JP2020170095A - Photochromic optical article - Google Patents

Abstract

PURPOSE: To provide a photochromic optical article having excellent adhesion and exerting excellent photochromic characteristics.SOLUTION: Provided is a photochromic optical article which is obtained by joining a pair of glass plates for an optical article having different properties with an adhesive layer containing (A) a photochromic compound and (B) a resin component consisting of an urethane resin or a cross-linking (meth) acrylic resin. The pair of glass plates for the optical article having different properties is used, thereby capable of providing the photochromic optical article having excellent impact resistance, ultraviolet absorption performance, and/and thinning.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel photochromic optical article in which a pair of glass plates for an optical article having different properties are bonded via an adhesive layer containing a photochromic compound and a resin component.

In recent years, mainly in the United States, demand for lightweight and transparent plastic base materials for sunglasses having antiglare properties has been rapidly increasing. In such plastic sunglasses, plastic photochromic sunglasses that can adjust the antiglare property by changing the transmittance according to the ambient brightness (ultraviolet ray amount) by combining the photochromic characteristics are rapidly becoming popular. Is getting. Such sunglasses are manufactured by the following methods.

For example, a method of manufacturing the sunglasses by dispersing a photochromic compound in a (meth) acrylic resin or a urethane resin is known (see Patent Documents 1 to 4). These documents include a method of making sunglasses as it is from a composition containing a (meth) acrylic resin or a urethane-urea resin and a photochromic compound (kneading method), or coating the composition on a substrate made of another material. A method of making sunglasses (coating method) and a method of making sunglasses using the composition as an adhesive between two plastic optical sheets (binder method) are described. By using these methods, sunglasses having excellent photochromic properties can be produced depending on the material of the sunglasses.

However, the manufacturing method in which the photochromic polymerizable composition is molded into a lens shape does not have sufficient durability of the obtained photochromic sunglasses, and the photochromic characteristics are likely to deteriorate when used in an environment exposed to sunlight for a long time. It was.

On the other hand, a manufacturing method in which a photochromic polymerizable composition is used as an adhesive and a pair of lenses are bonded can improve the durability of photochromic sunglasses as compared with a manufacturing method in which the photochromic polymerizable composition is molded into a lens shape. .. However, according to the studies by the present inventors, this manufacturing method has room for improvement in terms of high photochromic properties and high adhesion required in recent years.

International Publication No. 2014-136804 JP-A-2007-138186 International Publication No. 2004-050775 Japanese Unexamined Patent Publication No. 2012-052091 Japanese Patent Application Laid-Open No. 01-033154

Instead of the above plastic products, a method of joining a glass product (crow plate), which is an inorganic material, with a urethane resin containing a photochromic compound is also being studied (see Patent Document 5). According to this method, since an inorganic material is used, the durability of the photochromic compound is improved as compared with the above method using an organic material.

However, according to the study by the present inventors, it was found that even the method described in Patent Document 5 has room for improvement in the following points. That is, in the method described in Patent Document 5, there is room for improvement in terms of impact resistance, ultraviolet absorption performance, thinning, and the like.

Therefore, an object of the present invention is to bond a pair of glass plates for optical articles having different properties with an adhesive containing a photochromic compound, which has excellent impact resistance, ultraviolet absorption performance, and / and a thinned photochromic. To provide an optical article.

The present inventors have conducted diligent studies in order to solve the above problems. Then, various combinations of glass plates for optical articles were examined, and the present invention was completed.

That is, the present invention
A photochromic optical article formed by bonding a pair of glass plates for an optical article with an adhesive layer containing (A) a photochromic compound and (B) a resin component.
The pair of glass plates for optical articles is a photochromic optical article composed of glass plates for optical articles having different properties.

According to the present invention, a pair of glass plates for optical articles having different properties are bonded with an adhesive containing a photochromic compound to have excellent impact resistance, ultraviolet absorption performance, and / and a thinned photochromic optical article. Can be provided.

Then, while having the above physical properties, it is possible to exhibit excellent adhesion and excellent photochromic characteristics.

It is sectional drawing which shows the preferable aspect of the photochromic optical article of this invention. It is a schematic diagram which shows the molecular structure of polyrotaxane used in this invention.

The present invention is a photochromic optical article in which a pair of glass plates for an optical article having different properties are bonded with an adhesive containing a photochromic compound. The following will be described step by step. First, a glass plate for an optical article will be described.

<Glass plate for optical articles>
The glass plate for an optical article used in the present invention is not particularly limited as long as it is used for an optical glass lens or the like, and a known glass plate can be used.

Specifically, general-purpose glass materials such as soda glass, flint glass, and crown glass can be used. Among them, SiO ₂ , B ₂ O ₃ , Al ₃ O ₃ , Na ₂ CO ₃ , Na ₂ O, K ₂ O, CaO, Ca (OH) ₂ , CaCO ₃ , Ca, BaO, MgO, PbO, ZnO, MnO ₂ , Al ₂ O ₃ , Al ₂ O ₅ , Li ₂ O, Nb ₂ O ₅ , ZrO ₂ , Fe ₂ O ₃ , CeO ₂ , SrO ₂ , La ₂ O ₃ , SrO, As ₂ O ₃ , Sb ₂ it is preferred to use a glass material having at least one oxide of the O _3.

The present invention is characterized in that a pair of glass plates for optical articles is composed of glass plates for optical articles having different properties.

Among them, at least one glass plate for an optical article may be at least one functional glass selected from chemically strengthened glass, high refractive index glass having a refractive index of 1.6 or more, and ultraviolet absorbing performance glass. preferable.

As the chemically strengthened glass, known chemically strengthened glass can be used without any limitation. For example, chemically strengthened glass by a low temperature ion exchange method is common. The low temperature ion exchange method is a method of treating a glass by contacting it with a molten salt of an alkali having an ionic radius larger than that of the alkali contained in the glass at a temperature not exceeding the transition temperature. That is, in molten salt for a glass containing Li ⁺ containing Na ⁺ from such as sodium nitrate, low temperature by treatment with a molten salt containing K ⁺ from such potassium nitrate for glass containing Na ⁺ Ion exchange can be carried out. Chemically tempered glass produced by the low-temperature ion exchange method is cooled after being treated by the low-temperature ion exchange method, so that the difference in expansion coefficient between the surface layer and the inner layer of the glass causes compression on the surface and residual tensile stress inside. Therefore, the impact resistance is improved.

As the high refractive index glass having a refractive index of 1.6 or more, known glass can be used without any limitation. Among them, it is preferably 1.6 to 2.1, and particularly preferably 1.6 to 1.9.

As a method for increasing the refractive index to 1.6 or more, at least one oxide selected from TiO ₂ , La ₂ O ₃ , Nb ₂ O ₅ , and ZrO ₂ is included in the above-mentioned glass materials. It is preferable to use a glass material.

As the ultraviolet absorbing performance glass, known ones can be used without any limitation. As a method for imparting ultraviolet absorption performance, it is preferable to use a glass material containing at least one oxide selected from Fe ₂ O ₃ , CeO ₂ and TiO ₂ among the above-mentioned glass materials.

As for the ultraviolet absorption performance, the transmittance at 400 nm is preferably 50% or less, more preferably 30% or less, and most preferably 10% or less.

Further, as the weak ultraviolet absorbing performance glass, a glass having a transmittance of 50% to 90% at 360 nm can also be used.

In the present invention, the pair of glass plates for optical articles having different properties may be appropriately set in properties according to the purpose, but when used as a spectacle lens, it is preferably as follows.

That is, a pair of glass plates for optical articles having different properties when used as a spectacle lens are more irradiated with sunlight on the side closer to the eye (hereinafter, also referred to as the inner side) and far from the eye, outdoors. It is preferable that the side (hereinafter, also referred to as the outside) has the following properties.

Specifically, the outer glass plate for optical articles is preferably chemically strengthened glass in consideration of impact resistance. Further, in consideration of fully exerting the photochromic function, a glass having a weak ultraviolet absorbing performance is preferable, and specifically, a glass having a transmittance of 50% to 90% at 360 nm is preferable. From the viewpoint of impact resistance, chemically strengthened glass is preferable.

Further, as the inner glass plate for optical articles, considering that it is used as a spectacle lens for power correction, a high refractive index glass having a refractive index of 1.6 or more is preferable from the viewpoint of thinning and weight reduction. Further, from the viewpoint of protecting the eyes of ultraviolet rays, ultraviolet absorbing performance glass is preferable, and specifically, glass having a transmittance of 50% or less at 400 nm is preferable. By using the ultraviolet absorbing performance glass as the inner glass plate for an optical article, the ultraviolet absorbing performance can be imparted without impairing the photochromic performance.

When used as an spectacle lens, a pair of glass plates for optical articles having different properties is preferably in the following combination.

Specifically, when the outer glass plate for optical articles is ordinary glass, the inner glass plate for optical articles is a high-refractive index glass having a refractive index of 1.6 or more, and ultraviolet rays having a transmittance of 50% or less at 400 nm. It is preferable to combine a glass having at least one property selected from the absorption performance glass or the chemically strengthened glass.

When the outer glass plate for optical articles is chemically strengthened glass, the inner glass plate for optical articles is a glass having a high refractive index of 1.6 or more and a glass having a transmittance of 50% or less at 400 nm. , Or a combination of glasses having at least one property selected from ordinary glasses is preferred.

Among them, the following combinations are more preferable.

That is, the outer glass plate for optical articles is chemically strengthened glass, the inner glass plate for optical articles is high refractive index glass with a refractive index of 1.6 or more, and the ultraviolet absorption performance glass having a transmittance of 50% or less at 400 nm. It is more preferred to use at least one glass of choice. In this case, as the outer glass plate for the optical article, chemically strengthened glass having a weak ultraviolet absorption performance having a transmittance of 50% to 90% at 360 nm may be used.

In the present invention, the thickness of the glass plate for an optical article may be appropriately set according to the purpose, but for example, in the case of eyeglass applications such as sunglasses without prescription, the thickness is about 1.5 mm or less. A glass plate for articles can be used, and from the viewpoint of weight reduction, it is preferable to use a glass plate for optical articles of 1.0 mm or less. When producing a prescription spectacle lens for myopia, for example, the thickness of the center of the glass plate for optical articles used on the outside is 1.0 mm or less, and the glass for optical articles used on the inside. It is preferable that at least a part of the plate is thicker than 1.0 mm, and a glass plate for an optical article having an appropriate thickness of about 10 to 20 mm can also be used. When producing a prescription spectacle lens for hyperopia, for example, the thickness of the center of the glass plate for optical articles used on the outside is 20 mm or less, and at least one of the glass plates for optical articles used on the inside. It is preferable that the portion is thicker than 1.0 mm, and a glass plate for an optical article having an appropriate thickness of about 10 to 20 mm can also be used. Also in the case of a bifocal lens or a progressive lens, the thickness of the glass plate for an optical article to be used can be appropriately selected in the same manner as described above. In the case of a prescription spectacle lens, the dioptric power can be adjusted according to the visual acuity of the user by polishing the concave side of the glass plate for optical articles used inside as necessary.

Above all, in the present invention, an excellent effect is exhibited when a pair of glass plates for optical articles having a thickness of at least one of 1.5 mm or less, particularly 1.0 mm or less is used. The lower limit of the thickness of the glass plate for the optical article is not particularly limited, but 0.1 mm is preferable. Therefore, in the present invention, the thickness of at least one glass plate for an optical article is preferably 0.1 to 1.5 mm, and more preferably 0.5 to 1.0 mm.

When the thickness of one glass plate for optical articles is 0.1 to 1.5 mm, the thickness of the other glass plate for optical articles may be the same or different. When the thicknesses are different, the thickness is not limited and may be 10 to 20 mm.

The shape of the glass plate for an optical article may be a flat surface or a curved surface. A glass plate for an optical article having a form suitable for a desired application may be used.

Further, as the glass plate for an optical article of the present invention, glass having properties other than the above may be used. For example, for the purpose of improving the antiglare property, a neodymium compound or the like may be added.

In the present invention, a pair of glass plates for optical articles having different properties are bonded by an adhesive layer containing (A) a photochromic compound and (B) a resin component. Each component will be described below.

<(A) Photochromic compound>
As the (A) photochromic compound of the present invention (hereinafter, may be simply referred to as “component (A)”), a compound exhibiting a photochromic action can be adopted. For example, photochromic compounds such as flugide compounds, chromene compounds, and spirooxazine compounds are well known, and these photochromic compounds can be used without any limitation in the present invention. These may be used alone or in combination of two or more. Examples of the flugide compound, chromene compound, and spirooxazine compound are described in JP-A-2-28154, JP-A-62-288830, International Publication No. 94-2850, International Publication No. 96-14596, and the like. Examples include the listed compounds.

