阅读说明：本技术 光致变色光学物品及其制造方法 (Photochromic optical article and method of making same ) 是由 森力宏 野口誉夫 百田润二 于 2020-04-03 设计创作，主要内容包括：本发明为光致变色光学物品,是将一对光学物品用板用包含光致变色化合物、和选自聚氨酯树脂、环氧树脂和丙烯酸系树脂中的至少一种的树脂的粘接层接合而成的光致变色光学物品,其中,从一对光学物品用板的中心点在同心圆上的粘接层的厚度的偏移为±10％以内。根据本发明,能够提供光致变色光学物品,其为将一对光学物品用板用粘接层接合而成的光致变色光学物品,其中,规定包含光致变色化合物的粘接层的厚度,没有产生外观品位的降低等问题。(The present invention is a photochromic optical article comprising a pair of optical article plates joined together by an adhesive layer comprising a photochromic compound and at least one resin selected from the group consisting of a urethane resin, an epoxy resin and an acrylic resin, wherein the thickness of the adhesive layer on a concentric circle from the center point of the pair of optical article plates is within ± 10%. According to the present invention, a photochromic optical article in which a pair of plates for optical articles are bonded with an adhesive layer can be provided, in which the thickness of the adhesive layer containing a photochromic compound is defined and problems such as a reduction in appearance quality do not occur.)

1. A photochromic optical article comprising a pair of optical article plates joined together by an adhesive layer comprising a photochromic compound and at least one resin selected from the group consisting of a urethane resin, an epoxy resin and an acrylic resin, wherein the thickness of the adhesive layer on a concentric circle from the center point of the pair of optical article plates is within +/-10%.

2. The photochromic optical article of claim 1, wherein the bonding layer is a bonding layer comprising a photochromic compound and a polyurethane resin.

3. The photochromic optical article according to claim 2, wherein the adhesive layer is an adhesive layer obtained by curing a photochromic adhesive composition comprising (a) a photochromic compound, (B1) a polyiso (thio) cyanate compound having 2 or more iso (thio) cyanate groups in a molecule, and (B2) a poly (thio) alcohol compound having 2 or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in a molecule.

4. The photochromic optical article of claim 3, wherein the photochromic adhesive composition further comprises (B3) a monohydric (thio) alcohol compound having 1 active hydrogen-containing group selected from hydroxyl and thiol groups within the molecule.

5. The photochromic optical article according to claim 4, wherein the (B3) monohydric (thiol) compound having 1 active hydrogen-containing group selected from a hydroxyl group and a thiol group in the molecule is a compound represented by the following formula (XXI),

[ solution 1]

R²⁰⁰-J-R²⁰¹-K-R²⁰² (XXI)

In the formula, R²⁰⁰Is an organic radical of valency 1, R²⁰¹Is an organic radical of valency 2, R²⁰²Is an organic group having 1 hydroxyl group or thiol group, and J and K represent polymer chains different from each other.

6. The photochromic optical article according to any one of claims 1 to 5, wherein at least one of the pair of optical article plates is an optical article plate having a refractive index of 1.7 or more.

7. A method for manufacturing a photochromic optical article, which is a method for manufacturing a photochromic optical article in which a pair of optical article plates are bonded with an adhesive layer, and a deviation of a thickness of the adhesive layer on a concentric circle from a center point of the pair of optical article plates is within + -10%, the method comprising:

a step of applying a photochromic adhesive composition comprising (A) a photochromic compound and (B) at least one curable compound selected from the group consisting of a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound to a plate for an optical article,

a step of disposing a spacer on the coated surface of the optical article plate coated with the photochromic adhesive composition, and disposing another optical article plate so as to be overlapped with a predetermined gap, and

a step of curing the photochromic adhesive composition to form an adhesive layer, and bonding a pair of optical article plates,

the spacer is disposed on the outer periphery of the optical article plate, and the length of the spacer sandwiched between the pair of optical article plates is 0.25mm to 1.2 mm.

8. A method for manufacturing a photochromic optical article, which is a method for manufacturing a photochromic optical article in which a pair of optical article plates are bonded with an adhesive layer, and a deviation of a thickness of the adhesive layer on a concentric circle from a center point of the pair of optical article plates is within + -10%, the method comprising:

a step of arranging a spacer between the pair of optical article plates to form a gap part with a predetermined interval,

a step of injecting and filling a photochromic adhesive composition containing (A) a photochromic compound and (B) at least one curable compound selected from the group consisting of a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound into the gap, and

a step of curing the photochromic adhesive composition to form an adhesive layer, and bonding a pair of optical article plates,

the spacer is disposed on the outer periphery of the optical article plate, and the length of the spacer sandwiched between the pair of optical article plates is 0.25mm to 1.2 mm.

9. The method of manufacturing a photochromic optical article according to claim 7 or 8, wherein the step of curing the photochromic adhesive composition to form an adhesive layer and bonding the pair of optical articles by plates comprises: (i) a temperature raising step of raising the temperature from 0.1 to 1.6 ℃ per minute from a curing start temperature to a predetermined curing temperature, and (ii) a constant temperature step of maintaining the predetermined curing temperature for a predetermined time.

Technical Field

The present invention relates to a photochromic optical article in which a pair of optical articles are joined to each other by a plate via an adhesive layer obtained by curing a photochromic adhesive composition, and a method for producing the same.

Background

In recent years, photochromic sunglasses, which are provided with photochromic properties to sunglasses having an antiglare property, have been rapidly gaining favor in the united states. This photochromic sunglass can adjust the antiglare property because the transmittance of the lens changes according to the surrounding brightness (amount of ultraviolet rays).

As a method for producing such photochromic sunglasses, for example, a method of molding a photochromic polymerizable composition in which a photochromic compound is blended with a polymerizable composition into a lens shape, a method of bonding a pair of lenses using a photochromic polymerizable composition as an adhesive, and the like are known (for example, see patent documents 1 to 4).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/136804

Patent document 2: japanese laid-open patent publication No. 2007-138186

Patent document 3: japanese laid-open patent publication No. 2012 and 052091

Patent document 4: japanese laid-open patent publication No. H01-033154

Patent document 5: japanese patent laid-open publication No. 2003-139914

Disclosure of Invention

Problems to be solved by the invention

However, in the production method of molding the photochromic polymerizable composition into a lens shape, the durability of the obtained photochromic sunglasses is not sufficient, and the photochromic properties are liable to deteriorate if the photochromic sunglasses are used in an environment exposed to sunlight for a long time.

On the other hand, a manufacturing method of bonding a pair of lenses using a photochromic polymerizable composition as an adhesive can improve durability of photochromic sunglasses compared to a manufacturing method of molding a photochromic polymerizable composition into a lens shape, but has problems in bonding strength of a pair of lenses and durability of an adhesive layer. Therefore, the present inventors have proposed a photochromic optical article in which a pair of optical articles are joined using an adhesive composition having a specific composition containing a photochromic compound, the joining strength of the pair of optical articles and the durability of the adhesive layer are sufficient, and the durability of photochromic characteristics is improved (international application PCT/JP 2019/015319).

However, in the manufacturing method in which the photochromic adhesive is cured to bond the pair of lenses, variation in the thickness of the adhesive layer is likely to occur. Generally, since the photochromic coloration concentration depends on the photochromic layer thickness, if there is variation in the thickness of the photochromic adhesive layer, the photochromic sunglasses may exhibit color variation, which directly leads to a reduction in the appearance quality. Therefore, in order to define the thickness of the adhesive layer, it is conceivable to use a spacer, and there is room for improvement in the conventional production method (for example, see patent document 5) in producing a high-quality photochromic optical article. That is, bubbles are generated around the spacers during curing of the adhesive, resulting in poor appearance.

The present invention has been made in view of such conventional circumstances, and an object thereof is to provide a photochromic optical article in which the thickness of an adhesive layer containing a photochromic compound is defined and which does not cause problems such as a reduction in the quality of appearance.

Means for solving the problems

In order to solve the above problems, the present inventors have conducted extensive studies on photochromic optical articles in which the thickness of an adhesive layer containing a photochromic compound is defined and problems such as a reduction in appearance quality do not occur. As a result, the present invention was completed as follows.

That is, the photochromic optical article of the present invention is a photochromic optical article obtained by bonding a pair of optical article plates with an adhesive layer containing a photochromic compound and at least one resin selected from a urethane resin, an epoxy resin and an acrylic resin, wherein the deviation of the thickness of the adhesive layer on a concentric circle from the center point of the pair of optical article plates is within ± 10%.

The method for manufacturing a photochromic optical article according to the present invention, in which the deviation of the thickness of the adhesive layer on a concentric circle from the center point of the pair of plates for optical article is within ± 10%, comprises:

a step of applying a photochromic adhesive composition comprising (A) a photochromic compound and (B) at least one curable compound selected from the group consisting of a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound to a plate for an optical article,

a step of disposing a spacer on the coated surface of the optical article plate coated with the photochromic adhesive composition, and disposing another optical article plate so as to be overlapped with a predetermined gap, and

a step of curing the photochromic adhesive composition to form an adhesive layer, and bonding a pair of optical article plates,

the spacer is disposed on the outer periphery of the optical article plate, and the length of the spacer sandwiched between the pair of optical article plates is 0.25mm to 1.2mm, preferably,

the step of curing the photochromic adhesive composition to form an adhesive layer and joining the pair of optical article plates includes at least two steps of: (i) a temperature raising step of raising the temperature from 0.1 to 1.6 ℃ per minute from a curing start temperature to a predetermined curing temperature, and (ii) a constant temperature step of maintaining the predetermined curing temperature for a predetermined time.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a photochromic optical article in which the thickness of the photochromic adhesive layer is limited and which does not cause problems such as a reduction in the quality of appearance.

Drawings

Fig. 1 is a cross-sectional view showing one form of a photochromic optical article manufactured according to the present invention.

Fig. 2 is a diagram illustrating a deviation in the thickness of the adhesive layer.

FIG. 3 is a schematic view showing the molecular structure of a polyrotaxane monomer.

Fig. 4 is a diagram illustrating one embodiment of the shape of the spacer.

Detailed Description

< photochromic optical article >

The photochromic optical article of the present invention is a photochromic optical article obtained by bonding a pair of optical article plates with an adhesive layer containing a photochromic compound and a resin selected from a polyurethane resin, an epoxy resin and an acrylic resin, wherein the deviation of the thickness of the adhesive layer on a concentric circle from the center point of the pair of optical article plates is within ± 10%.

Fig. 1 shows one embodiment of a photochromic optical article according to the present invention. Fig. 1 shows a state in a specific step in a preferred manufacturing method described below, in which a photochromic optical article 1 is configured such that an optical article plate 2 and an optical article plate 4 are joined to each other via an adhesive layer 3 containing a resin and having a predetermined thickness by using a spacer 5. Fig. 1 is a schematic view, and the shape of the photochromic optical article according to the present invention is not limited to this example. Then, the spacer is removed, and if necessary, the spacer mark is removed by cutting, polishing, or the like, and the photochromic optical article of the present invention is one embodiment.

The photochromic optical article of the present invention will be described in detail below.

In the present invention, the shape of the optical article plate is not particularly limited, and for example, when the plate is used for spectacles, a circular optical article plate is generally used. The size of the pair of optical article plates is not particularly limited, and if the pair of optical article plates are joined and used, they are preferably the same shape.

The deviation of the thickness of the adhesive layer in the present invention will be described with reference to fig. 2. In fig. 2, the optical article plate 4, the adhesive layer 3, and the optical article plate 2 are shown with a gap therebetween for the sake of explanation, but actually, as shown in fig. 1, a pair of optical article plates are joined together by the adhesive layer 3.

The "thickness of the adhesive layer on a concentric circle from the center point of the pair of optical article plates" means the thickness of the adhesive layer on a circumference at a concentric circle a (radius r) from the center C2 of the adhesive layer 3 corresponding to the center C1 of the pair of optical article plates. In other words, the thickness of the adhesive layer 3 in the thickness direction (downward) of the circumference of a concentric circle having a radius r with respect to the center C1 of the optical article plate is defined. The center C1 of the optical article plate is a center point with respect to a shape viewed from above in the thickness direction of the optical article plate, and means the center if the shape is a circle, the intersection of the major axis and the minor axis if the shape is an ellipse, the intersection of the diagonal lines if the shape is a quadrangle, and the center of gravity of the shape may be the center if the shape is a shape other than a circle, an ellipse, or a quadrangle. Further, the center C2 of the adhesive layer 3 is located at the intersection point of a straight line downward in the thickness direction from the center C1 of the optical article plate and the adhesive layer 3.

In the present invention, it is preferable that the center C1 of the optical article plate 4 and the center C1 'of the optical article plate 2 are located on the same line parallel to the thickness direction, and strictly speaking, the center C1 of the optical article plate 4 and the center C1' of the optical article plate 2 may not be located on the same line. In such a case, the offset may be calculated based on one of C1 and C1' to satisfy the requirements specified in the present invention.

The thickness deviation of the adhesive layer is a deviation of the thickness on the circumference of the concentric circle a having the radius r, 12 points are uniformly measured with respect to the thickness on the circumference, and the average value thereof is calculated as the average thickness t_aveIt can be determined from the offset based on the deviation. More specifically, the deviation is. + -. X%, and the thickness t is determined from the average value among the 12-point measurement values_aveThickness t of the measurement point having the largest difference in thickness₁The term means that the absolute value of the value calculated by the following formula (1) is X%.

Formula (1) · [ (t)₁-t_ave)/t_ave]×100

In the present invention, any concentric circle a having a radius r may be used as long as the deviation of the thickness of the adhesive layer is within ± 10%. Thus, a photochromic optical article having less color unevenness can be obtained. The deviation is preferably within ± 7.5%, more preferably within ± 5%.

In addition, the radius r is defined as r, which is the maximum radius of the desirable concentric circle a_maxWhen r is 0.1r, it is preferable_max～0.9r_maxAmong them, r is more preferably 0.5r_max～0.7r_max。

For example, when the photochromic optical article of the present invention is used for spectacles, the maximum radius of the concentric circle a from the center C2 of the adhesive layer 3 is generally 20mm to 50mm, preferably 30mm to 40 mm.

Further, it is preferable that the deviation of the thickness of the adhesive layer is within ± 10% in a concentric circle a having an arbitrary radius r, and the deviation of the thickness of the adhesive layer is within ± 20% in a concentric circle a having a radius different from the radius r, and more preferably within ± 10%.

In addition, in concentric circles having a plurality of radii r, the deviation of the thickness of the adhesive layer is preferably within ± 10%, and for example, the radius is preferably 0.5r_maxDeviation of thickness of adhesive layer in concentric circles of (2), 0.2r_maxThe deviation of the thickness of the adhesive layer in the concentric circles of (1) and 0.8r_maxThe thickness deviation of the adhesive layer in the concentric circles of (2) is within ± 10%, more preferably within ± 7.5%, and still more preferably within ± 5%. Further, the thickness deviation of the adhesive layer in all the concentric circles of the radius is preferably within ± 10%, more preferably within ± 7.5%, and still more preferably within ± 5%. In this way, by setting the deviation of the thickness of the adhesive layer in concentric circles of a plurality of radii to be constant or less, a photochromic optical article in which color unevenness is highly suppressed can be obtained.

