JP2022031072A - Photochromic optical article - Google Patents

Abstract

To provide a photochromic curable composition which prevents both defect in appearance derived from a protective film, and defect in an orange peel state due to coating, and becomes a cured body for expressing excellent photochromic properties.SOLUTION: A photochromic curable composition contains: (A) a polyrotaxane compound obtained by modifying, with respect to a polyrotaxane compound which has a complex molecule configuration comprising an axial molecule and a plurality of cyclic molecules including the axial molecule, and in which side chains having hydroxy groups in the terminals are introduced to the cyclic molecules, 1 mol% or more and less than 100 mol% of the hydroxy groups of the side chains by a compound having a polymerizable group; (B) a polymerizable monomer having bifunctional or more (meth)acrylate groups containing silicon; and (C) a photochromic compound. In the photochromic curable composition, 0.01 pt.wt. or more and less than 10 pts.wt. of (B) the polymerizable monomer is contained based on 100 pts.mass of the photochromic curable composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel photochromic curable composition. Furthermore, the present invention relates to a novel photochromic cured product having an excellent photochromic action and a good appearance.

Photochromic compounds typified by chromene compounds, flugide compounds, spiroxazine compounds, etc. change color rapidly when irradiated with light containing ultraviolet rays such as sunlight or mercury lamp light, and when the light irradiation is stopped and left in a dark place. It has the property of returning to the original color (photochromic property), and by taking advantage of this property, it is used in various applications, especially applications of optical materials.

For example, a photochromic spectacle lens to which photochromic properties are imparted by using a photochromic compound quickly colors and functions as sunglasses outdoors when exposed to light including ultraviolet rays such as sunlight, and such light irradiation. It functions as normal transparent eyeglasses that fade in color indoors, and its demand has been increasing in recent years.

As a method for manufacturing a photochromic optical article used for this photochromic spectacle lens, for example, a method of directly molding an optical article such as a lens by mixing a polymerizable monomer and a photochromic compound and polymerizing the polymer, a plastic lens or the like, and the like. There are a method of coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article, a method of joining two optical articles with an adhesive layer formed of an adhesive resin in which a photochromic compound is dispersed, and the like (patented patent). See Documents 1, 2 and 3). Among them, a method of coating a resin layer in which a photochromic compound is dispersed on the surface of an optical article such as a plastic lens is preferably used. Further, in the coating method, it is common to use a leveling agent in order to improve the coating property of the resin.

The photochromic optical article manufactured by the above method responds quickly to high-concentration color when irradiated with light containing ultraviolet rays such as sunlight, and quickly fades indoors in the absence of such light. Was required, and further excellent photochromic properties were required to be exhibited.

As a method for coating the surface of an optical article such as a plastic lens with a resin layer in which a photochromic compound is dispersed, a method for imparting flexibility without firmly curing the resin layer in which the photochromic compound is dispersed is used. A method for improving photoresponsiveness and fading speed by softening the surface hardness of a resin layer in which a photochromic compound is dispersed has been proposed (see Patent Document 4).

Generally, a photochromic optical article, for example, a photochromic spectacle lens, is manufactured, wrapped in a relatively soft material called inner paper so that the lens surface is not scratched, and then shipped in a bag. Further, in the photochromic spectacle lens, it is widely known that a scratch prevention protective film is attached to the lens surface in order to obtain a defect-free lens surface in each manufacturing process, storage, and shipping. This is to prevent the lens surface from being scratched and dust from adhering during the process. In addition, since the photochromic spectacle lens is usually transparent, it is difficult to instantly determine whether or not a scratch prevention protective film is attached. Therefore, a colored protective film for preventing scratches is usually used, which enables easy identification.

In the above-mentioned photochromic spectacle lens shipping and manufacturing process, in the photochromic spectacle lens having a softened surface hardness as in Patent Document 4, the surface hardness of the resin layer in which the photochromic compound is dispersed is not sufficient, so that the lens surface is scratched. There was room for improvement in that it was easy to attach. Further, as described above, when the scratch prevention protective film is attached, the colorant and the adhesive adhere to the lens surface, impairing the initial coloring and the color tone, and the wrinkle-like appearance caused by the adhesive. There is room for improvement in that defects may occur and the appearance of the photochromic spectacle lens is impaired.

International Publication No. 2012/176439 International Publication No. 2011/125965 International Publication No. 2013/099640 International Publication No. 2008/001578 International Publication No. 2015/054036 International Publication No. 2015/06798

To solve the above problems, a method of laminating a curable resin on the surface of a resin layer in which a photochromic compound is dispersed has been proposed (see Patent Document 5). This method is a method of laminating a thermosetting epoxy resin or the like on the surface of a resin layer in which a photochromic compound is dispersed. According to this method, since another layer is further laminated on the surface of the resin layer in which the photochromic compound is dispersed, the effect of further improving scratch prevention and the like is expected.

However, according to the study by the present inventors, it was found that even with the method described in Patent Document 5, there is room for improvement in the following points. That is, in the method described in Patent Document 5, there is room for improvement in that the adhesion is insufficient at the time of manufacture and appearance defects such as cracks occur. In addition, since it is necessary to add layers, there are problems in terms of cost increase and work complexity, and there is room for improvement.

In Patent Document 6, an excellent photochromic curable composition and a cured product can be obtained by blending a polyrotaxane compound, but according to the studies by the present inventors, there is room for improvement in the following points. That is, since the photochromic curable composition containing the polyrotaxane compound tends to have a high viscosity, when a leveling agent is added to improve the coating property, the leveling agent adheres to and penetrates the adhesive of the protective film for scratch prevention. It was found that poor appearance is likely to occur because of the promotion of. However, when the leveling agent is not added, the appearance defect derived from the scratch prevention protective film can be reduced, but there is a problem that a new orange peel-like appearance defect occurs due to the deterioration of the coating property, and there is room for improvement.

Therefore, an object of the present invention is good, without laminating a further layer on the photochromic layer, while preventing both the appearance defect derived from the scratch prevention protective film and the orange peel-like appearance defect due to the coating. It is an object of the present invention to provide a photochromic curable composition capable of providing a photochromic optical article.

The present inventors have made extensive studies to solve the above problems. As a result, they have found that the above problems can be solved by precisely controlling the ratio of the polyrotaxane compound and the polymerizable monomer containing silicon without adding a leveling agent, and have completed the present invention. rice field.

That is, the first invention is
(1) In a polyrotaxane compound having a complex molecular structure consisting of an axis molecule and a plurality of cyclic molecules enclosing the axis molecule, and a side chain having a hydroxyl group at the end thereof is introduced into the cyclic molecule. A polyrotaxane compound in which the hydroxyl group of the side chain is modified with a compound having a polymerizable group in an amount of 1 mol% or more and less than 100 mol%.
(B) A polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing silicon,
and,
(C) A photoclock curable composition containing a photochromic compound.
The (B) polymerizable monomer is a photochromic curable composition in which the amount is 0.01 parts by weight or more and less than 10 parts by weight when the photochromic curable composition is 100 parts by mass.

Further, the photochromic curable composition of the present invention preferably takes the following aspects.
(2) The polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing (B) silicon is a photochromic curable composition which is silsesquioxane having a (meth) acrylate group. ..
(3) The photochromic curable composition according to claim 1, wherein the polymerizable group of the (A) polyrotaxane compound is a (meth) acrylate group.
(4) The photochromic curable composition according to claim 1, wherein the cyclic molecule of the (A) polyrotaxane compound is a cyclodextrin ring.
(5) The photochromic curable composition according to claim 1, wherein the shaft molecule of the (A) polyrotaxane compound is formed of polyethylene glycol and adamantyl groups are bonded to both ends of the shaft molecule.
(6) The photochromic curable composition according to claim 1, wherein the side chain having a hydroxyl group at the terminal introduced into the (A) polyrotaxane compound is introduced by a lactone-based compound.
(7) The composition is a photochromic curable composition having a weight average molecular weight of 1500 to 20000.

The second invention is a photochromic cured product obtained by curing the photochromic curable composition, and the third invention is a photochromic laminate in which the cured product is laminated on an optical substrate.

According to the present invention, it is possible to obtain a cured product that exhibits good photochromic properties by preventing both appearance defects derived from a scratch-preventing protective film and orange peel-like defects due to coating.

Schematic diagram showing the molecular structure of the polyrotaxane used in the present invention.

The photochromic curable composition of the present invention is
(A) In a polyrotaxane compound having a complex molecular structure consisting of an axial molecule and a plurality of cyclic molecules enclosing the axial molecule and having a side chain having a hydroxyl group at the terminal introduced into the cyclic molecule, the side chain of the axial molecule. A polyrotaxane compound in which the hydroxyl group is modified with a compound having a polymerizable group in an amount of 1 mol% or more and less than 100 mol%.
(B) A polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing silicon, and
(C) Photochromic compound,
A photoclock curable composition comprising:
The (B) polymerizable monomer is a photochromic curable composition in which the amount is 0.01 parts by weight or more and less than 10 parts by weight when the photochromic curable composition is 100 parts by mass.

Hereinafter, each component will be described.