Further, compounds newly found by the present inventors as compounds having excellent photochromic properties, for example, Japanese Patent Application Laid-Open No. 2001-114775, Japanese Patent Application Laid-Open No. 2001-031670, Japanese Patent Application Laid-Open No. 2001-011067, Japanese Patent Application Laid-Open No. 2001-011066, Japanese Patent Application Laid-Open No. 2000-347346, Japanese Patent Application Laid-Open No. 2000-344762, Japanese Patent Application Laid-Open No. 2000-344761, Japanese Patent Application Laid-Open No. 2000-327676, Japanese Patent Application Laid-Open No. 2000-327675, Japanese Patent Application Laid-Open No. 2000-256347, Japanese Patent Application Laid-Open No. 2000-229996, Kai 2000-229975, Japanese Patent Application Laid-Open No. 2000-229974, Japanese Patent Application Laid-Open No. 2000-229973, Japanese Patent Application Laid-Open No. 2000-229972, Japanese Patent Application Laid-Open No. 2000-296687, Japanese Patent Application Laid-Open No. 2000-296686, Japanese Patent Application Laid-Open No. 2000-219685 11-322739, Japanese Patent Application Laid-Open No. 11-286484, Japanese Patent Application Laid-Open No. 11-279171, Japanese Patent Application Laid-Open No. 10-298176, Japanese Patent Application Laid-Open No. 09-218301, Japanese Patent Application Laid-Open No. 09-124645, Japanese Patent Application Laid-Open No. 08-295690, Japanese Patent Application Laid-Open No. 08 -176139, JP-A-08-157467, US Pat. No. 5,645,767, US Pat. No. 5,658,501, US Pat. No. 5,961,892, US Pat. No. 6,296,785, Japanese Patent No. 4424981, Japanese Patent No. 4424962. , International Publication No. 2009-136668, International Publication No. 2008-023828, Japanese Patent No. 43697554, Japanese Patent No. 4301621, Japanese Patent No. 4256985, International Publication No. 2007-086532, Special Publication No. Kaihei 2009-12536, Japanese Patent Application Laid-Open No. 2009-67754, Japanese Patent Application Laid-Open No. 2009-67680, Japanese Patent Application Laid-Open No. 2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 4158881, Japanese Patent No. 4157245, Japan Japanese Patent No. 4157239, Japanese Patent No. 4157227, Japanese Patent No. 4118458, Japanese Patent Application Laid-Open No. 2008-74832, Japanese Patent No. 3982770, Japanese Patent No. 3801386, International Publication No. 2005-028465, International Publication 2003-042203, Japanese Patent Application Laid-Open No. 2005-289812, Japanese Patent Application Laid-Open No. 2005-289870, Japanese Patent Application Laid-Open No. 2005-112772, Japanese Patent No. 3522189, International Publication No. 2002-090342, Japanese Patent No. 3471073, Japanese Patent Application Laid-Open No. 2003-277381, International Publication No. 2001-060 811, International Publication No. 2000-071544, International Publication No. 2005-028465, International Publication No. 2011-16582, International Publication No. 2011-034202, International Publication No. 2012-12414, International Publication No. 2013-042800 , The compound disclosed in Japanese Patent No. 6031035 can be preferably used.

Among these components (A), a chromene compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton from the viewpoint of photochromic characteristics such as color density, initial coloring, durability, and fading speed. It is more preferable to use one or more kinds of. Further, among these chromium compounds, a compound having a molecular weight of 540 or more is suitable because it is particularly excellent in color development concentration and fading rate.

Further, as the component (A) of the present invention, a compound having a long chain group having a molecular weight of 300 or more as a substituent, among which molecular chains such as a polysiloxane chain, a polyoxyalkylene chain, a polyester chain, and a polyester polyether chain Any compound can be appropriately selected and used from the compounds having the above as a substituent. Since a molecular chain having a molecular weight of 300 or more has a high molecular weight, it may have a plurality of types of molecular chains instead of one type when producing a photochromic compound. In that case, the molecular weight of the molecular chain may be such that the average value of a plurality of types is within the specified range. Moreover, this average value is a number average molecular weight. This molecular weight can be confirmed by the type of raw material at the time of producing the photochromic compound, and when confirmed from the product, it can be confirmed by known means such as NMR, IR, and mass spectrometry.

It is considered that when the component (A) has a molecular chain having a molecular weight of 300 or more, more advanced photochromic properties can be exhibited even in the resin component (B) of the present invention. The molecular weight of the molecular chain is preferably 300 to 25,000, more preferably 400 to 20,000, in consideration of the photochromic characteristics, the blending amount thereof, and the productivity of the component (A) itself, 440. It is more preferably ~ 15,000, and particularly preferably 500 to 10,000.

The number of the molecular chains is preferably at least 0.5 or more per molecule of the photochromic compound. That is, even when the number of the molecular chains is the smallest, it is preferable that the structure is such that the two photochromic compounds are bonded 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 the molecular weight of the molecular chains, photochromic characteristics and the like.

Further, as the component (A), it is preferable that the molecular structure exhibiting photochromic properties is discolored by cleaving a part of the molecule by irradiation with light to develop color and recombining the cleaved portion. Therefore, in order for a photochromic compound to reversibly repeat color development and fading, the existence of a free space (degree of freedom of the molecule) that does not hinder the movement of the molecule when cleavage and recombination occur is very important. In the case of a compound having such a molecular structure, it is considered that the effect of the molecular chain is particularly exhibited.

Examples of such photochromic compounds include 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, and the like. International Publication No. 2009-146509, International Publication No. 2010-20770, International Publication No. 2012-12414, International Publication No. 2012-149599, International Publication No. 2012-162725, International Publication No. 2012-176918, International Publication No. 2012-176918 The photochromic compound having the molecular chain described in Japanese Patent Application No. 2013-0788086, International Publication No. 2019/013249, Japanese Patent Application No. 2018-079303, Japanese Patent Application No. 2018-136374, etc. can be used.

In the present invention, the blending ratio of the (A) photochromic compound contained in the adhesive layer of the photochromic optical article is preferably as follows. That is, the amount of the (A) photochromic compound is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and 0.1 to 100 parts by mass of the (B) resin component. It is more preferable to use ~ 3 parts by mass.

Next, the resin component (B) that forms the adhesive layer of the present invention will be described.
<(B) Resin component>
A known resin can be used as the resin component (B) of the present invention without any limitation, but from the viewpoint of exhibiting excellent photochromic properties and adhesion to a glass plate for an optical article, a urethane resin or It is preferable to use a crosslinkable (meth) acrylic resin. Among them, it is most preferable to use urethane resin from the viewpoint of adhesion to the glass plate for optical articles.
<(B) Urethane resin>
As the urethane resin, a known urethane resin can be used without any limitation. Among them,
(B1) A polyiso (thio) cyanate compound having two or more iso (thio) cyanate groups in the molecule (hereinafter, may be simply referred to as "(B1) component" or "(B1) poly (thio) cyanate compound". .)When,
(B2) A poly (thio) all compound having two or more active hydrogen-containing groups selected from a hydroxyl group and a thiol group in the molecule (hereinafter, simply “(B2) component” or “(B2) poly (thio) all”. In some cases, it is a compound.)
A resin obtained by at least polymerizing the above is preferable.

In the present invention, the iso (thio) cyanate group refers to an isocyanate group or an isothiocyanate group. And, having two or more isothiocyanate groups in the molecule means "having two or more isocyanate groups in the molecule", "having two or more isothiocyanate groups in the molecule", or "having two or more isothiocyanate groups in the molecule". The total number of groups of isocyanate groups and isothiocyanate groups in the molecule is 2 or more. "

In addition, "having two or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule" means "having two or more hydroxyl groups in the molecule" or "having two thiol groups in the molecule". It means "having or more" or "the total number of groups of hydroxyl groups and thiol groups is 2 or more in the molecule".

In addition, "having one active hydrogen-containing group selected from a hydroxyl group and a thiol group in the molecule" means having one hydroxyl group or thiol group in the molecule.

First, the (B1) polyiso (thio) cyanate compound will be described.

<(B1) Polyiso (thio) cyanate compound>
In the present invention, the (B) urethane resin preferably used for the adhesive layer is made from a (B1) polyiso (thio) cyanate compound as a raw material. Among the polyiso (thio) cyanate compounds, the polyisocyanate compound includes an aliphatic isocyanate compound, an alicyclic isocyanate compound, an aromatic isocyanate compound, a sulfur-containing aliphatic isocyanate compound, an aliphatic sulfide-based isocyanate compound, and an aromatic sulfide-based compound. Examples thereof include isocyanate compounds, aliphatic sulfone-based isocyanate compounds, aromatic sulfone-based isocyanate compounds, sulfonic acid ester-based isocyanate compounds, aromatic sulfonic acid amide-based isocyanate compounds, and sulfur-containing heterocyclic isocyanate compounds.

<(B1) component; polyisocyanate compound>
Among the above (B1) polyiso (thio) cyanate compounds, compounds suitable for forming an optical article having excellent adhesion to a glass plate for an optical article and excellent transparency and mechanical strength, particularly photochromic. Examples of compounds suitable for producing an optical article containing a compound include the following compounds. A preferred example of the (B1) polyisocyanate compound is a compound represented by the following formulas (I) to (IV).

<Component (B1); polyisocyanate compound having an alkylene chain>
The following formula (I)

(During the ceremony
R ¹⁰⁰ is an alkylene group having 1 to 10 carbon atoms, and may be a group in which a carbon atom in the chain of the alkylene group is replaced with a sulfur atom. ) Is preferably used.

R ¹⁰⁰ is an alkylene group having 1 to 10 carbon atoms, and may be a linear group or a branched chain group. Among them, some of the hydrogen atoms of the pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, linear group, pentamethylene group, hexamethylene group, heptamethylene group, and octamethylene group are methyl. A branched chain-like group substituted with a group is preferable. The alkylene group in which the carbon atom is replaced with a sulfur atom is preferably a −CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ − group.

Specific examples of the compound represented by the formula (I) include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,4,4-trimethylhexanemethylene diisocyanate, and 1,2-bis. 2-Isocyanatoethylthio) ethane and the like can be mentioned. These compounds may be used alone, or two or more kinds of compounds may be used.

<Component (B1); polyisocyanate compound having a phenyl group or cyclohexane group (ring)>
The following formula (II), the following formula (III)

(During the ceremony
R ¹⁰¹ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups.
R ¹⁰² is an alkyl group having 1 to 4 carbon atoms, and when a plurality of groups are present, it may be the same group or different groups.
a ¹⁰⁰ is an integer of 2 or 3, b ¹⁰⁰ is an integer of 0 to 4, and c ¹⁰⁰ is an integer of 0 to 4. ) Is preferably used. The difference between the compound represented by the formula (II) and the compound represented by the formula (III) is that the compound has a phenyl group (the compound represented by the formula (II)) and the compound has a cyclohexane group (ring) (the above. This is a difference from the compound represented by the formula (III).

In R ¹⁰¹ , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹⁰¹ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

In R ¹⁰² , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹⁰² is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

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

<Component (B1); polyisocyanate compound having two phenyl groups or two cyclohexane groups (rings)>
The following formula (IV), the following formula (V)

(During the ceremony
R ¹⁰³ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups.
d ¹⁰⁰ is an integer and is 0 to 4. ) Is preferably used. The difference between the compound represented by the formula (IV) and the compound represented by the formula (V) is that the compound has two phenyl groups (the compound represented by the formula (IV)) and two cyclohexane groups (rings). This is a difference from the compound having (the compound represented by the above formula (V)).

In R ¹⁰³ , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹⁰³ is particularly preferably 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, or two or more kinds of compounds may be used.

<Component (B1); polyisocyanate compound having a norbornane ring>
The following formula (VI)

(During the ceremony
R ¹⁰⁴ is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, respectively, and may be the same group or different groups, and e ¹⁰⁰ is an integer of 0 to 4. ) Is a compound.

In R ¹⁰⁴ , the alkyl group having 1 to 4 carbon atoms may be a linear group or a branched chain group. Of these, R ¹⁰⁴ is particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

Specific examples of the compound represented by the above formula (VI) are norbornane diisocyanate, 2,5-bis (isocyanate methyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanate methyl). -Bicyclo [2,2,1] -heptane can be mentioned. These compounds may be used alone, or two or more kinds of compounds may be used.

Further, the halogen-substituted product, the alkyl-substituted product, the alkoxy-substituted product, the nitro-substituted product of the polyisocyanate, the prepolymer-type modified product with a polyhydric alcohol, the carbodiimide-modified product, the urea-modified product, the biuret-modified product, the dimerized or trimmer. Chemical reaction products and the like can also be used.

<(B1) component; polyisothiocyanate compound>
Examples of the compound having two or more isothiocyanate groups in the molecule include compounds in which the isocyanate group is replaced with the isothiocyanate group in the polyisocyanate compounds represented by the formulas (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, and sulfur-containing compounds. Examples include heterocyclic isothiocyanate compounds. Specific examples of these polyisothiocyanate compounds include the following compounds.

Aliphatic isothiocyanate compounds include 1,2-diisothiocyanate ethane, 1,3-diisothiocyanate propane, 1,4-diisothiocyanate butane, 1,6-diisothiocyanate hexane, and p-phenylenediisopropyl. Examples include densiisothiocyanate.

As the alicyclic isothiocyanate compound, cyclohexylisothiocyanate, cyclohexanediisothiocyanate, 2,4-bis (isothiocyanatomethyl) norbornane, 2,5-bis (isothiocyanatomethyl) norbornane, 3,4-bis ( Examples thereof include isothiocyanatomethyl) norbornane and 3,5-bis (isothiocyanatomethyl) norbornane.