In addition, from the viewpoint of suppressing color unevenness more highly, it is preferable that the thickness deviation between a plurality of concentric circles having different radii is small. For example, 0.2r is preferable_max、0.5r_max、0.8r_maxWithin + -10% of the thickness of the different concentric circles. The deviation in thickness between different concentric circles is ± Y%, which means that the absolute value of the value calculated by the following formula (2) is Y%.

I.e. for 0.2r_max、0.5r_max、0.8r_maxThe thickness of each concentric circle of (2) was measured at 12 points uniformly over the circumference, and the total thickness of the concentric circles was measured at 36 points. The average value (T) of the thicknesses of the 36 points was calculated_ave) Determining the thickness T from the average value among the measured values at 36 points_aveThickness T of the measurement point having the largest difference in thickness₁This means that the absolute value of the value calculated by the following formula (2) is Y%.

Formula (2) · [ (T)₁-T_ave)/T_ave]×100

In addition, in the present invention, it is preferable that no bubble is present in a stage where a pair of optical articles are joined with plates to produce a photochromic optical article. Even if bubbles are present at the stage of joining the pair of optical article plates, they can be removed by cutting, polishing, or the like, but are not preferable because of limitations on the subsequent use.

[ plate for optical article ]

The material of the plate for optical articles is not particularly limited as long as it is a material used for optical articles such as lenses, and it may be an inorganic material or an organic material. In addition, the color tone may not be colorless and transparent, and may be a transparent color tone colored in a specific color such as black, gray, brown, beige, cyan, red, or the like.

Examples of the inorganic material include glass materials such as general soda glass, flint glass, and crown glass. For example, it is possible to cite the compound having SiO₂、B₂O₃、Al₃O₃、Na₂CO₃、Na₂O、K₂O、CaO、Ca(OH)₂、CaCO₃、Ca、BaO、MgO、PbO、ZnO、MnO₂、Al₂O₃、Al₂O₅、Li₂O、Nb₂O₅、ZrO₂、Fe₂O₃、CeO₂、TiO₂、La₂O₃、SrO、As₂O₃、Sb₂O₃At least one oxide of (a). Among these glass materials, crown glass is preferable.

The glass material may have a specific property, for example, a chemically strengthened glass material, a high refractive index glass material having a refractive index of 1.7 or more, a glass material having ultraviolet absorption characteristics, and a glass material for shielding blue light.

As the chemically strengthened glass material (hereinafter, also referred to as chemically strengthened glass), known chemically strengthened glass can be used without any limitation. For example, chemically strengthened glass is generally used by a low-temperature type ion exchange method. The low-temperature type ion exchange method is carried out by mixing a glass with a glass having a specific molecular weight at a temperature not exceeding the transition temperatureA method of treating an alkali metal containing an alkali metal with a large ionic radius by contacting the alkali metal with a molten salt. I.e. by incorporating Li⁺The glass contains Na derived from sodium nitrate or the like⁺In the case of Na-containing molten salt⁺K derived from potassium nitrate or the like for glass⁺The molten salt of (3) can be treated to perform low-temperature ion exchange. Chemically strengthened glass by the low-temperature ion exchange method is cooled after the treatment by the low-temperature ion exchange, and thus, due to the difference in expansion coefficient between the surface layer and the inner layer of the glass, compressive stress remains on the surface and tensile stress remains in the interior, and thus, impact resistance is improved.

As the high refractive index glass material having a refractive index of 1.7 or more, a known high refractive index glass material can be used without any limitation. Among them, the refractive index is preferably 1.7 to 2.1, and particularly preferably 1.7 to 1.9.

As the method for making the refractive index to be 1.7 or more, it is preferable to use a glass material containing TiO selected from the group consisting of₂、La₂O₃、Nb₂O₅、ZrO₂At least one oxide of (a).

As the glass material having ultraviolet absorption (hereinafter, also referred to as ultraviolet absorbing glass) and/or the glass material for shielding blue light (hereinafter, also referred to as blue light shielding glass), known glass materials can be used without any limitation. As a method for imparting ultraviolet absorbing ability and/or blue light shielding ability, it is preferable to use a glass material containing Fe selected from the group consisting of₂O₃、CeO₂、TiO₂At least one oxide of (a).

The ultraviolet absorption property is preferably a transmittance at 400nm of 50% or less, more preferably 30% or less, and most preferably 10% or less.

Further, as the glass having a low ultraviolet absorptivity, a glass having a transmittance at 360nm of 50% to 90% can be used.

The above-mentioned blue light shielding property is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less in transmittance at 425 nm.

On the other hand, examples of the organic material include polycarbonate resins, polyester resins, cellulose resins, polyamide resins, allyl resins, (meth) acrylic resins, polyurethane urea resins, polythiourethane resins, polyepisulfide resins, epoxy resins, polyimide resins, polyolefin resins, and the like. The "(meth) acrylic resin" means both of the "acrylic resin" and the "methacrylic resin".

In addition, the above organic material may be a high refractive index organic material having a refractive index of 1.7 or more, an organic material having ultraviolet absorption characteristics, and an organic material that shields blue light, for example, with specific properties. As the high refractive index organic material having a refractive index of 1.7 or more, a known high refractive index organic material can be used without any limitation. Examples of the organic material having ultraviolet absorption properties include organic materials containing known blending materials having ultraviolet absorption properties. In this case, the required ultraviolet absorption performance is the same as that of the inorganic material. As the organic material for shielding blue light, an organic material containing a known compounding material having blue light shielding performance can be cited. In this case, the required blue light shielding performance is the same as that of the inorganic material.

Among the materials of these optical article plates, the adhesive layer described later, particularly the adhesive layer containing a urethane resin, has very good adhesion to the optical article plate made of an inorganic material, and the inorganic material has excellent gas barrier properties compared to the organic material, and therefore, the photo-oxidation degradation of the photochromic compound is suppressed. Preferably, at least one of the pair of optical article plates has a refractive index of 1.7 or more.

The pair of optical article plates may be the same or different, and may be set as appropriate according to the purpose.

For example, when the photochromic optical article of the present invention is a spectacle lens, the combination of the optical article plate on the side close to the eyes (hereinafter also referred to as the inner side) and the optical article plate on the side far from the eyes and irradiated with sunlight outdoors (hereinafter also referred to as the outer side) is used.

In this case, if it is required that the outer optical article plate sufficiently exhibit photochromic properties, it is preferable to use a glass material or an organic material having weak ultraviolet absorption properties. Specifically, a glass material or an organic material having a transmittance of light having a wavelength of 380nm of 50% or more is preferably used. In addition, if impact resistance is required, organic materials or chemically strengthened glass may be used.

On the other hand, if it is required to protect the eyes from ultraviolet rays, it is preferable to use a glass material having a strong ultraviolet absorption property, a blue-light shielding glass, or an organic material for the inner optical article plate. Specifically, a glass material having a transmittance of light having a wavelength of 400nm of 10% or less, a glass material having a transmittance of light having a wavelength of 425nm of 30% or less, or an organic material is preferably used. Further, if it is required to be used as a spectacle lens for power correction, a glass material or an organic material having a high refractive index of 1.7 or more is preferable from the viewpoint of thinning and weight reduction.

Specific combinations for use as a spectacle lens include a combination of at least one property selected from the group consisting of an outer optical article plate made of a normal glass, an inner optical article plate made of a glass material or an organic material having a high refractive index of 1.7 or more, a glass or an organic material having a blue light shielding property, an ultraviolet absorbing glass or an organic material having a transmittance of 50% or less at 400nm, and an organic material or a chemically strengthened glass.

When the outer optical article plate is made of an organic material or chemically strengthened glass, the inner optical article plate may be made of a combination of at least one property selected from a glass material or an organic material having a high refractive index of 1.7 or more and an ultraviolet-absorbing glass or an organic material having a transmittance of 50% or less at 400nm, and a general glass. In addition, a combination of an inorganic material on one side and an organic material on the other side may be used as the pair of optical article plates. In this case, the inorganic material portion of the obtained photochromic optical article can be removed to obtain a photochromic optical article in which the adhesive layer and the organic material are laminated.

When the inorganic material is partially removed, the surface of the inorganic material in contact with the adhesive layer is preferably subjected to a release treatment in advance.

The thickness of the optical article sheet is not particularly limited and may be appropriately selected according to the purpose. For example, in the case of application to sunglasses and the like without power, an optical article plate having a thickness of 1.5mm or less can be used, and from the viewpoint of weight reduction, an optical article plate having a thickness of 1.0mm or less is preferably used. In the case of producing a lens with diopter power for near vision, for example, it is preferable that the thickness of the center of the outer optical article plate is 1.0mm or less and at least a part of the inner optical article plate is thicker than 1.0mm, and an optical article plate having an appropriate thickness of about 10 to 20mm can be used. In the case of producing a lens with dioptric power for hyperopia, for example, the thickness of the center of the outer optical article plate is preferably 20mm or less, and at least a part of the inner optical article plate is preferably thicker than 1.0mm, and an optical article plate having an appropriate thickness of about 10 to 20mm can be used. In the case of producing a bifocal lens, a progressive lens, or the like, the thickness of the optical article plate to be used can be appropriately selected as described above. When a lens with diopter is manufactured, diopter can be adjusted according to the user's eyesight by polishing the concave surface side of the inner optical article plate as necessary.

Among them, the photochromic optical article according to the present invention exhibits excellent effects when the thickness of at least one optical article plate is 1.5mm or less, particularly 1.0mm or less. The lower limit of the thickness of the plate for optical articles is, for example, 0.1 mm. The photochromic optical article of the present invention preferably has at least one optical article-use plate with a thickness of 0.1 to 1.5mm, more preferably 0.5 to 1.0 mm. When the thickness of one optical article plate is 0.1 to 1.5mm, the other optical article plate may have the same thickness or a different thickness. When the thickness is different, the thickness is not particularly limited, and may be 10 to 20 mm.

The shape of the plate for optical articles is not particularly limited, and a plate for optical articles having a shape (flat shape, curved shape, etc.) suitable for a desired use can be used. However, in the case of using a plate for an optical article having a curved surface, if a plate having the same radius of curvature of the joint surface is used for the joint, the thickness is generally larger than that of the center and the thickness of the end portion is smaller. Therefore, when a curved plate is used, it is preferable to use a pair of curved plates for optical articles that are optically designed so that the thickness of the adhesive layer is uniform from the center and the concentric circles.

[ thickness of adhesive layer ]

The photochromic optical article according to the present invention is characterized in that the photochromic compound dispersed in the adhesive layer exhibits excellent photochromic properties. Therefore, even if the adhesive layer is thin, excellent effects can be exhibited.

In view of workability and excellent effects, the thickness of the adhesive layer is preferably 0.02 to 0.8mm, more preferably 0.03 to 0.5mm, and still more preferably 0.05 to 0.2 mm. By setting the thickness of the adhesive layer to 0.02mm or more, the adhesiveness is improved, and the film thickness is easily made uniform, and the concentration unevenness in color development tends to be suppressed. In addition, by making the thickness of the adhesive layer 0.8mm or less, it tends to be possible to suppress deterioration of durability due to deterioration from the end portion. For example, when the photochromic optical article according to the present invention is used as sunglasses, it is necessary to maintain the thickness of the optical article plate to be about 0.1 to 1.5mm from the viewpoint of strength, and the thickness of the adhesive layer is preferably 0.8mm or less from the viewpoint of design in order to suppress the total thickness of the photochromic optical article.

[ Total thickness of photochromic optical article ]

The photochromic optical article according to the present invention is obtained by joining a pair of plates for optical articles with an adhesive layer, and the preferable total thickness of the photochromic optical article obtained by the above constitution varies depending on the purpose. For example, if the lens is used for spectacles, the use of sunglasses without power and the use of lenses with power are different.

When the photochromic optical article according to the present invention is a spectacle lens, the combination of the optical article plate on the side close to the eye (inner side) and the optical article plate on the side far from the eye (outer side) on which sunlight is irradiated outdoors is used.

In the case of sunglasses without power, the thicknesses of the outer and inner optical article plates are each preferably 1.5mm or less, more preferably 1.0mm or less. The thickness of the adhesive layer is preferably 0.8mm or less, and more preferably 0.05 to 0.2 mm. Therefore, the total thickness of the photochromic optical article in the case of the use for sunglasses without power is preferably 3.8mm or less, more preferably 2.2mm or less.

In addition, in the case of the lens application with power, the thickness of the outer optical article plate is preferably 1.5mm or less, more preferably 1.0mm or less. On the other hand, as the inner optical article plate, an optical article plate having an appropriate thickness of about 10 to 20mm can be used, and the concave surface can be polished and used according to the user's eyesight. The thickness of the adhesive layer is preferably 0.8mm or less, and more preferably 0.05 to 0.2 mm. Therefore, the total thickness of the photochromic optical article in the case of the lens application with power is preferably 22.3mm or less, more preferably 11.2mm or less. However, in the case of the lens application with power, the center thickness of the final polished photochromic optical article is preferably 2.5mm or less.

[ adhesive layer ]

The adhesive layer of the photochromic optical article according to the present invention is an adhesive layer containing a photochromic compound and a resin selected from a urethane resin, an epoxy resin and an acrylic resin. The resin selected from the group consisting of polyurethane resin, epoxy resin, and acrylic resin used in the adhesive layer is not particularly limited, and known resins can be used, and among these, an adhesive layer containing a photochromic compound and a polyurethane resin is preferable.

Further, the adhesive layer is preferably obtained by curing a photochromic adhesive composition containing a photochromic compound and at least one curable compound selected from a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound. The polyisocyanate (thio) cyanate/polyol mixture is preferably a mixture containing a polyisocyanate compound having 2 or more isocyanate (thio) groups in the molecule and a polyol compound having 2 or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule. The photochromic adhesive composition will be described in detail below.

[ photochromic adhesive composition ]

The photochromic adhesive composition according to the present invention is a photochromic adhesive composition comprising a photochromic compound and at least one curable compound selected from the group consisting of a polyiso (thio) cyanate/polythiol mixture, an epoxy compound and an acrylic compound, as described above, wherein the polyiso (thio) cyanate/polythiol mixture is cured to give a polyurethane resin, the epoxy compound is cured to give an epoxy resin, and the acrylic compound is cured to give an acrylic resin.

Among these, the polyisocyanate (thio) cyanate/polyol mixture is preferably a mixture containing a polyisocyanate compound having 2 or more isocyanate (thio) cyanate groups in the molecule and a polyol compound having 2 or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule. This is explained in detail below.

That is, the above-mentioned preferred photochromic adhesive composition comprises: (A) a photochromic compound (hereinafter also referred to as "component (a)"), (B1) a polyiso (thio) cyanate compound having 2 or more isocyanate groups in the molecule (hereinafter also referred to as "component (B1)" or "(B1) a polyiso (thio) cyanate compound"), (B2) a poly (thio) alcohol compound having 2 or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule (hereinafter also referred to as "component (B2)" or "(B2) a poly (thio) alcohol compound").

In addition, the photochromic adhesive composition preferably contains, in addition to the above-mentioned component (a), component (B1), and component (B2): if necessary, (B3) a monohydric (thio) alcohol compound having 1 active hydrogen-containing group selected from a hydroxyl group and a thiol group in the molecule (hereinafter also referred to simply as "(B3) component" or "(B3) a monohydric (thio) alcohol compound"), and/or (B4) a polyrotaxane monomer having a composite molecular structure comprising a shaft molecule and a plurality of cyclic molecules including the shaft molecule, the cyclic molecules having an isocyanate group or an active hydrogen-containing group selected from a hydroxyl group and a thiol group (hereinafter also referred to as "(B4) component" or "(B4) a polyrotaxane monomer") (hereinafter also referred to as "(B1) component", "(B2) component", and if necessary, the "(B3) component" (B4) is "collectively referred to as" (B) component ").