<(A) Polyrotaxane compound>
Polyrotaxane is a known compound and exhibits a structure as shown in FIG. In the (A) polyrotaxane compound (hereinafter, also referred to as (A) component) used in the present invention, various kinds of shaft molecules are known, and for example, the shaft molecule includes a ring contained in a cyclic molecule. It may be linear or branched as long as it can penetrate, and is generally formed of a polymer.

Among the components (A) used in the present invention, those suitable as the polymer forming the shaft molecule are polyethylene glycol, polyisobutylene, polyisobutylene, polybutadiene, polypropylene glycol, polytetratetra, polydimethylsiloxane, polyethylene, polypropylene, and polyvinyl alcohol. Alternatively, it is polyvinyl methyl ether, and polyethylene glycol is most suitable.

Further, the group formed at both ends of the shaft molecule is not particularly limited as long as it is a group that prevents the cyclic molecule from being detached from the shaft molecule, but is preferably a bulky group, for example, an adamantyl group. Examples thereof include a trityl group, a fluoresenyl group, a dinitrophenyl group, and a pyrenyl substrate, and an adamantyl group is particularly preferable in terms of ease of introduction and the like.

The molecular weight of the shaft molecule is not particularly limited, but if it is too large, compatibility with other components such as other polymerizable monomers tends to deteriorate, and if it is too small, it is a cyclic molecule. There is a tendency for the mobility to decrease and the photochromic property 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 8,000 to 30,000. Is. The weight average molecular weight Mw is a value measured by the GPC measuring method described in Examples described later.

Further, the cyclic molecule may have a ring having a size capable of including the axial molecule as described above, and examples of such a cyclic molecule include a cyclodextrin ring, a crown ether ring, a benzocrown ring, and a dibenzo. Crown rings and dicyclohexanocrown rings can be mentioned, with cyclodextrin rings being particularly preferred. The cyclodextrin ring contains an α-form (ring inner diameter 0.45 to 0.6 nm), a β-form (ring inner diameter 0.6 to 0.8 nm), and a γ-form (ring inner diameter 0.8 to 0.95 nm). However, in the present invention, the α-cyclodextrin ring and the γ-cyclodextrin ring are particularly preferable, and the α-cyclodextrin ring is most preferable.

A plurality of cyclic molecules having a ring as described above are included in one axial molecule. Generally, when the maximum number of cyclic molecules that can be included in one axial molecule is 1, the cyclic molecule is cyclic. The number of inclusions of the molecule is preferably in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, still more preferably 0.003 to 0.4. If the number of inclusions of the cyclic molecule is too large, the cyclic molecule is densely present with respect to one axis molecule, so that the mobility thereof tends to decrease and the photochromic property tends to decrease. Further, if the number of inclusions is too small, the gap between the axial molecules becomes narrow, the gap that allows the reversible reaction of the photochromic compound molecule decreases, and the photochromic property also tends to decrease.

The component (A) used in the present invention is a polyrotaxane compound in which a side chain having a hydroxyl group at the terminal is introduced into the cyclic molecule, and the hydroxyl group of the side chain is modified with a compound having a polymerizable group. .. This side chain is indicated by "5" in FIG.

The side chain having hydroxide at the end is not particularly limited, but is formed by repeating an organic chain having a hydroxyl group at the end and having a carbon number in the range of 3 to 20. Is preferable. The average molecular weight of such side chains is preferably in the range of 300 to 10,000, preferably 350 to 8,000, more preferably 350 to 5,000, and most preferably in the range of 400 to 1,500. It is in. The average molecular weight of this side chain can be adjusted by the amount used at the time of introduction of the side chain and can be obtained by calculation, but it can also be obtained by ¹ H-NMR measurement.

Further, the side chain as described above is introduced by utilizing the functional group of the cyclic molecule and modifying this functional group. 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. .. The functional group of the cyclic molecule may affect the compatibility with other components, and in particular, when the functional group is a hydroxyl group, the compatibility with other components is greatly affected. Therefore, the ratio (degree of modification) in which the functional group is modified is preferably 6% or more and 80% or less, and more preferably 30% or more and 70% or less.

In the present invention, the side chain as described above may be linear or branched as long as it has a hydroxyl group at the terminal. Further, by utilizing ring-opening polymerization; radical polymerization; cationic polymerization; anionic polymerization; living radical polymerization such as atomic transfer radical polymerization, RAFT polymerization, NMP polymerization, etc., the functional group of the cyclic molecule may have a hydroxyl group at the terminal. By introducing a side chain, a desired side chain can be obtained.

For example, ring-opening polymerization can introduce side chains derived from cyclic compounds such as lactones and cyclic ethers. In the side chain introduced by ring-opening polymerization of a cyclic compound such as lactone or cyclic ether, a hydroxyl group is introduced at the end of the side chain.

Among the cyclic compounds, cyclic ethers and lactone compounds are preferably and preferably used from the viewpoints of being easily available, highly reactive, and easy to adjust the size (molecular weight). Among the lactone compounds, lactone compounds such as ε-caprolactone, α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone and γ-butyrolactone are particularly preferable, and the most preferable one is ε-caprolactone. Is.

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 in particular, a large molecule may be directly reacted 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 functional group highly reactive (for example, a hydroxyl group) is carried out at the terminal. ) Is introduced, and then a side chain is introduced by ring-opening polymerization using the above-mentioned cyclic compound. In this case, the hydroxypropylated portion can also be regarded as a side chain.

In the component (A) used in the present invention, in order to introduce a side chain having a hydroxyl group at the terminal into a cyclic molecule, the ease of introducing the side chain and the size (molecular weight) of the side chain should be adjusted. Considering the ease and modification of the hydroxyl group, it is preferable to adopt the method of introducing a side chain having a hydroxyl group at the terminal by the ring-opening polymerization.

(Polyrotaxane compound having a polymerizable group at the terminal)
In the component (A) used in the present invention, the hydroxyl group at the end of the side chain of the polyrotaxane was reacted with a compound having a polymerizable group to introduce a polymerizable group into the side chain of the polyrotaxane compound. It is a thing. In the present invention, this reaction is referred to as "denaturation".

The compound having a polymerizable group is introduced by utilizing the side chain having a hydroxyl group at the terminal, and a compound that reacts with the hydroxyl group of the side chain can be appropriately used. The compound having a polymerizable group is preferably a compound having no hydroxyl group in the molecule, considering compatibility with other components.

Typical examples of the polymerizable group are radically polymerizable groups such as a (meth) acrylate group (methacrylate group and / or an acrylate group), a vinyl group, and an allyl group. Among them, the (meth) acrylate group is the most suitable in consideration of the ease of manufacturing the cured product, the versatility of the obtained cured product, and the like.

The compound having a polymerizable group is a compound having both a functional group capable of reacting with a hydroxyl group of a side chain and a group of the polymerizable group in one molecule. Examples of the functional group capable of reacting with the hydroxyl group include an isocyanate group, a carboxyl group, and an acid chloride group (for example, -COCl group). By reacting a compound having an isocyanate group, a polymerizable group is introduced via a urethane bond. Alternatively, a polymerizable group is introduced via an ester bond by reacting a compound having a carboxyl group, a acid chloride group, or the like.

Specific examples of the compound having a polymerizable group include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and 1,1- (bisacryloyloxy) as compounds having an isocyanate group and a (meth) acrylate group. Methyl) ethyl isocyanate and the like can be mentioned.

Further, a compound having an acid chloride group (for example, -COCl group) and a (meth) acrylate group is synthesized by reacting a compound having a carboxyl group and a (meth) aclate group with a chlorinating agent such as thionyl chloride. be able to.

Examples of the compound having a carboxyl group and a (meth) acrylate group include 2-methacryloyloxyethyl succinate and β-carboxyethyl acrylate.

For the reaction between the compound having a polymerizable group and the hydroxyl group of the side chain, reaction conditions of a known functional group capable of reacting with the hydroxyl group and the hydroxyl group can be adopted.

In the polyrotaxane compound (A) used in the present invention, the modification ratio of the polymerizable group to the hydroxyl group at the end of the side chain, that is, the reaction ratio of the compound having a polymerizable group to the number of moles of all the hydroxyl groups in the side chain is determined. It is preferably 1 mol% or more and less than 100 mol%, and considering the yield, mechanical strength, photochromic properties, etc. of the obtained cured product, the modification ratio by the compound having a polymerizable group is 10 mol% or more and 95 mol. % Or less, more preferably 30 mol% or more and 95 mol% or less, and particularly preferably 70 mol% or more and 95 mol% or less in consideration of the productivity of the polylotaxane compound itself.

The modification ratio can be calculated by (the number of moles into which the polymerizable group is introduced) / (the number of moles of all the hydroxyl groups in the side chain) × 100. As will be described in detail below, the component (A) can also be modified with a compound having no polymerizable group. Therefore, the remaining hydroxyl groups in the side chain can also be modified with compounds that do not have polymerizable groups, as described in detail below. However, in this case, since the modification rate is high, the hydroxyl group may remain.

In the component (A) used in the present invention, it is essential that the hydroxyl group at the end of the side chain introduced into the cyclic molecule is modified with the compound having a polymerizable group. The remaining hydroxyl groups of the side chain (that is, the hydroxyl groups at the ends of the side chains introduced into the cyclic molecule, which are not modified with the compound having a polymerizable group) may remain as hydroxyl groups. It may be modified with a compound having no polymerizable group.