Examples of the aromatic isothiocyanate compound include phenylisothiocyanate, 1,2-diisothiocyanate benzene, 1,3-diisothiocyanate benzene, 1,4-diisothiocyanate benzene, 2,4-diisothiocyanate toluene, 2, 5-Diisothiocyanate m-xylene diisocyanate, 4,4'-diisothiocyanate 1,1'-biphenyl, 1,1'-methylenebis (4-isothiocyanate benzene), 1,1'-methylenebis (4-isothiocyanate) 2-Methylbenzene), 1,1'-methylenebis (4-isothiocyanate3-methylbenzene), 1,1'-(1,2-ethandyl) bis (4-isothiocyanatebenzene), 4,4'-di Isothiocyanate benzophenone, 4,4'-diisothiocyanate 3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenylether-4,4'-diisothiocyanate, diphenylamine-4,4'-di Examples include isothiocyanate.

Examples of the heterocyclic isothiocyanate compound include 2,4,6-triisothiocyanate 1,3,5-triazine. Examples of the carbonyl isothiocyanate compound include hexanedioil diisothiocyanate, nonanedioil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenedicarbonyldiisothiocyanate, and 1,4-benzenedicarbonyldiisothiocyanate, (2, Examples thereof include 2'-bipyridine) -4,4'-dicarbonyldiisothiocyanate.

Further, in addition to the sulfur atom of the isothiocyanate group, a polyfunctional isothiocyanate compound having at least one sulfur atom can also be used. Examples of such a polyfunctional isothiocyanate compound include the following compounds.

Examples of the sulfur-containing aliphatic isothiocyanate compound include thiobis (3-isothiocyanate propane), thiobis (2-isothiocyanate ethane), and dithiobis (2-isothiocyanate ethane). Examples of the sulfur-containing aromatic isothiocyanate compound include 1-isothiocyanate 4-{(2-isothiocyanate) sulfonyl} benzene, thiobis (4-isothiocyanate benzene), sulfonylbis (4-isothiocyanate benzene), and sulfinylbis (4). -Isothiocyanate benzene), dithiobis (4-isothiocyanate benzene), 4-isothiocyanate 1-{(4-isothiocyanate phenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanate benzenesulfonyl-4 '-Isothiocyanate phenyl ester, 4-methyl-3-isothiocyanate benzenesulfonylanilide-3'-methyl-4'-isothiocyanate and the like can be mentioned.

Examples of the sulfur-containing heterocyclic isothiocyanate compound include thiophene-2,5-diisothiocyanate and 1,4-dithian-2,5-diisothiocyanate.

<Component (B1); compound having isocyanate group and isothiocyanate group>
In the present invention, examples of the compound having both an isocyanate group and an isothiocyanate group as the component (B1) include the following compounds. For example, in the polyisocyanate compound specifically exemplified above, at least one isocyanate group is an isothiocyanate group. Further, in the polyisothiocyanate compound specifically exemplified above, it is a compound in which at least one isothiocyanate group is an isocyanate group.

<Preferable example of component (B1)>
Among the (B1) polyiso (thio) cyanate compounds, a compound having 2 or more and 6 or less iso (thio) cyanate groups in the molecule is preferable in consideration of the uniformity of the urethane resin forming the adhesive layer. Two or more and four or less compounds are more preferable, and two compounds are most preferable. Specific compounds include pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, norbornan diisocyanate, 2,5-bis (isocyanatemethyl) -bicyclo [2,2,1] -heptane, 2,6-bis (isocyanate methyl) -bicyclo [2,2,1] -heptane, 1,2-bis (2-isocyanatoethylthio) ethane, xylene diisocyanate (o-, m-, p-), 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane (isomer mixture), and 4,4'-diphenylmethane diisocyanate can be mentioned and used alone. It can also be used as a mixture thereof. Among them, isophorone diisocyanate, norbornane diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane (isomer mixture) are most preferable from the viewpoint of weather resistance, photochromic properties, and operability.

Next, the component (B2) will be described.

<(B2) component; poly (chi) all compound>
In the present invention, the urethane resin preferably used for the adhesive layer is made from a (B2) poly (thio) all compound as a raw material. Among the poly (thio) all compounds, for example, the polyol compound is a di-, tri-, tetra-, penta-, hexa-hydroxy compound, and examples thereof include an aliphatic polyol compound and an aromatic polyol compound. .. Specifically, the following compounds can be mentioned as an example of poly (thio) all compounds.

<Preferable compound of (B2) poly (chi) all compound>
Among the (B2) poly (thio) all compounds as described above, a compound suitable for forming an optical article having excellent transparency and mechanical strength, particularly suitable for producing an optical article containing a photochromic compound. Examples of the compound are as follows. Specific examples thereof include compounds represented by the following formulas (VII) to (IX), (XI) to (XIII), and (XV) to (XIX).

<(B2) component; poly (ti) all compound having an alkylene chain or the like>
The following formula (VII)

(During the ceremony
B ¹⁰⁰ is an alkylene group or an alkenyl group having 2 to 30 carbon atoms.
R ¹⁰⁵ is a hydroxyl group or an SH group, respectively, and may be the same group or different groups. ) Is preferably used.

B ¹⁰⁰ is an alkylene group or an alkenyl group having 2 to 30 carbon atoms, and may be either linear or branched. It is preferably a linear alkylene group having 2 to 15 carbon atoms.

Specific examples of the compound represented by the following formula (VII) include polyethylene polyol (2 to 15 carbon atoms), 1,10-decandithiol, and 1,8-octanedithiol.

<Component (B2); suitable poly (thio) all compound having two or more ether bonds or ester bonds>
The following formula (VIII) or the following formula (IX)

{In the ceremony,
D ¹⁰⁰ is an alkylene group or an alkenyl group having 2 to 15 carbon atoms.
R ¹⁰⁶ is a hydrogen atom or the following formula (X), respectively.

(During the ceremony
R ¹⁰⁷ is an alkylene group having 1 to 6 carbon atoms. )
It is a group indicated by, and may be the same group or a different group.
l ¹⁰⁰ is an average value of 1 to 100. } Is preferably used.

D ¹⁰⁰ is an alkylene group or an alkenyl group having 2 to 15 carbon atoms, and may be a linear group or a branched chain group. It is preferably a linear alkylene group having 2 to 6 carbon atoms.

R ¹⁰⁷ is an alkylene group having 1 to 6 carbon atoms, and may be a linear group or a branched chain group. Of these, R ¹⁰⁷ is particularly preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group.

Specific examples of the compound represented by the formula (VII) or the compound represented by the formula (IX) include polyethylene glycol (l ¹⁰⁰ = 1 to 100), polycaprolactone polyol (l ¹⁰⁰ = 1 to 100), and the like. Examples thereof include tetraethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptopropionate), and 1,6-hexanediolbis (3-mercaptopropionate).

<Component (B2); suitable carbonate polyol compound>
The following formula (XI)

(During the ceremony
E ^100, and ^{E 100} 'are each an alkylene group having from 2 to 15 carbon atoms, even for the same group may be a different group,
g ¹⁰⁰ is a number of 1 to 20 on average. ) Is preferably used.

E ^100, and ^{E 100} 'is an alkylene group having 2 to 15 carbon atoms and may be linear, or branched chain groups. Among ^{them, E 100,} and ^{E 100} 'is a trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, nonamethylene group, dodecamethylene group, a pentadecamethylene group, 1-methyl triethylene group, 1 -It is particularly preferable that it is an ethyltriethylene group or a 1-isopropyltriethylene group. If Specific examples of the compound represented by the formula (XI), polycarbonate polyol ^{(E 100,} E 100 'pentamethylene group, a hexamethylene ^group, g 100 = 4 to 10), and the like.

<(B2) component; polyfunctional polyol compound>
The following formula (XII)

(During the ceremony
R ¹⁰⁸ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of the alkyl groups are present, they may be the same or different.
R ¹⁰⁹ is a hydrogen atom or the same as the above formula (X) and may be the same or different. R ¹¹⁰ is a hydrogen atom, a methyl group, an ethyl group or a hydrogen atom, respectively, and is the same or different. May be
o ¹⁰⁰ is 0 to 2, q ¹⁰⁰ is 2 to 4, o ¹⁰⁰ + q ¹⁰⁰ is 4, p ¹⁰⁰ is 0 to 10, and r ¹⁰⁰ is 1 to 6. ) Is preferably used.

R ¹⁰⁸ is an alkyl group having 2 to 15 carbon atoms, and may be a linear group or a branched chain group. Of these, R ¹⁰⁸ is particularly preferably a methyl group, an ethyl group, a trimethyl group, or a propyl group.

Specific examples of the compound represented by the above formula (XII) include trimethylolpropane, trimethylolpropane tripolyoxyethylene ether (TMP-30 manufactured by Nippon Emulsifier Co., Ltd.), trimethylolpropane, pentaerythritol, and trimethylolpropane tris. (3-Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane trimercaptoacetate and the like can be mentioned.

<Component (B2); polyol compound having an ether bond>
The following formula (XIII)

{In the ceremony,
F ¹⁰⁰ is an alkyl group of 1 to 6, respectively, or the following formula (XIV).

(During the ceremony
R ¹¹¹ is a hydrogen atom or a group synonymous with the above formula (X), and may be the same group or a different group.
R ¹¹² is a methyl group, an ethyl group, or a hydrogen atom, respectively, and may be the same group or different groups.
s ¹⁰⁰ is 0 to 10, and t ¹⁰⁰ is 1 to 6. )
However, at least two or more of the groups F ¹⁰⁰ are the groups represented by the above formula (XIV). } Is preferably used.

F ¹⁰⁰ is at least two groups represented by the above formula (XIV). Examples of the other group include alkyl groups 1 to 6, which may be chain-like or branched-chain-like groups. Of these, F ¹⁰⁰ is particularly preferably a methyl group, an ethyl group, a trimethyl group, or a propyl group. Further, F may be the same group or different groups as long as two or more are groups represented by the above formula (XIV).

Specific examples of the compound represented by the formula (XIII) include ditrimethylolpropane, dipentaerythritol hexakis (3-mercaptopropionate) and the like.

<Component (B2); polyol compound having two hydroxyl groups>
The following formula (XV)

(During the ceremony
R ¹¹³ is an alkyl group or an alkenyl group having 1 to 30 carbon atoms. ) Is preferably used.

R ¹¹³ is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and may be a linear group or a branched chain group. Since the above formula (XV) can be obtained from the condensation reaction of fatty acid and glycerin, R ¹¹² specifically includes an alkyl of a fatty acid and an alkenyl group moiety. Examples of fatty acids include capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, arachidic acid, bechenic acid, lignoseric acid and the like.

Specific examples of the compound represented by the formula (XV) include glyceryl monooleate (monoolein manufactured by Tokyo Chemical Industry Co., Ltd.), monoellaidine, glyceryl monolinoleate, glyceryl monobehenate and the like.

<(B2) component; polyfunctional polythiol compound>
The following formula (XVI)

(During the ceremony
R ¹¹⁴ has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a part of carbon atoms in the chain of the alkyl group having 1 to 6 carbon atoms forms an —S— bond, and a plurality of R ^114s are present. If so, they may be the same group or different groups.
R ¹¹⁵ is an alkylene group having 1 to 10 carbon atoms, and is a group in which a part of carbon atoms in the chain of the alkylene group having 1 to 10 carbon atoms forms an −S— bond, or the group having 1 to 10 carbon atoms. In the case where a part of the hydrogen atom of the alkylene group is substituted with an SH group and a plurality of R ^115s are present, the group may be the same group or a different group.
u ¹⁰⁰ is an integer of 2 to 4, and v ¹⁰⁰ is an integer of 0 to 2. ) Is preferably used.

In R ¹¹⁴ , the alkyl group having 1 to 6 carbon atoms may be a linear group or a branched chain group, and among them, R ¹¹⁴ is preferably a hydrogen atom, a methyl group or an ethyl group. Further, as a specific group in which a part of carbon atoms in the chain of an alkyl group having 1 to 6 carbon atoms forms an −S— bond, −CH ₂ SCH ^{3 and the} like can be mentioned.

In R ¹¹⁵ , the alkylene group having 1 to 10 carbon atoms may be a linear group or a branched chain group. Of these, R ¹¹⁵ is particularly preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Specific groups in which some of the carbon atoms in the chain of the alkylene group having 1 to 10 carbon atoms form an -S- bond include -CH ₂ S-, -CH ₂ CH ₂ S-, and -CH _2. CH ₂ CH ₂ S- and the like can be mentioned. Further, examples of the group in which a part of the hydrogen atom of the alkyl group having 1 to 6 carbon atoms is substituted with an SH group include a group such as −CH ₂ SCH (SCH ₂ SH) −.

Specific examples of the compound represented by the above formula (XVI) are 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane and 2,2-bis (mercaptomethyl) -1,4. -Butanedithiol, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane , 1,1,2,2-tetrakis (mercaptomethylthio) ethane and the like.