In the present specification, "isocyanate (thio) group" means both "isocyanate group" and "isothiocyanate group".

The phrase "having 2 or more isocyanate (thio) groups in a molecule" means "having 2 or more isocyanate groups in a molecule", "having 2 or more isothiocyanate groups in a molecule", or "having isocyanate groups and isothiocyanate groups in a molecule, and the total of these groups being 2 or more".

The phrase "having 2 or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule" means "having 2 or more hydroxyl groups in the molecule", "having 2 or more thiol groups in the molecule", or "having hydroxyl groups and thiol groups in the molecule, and the total of these groups is 2 or more".

By "(thio) alcohol" is meant both "alcohol (OH)" and "thiol (SH)".

The method for producing the photochromic adhesive composition is not particularly limited, and the respective components may be mixed by a known method. The respective components will be described below.

((A) photochromic Compound)

As the photochromic compound (a), for example, a fulgide compound, a chromene compound, a spirooxazine compound and the like are known, and in the present invention, these photochromic compounds can be used without any limitation. These can be used alone in 1 kind, also can be used in2 or more. Examples of the fulgide compound, the chromene compound and the spirooxazine compound include compounds described in Japanese patent application laid-open No. 2-28154, Japanese patent application laid-open No. 62-288830, International publication No. 94/22850, International publication No. 96/14596 and the like.

Among them, as the compound exhibiting an excellent photochromic action, for example, Japanese patent laid-open Nos. 2001-114775, 2001-031670, 2001-011067, 2001-011066, 2000-347346, 2000-344762, 2000-344761, 2000-344776, 2000-327676, 2000-327675, 2000-256347, 2000-229976, 2000-229975, 2000-229974, 2000-229973, 2000-229972, 2000-219687, 2000-19686, 2000-219685, 2000-19685, Japanese patent laid-open Nos. 11-322739, 11-286484, 11-279171, 10-298176, 09-218301, 09-124645, 08-295690, 08-176139, 08-157467, 5645767, 5658501, 5961892, 6296785, 4424981, 4424962, 56 2009/136668, 2008/023828, 4369754, 4301621, 4256985, 2007/086532, 2009-120536, Japanese patent laid-open Nos. 2009-67754, 2009-67680, 2009-57300, 4195615, 4158881, 4157245, 4157239, 4157227, 4118458, 2008-74832, 3982770, 3801386, 2005/028465, 2003/042203, 2005-289812, 2005-289870, 2005-112772, 3522189, 2002/090342, 3471073, 2003-277381, 2001/060811, 2000/071544, Chromene compounds disclosed in international publication No. 2005/028465, international publication No. 2011/16582, international publication No. 2011/034202, international publication No. 2012/121414, international publication No. 2013/042800, japanese patent No. 6031035, and the like.

Generally, the chromene compound can be represented by the following general formula (1).

[ solution 1]

The chromene compound having a structure represented by the above general formula (1) may have a known substituent without particular limitation.

Among the above chromene compounds, a chromene compound having an indeno (2, 1-f) naphtho (1, 2-b) pyran structure represented by the following general formula (2) is more preferable from the viewpoint of photochromic characteristics such as color development concentration, initial coloration, durability, and fading speed.

[ solution 2]

The chromene compound having a structure represented by the above general formula (2) is not particularly limited as to its substituent, and may have a known substituent.

Examples of the photochromic compound that can be used in the present invention include the following photochromic compounds, but are not limited thereto.

[ solution 3]

Further, as the component (a), any one of photochromic compounds having a long-chain group having a molecular weight of 300 or more, particularly a molecular chain such as a polysiloxane chain, a polyoxyalkylene chain, a polyester chain or a polyester polyether chain as a substituent can be appropriately selected and used. Since the molecular chain having a molecular weight of 300 or more is a high molecular weight, there are cases where the photochromic compound is produced so that the photochromic compound has not 1 molecular chain but a plurality of molecular chains. In this case, the molecular weight of the molecular chain may be an average value (number average molecular weight) of the molecular chains of plural kinds within the above-mentioned predetermined range. The molecular weight can be confirmed by the kind of the raw material used in the production of the photochromic compound, or by a product using a known means such as NMR, IR, mass analysis, or the like.

It is considered that the photochromic compound has a molecular chain having a molecular weight of 300 or more, and thus the adhesive layer of the present invention can exhibit a high photochromic property. The molecular weight of the molecular chain is preferably 300 to 25000, more preferably 400 to 20000, still more preferably 440 to 15000, and particularly preferably 500 to 10000, in consideration of photochromic properties, the amount of photochromic compound to be incorporated and the productivity of the photochromic compound itself.

When the photochromic compound has a molecular chain having a molecular weight of 300 or more, the number of the molecular chain is preferably 0.5 or more per 1 molecule of the photochromic compound. That is, even when the number of the molecular chains is minimized, it is preferable that 2 photochromic compounds are bonded to each other by the molecular chains. The upper limit of the number of the molecular chains is preferably 4 or less, more preferably 2 or less, and further preferably 1, in consideration of compatibility with the molecular weight of the molecular chains, photochromic properties, and the like.

In addition, the photochromic compound preferably has a molecular structure that exhibits photochromic properties, and when irradiated with light, the molecule is partially cleaved and developed, and then the cleaved site is recombined and discolored. Therefore, in order for the photochromic compound to reversibly repeat color development and color fading, it is important that a free space (degree of freedom of molecules) which does not interfere with the movement of molecules is present at the time of occurrence of cleavage and recombination. In the case of a compound having such a molecular structure, the effect of the molecular chain is particularly considered to be exerted.

Examples of the photochromic compound having a molecular chain with a molecular weight of 300 or more include compounds described in international publication No. 2000/015630, international publication No. 2004/041961, international publication No. 2005/105874, international publication No. 2005/105875, international publication No. 2006/022825, international publication No. 2009/146509, international publication No. 2010/20770, international publication No. 2012/121414, international publication No. 2012/149599, international publication No. 2012/162725, international publication No. 2012/176918, international publication No. 2013/078086, international publication No. 2019/013249, japanese patent application No. 2018-079303, japanese patent application No. 2018-136374 and the like.

In the present invention, the photochromic compound having a molecular chain with a molecular weight of 300 or more is preferably at least 1 photochromic compound selected from the following formulae (3) and (4).

PC- (L-chain) (3)

PC- (L-chain-L ') -PC' (4)

In the above formula (3) or formula (4),

l and L 'are each a 2-valent organic group containing at least 1 group selected from a polyoxyalkylene chain, (thio) ester group, (thio) amide group, L and L' may be the same or different,

the chain is a 1-or 2-valent organic group containing at least 1 chain selected from a polyoxyalkylene chain, a polyester polyether chain, and a polysiloxane chain,

the total molecular weight of L and the chain, or L, L' and the chain corresponds to the molecular weight of the above molecular chain. That is, L and the chain, or L, L' and the part of the chain correspond to the molecular chain.

In the above formula (3) or formula (4),

each of PC and PC' is selected from compounds having a basic skeleton represented by the following formulae (5) to (9).

[ solution 4]

In the above formulas (5) to (9), the molecular structure in parentheses is a basic skeleton of PC or PC ', and the line indicates the bond to L or L'.

In the basic skeleton represented by the above formulas (5) to (9), 1 atom of the carbon atom or nitrogen atom which may have a substituent may be directly bonded to L or L 'which is a 2-valent organic group, and the other atom may have another substituent, or 1 atom of the carbon atom or nitrogen atom which may have a substituent may be bonded to L or L' which is a 2-valent organic group via a substituent, and the other atom may have another substituent.

Next, preferred basic skeletons of the above formulas (5) to (9) will be described.

< basic skeleton represented by formula (5') (preferred basic skeleton of formula (5) >)

Among the basic skeletons represented by the above formula (5), preferred ones are those represented by the following formula (5').

[ solution 5]

In the above formula (5 '), the molecular structure in brackets is a basic skeleton of PC or PC ', and the line indicates the bond to L or L '.

R in the above formula (5')¹And R²Each of which may be mentioned a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, an alkylthio group having a substituentAn arylthio group having 6 to 10 carbon atoms, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, an aralkyl group having 7 to 11 carbon atoms which may have a substituent, an aralkyloxy group having 7 to 11 carbon atoms which may have a substituent, an aryloxy group having 6 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, a heteroaryl group having 3 to 12 carbon atoms which may have a substituent, a thiol group, an alkoxyalkylthio group having 2 to 9 carbon atoms, a haloalkylthio group having 1 to 6 carbon atoms, a cycloalkylthio group having 3 to 8 carbon atoms which may have a substituent, and the like.

R in the above formula (5')³And R⁴Each is a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 3 to 20 carbon atoms which may have a substituent.

The substituent of the aryl or the heteroaryl includes a substituent selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a heterocyclic group, a cyano group, a halogen atom, an alkylthio group having 1 to 6 carbon atoms, an arylthiohydroxy group having 6 to 10 carbon atoms which may have a substituent, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a nitro group, and a halogen atom.

R in the above formula (5')⁵And R⁶Examples thereof include a hydrogen atom, a halogen atom, a carboxyl group, an acetyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a heteroaryl group having 3 to 20 carbon atoms which may have a substituent.

In the basic skeleton represented by the above formula (5 '), R is represented by the above-mentioned- (L-chain) or- (L-chain-L') -, with respect to the molecular chain¹～R⁶Any of which can be a bonding end to bond with the basic skeleton. Furthermore, R¹～R⁶Is a reaction of R¹、R²、R³、R⁴、R⁵、R⁶Summary representation. The following applies to the case where "to" is used in the examples of the group.

In addition, R can also be passed¹～R⁶One group of (a) (however, excluding hydrogen atoms) is bonded to the molecular chain. Further, R can be also passed¹～R⁶One group of (2) is bonded to the molecular chain.

Among them, R in the above formula (5') is preferably R in consideration of the color development concentration, color development hue and the like of the obtained photochromic compound¹～R⁶As described below.

Preferred R¹、R²Is a hydrogen atom, the above alkyl group, the above alkoxy group, the above heterocyclic group, the above aryl group, the above arylthio group. Preferred R³、R⁴The alkyl group, the alkoxy group, the substituted amino group, and the heterocyclic group. Preferred R⁵、R⁶The alkyl group, the alkenyl group, the alkoxy group, the aryl group, and the heteroaryl group. Furthermore, the above molecular chain is preferably bonded to R³～R⁶Either directly or via a substituent.

< basic skeleton represented by formula (6') (preferred basic skeleton of formula (6) >)

Among the basic skeletons represented by the above formula (6), preferred ones are those represented by the following formula (6').

[ solution 6]

In the above formula (6 '), the molecular structure in brackets is a basic skeleton of PC or PC ', and the line indicates the bond to L or L '.

R in the above formula (6')¹～R⁴Examples thereof include R in the above formula (5')¹～R⁴The same groups as those described in (1).

R in the above formula (6')⁷Examples thereof include R in the above formula (5')¹～R²The same groups as those described in (1).

R in the above formula (6')⁸And R⁹Each of which is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group which may have a substituent, a cyano group, a nitro group, an alkoxyalkyl group having 1 to 6 carbon atoms, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a halogen atom, an aralkyl group having 7 to 11 carbon atoms which may have a substituent, an aralkyloxy group having 7 to 11 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, a thiol group, an alkylthio group having 1 to 6 carbon atoms, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms which may have a substituent.

R in the above formula (6')⁸And R⁹These two groups may together form an aliphatic ring having a ring member carbon number of 3 to 20, a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the aliphatic ring, a heterocyclic ring having a ring member carbon number of 3 to 20, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the heterocyclic ring, and these rings may have a substituent.

In the basic skeleton represented by the above formula (6 '), R is represented with respect to the above-mentioned molecular chain of- (L-chain) or- (L-chain-L') -¹～R⁴、R⁷～R⁹Any of which can be bonded to the basic skeleton as a bonding end.

In addition, R can also be passed¹～R⁴、R⁷～R⁹One group of (a) (however, excluding hydrogen atoms) is bonded to the molecular chain. Further, R can be also passed¹～R⁴、R⁷～R⁹One group of (2) has a substituent bonded to the molecular chain.

Among them, preferred R in the above formula (6')¹～R⁴、R⁷～R⁹As described below.

Preferred R¹、R²、R³、R⁴The preferred R is the same as the preferred group represented by the above formula (5')⁷Is a hydrogen atom, orThe alkoxy group, the heterocyclic group, the aryl group, and preferably R⁸And R⁹Is the above-mentioned hydroxyl group, the above-mentioned alkyl group, the above-mentioned alkoxy group, or with R⁸And R⁹The carbon atom at the 13-position of the bond forms a ring. Furthermore, the above molecular chain is preferably bonded to R³～R⁴、R⁷～R⁹Either directly or via a substituent.

< basic skeleton represented by formula (7') (preferred basic skeleton of formula (7) >)

Among the basic skeletons represented by the above formula (7), preferred ones are those represented by the following formula (7').

[ solution 7]

In the above formula (7 '), the molecular structure in brackets is the basic skeleton of PC or PC ', and the line indicates the bond to L or L '.

R in the above formula (7')³～R⁴Examples thereof include R in the above formula (5')³～R⁴The same groups as those described in (1).

R in the above formula (7')¹⁰～R¹²Examples thereof include R in the above formula (5')¹～R²The same groups as those described in (1).

In the basic skeleton represented by the above formula (7 '), R is represented by the above-mentioned- (L-chain) or- (L-chain-L') -, with respect to the molecular chain³～R⁴、R¹⁰～R¹²Can be a bonding end to bond with the basic skeleton.

In addition, R can also be passed³～R⁴、R¹⁰～R¹²One group of (a) (however, excluding hydrogen atoms) is bonded to the molecular chain. Further, R can be also passed³～R⁴、R¹⁰～R¹²One group of (a) has a substituent to bond with the molecular chain.

< basic skeleton represented by formula (8') (preferred basic skeleton of formula (8) >)

Among the basic skeletons represented by the above formula (8), preferred ones are those represented by the following formula (8').

[ solution 8]

In the above formula (8 '), the molecular structure in brackets is a basic skeleton of PC or PC ', and the line indicates the bond to L or L '.

R in the above formula (8')¹³、R¹⁷、R¹⁸And R¹⁹Examples thereof include R in the above formula (5')¹～R²The same groups as those described in (1).

R in the above formula (8')¹⁶Examples thereof include a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a dihaloalkyl group having 1 to 5 carbon atoms, a trihaloalkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms and which may have a substituent, a bicycloalkyl group having 6 to 20 carbon atoms and which may have a substituent, and an aryl group having 6 to 20 carbon atoms and which may have a substituent.

R in the above formula (8')¹⁴And R¹⁵Examples thereof include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent, and the like.

In the basic skeleton represented by the above formula (8 '), R is represented by the above-mentioned- (L-chain) or- (L-chain-L') -, with respect to the molecular chain¹³～R¹⁹Can be a bonding end to bond with the basic skeleton.

In addition, R can also be passed¹³～R¹⁹One group of (a) (however, excluding hydrogen atoms) is bonded to the molecular chain. Further, R can be also passed¹³～R¹⁹One group of (2) has a substituent bonded to the molecular chain.

