be mixed in the optical article. By doing so, an optical article that is tan when not irradiated and gray when irradiated can be obtained. In addition, the antiglare property can be improved in the room.

Examples of the dye to be used include anthraquinone-based, azo-based, 2- (2-quinolyl) -1H-phenalene-1, 3-dione (quinonaphtalone) -based, anthraquinone-based, pyrenone-based, quinoline-based, methine-based, and bromoanthraquinone-based compounds. Among them, anthraquinone-based, pyrenone-based, and quinoline-based compounds are preferable.

Examples of the anthraquinone dyes include dyes commercially available in dye indexes such as solvent red 52, solvent red 111, solvent red 149, solvent red 150, solvent red 151, solvent red 168, solvent red 191, solvent red 207, disperse red 22, and disperse red 60.

Examples of the pyrenone-based dye include dyes commercially available in dye indexes such as solvent orange 60, solvent orange 78, solvent orange 90, solvent red 135, solvent red 162, and solvent red 17.

Examples of quinoline dyes include dyes commercially available in the dye index such as solvent yellow 33, solvent yellow 98, solvent yellow 157, disperse yellow 54, and disperse yellow 160.

The layer to which these dyes are compounded is not particularly limited. The optical sheet may be a lens substrate or may be blended with an optical sheet. Among them, in order to achieve good dispersion and to maintain high transmittance, it is preferable to blend the polymer in the first functional layer and/or the second functional layer. The compounding amount is not particularly limited as long as it satisfies the characteristics of the aforementioned optical article. Specifically, it is preferable to use the dye in an amount of about 5 to 25 parts by mass per 100 parts by mass of the photochromic compound.

< other treatments >)

In the present invention, an optical article having the above-described laminated structure can be produced. The optical article of the present invention may be implemented according to the use thereof, in addition to the laminated structure described above: using silane coupling agents toFormation of a hard coat film of a hard coat agent containing a sol of silicon, zirconium, antimony, aluminum, tin, tungsten or the like as a main component; siO-based ₂ 、TiO ₂ 、ZrO ₂ A thin film formed by vapor deposition of metal oxide; post-processing based on antireflection treatment, antistatic treatment, antifouling treatment, antifogging treatment, and the like of a film coated with an organic polymer. In order to improve the designability, the surface of the optical article may be modified by a known method, for example, dip dyeing or sublimation dyeing. In order to improve the design and maintain the transmittance, an optical article having a gradation region in which the color is gradually changed may be manufactured.

< assignment of gradient region >)

The optical article of the present invention can have a gradation region in which the color gradually changes as long as the characteristics of (1) light transmittance and (2) minimum transmittance at a wavelength of 550 to 600nm at the time of light irradiation are satisfied. Further, in addition to the above (1) and (2), the above (3) other features and the above feature of < contrast > may be satisfied, and the gradation region may be provided.

The method of forming the gradation region includes a sublimation dyeing method and a dipping method.

As the sublimation dyeing method, japanese patent laid-open No. 2005-099842 can be referred to. Further, as the impregnation method, japanese patent application laid-open No. 03-072978 and Japanese patent application laid-open No. 2004-036032 can be referred to.

The gradation region is not particularly limited as long as it is located at a part of the optical article. For example, the optical element is not limited to the outermost surface of the optical article. For example, it may be formed on a surface portion of each layer forming the laminated structure of the optical article. The gradation region may be provided in advance in the material forming each layer. For example, if an adhesive method described in detail below is used, a gradation region can be formed on the surface of the first optical sheet. However, in order to satisfy the respective features, it is preferable to form a gradation region according to the aforementioned method on the outermost surface of the optical article having a laminated structure.

Even when these other treatments are performed, the optical article of the present invention satisfies the features (including the features (3) as needed) of the aforementioned (1) (2).

< other compounding agent >)

The optical article of the present invention may be blended with various compounding agents known per se, for example, various stabilizers and additives such as a mold release agent, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, and a perfume, as required, within a range that does not impair the effects of the present invention. These additives may also be contained in any part of the laminated structure. That is, the resin composition may be contained in (a) a first functional layer, (B) a lens base material, (C) a second functional layer, which is optionally provided, (D) a polarizing functional layer, an undercoat layer, an adhesive layer, a pre-adhesive resin layer, or the like. The stabilizer is preferably contained in the first functional layer (a) as described above.

As is clear from the above description, the optical article of the present invention can be suitably used as an eyeglass lens. Accordingly, spectacles having the spectacle lenses formed of the optical article of the present invention have high industrial utility value.

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The compounds used in this example are as follows.

(a) photochromic Compounds

PC1: a compound represented by the following formula (absorbance of 1mmol/l toluene solution measured using a quartz cuvette having a path length of 10mm was 0.005 at a wavelength of 420nm, and 0.003 at a wavelength of 430 nm).

PC2: a compound represented by the following formula (absorbance of 1mmol/l toluene solution measured using a quartz cuvette having a path length of 10mm was 0.075 at a wavelength of 420nm, and 0.008 at a wavelength of 430 nm).

PC3: a compound represented by the following formula (absorbance of 1mmol/l toluene solution measured using a quartz cuvette having a path length of 10mm was 0.094 at a wavelength of 420nm, and 0.012 at a wavelength of 430 nm).

/>

Photochromic compound (b)

PC4: compounds represented by the following formula (absorbance of 1mmol/l toluene solution measured using a quartz cuvette having a light path length of 10 mm: 0.512 at a wavelength of 420nm, and 0.112 at a wavelength of 430 nm.)

PC5: compounds represented by the following formula (absorbance of 1mmol/l toluene solution measured using a quartz cuvette having a light path length of 10 mm: 0.325 at a wavelength of 420nm, and 0.056 at a wavelength of 430 nm.)

< Compound 1 having an absorption peak in the range of 550 to 600nm >)

1 st dye; tetraazaporphyrin compound (FDG-006, manufactured by mountain chemical industries Co.). As a result of measurement in chloroform, the absorption peak (maximum absorption wavelength) was 585nm, and the absorption intensity at 585nm was 0.7X10 ⁵ ml/g.cm. The central metal atom is palladium (Pd).

Dye 2; tetraazaporphyrin compound (FDG-005, manufactured by mountain chemical industry Co.). As a result of measurement in chloroform, the absorption peak (maximum absorption wavelength) was 583nm, and the absorption intensity at 583nm was 1.4X10 ⁵ ml/g.cm. The central metal atom is palladium (Pd).

3 rd dyeingMaterial preparation; tetraazaporphyrin compound (FDG-007, manufactured by mountain chemical industry Co.). As a result of measurement in chloroform, the absorption peak (maximum absorption wavelength) was 594nm, and the absorption intensity at 594nm was 1.5X10 ⁵ ml/g.cm. The central metal atom is copper (Cu).

A polarization functional layer; polarizer >

PS1; a polyvinyl alcohol polarizing film (thickness 27 μm) containing a 2-color dye, which had a light transmittance of 44%, a polarization degree of 94.4% and a gray color tone.

PS2; a polyvinyl alcohol polarizing film (thickness 27 μm) containing a 2-color dye, which had a light transmittance of 48%, a polarization degree of 86.4% and a gray color tone.

PS3; a polyvinyl alcohol polarizing film (thickness 27 μm) containing a 2-color dye, which had a light transmittance of 53%, a polarization degree of 64.7% and a gray color tone.

PS4; a polyvinyl alcohol polarizing film (thickness 27 μm) containing a 2-color dye, which had a light transmittance of 68%, a polarization degree of 29.9% and a gray color tone.

PS5; a polyvinyl alcohol polarizing film (thickness 27 μm) containing a 2-color dye, which had a light transmittance of 37% and a polarization degree of 99.5% and a gray color tone.

Example 1 >

First functional layer comprising photochromic compound and 1 st compound

(1) Preparation of an adhesive resin for an adhesive method; production of polyurethaneurea resin as adhesive resin

A5L separable flask (4-neck) equipped with a stirring blade, a condenser, a thermometer, and a nitrogen gas inlet tube was prepared, 885 parts by mass of polycarbonate diol having a number average molecular weight of 800, 350 parts by mass of isophorone diisocyanate, and 250 parts by mass of toluene were charged into the flask, and the reaction was performed under a nitrogen gas atmosphere at 100℃for 7 hours to synthesize a urethane prepolymer having an isocyanate group at the end. After the urethane prepolymer reaction was completed, the reaction solution was cooled to a temperature of around 0 ℃, dissolved in 715 parts by mass of isopropyl alcohol and 1335 parts by mass of diethyl ketone, and then the solution temperature was maintained at 0 ℃. Then, a mixed solution of 85 parts by mass of bis- (4-aminocyclohexyl) methane and 70 parts by mass of diethyl ketone as a chain extender was added dropwise thereto over 30 minutes, and the reaction was carried out at 0℃for 1 hour. Then, 20 parts by mass of 1,2, 6-pentamethyl-4-aminopiperidine was further added dropwise thereto, and the reaction was carried out at 0℃for 1 hour, thereby obtaining a diethyl ketone solution of a polyurethaneurea resin. The concentration of the solid content of the obtained polyurethaneurea resin solution (the concentration of the polyurethaneurea resin) was 36.8 mass%.