<Component (B2); cyclic polythiol compound>
The following formula (XVII)

(During the ceremony
R- ¹¹⁶ is a methylene group or a sulfur atom, and at least two of the three R- ^116s are sulfur atoms.
R ¹¹⁷ is an alkylene group having 1 to 6 carbon atoms, or a group in which a part of carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms forms an —S— bond. ) Is preferably used.

In R ¹¹⁷ , the alkylene group having 1 to 6 carbon atoms may be a linear group or a branched chain group. Of these, R ¹¹⁷ is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Further, the group in which a part of the carbon atom in the chain of the alkylene group having 1 to 6 carbon atoms has an -S- bond is specifically -CH ₂ S-, -CH ₂ CH ₂ S-, etc. Can be mentioned.

Specific examples of the compound represented by the formula (XVII) include 2,5-bis (mercaptomethyl) -1,4-dithiane and 4,6-bis (mercaptomethylthio) -1,3-dithiane. Can be mentioned.

<Component (B2); Phenyl group-containing polythiol compound>
The following formula (XVIII)

(During the ceremony
R ¹¹⁸ is an alkylene group having 1 to 6 carbon atoms, or a part of carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms forms an −S— bond, and w ¹⁰⁰ is 2 to 2. It is 3. ) Can be used.

In R ¹¹⁸ , the alkylene group having 1 to 6 carbon atoms may be a linear group or a branched chain group. Of these, R ¹¹⁸ is preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group. Further, the groups in which some of the carbon atoms in the chain of the alkylene group having 1 to 6 carbon atoms form an −S− bond are specifically −CH ₂ CH ₂ CH ₂ SCH ₂ −, −CH ₂ CH. ₂ SCH ₂ −, −CH ₂ SCH ₂ − and the like can be mentioned.

Specific examples of the compound represented by the formula (XVIII) include 1,4-bis (mercaptopropylthiomethyl) benzene.

<(B2) component; poly (ti) all compound having a triazine ring>
The following formula (XIX)

{In the ceremony,
Each of R ¹¹⁹ is an alkyl group having 1 to 6 carbon atoms or the following formula (XX).

(During the ceremony
R ¹²⁰ and R ¹²¹ are alkylene groups having 1 to 6 carbon atoms.
R ¹²² is an oxygen atom or a sulfur atom)
However, at least two of the R ^119s are groups represented by the formula (XX), and the R ¹¹⁹ may be the same group or different groups. } Is preferably used.

In R ¹²⁰ and R ¹²¹ , the alkylene group having 1 to 6 carbon atoms may be a linear group or a branched chain group. Of these, R ¹²⁰ and R ¹²¹ are preferably methylene groups, ethylene groups, trimethylene groups, and propylene groups.

Specific examples of the compound represented by the formula (XX) include 2-mercaptomethanol and tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanurate. One of these compounds may be used alone, or two or more of these compounds may be used in combination.

Further, as polyol compounds other than the compounds represented by the above formulas (VII) to (IX), (XI) to (XIII), (XV) to (XIX), glycerin, diglycerin, sorbitol, and polyethylene glycol thereof. , Polypropylene glycol, polybutylene glycol and the like reacted with derivatives can also be preferably used.

<Preferable example of component (B2)>
In the present invention, the above-mentioned component (B2) can be used without particular limitation, can be used alone, or can be used in combination of two or more. Considering the photochromic properties of the obtained photochromic optical article, it is preferable to have 2 or more and 6 or less active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule, and more preferably 3 or more and 6 or less. It is preferable that the number is 4 or more and 6 or less. I. As a preferable example of the poly (thio) all compound of the component (B2), those having three active hydrogen-containing groups are trimethylolpropane, trimethylolpropanetris (3-mercaptopropionate), and trimethylolpropanetris (3-mercaptopropionate). 3-Mercaptobutyrate), Trimethylol Propane Trimercaptoacetate, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, Tris-{(3-mercaptopropionyloxy) -ethyl} -isocyanure -To, those having 4 or more and 6 or less active hydrogen-containing groups are pentaerythritol, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1, It is preferably 1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, and 1,1,2,2-tetrakis (mercaptomethylthio) ethane.

<(B3) component; mono (chi) all compound>
In the present invention, the urethane resin preferably used for the adhesive layer contains the (B1) component and, if the (B2) component is essential, another monomer (isothiocyanate group or active hydrogen-containing group). Other monomers including) can be included. Above all, in order to further enhance the photochromic property and further improve the adhesion, a mono-all compound having one active hydrogen-containing group selected from a hydroxyl group and a thiol group in the following (B3) molecule (hereinafter , It may be simply referred to as "(B3) mono (thio) all compound" or "(B3) component").
Next, a mono-all compound having one active hydrogen-containing group selected from a hydroxyl group and a thiol group in the (B3) molecule will be described.

In the present invention, in addition to the above components (B1) and (B2), a (B3) mono-(chi) all compound can also be used as the urethane resin preferably used for the adhesive layer.

In the present invention, by reacting the (B1) polyiso (thio) cyanate compound with the (B2) poly (thio) all compound, a rigid cured product having a network structure having a (thio) urethane bond can be obtained. By blending the component (B3) there, the mono (chi) all compound having a one-terminal free structure is incorporated into the network structure, so that a flexible space is formed around the mono (chi) all compound. Will be done. Therefore, since the reversible structural change of the photochromic compound existing in the vicinity of this space can be generated more quickly, it is possible to manufacture a photochromic optical article having excellent photochromic characteristics (color development density, fading speed). It can be inferred and the adhesion can be improved.

Furthermore, since the mono (thio) compound has only one hydroxyl group or thiol group, it has fewer hydrogen bonds than the poly (thio) compound, and as a result, the viscosity when each component is mixed is reduced. It is considered that the handling performance at the time of manufacturing a photochromic optical article can be improved, and the moldability of the adhesive layer can be improved. Specific examples of the mono-all compound used in the present invention include the following compounds.

One hydroxyl group compound in one molecule; polyoxyethylene monoalkyl ether, polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene monoalkyl ether, polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaur Lat, Polyethylene Glycol Monosteert, Polyethylene Glycol Mono-4-octylphenyl Ether, Linear Polyoxyethylene Alkyl Ether (Polyethylene Glycol Monomethyl Ether, Polyoxyethylene Lauryl Ether, Polyoxyethylene-2-ethylhexyl Ether, Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), a linear or branched saturated alkyl alcohol having 5 to 30 carbon atoms, one thiol compound in one molecule; 3-methoxybutylthioglycolate, 2-ethylhexylthioglycolate, 2-mercaptoethyl octanoic acid ester, 3-mercaptopropionic acid-3-methoxybutyl, 3-mercaptopropionate ethyl, 3-mercaptopropionic acid -2-octyl, n-octyl-3-mercaptopropionate, methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, direct with 5 to 30 carbon atoms Saturated or unsaturated alkyl thiol having a chain or branched structure In the present invention, if the content of the component (B3) is too small, the contribution of improving the photochromic characteristics is small, and if it is too large, the adhesion containing (B) urethane resin is contained. The heat resistance of the layer is reduced. Therefore, the content of (B3) is preferably 2 to 40 parts by mass, preferably 5 to 25 parts by mass, when the total amount of (B1), (B2), and (B3) is 100 parts by mass. It is more preferable that it is a part. The component (B3) of the present invention has excellent photochromic properties if it is blended in the composition in the above blending ratio, but in order to exhibit more excellent photochromic properties, the compound of the component (B3) The compound has a molecular weight of 100 or more, and more preferably 150 or more.

Further, in order to improve the moldability of the adhesive layer containing the urethane resin (B), the low molecular weight (low viscosity) (B3) and the high molecular weight (B3) are used for the purpose of lowering the viscosity when each component is mixed. It is also effective to mix.

<(B3) component: suitable mono (chi) all compound>
In the present invention, polyoxyethylene monoalkyl ether, polyoxypropylene monoalkyl ether, polyoxyethylene polyoxypropylene, from the viewpoint that adhesion to a glass plate for optical articles and photochromic properties can be improved by adding a small amount. Monoalkyl ether, polyethylene glycol monooleyl ether, polyoxyethylene oleate, polyethylene glycol monolaurate, polyethylene glycol monosteert, polyethylene glycol mono-4-octylphenyl ether, linear polyoxyethylene alkyl ether ( Polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), linear with 5 to 30 carbon atoms, Or branched saturated alkyl alcohol, 3-mercaptopropionic acid-2-octyl, n-octyl-3-mercaptopropionate, methyl-3-mercaptopropionate, tridecyl-3-mercaptopropionate, Stearyl-3-mercaptopropionate, saturated or unsaturated alkylthiol having a linear or branched structure having 5 to 30 carbon atoms is preferable.

In the present invention, the urethane resin preferably used for the adhesive layer is preferably obtained by polymerizing the component (B3) in addition to the components (B1) and (B2) as a monomer. Next, a suitable blending ratio of these components will be described.

<Mixing ratio of (B1) component, (B2) component, and (B3) component>
In the present invention, the urethane resin (B) that mainly forms the adhesive layer is preferably obtained by polymerizing in the following blending ratio in order to exhibit excellent adhesion and photochromic properties.

The total number of moles of the isothiocyanate group in the component (B1) is n1, the total number of moles of active hydrogen (active hydrogen-containing group) in the component (B2) is n2, and the total number of moles of the active hydrogen in the component (B3) is n2. When the total number of moles of (active hydrogen-containing group) is n3,
n1: (n2 + n3) = 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1.

Further, n2: n3 = 1 to 300: 1 is preferable, and 3 to 50: 1 is more preferable.

It is preferable to use the above-mentioned compounding ratio, and further, when converted into mass, (B1) is 20 to 74 parts by mass, (B2) per 100 parts by mass of the total of (B1), (B2), and (B3). ) Is preferably contained in the range of 21 to 75 parts by mass, (B3) is preferably contained in the range of 2 to 40 parts by mass, (B1) is contained in the range of 35 to 64 parts by mass, (B2) is contained in 29 to 59 parts by mass, and (B3) is contained. It is more preferably contained in the range of 5 to 2515 parts by mass.

In the present invention, the (B) urethane resin preferably used for the adhesive layer preferably uses the (B3) component in addition to the (B1) component and the (B2) component, and further, the (B4) shaft. It has a complex molecular structure consisting of a molecule and a plurality of cyclic molecules that encapsulate the axial molecule, and the cyclic molecule contains at least one active hydrogen-containing group selected from an iso (thio) cyanate group or a hydroxyl group and a thiol group. It is preferable to contain one or more polyrotaxane monomers (hereinafter, may be simply referred to as "(B4) polyrotaxane monomer" or "(B4) component").

<(B4) It has a complex molecular structure consisting of an axial molecule and a plurality of cyclic molecules that encapsulate the axial molecule, and the cyclic molecule has an activity selected from an iso (thio) cyanate group, a hydroxyl group, and a thiol group. Polyrotaxane monomer having at least one hydrogen-containing group>
In the present invention, the urethane resin (B) that mainly forms the adhesive layer is more preferably obtained by polymerizing the (B4) polyrotaxane monomer in addition to the above components (B1), (B2), and (B3). .. By using the component (B4), the photochromic characteristics and the adhesion to the glass plate for an optical article can be further improved.

(B4) The polyrotaxane monomer is a known compound, and as shown in FIG. 2, the polyrotaxane molecule represented by “10” as a whole is a chain shaft molecule “20” and a cyclic molecule “30”. It has a complex molecular structure formed from. That is, a plurality of cyclic molecules "30" are included in the chain-shaped shaft molecule "20", and the shaft molecule "20" penetrates the inside of the ring of the cyclic molecule "30". Therefore, the cyclic molecule "30" can freely slide on the axial molecule "20", but bulky terminal groups "40" are formed at both ends of the axial molecule "20", and the cyclic molecule is formed. The "30" shaft molecule "20" is prevented from falling off.

As described above, since the cyclic molecule "30" contained in the (B4) polyrotaxane monomer can slide on the axial molecule "20", it relieves local pressure from the outside when it is formed into an adhesive layer. This facilitates the process and makes it possible to improve the adhesion between the adhesive layer and the glass plate for an optical article. The (B4) polyrotaxane monomer can be synthesized by the method described in International Publication No. 2015-066798 and the like. The composition of the component (B4) will be described.

<(B4) component axis molecule>
In the (B4) polyrotaxane monomer, various shaft molecules are known. For example, the chain portion is a linear or branched chain as long as it can penetrate the ring of the cyclic molecule. Well, it is generally formed of polymers. Specifically, it is described in International Publication No. 2015-066798 and the like.

Suitable polymers for forming the chain portion of such shaft molecules include, for example, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, poly tetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol or polyvinylmethyl. It is ether and includes polyethylene glycol.

Further, the bulky group formed at both ends of the chain portion is not particularly limited as long as it is a group that prevents the elimination of the cyclic molecule from the axial molecule, but from the viewpoint of bulkiness, for example, an adamantyl group or a trityl group. , A fluoresenyl group, a dinitrophenyl group, and a pyrenyl substrate, and an adamantyl group can be mentioned particularly in terms of ease of introduction.