< basic skeleton represented by formula (9') (preferred basic skeleton of formula (9) >)

Among the basic skeletons represented by the above formula (9), preferred ones are those represented by the following formula (9').

[ solution 9]

In the above formula (9 '), the molecular structure in brackets is a basic skeleton of PC or PC ', and the line indicates the bond to L or L '.

R in the above formula (9')¹³、R¹⁸And R¹⁹Examples thereof include the compounds represented by the formula (5') and R¹～R²The same groups as those described in (1).

R in the above formula (9')¹⁴、R¹⁵、R²⁰And R²¹Examples thereof include R in the above formula (8')¹⁴～R¹⁵The same groups as those described in (1).

In the basic skeleton represented by the above formula (9 '), R is represented by the above-mentioned- (L-chain) or- (L-chain-L') -, with respect to the molecular chain¹³～R¹⁵And R¹⁸～R²¹Can be a bonding end to bond with the basic skeleton.

In addition, R can also be passed¹³～R¹⁵And R¹⁸～R²¹One group of (a) (however, excluding hydrogen atoms) is bonded to the molecular chain. Further, R can be also passed¹³～R¹⁵And R¹⁸～R²¹One group of (2) has a substituent bonded to the molecular chain.

In the formula (3) or the formula (4), L or L' is a 2-valent linking group containing at least one group selected from a polyoxyalkylene chain, (thio) ester group, and (thio) amide group, as described above, and more specifically, a 2-valent organic group represented by the following formula (10) is preferable.

[ solution 10]

In the formula (I), the compound is shown in the specification,

R²²is 2 valentThe group is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms in a ring and optionally having a substituent, an aryl group having 6 to 12 carbon atoms in a ring and optionally having a substituent, or a heterocyclic group having 3 to 12 atoms in a ring and optionally having a substituent,

R²³the group having a valence of 2 is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms in a ring and optionally having a substituent, or an aryl group having 6 to 12 carbon atoms in a ring and optionally having a substituent,

R²⁴the group having a valence of 2 is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms in a ring and optionally having a substituent, or an aryl group having 6 to 12 carbon atoms in a ring and optionally having a substituent,

X¹and X²Is a 2-valent radical, each independently a direct bond, O, S, an amino group, a substituted amino group, a (thio) amide group, or a (thio) ester group,

d is an integer of 0 to 50, e is an integer of 0 to 50, f is an integer of 0 to 50,

when d is 2 or more, there are plural Rs²²May be the same as or different from each other,

when e is 2 or more, the 2-valent groups of the units of a plurality of e may be the same or different from each other,

when f is 2 or more, the 2-valent groups of the units having a plurality of f may be the same or different from each other.

L, L' may be the same or different from each other, and the dotted line indicates the bond with the photochromic portion.

Examples of the preferable group of the above-mentioned (10) include those represented by the following formula

[ solution 11]

The 2-valent radical of the formula.

In the above formulae (3) and (4), the chain is a 1-or 2-valent group containing at least one chain selected from a polyoxyalkylene chain, a polyester polyether chain and a polysiloxane chain, and among them, a chain having a repeating unit represented by the following formulae (11a) to (11d) is preferable.

[ solution 12]

In the formulae (11a) to (11c),

R²⁵is a linear or branched alkylene group having 1 to 20 carbon atoms and containing a plurality of R's in the same molecule²⁵In the case of (1), R²⁵May be the same as or different from each other,

n is a repeating unit and is an integer of 3 to 200, and the 2-valent groups of a plurality of repeating units may be the same or different from each other.

In the formula (11d), the metal salt,

R²⁶is a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms, and contains a plurality of R in the same molecule²⁶In the case of (1), R²⁶May be the same as or different from each other.

Examples of the chromene compound having a molecular chain with a molecular weight of 300 or more are shown below, but the present invention is not limited thereto.

[ solution 13]

(A) The blending ratio of the component (A) is suitably set according to the purpose, and is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the component (B) described later.

(component (B))

[ (B1) polyiso (thio) cyanate Compound ]

((B1) component: polyisocyanate Compound)

Examples of the polyisocyanate compound in the polyiso (thio) cyanate compound include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic isocyanate compounds, sulfur-containing aliphatic isocyanate compounds, aliphatic thioether isocyanate compounds, aromatic thioether isocyanate compounds, aliphatic sulfone isocyanate compounds, aromatic sulfone isocyanate compounds, sulfonate isocyanate compounds, aromatic sulfonamide isocyanate compounds, and sulfur-containing heterocyclic isocyanate compounds.

Among these, compounds suitable for forming a photochromic optical article having high adhesion between a pair of optical article plates and excellent transparency and mechanical strength include compounds represented by the following formulae (I) to (VI).

(component (B1): the following formula (I) (polyisocyanate compound having alkylene group))

[ solution 14]

OCN-R¹⁰⁰-NCO (I)

(in the formula, R¹⁰⁰Represents an alkylene group having 1 to 10 carbon atoms, and a part of carbon atoms in the chain of the alkylene group may be replaced with sulfur atoms. )

As R¹⁰⁰The alkylene group(s) may be linear or branched. Among the alkylene groups, a linear group which is pentamethylene, hexamethylene, heptamethylene, or octamethylene is preferable; a branched chain group in which a part of hydrogen atoms of pentamethylene, hexamethylene, heptamethylene, or octamethylene is substituted with methyl. Further, the alkylene group having a carbon atom partially replaced with a sulfur atom is preferably-CH₂CH₂SCH₂CH₂SCH₂CH₂-。

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

(component (B1): the following formula (II) (polyisocyanate compound having benzene ring) or the following formula (III) (polyisocyanate compound having cyclohexane ring))

[ solution 15]

[ solution 16]

(in the formula, R¹⁰¹Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R¹⁰²The alkyl groups having 1 to 4 carbon atoms may be the same or different when a plurality of groups are present. a is¹⁰⁰Represents 2 or 3, b¹⁰⁰Represents an integer of 0 to 4, c¹⁰⁰Represents an integer of 0 to 4. )

The compound represented by the above formula (II) is different from the compound represented by the above formula (III) in that the former is a compound having a benzene ring and the latter is a compound having a cyclohexane ring.

As R¹⁰¹The alkyl group (b) may be linear or branched. Wherein R is¹⁰¹Preferably a hydrogen atom, a methyl group, or an ethyl group.

As R¹⁰²The alkyl group (b) may be linear or branched. Wherein R is¹⁰²Preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the above formula (II) or the above formula (III) include isophorone diisocyanate, xylene diisocyanate (o-, m-, p-), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1, 4-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane (isomer mixture), and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B1): the following formula (IV) (polyisocyanate compound having 2 benzene rings) or the following formula (V) (polyisocyanate compound having 2 cyclohexane rings))

[ solution 17]

[ solution 18]

(in the formula, R¹⁰³Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. d¹⁰⁰Represents an integer of 0 to 4. )

As for the compound represented by the above formula (IV) and the compound represented by the above formula (V), the former is a compound having 2 benzene rings, and the latter is a compound having 2 cyclohexane rings, which are different in this point.

As R¹⁰³The alkyl group (b) may be linear or branched. Wherein R is¹⁰³Preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the formula (IV) or the formula (V) include 4, 4 '-diphenylmethane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B1): the following formula (VI) (polyisocyanate compound having norbornane ring))

[ solution 19]

(in the formula, R¹⁰⁴Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. e.g. of the type¹⁰⁰Represents an integer of 0 to 4. )

As R¹⁰⁴The alkyl group (b) may be linear or branched. Wherein R is¹⁰⁴Preferably a hydrogen atom, a methyl group, or an ethyl group.

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

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

((B1) component: polyisothiocyanate compound)

Examples of the polyisothiocyanate compound in the polyiso (thio) cyanate compound include compounds in which an isocyanate group is replaced with an isothiocyanate group in the polyiso-cyanate compounds represented by the above-mentioned formulae (I) to (VI). More specifically, aliphatic isothiocyanate compounds, alicyclic isothiocyanate compounds, aromatic isothiocyanate compounds, heterocyclic isothiocyanate compounds, sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds and the like are exemplified.

Examples of the aliphatic isothiocyanate compound include 1, 2-diisothiocyanate ethane, 1, 3-diisothiocyanate propane, 1, 4-diisothiocyanate butane, 1, 6-diisothiocyanate hexane, p-phenylenediisopropylidene diisothiocyanate and the like.

Examples of the alicyclic isothiocyanate compound include cyclohexyl isothiocyanate, cyclohexane diisothiocyanate, 2, 4-bis (methylthioninocyanate) norbornane, 2, 5-bis (methylthioninocyanate) norbornane, 3, 4-bis (methylthioninocyanate) norbornane, and 3, 5-bis (methylthioninocyanate) norbornane.

As the aromatic isothiocyanate compound, there may be mentioned phenylisothiocyanate, 1, 2-diisothiocyanatobenzene, 1, 3-diisothiocyanatobenzene, 1, 4-diisothiocyanatobenzene, 2, 4-diisothiocyanatotoluene, 2, 5-diisothiocyanatom-xylene, 4 '-diisothiocyanato1, 1' -biphenyl, 1 '-methylenebis (4-isothiocyanatobenzene), 1' -methylenebis (4-isothiocyanato-2-methylbenzene), 1 '-methylenebis (4-isothiocyanato-3-methylbenzene), 1' - (1, 2-ethylene) bis (4-isothiocyanatobenzene), 4 '-diisothiocyanatobenzophenone, 1, 3' -diisothiocyanatobenzene, and the like, 4, 4' -diisothiocyanato-3, 3 ' -dimethylbenzophenone, benzanilide-3, 4' -diisothiocyanate, diphenyl ether-4, 4' -diisothiocyanate, diphenylamine-4, 4' -diisothiocyanate, etc.

Examples of the heterocycle-containing isothiocyanate compound include 2, 4, 6-triisothiocyanato 1, 3, 5-triazine and the like.

Examples of the carbonyl isothiocyanate compound include adipoyl diisothiocyanate, azeloyl diisothiocyanate, carbonyl diisothiocyanate, 1, 3-benzenedicarbonyl diisothiocyanate, 1, 4-benzenedicarbonyl diisothiocyanate, (2, 2 '-bipyridine) -4, 4' -dicarbonyl diisothiocyanate and the like.

Further, a polyfunctional isothiocyanate compound having at least 1 sulfur atom in addition to the sulfur atom of the isothiocyanate group can also be used. Examples of such polyfunctional isothiocyanate compounds include sulfur-containing aliphatic isothiocyanate compounds, sulfur-containing aromatic isothiocyanate compounds, sulfur-containing heterocyclic isothiocyanate compounds, and the like.

Examples of the sulfur-containing aliphatic isothiocyanate compound include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane), and the like.

Examples of the sulfur-containing aromatic isothiocyanate compounds include 1-isothiocyanate 4- { (2-isothiocyanate) sulfonyl } benzene, thiobis (4-isothiocyanate) benzene, sulfonylbis (4-isothiocyanate) benzene, sulfinylbis (4-isothiocyanate) benzene, dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato 1- { (4-isothiocyanatophenyl) sulfonyl } -2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4 ' -isothiocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide-3 ' -methyl-4 ' -isothiocyanate, and the like.

Examples of the sulfur-containing heterocyclic isothiocyanate compounds include thiophene-2, 5-diisothiocyanate, 1, 4-dithiane-2, 5-diisothiocyanate and the like.

(component (B1): Compound having isocyanate group and isothiocyanate group)

Examples of the compound having both an isocyanate group and an isothiocyanate group in the polyisocyanate (thio) cyanate compound include a compound having at least one isocyanate group replaced with an isothiocyanate group in the polyisocyanate compound of the above-mentioned specific example, and a compound having at least one isothiocyanate group replaced with an isocyanate group in the polyisothiocyanate compound of the above-mentioned specific example.

(preferred example of component (B1))

Among the polyisocyanate (B1), in view of uniformity of the adhesive layer containing the polyurethane resin, the polyisocyanate (B1) is preferably a compound having 2 to 6 isocyanate groups in the molecule, more preferably a compound having 2 to 4 isocyanate groups in the molecule, and still more preferably a compound having 2 isocyanate groups in the molecule. Specific examples thereof include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2, 2, 1] -heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2, 2, 1] -heptane, 1, 2-bis (2-isocyanatoethylthio) ethane, xylene diisocyanate (o-, m-, p-), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane (isomer mixture), 4' -diphenylmethane diisocyanate, and the like. Among these, isophorone diisocyanate, norbornane diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane (isomer mixture) are particularly preferable from the viewpoints of durability such as weatherability and photochromic properties of an adhesive layer comprising a polyurethane resin, and workability in forming an adhesive layer comprising a polyurethane resin. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

[ (B2) polyol (thio) compound ]

The photochromic adhesive composition of the present invention contains (B2) a poly (thiol) compound. Examples of the polyol compound in the poly (thio) alcohol compound include aliphatic polyol compounds having 2 to 6 hydroxyl groups, aromatic polyol compounds, and the like. Among the poly (thio) alcohol compounds, compounds represented by the following formulae (VII) to (IX), (XI) to (XIII), and (XV) to (XIX) are listed as compounds suitable for forming photochromic optical articles excellent in transparency and mechanical strength.

(component (B2): the following formula (VII) (a polyhydric (thio) alcohol compound having an alkylene group or the like))

[ solution 20]

R¹⁰⁵-B¹⁰⁰-R¹⁰⁵ (VII)

(in the formula, B¹⁰⁰Represents an alkylene or alkenyl group having 2 to 30 carbon atoms. R¹⁰⁵Each independently represents a hydroxyl group or a thiol group. )

As B¹⁰⁰The alkylene group or alkenyl group of (a) may be linear or branched. Wherein, B¹⁰⁰Preferably a linear alkylene group having 2 to 15 carbon atoms.

Specific examples of the compound represented by the formula (VII) include polyethylene polyol (having 2 to 15 carbon atoms), 1, 10-decanedithiol, 1, 8-octanedithiol and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): component (VIII) (a poly (thiol) compound having 2 or more ether bonds) or component (IX) (a poly (thiol) compound having ester bonds))

[ solution 21]

[ solution 22]

[ in the formula, D¹⁰⁰Represents an alkylene or alkenyl group having 2 to 15 carbon atoms. R¹⁰⁶Each independently represents a hydrogen atom or represented by the following formula (X):

[ solution 23]

(in the formula, R¹⁰⁷Represents an alkylene group having 1 to 6 carbon atoms. )

The group shown. I is¹⁰⁰The average value is a number of 1 to 100.]

As D¹⁰⁰The alkylene group or alkenyl group of (a) may be linear or branched. Wherein D is¹⁰⁰Preferably a linear alkylene group having 2 to 6 carbon atoms.

As R¹⁰⁷The alkylene group(s) may be linear or branched. Wherein R is¹⁰⁷Preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

Specific examples of the compound represented by the above formula (VIII) or the above formula (IX) include polyethylene glycol (I)¹⁰⁰1-100), polycaprolactone polyol (I)¹⁰⁰1 to 100), tetraethylene glycol bis (3-mercaptopropionate), 1, 4-butanediol bis (3-mercaptopropionate), 1, 6-hexanediol bis (3-mercaptopropionate), and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XI) (carbonate polyol Compound))

[ solution 24]

(in the formula, E¹⁰⁰And E^100’Each independently represents an alkylene group having 2 to 15 carbon atoms. g¹⁰⁰The average value represents a number of 1 to 20. )

As E¹⁰⁰And E^100’The alkylene group(s) may be linear or branched. Wherein E is¹⁰⁰And E^100’Preferably trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, nonamethylene, dodecamethylene, pentadecylene, 1-methyltriethylene, 1-ethyltriethylene, or 1-isopropyltriethylene.