(2) Preparation of adhesive composition 1 comprising a photochromic compound

500 parts by mass of the solution of the polyurethaneurea resin obtained in the above (1), 3.1 parts by mass of the photochromic compound (PC 1/PC2/PC3 = 0.53 parts by mass/0.35 parts by mass/2.2 parts by mass), 0.16 parts by mass of the 1 st compound (1 st dye) having an absorption peak at 550 to 600nm, 24 parts by mass of the isomer mixture of 4,4' -methylenebis (cyclohexyl isocyanate), and further 2.1 parts by mass of ethylenebis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol antioxidant), and 0.2 parts by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and stirred and mixed at room temperature to obtain an adhesive composition 1 containing the photochromic compound for an adhesive method. Since the adhesive composition 1 contains the photochromic compound and the 1 st compound, the layer formed from the adhesive composition 1 serves as a layer having both the first functional layer and the second functional layer.

(3) Preparing a resin for a pre-adhesive layer on an optical sheet; production of polyurethaneurea resin for Forming Pre-adhesive layer

A5L separable flask (4-neck) equipped with a stirring blade, a condenser, a thermometer, and a nitrogen gas inlet tube was prepared, and 400 parts by mass of a polycarbonate diol having a number average molecular weight of 1000, 175 parts by mass of isophorone diisocyanate, and 120 parts by mass of toluene were charged into the flask, and the reaction was performed under a nitrogen gas atmosphere at 110℃for 7 hours to synthesize a urethane prepolymer having an isocyanate group at the end. After the urethane prepolymer reaction was completed, the reaction solution was cooled to a temperature of around 20 ℃, and dissolved in 2500 parts by mass of propylene glycol-monomethyl ether, and then the solution temperature was maintained at 20 ℃. Subsequently, 60 parts by mass of isophorone diamine as a chain extender was added dropwise, and the reaction was performed at 20℃for 1 hour. Then, 3 parts by mass of n-butylamine was further added dropwise thereto, and the reaction was carried out at 20℃for 1 hour, thereby obtaining a propylene glycol-monomethyl ether solution of a polyurethaneurea resin.

(4) Preparation of adhesive 1 for Pre-adhesive layer for Forming Pre-adhesive layer on optical sheet

To 500 parts by mass of the polyurethaneurea resin solution obtained in the above (3), DOW CORNING TORAY L to 7001.2 parts by mass of a surfactant was added, and the mixture was stirred and mixed at room temperature to obtain an adhesive 1 for a pre-adhesive layer.

Production of photochromic optical articles based on the adhesive method 1 >

(5) Preparation of photochromic laminate before lens substrate

The pre-adhesive layer adhesive 1 obtained in (4) was applied to polycarbonate sheets (first and second optical sheets) having a thickness of 300 μm at a coating speed of 0.5 m/min using a coater (manufactured by TESTER SANGYO CO., LTD.). Then, the polycarbonate sheet was dried at a drying temperature of 110℃for 3 minutes to obtain a pre-adhesive layer having a film thickness of 10. Mu.m.

Next, the adhesive composition 1 containing a photochromic compound obtained in (2) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. Made PUREX film, with a silicon coating film) having a thickness of 50 μm at a coating rate of 0.3 m/min using a coater (manufactured by ster SANGYO co., ltd.) and dried at a drying temperature of 100 ℃ for 5 minutes, to prepare a functional layer sheet on the PET. The functional layer sheet (photochromic layer (thickness: 40 μm); which finally becomes the first functional layer/second functional layer) was placed on the side of the pre-adhesive layer of the first optical sheet having the pre-adhesive layer obtained in (5) above and adhered thereto.

Further, the PET film (preparation structure) was peeled from the material obtained by stacking the first optical sheet, the pre-adhesive layer, and the functional layer sheet (photochromic layer; eventually the first functional layer)/the PET film prepared by the above method in this order. The obtained structure was bonded to a polycarbonate sheet (second optical sheet) having a pre-adhesive layer in the following manner. That is, the functional layer sheet (photochromic layer; eventually first functional layer/second functional layer) was bonded to the pre-adhesive layer on the polycarbonate sheet (second optical sheet) by bonding. Then, the obtained laminate was left to stand at 40℃under vacuum for 24 hours, then subjected to heat treatment at 110℃for 60 minutes, then subjected to humidification treatment at 60℃and 100% RH for 24 hours, and finally left to stand at 40℃under vacuum for 24 hours, thereby obtaining a photochromic laminate.

Circular processing of photochromic laminate

2 layers (total thickness: 80 μm) of protective films composed of a polyethylene layer and a polypropylene layer were adhered to both surfaces of the obtained photochromic laminate to obtain a protective film laminate. The protective film laminate was cut out using a thomson knife (two knife, knife angle 42 °) to produceIs a circular laminate of (a) and (b). For the obtained- >By performing a vacuum suction process (thermal bending process) and performing a bending process in a spherical shape, a circular laminate having a 6.0 curve was obtained. In the vacuum suction process, a concave mold having a 6.0 curve in which a circular laminate is stored was set in an atmosphere at 145 ℃, and 1 hole was emptied from the concave mold, and vacuum suction was performed by a vacuum pump. The processing time was set to about 2 minutes, and after the implementation, the laminate was removed from the mold, thereby obtaining a circular laminate having a 6.0 curve, which was processed into a spherical shape. The protective films present on both sides of the obtained circular laminate having a 6.0 curve were peeled off to obtain a circular photochromic laminate (photochromic laminate 6 in fig. 1) by the adhesive method.

(6) Manufacture of photochromic optical articles 1

(molding of lens base material/integration of lens base material)

The circular photochromic laminate obtained in the above (5) by the adhesive method is integrated with a polycarbonate resin to produce a photochromicAn optical article. Specifically, first, the circular photochromic laminate obtained in the above (5) was placed on the concave surface of a mold of an injection molding machine, and heated to 100 ℃. The injection molding machine was filled with pellets of a polycarbonate resin (floodlight made by Di humanized) preheated at 120℃for 5 hours, and the pellets were melted by heating at 300℃and 60rpm, and the injection pressure was 14000N/cm ² Injection is performed towards the circular photochromic stack. Thus, a photochromic optical article (center thickness 3mm, edge thickness 10 mm) was produced by integrating a lens substrate made of a polycarbonate resin with a photochromic laminate.

The resulting photochromic optical article had a layered structure as shown in fig. 1.

That is to say,

the photochromic optical article 8 was obtained by stacking the first optical sheet 1 (thickness 300 μm)/the pre-adhesive layer 2 (thickness 10 μm) formed of the adhesive 1 for pre-adhesive layer/the first functional layer 3 (thickness 40 μm, containing the photochromic compound and the 1 st compound, and having the second functional layer) formed of the adhesive composition 1/the pre-adhesive layer 2 '(thickness 10 μm) formed of the adhesive 1 for pre-adhesive layer/the second optical sheet 1' (thickness 300 μm)/the lens base material 7 formed of the polycarbonate resin in this order. In this case, the first functional layer 3 also has the second functional layer. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave).

The photochromic optical article obtained had the following physical properties. The light transmittance before color development was 66.5%. The absorbance at 420nm was 0.15. The minimum transmittance at 550 to 600nm is 44.8%. The light transmittance at the time of color development, which is a photochromic property after ultraviolet irradiation, was 17.5%. The minimum transmittance at 550 to 600nm is 9.0%. The fade half-life was 42 seconds.

In addition, in the obtained photochromic optical article, no color unevenness was observed before and during the development (the thickness of the first functional layer was 40 μm, and no color unevenness was observed during the development). The evaluation of photochromic properties such as light transmittance before development, absorbance at 420nm, minimum transmittance at 550 to 600nm, light transmittance at development and fading speed, visibility (indoor), antiglare property (outdoor), contrast (outdoor), color unevenness and initial coloring were carried out by the methods shown below. The evaluation results are shown in table 1.

< light transmittance before color development of photochromic optical article, absorbance at 420nm and minimum transmittance at 550 to 600nm >

The photochromic optical article obtained in the present invention was measured at a measurement temperature of 23℃using a UV/VIS spectrometer (model: UV-2500, manufactured by Shimadzu corporation) for light transmittance (initial light transmittance), absorbance at 420nm and minimum transmittance at 550 to 600nm in an uncolored state of the photochromic compound. The "light transmittance" may be measured in accordance with ISO 8980-3.