The molecular weight of the shaft molecule is not particularly limited, but if it is too large, the compatibility with other components tends to deteriorate, and if it is too small, the mobility of the cyclic molecule tends to decrease. From this point of view, the weight average molecular weight Mw of the shaft molecule is preferably in the range of 1,000 to 100,000, particularly 5,000 to 80,000, particularly preferably 10,000 to 50,000. is there.

<(B4) component cyclic molecule>
Further, the cyclic molecule has a ring having a size capable of including the axial molecule as described above, and examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ring, a dibenzocrown ring and the like. A dicyclohexanocrown ring can be mentioned, and a cyclodextrin ring is particularly preferable.

Cyclodextrin rings include α-form (ring inner diameter 0.45 to 0.6 nm), β-form (ring inner diameter 0.6 to 0.8 nm), and γ-form (ring inner diameter 0.8 to 0.95 nm). In particular, the α-cyclodextrin ring is most preferable.

A plurality of cyclic molecules having a ring as described above are included in one axial molecule. In general, when the maximum number of cyclic molecules that can be included per shaft molecule is 1, the number of cyclic molecules involved is 0.001 to 0.6, more preferably 0.002 to 0. 5, more preferably in the range of 0.003 to 0.4.

The maximum number of inclusions of a cyclic molecule with respect to one axial molecule can be calculated from the length of the axial molecule and the thickness of the ring of the cyclic molecule.

For example, taking the case where the chain portion of the axis molecule is formed of polyethylene glycol and the ring of the cyclic molecule is an α-cyclodextrin ring, the maximum number of inclusions is calculated as follows. ..

That is, _two repeating units [-CH _2- CH ₂ O-] of polyethylene glycol approximate the thickness of one α-cyclodextrin ring. Therefore, the number of repeating units is calculated from the molecular weight of this polyethylene glycol, and 1/2 of the number of repeating units is obtained as the maximum number of inclusions of the cyclic molecule. The maximum number of inclusions is set to 1.0, and the number of inclusions of the cyclic molecule is adjusted within the above-mentioned range.

<(B4) component side chain>
Further, a side chain may be introduced into the ring of the cyclic molecule described above, and this side chain is indicated by "50" in FIG.

Further, such a side chain "50" forms a pseudo-crosslinked structure in the (B4) polyrotaxane monomer, whereby the flexibility of the adhesive layer formed by using the photochromic adhesive can be imparted. Therefore, the adhesion to the glass plate for an optical article can be improved.

The side chain is preferably formed of repeating units of organic chains having a carbon number in the range of 3 to 20, and the average weight molecular weight of such a side chain is preferably 200 to 10000. It is preferably in the range of 250 to 8000, more preferably 300 to 5,000, and most preferably in the range of 300 to 1500. That is, if the side chain is too small, it becomes difficult to form a crosslinked structure, and if the side chain is too large, the viscosity of the photochromic adhesive increases, making it difficult to handle when manufacturing a photochromic optical article. Tends to be.

Further, the side chain as described above is introduced by modifying the functional group (for example, a hydroxyl group) of the ring of the cyclic molecule. For example, the α-cyclodextrin ring has 18 hydroxyl groups as functional groups, and a side chain is introduced via these hydroxyl groups. That is, a maximum of 18 side chains can be introduced into one α-cyclodextrin ring. In the present invention, in order to fully exert the function of the side chain described above, it is preferable that 6% or more, particularly 30% or more, of the total number of functional groups of such a ring is modified with the side chain. .. Incidentally, when a side chain is bonded to 9 of the 18 hydroxyl groups of the α-cyclodextrin ring, the degree of modification is 50%.

In the present invention, the side chain (organic chain) as described above may be linear or branched as long as its size is within the above-mentioned range, and may be ring-opened polymerization. Radical polymerization; Cationic polymerization; Anionic polymerization; Living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, etc. is used, and an appropriate compound is reacted with the functional group of the ring to obtain an appropriate size. Side chains can be introduced.

For example, by ring-opening polymerization, 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. Cyclic ether, cyclic siloxane, cyclic lactone, and cyclic carbonate are preferably used from the viewpoint of easy availability, high reactivity, and easy adjustment of size (molecular weight). As specific examples of suitable cyclic compounds, those described in International Publication No. 2015-066798 and the like can be used. Among them, cyclic lactones and cyclic carbonates are preferably used, and lactones such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone and γ-butyrolactone are particularly preferable. Suitable and most preferred are ε-caprolactone.

Further, when a cyclic compound is reacted by ring-opening polymerization to introduce a side chain, the functional group (for example, a hydroxyl group) bonded to the ring has poor reactivity, and a large molecule may be directly reacted particularly due to steric hindrance or the like. It can be difficult. In such a case, for example, in order to react caprolactone or the like, a low molecular weight compound such as propylene oxide is reacted with a functional group to carry out hydroxypropylation, and a highly reactive functional group (hydroxyl group) is introduced. After that, a means of introducing a side chain by ring-opening polymerization using the above-mentioned cyclic compound can be adopted. In addition, this 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 of course, the side chain can also be introduced by other known methods and compounds. ..

Since the (B4) polyrotaxane monomer used in the present invention can impart flexibility to the adhesive layer by polymerizing with at least one compound of the component (B1) and the component (B2), it can be applied to a glass plate for an optical article. It is estimated that the adhesion will be improved. Further, it is considered that the presence of the (A) photochromic compound around the (B4) component allows the photochromic compound to be uniformly maintained in a dispersed state, and the excellent photochromic property can be continuously expressed.

As described above, by blending the component (B4), the flexibility of the obtained adhesive layer can be imparted, the adhesion to the glass plate for optical articles can be improved, and the photochromic characteristics can be further improved. it can.

<(B4) component Iso (thio) cyanate group or active hydrogen-containing group>
In the (B4) polyrotaxane monomer, an isothiocyanate group or an active hydrogen-containing group selected from a hydroxyl group and a thiol group is introduced into the side chain in consideration of the photochromic characteristics and adhesion of the obtained photochromic optical article. Is preferable. Among them, the component (B4) having a hydroxyl group in the side chain is preferable in consideration of the productivity of the (B4) polyrotaxane monomer itself.

Further, it is preferable to introduce an iso (thio) cyanate group or an active hydrogen-containing group at the end of the side chain. This side chain is not particularly limited, but preferably has an average molecular weight of 300 to 1500.

<(B4) component suitable polyrotaxane monomer>
In the present invention, the (B4) polyrotaxane monomer most preferably used has polyethylene glycol bonded to both ends with an adamantyl group as a shaft molecule, a cyclic molecule having an α-cyclodextrin ring, and polycaprolactone. A side chain (OH group at the end) is introduced into the ring.

Next, a suitable blending ratio when the components (B1) and (B2) of the present invention, and further the components (B3) and (B4) are used will be described.

<Mixing ratio of (B1), (B2), (B3), and (B4) components>
If the polyrotaxane monomer (B4) described above is used, even better photochromic properties and adhesion can be obtained, but if the amount of the polyrotaxane monomer (B4) is too large, a handling problem due to an increase in viscosity arises. On the other hand, if the amount of polyrotaxane monomer (B4) is too small, the contribution to photochromic properties and adhesion is small. The optimum blending ratio of the photochromic adhesive containing the polyrotaxane monomer (B4) is 20 (B1) with respect to 100 parts by mass in total of (B1), (B2), (B3), and (B4). It is preferable that the content is in the range of ~ 74 parts by mass, (B2) is 20 to 74 parts by mass, (B3) is 2 to 40 parts by mass, (B4) is 1 to 30 parts by mass, and (B1) is 35 to 64 parts by mass. It is more preferable to contain parts by mass, (B2) in the range of 26 to 59 parts by mass, (B3) in the range of 5 to 25 parts by mass, and (B4) in the range of 2 to 9 parts by mass.

Further, in the present invention, the blending amounts of the above (B1), (B2), (B3), and (B4) components may be appropriately adjusted in consideration of the photochromic characteristics, durability, and adhesion of the photochromic optical article. it can.

When the component (B4) has an iso (thio) cyanate group, the total number of moles of the isothiocyanate group in the component (B1) is set to n1, and the total number of moles of active hydrogen in the component (B2) is defined as n1. When n2 is defined, the total number of moles of active hydrogen in the component (B3) is n3, and the total number of moles of isothiocyanate groups in the component (B4) is n4.
(N1 + n4): (n2 + n3) = 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1.

When the component (B4) has an active hydrogen-containing group, the total number of moles of the iso (thio) cyanate group in the component (B1) is set to n1, and the total number of moles of active hydrogen in the component (B2) is set to n1. When n2 is defined, the total number of moles of active hydrogen in the component (B3) is n3, and the total number of moles of active hydrogen in the component (B4) is n4.
n1: (n2 + n3 + n4) = 0.9 to 1.5: 1, more preferably 1.0 to 1.15: 1. In this case, n2: n3: n4 = 1 to 300: 1: 0.05 to 10 is preferable, and 3 to 50: 1: 0.1 to 2 is more preferable. In this case, n4 is the number of moles of the total active hydrogen-containing group contained in the (B4) polyrotaxane monomer. That is, not only the active hydrogen-containing group contained in the side chain of the component (B4), but also, for example, the total number of moles of the active hydrogen-containing group contained in the cyclic molecule corresponds to the above n4.

<(C) Polymerization curing accelerator>
In the present invention, in order to rapidly accelerate the polymerization curing of urethane, a reaction catalyst or condensing agent for urethane, which is effective for the reaction between the active hydrogen-containing group and the iso (thio) cyanate group, is a polymerization curing accelerator (hereinafter referred to as a polymerization curing accelerator). It may be simply referred to as "component (C)").

<Component (C); Reaction catalyst for urethane>
This reaction catalyst is used in the formation of poly (thio) urethane bonds by the reaction of polyiso (thia) cyanate with polyols or polythiols. Examples of these polymerization catalysts include tertiary amines and their corresponding inorganic or organic salts, phosphines, quaternary ammonium salts, quaternary phosphonium salts, Lewis acids, or organic sulfonic acids. The following can be exemplified as a specific example of this. Further, depending on the type of the above-mentioned compound to be selected, if the catalytic activity is too high, the catalytic activity can be suppressed by using a mixture of the tertiary amine and the Lewis acid.

Tertiary amines; triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, triethylamine, hexamethylenetetramine, N, N-dimethyloctylamine, N, N, N', N ′ -Tetramethyl-1,6-diaminohexane, 4,4′-trimethylethylenebis (1-methylpiperidin), 1,8-diazabicyclo- (5,4,0) -7-undecene.

Phosphines; trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphine) ethane, 1, 2-Bis (dimethylphosphine) ethane.

Quaternary ammonium salts; tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.

Tertiary phosphonium salts; tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide.

Luis acid; triphenylaluminum, dimethyltin dichloride, dimethyltinbis (isooctylthioglycolate), dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate, dibutyltinmalate polymer, dibutyltin diricinolate, dibutyltinbis (dodecyl Mercaptide), dibutyltin bis (isooctylthioglycolate), dioctyl tin dichloride, dioctyl tin maleate, dioctyl tin maleate polymer, dioctyl tin bis (butyl maleate), dioctyl tin dilaurate, dioctyl tin dilysinolate, dioctyl tin Dioleate, dioctyl tin di (6-hydroxy) caproate, dioctyl tinbis (isooctyl thioglycolate), didodecyl tin diricinolate, or various metal salts such as copper oleate, copper acetylacetoneate, iron acetylacetoneate. , Iron naphthenate, iron lactate, iron citrate, iron gluconate, potassium octanate, 2-ethylhexyl titanate and the like.

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

<Component (C); Condensing agent>
Specific examples of the condensing agent include the following.

Inorganic acid; hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, etc.
Organic acids; p-toluenesulfonic acid, camphorsulfonic acid, etc.
Acid ion exchange resin; Amberlite (product name), Amberlist (product name), etc.
Carbodiimide; dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide.

<Amount of component (C)>
The above-mentioned (C) polymerization curing accelerator may be used alone or in combination of two or more. The amount used may be a so-called catalyst amount, for example, 0.001 to 10 parts by mass, particularly 0, based on 100 parts by mass of the total of the (B1) component, the (B2) component, and the (B3) component. A small amount in the range of 0.01 to 5 parts by mass may be used. When the component (B4) is contained, 0.001 to 10 parts by mass, particularly 0.01, with respect to a total of 100 parts by mass of the above (B1), (B2), (B3), and (B4) components. It may be in the range of ~ 5 parts by mass.
<(B) Crosslinkable (meth) acrylic resin>
As the crosslinkable (meth) acrylic resin in the present invention, a known crosslinkable (meth) acrylic resin can be used without any limitation. Specifically, the crosslinkable (meth) acrylic is obtained by polymerizing and curing a composition containing a crosslinkable (meth) acrylic monomer containing the following (meth) acrylic group and having two or more polymerizable groups. It can be a resin.