The compound having no polymerizable group has a functional group capable of reacting with a hydroxyl group of a side chain in one molecule, and the molecule does not contain a polymerizable group. The term "not containing a polymerizable group" means that the compound described in "The compound having a polymerizable group" is not contained. Therefore, the compound having no polymerizable group has an alkyl group having 2 to 20 carbon atoms, an alkyleneoxy group having 2 to 30 carbon atoms, and an aryl group having 6 to 20 carbon atoms instead of the polymerizable group. Is preferable. Incidentally, as the functional group capable of reacting with the hydroxyl group of the side chain, the same functional group as described in "The compound having a polymerizable group" can be mentioned.

The compound having no polymerizable group has 2 to 20 carbon atoms (excluding the carbon atom of the isocyanate group) from the viewpoint of easy availability of a raw material and high reactivity with a hydroxyl group as a compound having an isocyanate group. ) Is preferably an isocyanate compound, and an isocyanate compound having 3 to 10 carbon atoms is particularly preferable. Specific examples of suitable isocyanate compounds include n-propyl isocyanate, n-butyl isocyanate, n-pentyl isocyanate, n-hexyl isocyanate, and phenyl isocyanate.

The compound having no polymerizable group has 2 to 20 carbon atoms (excluding the carbon atom of the carbonyl group) from the viewpoint of easy availability of a raw material and high reactivity with a hydroxyl group as a carboxylic acid chloride. The carboxylic acid chloride compound of the above is preferable, and the carboxylic acid chloride compound having 2 to 10 carbon atoms is particularly preferable. Specific examples of suitable acid chlorides include acetyl chloride, propionyl chloride, butyryl chloride, pivaloyl chloride, hexanoyl chloride, benzoyl chloride and the like.

The modification ratio of the compound having no polymerizable group can be calculated by (the number of moles into which the compound having no polymerizable group is introduced) / (the number of moles of all the hydroxyl groups in the side chain) × 100. This denaturation rate is not particularly limited. In particular, considering the yield, mechanical strength, photochromic properties, etc. of the obtained cured product, the modification ratio with the compound having no polymerizable group is preferably 0 to 99 mol%, preferably 0 to 90 mol%. It is more preferably 0 to 70 mol%, further preferably 0 to 30 mol%, and particularly preferably 0 to 30 mol%.

(Suitable structure / molecular weight of component (A))
In the present invention, the component (A) preferably used is, among the above-mentioned components, a polyethylene glycol bonded to both ends with an adamantyl group as a shaft molecule, a cyclic molecule having an α-cyclodextrin ring, and further. , Polycaprolactone is preferably introduced into the cyclic molecule with a side chain having a hydroxyl group at the end.

Further, the weight average molecular weight Mw of the component (A) modified with the compound having a polymerizable group and the compound having no polymerizable group to be used as needed is 100,000 to 1,000,000. It is preferably in the range. When the weight average molecular weight Mw of the component (A) is in this range, the compatibility with other components can be improved, and the transparency of the cured product can be further improved. Considering compatibility with other components, transparency of the cured product, etc., the weight average molecular weight Mw of the (A) polyrotaxane compound is more preferably in the range of 100,000 to 800,000 to 100,000 to 800,000. It is more preferably in the range of 500,000. The weight average molecular weight Mw is a value measured by the GPC measuring method described in the following examples.

<(B) Polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing silicon>
The polymerizable monomer (hereinafter, also referred to as the component (B)) having a bifunctional or higher functional (meth) acrylate group containing (B) silicon used in the present invention has silicon in the molecule and 2 As long as it is a polymerizable monomer having a functional or higher (meth) acrylate group and does not have a group containing a chain-like organic siloxane group, it is not particularly limited, and a known one is used. be able to.

In the present invention, the organic siloxane group means a group in which an organic group is directly bonded to a silicon atom constituting the siloxane group.

Among them, a particularly suitable component (B) is silsesquioxane having a bifunctional or higher functional (meth) acrylate group. The silsesquioxane has various molecular structures such as cage-like, ladder-like, and random. In the present invention, silsesquioxane having one kind of structure can be used, or a plurality of structures can be used. It can also be used as a mixture of silsesquioxane.

Examples of the silsesquioxane having a bifunctional or higher functional (meth) acrylate group include those represented by the following formula (1).

(In the formula, a is a degree of polymerization, which is an integer of 3 to 100, and a plurality of R ^1s may be the same or different from each other, and may be an organic group containing at least two (meth) acrylate groups. However, R ¹ does not contain a group containing a chain-like organic siloxane group.)

Here, the organic group containing a (meth) acrylate group in R ¹ includes only a (meth) acrylate group (including a group in which a (meth) acrylate group is directly bonded to a silicon atom). In the present invention, the (meth) acrylate group may specifically include not only a (meth) acrylate group, but also a (meth) acryloxypropyl group and a (3- (meth) acryloxypropyl) dimethylsiloxy group. Among them, the (meth) acryloxypropyl group is particularly preferable because it is easy to obtain a raw material at the time of producing the component (B) and it is possible to obtain high film strength while exhibiting excellent photochromic properties.

The weight average molecular weight Mw of the component (B) is preferably 1,500 to 20,000, and the (meth) acrylic equivalent is preferably 150 to 800. The weight average molecular weight Mw of the component (B) is a value measured by a gel permeation chromatography method (GPC method).

Further, the component (B) preferably contains 10 or more (meth) acrylate groups in one molecule on average, and among them, 10 to 100 (meth) acrylate groups are contained in one molecule. It is preferable, and it is more preferable that 15 to 35 pieces are contained.

In general, silsesquioxane can have various structures such as cage-like, ladder-like, and random, but the component (B) used in the present invention may be a compound having one kind of structure. It can also be used as a mixture of compounds of multiple structures. In the case of a mixture, the total mass of the mixture is regarded as the blending amount of the component (B). Among them, the component (B) is preferably a mixture composed of compounds having a plurality of structures.

Examples of the method for synthesizing the component (B) include cited documents (see Appl. Organometallic. Chem. 2001, p. 683-692) and patent documents (Japanese Patent Laid-Open Nos. 2004-143449, 1999-29640). It can also be manufactured according to the method described in Japanese Patent Publication (Japanese Patent Publication).

The blending amount of the component (B) is determined in 100 parts by mass of the photochromic curable composition in consideration of the hardness and mechanical properties of the obtained photochromic cured product, the photochromic characteristics such as the color development density and the fading speed, and the appearance defect. It is necessary to be 0.01 part by mass or more and less than 10 parts by mass, more preferably 0.02 part by mass or more and less than 10 parts by weight, and further preferably 0.03 part by mass or more and 9 parts by weight or less. It is preferable that the amount is 0.05 parts by mass or more and 7.5 parts by mass or less in consideration of the viscosity and coating property of the photochromic curable composition.

<(C) Photochromic compound>
As the (C) photochromic compound (hereinafter, also referred to as (C) component) used in the present invention, known compounds can be used without any limitation, and these can also be used alone. However, two or more types can be used in combination.

Typical examples of such photochromic compounds are flugide compounds, chromene compounds and spirooxazine compounds. For example, JP-A-2-28154, JP-A-62-288830, WO94 / 22850 pamphlet, It is disclosed in many documents such as the WO96 / 14596 pamphlet.

In the present invention, among known photochromic compounds, indeno [2,1-f] naphtho [1,2-b] pyran skeleton from the viewpoint of photochromic properties such as color development density, initial colorability, durability, and fading speed. It is more preferable to use a chromene compound having a molecular weight of 540 or more, and a chromene compound having a molecular weight of 540 or more is particularly preferably used because it is particularly excellent in color development concentration and fading rate.

The chromen compounds shown below are examples of chromen compounds particularly preferably used in the present invention, but are not limited thereto.

In addition to the above, a photochromic compound having an oligomer chain group in the molecule can also be preferably used. Examples of the photochromic compound having such an oligomer chain group include WO2000 / 015630 pamphlet, WO2004 / 041961 pamphlet, WO2009 / 146509 pamphlet, WO2012 / 149599 pamphlet, WO2012 / 162725 pamphlet, WO2013 / 078086 pamphlet, WO2019. It is disclosed in many documents such as Pamphlet No. 013249 and Pamphlet No. WO2019 / 203205. Among the photochromic compounds having an oligomer chain group in these molecules, those having the oligomer chain group described in WO2019 / 013249 pamphlet and WO2019 / 203205 pamphlet in order to show better photochromic property and durability. It is preferable to use a photochromic compound. The photochromic compound having an oligomer chain group shown below is an example of a compound particularly preferably used in the present invention, but is not limited thereto.

The blending amount of the component (C) is 0.001 part by mass or more and 20 parts by weight or less in 100 parts by mass of the photochromic curable composition, considering the photochromic characteristics such as the color development concentration and the fading rate of the obtained photochromic cured product. It is preferably 0.05 parts by mass or more and 15 parts by weight or less, and further preferably 0.1 parts by mass or more and 10 parts by weight or less.