< evaluation of photochromic Properties >)

The obtained photochromic optical article was used as a sample, and the photochromic characteristics of the optical article were measured by irradiating the surface of the optical article with light at 23 ℃ ±1 ℃ for 900 seconds using a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics with an air quality filter having an illuminance of 50000 lux and an illuminance value of radiation specified in ISO8980-3 as an irradiation light source. Each photochromic property was evaluated by the following method.

1) Light transmittance in the developed state of the photochromic compound: the above light (light having illuminance of 50000 lux and an illuminance value of radiation prescribed in ISO8980-3 for a sample) was irradiated at 23 ℃ for 900 seconds to the above optical article using a spectrometer (i.e., multichannel photometry system MCPD 1000) manufactured by the electronic industry, available from the tsuka corporation, and then the spectral transmittance was measured, and the light transmittance at the time of color development was calculated based on ISO 8980-3.

The light transmittance in the state of development of the photochromic compound is indicated as "light transmittance at development" or "light transmittance at light irradiation" in the table.

2) Minimum transmittance at a wavelength of 550 to 600nm in a state of color development using a photochromic compound: the optical article was irradiated with the light (light having illuminance of 50000 lux and an irradiance value specified in ISO 8980-3) at 23 ℃ for 900 seconds by a spectrometer (i.e., multichannel photometry system MCPD 1000) manufactured by the electric industry, and the minimum transmittance at a wavelength of 550 to 600 nm. The minimum transmittance at a wavelength of 550 to 600nm in a state where the photochromic compound is colored is indicated as "minimum transmittance at the time of light irradiation" in the table.

3) Fading speed [ t1/2 (sec.): first, the maximum absorption wavelength after color development was determined by a spectrometer (i.e., multichannel photometry system MCPD 1000) manufactured by the electronic industry of tsuka (ltd). Then, the difference [ ε (900) - ε (0) ] between the absorbance ε (900) after 900 seconds of irradiation at the maximum absorption wavelength and the absorbance ε (0) when the absorbance ε (900) - ε (0)) was not irradiated at the maximum absorption wavelength was obtained, and the time (fading rate) required for the absorbance ε (900) - ε (0)) at the maximum wavelength of the sample to decrease to 1/2 was obtained when the light irradiation was stopped after 900 seconds of irradiation. It can be said that the shorter the time, the more excellent the photochromic property.

Evaluation of visibility (indoor), antiglare (outdoor), contrast (outdoor)

An ophthalmic lens formed from the photochromic optical article fabricated by the foregoing method was fabricated. For visibility in the room, the visibility was confirmed in the room at 10 to 15 points (places; japan) for 4 months. In the room, 10 subjects were allowed to wear the spectacle lenses, and the evaluation was performed by the number of persons who felt to have a higher visibility than when the spectacle lenses were not worn.

The antiglare property in the outdoor was evaluated by the following method. The antiglare property was evaluated outdoors at 10 to 15 points (places; japan) for 4 months. In the outdoor, 10 subjects were allowed to wear the spectacle lenses, and the evaluation was made by the number of persons who perceived high antiglare properties (no glare) than when the spectacle lenses were not worn.

Further, the contrast in the outdoor was evaluated by the following method. The contrast was evaluated outdoors at 10 to 15 points (places; japan) for 4 months. In this outdoor area, 10 subjects were wearing the spectacle lenses, and the evaluation was made by the number of persons who perceived that the contrast of red, green, and blue was high, and that the outlines of road signs (white lines, etc.), trees, buildings, etc. were clear, and that the objects could be clearly identified (contrast was high) as compared with the case where the spectacle lenses were not worn.

< color unevenness and initial coloring >)

The obtained photochromic optical article was placed on a white or transparent plate, and the color tone and the density before color development were evaluated by whether or not the photochromic optical article was uniformly visible without color unevenness over the entire surface of the photochromic optical article. The evaluation was performed visually (whether or not unevenness was evaluated). Furthermore, initial coloration (particularly, a hue of 550 to 600 nm; violet to blue) was evaluated visually. Regarding the initial coloration, 10 subjects were visually evaluated, and the evaluation was performed by the number of persons who felt no problem in the degree of coloration of the photochromic optical article.

The photochromic optical article was arranged on a white or transparent plate, and after exposure to sunlight, the color tone and the density of the photochromic optical article at the time of color development were evaluated so as to be uniform and visible without color unevenness over the entire surface of the photochromic optical article. The evaluation was performed visually (whether or not unevenness was evaluated).

Contrast evaluation (R1/R2) based on hyperspectral camera

The hyperspectral camera used a system for outdoor measurement of Pika manufactured by the company RESONON. The reflectance reference (reflectance 100%) of the hyperspectral camera was corrected using spectrolon (registered trademark).

For a specific photographing, the photographing is performed outdoors at 10 to 15 points (places; japan) for 6 months when the photochromic compound is sufficiently developed. Blue films satisfying L69, a-42, b-34 and yellow films satisfying L81, a-0, b-85 in the hue in the CIE1976 (L, a, b) color space measured with a colorimeter (Suga Test Instruments co., ltd. System, colorimeter SM-T45) were prepared. The blue film or yellow film was adhered to the above spectrolon (registered trademark), and the obtained optical article was photographed by a hyperspectral camera to obtain hyperspectral data. Further, from the obtained hyperspectral data, an average reflectance spectrum of the blue thin film and an average reflectance spectrum of the yellow thin film are obtained.

The average reflectance (R1) at a wavelength of 420 to 519nm (precisely, at a wavelength of 420.39 to 519.15 nm) was measured from the reflectance spectrum of the blue film. The average reflectance (R2) at a wavelength of 580 to 595nm (precisely, at a wavelength of 580.03 to 594.63 nm) was measured from the reflectance spectrum of the yellow film. Based on this value, the ratio of R1 to R2 (R1/R2) was obtained.

The above measurement results, layer structures, and contrast evaluation results are summarized in tables 1 and 2.

Examples 2 to 9, comparative examples 1 and 2 >, and

a photochromic optical article was produced in the same manner as in example 1 except that the photochromic compounds shown in table 1 and the 1 st compound having an absorption peak at 550 to 600nm were used, and the properties of the obtained photochromic optical article (adhesive article) were evaluated. The results are shown in Table 1. These optical articles contain ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 1.

Example 10 >

Production example of photochromic optical article comprising compound 1 (dye 1) blended in the pre-adhesive layer 2' of FIG. 1 by the adhesive method

(7) Preparation of adhesive composition 2 comprising a photochromic compound

500 parts by mass of the solution of the polyurethaneurea resin obtained in (1), 3.1 parts by mass of the photochromic compound (PC 1/PC2/PC3 = 0.53 parts by mass/0.35 parts by mass/2.2 parts by mass), 24 parts by mass of the isomer mixture of 4,4' -methylenebis (cyclohexyl isocyanate), 2.1 parts by mass of ethylenebis (ethylenebis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant), and 0.2 parts by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and stirred/mixed at room temperature to obtain an adhesive composition 2 containing the photochromic compound for an adhesive method. The composition of the adhesive composition 2 containing the photochromic compound was the same as that of the adhesive composition 1 except that the compound 1 was not contained.

(8) Preparation of adhesive 2 for Pre-adhesive layer

To 500 parts by mass of the polyurethaneurea resin solution obtained in the above (3), 0.23 part by mass of a 1 st compound (1 st dye) having an absorption peak at 550 to 600nm and 0.2 part by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and the mixture was stirred and mixed at room temperature to obtain an adhesive 2 for a pre-adhesive layer. The composition of the adhesive 2 for a pre-adhesive layer is the same as that of the adhesive 1 for a pre-adhesive layer except that the compound 1 is contained. The pre-adhesive layer formed by the pre-adhesive layer adhesive 2 is a layer corresponding to the second functional layer.

Production of photochromic optical articles 2 Using adhesive method

(9) Preparation of photochromic laminate before lens substrate

The pre-adhesive layer adhesive 1 obtained in the above (4) was applied to a polycarbonate sheet (first optical sheet) having a thickness of 300 μm at a coating speed of 0.5 m/min using a coater (manufactured by TESTER SANGYO CO., LTD.). Then, the polycarbonate sheet was dried at a drying temperature of 110℃for 3 minutes to obtain a pre-adhesive layer having a film thickness of 10. Mu.m.

The pre-adhesive layer adhesive 2 obtained in the above (8) was applied to a polycarbonate sheet (second optical sheet) having a thickness of 300 μm at a coating speed of 0.5 m/min using a separate coater (manufactured by TESTER SANGYO CO., LTD.). Then, the polycarbonate sheet was dried at a drying temperature of 110℃for 3 minutes to obtain a pre-adhesive layer (second functional layer) having a film thickness of 10. Mu.m.