Examples of the crosslinkable (meth) acrylic monomer include trimethylolpropane trimethacrylate, trimethylolpropanetriacrylate, tetramethylolmethanetrimethacrylate, tetramethylolmethanetriacrylate, tetramethylolmethanetetramethacrylate, tetramethylolmethanetetraacrylate, and trimethylolpropane. Triethylene Glycol Trimethacrylate, Trimethylol Propane Triethylene Glycol Triacrylate, Ditrimethylol Propane Tetra Methacrylate, Ditrimethylol Propane Tetraacrylate, Dipentaerythritol Hexaacrylate, Bisphenol A Dimethacrylate, 2,2-Bis (4-methacryloyloxyethoxyphenyl) ) Propane, 2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane with an average molecular weight of 628, 2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane with an average molecular weight of 804, 2,2 with an average molecular weight of 776. -Bis (4-acryloyloxypolyethylene glycol phenyl) propane, methoxypolyethylene glycol methacrylate with an average molecular weight of 468, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate, polyethylene glycol dimethacrylate with an average molecular weight of 330, average Polyethylene glycol dimethacrylate with a molecular weight of 536, polytetramethylene glycol dimethacrylate with an average molecular weight of 736, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate with an average molecular weight of 536, polyethylene glycol diacrylate with an average molecular weight of 258, average. Polyethylene glycol diacrylate with molecular weight 308, polyethylene glycol diacrylate with average molecular weight 508, average molecular weight 7 Polyfunctional urethane such as 08 polyethylene glycol diacrylate, polycarbonate di (meth) acrylate which is a reaction product of polycarbonate diol and (meth) acrylic acid, urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate ( Polyfunctional polyester (meth) acrylates such as meta) acrylates and polyester oligomer hexaacrylates, silsesquioxane monomers having (meth) acrylic groups and various structures such as cage-like, ladder-like, and random, (meth). Examples thereof include polyrotaxane compounds having an acrylic group in the side chain, 2-isocyanatoethyl methacrylate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and glycidyl methacrylate.

Further, in the composition containing the crosslinkable (meth) acrylic monomer containing the (meth) acrylic group and having two or more polymerizable groups, a (meth) acrylic group is added in addition to the crosslinkable (meth) acrylic monomer. Non-crosslinkable (meth) acrylic monomers and monomers having a vinyl group may also be blended.

In the present invention, a polymerization initiator can also be added to the composition containing a crosslinkable (meth) acrylic monomer containing a (meth) acrylic group and having two or more polymerizable groups.

As the polymerization initiator, it is preferable to use a photopolymerization initiator, and known ones can be adopted. Specifically, as the photopolymerization initiator, benzophenone; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-on, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-Morphorinopropane-1-one, 2-benzyl-2dimethylamino-1- (4-morpholinophenyl) -butanone-1,1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- Acetphenone compounds such as 1-one; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; 2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6 Acylphosphine oxide compounds such as -trimethylbenzoyldiphenylphosphinic acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide; 1,2-octanedione-1- [4- (Phenylthio) -2- (O-benzoyloxime)], oxy-phenyl-acetylid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid Examples thereof include 2- [2-hydroxy-ethoxy] -ethyl ester.

The amount of the polymerization initiator used is preferably 0.001 to 100 parts by mass with respect to 100 parts by mass of the composition containing the (meth) acrylic group and the crosslinkable (meth) acrylic monomer having two or more polymerizable groups. It is in the range of 10 parts by mass, more preferably 0.01 to 5 parts by mass.

<Other ingredients>
In the present invention, the adhesive layer is subjected to various compounding agents known per se, for example, ultraviolet absorbers, antistatic agents, infrared absorbers, ultraviolet stabilizers, antioxidants, and colorings, as long as the effects of the present invention are not impaired. Various stabilizers such as inhibitor, fluorescent dye, dye, pigment, fragrance, surfactant, plasticizer, additives, solvent, leveling agent, and thiols such as t-dodecyl mercaptan are required as polymerization modifiers. Can be blended according to the above. The amount of the additive added can be blended within a range that does not impair the effects of the present invention. Specifically, the total amount of the additives is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the adhesive layer.

Above all, it is preferable to use an ultraviolet stabilizer because the durability of the photochromic compound can be improved. As such an ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, a sulfur-based antioxidant and the like are known. Particularly suitable UV stabilizers are as follows.

Bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sevacate, Adecastab LA-52, LA-57, LA-62, LA-63, LA-67, LA-, manufactured by Asahi Denka Kogyo Co., Ltd. 77, LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) ) Propionate], IRGANOX 1010, 1035, 1075, 1098, 1135, 1141, 1222, 1330, 1425, 1520, 259, 3114, 3790, 5057, 565, manufactured by Ciba Specialty Chemicals.

The amount of such an ultraviolet stabilizer to be used is not particularly limited as long as the effect of the present invention is not impaired, but usually, the amount of the component (B1) and the component (B2) to be used is 100 parts by mass in total. It is in the range of 0.001 part by mass to 10 parts by mass, particularly 0.01 part by mass to 1 part by mass. When the component (B3) or / and the component (B4) are contained, the total amount of the component (B1), the component (B2), the component (B3), and the component (B4) is 100 parts by mass. It is in the range of 0.001 part by mass to 10 parts by mass, particularly 0.01 part by mass to 1 part by mass. In particular, when a hindered amine light stabilizer is used, in order to prevent color deviation of the adjusted color tone as a result of differences in the effect of improving durability depending on the type of the photochromic compound, (A) per mole of the photochromic compound, The amount is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol.

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). Agent), an ionic liquid (a salt that exists as a liquid at room temperature and exists as a pair of cations and anions) and the like. Specific examples are as follows.

Alkali metal or alkaline earth metal salt; alkali metal (lithium, sodium and potassium, etc.) or alkaline earth metal (magnesium, calcium, etc.) and organic acid [mono or dicarboxylic acid with 1 to 7 carbon atoms (geic acid, acetic acid, etc.) Propionic acid, oxalic acid, succinic acid, etc.), salts with sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.) and thiocyanic acid], and the organic acid and inorganic. Salts of acids [hydrochloric acid halides (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.)].

Quaternary ammonium salt; salt of amidinium (1-ethyl-3-methylimidazolium, etc.) or guanidium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) and the organic acid or inorganic acid, etc. ..

Surfactants; sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, alkyl glycoside, polyoxyethylene alkyl phenyl ether, higher fatty acid salt (soap) ), α-Sulphonic fatty acid methyl ester salt, linear alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, (mono) alkyl phosphate ester salt, α-olefin sulfonate, alkane sulfonate, alkyl Trimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N-methylbishydrochiethylamine fat, fatty acid ester / hydrochloride, alkylamino fatty acid salt, alkylbetaine, alkylamine oxide, etc.

Ionic liquid; 1,3-ethylmethylimidazolium bistrifluoromethanesulfonimide, 1,3-ethylmethylimidazolium tetrafluoroborate, 1-ethylpyridinium bistrifluoromethanesulfonimide, 1-ethylpyridinium tetrafluoroborate, 1- Ethylpyridinium hexafluorophosphate, 1-methylpyrazolium bistrifluoromethanesulfonimide, etc.

Among the additives, a dye having an absorption peak in the range of 550 to 600 nm is useful from the viewpoint of improving antiglare, and the dye includes a nitro compound, an azo compound, an anthraquinone compound, and a slene compound. , Porphyrin compounds, rare earth metal compounds and the like. Among them, porphyrin compounds and rare earth compounds are preferable from the viewpoint of the balance between antiglare and visibility. Further, a porphyrin-based compound is most preferable from the viewpoint of dispersion stability in a plastic material.

Examples of the rare earth metal compound include aquahydroxy (1-phenyl1,3-butandionato) neodymium, aquahydroxy (phenacylphenylketonato) neodymium, and aquahydroxy (1-phenyl-2-methyl-1,3-butandionato) neodymium. , Aquahydroxy (1-thiophenyl-1,3-butandionato) neodymium, aquahydroxy (1-phenyl1,3-butandionato) erbium, aquahydroxy (1-phenyl1,3-butandionato) holonium and other complexes can be mentioned. ..

The porphyrin-based compound is a compound which may have various substituents on the porphyrin skeleton. For example, JP-A-5-194616, JP-A-5-195446, JP-A-2003-105218. , Japanese Patent Application Laid-Open No. 2008-134618, Japanese Patent Application Laid-Open No. 2013-61653, Japanese Patent Application Laid-Open No. 2015-180942, WO2012 / 02570 Pamphlet, Japanese Patent No. 5626081, Japanese Patent No. 5619472, Japanese Patent No. The compounds described in No. 5778109 and the like can be preferably used.
<(B) Method for manufacturing resin component>
In the present invention, the method for producing the (B) resin component is not particularly limited, and the method for polymerizing and curing the composition of each component (B) for obtaining the resin component is adopted.

Among them, as will be described later, a method of polymerizing and curing a photochromic polymerizable composition of (B) each component for obtaining a resin component and (A) a photochromic compound is preferable.

For example, in order to obtain a urethane resin suitably used for an adhesive layer, the components (B3) and (B4), which are blended in addition to the components (B1) and (B2) and, if necessary, are added. A photochromic compound (A) may be added to a composition containing (C) a polymerization curing accelerator and other components to obtain a photochromic polymerizable composition, which may be polymerized and cured.

Among them, in addition to the components (B1), (B2), and (B3), the (A) photochromic compound is added to the composition containing the (C) polymerization curing accelerator and other components to be blended as necessary. It is preferable to polymerize and cure the photochromic polymerizable composition, and in addition to the components (B1), (B2), (B3), and (B4), the (C) polymerization curing accelerator, which is blended as necessary, It is most preferable to polymerize and cure a photochromic polymerizable composition obtained by adding (A) a photochromic compound to a composition containing other components.

Further, in order to obtain a crosslinkable (meth) acrylic resin preferably used for the adhesive layer, other monomers, a polymerization initiator, and other components to be blended with the crosslinkable (meth) acrylic monomer as necessary. The photochromic compound (A) may be added to the composition containing the above to obtain a photochromic polymerizable composition, which may be polymerized and cured.

Examples of the photochromic polymerizable composition for obtaining a crosslinkable (meth) acrylic resin preferably used for the adhesive layer include International Publication No. 03/011967 Pamphlet, International Publication No. 04/050775 Pamphlet, and International Publication No. 05. / 014717 Pamphlet, International Publication 2011/125596 Pamphlet, Japanese Patent Application No. 5991980, International Publication No. 2013/008825, Japanese Patent Application Laid-Open No. 2013-072000, Japanese Patent Application Laid-Open No. 2015-055063, International Publication No. 2014/136919 Pamphlet, International Publication 2014/136804 Pamphlet, International Publication 2015/068798 Pamphlet, International Publication 2016/013677 Pamphlet, Japanese Patent Application Laid-Open No. 2017-052869, Japanese Patent Application Laid-Open No. 2017-19973, International Publication No. 2017/038957 Pamphlet, etc. Examples of the compositions described in.

<Photochromic optical articles>
<Thickness of adhesive layer>
In the present invention, the thickness of the adhesive layer is not particularly limited, but when the photochromic optical article of the present invention is used as a spectacle lens, the thickness of the glass plate for the optical article is about 0.1 to 1.5 mm from the viewpoint of strength. From the viewpoint of design, the thickness of the adhesive layer is preferably 0.8 mm or less in order to suppress the total thickness of the photochromic optical article.

Among them, in consideration of operability and excellent effect, it is preferably 0.02 mm or more and 0.8 mm or less, more preferably 0.03 mm or more and 0.5 mm or less, and 0.05 mm or more and 0.2 mm. Most preferably: When the film thickness is less than 0.02 mm, the adhesion tends to decrease, the film thickness tends to be non-uniform, and uneven density at the time of color development tends to occur. Further, when the film thickness exceeds 0.8 mm, the film thickness tends to deteriorate from the end portion, and the durability tends to decrease.
<Total thickness of photochromic optical articles>
The photochromic optical article of the present invention is formed by joining a pair of glass plates for optical articles having different properties with an adhesive layer containing (A) a photochromic compound and (B) a resin component. The preferred total thickness of the resulting photochromic optical article varies depending on the intended purpose, for example, for spectacle applications, for non-prescription sunglasses or for prescription lenses.

In the case of non-prescription sunglasses, the thickness of the glass plate for optical articles used on the outside and inside is preferably 1.5 mm or less, more preferably 1.0 mm or less as described above. .. The thickness of the adhesive layer is preferably 0.8 mm or less, most preferably 0.05 mm or more and 0.2 mm or less, as described above. Therefore, the total thickness of the photochromic optical article in the case of non-prescription sunglasses is preferably 3.8 mm or less, and more preferably 2.2 mm or less.

Further, in the case of a prescription lens application, it differs between myopia and hyperopia, and the thickness of one glass plate for optical articles used inside or outside is more preferably 1.0 mm or less, but it is used for the other. The glass plate for an optical article to be used may have an appropriate thickness of about 10 to 20 mm, and may be polished and used according to the eyesight of the user. The thickness of the adhesive layer is preferably 0.8 mm or less, most preferably 0.05 mm or more and 0.2 mm or less, as described above. Therefore, the total thickness of the photochromic optical article in the case of prescription lens applications is preferably 22.3 mm or less, and more preferably 11.2 mm or less. Among them, when used as a prescription lens, the center thickness of the photochromic optical article after polishing according to the visual acuity of the user is preferably 2.5 mm or less.