<(D) Polymerizable monomer other than the above>
The photochromic curable composition of the present invention contains a polymerizable monomer other than the components (A) and (B) (hereinafter, also referred to as (D) polymerizable monomer or (D) component). You may be.

The component (D) is not particularly limited, and known components can be used.

Above all, it is preferable to contain a polyfunctional (meth) acrylate having two or more (meth) acrylate groups in the molecule. Among them, bifunctional (meth) acrylate having two (D1) (meth) acrylate groups in the molecule (hereinafter, also referred to as (D1) bifunctional (meth) acrylate or (D1) component), (D2) ( It is preferable to contain a polyfunctional (meth) acrylate having three or more meta) acrylate groups in the molecule (hereinafter, also referred to as (D2) polyfunctional (meth) acrylate or (D2) component). Further, it can also contain a monofunctional (meth) acrylate having one (D3) (meth) acrylate group (hereinafter, also referred to as (D3) monofunctional (meth) acrylate or (D3) component).
These (D) polymerizable monomers will be described.

((D1) Bifunctional (meth) acrylate)
The photochromic curable composition of the present invention preferably further contains the component (D1). A specific example is shown below. Specifically, the following formula (2) (hereinafter, also referred to as (D1-1) component), the following formula (3) (hereinafter, also referred to as (D1-2) component) and the following formula (4) (hereinafter, also referred to as component). , (Also referred to as component (D1-3))) is suitable. In addition, there is also a bifunctional (meth) acrylate having a urethane bond (hereinafter, also referred to as (D1-4) component). A bifunctional (meth) acrylate component (hereinafter, (D1-5) component) that does not correspond to the (D1-1) component, the (D1-2) component, the (D1-3) component, and the (D1-4) component. Also called.).

These (D) components will be described.

(D1-1) The compound represented by the following formula (2)

(In the equation, R ² and R ³ are hydrogen atoms or methyl groups, respectively, b and c are each independently an integer of 0 or more, and b + c is an integer of 2 or more.)
Specific examples of the compound represented by the above formula (2) are as follows.

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, dimethacrylate consisting of a mixture of polypropylene glycol and polyethylene glycol (two polyethylene and two polyethylene repeating units), polyethylene glycol di. Methacrylate (especially b = 4, c = 0, average molecular weight 330), polyethylene glycol dimethacrylate (especially b = 9, c = 0, average molecular weight 536), polyethylene glycol dimethacrylate (especially b = 14, c = 0, average). Molecular weight 736), tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate (especially b = 0, c = 7, average molecular weight 536), polyethylene glycol diacrylate (especially average molecular weight 258), polyethylene glycol diacrylate (Especially average molecular weight b = 4, c = 0, 308), polyethylene glycol diacrylate (especially b = 9, c = 0, average molecular weight 508), polyethylene glycol diacrylate (especially b = 14, c = 0, average molecular weight). 708), polyethylene glycol methacrylate acrylate (particularly b = 9, c = 0, average molecular weight 522).

(D1-2) The compound represented by the following formula (3)

(In the formula, R ⁴ and R ⁵ are hydrogen atoms or methyl groups, respectively, and
R ⁶ and R ⁷ are hydrogen atoms or methyl groups, respectively, and are
R ⁸ is a hydrogen atom or a halogen atom,
A is -O-, -S-,-(SO ₂ )-, -CO-, -CH _2- ,
-CH = CH-, -C (CH ₃ ) 2-, -C (CH ₃ ) (C ₆ H ₅ )-
Is one of
d and e are integers of 1 or more, respectively, and d + e is an average value of 2 or more and 30 or less. )
The bifunctional (meth) acrylate represented by the above formula (3) is usually obtained in the form of a mixture of molecules having different molecular weights. Therefore, d and e are shown as average values.

Specific examples of the bifunctional (meth) acrylate represented by the above formula (3) include the following bisphenol A di (meth) acrylate.

2,2-Bis [4- (methacryloyloxyethoxy) phenyl] propane (d + e = 2, average molecular weight 452), 2,2-bis [4- (methacryloyloxydiethoxy) phenyl] propane (d + e = 4, average molecular weight) 540), 2,2-bis [4- (methacryloyloxypolyethoxy) phenyl] propane (d + e = 7, average molecular weight 672), 2,2-bis [3,5-dibromo-4- (methacryloyloxyethoxy) phenyl ] Propane (d + e = 2, average molecular weight 768), 2,2-bis (4- (methacryloyloxydipropoxy) phenyl) Propane (d + e = 4, average molecular weight 596), 2,2-bis [4- (acryloyloxy) Diethoxy) phenyl] propane (d + e = 4, average molecular weight 512), 2,2-bis [4- (acryloyloxypolyethoxy) phenyl] propane (d + e = 3, average molecular weight 466), 2,2-bis [4 -(Acryloyloxypolyethoxy) phenyl] propane (d + e = 7, average molecular weight 642), 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (d + e = 10, average molecular weight 804), 2,2 -Bis [4- (methacryloylxipolyethoxy) phenyl] propane (d + e = 17, average molecular weight 1116), 2,2-bis [4- (methacryloylxipolyethoxy) phenyl] propane (d + e = 30, average molecular weight 1684) , 2,2-bis [4- (acryloylxipolyethoxy) phenyl] propane (d + e = 10, average molecular weight 776), 2,2-bis [4- (acryloylxipolyethoxy) phenyl] propane (d + e = 20, Average molecular weight 1216).

(D1-3) The compound represented by the following formula (4)

(In the formula, R ⁹ and R ¹⁰ are hydrogen atoms or methyl groups, respectively, and
f is a number from 1 to 20 on average,
B and B'may be the same or different from each other, and are linear or branched alkylene groups having 2 to 15 carbon atoms, respectively. When a plurality of Bs are present, the plurality of Bs are the same group. It may be a different group. )
The bifunctional (meth) acrylate represented by the above formula (4) can be produced by reacting a polycarbonate diol with (meth) acrylic acid.

Here, examples of the polycarbonate diol used include the following. Specifically, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenization of tetramethylene glycol, and phosgenization of pentamethylene glycol Obtained polycarbonate diol (average molecular weight 500 to 2000), polycarbonate diol obtained by phosgenation of hexamethylene glycol (average molecular weight 500 to 2000), polycarbonate diol obtained by phosgenization of octamethylene glycol (average molecular weight 500 to 2000), Polycarbonate diol obtained by phosgenation with nonamethylene glycol (average molecular weight 500-2000), polycarbonate diol obtained by phosgenation of triethylene glycol and tetramethylene glycol (average molecular weight 500-2000), tetramethylene glycol and hexamethylene Polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation with diglycol, polycarbonate diol (average molecular weight 500-2000) obtained by phosgenation of pentamethylene glycol and hexamethylene glycol, tetramethylene glycol and octamethylene. Polycarbonene diol (average molecular weight 500 to 2000) obtained by phosgenation with glycol, polycarbonate diol (average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, and 1-methyltrimethylene glycol. Examples thereof include polycarbonate diols (average molecular weight 500 to 2000) obtained by phosgenation of (D1-4). The bifunctional (meth) acrylate (D1-4) component having a urethane bond is a reaction product of a polyol and a polyisocyanate. It is typical. Here, examples of the polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-hexamethylene diisocyanate, dimerate diisocyanate, isopropyridenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate or Methylcyclohexane diisocyanate can be mentioned.

On the other hand, examples of the polyol include ethylene oxide having 2 to 4 carbon atoms, propylene oxide, polyalkylene glycol having a repeating unit of hexamethylene oxide, and polyester diol such as polycaprolactone diol. Also, polycarbonate diol, polybutadiene diol, or pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9- Examples thereof include nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, and trimethylolpropane.

Further, a reaction mixture obtained by further reacting a urethane prepolymer obtained by the reaction of these polyisocyanates and a polyol with 2-hydroxy (meth) acrylate, or a reaction in which the diisocyanate is directly reacted with 2-hydroxy (meth) acrylate. Urethane (meth) acrylate and the like, which are mixtures, can also be used.

As bifunctional products, U-2PPA (molecular weight 482), UA-122P (molecular weight 1,100), U-122P (molecular weight 1,100), and Daicel manufactured by Shin Nakamura Chemical Industry Co., Ltd. are commercially available products. Examples thereof include EB4858 (molecular weight 454) manufactured by UCB, TEAI-1000 and TE-2000 manufactured by Nippon Soda Co., Ltd., and CN9014 manufactured by Arkema.

(D1-5) Bifunctional (meth) acrylate not applicable to the above (D1-5) The bifunctional (meth) acrylate not applicable to the above includes (meth) at both ends of an alkylene group which may have a substituent. ) Examples thereof include compounds having an acrylate group. Among them, those having an alkylene group having 6 to 20 carbon atoms are preferable. Specifically, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol diacrylate, Examples thereof include 1,10-decanediol dimethacrylate.

Further, as the bifunctional (meth) acrylate that does not correspond to the above, butadiene di (meth) acrylate represented by the following formula (7) can also be mentioned.

(During the ceremony,
R ¹⁶ and R ¹⁷ are hydrogen atoms or methyl groups, respectively, and are
k, l and m are independently integers of 0 or more, respectively.
Moreover, k + l + m is an integer of 1 or more. )
The bifunctional (meth) acrylate represented by the above formula (7) is not particularly limited, and for example, as commercially available products, butadiene di (BAC-45 manufactured by Osaka Organic Chemical Industry Co., Ltd., CN307 manufactured by Arkema Co., Ltd.) ( Meta) acrylate can be mentioned.