Next, the adhesive composition 2 containing a photochromic compound obtained in the above (7) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. Made PUREX film, with a silicon coating film) having a thickness of 50 μm at an application rate of 0.3 m/min using a coater (ltd. System). Subsequently, the resultant was dried at a drying temperature of 100℃for 5 minutes to prepare a functional layer sheet on PET. The functional layer sheet (photochromic layer (thickness: 40 μm), which is finally the first functional layer) formed on PET, was placed on the side of the pre-adhesive layer of the first optical sheet having the pre-adhesive layer.

Further, the PET film (preparation structure) was peeled from the laminate obtained by laminating the first optical sheet, the pre-adhesive layer, and the functional layer (photochromic layer; eventually the first functional layer)/the PET film prepared by the above method. The obtained structure was bonded to a polycarbonate sheet (second optical sheet) having a pre-adhesive layer (eventually, a second functional layer) containing the compound 1 in the following manner. That is, the functional layer sheet (photochromic layer; eventually, first functional layer) is bonded to the pre-adhesive layer (eventually, second functional layer) on the polycarbonate sheet (second optical sheet) by bonding. The resulting laminate was allowed to stand at 40℃for 24 hours under vacuum, then subjected to heat treatment at 110℃for 60 minutes, then subjected to humidification treatment at 60℃and 100% RH for 24 hours, and finally allowed to stand at 40℃under vacuum for 24 hours, to obtain a photochromic laminate.

Circular processing of photochromic laminate

The photochromic laminate obtained in the above-described method was subjected to a rounding process in the same manner as in example 1, to obtain a rounded photochromic laminate.

< lamination of lens base material >

Then, the obtained circular photochromic laminate was integrated with a polycarbonate resin by the same method as in (6) above, and a photochromic optical article (center thickness 3mm, edge thickness 10 mm) was produced. The obtained photochromic optical article was a photochromic optical article in which a first optical sheet (thickness 300 μm)/a pre-adhesive layer (thickness 10 μm) formed of an adhesive 1 for pre-adhesive layer/a first functional layer (thickness 40 μm, containing a photochromic compound) formed of an adhesive composition 2/a second functional layer (thickness 10 μm, pre-adhesive layer containing a 1 st compound)/a second optical sheet (thickness 300 μm)/a lens base material formed of a polycarbonate resin were laminated in this order. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave). No color unevenness was observed in the obtained photochromic optical article (adhesive article) (the thickness of the first functional layer was 40 μm, and no color unevenness in the case of color development was observed). Further, the properties of the obtained photochromic optical article (adhesive article) were evaluated. The results are shown in Table 1.

Comparative example 3 >

A photochromic optical article was produced in the same manner as in example 1 except that pellets of a polycarbonate resin in which the light transmittance of the finally obtained photochromic optical article before color development was adjusted to 28.2% were used, and the properties of the obtained photochromic optical article (adhesive article) were evaluated. The results are shown in Table 1.

TABLE 1

TABLE 2

Example 11 >

Method for producing photochromic optical article having (A) first functional layer (having second functional layer), (D) polarizing functional layer and (B) lens base material by adhesive method

Next, the adhesive composition 3 containing a photochromic compound obtained in the following (11) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. Made PUREX film, with a silicon coating film) having a thickness of 50 μm at an application rate of 0.3 m/min using a coater (ltd. System). Subsequently, the resultant was dried at a drying temperature of 100℃for 5 minutes to prepare a functional layer sheet on PET. Then, the functional layer sheet (photochromic layer (thickness: 40 μm, eventually first functional layer/second functional layer)) on PET was placed on the side and bonded to the pre-adhesive layer of the first optical sheet having the pre-adhesive layer.

The pre-adhesive layer obtained in the above (4) was applied to a polycarbonate sheet (second optical sheet) having a thickness of 300 μm with an adhesive 1 at a coating speed of 0.5 m/min using a separate coater (manufactured by TESTER SANGYO CO. LTD.). Then, the polycarbonate sheet was dried at a drying temperature of 110℃for 3 minutes to obtain a pre-adhesive layer having a film thickness of 10. Mu.m.

The adhesive 3 for a pre-adhesive layer obtained in the following (10) was separately applied to a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. PUREX film, with a silicon coating film). Subsequently, the mixture was dried at 110℃for 10 minutes to prepare a layer (pre-bonded layer sheet, thickness 40 μm) of the pre-bonding adhesive 3 on PET. Then, the pre-adhesive sheet is bonded to the pre-adhesive layer on the polycarbonate sheet (second optical sheet).

The PET film is peeled from the laminate having the first and second optical sheets. Then, a polarizing film (PS 1; polarizing functional layer) was sandwiched and laminated between a functional layer (photochromic layer (thickness: 40 μm; eventually first functional layer/second functional layer)) on the first optical sheet and a pre-adhesive layer on the second optical sheet, and the obtained laminate was left to stand at 40℃under vacuum for 24 hours, then subjected to heat treatment at 90℃for 60 minutes, then subjected to humidification treatment at 60℃for 100% RH for 24 hours, and finally left to stand at 40℃under vacuum for 24 hours, thereby obtaining a photochromic laminate having polarizing characteristics.

Circular processing of photochromic laminate

The photochromic laminate obtained in the above-described method was subjected to a rounding process in the same manner as in example 1, to obtain a rounded photochromic laminate having a polarizing functional layer (including a polarizing functional layer).

< lamination of lens base material >

Next, a circular photochromic laminate (including a polarizing functional layer) was integrated with a polycarbonate resin by the same method as in the above (6), and a photochromic optical article (center thickness 3mm, edge thickness 10 mm) having a polarizing functional layer was produced. The obtained photochromic optical article was laminated in the order of first optical sheet (thickness 300 μm)/pre-adhesive layer (thickness 10 μm) formed of adhesive for pre-adhesive layer 1/first functional layer (thickness 40 μm comprising photochromic compound and 1 st compound, having both second functional layer.)/polarizing functional layer (thickness 27 μm)/pre-adhesive layer (thickness 40 μm) formed of adhesive for pre-adhesive layer 3/pre-adhesive layer (thickness 10 μm)/second optical sheet (thickness 300 μm)/lens base material formed of polycarbonate resin. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave).

The light transmittance of the obtained photochromic optical article having the polarizing functional layer before color development was 31.6%. The absorbance at 420nm was 0.55. The minimum transmittance at 550 to 600nm is 20.2%. The light transmittance at the time of color development, which is a photochromic property after ultraviolet irradiation, was 10.7%. The fade half-life was 41 seconds. The visibility (indoor), antiglare (outdoor), and contrast (outdoor) were evaluated by the same procedure as in example 1, and the results are shown in table 3. No color unevenness was observed on the obtained photochromic optical article (binder article) before and at the time of color development. The results are shown in tables 3 and 4.

(10) Preparation of adhesive 3 for pre-adhesive layer

500 parts by mass of the solution of the polyurethaneurea resin obtained in the above (1), 24 parts by mass of the isomer mixture of 4,4' -methylenebis (cyclohexyl isocyanate), and 0.2 part by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and stirred and mixed at room temperature to obtain an adhesive 3 for a pre-adhesive layer. The adhesive 3 for a pre-adhesive layer has the same composition as the adhesive composition 1 containing the photochromic compound except that the adhesive does not contain the photochromic compound and the 1 st compound.

(11) Preparation of adhesive composition 3 comprising a photochromic compound

500 parts by mass of the solution of the polyurethaneurea resin obtained in the above (1), 1.9 parts by mass of the photochromic compound (PC 1/PC2/PC 3=0.32 parts by mass/0.21 parts by mass/1.3 parts by mass), 0.17 parts by mass of the 1 st compound (1 st dye) having an absorption peak at 550 to 600nm, 24 parts by mass of the isomer mixture of 4,4' -methylenebis (cyclohexyl isocyanate), and further 2.1 parts by mass of ethylenebis (ethylenebis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol antioxidant), and 0.2 parts by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and stirred and mixed at room temperature to obtain an adhesive composition 3 containing the photochromic compound for an adhesive method.

Examples 12 to 16, comparative examples 4 and 5 >, respectively

A photochromic optical article was produced in the same manner as in example 11 except that the types of polarizing films and the types and amounts of the 1 st compound were changed as shown in table 3, and the properties of the obtained photochromic optical article (adhesive article) were evaluated. The results are shown in tables 3 and 4. No color unevenness was observed on the obtained photochromic optical article (binder article). These optical articles contained ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 11.

Example 17 >

Next, the adhesive composition 4 containing a photochromic compound obtained in the following (12) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. Made PUREX film, with a silicon coating film) having a thickness of 50 μm at an application rate of 0.3 m/min using a coater (ltd. System). Subsequently, the resultant was dried at a drying temperature of 100℃for 5 minutes to prepare a functional layer sheet on PET. Then, a functional layer sheet (photochromic layer (thickness: 40 μm; eventually first functional layer)) on PET was placed on the side of the pre-adhesive layer of the first optical sheet having the pre-adhesive layer.