<Manufacturing method of photochromic optical articles>
In the present invention, the method for producing a photochromic optical article is not particularly limited. For example, each component for obtaining the (B) resin component is polymerized and cured, and the (B) resin component and the (A) photochromic compound are sufficiently mixed to form an adhesive layer component. Then, the obtained adhesive layer component is placed on one glass plate for optical articles, and the glass plate for the other optical article is pressed so as to sandwich the adhesive layer component to form the photochromic optical article of the present invention. be able to.

Further, when joining relatively thin glass plates for optical articles with an adhesive layer, it is preferable to adopt the following method.

As described above, a photochromic polymerizable composition in which (A) a photochromic compound is blended with each component for obtaining (B) a resin component is prepared. Then, a mold having a gap is formed by a pair of glass plates for optical articles. Then, the photochromic optical article of the present invention can be produced by injecting the photochromic polymerizable composition into the gaps between the glass plates for optical articles and then polymerizing and curing the photochromic polymerizable composition. According to this method, an adhesive layer in which the (A) photochromic compound is well dispersed in the (B) resin component can be formed.

In this method, the thickness of the adhesive layer can be adjusted by adjusting the gap between the pair of glass plates for optical articles. It is preferable to adjust the gap between the pair of glass plates for optical articles so that the thickness of the adhesive layer is 0.8 mm or less in consideration of slight polymerization shrinkage and the like.

The method for polymerizing and curing the photochromic polymerizable composition is not particularly limited, and a known method can be adopted. Among them, the urethane resin is preferably polymerized and cured by heat, and the crosslinkable (meth) acrylic resin is preferably polymerized and cured by light.

When the crosslinkable (meth) acrylic resin is polymerized and cured by light, the ultraviolet intensity particularly affects the properties of the obtained photochromic layer among the polymerization conditions. This illuminance condition is affected by the type and amount of the photopolymerization initiator and the type of the crosslinkable (meth) acrylic monomer, and therefore cannot be unconditionally limited, but is generally 50 to 500 mW / cm ² at a wavelength of 365 nm. It is preferable to select the conditions so that the ultraviolet rays of the above are irradiated with light for a time of 0.5 to 5 minutes.

In the present invention, after the adhesive layer is polymerized and cured by ultraviolet rays, it can be heat-treated in a temperature range of 60 to 120 ° C. for about 0.5 to 6 hours in order to further improve the adhesion to the glass plate for optical articles. ..

When the urethane resin is polymerized and cured by heat, it is preferable to control the polymerization temperature in order to form an adhesive layer having high properties (smoothness, etc.). This temperature condition is affected by the type and amount of the polymerization curing accelerator and cannot be unconditionally limited, but in general, a method of starting polymerization at a relatively low temperature and slowly raising the temperature is preferable. However, in the present invention, since it also exerts an excellent effect as an adhesive layer of a thin film, the photochromic polymerizable composition can be polymerized in a relatively short time without strict temperature control. Since the optimum polymerization conditions differ depending on the materials used and the like, it is preferable to carry out preliminary experiments to determine the optimum values for the conditions such as the polymerization time and the polymerization temperature. In the present invention, when a temperature of 90 ° C. or higher is adopted, the polymerization can be completed in a polymerization time of 2 hours or less.

When the photochromic optical article of the present invention is produced using the above-mentioned photochromic polymerizable composition, the following conditions can be adopted. For example, the photochromic polymerizable composition is injected into the gap between the glass plates for optical articles held by an elastomer gasket, adhesive tape, spacer, etc., sufficiently defoamed, and then polymerized by heating in an air furnace. It is preferable to cure.

However, although there is an influence of the viscosity of the photochromic polymerizable composition, when the thickness of the adhesive layer (the gap between the pair of glass plates for optical articles) is relatively narrow, for example, when it is 0.5 mm or less, the above-mentioned case. It can be difficult to inject the photochromic polymerizable composition by the method. In that case, an amount of the photochromic polymerizable composition required to obtain a desired film thickness was applied onto one glass plate for optical articles, and the other glass plate for optical articles was placed on the photochromic polymerizable composition. After that, the adhesive layer can be formed by polymerizing and curing the photochromic polymerizable composition. In this case, since only one pair of glass plates for optical articles are overlapped with each other, the photochromic polymerizable composition may flow out. In this case, in order to suppress the outflow, it is preferable that the viscosity of the photochromic polymerizable composition at 25 ° C. is 100 mPa · s or more. When the initial viscosity of the photochromic polymerizable composition is less than 100 mPa · s, the monomer component can be slightly polymerized and cured by leaving it to stand so that the viscosity becomes 100 mPa · s or more.

As described above, when the photochromic polymerizable composition is applied onto one glass plate for optical articles, and the other glass plate for optical articles is placed on the photochromic polymerizable composition and polymerized and cured, the resulting adhesive layer The film thickness may be non-uniform. Therefore, in this case, the polymerization may be cured at a temperature of less than 90 ° C. with a relaxation time (polymerization time) so that the thickness of the adhesive layer becomes uniform.

<Use of photochromic optical articles>
When the photochromic optical article of the present invention is used for eyeglass applications, it is preferable to use a glass plate for an optical article having a curvature (curved surface). At this time, the photochromic polymerizable composition is applied to the concave side of the glass plate for optical articles arranged on the opposite side of the eye, and the convex side of the glass plate for optical articles arranged on the eye side is brought into contact with the photochromic polymerizable composition. You can do it like this. According to such a method, sunglasses for eyeglasses or the like to which photochromic properties are directly obtained can be obtained.

<Others>
The photochromic optical article of the present invention may be further laminated with a polarizing film for the purpose of imparting polarization characteristics, and is not limited to a glass plate for an optical article on the outside of the photochromic optical article and inside the photochromic optical article. It may be laminated between the and the adhesive layer or in the adhesive layer, but it is preferable to embed it in the adhesive layer from the viewpoint of adhesiveness.

Further, the method of laminating the polarizing film is not limited, and a known method may be used. For example, in the method for producing a photochromic optical article described above, when the photochromic polymerizable composition is injected between the glass plates for the optical article, the composition is between the glass plate for the optical article and the photochromic polymerizable composition or the photochromic polymerizable composition. A method of laminating by arranging a polarizing film inside and then polymerizing the photochromic polymerizable composition can be mentioned.

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

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

When a polarizing film is used in the present invention, it is preferable to use the following polarizing film. Specifically, as the dichroic dye contained in the polarizing film, a commercially available dichroic dye can be used without limitation. For example, azo dyes, anthraquinone dyes and the like can be mentioned. Specifically, chlorantin fast red (CI 28160), congo red (CI 22120), brilliant blue B (CI 24410), benzopurine (CI 23500), chlora. Zol Black BH (CI 22590), Direct Blue 2B (CI 22610), Diamine Green (CI 30295), Chrysophenin (CI 24895), Sirius Yellow (CI 29000) , Direct First Red (CI 23630), Acid Black (CI 20470), Direct Sky Blue (CI 24400), Solophenyl Blue 4GL (CI 34200), Direct Copper Blue 2B (C.I. 34200) CI 24185), Nippon Brilliant Violet BKconc (CI 27885) and the like. It is also possible to select and use two or more dyes from these dichroic dyes according to the purpose. In parentheses, Color Index No. described in "New Edition Dye Handbook" edited by the Organic Synthesis Association (Maruzen Co., Ltd., 1970). showed that.

The polarizing film containing the dichroic dye is not particularly limited, but if the photochromic polymerizable composition of the present invention is used, the visual transmittance is 10 to 60% and the degree of polarization is 70. Even the polarizing film having a thickness of 0 to 99.9 can be firmly bonded.

The polarizing film may be one in which a cellulose triacetate film is laminated on both sides in order to enhance its function and adhesiveness. The thickness of the cellulose triacetate film is preferably 20 to 200 μm, more preferably 20 to 100 μm.

Further, in order to adjust the amount of water contained in the polarizing film and to stabilize the size of the polarizing film, the polarizing film is used in a range of 40 to 100 ° C. for 5 seconds before producing the photochromic optical article of the present invention. It is also possible to use a product that has been heat-treated for about 30 minutes.

The photochromic optical article of the present invention can be post-processed by a known method such as hard coating treatment, water repellent treatment, anti-fog treatment, anti-reflection film, etc. on one side or both sides thereof, depending on the intended use.

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the present Examples. In the following Examples and Comparative Examples, the methods for evaluating each of the above components and photochromic characteristics are as follows.
<Glass plate>: Glass plates with the same curved surface <Glass plates that are not functional glass>
G1: A glass plate with a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm <Glass plate that is functional glass>
G2: A glass plate in which the surface of G1 is chemically strengthened with potassium nitrate G3: A glass plate having a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm having an ultraviolet absorption characteristic with a transmittance of 360 nm of 70% G4: Glass plate with the surface of G3 chemically strengthened with potassium nitrate G5: Glass plate with a refractive index of 1.52, Abbe number 60, and center thickness of 1.0 mm, which has an ultraviolet absorption characteristic with a transmittance of 10% at 400 nm G6: G5 Glass plate whose surface is chemically strengthened with potassium nitrate G7: High refractive index glass plate with a refractive index of 1.7, Abbe number of 34, and a center thickness of 4.0 mm G8: Refractive coefficient of 1.8, Abbe number of 25, center thickness of 4.0 mm High refractive index glass plate <(A) photochromic compound>
PC1: Compound represented by the following formula

PC2: Compound represented by the following formula

PC3: Revised's Reversacol Trent Blue
PC4: Revised's Reversacol Heath Green
The PC2 can be manufactured by referring to, for example, the manufacturing method described in International Publication No. 2009/146509. Specifically, it can be produced by reacting a naphthopyrane compound having a 2-hydroxy-ethoxycarbonyl group with a polydimethylsiloxane having a carboxy group at both ends in International Publication No. 2009/146509. The (average) molecular weight of the molecular chain is 1350.
<(B1) Polyiso (thio) cyanate compound>
IPDI: Isophorone diisocyanate NBDI: Norbornane diisocyanate H12MDI: Dicyclohexylmethane-4,4'-diisocyanate H6XDI: 1,3-bis (isocyanatomethyl) cyclohexane <(B2) poly (ti) all compound>
[Polycarbonate]
PL1: Polypropylene glycol derivative of glycerin (number average molecular weight 1500)
PL2: NOF Corporation Uniox G-450 (polyoxyethylene glyceryl ether, number average molecular weight 450)
[Polythiol]
PT1: 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Mixture of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane PEMP: pentaerythritol tetrakis (3-mercaptopropionate)
DEMP: Dipentaerythritol Hexakis (3-mercaptopropionate)
<(B3) mono (chi) all compound>
PGME10: Polyethylene glycol monooleyl ether (n≈10, Mw = 668)
SMP: Stearyl-3-mercaptopropionate (Mw = 359)
<(B4) Polyrotaxan monomer>
RX-1: Polyrotaxane monomer prepared in Preparation Example 1 below.
<(C) Polymerization curing accelerator>
[Reaction catalyst for urethane or urea]
C1: Dimethyldichlorotin <Other ingredients>
[Stabilizer]
HP: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate]
[UV absorber]
UVA1: p-methoxybenzylidene malonate dimethyl ester <Preparation Example 1>
The method for adjusting RX-1, which is a component (B4), is described below.
(1-1) Preparation of PEG-COOH As a polymer for forming an axial molecule, linear polyethylene glycol (PEG) having a molecular weight of 20000 was prepared. PEG (10 g), TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) (100 mg), and sodium bromide (1 g) were dissolved in 100 mL of water. To this solution was added 5 mL of a commercially available sodium hypochlorite aqueous solution (effective chlorine concentration 5%), and the mixture was stirred at room temperature for 10 minutes. Then, etanol was added in a range of up to 5 mL to terminate the reaction. Then, after extraction with 50 mL of methylene chloride, methylene chloride was distilled off, dissolved in 250 mL of ethanol, and then reprecipitated at a temperature of -4 ° C. for 12 hours to PEG-COOH. Was collected and dried.
(1-2) Preparation of Polyrotaxane The PEG-COOH (3 g) and α-cyclodextrin (α-CD) (12 g) prepared above are each dissolved in 50 mL of warm water at 70 ° C., and the obtained solutions are mixed. And shake well. The mixed solution was then reprecipitated at 4 ° C. for 12 hours and the precipitated inclusion complex was lyophilized and recovered. Then, adamantaneamine (0.13 g) was dissolved in 50 mL of dimethylformamide (DMF) at room temperature, the above inclusion complex was added, and the mixture was swiftly shaken well. Then, a solution prepared by dissolving a BOP reagent (benzotriazole 1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) (0.38 g) in DMF was further added and shaken well. Further, a solution prepared by dissolving 0.14 mL of diisopropylethylamine in DMF was added and shaken well to obtain a slurry-like reagent. The slurry-like reagent obtained above was allowed to stand at 4 ° C. for 12 hours. Then, 50 mL of a mixed solvent of DMF / methanol (volume ratio: 1/1) was added and mixed, and the mixture was centrifuged and the supernatant was discarded. Further, after washing with the above DMF / metalol mixed solution, washing with metall was performed, and centrifugation was performed to obtain a precipitate. The obtained precipitate was dried by vacuum drying, then dissolved in 50 mL of DMSO, and the obtained transparent solution was added dropwise to 700 mL of water to precipitate polyrotaxane. The precipitated polyrotaxane was recovered by centrifugation and dried in vacuum. Further, it was dissolved in DMSO, precipitated in water, and then recovered and dried to obtain purified polyrotaxane. The inclusion amount of α-CD at this time is 0.25.