Specific examples of the compound represented by the above formula (XI) include polycarbonate polyol (E)¹⁰⁰And E^100’Are, respectively, pentamethylene and hexamethylene, g¹⁰⁰4-10), and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XII) (polyfunctional polyol compound))

[ solution 25]

(in the formula, R¹⁰⁸The alkyl groups having 1 to 6 carbon atoms, and when a plurality of groups are present, they may be the same or different from each other. R¹⁰⁹Each independently represents a hydrogen atom or a group represented by the above formula (X). R¹¹⁰Each independently represents a hydrogen atom, a methyl group, or an ethyl group. o¹⁰⁰Q represents an integer of 0 to 2¹⁰⁰Represents an integer of 2 to 4, o¹⁰⁰+q¹⁰⁰＝4。p¹⁰⁰Represents an integer of 0 to 10, r¹⁰⁰Represents an integer of 1 to 6. )

As R¹⁰⁸The alkyl group (b) may be linear or branched. Wherein R is¹⁰⁸Preferably methyl, ethyl, trimethyl, or propyl.

Specific examples of the compound represented by the formula (XII) include ditrimethylolpropane, trimethylolpropane triethyoxyvinylether (for example, TMP-30 manufactured by Nippon emulsifier Co., Ltd.), trimethylolpropane, pentaerythritol, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XIII) (polyol compound having ether bond))

[ solution 26]

[ in the formula, F¹⁰⁰Each independently represents an alkyl group having 1 to 6 carbon atoms, or represented by the following formula (XIV):

[ solution 27]

(in the formula, R¹¹¹Represents a hydrogen atom or a group represented by the above formula (X). R¹¹²Each independently represents a hydrogen atom, a methyl group, or an ethyl group. s¹⁰⁰Represents an integer of 0 to 10, t¹⁰⁰Represents an integer of 1 to 6. )

The group shown. However, at least 2F¹⁰⁰Is a group represented by the above formula (XIV).]

For F¹⁰⁰At least 2 thereof are groups represented by the above formula (XIV). Examples of the other groups include alkyl groups having 1 to 6 carbon atoms. As F¹⁰⁰The alkyl group (b) may be linear or branched. Wherein, F¹⁰⁰Preferably methyl, ethyl, trimethyl, or propyl.

Specific examples of the compound represented by the formula (XIII) include ditrimethylolpropane, dipentaerythritol hexa (3-mercaptopropionate), and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XV) (polyol compound having 2 hydroxyl groups))

[ solution 28]

(in the formula, R¹¹³Represents an alkyl group or alkenyl group having 1 to 30 carbon atoms. )

As R¹¹³The alkyl group or alkenyl group of (b) may be linear or branched. The compound represented by the formula (XV) can be obtained by a condensation reaction of a fatty acid and glycerin, and is therefore R¹¹³Examples thereof include alkyl moieties and alkenyl moieties of fatty acids. Examples of the fatty acid include capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, and lignoceric acid.

Specific examples of the compound represented by the formula (XV) include glycerol monooleate (for example, モノオレイン manufactured by Tokyo chemical Co., Ltd.), glycerol monooleate, glycerol monolinoleate, and glycerol monobehenate. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XVI) (polyfunctional polythiol compound))

[ solution 29]

(in the formula, R¹¹⁴And a group in which a part of carbon atoms in a chain of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms is a-S-bond, and when a plurality of groups are present, they may be the same or different. R¹¹⁵The alkylene group having 1 to 10 carbon atoms, a group in which a part of carbon atoms in a chain of the alkylene group having 1 to 10 carbon atoms is a-S-bond, or a group in which a part of hydrogen atoms of these groups is substituted with a thiol group, may be the same or different when a plurality of groups are present. u. of¹⁰⁰Represents an integer of 2 to 4, v¹⁰⁰Represents an integer of 0 to 2. )

As R¹¹⁴The alkyl group (b) may be linear or branched. Wherein R is¹¹⁴Preferably a hydrogen atom, a methyl group, or an ethyl group. Examples of the group in which a part of carbon atoms in the chain of the alkyl group having 1 to 6 carbon atoms is a-S-bond include-CH₂SCH₃And the like.

AsR¹¹⁵The alkylene group(s) may be linear or branched. Wherein R is¹¹⁵Preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Examples of the group in which a part of carbon atoms in the chain of the C1-10 alkylene group is an-S-bond include-CH₂S-、-CH₂CH₂S-、-CH₂CH₂CH₂S-, and the like. Further, examples of the group in which a part of hydrogen atoms such as C1-10 alkylene group is substituted with a thiol group include-CH₂SCH(SCH₂SH) -, etc.

Specific examples of the compound represented by the formula (XVI) include 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 2, 2-bis (mercaptomethyl) -1, 4-butanedithiol, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiaoctane, 1, 1-tetrakis (mercaptomethyl) methane, 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane, and 1, 1, 2, 2-tetrakis (mercaptomethylthio) ethane. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XVII) (Cyclic polythiol Compound))

[ solution 30]

(in the formula, R¹¹⁶Represents a methylene group or a sulfur atom. However, at least 2R¹¹⁶Is a sulfur atom. R¹¹⁷A group in which a part of carbon atoms in the chain of an alkylene group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms is a-S-bond. )

As R¹¹⁷The alkylene group(s) may be linear or branched. Wherein R is¹¹⁷Preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Examples of the group in which a part of carbon atoms in the chain of the C1-6 alkylene group is an-S-bond include-CH₂S-、-CH₂CH₂S-, and the like.

Specific examples of the compound represented by the formula (XVI) include 2, 5-bis (mercaptomethyl) -1, 4-dithiane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2): the following formula (XVII I I) (polythiol compound having benzene ring))

[ solution 31]

(in the formula, R¹¹⁸Each independently represents a C1-C6 alkylene group or a group in which a part of carbon atoms in the chain of a C1-C6 alkylene group is an-S-bond. w is a¹⁰⁰Represents 2 or 3. )

As R¹¹⁸The alkylene group(s) may be linear or branched. Wherein R is¹¹⁸Preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Examples of the group in which a part of carbon atoms in the chain of the C1-6 alkylene group is an-S-bond include-CH₂CH₂CH₂SCH₂-、-CH₂CH₂SCH₂-、-CH₂SCH₂-and the like.

Specific examples of the compound represented by the above formula (XVI I I I) include 1, 4-bis (mercaptopropylthiomethyl) benzene and the like. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(component (B2); the following formula (XIX) (triazine ring-containing poly (thiol) compound))

[ solution 32]

[ in the formula, R¹¹⁹Each independently represents an alkyl group having 1 to 6 carbon atoms, or represented by the following formula (XX):

[ solution 33]

(in the formula, R¹²⁰And R¹²¹Each independently represents an alkylene group having 1 to 6 carbon atoms. R¹²²Represents an oxygen atom or a sulfur atom. )

The group shown. However, at least 2R¹¹⁹Is a group represented by the above formula (XX).]

As R¹²⁰And R¹²¹The alkylene group(s) may be linear or branched. Wherein R is¹²⁰And R¹²¹Preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

Specific examples of the compound represented by the formula (XIX) include 2-mercaptomethanol and tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Further, preferable polyhydric alcohol compounds other than the compounds represented by the above formulas (VI I) to (IX), (XI) to (XI I), and (XV) to (XIX) include glycerin, diglycerin, sorbitol, and derivatives thereof obtained by reacting with polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.

(preferred example of component (B2))

Among the (B2) polyhydric (thio) alcohol compounds, compounds having 2 to 6 active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule, and more preferably compounds having 4 to 6 active hydrogen-containing groups, are preferable in view of the photochromic properties of the photochromic optical article to be obtained. Specific examples of the compound having 3 active hydrogen-containing groups include trimethylolpropane, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (mercaptoacetate), 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, and tris- { (3-mercaptopropionyloxy) -ethyl } -isocyanurate. Specific examples of the compound having 4 to 6 active hydrogen-containing groups include pentaerythritol, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), 1, 1-tetrakis (mercaptomethyl) methane, 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane, and 1, 1, 2, 2-tetrakis (mercaptomethylthio) ethane. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

[ (B3) ingredient: monohydric (thiol) compounds

In the present invention, (B3) a monohydric (thio) alcohol compound, preferably a monohydric (thio) alcohol compound having a molecular weight of 200 or more, is preferably used in addition to the component (B1) and the component (B2). By using the component (B3), the adhesion of the adhesive layer containing a urethane resin is improved, and the photochromic properties such as the color development concentration and the fading speed of the photochromic optical article tend to be improved. The reason for the improvement of photochromic properties is not clear, and is presumed as follows. When the component (B1) is reacted with the component (B2), a rigid cured product having a network structure of (thio) urethane bonds is obtained. Further, if the component (B3) is blended, the monohydric (thiol) compound having a structure in which one end is free enters into a network structure, and therefore a flexible space (soft segment) is formed around the monohydric (thiol) compound. As a result, reversible structural changes of the photochromic compound present in the vicinity of the space occur more rapidly, and photochromic properties such as color development density and fading speed are considered to be improved.

Further, since the component (B3) has only 1 hydroxyl group or thiol group, hydrogen bonds are less than in the case of the poly (thiol) compound. As a result, it is considered that the viscosity of the photochromic adhesive composition can be reduced, and the handling property in the production of the photochromic optical article can be improved.

Among the above-mentioned components (B3), compounds represented by the following formula (XXI) are exemplified as compounds suitable for photochromic properties and improvement in handling property in the production of photochromic optical articles.

[ chemical 34]

R²⁰⁰-J-R²⁰¹-K-R²⁰² (XXI)

(in the formula, R²⁰⁰Is an organic radical of valency 1, R²⁰¹Is an organic radical of valency 2, R²⁰²Is an organic group having 1 hydroxyl group or thiol group, and J and K represent polymer chains different from each other. )

As R²⁰⁰As the 1-valent organic group, there may be mentionedAlkyl groups such as methyl, ethyl, 1-propyl and 2-propyl, alkoxy groups such as methoxy, ethoxy, 1-propoxy and 2-propoxy, alkylthio groups such as methylthio and ethylthio, and acetyl groups.

As R²⁰¹The 2-valent organic group in (1) is a 2-valent linking group having 1 to 10 carbon atoms linking J and K in formula (XXI), and examples thereof include ether-type linking groups such as ethylene glycol group and propylene glycol group, dicarboxylic acid ester-type linking groups such as michael adduct of β -mercaptopropionic acid and (meth) acrylic acid group, and ether carboxylic acid ester-type linking groups such as glycolic acid group, and any linking group can be used depending on the type (synthesis method) of J and K in formula (XXI).

As R²⁰²Examples of the organic group having 1 hydroxyl group or thiol group include organic groups having a hydroxyl group such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and a dihydroxypropyl group, and organic groups having a thiol group such as a mercaptomethyl group, a mercaptoethyl group, a mercaptopropionyl group, a mercaptoethylcarbonyl group, a mercaptopropylcarbonyl group and a mercaptoacetate group.

Examples of the polymer chain represented by J and K include a polyalkylene chain, a polyester chain, a polysiloxane chain, a polyethyleneimine chain, and a polyoxyalkylene chain. As the polymer chain, a polyalkylene chain or a polyoxyalkylene chain is preferable. Further, a part of the polymer chain may contain a carbon-carbon double bond.

Examples of the polyalkylene chain that is a polymer chain represented by J and K include a polyethylene chain, a polypropylene chain, a polybutene chain, a polystyrene chain, a poly (meth) acrylate chain, and a polymethyleneindane chain.

Examples of the polyester chain as the polymer chain represented by J and K include a poly α -caprolactone chain, a poly β -propiolactone chain, a poly γ -butyrolactone chain, a poly δ -valerolactone chain, a poly ∈ -caprolactone chain, a polylactic acid chain, a polyglycolic acid chain, a poly (lactic-co-glycolic acid) chain, and a polyethylene terephthalate chain.

Examples of the polysiloxane chain, which is a polymer chain represented by J and K, include a polydimethylsiloxane chain and a polymethylphenylsiloxane chain.

Examples of the polyethyleneimine chain as the polymer chain represented by J and K include a polyethyleneimine chain, a polypropylenylaziridine chain, a polyacetylaziridine chain, and a polymethacrylimine chain.

Examples of the polyoxyalkylene chain as the polymer chain represented by J and K include a polyethylene glycol chain, a polypropylene glycol chain, a polytetramethylene glycol chain, a polypentylene glycol chain, a polyhexamethylene glycol chain, a polyheptamethylene glycol chain, a block copolymer chain of polyethylene glycol and polypropylene glycol, and a random copolymer chain of polyethylene glycol and polypropylene glycol.

Examples of the monohydric alcohol compound among the monohydric (thio) alcohol compounds represented by the formula (XXI) include polyoxyethylene monoalkyl ether, polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, linear polyoxyethylene alkyl ether (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, etc.), linear or branched saturated alkyl alcohols having 5 to 30 carbon atoms, and examples of the monohydric thiol compound include linear or branched saturated or unsaturated alkyl thiols having 5 to 30 carbon atoms.

Examples of the monohydric alcohol compound other than the monohydric (thio) alcohol compound represented by formula (XXI) include polyethylene glycol mono-4-octylphenyl ether, and examples of the monohydric thiol compound include 3-methoxybutyl thioglycolate, 2-ethylhexyl thioglycolate, 2-mercaptoethyl octanoate, 3-methoxybutyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 2-octyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, and octadecyl 3-mercaptopropionate.

Among these mono (thio) alcohol compounds, polyoxyethylene monoalkyl ethers, polyoxypropylene monoalkyl ethers, polyoxyethylene polyoxypropylene monoalkyl ethers, polyethylene glycol monooleyl ethers, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol mono-4-octylphenyl ether, linear polyoxyethylene alkyl ethers (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, etc.), linear or branched saturated alkyl alcohols having 5 to 30 carbon atoms, 2-octyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, photochromic properties, etc., are preferable in that the adhesion and photochromic properties can be improved by adding a small amount of the compound, Methyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, or a linear or branched saturated or unsaturated alkyl mercaptan having 5 to 30 carbon atoms. These compounds may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The component (B3) is preferably a compound having a molecular weight of 100 or more, more preferably a compound having a molecular weight of 150 or more, from the viewpoint of further improving photochromic properties. In order to further improve the handling property of the photochromic adhesive composition, it is also effective to mix the low molecular weight (low viscosity) component (B3) and the high molecular weight (high viscosity) component (B3) for the purpose of reducing the viscosity of the photochromic adhesive composition.

The content ratio of the component (B3) is preferably 2 to 40 parts by mass, more preferably 5 to 15 parts by mass, when the total amount of the component (B1), the component (B2) and the component (B3) is 100 parts by mass. When the content of the component (B3) is 2 parts by mass or more, the adhesion and photochromic properties tend to be further improved. Further, when the content ratio of the component (B3) is 40 parts by mass or less, the decrease in durability such as heat resistance of the adhesive layer containing a polyurethane resin tends to be suppressed.