The adhesive 3 for a pre-adhesive layer obtained in the above (10) was separately coated on a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. PUREX film, with a silicon coating film). Subsequently, the mixture was dried at 110℃for 10 minutes to prepare a layer (pre-adhesive sheet) of 40 μm thick of the adhesive 3 on PET. The pre-adhesive sheet is arranged and bonded on the pre-adhesive layer of the second optical sheet having the pre-adhesive layer.

The PET film is peeled from the laminate having the first and second optical sheets. Further, a polarizing film (PS 1; polarizing functional layer) was sandwiched and laminated between a functional layer (photochromic layer (thickness: 40 μm; eventually first functional layer)) on the first optical sheet and a pre-adhesive layer on the second optical sheet, and the obtained laminate was left to stand at 40℃under vacuum for 24 hours, and then was subjected to heat treatment at 90℃for 60 minutes, and then was subjected to humidification treatment at 60℃for 100% RH for 24 hours, and finally was left to stand at 40℃under vacuum for 24 hours, whereby a photochromic laminate having polarizing characteristics was obtained.

Circular processing of photochromic laminate

The photochromic laminate obtained in the above-described method was subjected to a circular processing in the same manner as in example 1, to obtain a circular photochromic laminate having a polarizing functional layer.

< lamination of lens base material >

Next, a circular photochromic laminate (including a polarizing functional layer) was integrated with a polycarbonate resin by the same method as in the above (6), and a photochromic optical article (center thickness 3mm, edge thickness 10 mm) having a polarizing functional layer was produced. For the obtained photochromic optical article, a photochromic optical article was obtained in which a first optical sheet (thickness 300 μm)/a pre-adhesive layer (thickness 10 μm) formed by the adhesive 1 for pre-adhesive layer/a first functional layer (thickness 40 μm, containing a photochromic compound)/a polarizing functional layer (thickness 27 μm)/a pre-adhesive layer (thickness 40 μm) formed by the adhesive 3 for pre-adhesive layer/a second functional layer (thickness 10 μm, a second functional layer formed by the pre-adhesive layer)/a second optical sheet (thickness 300 μm)/a lens base material formed of a polycarbonate resin were laminated in this order. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave).

The properties of the obtained photochromic optical article (adhesive article) having polarizing properties were evaluated. The results are shown in tables 3 and 4. No color unevenness was observed on the obtained photochromic optical article (binder article).

(12) Preparation of adhesive composition 4 comprising a photochromic compound

Adhesive composition 4 was obtained in the same manner as adhesive composition 3 containing a photochromic compound for the adhesive method obtained in the above (11), except that the compound 1 (dye 1) having an absorption peak at 550 to 600nm was not contained. It is needless to say that the adhesive composition contains ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol antioxidant) in the same amount as the adhesive composition 3.

Example 18 >

The pre-adhesive layer adhesive 1 obtained in the above (4) was applied to polycarbonate sheets (first and second optical sheets) having a thickness of 300 μm at a coating speed of 0.5 m/min using a coater (manufactured by TESTER SANGYO CO., LTD.). Then, the polycarbonate sheet was dried at a drying temperature of 110℃for 3 minutes to obtain a pre-adhesive layer having a film thickness of 10. Mu.m.

Next, the adhesive composition 4 containing a photochromic compound obtained in the above (12) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. Made PUREX film, with a silicon coating film) having a thickness of 50 μm at an application rate of 0.3 m/min using a coater (ltd. System). Subsequently, the resultant was dried at a drying temperature of 100℃for 5 minutes to prepare a functional layer sheet on PET. Then, the functional layer sheet (photochromic layer (thickness: 40 μm), which is finally the first functional layer), was placed on the side of the pre-adhesive layer of the first optical sheet having the pre-adhesive layer.

Next, an adhesive 4 for a pre-adhesive layer obtained in the following (13) was applied onto a PET (polyethylene terephthalate) film (Teijin DuPont Films ltd. PUREX film, with a silicon coating film). Subsequently, the resultant mixture was dried at 110℃for 10 minutes to prepare a layer (pre-bonded layer sheet, thickness 40 μm, and finally a second functional layer) of the adhesive 4 for a pre-bonding layer on PET. Then, the pre-adhesive sheet is bonded to a pre-adhesive layer on the polycarbonate sheet (second optical sheet).

The PET film is peeled from the laminate having the first and second optical sheets. Further, a polarizing film (PS 1) was sandwiched between a functional layer (photochromic layer (thickness: 40 μm; eventually, first functional layer)) on the first optical sheet and a pre-adhesive layer (eventually, second functional layer) on the second optical sheet, and the obtained laminate was left to stand at 40℃for 24 hours under vacuum, then heat-treated at 90℃for 60 minutes, then humidified at 60℃for 100% RH for 24 hours, and finally left to stand at 40℃under vacuum for 24 hours, whereby a photochromic laminate having polarizing characteristics was obtained.

Circular processing of photochromic laminate

The photochromic laminate obtained in the above-described method was subjected to a rounding process in the same manner as in example 1, to obtain a rounded photochromic laminate having a polarizing functional layer (photochromic laminate 6' in fig. 2).

< lamination of lens base material >

Next, the obtained circular photochromic laminate having the polarizing function layer was integrated with a polycarbonate resin by the same method as in the above (6), and a photochromic optical article (center thickness 3mm, edge thickness 10 mm) having polarizing characteristics was produced. The resulting photochromic optical article had a layered structure as shown in fig. 2. That is, a photochromic optical article 8' was obtained by stacking in this order of first optical sheet 1 (thickness 300 μm)/pre-adhesive layer 2 (thickness 10 μm) formed of adhesive 1 for pre-adhesive layer, first functional layer 3 (thickness 40 μm) formed of adhesive composition 4, polarizing functional layer 4 (thickness 27 μm)/second functional layer 5 (thickness 40 μm, second functional layer formed of adhesive 4 for pre-adhesive layer), pre-adhesive layer 2' (thickness 10 μm)/second optical sheet 1' (thickness 300 μm) formed of adhesive 1 for pre-adhesive layer, and lens substrate 7 formed of polycarbonate resin. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave). The properties of the obtained photochromic optical article (adhesive article) having polarizing properties were evaluated. The results are shown in tables 3 and 4. No color unevenness was observed on the obtained photochromic optical article (binder article).

(13) Preparation of adhesive 4 for pre-adhesive layer

500 parts by mass of the solution of the polyurethaneurea resin obtained in the above (1), 0.16 part by mass of the 1 st compound (1 st dye), 24 parts by mass of the isomer mixture of 4,4' -methylenebis (cyclohexyl isocyanate), 2.1 parts by mass of ethylenebis (ethyleneoxy) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant), and 0.2 part by mass of "DOW CORNING TORAY L-7001" as a surfactant were added, and stirred and mixed at room temperature to obtain an adhesive 4 for a pre-adhesive layer containing the 1 st compound. The pre-adhesive 4 does not contain a photochromic compound, and has the same composition as the adhesive composition 3 containing a photochromic compound obtained in the above (11).

TABLE 3

/>

TABLE 4

TABLE 4 Table 4

Example 19 >

Method for manufacturing photochromic optical article by coating method

Preparation of photochromic curable composition

30 parts by mass of polyethylene glycol methyl diacrylate (average chain length of ethylene glycol chain: 14, average molecular weight: 736), 30 parts by mass of 2, 2-bis [4- (methacryloyloxy-polyethoxy) phenyl ] propane (average chain length of ethylene glycol chain: 10, average molecular weight: 804), 10 parts by mass of an esterified product of polyalkylene carbonate glycol and acrylic acid (average molecular weight: 640, (meth) acrylic acid equivalent: 320), 29 parts by mass of trimethylol propane methyl triacrylate, 1 part by mass of glycerin methacrylate, 0.16 part by mass of compound 1 (dye 1), and 3.1 parts by mass of a photochromic compound (PC 1/PC2/PC3 = 0.52 part by mass/0.34 part by mass/2.2 part by mass) were added, and stirred and mixed at 70 ℃ for 15 minutes to dissolve the photochromic compound. After cooling to room temperature, 5 parts by mass of γ -methacryloxypropyl trimethoxysilane, 3 parts by mass of bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate (molecular weight 508; hindered amine light stabilizer), 3 parts by mass of ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] (Chiba Specialty Chemicals co., ltd., irganox (registered trademark) 245; hindered phenol antioxidant), 3 parts by mass of phenylbis (2, 4, 6-trimethylbenzo) -phosphine oxide (trade name: irgacure (registered trademark) 819, manufactured by BASF corporation; polymerization initiator); 0.3 parts by mass, and "DOW CORNING TORAY L-7001"0.1 parts by mass as a leveling agent were further added to obtain a photochromic curable composition for a coating method.