Here, the inclusion amount was calculated by dissolving polyrotaxane in DMSO-d ₆ and measuring with a ¹ H-NMR measuring device (JNM-LA500 manufactured by JEOL Ltd.) and the following method.

Here, X, Y, X / (YX) have the following meanings.

X: Integrated value of hydroxyl group-derived protons of cyclodextrin at 4 to 6 ppm Y: Integrated value of cyclodextrin and protons derived from methylene chain of PEG X / (YX): Proton ratio of cyclodextrin to PEG First, Theoretically, X / (YX) when the maximum inclusion amount is 1.0 is calculated in advance, and this value is compared with X / (YX) calculated from the analysis value of the actual compound. The inclusion amount was calculated by
(1-3) Introduction of side chain to polyrotaxane The above-purified polyrotaxane (500 mg) was dissolved in 50 mL of a 1 mol / L NaOH aqueous solution, propylene oxide (3.83 g, 66 mmol) was added, and the mixture was subjected to an argon atmosphere. The mixture was stirred at room temperature for 12 hours. Next, the above polyrotaxane solution was neutralized to a pH of 7 to 8 using a 1 mol / L HCl aqueous solution, dialyzed in a dialysis tube, and then freeze-dried to obtain hydroxypropylated polyrotaxane. It was. The degree of modification of the cyclic molecule to the hydroxyl group by the hydroxypropyl group was 50%. The obtained hydroxypropylated polyrotaxane (5 g) was dissolved in ε-caprolactone (30 g) at 80 ° C. to prepare a mixed solution. This mixed solution is stirred at 110 ° C. for 1 hour while blowing dry nitrogen, a 50 mass% xylene solution (0.16 g) of tin 2-ethylhexanoate (II) is added, and the mixture is stirred at 130 ° C. for 6 hours. did. Then, xylene was added to obtain a polycaprolactone-modified polyrotaxane xylene solution into which a side chain having a non-volatile concentration of about 35% by mass was introduced.

The polycaprolactone-modified polyrotaxane xylene solution prepared above was added dropwise to hexane, and the solution was recovered and dried to obtain a side chain-modified polyrotaxane monomer having a hydroxyl group as a polymerizable functional group. The obtained hydroxypropylated polyrotaxane was identified by ¹ H-NMR and GPC, and it was confirmed that it was a hydroxypropylated polyrotaxane having a desired structure. In this polyrotaxane monomer, the degree of modification of the side chain was 50%, the (average) molecular weight of the side chain was about 600, and the mass average molecular weight (Mw) measured by GPC was 700,000.
<Composition 1>
According to the following formulation, each component was mixed to prepare a uniform liquid (photochromic polymerizable composition 1. Hereinafter, it may be simply referred to as “composition 1”). Table 1 shows each compounding amount. Further, the total number of moles of the iso (thio) cyanate group of the polyisocyanate compound of the component (B1) is n1, the total number of moles of the active hydrogen-containing group of the component (B2) is n2, and the total number of moles of the active hydrogen-containing group of the component (B3) is n2. The total number of moles is n3, the total number of moles of the active hydrogen-containing group of the component (B4) is n4, and the ratio of each mole number is shown in Table 1.
Prescription;
(A) Photochromic compound: PC1 1.44 parts by mass (B1) Polyiso (thio) cyanate compound: PL2 42 parts by mass (B2) Poly (chi) All compound: PEMP 41 parts by mass (B3) Mono (chi) All compound: PGME10 4 parts by mass Mono (chi) All compound: SMP 10 parts by mass (B4) RX-1: 3 parts by mass (C) Curing accelerator: C1 0.05 parts by mass Stabilizer: HP 1 part by mass <Composition 2- 8>
Photochromic compound (A component), polyiso (thio) cyanate compound (B1 component), poly (chi) all compound (B2 component), mono (chi) all compound (B3 component), polyrotaxane monomer (B4 component) shown in Table 1. , Polymerization curing accelerator (C component), and other compounding components were used to prepare compositions 2 to 8 in the same manner as in composition 1.

<Example 1>
Using the above photochromic polymerizable composition 1, a photochromic optical article was produced by the following method. First, after sufficiently defoaming the photochromic polymerizable composition 1, the photochromic polymerizable composition 1 is formed on a concave surface of a glass plate (G1) having a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm. The coating was applied so that the thickness of the obtained adhesive layer was 0.1 mm. Next, a glass plate (G4) in which the surface of a glass plate (G3) having a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm having an ultraviolet absorbing property having a transmittance of 360 nm of 70% was chemically strengthened with potassium nitrate. ) Was placed so that the convex surface was bonded to the photochromic polymerizable composition 1.

Then, after leaving it in an oven heated to 50 ° C. for 30 minutes, the photochromic polymerizable composition was polymerized and cured by heating at 120 ° C. for 1 hour to obtain a photochromic optical article. Explaining with reference to FIG. 1, the obtained photochromic optical article 1 is bonded to a pair of glass plates 2 and 4 for optical articles by an adhesive layer 4 formed by polymerizing and curing a photochromic polymerizable composition. It becomes a thing. Note that FIG. 1 is a schematic view, and although it has a curved surface, it is not a diagram.

As a result of measuring the obtained photochromic optical article with the following evaluation items, the transmittance at 400 nm was 7%, the impact resistance was 32 g, and the durability was 90%. Further, the maximum absorption wavelength of the photochromic optical article was 595 nm, the color development density was 0.93, and the fading speed was 60 seconds. The 400 nm transmittance, impact resistance, durability, maximum absorption wavelength, color development density, and fading rate were evaluated as follows.

〔Evaluation item〕
(1) 400 nm transmittance: The transmittance of 400 nm at the time of color development determined by a spectrophotometer (instantaneous multi-channel photodetector-MCPD1000) manufactured by Otsuka Electronics Co., Ltd.

(2) Impact resistance: 16 g, 32 g, 50 g, 80 g, 95 g, 112 g, and 138 g steel balls are dropped from a height of 127 cm into the center of the plastic lens to be tested in order from the lightest mass steel ball. , It was evaluated whether or not the plastic lens was broken. The evaluation result was expressed by the mass of the maximum steel ball in which the plastic lens did not break.

(3) Durability (%) = [(A60days) / (A0) × 100]: The following deterioration acceleration test was conducted to evaluate the durability of color development when exposed to sunlight outdoors. That is, the obtained photochromic optical article was left continuously for 60 days outdoors in which sunlight was sufficiently irradiated. The evaluation of the color development density was performed with a photochromic optical article before and after the test, the color development density (A0) before the test and the color development density (A60days) after the test were measured, and the value of [(A60days) / (A0) × 100] was measured. Was used as the residual rate (%) and was used as an index of color development durability. The higher the residual rate, the higher the durability of color development.

(4) Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development determined by a spectrophotometer (instantaneous multi-channel photodetector-MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

(5) Color development density {ε (120) -ε (0)}: Difference between the absorbance {ε (120)} after light irradiation for 120 seconds and the absorbance ε (0) before light irradiation at the maximum absorption wavelength. .. It can be said that the higher this value is, the better the photochromic property is.

(6) Fading rate [t1 / 2 (sec.)]: When the light irradiation is stopped after the light irradiation for 120 seconds, the absorbance of the sample at the maximum absorption wavelength is {ε (120) −ε (0)}. Time required to reduce to 1/2 of. It can be said that the shorter this time is, the better the photochromic property is.

<Examples 2 to 5, Comparative Example 1>
A glass plate having a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm was used on the outside, which is not functional glass as in Example 1, except that the glass plate shown in Table 2 was used on the inside. A photochromic optical article was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

As is clear from Examples 1 to 5, the photochromic optical article of the present invention has an excellent balance of photochromic properties, 400 nm transmittance, durability, and impact resistance. On the other hand, in Comparative Example 1, all of the photochromic characteristics, the 400 nm transmittance, the durability, and the impact resistance were slightly inferior.

<Examples 6 to 12>
G2 on the outside: A glass plate with a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm is chemically strengthened with potassium nitrate on the surface, and the glass plate shown in Table 3 is used on the inside. A photochromic optical article was prepared and evaluated in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 3.

As is clear from Examples 6 to 12, the photochromic optical article of the present invention is particularly excellent in impact resistance, and also has an excellent balance of photochromic properties, 400 nm transmittance, and durability.

<Examples 13 to 19>
Use a glass plate with a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm, which has an ultraviolet absorption characteristic with a G3: 360 nm transmittance of 70% on the outside, and use the glass plate shown in Table 4 on the inside. A photochromic optical article was prepared and evaluated in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 4.

As is clear from Examples 13 to 19, the photochromic optical article of the present invention is particularly excellent in durability, and also has an excellent balance of photochromic properties, 400 nm transmittance, and impact resistance.

<Examples 20 to 26>
A glass plate with a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm, which has a transmittance of 70% at G4: 360 nm on the outside and is chemically strengthened with potassium nitrate on the surface of the glass plate (G3). A photochromic optical article was prepared and evaluated in the same manner as in Example 1 except that the glass plate shown in Table 5 was used inside. The evaluation results are shown in Table 5.

As is clear from Examples 20 to 26, the photochromic optical article of the present invention is particularly excellent in durability and impact resistance, and is also excellent in balance between photochromic characteristics and 400 nm transmittance.

<Examples 27 to 34>
A glass plate with a refractive index of 1.52, an Abbe number of 60, and a center thickness of 1.0 mm, which has a transmittance of 70% at G4: 360 nm on the outside and is chemically strengthened with potassium nitrate on the surface of the glass plate (G3). A photochromic optical article was prepared and evaluated in the same manner as in Example 1 except that the glass plate shown in Table 6 was used inside. In Example 34, a gray polarizing film (thickness 27 μm, visual transmittance 42.5%, polarization degree 99.2%) further dyed with a bicolor dye was embedded in the photochromic polymerizable composition. Then, a photochromic optical article was produced. The evaluation results are shown in Table 6.

As is clear from Examples 27 to 34, the photochromic optical article of the present invention has an excellent balance of photochromic properties, 400 nm transmittance, durability and impact resistance.

1: Photochromic optical article 2: Glass plate for optical article 3: Adhesive layer 4: Glass plate for optical article 10: Polyrotaxan 20: Shaft molecule 30: Cyclic molecule 40: Bulky terminal group 50: Side chain

Claims (8)

A photochromic optical article formed by bonding a pair of glass plates for an optical article with an adhesive layer containing (A) a photochromic compound and (B) a resin component.
A photochromic optical article comprising a glass plate for an optical article in which the pair of glass plates for an optical article has different properties. Claim 1 characterized in that at least one glass plate for an optical article is at least one functional glass selected from chemically tempered glass, glass having a refractive index of 1.6 or more, and ultraviolet absorbing performance glass. The photochromic optical article described. The claim is characterized in that the pair of glass plates for optical articles is a glass plate for optical articles having a curvature, and the glass plate for optical articles arranged at least on the side opposite to the eye is chemically strengthened glass. The photochromic optical article according to 1 or 2. The spectacle lens having photochromic properties according to claim 1 to 3, wherein the resin component (B) is a urethane resin. The urethane resin (B) is
(B1) A polyiso (thio) cyanate compound having two or more iso (thio) cyanate groups in the molecule, and
(B2) A poly (thio) all compound having two or more active hydrogen-containing groups selected from hydroxyl groups and thiol groups in the molecule, and
(B3) A mono-all compound having one active hydrogen-containing group selected from a hydroxyl group and a thiol group in the molecule, and
The photochromic optical article according to claim 4, wherein the resin is obtained by polymerizing. The urethane resin (B) further
(B4) It has a complex molecular structure composed of an axis molecule and a plurality of cyclic molecules that include the axis molecule.
The photochromic optical article according to claims 4 to 5, wherein the cyclic molecule is a resin obtained by polymerizing a polyrotaxane monomer having an iso (thio) cyanate group or an active hydrogen-containing group selected from a hydroxyl group and a thiol group. .. The cyclic molecule of the (B4) polyrotaxane monomer is
It has a side chain composed of repeating units of organic groups having 3 to 20 carbon atoms.
The photochromic optical article according to claim 6, wherein at least a part of the end of the side chain is the active hydrogen-containing group. (1) A method of injecting a photochromic polymerizable composition containing (B) a composition of each component for obtaining a resin component and (A) a photochromic compound between a pair of glass plates for optical articles, or (2). ) A photochromic polymerizable composition containing (B) a composition of each component for obtaining a resin component and (A) a photochromic compound is applied onto one pair of glass plates for optical articles, and then on the coated surface. By arranging the photochromic polymerizable composition between the pair of glass plates for optical articles by one of the methods of stacking another glass plates for optical articles, and then polymerizing and curing the photochromic polymerizable composition. The method for producing a photochromic optical article according to any one of claims 1 to 7.

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