[ (B1) component, blending ratio of (B2) component to (B3) component ]

From the viewpoint of further improving the adhesion and photochromic properties of the adhesive layer comprising a polyurethane resin, it is preferable that the component (B1), the component (B2), and the component (B3) are cured at the following blending ratio. That is, when the total number of moles of isocyanate groups in the (B1) component is n1, the total number of moles of active hydrogen-containing groups in the (B2) component is n2, and the total number of moles of active hydrogen-containing groups in the (B3) component is n3, n 1: (n2+ n3) 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1. further, n 2: n3 is 1-300: 1, more preferably 3 to 50: 1. in terms of mass, the amount of the component (B1) is preferably 20 to 74 parts by mass, the amount of the component (B2) is 21 to 75 parts by mass, the amount of the component (B3) is 2 to 40 parts by mass, the amount of the component (B1) is more preferably 35 to 64 parts by mass, the amount of the component (B2) is 29 to 59 parts by mass, and the amount of the component (B3) is 5 to 15 parts by mass, based on 100 parts by mass of the total of the component (B1), the component (B2) and the component (B3).

In the present invention, the component (B1) and the component (B2) are essential, and the component (B3) is preferably blended, and other monomer having an isocyanate group or an active hydrogen-containing group may be further blended. Among other monomers having an isocyanate group or an active hydrogen-containing group, (B4) is preferably a polyrotaxane monomer having a complex molecular structure including a shaft molecule and a plurality of cyclic molecules including the shaft molecule, the cyclic molecules having an isocyanate group or an active hydrogen-containing group selected from a hydroxyl group and a thiol group.

By containing the component (B4), the adhesion of the adhesive layer which tends to contain a urethane resin is further improved, and the photochromic properties of the photochromic optical article are further improved. The reason for this is not clear, but is presumed as follows. That is, it is considered that the component (B4) reacts with at least one compound of the components (B1) and (B2) to impart flexibility to the adhesive layer containing the urethane resin, thereby improving adhesion to the optical article plate. Further, it is considered that the presence of the photochromic compound around the component (B4) allows the photochromic compound to be uniformly dispersed and maintained, thereby continuously exhibiting excellent photochromic properties.

Hereinafter, the component (B4) will be described.

[ (B4) ingredient; polyrotaxane monomer

As shown in fig. 2, the polyrotaxane monomer 10 has a composite molecular structure formed of chain-like axial molecules 20 and cyclic molecules 30. More specifically, the structure is such that a plurality of cyclic molecules 30 are wrapped around a chain-like axial molecule 20, and the axial molecule 20 penetrates the inside of a ring included in the cyclic molecule 30. The cyclic molecule 30 can freely slide on the shaft molecule 20, and terminal groups 40 having a large volume are formed at both ends of the shaft molecule 20, thereby preventing the cyclic molecule 30 from falling off from the shaft molecule 20. Therefore, since the cyclic molecules 30 of the polyrotaxane monomer 10 can slide on the axial molecules 20, when the adhesive layer containing the urethane resin is formed, local pressure from the outside can be easily relaxed, and the adhesion between the adhesive layer containing the urethane resin and the plate for optical articles can be improved. In the polyrotaxane monomer 10 shown in FIG. 2, the side chain 50 is introduced into the ring included in the cyclic molecule 30.

The polyrotaxane monomer is a known compound and can be synthesized by the method described in international publication No. 2015/068798, etc.

((B4) component; axial molecule)

The chain portion of the axial molecule is not particularly limited as long as it can pass through the ring of the cyclic molecule, and may be linear or branched. The chain portion is generally formed using a polymer. Examples of polymers suitable for forming the chain portion of the axial molecule include polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether.

The terminal group having a large volume formed at each end of the chain portion is not particularly limited as long as it is a group that prevents the cyclic molecule from being detached from the shaft molecule. Specific examples thereof include adamantyl group, trityl group, fluorescein group, dinitrophenyl group, pyrenyl group, etc., and adamantyl group is preferable from the viewpoint of easy introduction, etc.

The mass average molecular weight (Mw) of the shaft molecule is not particularly limited, but is preferably in the range of 1000 to 100000, more preferably in the range of 5000 to 80000, and still more preferably in the range of 10000 to 50000. When the mass average molecular weight (Mw) of the axial molecule is 1000 or more, the mobility of the cyclic molecule tends to be improved. In addition, when the mass average molecular weight (Mw) of the axial molecule is 100000 or less, the compatibility with other components tends to be improved.

((B4) component: Cyclic molecule)

The cyclic molecule has a ring of a size that can enclose the shaft molecule. Examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ether ring, a dibenzocrown ether ring, and a bicyclohexanocycloether ring, and a cyclodextrin ring is preferable. Alpha-body (ring inner diameter: 0.45-0.6 nm) is arranged in the cyclodextrin ring,

Beta-form (ring inner diameter: 0.6 to 0.8nm) and gamma-form (ring inner diameter: 0.8 to 0.95nm), preferably alpha-cyclodextrin ring.

Multiple cyclic molecules are wrapped around 1 axis molecule. When the maximum number of the cyclic molecules capable of being included per 1 axial molecule is 1.0, the number of the cyclic molecules is generally in the range of 0.001 to 0.6, preferably in the range of 0.002 to 0.5, and more preferably in the range of 0.003 to 0.4.

The maximum number of contacts of the cyclic molecule with respect to 1 axis molecule can be calculated from the length of the axis molecule and the thickness of the ring of the cyclic molecule. For example, the maximum number of inclusion bonds is calculated as follows, taking as an example the case where the chain portion of the axial molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α -cyclodextrin ring. I.e., the repeating unit [ -CH ] of polyethylene glycol₂-CH₂O-]Approximately 1 thickness of the a-cyclodextrin ring. Therefore, the number of repeating units was calculated from the molecular weight of the polyethylene glycol, and 1/2, which is the number of repeating units, was determined as the maximum number of entrapments of the cyclic molecule. The maximum number of inclusion was set to 1.0, and the number of inclusion of the cyclic molecule was adjusted to the above range.

((B4) component: side chain)

A side chain may be introduced into the ring of the cyclic molecule. If such a side chain is introduced, a pseudo-crosslinked structure can be formed in the (B4) polyrotaxane monomer. This can impart flexibility to the adhesive layer containing the urethane resin, and can improve adhesion to the optical article plate.

The side chain is preferably formed by repeating units of an organic group having 3 to 20 carbon atoms. The mass average molecular weight (Mw) of the side chain is not particularly limited, but is preferably in the range of 200 to 10000, more preferably 250 to 8000, still more preferably 300 to 5000, and particularly preferably 300 to 1500. When the mass average molecular weight (Mw) of the side chain is 200 or more, a quasi-crosslinked structure tends to be easily formed. In addition, when the mass average molecular weight (Mw) of the side chain is 10000 or less, the increase in viscosity of the photochromic adhesive composition is suppressed, and handling property in the production of the photochromic optical article tends to be good.

The side chain can be introduced by modifying a functional group (for example, a hydroxyl group) of a ring of the cyclic molecule. For example, α -cyclodextrin rings have 18 hydroxyl groups as functional groups, via which side chains can be introduced. That is, for 1 α -cyclodextrin ring, a maximum of 18 side chains can be introduced. In order to sufficiently exert the functions of the side chains, it is preferable that 6% or more, particularly 30% or more, of the total number of functional groups of the ring be modified with the side chains. When 9 of the 18 hydroxyl groups of the α -cyclodextrin ring were bonded with a side chain, the degree of modification was 50%.

The side chain (organic chain) may be linear or branched. By using ring opening polymerization; free radical polymerization; cationic polymerization; anionic polymerization; living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, and the like, and a suitable compound is reacted with a ring of a cyclic molecule, so that a side chain having an appropriate size can be introduced. For example, a side chain derived from a cyclic compound such as a cyclic lactone, a cyclic ether, a cyclic acetal, a cyclic amine, a cyclic carbonate, a cyclic imino ether, or a cyclic thiocarbonate can be introduced by ring-opening polymerization. Among these, cyclic ethers, cyclic siloxanes, cyclic lactones, and cyclic carbonates are preferably used from the viewpoint of easy availability, high reactivity, and easy adjustment of the size (molecular weight). Specific examples of preferred cyclic compounds are described in international publication No. 2015/068798, etc. Among these, the cyclic compounds are preferably cyclic lactones and cyclic carbonates, more preferably lactones such as e-caprolactone, α -acetyl- γ -butyrolactone, α -methyl- γ -butyrolactone, γ -valerolactone and γ -butyrolactone, and still more preferably e-caprolactone.

Further, when a cyclic compound is reacted by ring-opening polymerization to introduce a side chain, a functional group (for example, a hydroxyl group) bonded to a ring is poor in reactivity, and it is sometimes difficult to directly react a large molecule due to steric hindrance or the like. In such a case, for example, the following means can be adopted: a low-molecular-weight compound such as propylene oxide is reacted with a functional group to hydroxypropylate the functional group, and after introducing a functional group (hydroxyl group) rich in reactivity, a side chain is introduced by ring-opening polymerization using the above cyclic compound. The low molecular weight compound such as propylene oxide can also be regarded as a side chain.

As described above, the side chain can be introduced into the (B4) polyrotaxane monomer by ring-opening polymerization, but it is needless to say that other known methods and compounds can be used for introducing the side chain.

(component (B4): isocyanate (thio) group or active hydrogen-containing group)

In the present invention, the cyclic molecule has an active hydrogen-containing group selected from a hydroxyl group and a thiol group, or an isocyanate group. From the viewpoint of adhesion and photochromic properties, it is preferable to introduce the active hydrogen-containing group or the isocyanate group into the above-mentioned side chain (particularly, the end of the side chain). Among them, when considering the productivity of the (B4) polyrotaxane monomer itself, it is preferable to have a hydroxyl group in the side chain.

(preferred example of component (B4))

Among the polyrotaxane monomers (B4), a polyrotaxane monomer is preferred in which a polyethylene glycol having an adamantyl group bonded to both ends is used as an axial molecule, an α -cyclodextrin ring is used as a cyclic molecule, and a side chain having a hydroxyl group at the end is introduced into the ring by polycaprolactone.

[ (B1) component, (B2) component, (B3) component and (B4) component

When the component (B4) is used, the adhesion and photochromic properties are further improved, and if the component (B4) is too much, there is a possibility that a problem of handling property due to an increase in viscosity may occur. On the other hand, if the amount of the component (B4) is too small, the contribution to the adhesion and photochromic properties is small. The blending ratio of the component (B4) is preferably 20 to 74 parts by mass of the component (B1), 20 to 74 parts by mass of the component (B2), 2 to 40 parts by mass of the component (B3), 1 to 30 parts by mass of the component (B4), more preferably 35 to 64 parts by mass of the component (B1), 26 to 59 parts by mass of the component (B2), 5 to 25 parts by mass of the component (B3), and 2 to 9 parts by mass of the component (B4) with respect to 100 parts by mass of the total of the component (B1), the component (B2), the component (B3) and the component (B4).

In the present invention, the blending ratio of the component (B1), the component (B2), the component (B3) and the component (B4) can be appropriately adjusted in view of the photochromic properties, durability and adhesiveness of the photochromic optical article.

When the component (B4) has an isocyanate group, when the total number of moles of isocyanate groups in the component (B1) is n1, the total number of moles of active hydrogen-containing groups in the component (B2) is n2, the total number of moles of active hydrogen-containing groups in the component (B3) is n3, and the total number of moles of isocyanate groups in the component (B4) is n4, it is preferable that (n1+ n 4): (n2+ n3) 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1.

when the active hydrogen-containing group is contained in the component (B4), when the total number of moles of isocyanate (thio) groups in the component (B1) is n1, the total number of moles of active hydrogen-containing groups in the component (B2) is n2, the total number of moles of active hydrogen-containing groups in the component (B3) is n3, and the total number of moles of active hydrogen-containing groups in the component (B4) is n4, n 1: (n2+ n3+ n4) 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1. in this case, n2 is preferable: n 3: n4 is 1-300: 1: 0.05 to 10, more preferably 3 to 50: 1: 0.10 to 2. N4 represents the number of moles of all active hydrogen-containing groups of component (B4). That is, not only the active hydrogen-containing groups of the side chain of component (B4), but also the total number of moles of active hydrogen-containing groups of cyclic molecules, for example, corresponds to n 4.

[ (C1) liquid organic Compound having a molecular weight of less than 200 ]

In the present invention, the photochromic adhesive composition may further contain a liquid organic compound having a molecular weight of 200 or less "hereinafter also referred to as a (C1) component" in order to improve photochromic properties such as a color development density and a fading speed. As the liquid organic compound having a molecular weight of less than 200, known liquid organic compounds having no active hydrogen-containing group can be used without any limitation, and among them, liquid organic compounds having a molecular weight of 50 or more and less than 200 are preferable. It should be noted that the liquid organic compound having an active hydrogen-containing group is not suitable because it may inhibit the effect of the present invention by reacting with the component (B1).

Specific examples of the component (C1) include hydrocarbon compounds such as hexane, heptane, octane, toluene, and xylene, ketone compounds such as acetone, methyl ethyl ketone, and diethyl ketone, ether compounds such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, and methylene chloride, chloroform, dimethyl sulfoxide, and dimethylformamide.

Among the above, in the present invention, if considering that no appearance defect is caused and adhesion to the optical article plate is not lowered, a compound having a boiling point in the range of 65 to 150 ℃ is preferable, and among them, a hydrocarbon compound such as cyclohexane, heptane, octane, or toluene, and methyl ethyl ketone, diethyl ketone, or diethylene glycol dimethyl ether are particularly preferable.

(C1) The blending ratio of the components is appropriately set within a range that does not impair the appearance of the cured adhesive layer containing a polyurethane resin. Specifically, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, based on 100 parts by mass of the component (B).

[ (C2) curing Accelerator ]

In the present invention, the photochromic adhesive composition may further contain (C2) a curing accelerator (hereinafter, also referred to as a "(C2) component) for accelerating curing.

As the component (C2), in order to rapidly accelerate curing of the photochromic adhesive composition, a reaction catalyst for urethane or urea, a condensing agent, or the like, which is effective for the reaction between the active hydrogen-containing group and the isocyanate group, can be used.

(component (C2); reaction catalyst for urethane or urea)

The reaction catalyst for urethane or urea is used for the formation of a poly (thio) urethane bond by the reaction of polyiso (thio) cyanate with a polyol or polythiol. Examples of the reaction catalyst for urethane or urea include tertiary amines, and inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, lewis acids, and organic sulfonic acids corresponding thereto. These reaction catalysts may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the tertiary amines include triethylamine, tri-N-propylamine, triisopropylamine, tri-N-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, N ', N ' -tetramethyl-1, 6-diaminohexane, 4' -trimethylenebis (1-methylpiperidine), 1, 8-diazabicyclo- (5, 4, 0) -7-undecene, and the like.

The phosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1, 2-bis (diphenylphosphino) ethane, and 1, 2-bis (dimethylphosphino) ethane.

Examples of the quaternary ammonium salts include tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, and the like.

Examples of the quaternary phosphonium salt include tetramethylphosphonium bromide, tetrabutylphosphonium chloride and tetrabutylphosphonium bromide.