Further, as the bifunctional (meth) acrylate that does not fall under the above, bifunctional (meth) acrylate containing a sulfur atom can also be mentioned. The sulfur atom preferably forms part of a molecular chain as a sulfide group. Specifically, bis (2-methacryloyloxyethylthioethyl) sulfide, bis (methacryloyloxyethyl) sulfide, bis (acryloyloxyethyl) sulfide, 1,2-bis (methacryloyloxyethylthio) ethane, 1,2- Bis (acryloyloxyethyl) ethane, bis (2-methacryloyloxyethylthioethyl) sulfide, bis (2-acryloyloxyethylthioethyl) sulfide, 1,2-bis (methacryloyloxyethylthioethylthio) ethane, 1,2 -Bis (acryloyloxyethylthioethylthio) ethane, 1,2-bis (methacryloyloxyisopropylthioisopropyl) sulfide, 1,2-bis (acryloyloxyisopropylthioisopropyl) sulfide can be mentioned.

In the above (D1-1) component, (D1-2) component, (D1-3) component, (D1-4) component, and (D1-5) component, a single component in each component may be used. It is possible, and a plurality of types described above can be used. When a plurality of types are used, the reference mass of the component (D1) is the total amount of the plurality of types.

((D2) Polyfunctional (meth) acrylate)
The component (D2) includes a compound represented by the following formula (5) (hereinafter, also referred to as (D2-1) component) and a polyfunctional (meth) acrylate having a urethane bond (hereinafter, also referred to as (D2-2) component). ), And the above-mentioned (D2-1) component and the polyfunctional (meth) acrylate (hereinafter, also referred to as (D2-3) component) which does not correspond to the above-mentioned (D2-2) component.

(D2-1) The compound represented by the following formula (5)

(In the formula, R ¹¹ is a hydrogen atom or a methyl group, and
R ¹² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
R ¹³ is a 3- to hexavalent organic group having 1 to 10 carbon atoms (however, it does not include a chain-like organic siloxane group).
g is a number of 0 to 3 on average, and h is a number of 3 to 6. )
As the alkyl group having 1 to 2 carbon atoms represented by R ¹² , a methyl group is preferable. Examples of the organic group represented by R ¹³ include a group derived from a polyol, a 3- to 6-valent hydrocarbon group, and an organic group containing a 3- to 6-valent urethane bond.

Specific examples of the compound represented by the above formula (5) are as follows.

Trimethylolpropane Trimethacrylate, Trimethylolpropane Triacrylate, Tetramethylolmethanetrimethacrylate, Tetramethylolmethanetriacrylate, Tetramethylolmethanetetramethacrylate, Tetramethylolmethanetetraacrylate, Trimethylolpropane Triethylene Glycoltrimethacrylate, Trimethylolpropanetriethylene Glycoltriacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.

(D2-2) The polyfunctional (meth) acrylate (D2-2) component having a urethane bond is obtained by reacting the polyisocyanate compound described in (D1-5) component with a polyol compound, and is obtained in the molecule. It is a compound having three or more (meth) acrylate groups. As commercial products, U-4HA (molecular weight 596, functional group number 4), U-6HA (molecular weight 1,019, functional group number 6), U-6LPA (molecular weight 818, functional group number 6) manufactured by Shin Nakamura Chemical Industry Co., Ltd. , U-15HA (molecular weight 2,300, number of functional groups 15).

(D2-3) The polyfunctional (meth) acrylate (D2-3) component that does not fall under the above is a compound in which the end of the polyester compound is modified with a (meth) acrylate group. Various commercially available polyester (meth) acrylate compounds can be used depending on the molecular weight of the polyester compound as a raw material and the modification amount of the (meth) acrylate group. Specifically, tetrafunctional polyester oligomers (molecular weight 2,500 to 3,500, molecular weight CB, EB80, etc.), hexafunctional polyester oligomers (molecular weight 6,000 to 8,000, molecular weight CB, EB450, etc.) , 6-functional polyester oligomer (molecular weight 45,000 to 55,000, Dycel UCB, EB1830, etc.), 4-functional polyester oligomer (particularly, Daiichi Kogyo Seiyaku Co., Ltd., GX8488B, etc. with a molecular weight of 10,000) and the like. .. As commercial products, CN2300, CN2301, CN2302, CN2303, CN2304, SB401, SB402, SB404, SB500E50, SB500K60, SB510E35, SB520E35, SB520M35, CN550, CN551, Shin Nakamura Chemical Industry Co., Ltd. -DPH-6E, A-DPH-12E, A-DPH-6EL, A-DPH-12EL, A-DPH-6P and the like can also be mentioned.

By using the component (D2) ((D2-1) component, (D2-2) component, (D2-3) component) exemplified above, the crosslink density is improved by polymerization, and the surface of the obtained cured product is obtained. Hardness can be increased. Therefore, in particular, in the case of a photochromic cured product (laminated product) obtained by the coating method, it is preferable to contain the component (D2). In particular, it is preferable to use the component (D2-1) among the components (D2).

As the above (D2-1) component, (D2-2) component, and (D2-3) component, a single component in each component may be used, or a plurality of types described above may be used. You can also. When a plurality of types are used, the reference mass of the component (D2) is the total amount of the plurality of types.

((D3) monofunctional (meth) acrylate)
Examples of the component (D3) include compounds represented by the following formula (6).

(In the formula, R ¹⁴ is a hydrogen atom or a methyl group, and
R ¹⁵ is a hydrogen atom, a methyldimethoxysilyl group, a trimethoxysilyl group, or a glycidyl group.
i is an integer from 0 to 10 and
j is an integer from 0 to 20. )
Specific examples of the compound represented by the above formula (6) are as follows.

Methoxypolyethylene glycol methacrylate (especially average molecular weight 293), methoxypolyethylene glycol methacrylate (especially average molecular weight 468), methoxypolyethylene glycol acrylate (especially average molecular weight 218), methoxypolyethylene glycol acrylate, (especially average molecular weight 454), stearyl methacrylate, lauryl methacrylate. , Methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, glycidyl methacrylate, tridecyl acrylate, tridecyl methacrylate, isooctyl acrylate, iso Octyl methacrylate, isodecyl acrylate, isodecyl methacrylate.

The blending amount of the component (D) is 0 parts by mass in 100 parts by mass of the photochromic curable composition in consideration of the hardness and mechanical properties of the obtained photochromic cured product, and the photochromic characteristics such as the color development concentration and the fading rate. It is preferably 99 parts by weight or less, more preferably 10 parts by mass or more and 99 parts by weight or less, and further preferably 50 parts by mass or more and 99 parts by weight or less.

Further, the component (D) preferably contains the component (D1), the component (D2), and, if necessary, the component (D3). The compounding ratio of each component is 30 to 80% by mass of the (D1) component and the (D2) component in consideration of the hardness, mechanical properties, and photochromic properties such as the color development density and the fading speed of the obtained photochromic cured product. It is preferably 10 to 60% by mass and 0 to 20% by mass of the (D3) component.

<(E) Compound having an organic siloxane group>
The photochromic curable composition of the present invention may further contain (E) a compound having an organic siloxane group (hereinafter, also referred to as (E) component).

The component (E) is not particularly limited, and known components can be used, and a compound having a chain-like organic siloxane group is particularly preferable.

Among them, as the organic group, a chain-like organic siloxane group having an alkyl group, an aryl group or a polymerizable group is preferable, and (E1) a silsesquioxane compound having a chain-like organic siloxane group (hereinafter, (E1)). (Also also referred to as a component), (E2) a bifunctional (meth) acrylate having two chain-like organic siloxane groups and (meth) acrylate groups in the molecule (hereinafter, also referred to as (E2) component), (E3). A monofunctional (meth) acrylate having one chain-like organic siloxane group and one (meth) acrylate group (hereinafter, also referred to as (E3) component) is preferable.
These (E) components will be described.

(E1) The silsesquioxane compound (E1) having a chain-like organic siloxane group is a compound represented by the following formula (8).

(In the formula, n is the degree of polymerization, which is an integer of 3 to 100, and a plurality of R ^18s may be the same or different from each other, and at least one organic group containing a chain-like organic siloxane group. Is.)
Here, R ¹⁸ is an organic group containing at least one chain-like organic siloxane group. The organic group of the chain organic siloxane group is preferably an alkyl group, an aryl group or a polymerizable group, and the alkyl group and the aryl group are an unsubstituted or fluorine-substituted alkyl group having 1 to 20 carbon atoms. , Cycloalkyl groups, arylalkyl groups, and groups selected from aryl groups are preferred. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an octyl group and the like, and the methyl group is particularly preferable. preferable. Examples of the aryl group include a phenyl group, a 4-trifluoromethylphenyl group, and a 4-fluorophenyl group. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 15 carbon atoms. Examples of the polymerizable group include a (meth) acrylate group.