Next, an undercoat layer was formed on the lens substrate using a spin coater (manufactured by 1H-DX2, MIKASA). Specifically, a moisture-curable urethane resin solution (product name: made of TR-SC-P, tokuyama Corporation; primer composition) was applied on the surface of an allyl plastic lens (center thickness: 2mm, edge thickness: 8mm, refractive index: 1.50) (center thickness: 2mm, concave base curve: 6.0 (concave)), convex base curve: 2.0 (2.0 curve), lens base material) substrate at a rotation speed of 70rpm for 15 seconds, followed by spin coating at 1500 to 2000rpm for 4 seconds, and dried at room temperature for 15 minutes. At this time, the rotation condition was adjusted so that the film thickness of the dried adhesive resin layer (primer layer formed of the moisture-curable urethane resin) was 5. Mu.m.

Then, about 2g of the photochromic curable composition prepared by the above method was spin-coated on the lens substrate on which the primer layer was formed so that the film thickness after curing was 40. Mu.m. Next, the power was used in a nitrogen atmosphere at 200mW/cm ² The metal halide lamp of (2) was irradiated with light for 90 seconds to cure the coating film. Further, the resultant was heated at 100℃for 1 hour to obtain a photochromic optical article (laminate; coating method) having a photochromic layer (first functional layer: 40 μm). The laminated structure was a first functional layer (having a second functional layer) of 40 μm in thickness, a primer layer of 5 μm in thickness, and the lens base material. Color unevenness in color development was not observed in the photochromic optical article (laminate; coating method) having the laminate structure.

The obtained photochromic optical article had a light transmittance of 66.6% before development, an absorbance at 420nm of 0.25, a minimum transmittance at 550 to 600nm of 44.5%, a light transmittance at development as a photochromic property after ultraviolet irradiation of 17.5%, and a half-life of 45 seconds. These physical properties were obtained by performing the same operations as in example 1. The visibility (indoor), antiglare (outdoor), and contrast (outdoor) were evaluated by the same method as in example 1, and the results are shown in table 5. No color unevenness was observed on the obtained photochromic optical article (binder article) before and at the time of color development. The results are shown in tables 5 and 6.

The resulting photochromic optical article had a center thickness of about 2.045mm, an edge thickness of about 8.045mm, a 6.0 curve (concave), a 2.0 curve (convex).

Example 20 >

Method for manufacturing photochromic optical article comprising polarizing functional layer by coating method

Preparation of lens substrate with polarizing functional layer

A polarizing film PS1 (polarizing functional layer) was buried in 45.6 parts by mass of norbornane diisocyanate and 54.4 parts by mass of a polymerizable monomer containing pentaerythritol tetrakis (3-mercaptopropionate) as a main component, and the resultant was thermally polymerized to obtain a thiourethane plastic lens (concave base curve 6.0 (6.0 curve (concave)), convex base curve 2.0 (2.0 curve (convex)) having a center thickness of 2mm and a refractive index of 1.6, which had polarizing characteristics.

Preparation of photochromic curable composition

A photochromic curable composition was prepared in the same manner as in example 19 except that the blending ratio of the photochromic compound was changed to PC1/PC2/PC 3=0.26 parts by mass/0.17 parts by mass/1.1 parts by mass in preparation of the photochromic curable composition of example 19.

A photochromic optical article was produced in the same manner as in example 19, except that the lens substrate having the polarizing property was used and the photochromic curable composition prepared by the method was further used. The laminated structure was 40 μm thick first functional layer (having a second functional layer as well)/5 μm thick primer layer/lens substrate having a polarizing functional layer. The properties of the obtained photochromic optical article (laminate; coating method) were evaluated by the same method as in example 1. The results are shown in tables 5 and 6. The resulting photochromic optical article (laminate; coating method) was free from color unevenness before and during development.

The resulting photochromic optical article had a center thickness of 2.045mm, an edge thickness of 8.045mm, a 6.0 curve (concave), and a 2.0 curve (convex).

Comparative example 6 >

A photochromic optical article (laminate; coating method) having polarizing properties was obtained in the same manner as in example 20, except that the compound No. 1 having an absorption peak at 550 to 600nm was not used. The properties of the obtained photochromic optical article (laminate; coating method) were evaluated by the same method as in example 1. The results are shown in tables 5 and 6. The resulting photochromic optical article (laminate; coating method) was free from color unevenness before and during development.

Example 21 >

Method for manufacturing photochromic optical article by casting polymerization

Preparation of photochromic curable composition

A photochromic curable composition for use in the casting polymerization method was obtained by adding 44 parts by mass of 1, 3-bis (isocyanatomethyl) cyclohexane, 36 parts by mass of dipentaerythritol hexa (3-mercaptopropionate), 15 parts by mass of a surfactant (a natural C12-C14 alcohol-based nonionic surfactant, "WANDERSURF (registered trademark) 140" manufactured by the Kabushiki Kaisha Co., ltd.), 5 parts by mass of stearyl-3-mercaptopropionate, 0.014 parts by mass of the 1 st compound (dye 1) and 0.12 parts by mass of a photochromic compound (PC 1/PC2/PC3 = 0.020 parts by mass/0.014 parts by mass/0.086 parts by mass), 0.12 parts by mass of ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] (Ciba Specialty Chemicals Co., irganox (registered trademark) 245; a hindered phenol-based antioxidant), and 0.12 parts by mass of dimethyltin dichloride.

The obtained photochromic curable composition was used in a mold in which a glass plate was used as an upper mold, an allyl plastic lens having a center thickness of 2mm and a refractive index of 1.50 (center thickness of 2mm, concave base curve 6.0 (6.0 curve (concave)), convex base curve 2.0 (2.0 curve (convex)) was used as a lower mold, and an adhesive tape (with a silicon-based adhesive) was wound around the outer side Zhou Zhuru.

Then, the resulting mixture was left in an oven heated to 50℃for 30 minutes, and then heated at 120℃for 2 hours to polymerize and cure the photochromic curable composition, and the tape was removed, whereby a photochromic optical article having a photochromic layer of 0.5mm thickness was obtained (laminate; casting polymerization method). The first functional layer (having a second functional layer) having a laminated structure of 0.5mm in thickness was used in combination with the lens base material.

The obtained photochromic optical article had a light transmittance of 66.8% before development, an absorbance at 420nm of 0.25, a minimum transmittance at 550 to 600nm of 45.3%, a light transmittance at development as a photochromic property after ultraviolet irradiation of 17.5%, and a half life of 75 seconds. These physical properties were obtained by performing the same operations as in example 1. In addition, the visibility (indoor), antiglare property, and visibility (outdoor) were evaluated by the same procedure as in example 1. The results are shown in tables 5 and 6. Color unevenness was not observed on the obtained photochromic optical article (casting polymerization method) before and at the time of color development.

The resulting photochromic optical article had a center thickness of 2.5mm, an edge thickness of 8.5mm, a curve of 6.0 (concave), and a curve of 2.0 (convex).

Example 22 >

Photochromic optical article with polarizing functional layer using cast polymerization method

Preparation of lens substrate with polarizing functional layer

The lens substrate having the polarizing functional layer used in example 20 was prepared.

Preparation of lens substrate having polarizing functional layer

A photochromic curable composition was prepared in the same manner as in example 21 except that the blending ratio of the photochromic compound was PC1/PC2/PC 3=0.020 parts by mass/0.014 parts by mass/0.09 parts by mass.

A photochromic optical article was produced in the same manner as in example 21, except that the lens substrate having the polarizing functional layer used in example 20 was used and the photochromic curable composition was used. The first functional layer (having a second functional layer) having a laminated structure of 0.5mm in thickness was used in combination with the lens base material. The properties of the obtained photochromic optical article (laminate; casting polymerization method) were evaluated. The results are shown in tables 5 and 6. The resulting photochromic optical article (laminate; casting polymerization method) was free from color unevenness before and during the development.

Comparative example 7 >

A photochromic optical article was produced in the same manner as in example 22 except that the compound No. 1 having an absorption peak at 550 to 600nm was not used, and the properties of the obtained photochromic optical article (laminate; casting polymerization method) were evaluated. The results are shown in tables 5 and 6. The resulting photochromic optical article (laminate; casting polymerization method) was free from color unevenness before and during the development.

Comparative example 8 >

55 parts by mass of meta-xylene diisocyanate, 30 parts by mass of dipentaerythritol hexa (3-mercaptopropionate), 15 parts by mass of polyethylene glycol monooleether (n.apprxeq.10, mw=668), 0.0035 parts by mass of compound 1 (dye 1), 0.010/0.007/0.045 parts by mass of photochromic compound PC1/PC2/PC 3=0.010/0.045 parts by mass, 0.1 part by mass of Zelec (registered trademark) UN (acid phosphate, manufactured by STEPAN) as an internal mold release agent, and 0.01 part by mass of dibutyltin dilaurate as a curing catalyst were added and sufficiently mixed to obtain a photochromic curable composition for a kneading method.