As Lewis acids, there may be mentioned triphenylaluminum, dimethyltin dichloride, dimethyltin bis (isooctylmercaptoacetate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate polymer, dibutyltin dinricinoleate, dibutyltin bis (dodecylmercaptide), dibutyltin bis (isooctylmercaptoacetate), dioctyltin dichloride, dioctyltin maleate polymer, dioctyltin bis (butylmaleate), dioctyltin dilaurate, dioctyltin dinricinoleate, dioctyltin dioleate, dioctyltin bis (isooctylmercaptoacetate), dioctyltin di (6-hydroxy) hexanoate, dioctyltin bis (isooctylmercaptoacetate), didodecyltin dinricinoleate, or various metal salts (e.g.copper oleate, copper acetylacetonate, iron acetylacetonate, etc.), Iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanoate, 2-ethylhexyl titanate, and the like).

Examples of the organic sulfonic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like.

When the catalytic activity is too high depending on the type of the selected compound, the catalytic activity can be suppressed by using a mixture of a tertiary amine and a lewis acid, for example.

((C2) ingredient: condensing agent)

Examples of the condensing agent include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid and camphorsulfonic acid; アンバーライト (product name), アンバーリスト (product name), and the like; and carbodiimides such as dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide. These condensing agents may be used alone in 1 kind, or 2 or more kinds may be used in combination.

(C2 ratio of component)

(C2) The compounding ratio of the components may be a so-called catalyst amount. For example, the amount of the component (B) may be about 0.001 to 10 parts by mass, particularly about 0.01 to 5 parts by mass, based on 100 parts by mass of the component (B).

[ other compounding ingredients ]

The photochromic adhesive composition may contain various known additives, for example, an ultraviolet absorber, an antistatic agent, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, a fluorescent dye, a pigment, a perfume, a surfactant, a plasticizer, a solvent, a leveling agent, and a curing regulator (for example, thiols such as t-dodecyl mercaptan) within a range not to impair the effects of the present invention.

The blending ratio of the various additives is appropriately set within a range not to impair the effects of the present invention. Specifically, the total amount of the various additives is preferably in the range of 0.001 to 10 parts by mass per 100 parts by mass of the photochromic adhesive composition.

Among various additives, an ultraviolet stabilizer is preferable because it can improve the durability of the photochromic compound. Examples of such an ultraviolet stabilizer include hindered amine light stabilizers, hindered phenol antioxidants, and sulfur antioxidants. Examples of particularly preferred ultraviolet stabilizers include bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate; ADEKA STAB (アデカスタブ) LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87 (manufactured by ADEKA Co., Ltd.); 2, 6-di-tert-butyl-4-methylphenol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ]; IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565; tinuvin249, 123, 144, 171, 292, 5100, 770D, 765, XT55FB, PA144, 622SF (manufactured by BASF corporation).

The blending ratio of the ultraviolet stabilizer is appropriately set within a range not to impair the effects of the present invention. Specifically, the amount is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the component (B). In particular, when the hindered amine light stabilizer is used, the effect of improving durability varies depending on the type of the photochromic compound, and as a result, the amount is preferably 0.5 to 30 moles, more preferably 1 to 20 moles, and further preferably 2 to 15 moles per 1 mole of the (a) photochromic compound in order to prevent the occurrence of color variation in the adjusted developed color tone.

Examples of the antistatic agent include alkali metal or alkaline earth metal salts, quaternary ammonium salts, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants), ionic liquids (salts which exist as liquids at room temperature and exist as cation and anion pairs), and the like.

Examples of the alkali metal or alkaline earth metal salt include salts of an alkali metal (lithium, sodium, potassium, etc.) or an alkaline earth metal (magnesium, calcium, etc.) with an organic acid [ a mono-or dicarboxylic acid having 1 to 7 carbon atoms (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), a sulfonic acid having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.), thiocyanic acid, etc. ]; and salts of alkali metals or alkaline earth metals with inorganic acids [ hydrogen halide acids (hydrochloric acid, hydrogen bromide acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. ], and the like.

Examples of the quaternary ammonium salt include salts of amidinium (e.g., 1-ethyl-3-methylimidazolium) and guanidinium (グアニジウム) (e.g., 2-dimethylamino-1, 3, 4-trimethylimidazolinium) with the above-mentioned organic acid or inorganic acid.

Examples of the surfactant include sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, fatty acid alkanolamides, polyoxyethylene alkyl ethers, alkyl glycosides, polyoxyethylene alkylphenyl ethers, higher fatty acid salts (soaps), α -sulfo fatty acid methyl ester salts, linear alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ether sulfates, (mono) alkyl phosphate ester salts, α -olefin sulfonates, alkane sulfonates, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, N-methyldihydroxyethylamine esters, fatty acid ester hydrochlorides, alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides.

Examples of the ionic liquid include 1, 3-ethylmethylimidazolium bistrifluoromethylsulfonyl imide salt, 1, 3-ethylmethylimidazolium tetrafluoroborate, 1-ethylpyridinium bistrifluoromethylsulfonyl imide salt, 1-ethylpyridinium tetrafluoroborate, 1-ethylpyridinium hexafluorophosphate, and 1-methylpyrazolium bistrifluoromethylsulfonyl imide salt.

Among the additives, a dye having an absorption peak in a wavelength range of 550 to 600nm is useful from the viewpoint of improving the antiglare property. Examples of the coloring matter include nitro compounds, azo compounds, anthraquinone compounds, threne (スレン) compounds, porphyrin compounds, and rare earth metal compounds. Among them, porphyrin-based compounds and rare earth-based compounds are preferable from the viewpoint of both anti-glare properties and visibility, and porphyrin-based compounds are more preferable from the viewpoint of dispersion stability in the adhesive layer containing a urethane resin.

Examples of the rare earth metal compound include complexes such as tetrahydroxy (1-phenyl-1, 3-butanedione) neodymium, tetrahydroxy (phenacylphenyl-dione) neodymium, tetrahydroxy (1-phenyl-2-methyl-1, 3-butanedione) neodymium, tetrahydroxy (1-phenylthio-1, 3-butanedione) neodymium, tetrahydroxy (1-phenyl-1, 3-butanedione) erbium, and tetrahydroxy (1-phenyl-1, 3-butanedione) thorium (ホロニウム).

The porphyrin-based compound may have various substituents on the porphyrin skeleton, and for example, compounds described in Japanese patent application laid-open Nos. 5-194616, 5-195446, 2003-105218, 2008-134618, 2013-61653, 2015-180942, International publication No. 2012/020570, 5626081, 5619472, 5778109 and the like can be preferably used.

The viscosity of the photochromic adhesive composition of the present invention can be appropriately set according to various conditions such as a production method. For example, when a photochromic adhesive composition is applied to one optical article plate described later, and after another optical article plate is placed thereon, the photochromic adhesive composition is cured to bond the plates with an adhesive layer containing a urethane resin, there is a possibility that the photochromic adhesive composition flows out before curing, and in order to suppress the flow-out, it is preferable that the viscosity of the photochromic adhesive composition at 25 ℃ is 100mPa · s or more.

The photochromic optical article of the present invention may have a separate layer, for example, a polarizing layer, on the outer surface, between the plate for optical article and the adhesive layer, or in the adhesive layer, depending on the purpose.

As the layer having a polarizing property, a known polarizing film can be used without any limitation. The thickness of the polarizing film is preferably 10 to 100 μm. The polarizing film is obtained by stretching polyvinyl alcohol dyed with a dichroic material such as iodine or a dichroic dye, and treating the stretched polyvinyl alcohol with a crosslinking agent such as boric acid. In order to improve the function and adhesiveness of the polarizing film, triacetoxy cellulose sheet films may be laminated on both surfaces. The cellulose triacetate sheet film preferably has a thickness of 20 to 200 μm, more preferably 20 to 100 μm.

In addition, for the polarizing film, a polarizing film subjected to a heat treatment at 40 to 100 ℃ for about 5 seconds to 30 minutes before the production of the laminate of the present invention may be used for the purpose of adjusting the amount of water contained in the polarizing film and the dimensional stability of the polarizing film.

< method for producing photochromic optical article >

When the photochromic adhesive composition is used to produce the photochromic optical article according to the present invention, the following method is employed.

A method of applying a necessary amount of photochromic adhesive composition on one optical article plate provided with a spacer, curing the photochromic adhesive composition after another optical article plate is provided thereon, and joining the pair of optical article plates; alternatively, a photochromic optical article can be produced by a method in which a spacer is used, a gap portion is provided so that a predetermined gap is provided between a pair of optical article plates, the photochromic adhesive composition is injected into the gap portion between the pair of optical article plates, and then the photochromic adhesive composition is cured to join the pair of optical article plates.

That is, the method for manufacturing a photochromic optical article of the present invention includes: a step of applying a photochromic adhesive composition comprising (A) a photochromic compound and (B) at least one curable compound selected from the group consisting of a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound to a plate for an optical article; disposing a spacer on a coated surface of the optical article plate coated with the photochromic adhesive composition, and disposing another optical article plate so as to overlap with a predetermined gap; and a step of curing the photochromic adhesive composition to form an adhesive layer, and bonding the pair of optical articles together by using the plates.

In addition, another method for manufacturing a photochromic optical article of the present invention includes: disposing a spacer between the pair of optical article plates to provide a gap portion having a predetermined interval; injecting and filling a photochromic adhesive composition containing (a) a photochromic compound and (B) at least one curable compound selected from a polyiso (thio) cyanate/poly (thio) alcohol mixture, an epoxy compound and an acrylic compound into the gap portion; and a step of curing the photochromic adhesive composition to form an adhesive layer, and bonding the pair of optical articles together by using the plates.

The method for curing the photochromic adhesive composition is not particularly limited, and a known method can be used. Among them, thermal polymerization is preferably carried out.

In the present invention, in order to suppress the occurrence of appearance defects caused by air taken in from the minute gaps generated by the arrangement of the spacers due to curing shrinkage during curing, it is necessary to control the length of the spacers sandwiched between the pair of optical article plates. The length of the spacer sandwiched between the pair of optical article plates is a length D of the spacer sandwiched between the extended portions P of the pair of optical article plates and the inside (see fig. 1).

In the present invention, the length of the spacer sandwiched between the pair of optical article plates needs to be 0.25mm to 1.2 mm. If the length of the spacer sandwiched between the pair of optical article plates is shorter than 0.25mm, the spacer is likely to fall off in the manufacturing operation. On the other hand, if the length is longer than 1.2mm, bubbles are mixed in during curing as described above, and appearance defects are likely to occur.

Further, in the present invention, it is preferable to control the curing temperature conditions. The curing temperature conditions are not limited in general because they are influenced by the kind and amount of the curing accelerator, and a method of starting curing at a relatively low temperature, raising the temperature slowly and maintaining at a predetermined temperature is preferable.

That is, in the present invention, the step of curing the photochromic adhesive composition to form an adhesive layer and bonding the pair of optical article plates preferably includes at least the following 2 steps:

(i) a temperature raising step of raising the temperature from the curing start temperature to a predetermined curing temperature at 0.1 to 1.6 ℃ per minute, and then

(i i) constant temperature step of maintaining a predetermined curing temperature for a predetermined time

The process (2).

The curing start temperature and the predetermined curing temperature in the present invention may be appropriately set according to the kind and amount of the curing accelerator, and it is preferable to set the curing start temperature to 25 ℃ to 60 ℃ so as not to rapidly gel (cure) the photochromic adhesive composition.

The predetermined curing temperature and the predetermined holding time are preferably set to 65 ℃ to 140 ℃, more preferably 70 ℃ to 130 ℃ so as not to cause curing failure and prevent yellowing of the adhesive layer due to heat. The holding time is preferably 0.25 hours or more and 6 hours or less, and more preferably 0.5 hours or more and 3 hours or less.

In the temperature raising step (i), a plurality of temperature raising rates may be continuously set within a predetermined temperature raising rate range.

< spacer >

The shape of the spacer in the present invention is not particularly limited, and may be a spacer having an intermittent shape or a spacer having a continuous shape. The spacers having the intermittent shape are spacers that are not all in contact with a part of the outer periphery of the optical article plates when the pair of optical article plates are arranged therebetween, and the spacers having the continuous shape are spacers that are in continuous contact with the outer periphery of the optical article plates when the pair of optical article plates are arranged therebetween.

The intermittent spacers may be in the form of an elongated shape, or a spacer in the form of an elongated shape having one end in the form of an arc or a triangle. The elongated spacer is, for example, a spacer having a thin plate shape.

In fig. 4, a view of the spacer as viewed in the thickness direction is shown, where a in fig. 4 is an example of an elongated spacer, b is an example of an elongated spacer having an arc-shaped one end, and c is an example of an elongated spacer having a triangular one end.

Among them, in order to suppress the occurrence of appearance defects described later, it is more preferable that the spacers have an arc shape or a triangular shape at one end of the elongated shape having a smaller area sandwiched between the pair of optical article plates. In this case, the spacers are preferably arranged so that one ends of the circular arc shape or the triangular shape are sandwiched between the optical article plates.

In the case of a spacer having an arc-shaped elongated end and a spacer having a triangular elongated end, the length of the spacer sandwiched between the pair of optical article plates means the maximum value D of the length of the spacer sandwiched from the extended portion P of the optical article plates toward the inside (see fig. 4).

The material used for the intermittent spacers may be a resin sheet, a metal foil, or the like, without limitation, as long as the material is not deformed during curing.

As the continuous spacer, a general-purpose elastomer gasket can be used.

The number of spacers used is not particularly limited, but preferably 4 to 8 spacers are used to fix the gap between the pair of optical article plates. The spacers are preferably arranged so as to be equal, and for example, when 4 spacers are used, the spacers may be arranged at 90 ° intervals.

On the other hand, in the case of using a gasket, if the removal of air mixed in when applying the photochromic adhesive composition or the removal of gas generated when curing is considered, it is preferable to use a gasket having a gap at a constant interval. In this case, the portion where the pair of optical article plates are sandwiched by the gaskets is a plurality of portions. When the clamped portion is 2 to 3 points, it is preferable to clamp 50% or more of the entire circumference. When the number of points is 4 or more, the sandwiched portions are preferably arranged so as to be uniform.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, the above-described components and evaluation methods of photochromic optical articles are as follows.

(Components)

< (A) photochromic Compound

PC 1: a compound represented by the following formula

[ solution 35]

PC 2: a compound represented by the following formula

[ solution 36]

PC 3: a compound represented by the following formula

[ solution 37]

PC 4: a compound represented by the following formula

[ solution 38]

< (B1) polyiso (thio) cyanate compound

H6 XDI: 1, 3-bis (isocyanatomethyl) cyclohexane (isomer mixture)

NBDI: norbornane diisocyanate

< (B2) Poly (thio) alcohol Compound

And (3) PEMP: pentaerythritol tetrakis (3-mercaptopropionate)

DPMP: dipentaerythritol hexa (3-mercaptopropionate)

< (B3) Mono (thio) alcohol Compound

PGME 10: polyethylene glycol monooleyl ether (n ≈ 10)

SMP: 3-mercaptopropionic acid stearyl ester

TDMP: tridecyl 3-mercaptopropionate

MA 1: polyoxyethylene lauryl ether (n ≈ 9)

MA 2: polyoxyethylene cetyl ether (n ≈ 8)

MA 3: polyoxyethylene cetyl ether (n ≈ 10)

MA 4: polyoxyethylene cetyl ether (n ≈ 15)

MA 5: polyoxyethylene octadecyl ether (n ≈ 11)

MA 6: polyoxyethylene polyoxypropylene lauryl ether (polyoxyethylene chain repeating unit n ≈ 7.4, polyoxypropylene chain repeating unit m ≈ 1.8)

MA 7: polyoxyethylene polyoxypropylene lauryl ether (polyoxyethylene chain repeating unit n ≈ 10, polyoxypropylene chain repeating unit m ≈ 2)

MA 8: polyoxyethylene polyoxypropylene lauryl ether (polyoxyethylene chain repeating unit n ≈ 15, polyoxypropylene chain repeating unit m ≈ 2.8)

< (B4) polyrotaxane monomer

RX-1: polyrotaxane monomers synthesized by the method described in International publication No. 2015/068798 and the like.