Further, R ¹⁸ may have another group as long as at least one is a chain-like organic siloxane group, and may have an organic group including, for example, a (meth) acrylate group. Examples of the organic group containing the (meth) acrylate group include a (meth) acrylate group, a (meth) acryloxypropyl group, a (3- (meth) acryloxipropyl) dimethylsiloxy group and the like. Among them, the (meth) acryloxypropyl group is particularly preferable because it is easy to obtain a raw material at the time of producing the component (E) and it is possible to obtain high film strength while exhibiting excellent photochromic properties.

The weight average molecular weight Mw of the component (E1) is preferably 500 to 5,000, and the (meth) acrylic equivalent when containing a (meth) acrylate group is preferably 100 to 5,000. The weight average molecular weight Mw of the component (E1) is a value measured by a gel permeation chromatography method (GPC method).

In general, silsesquioxane can have various structures such as cage-like, ladder-like, and random, but the (E1) component used in the present invention may be a compound having one kind of structure. It can also be used as a mixture of compounds of multiple structures. In the case of a mixture, the total mass of the mixture is regarded as the blending amount of the component (E1). Among them, the component (E1) is preferably a mixture composed of compounds having a plurality of structures.

Examples of the bifunctional (meth) acrylate (E2) component having two (E2) chain-like organic siloxane groups and two (meth) acrylate groups in the molecule include compounds represented by the following formula (9).

(In the formula, R ¹⁹ to R ²⁴ are independently unsubstituted or fluorinated monovalent hydrocarbon groups, preferably unsubstituted or fluorinated alkyl groups having 1 to 20 carbon atoms, cyclo. A group selected from an alkyl group, an arylalkyl group, and an aryl group, wherein the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. , Se-butyl group, pentyl group, octyl group are preferable, and methyl group is particularly preferable.
o is an integer of 1 or more, preferably an integer of 1 to 20.
R ²⁵ and R ²⁶ are hydrogen atoms or methyl groups. )
The component (E2) represented by the above formula (9) is not particularly limited, and is, for example, X-22-164, X-22-164AS, X-22-A manufactured by Shin-Etsu Chemical Co., Ltd., which are the following commercially available products. 164A, X-22-164B, X-22-164C, X-22-164E, X-22-2245 and the like can be used.

Examples of the monofunctional (meth) acrylate (E3) component having one (E3) chain-like organic siloxane group and one (meth) acrylate group include compounds represented by the following formula (10).

(In the formula, R ²⁷ to R ³³ are independently unsubstituted or fluorinated monovalent hydrocarbon groups, preferably unsubstituted or fluorinated alkyl groups having 1 to 20 carbon atoms, cyclo. A group selected from an alkyl group, an arylalkyl group, and an aryl group, wherein the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. The sec-butyl group, pentyl group and octyl group are preferable, and the methyl group is particularly preferable.
p is an integer of 1 or more, preferably an integer of 1 to 20.
R ³⁴ is a hydrogen atom or a methyl group. )
The component (E3) represented by the above formula (10) is not particularly limited, and is, for example, X-22-174ASX, X-22-174BX, KF-2012 manufactured by Shin-Etsu Chemical Co., Ltd., which are the following commercially available products. X-22-2426, X-22-2404 and the like can be used.

The blending amount of the component (E) is determined in 100 parts by mass of the photochromic curable composition in consideration of the hardness and mechanical properties of the obtained photochromic cured product, the photochromic characteristics such as the color development density and the fading speed, and the appearance defect. It is preferably 0.0001 parts by mass or more and 15 parts by weight or less, more preferably 0.0005 parts by mass or more and 12 parts by weight or less, and further preferably 0.001 parts by mass or more and 10 parts by weight or less. It is preferable that the amount is 0.005 parts by mass or more and 5 parts by mass or less in consideration of the viscosity and coating property of the photochromic curable composition.

<Other additive ingredients>
The photochromic curable composition used in the present invention includes various formulations known per se, such as polymerization initiators, UV absorbers, infrared absorbers, UV stabilizers, and oxidations, as long as the effects of the present invention are not impaired. Various stabilizers such as inhibitors, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments and fragrances, additives, solvents, leveling agents and the like can be blended as needed.

The amount of the other additive component used is not particularly limited as long as the effect of the present invention is not impaired, but is usually 0.001 to 10 parts by mass, particularly 0.001 to 10 parts by mass with respect to 100 parts by mass of the photochromic curable composition. The range is 0.01 to 7.5 parts by mass, and further 0.05 to 6 parts by mass.

(Polymer initiator)
The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator, and specific examples thereof are as follows.

As a thermal polymerization initiator,
Diacyl peroxide; benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyle peroxide, lauroyl peroxide, acetyl peroxide,
Peroxyester; t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate,
Percarbonate; diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate,
Azo compounds; azobisisobutyronitrile and the like can be mentioned.

As a photopolymerization initiator,
Acetophenone compounds; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one,
α-Dicarbonyl compounds; 1,2-diphenylethandione, methylphenylglycoxylate,
Acylphosphine oxide compounds; 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinic acid methyl ester, 2,6- Dichlorbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide,
Can be mentioned.

When a photopolymerization initiator is used, a known polymerization curing accelerator such as a tertiary amine can also be used in combination.

(UV stabilizer)
Ultraviolet stabilizers are preferably used because they can improve the durability of photochromic compounds. As such ultraviolet stabilizers, hindered amine light stabilizers, hindered phenol antioxidants, sulfur-based antioxidants 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-77 manufactured by Asahi Denka Kogyo Co., Ltd. , LA-82, LA-87, 2,6-di-t-butyl-4-methyl-phenol ethylene bis (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, 254 manufactured by Ciba Specialty Chemicals.

The amount of the ultraviolet stabilizer to be used is not particularly limited as long as the effect of the present invention is not impaired, but is 0.001 to 10 parts by mass, particularly 0.01 with respect to 100 parts by mass of the photochromic curable composition. It is in the range of ~ 3 parts by mass. In particular, when a hindered amine light stabilizer is used, 0.5 per mole of the photochromic compound is used to prevent color shift in the adjusted color tone as a result of differences in the effect of improving durability depending on the type of the photochromic compound. The amount is preferably 30 mol, more preferably 1 to 20 mol, still more preferably 2 to 15 mol.

Further, the photochromic curable composition of the present invention may contain a non-reactive silicone oil. The non-reactive silicone oil has an effect of preventing the adhesive of the scratch-preventing protective film from adhering to the surface of the photochromic-cured body when the scratch-preventing protective film is attached to the surface of the photochromic cured product of the present invention. Can be given. The non-reactive silicone oil is not particularly limited, and is commercially available KF-351A, KF-352A, FL-5, X-22-821, X-22-822, KF-421 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-414 and the like can be used.

The SP value of the photochromic curable composition is not particularly limited, but is preferably 5.0 to 15.0 and more preferably 6.0 to 14.0 in consideration of coating properties. It is preferably 7.0 to 13.0, more preferably 8.0 to 12.0, and particularly preferably 8.0 to 12.0.

<Photochromic cured body and laminated body>
The photochromic cured product of the present invention can be obtained by kneading each component to prepare the photochromic curable composition and curing the photochromic cured product. It is carried out by a radical polymerization reaction by irradiation with active energy rays such as β-rays, γ-rays and LEDs, heat, or a combination of both. That is, an appropriate effect means may be adopted depending on the type of the polymerizable monomer and the polymerization curing accelerator to be used and the form of the photochromic cured product formed. In the present invention, when the photochromic cured product is formed by the coating method described later, it is preferable to adopt photopolymerization because a uniform film thickness can be obtained.

In the present invention, when the photochromic curable composition is photopolymerized, among the curing conditions, UV intensity particularly affects the properties of the obtained photochromic cured product. This illuminance condition cannot be unconditionally limited because it is affected by the type and amount of the photopolymerization initiator and the type of the polymerizable monomer, but generally UV light of 10 to 500 mW / cm ² is emitted at a wavelength of 365 nm. It is preferable to select the conditions so that the light is irradiated in 0.1 to 5 minutes.

When a photochromic laminate is obtained by a laminating method (coating method), a photochromic curable composition is used as a coating liquid, and the coating liquid is applied to the surface of an optical base material such as a lens base material by spin coating or dipping. A photochromic layer made of a photochromic cured product is laminated on the surface of the optical substrate by coating and then polymerizing and curing by UV irradiation or heating in an inert gas such as nitrogen.

When the photochromic laminate is formed on the surface of the optical substrate by the above-mentioned lamination method (coating method), the surface of the optical substrate is previously chemically treated with an alkaline solution, an acid solution, or the like, corona discharge, or plasma. By performing physical treatment such as discharge and polishing, the adhesion between the photochromic laminate and the optical substrate can be improved. Of course, it is also possible to provide a transparent adhesive resin layer on the surface of the optical base material.

The above-mentioned photochromic curable composition of the present invention can exhibit excellent photochromic properties such as color development density and fading speed, and can impart photochromic properties without reducing characteristics such as mechanical strength. It is effectively used for manufacturing an optical substrate, for example, a photochromic lens. Although the coating method has been described above, the photochromic curable composition of the present invention can also produce a photochromic cured product by cast polymerization.