The obtained photochromic curable composition was deaerated and then poured into a mold composed of a glass plate and a gasket composed of an ethylene-vinyl acetate copolymer, and the photochromic curable composition was polymerized by casting polymerization. The polymerization was carried out using an air oven and allowed to cure for 24 hours while slowly heating from 27℃to 120 ℃. After the polymerization was completed, the cured product was removed from the glass mold of the mold to obtain a photochromic optical article (kneaded product) having a center thickness of 2mm, an edge thickness of 8mm, a concave base curve of 6.0 (6.0 curve (concave)), and a convex base curve of 2.0 (2.0 curve (convex)). The properties of the obtained photochromic optical article (kneaded material) were evaluated. The results are shown in tables 5 and 6. The resulting photochromic optical article (kneaded material) was observed to have color unevenness before and during the development of color.

TABLE 5

TABLE 6

As is clear from examples 1 to 22, the photochromic optical article of the present invention is excellent in photochromic characteristics, visibility in the room, antiglare property and contrast in the outdoor, and is free from color unevenness before and after development. The reason why such visibility, antiglare property, contrast, and no color unevenness are observed is that the first functional layer and the lens substrate have a separate laminated structure, because the first functional layer includes a photochromic compound, a compound having an absorption peak in a wavelength range of 550 to 600nm (compound 1), and the light transmittance before and after the development of the photochromic compound and the minimum transmittance at a wavelength of 550 to 600nm after the development of the photochromic compound are within predetermined ranges. The light transmittance and the minimum transmittance may be adjusted by using a polarizing film or by making the thickness of each functional layer uniform, if necessary.

On the other hand, in comparative examples 1 to 8, the photochromic properties were not problematic, but lenses in which visibility in the room, antiglare property and contrast in the outside, and/or color unevenness before and after development were all satisfied at the same time were not obtained.

Example 23

In the preparation of the adhesive composition 1 containing the photochromic compound (2) of example 1, an adhesive composition (1A) containing no photochromic compound and no 1 st compound was prepared, unlike the adhesive composition 1.

In addition, in the preparation of the adhesive 1 for a pre-adhesive layer for forming a pre-adhesive layer on an optical sheet of example 1 (4), 0.23 parts by mass of the 1 st compound (1 st dye) having an absorption peak at 550 to 600nm was blended, and the adhesive (1B) for a pre-adhesive layer for a second functional layer formed of the adhesive 1 for pre-adhesive was prepared differently from the adhesive 1 for pre-adhesive.

Further, by the same method as in example 1, a photochromic optical article was obtained in which the first optical sheet 1 (thickness 300 μm)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the first functional layer (thickness 40 μm, containing only the photochromic compound) formed by the adhesive composition 1)/the protective adhesive layer (thickness 40 μm) formed by the adhesive composition (1A)/the second functional layer (thickness 10 μm) formed by the pre-adhesive layer adhesive (1B)/the second optical sheet (thickness 300 μm)/the lens base material formed by the polycarbonate resin were laminated in this order. However, the first functional layer contained the same amount of antioxidant as in example 1.

Photochromic optical articles (3 mm thick in the center and 10mm thick at the edges) were obtained. In this case, the first functional layer and the second functional layer are bonded by the protective adhesive layer. The resulting photochromic optical article had a 6.0 curve (convex) and an 8.0 curve (concave).

The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in tables 7 and 8. However, visibility (indoor), antiglare property (outdoor), and contrast (outdoor) were confirmed again based on example 1 at the same time to obtain matching properties. In the photochromic optical article obtained in example 1, these evaluations were unchanged, whether at 4 months or 6 months.

Example 24

In example 5, (2) the adhesive composition 1 containing a photochromic compound was further blended with 295 parts by mass of an ultraviolet absorber (benzotriazole-based ultraviolet absorber) as a stabilizer per 100 parts by mass of the photochromic compound, together with the photochromic compound and the 1 st compound (3 rd dye), and TINUVIN1130 (manufactured by BASF Co., ltd.; about 12% by mass of H (OCH) ₂ CH ₂ ) _6-7 OH, about 50% by mass beta- [3- (2H-benzo)Triazol-2-yl) -4-hydroxy-5-tert-butylphenyl]-poly (ethylene glycol) 300-propionate, about 38 mass% bis { beta- [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-tert-butylphenyl } - ]-propionic acid } poly (ethylene glycol) 300-ester) to prepare an adhesive composition (1B). Further, using the adhesive composition (1B), a photochromic optical article was produced in the same manner as in example 5.

That is, a photochromic optical article was obtained in which the first optical sheet 1 (thickness 300 μm)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the first functional layer (thickness 40 μm, containing the photochromic compound, the 1 st compound (3 rd dye) and the ultraviolet absorber) formed by the adhesive composition (1B)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the second optical sheet (thickness 300 μm)/the lens base material formed by the polycarbonate resin were laminated in this order. However, the first functional layer contained the same amount of antioxidant as in example 5.

The obtained photochromic optical articles were evaluated in the same manner as in example 23, and the results are shown in tables 7 and 8.

Example 25

In example 5, in addition to the photochromic compound and the 1 st compound (3 rd dye), 118 parts by mass of hindered amine-based light stabilizer 1,2, 6-pentamethyl-4-piperidinyl methyl acrylate (ADK tab LA-82 (manufactured by ADEKA CORPORATION)) as a stabilizer was further blended with respect to 100 parts by mass of the photochromic compound in (2) adhesive composition 1 containing the photochromic compound, to prepare adhesive composition (1B). Then, using the adhesive composition (1B), a photochromic optical article was produced in the same manner as in example 5.

That is, a photochromic optical article was obtained in which the first optical sheet 1 (thickness 300 μm)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the first functional layer (thickness 40 μm comprising the photochromic compound, the 1 st compound (3 rd dye) and the hindered amine light stabilizer) formed by the adhesive composition (1B)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the second optical sheet (thickness 300 μm)/the lens base material formed by the polycarbonate resin were laminated in this order. However, the first functional layer contained the same amount of antioxidant as in example 5.

Example 26

In example 5, in (2) adhesive composition 1 containing a photochromic compound, 59 parts by mass of bis (dithiobenzyl) nickel as a stabilizer with respect to 100 parts by mass of the photochromic compound was further blended as a singlet oxygen quencher in addition to the photochromic compound and the 1 st compound (3 rd dye), to prepare adhesive composition (1B). However, using this adhesive composition (1B), a photochromic optical article was produced in the same manner as in example 5.

That is, a photochromic optical article was obtained in which the first optical sheet 1 (thickness 300 μm)/the pre-adhesive layer (thickness 10 μm) formed by the pre-adhesive layer adhesive 1/the first functional layer (thickness 40 μm, containing the photochromic compound, the 1 st compound (3 rd dye) and the singlet oxygen quencher) formed by the adhesive composition (1B)/the pre-adhesive layer (thickness 10 μm)/the second optical sheet (thickness 300 μm) formed by the pre-adhesive layer adhesive 1/the lens base material formed by the polycarbonate resin were laminated in this order. However, the first functional layer contained the same amount of antioxidant as in example 5.

TABLE 7

TABLE 8

Evaluation of photochromic residue (durability) and contrast durability

The photochromic optical articles obtained in examples 1, 5, 10, 18 and 23 to 26 were evaluated for the residual rate of photochromic property and the contrast durability by the following methods. The characteristics, residual ratio, and durability of the layer structures of these examples are shown in table 9. The first functional layer of the optical article of these embodiments includes a hindered phenol-based antioxidant.

< rate of photochromic residue >)

In order to evaluate the durability of the color development by light irradiation, a 96-hour accelerated degradation test of the optical article was performed by Suga Test Instruments co., ltd. Xenon Weather MeterX. The evaluation of the color development concentration was performed before and after the test, and the photochromic residual rate was obtained from the color development concentration before the test (A0) and the color development concentration after the test (a 96) according to the following formula.

The color development concentration { ε (900) - ε (0) } is the difference between the absorbance { ε (900) } after 900 seconds of light irradiation and the absorbance ε (0) before light irradiation in the absorption peak after color development obtained by a spectrometer (i.e., multichannel photodetector MCPD 1000) manufactured by Otsuka electronics (Inc.).

Photochromic residual ratio (%) = (a 96/A0) ×100

The higher the residual rate, the higher the durability of the color development can be said to be, using the photochromic residual rate as an index of durability.