< (C2) curing accelerator

[ reaction catalyst for Carbamate or for Urea ]

C2: dimethyl tin dichloride

< other compounding ingredients >

[ stabilizer ]

HP: ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ]

(evaluation method)

[ offset ]

In a photochromic optical article formed by bonding a pair of optical article plates with an adhesive layer, the maximum radius at the concentric circle a in FIG. 2 is defined as r_maxIn the case of (2), the radius r was found to be 0.2r_maxRadius r is 0.5r_maxRadius r is 0.8r_maxOf the thickness of the respective concentric circles. In the photochromic optical article obtained in the present example, specifically, 0.2r_maxCorresponding to a radius of 7mm, 0.5r_maxEquivalent to radius17.5mm，0.8r_maxCorresponding to a radius of 28 mm.

As a specific method for calculating the misalignment of the joining layer, first, the thickness of a portion overlapping a measurement portion measured after joining is measured for each of the pair of optical article plates before joining. Next, the thickness of the same portion of the photochromic optical article after bonding as the portion measured before bonding was measured. Then, the total of the thicknesses of the pair of optical article plates measured before the joining was subtracted from the thickness of the photochromic optical article after the joining to obtain the thickness of the adhesive layer.

The average thickness was calculated from the measured thicknesses of the 12-point adhesive layers, and the deviation was calculated from the average thickness and the thickness at each measurement point.

[ appearance evaluation ]

The cured photochromic optical article was visually observed from the front. In particular, the appearance of the adhesive layer containing a urethane resin was evaluated according to the following criteria.

O: the obtained optical article had no bubbles in the vicinity of the outer periphery, no color unevenness in visual evaluation under sunlight, and no yellowing in indoor visual evaluation

And (delta): there is at least one appearance defect of 1-5 bubbles in the vicinity of the outer periphery of the obtained optical article, some color unevenness in the case of visual evaluation under sunlight, or some yellowing in the case of visual evaluation indoors

X: there is a significant appearance defect of at least one of 6 or more bubbles in the vicinity of the outer periphery of the obtained optical article, significant color unevenness in the case of visual evaluation under sunlight, or significant yellowing in the case of visual evaluation indoors

[ Adhesivity ]

The adhesion was evaluated by the presence or absence of peeling at the time of pressing a metal sheet having a width of 5mm with a force of 10kgf to form an adhesive layer portion of the optical article. The evaluation criteria are as follows.

1: the sealing property is very good; even after the obtained optical article was immersed in distilled water at 100 ℃ for 3 hours, no peeling was observed.

2: the sealing property is good; the obtained optical article was immersed in distilled water at 100 ℃ for 1 hour and then peeled off, but peeled off after 2 hours of immersion.

3: poor adhesion; peeling was observed before the obtained optical article was immersed in distilled water at 100 ℃.

[ photochromic Properties ]

The values measured by a spectrophotometer (instant multi-channel photodetector MCPD3000) manufactured by Otsuka electronics Co., Ltd were used.

[1] Maximum absorption wavelength (λ max): the maximum absorption wavelength after color development.

[2] Color development concentration: the difference between the absorbance { ε (300) } at the maximum absorption wavelength after light irradiation at 23 ℃ for 300 seconds and the absorbance ε (0) at the time of no light irradiation.

[3] Fade half-life [ τ 1/2 (sec) ]: the time required for the absorbance at the maximum absorption wavelength of the sample to decrease to 1/2 of { ε (300) - ε (0) } when the irradiation with light was stopped after the irradiation with light for 300 seconds at 23 ℃.

< example 1 >

The respective components were mixed according to the following formulation to prepare a photochromic adhesive composition. Wherein the ratio of the total number of moles of isocyanate groups in the polyisocyanate compound of the component (B1) to the total number of moles of active hydrogen-containing groups of the components (B2 to B4) is n 1: (n2+ n3+ n4) ═ 1.05: 1.

the formula is as follows:

(A) photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 37 parts by mass

(B3) Monohydric (thio) alcohol compounds: 104 parts by mass of PGME

(B3) Monohydric (thio) alcohol compounds: SMP 18 parts by mass

(B4) Polyrotaxane monomer: RX-14 parts by mass

(C2) Curing accelerator: c20.05 parts by mass

A stabilizer: HP 0.3 parts by mass

Using the photochromic adhesive composition, a photochromic optical article was produced by the following method. First, after the photochromic adhesive composition was sufficiently degassed, about 0.5g of the photochromic adhesive composition was applied to a concave surface of a circular glass plate (plate for optical articles) having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 6-curve (カーブ) and a diameter of 70mm, the surface of which was chemically strengthened with potassium nitrate. Next, a spacer made of nylon having a thickness of 0.1mm and an arc shape at one end thereof and having a shape of a long strip was disposed on the outer peripheral portion of the glass plate so as to have a gap of 4 and 90 °, and a circular glass plate (optical article plate) having a refractive index of 1.52, an abbe number of 60, a thickness of 1.0mm, a 6-curve, and a diameter of 70mm, which has a transmittance of 10% at 400nm and a surface chemically strengthened with potassium nitrate and has ultraviolet absorption properties, was provided with center points thereof aligned so that the convex surface was bonded to the photochromic adhesive composition. The length of the spacer sandwiched between the pair of glass plates (optical article plates) was set to 1.0 mm. The spacer is disposed in a direction in which the arc-shaped single end is sandwiched between the pair of glass plates.

Next, the composition was allowed to stand in an air oven heated to 60 ℃ for 15 minutes to start curing, then, the temperature was raised (temperature raising rate: 0.58 ℃/min) to a curing temperature of 130 ℃ over 120 minutes, and then, the temperature was maintained at 130 ℃ for 1 hour to cure the photochromic adhesive composition, and a pair of glass plates (optical article plates) was joined to obtain a photochromic optical article.

The obtained photochromic optical article was evaluated by the above-described method. The evaluation results are shown in table 1.

< examples 2 to 4 >: examples of adhesive compositions having different compositions

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the following composition was used as the photochromic adhesive composition. The evaluation results are shown in table 1.

(example 2)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 63 parts by mass

(C2) Curing accelerator: c20.05 parts by mass

A stabilizer: HP 0.3 parts by mass

(example 3)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: NBDI 39 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 37 parts by mass

(B3) Monohydric (thio) alcohol compounds: 104 parts by mass of PGME

(B3) Monohydric (thio) alcohol compounds: SMP 16 parts by mass

(B4) Rotaxane monomer: RX-14 parts by mass

(C2) Curing accelerator: c20.05 parts by mass

A stabilizer: HP 0.3 parts by mass

(example 4)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: DPMP 39 parts by mass

(B3) Monohydric (thio) alcohol compounds: 104 parts by mass of PGME

(B3) Monohydric (thio) alcohol compounds: SMP 16 parts by mass

(B4) Rotaxane monomer: RX-14 parts by mass

(C2) Curing accelerator: c20.05 parts by mass

A stabilizer: HP 0.3 parts by mass

(example 5)

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the following composition was used as the photochromic adhesive composition. The evaluation results are shown in table 1.

Photochromic compound (b): 11.86 parts by mass of PC

Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain 14, average molecular weight 736): 30 parts by mass

2, 2-bis [4- (methacryloyloxy-polyethoxy) phenyl ] propane (average chain length of ethylene glycol chain 10, average molecular weight 804): 30 parts by mass

Esterified product of polyalkylene carbonate diol containing pentanediol and hexanediol as main components and acrylic acid (average molecular weight 640, (meth) acryloyl equivalent weight 320): 10 parts by mass

Trimethylolpropane trimethacrylate: 29 parts by mass

Glycidyl methacrylate: 1 part by mass

Gamma-methacryloxypropyltrimethoxysilane: 5 parts by mass

Bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) sebacate: 3 parts by mass

Phenyl bis (2, 4, 6-trimethylbenzoyl) -phosphine oxide: 0.3 part by mass

A stabilizer: HP 0.3 parts by mass

(example 6)

A photochromic optical article was produced and evaluated in the same manner as in example 1, except that PC2 was used in place of PC1 in example 1. The evaluation results are shown in table 1.

[ Table 1]

TABLE 1

Examples 7 to 11 and comparative example 1 >: examples of different lengths of sandwiched spacers

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the spacers sandwiched between a pair of glass plates (optical article plates) were made to have lengths of 0.2mm (comparative example 1), 0.25mm (example 7), 0.3mm (example 8), 0.5mm (example 9), 1.2mm (example 10), and 1.5mm (example 11). The evaluation results are shown in table 2.

[ Table 2]

TABLE 2

< examples 12 to 16 >: examples of different rates of temperature rise

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the temperature increase rate was changed to the rate shown in table 3, the curing temperature was changed to 70 ℃ (example 12), 90 ℃ (example 13), 110 ℃ (example 14), 130 ℃ (example 15), and 140 ℃ (example 16), and the holding time was changed to 3 hours in example 12. The evaluation results are shown in table 3.

[ Table 3]

TABLE 3

< examples 17 to 25 >; examples of different rates of temperature rise

Photochromic optical articles were produced and evaluated in the same manner except that the curing start time, curing temperature, temperature rise rate and holding time were as shown in table 4. The evaluation results are shown in table 4.

[ Table 4]

TABLE 4

< examples 26 to 33 >: examples using plates for different optical articles

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the following combinations were used as combinations of a pair of glass plates (plates for optical articles). The evaluation results are shown in table 5.

(example 26)

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 0.5 curve and a diameter of 70mm, the surface of which is chemically strengthened with potassium nitrate

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 0.5 curve and a diameter of 70mm, and having a transmittance of 10% at 400nm, the surface of which is chemically strengthened with potassium nitrate, and having ultraviolet absorption characteristics

(example 27)

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, an 8-curve and a diameter of 70mm, the surface of which is chemically strengthened with potassium nitrate

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, an 8-curve and a diameter of 70mm, which has a transmittance of 10% at 400nm and is obtained by chemically strengthening the surface with potassium nitrate, and has ultraviolet absorption characteristics

(example 28)

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 6-curve diameter of 70mm and having a surface chemically strengthened with potassium nitrate

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 6-curve and a diameter of 70mm and obtained by shielding blue light having a wavelength of 430nm or less

(example 29)

Circular glass plate with refractive index of 1.8, Abbe number of 34, thickness of 1.0mm, 6 curves,. phi.70 mm

Circular glass plate with refractive index of 1.8, Abbe number of 34, thickness of 1.0mm, 6 curves,. phi.70 mm

(example 30)

Circular glass plate with refractive index of 1.9, Abbe number of 30, thickness of 1.0mm, 6 curves,. phi.70 mm

Circular glass plate with refractive index of 1.9, Abbe number of 30, thickness of 1.0mm, 6 curves,. phi.70 mm

(example 31)

Circular glass plate with refractive index of 1.8, Abbe number of 34, thickness of 1.0mm, 6 curves,. phi.70 mm

Circular glass plate with refractive index of 1.8, Abbe number of 34, thickness of 4.0mm, 6 curves,. phi.70 mm

(example 32)

Circular glass plate with refractive index of 1.9, Abbe number of 30, thickness of 1.0mm, 6 curves,. phi.70 mm

Circular glass plate with refractive index of 1.9, Abbe number of 30, thickness of 4.0mm, 6 curves,. phi.70 mm

(example 33)

Photochromic optical articles were produced in the same manner as in example 1 except that the following combinations were used as combinations of a pair of glass plates (plates for optical articles), and the photochromic adhesive composition was cured together with a gray polarizing film dyed with a 2-color dye having a thickness of 27 μm, a visual transmittance of 42.5%, and a degree of polarization of 99.2%, and evaluated. The evaluation results are shown in table 5.

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 6-curve diameter of 70mm and having a surface chemically strengthened with potassium nitrate

A circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a 6-curve and a diameter of 70mm and obtained by shielding blue light having a wavelength of 430nm or less

[ Table 5]

TABLE 5

Examples 34 to 35 and comparative examples 2 to 3 >: examples of different spacer arrangements photochromic optical articles were produced and evaluated in the same manner as in example 1, except that the spacers were not used (comparative example 2), and were arranged at the spacers 2 and at the 180 ° intervals (comparative example 3), at the spacers 3 and at the 120 ° intervals (example 34), and at the spacers 8 and at the 45 ° intervals (example 35). The evaluation results are shown in table 6.

[ Table 6]

TABLE 6

< example 36 to 45 >: examples of combinations of glass with organic materials

Photochromic optical articles were produced and evaluated in the same manner as in example 1, except that as the plate for optical articles, a circular glass plate having a refractive index of 1.52, an Abbe number of 60, a thickness of 1.0mm, a curve of 5,. phi.70 mm and a circular polythiourethane plate having a refractive index of 1.6, a thickness of 2.0mm, a curve of 5,. phi.70 mm were used, and the plates were cured under the conditions shown in Table 7 using the following compositions. The evaluation results are shown in table 7.

(example 36)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 38 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA114 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 37)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 38 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 214 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 38)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 315 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 39)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 36 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 42 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 415 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 40)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 515 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 41)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 38 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 43 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 615 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 42)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 37 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 715 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 43)

(A) Photochromic compound (b): 11.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 36 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 42 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA 815 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 44)

(A) Photochromic compound (b): 31.86 parts by mass of PC

(B1) Polyiso (thio) cyanate compound: h6XDI 38 parts by mass

(B2) Poly (thio) alcohol compounds: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA114 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

(example 45)

(A) Photochromic compound (b): PC 41.86 parts by mass

(B1) Polyiso (thio) cyanate compound: h6XDI 38 parts by mass (B2) of a poly (thio) alcohol compound: PEMP 41 parts by mass

(B3) Monohydric (thio) alcohol compounds: MA114 parts by mass

(B3) Monohydric (thio) alcohol compounds: TDMP 3 part by mass

(C2) Curing accelerator: c20.05 parts by mass

Releasing agent: 0.1 part by mass

A stabilizer: HP 0.3 parts by mass

[ Table 7]

TABLE 7

From the above results, it is understood that the photochromic optical article of the present invention in which the variation in the thickness of the adhesive layer is constant or less reduces the appearance defect.

From the above results, it was found that a photochromic optical article free from appearance defects can be produced by adjusting the length of the spacer sandwiched between the pair of soda glass plates (optical article plates).

Further, by adjusting the temperature increase rate, a photochromic optical article free from appearance defects can be produced. That is, by setting the temperature rise rate to 1.6 ℃ per minute or less, particularly 0.1 to 1.6 ℃ per minute, the appearance defects of the bubbles remaining around the spacers are reduced.

Further, even if the pair of optical article plates are different in type, the same effect can be exhibited.

Description of reference numerals

1: photochromic optical article

2: plate for optical article

3: adhesive layer comprising polyurethane resin

4: plate for optical article

5: spacer

10: polyrotaxane monomer

20: axial molecules

30: cyclic molecules

40: bulky terminal group

50: side chains