Further, the photochromic layer and the photochromic cured product formed by the photochromic curable composition of the present invention can be dyed with a dye such as a disperse dye, a silane coupling agent, silicon, zirconium, antimony, aluminum, depending on the application. Preparation of a hard coat film using a hard coat agent containing a sol as a main component such as tin and tungsten, thin film formation by vapor deposition of metal oxides such as SiO ₂ , TiO ₂ and ZrO ₂ , and application of an organic polymer. It is also possible to perform post-processing such as antireflection treatment and antistatic treatment with the thin film of.

From the viewpoint of improving the appearance of the photochromic cured product, the Vickers hardness of the photochromic cured product is preferably 3 or more and 8 or less, more preferably 3.5 or more and 7.5 or less, and 4 or more and 7 or less. Is particularly preferable.

The photochromic cured product of the present invention may be attached with a scratch-preventing protective film for the purpose of protecting the surface.

When the scratch-preventing protective film is attached to the surface of the photochromic cured product as described above, the adhesive of the scratch-preventing protective film adheres to the surface of the cured product, and the cured product has a wrinkle-like appearance due to the adhesive. From the viewpoint of improving the occurrence of defects, it is preferable that the SP values of the photochromic curable composition and the pressure-sensitive adhesive have a certain difference.

The upper limit of the difference in SP value between the photochromic curable composition and the adhesive for the scratch prevention protective film is not particularly limited, but is preferably 5 or less from the viewpoint of adhesiveness. The difference in SP value between the photochromic curable composition and the adhesive for the scratch prevention protective film is preferably 0.05 to 5, more preferably 0.075 to 4, and 0.1 to 3. Is particularly preferred. The SP (solubility parameter) value here is an index related to the polarity of the substance and is empirically related to the mutual solubility of many chemical species. This SP value is calculated according to the description of the solubility parameter δ in the Chemical Society of Japan edited by Chemistry Handbook Application (1973) and Polymer Handbook (4th edition, Johannes Brandrup and E.H. Immunogut). can do.

Further, when the scratch prevention protective film is attached to the photochromic cured product, the photochromic cured product has a high contact angle with ethylene glycol from the viewpoint of improving the appearance defect that the adhesive of the scratch prevention protective film adheres to the surface of the cured product. It is more preferable, and it is preferable that the temperature is 50 degrees or higher. The upper limit of the contact angle between the photochromic cured product and ethylene glycol is not particularly limited as long as it is 50 degrees or more, but it is preferably less than 180 degrees. The value of 50 degrees or more is sufficient to reduce the appearance defect, and the contact angle is more preferably 50 degrees or more and 150 degrees or less, and further preferably 50 degrees or more and 90 degrees or less.

Further, the present invention is a photoclock curable composition containing (C) a photochromic compound.
(I) The SP value of photochromic curability is 8.0 to 12.0,
(II) The difference between the SP value of the pressure-sensitive adhesive for the scratch prevention protective film attached to the surface of the photochromic cured product obtained by curing the photochromic curable composition and the SP value of the photochromic curable composition is 0. 05-5,
(III) The contact angle of the photochromic cured product obtained by curing the photochromic curable composition with ethylene glycol is 50 degrees or more and less than 180 degrees.
(IV) The Vickers hardness of the photochromic cured product obtained by curing the photochromic curable composition is 3 or more and 8 or less.
Also provided is a photochromic curable composition.

The photochromic curable composition is not particularly limited as long as the above is satisfied, and may be a composition other than the combination of the component (A) and the component (B) other than the component (C) described above.

Above all, by using the above-mentioned component (E), the photochromic curable composition can be suitably obtained. That is, the photochromic curable composition preferably contains (E) a compound having an organic siloxane group, and the compound having (E) an organic siloxane is 0.0001 in 100 parts by mass of the photochromic curable composition. The amount is preferably 1 part by mass or more and 15 parts by mass or less, and the compound having an organic siloxane group is preferably a compound having an alkyl group and / or a polymerizable group as an organic group, and at least one of the polymerizable groups. It is preferable that one is a (meth) acrylate group.

The SP value of the photochromic curable composition is 8.0 to 12.0, preferably 8.5 to 12.0, and preferably 9.0 to 11.5 from the viewpoint of coating property. More preferred.

Further, the difference between the SP value of the adhesive for the scratch prevention protective film to be attached to the surface of the photochromic cured product obtained by curing the photochromic curable composition and the SP value of the photochromic curable composition is the scratch prevention. From the viewpoint of improving the wrinkle-like appearance defect caused by the adhesive on the photochromic cured product due to the adhesive of the protective film for use adhering to the surface of the cured product, the value is 0.05 to 5, which is 0. .075 to 4 is more preferable, and 0.1 to 3 is particularly preferable. The SP (solubility parameter) value here is an index related to the polarity of the substance and is empirically related to the mutual solubility of many chemical species. This SP value is calculated according to the description of the solubility parameter δ in the Chemical Society of Japan edited by Chemistry Handbook Application (1973) and Polymer Handbook (4th edition, Johannes Brandrup and E.H. Immunogut). can do.

The contact angle of the photochromic cured product obtained by curing the photochromic curable composition with ethylene glycol is 50 degrees from the viewpoint of improving the appearance defect that the adhesive of the protective film for scratch prevention adheres to the surface of the photochromic cured product. It is more preferably less than 180 degrees, more preferably 50 degrees or more and 150 degrees or less, and further preferably 50 degrees or more and 90 degrees or less.

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. Each of the above components, evaluation method, etc. is as follows.

(A) Component RX-1: Polyrotaxane having a (meth) acrylate group (A polyrotaxane having a (meth) acrylate group satisfying the following characteristics was synthesized according to the method described in International Publication No. WO 2018/030275.
Weight average molecular weight Mw (GPC) of polyrotaxane having (meth) acrylate group; 180,000
Acrylate group modification rate: 80 mol%
Percentage of OH groups remaining in the side chain; 20 mol%)
Axial molecule; linear polyethylene glycol (PEG) with a molecular weight of 11,000
Inclusion ring; α-cyclodextrin (α-CD) introduction rate 0.25
End of shaft molecule; side chain introduced into the encapsulated ring sealed with adamantane; (average) molecular weight of the side chain is about 500

(B) Component PMS-1: Sylsesquioxane having a (meth) acrylate group synthesized by the following method (synthesis of PMS1)
To 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate, 248 ml of ethanol and 54 g (3.0 mol) of water were added, 0.20 g (0.005 mol) of sodium hydroxide was added as a catalyst, and the reaction was carried out at 30 ° C. for 3 hours. I let you. After confirming the disappearance of the raw materials, the mixture was neutralized with dilute hydrochloric acid, 174 ml of toluene, 174 ml of heptane, and 174 g of water were added, and the aqueous layer was removed. Then, the organic layer was washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain silsesquioxane (PMS1) used in the present invention. From ¹ H-NMR, it was confirmed that the raw material was completely consumed. Moreover, it was confirmed from ²⁹ Si-NMR that it was a mixture of cage-like structure, ladder-like structure and random structure.

The acidic component contained in silsesquioxane (PMS1) used in the present invention was evaluated by quantifying the acid value by performing the following titration.

A 0.1 mol / L potassium hydroxide alcohol solution (ethanolic) solution (hereinafter referred to as a measuring solution) was set in a 2 ml microburette to prepare a stirrer. Using a measuring cylinder, 50 ml each of ethanol and toluene were precisely weighed, placed in a 200 ml beaker, and stirred and mixed with a stirrer. Three drops of phenolphthalein solution were added, and the titration solution was used for dry titration. 20 g of the sample was put into the solution after the air titration, and the mixture was stirred and mixed with a stirrer. Further, 3 drops of a phenolphthalein solution was added, and a sample titration was performed with a titration solution to obtain a titration amount. The acid value was calculated based on the following formula.

Acid value (mgKOH / g) = Titration (ml) x Titration solution f x 5.6 / Sample amount (g)
Here, f indicates the factor of the titrant obtained by using the standard hydrochloric acid solution. The f of the N / 10 potassium hydroxide alcohol solution used in the above method was 0.094. The sample amount is the weight of silsesquioxane contained in the sample.

The acid value of PMS1 measured according to this method was 1.1 mgKOH / g.

The molecular weight distribution of silsesquioxane (PMS1) used in the present invention was measured by gel permeation chromatography (GPC method).

A liquid chromatograph device (manufactured by Japan Waters Corp.) was used as the device. The columns include Shodex GPC KF-802 (exclusion limit molecular weight: 5000, manufactured by Showa Denko KK), Shodex GPC GPC KF802.5 (exclusion limit molecular weight: 20000, manufactured by Showa Denko KK) and Shodex GPC KF-803 (excluded). The limit molecular weight: 70,000, manufactured by Showa Denko KK) was used.

Further, tetrahydrofuran was used as the developing solution, and the measurement was carried out under the conditions of a flow rate of 1 ml / min and a temperature of 40 ° C. When polystyrene was used as a standard sample and the weight average molecular weight was determined by comparative conversion, the weight average molecular weight of PMS1 was 4800.

(C) Component PC1: Compound represented by the following formula

PC2: A compound represented by the following formula synthesized by the method described in Japanese Patent Application No. 2017/213247 and the like.