< contrast durability >

In order to evaluate the durability of the contrast based on light irradiation, a 96-hour accelerated degradation test of an optical article was performed by Suga Test Instruments co., ltd. Xenon Weather MeterX. The absorbance of the absorption peak (dye 1: 585nm, dye 3: 594 nm) of the 1 st compound was measured before and after the test at a measurement temperature of 23℃using a UV/VIS spectrometer (model: UV-2500, manufactured by Shimadzu corporation). The contrast ratio was obtained from the absorbance before test (a 0) and the absorbance after test (a 96) according to the following formula.

Contrast residual ratio (%) = (a 96/a 0) ×100

The higher the contrast ratio is, the higher the durability of the color development is, which is an index of the durability.

In addition, contrast after the durability test was evaluated by a hyperspectral camera.

TABLE 9

As the 1 st compound, the durability (photochromic residual rate, contrast durability) can be improved by using a copper-containing tetrazaporphyrin compound. (A) When the first functional layer contains the photochromic compound and the 1 st compound, the photochromic residue ratio and contrast durability can be improved by further compounding a stabilizer.

In addition, when the first functional layer (a) (not including the 1 st compound) and the second functional layer (C) are independently provided and bonded to each other by other layers, the photochromic residual ratio and the contrast durability can be maintained high.

Example 27

A photochromic optical article was produced in the same manner as in example 18 except that 0.11 parts by mass of the 1 st dye was used instead of the 3 rd dye as the 1 st compound having an absorption peak at 550 to 600nm in example 18, and the properties of the obtained photochromic optical article (adhesive article) were evaluated in the same manner as in example 1. The results are shown in tables 10 and 11. These optical articles contain ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 1.

Example 28

A photochromic optical article was produced in the same manner as in example 27 except that 3.7 parts by mass of PC4 was used instead of PC1/PC2/PC 3=0.32 parts by mass/0.21 parts by mass/1.3 parts by mass as the photochromic compound of the adhesive composition 4 containing the photochromic compound of example 27, and the properties of the obtained photochromic optical article (adhesive article) were evaluated in the same manner as in example 1. The results are shown in tables 10 and 11. These optical articles contain ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 1.

Example 29

A photochromic optical article was produced in the same manner as in example 27 except that 0.16 parts by mass of Sumiplast (registered trademark) Red HL2B (solvent Red 151) manufactured by Sumika Chemtex Company and 0.33 parts by mass of Sumiplast Orange HRP (solvent orange 60) manufactured by Sumika Chemtex Company were added to the adhesive composition 4 containing a photochromic compound, and PC 5.9 parts by mass was used as the photochromic compound instead of PC1/PC 2/pc3=0.32 parts by mass/0.21 parts by mass/1.3 parts by mass, and the properties of the obtained photochromic optical article (adhesive article) were evaluated in the same manner as in example 1. The results are shown in tables 10 and 11. These optical articles contain ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 1.

TABLE 10

TABLE 11

Example 30

The optical article obtained in example 5 was subjected to sublimation dyeing treatment by the following method.

As the sublimation ink, a commercially available aqueous disperse dye having a gray color is used. The dye was printed in a circular shape slightly larger than the cured product on a commercially available A4 paper (upper PPC (upper Plain Paper Copier)) for use in the dye. Sublimation inks are printed in a manner having a gradient.

The printed matter is disposed on the dyeing device in such a manner that the printed surface of the printed matter is opposite to the concave surface of the solidified body. The distance between the printed surface and the concave surface of the cured body at this time was 15mm.

Then, the switch of the vacuum pump was turned on, the air pressure in the dyeing apparatus was reduced to 60Pa, and the back surface of the printed matter was heated to a surface temperature of about 200 ℃ by a halogen lamp. Thereby, the dye sublimates and adheres to the concave surface of the solidified body.

Then, the air pressure in the sublimation dyeing apparatus was returned to normal pressure, and the cured body having the dye attached to the concave surface was taken out. The obtained cured product was heated in an oven at 130℃for 2 hours to fix the dye. Thus, an optical article with graded coloration is obtained. The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in Table 12.

Example 31

The optical article obtained in example 27 was subjected to gradation dyeing in the same manner as in example 30, to obtain an optical article having gray gradation dyeing. The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in Table 12.

Example 32

The optical article obtained in example 28 was subjected to gradient dyeing in the same manner as in example 30, to obtain an optical article having gray gradient dyeing. The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in Table 12.

Example 33

The optical article obtained in example 5 was dyed by dipping. As the staining solution, an aqueous solution containing a gray dye manufactured by BPI corporation was used. In dyeing, first, the optical article is immersed in a dye liquid heated to 90 ℃ while periodically moving up and down so that the lowest position of the optical article gradually rises. After dipping, the optical article taken out of the dye solution was washed with tap water, followed by distilled water. Thus, an optical article with grey gradient dyeing is obtained. The immersion time of the optical article in the dye solution was adjusted so that the light transmittance of the optical article before color development was 52.0%. The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in Table 12.

Example 34

The optical article obtained in example 27 was dyed by dipping. As the staining solution, an aqueous solution containing a gray dye manufactured by BPI corporation was used. In dyeing, first, the optical article is immersed in a dye liquid heated to 90 ℃ while periodically moving up and down so that the lowest position of the optical article gradually rises. After dipping, the optical article taken out of the dye solution was washed with tap water, followed by distilled water. Thus, an optical article with grey gradient dyeing is obtained. The immersion time of the optical article in the dye solution was adjusted so that the light transmittance of the optical article before color development was 31.0%. The photochromic optical article obtained was evaluated in the same manner as in example 1. The results are shown in Table 12.

TABLE 12

Example 35

A photochromic optical article was produced in the same manner as in example 5 except that 6.2 parts by mass (PC 1/PC2/PC 3=1.1 parts by mass/0.7 parts by mass/4.5 parts by mass) of the photochromic compound was used as the photochromic compound in example 5, and the properties of the obtained photochromic optical article (adhesive article) were evaluated in the same manner as in example 1. The results are shown in tables 13 and 14. These optical articles contain ethylene bis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate ] as an antioxidant (hindered phenol-based antioxidant) in the same amount as the first functional layer of example 1.

TABLE 13

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TABLE 14

Description of the reference numerals

1. Optical sheet

1' optical sheet

2. Pre-adhesive layer

2' Pre-adhesive layer

3 (A) a first functional layer (optionally also having (C) a second functional layer)

4 (D) polarization functional layer

5 (C) a second functional layer (which may also be formed of a pre-adhesive layer)

6. Photochromic laminate

7 (B) lens substrate

8. Photochromic optical articles.

Claims

1. An optical article comprising a photochromic compound and a 1 st compound having an absorption peak in the wavelength range of 550 to 600nm,

2. The optical article of claim 1, wherein the (a) first functional layer comprises the 1 st compound.

3. The optical article according to claim 1 or 2, wherein the (a) first functional layer comprises at least 1 stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine-based light stabilizer, and a singlet oxygen quencher.

4. An optical article according to any one of claims 1 to 3, wherein the compound 1 comprises a tetrazaporphyrin compound having a copper atom.

5. The optical article according to any one of claims 1-4, wherein the (a) first functional layer comprises an antioxidant.

6. The optical article of any one of claims 1-5, wherein the photochromic compound comprises the following compounds:

when a toluene solution adjusted to a concentration of 1.0mmol/l was used as a measurement sample at 23 ℃, the absorbance at 420nm was lower than 0.100 and the absorbance at 430nm was lower than 0.015.

7. The optical article according to any one of claims 1 to 6, wherein the thickness of the (a) first functional layer is 10 to 1000 μm.

8. The optical article according to any one of claims 1 to 7, further comprising (D) a polarizing functional layer having a polarizing function.

9. The optical article of claim 8, wherein the photochromic compound comprises the following compounds:

when a toluene solution having a concentration of 1.0mmol/l was used as a measurement sample at 23 ℃, the absorbance at 420nm was 0.100 or more and the absorbance at 430nm was 0.015 or more.

10. The optical article of claim 8 or 9, comprising a dye.

11. The optical article of claim 1, independently provided with (C) a second functional layer comprising the 1 st compound.

12. The optical article of claim 11, having other layers between the (a) first functional layer and the (C) second functional layer.

13. The optical article according to any one of claims 1 to 12, having a graded region of progressively changing colour.

14. The optical article according to any one of claims 1 to 13, wherein,

the blue thin film with L of 69, a of-42, b of-34 and the yellow thin film with L of 81, a of 0, b of 85 in the hue in CIE1976 (L, a, b) color space was photographed with an optical article in a state in which the hyperspectral camera developed through the photochromic compound,

the ratio of R1 to R2, i.e., R1/R2, is 0.9 to 2.0.

15. An ophthalmic lens comprising the optical article of any one of claims 1-14.

16. An eyeglass comprising the eyeglass lens of claim 15.