PC3: A compound represented by the following formula in which a photochromic compound is bonded to both ends of a polypropylene glycol chain having a molecular weight of 2000 synthesized by the method described in WO2012 / 149599.

(D) component (D1-1) component;
9G: Polyethylene glycol dimethacrylate (average difference of ethylene glycol chains 9, average molecular weight 536)
14G; Polyethylene Glycol Dimethacrylate (Average Chain Length 14 of Ethylene Glycol Chain, Average Molecular Weight 736)
(D1-3) component;
A-400; Polyethylene glycol diacrylate (average chain length of ethylene glycol chain 9, average molecular weight 508)
(D1-5) component;
PBA; polybutadiene diacrylate (CN307)
(D2-1) component;
TMPT; trimethylolpropane trimethacrylate D-TMP; dimethylolpropane tetraacrylate (D2-3) component;
DPH; A-DPH-6P
HBA; polyester acrylate (CN2300)
(D3) component;
SI-1: γ-methacryloyloxypropyltrimethoxysilane GMA: glycidyl methacrylate STM; stearyl methacrylate

(E) Component (E1) Component: A SI-20 (AC-SQ SI-20, manufactured by Toagosei Co., Ltd.); Sylsesquioxane (E2) component having an acryloxypropyl group and a polydimethylsiloxane group; X- 22-164A (manufactured by Shin-Etsu Chemical Co., Ltd.)
(E3) Ingredient; X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Polymer initiator)
CGI1: Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (trade name: Omnirad819, manufactured by IGM) (polymerization initiator)
CGI2: 1-Hydroxycyclohexylphenyl ketone (trade name: Omnirad184, manufactured by IGM) (polymerization initiator)

(Other additive ingredients)
HALS: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508) (ultraviolet stabilizer)
HP: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Ciba Specialty Chemicals, Irganox245) (stabilizer)
FZ2110: (Product name: FZ2110, manufactured by Toray Dow Corning Co., Ltd.) (Leveling agent)
L7001: (Product name: L7001, manufactured by Toray Dow Corning Co., Ltd.) (Leveling agent)

<Example 1>
Regarding the preparation of the photochromic curable composition and the preparation / evaluation of the photochromic cured product (photochromic cured product), each component was sufficiently mixed according to the following formulation to prepare a photochromic curable composition.
Prescription;
(Photochromic curable composition)
(A) component; RX-1 3 parts by mass (B) component; PMS-1 0.015 parts by mass (C) component; PC1 2 parts by mass (D) component;
(D1-1) component; 9G 40 parts by mass (D1-2) component; A-400 18.485 parts by mass (D2-1) component; TMPT 30 parts by mass (D3) component; SI-1 5.5 parts by mass , GMA 1 part by mass Other additive components:
(Initiator); 0.3 parts by mass of CGI-1; 0.3 parts by mass of CGI-2 (Stabilizer); 3 parts by mass of HALS, 1 part by mass of HP (Preparation and evaluation of photochromic laminate (photochromic cured product)) )
Using the photochromic curable composition, a photochromic laminate was obtained by a lamination method. The curing method is shown below.

First, a thiourethane-based plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was prepared as an optical substrate. This thiourethane-based plastic lens was previously subjected to alkaline etching at 50 ° C. for 5 minutes using a 10% aqueous sodium hydroxide solution, and then sufficiently washed with distilled water.

Using a spin coater (1H-DX2, manufactured by MIKASA), a moisture-curable primer (product name; TR-SC-P, manufactured by Tokuyama Co., Ltd.) was applied to the surface of the above plastic lens at a rotation speed of 70 rpm for 15 seconds. Then, it was coated at 1000 rpm for 10 seconds. Then, about 2 g of the photochromic composition obtained above was spin coated at a rotation speed of 60 rpm for 40 seconds and then at 600 rpm for 10 to 20 seconds so that the film thickness of the photochromic coating layer became 40 μm.

The lens coated with the coating agent on the surface was irradiated with light for 90 seconds using a metal halide lamp having an output of 200 mW / cm ² in a nitrogen gas atmosphere to cure the coating film. After that, it was further heated at 110 ° C. for 1 hour to prepare a photochromic laminate having a photochromic layer.

(Evaluation methods)
(Photochromic)
Using the obtained photochromic optical article as a sample, a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd. was passed through an aeromas filter (manufactured by Corning Inc.) at 20 ± 1 ° C., and the photochromic optical article was used. The photochromic property was measured by irradiating the surface with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² for 120 seconds to develop a color.
-Maximum absorption wavelength (λmax):
This is the maximum absorption wavelength after color development obtained 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.
-Color density {ε (120) -ε (0)}:
The 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.
Fading speed [t1 / 2 (sec.)]:
The time required for the absorbance of the sample at the maximum absorption wavelength to decrease to 1/2 of {ε (120) -ε (0)} when the irradiation of light is stopped after irradiation with light for 120 seconds. It can be said that the shorter this time is, the better the photochromic property is.

(Appearance, etc.)
-Evaluation of appearance (orange peel, cracks, wrinkle defects) The obtained photochromic optical article was observed and evaluated with an optical microscope and a lighting device (QC X75, manufactured by Valvetronics). For wrinkle defects, Blue Film (HYN-06) was attached to the obtained photochromic optical article and heated at 70 ° C. for 1 hour. The photochromic optical article after the film was peeled off was observed and evaluated with an optical microscope and a lighting device (QC X75, manufactured by Valvetronics). The evaluation criteria are shown below.
A: Uniform and no appearance defects B: Very slight appearance defects C: Partial appearance defects D: Overall appearance defects

(Adhesion)
It was carried out by a cross-cut tape test according to JISD-0202. That is, using a cutter knife, cuts are made on the surface of the obtained photochromic optical article at 1 mm intervals to form 100 squares. A cellophane adhesive tape (cellotape manufactured by Nichiban Co., Ltd. (registered trademark)) was strongly attached onto the cellophane adhesive tape, and then the cells were peeled off by pulling them at a stretch in the 90 ° direction from the surface, and then the squares on which the photochromic optical article remained were evaluated.

(Contact angle with ethylene glycol)
Using an automatic contact angle meter DM500 (manufactured by Kyowa Surface Chemistry Co., Ltd.) for the photochromic laminate, the droplets formed when ethylene glycol (2.0 μl) was dropped onto the photochromic layer were photochromic 5 seconds after the dropping. The contact angle of the laminate with respect to ethylene glycol was measured 5 times, and the average value was used as the result.

(Vickers hardness)
The Vickers hardness was measured using a Micro Vickers hardness tester PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A quadrangular pyramid diamond indenter was used as the indenter, and the measurement was performed under the conditions of a load of 10 gf and an indenter holding time of 30 seconds. The measurement result was shown by the average value of a total of 3 times excluding the first value having a large measurement error after performing the measurement 4 times in total.

(SP value evaluation)
The SP value of the photochromic curable composition to be used and the adhesive on the scratch prevention protective film (trade name: HYN-06) are described in the Chemical Society of Japan (Chemical Handbook Application Edition) (1973) and Polymer Handbook (4th). It was calculated and evaluated according to the description of the solubility parameter δ in the edition, Johannes Brandrup and E.H. Polymergut ed., 1998).

<Examples 2 to 19>
A photochromic curable composition was prepared in the same manner as in Example 1 except that each component shown in Table 1 or 3 was used, and a photochromic laminate was prepared in the same manner as in Example 1 and evaluated. rice field. The evaluation results are shown in Table 2 or Table 4.

<Comparative Examples 1 to 4>
A photochromic curable composition was prepared in the same manner as in Example 1 except that each component shown in Table 1 or 3 was used, and a photochromic laminate was prepared in the same manner as in Example 1 and evaluated. rice field. The evaluation results are shown in Table 2 or Table 4.

1: Polyrotaxane 2: Shaft molecule 3: Cyclic molecule 4: Bulky terminal group 5: Side chain

Claims (16)

(A) In a polyrotaxane compound having a complex molecular structure consisting of an axial molecule and a plurality of cyclic molecules enclosing the axial molecule and having a side chain having a hydroxyl group at the terminal introduced into the cyclic molecule, the side chain. Polyrotaxane compound in which the hydroxyl group of the above is modified with a compound having a polymerizable group in an amount of 1 mol% or more and less than 100 mol%.
(B) A polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing silicon,
and,
(C) Photochromic compound,
A photoclock curable composition comprising:
(B) A photochromic curable composition in which the polymerizable monomer is 0.01 parts by weight or more and less than 10 parts by weight in 100 parts by mass of the photochromic curable composition. The photochromic curable composition according to claim 1, wherein the polymerizable monomer having a bifunctional or higher functional (meth) acrylate group containing (B) silicon is silsesquioxane having a (meth) acrylate group. The photochromic curable composition according to claim 1, wherein the polymerizable group of the (A) polyrotaxane compound is a (meth) acrylate group. The photochromic curable composition according to claim 1, wherein the cyclic molecule of the (A) polyrotaxane compound is a cyclodextrin ring. The photochromic curable composition according to claim 1, wherein the shaft molecule of the polyrotaxane compound (A) is formed of polyethylene glycol and adamantyl groups are bonded to both ends of the shaft molecule. The photochromic curable composition according to claim 1, wherein the side chain having a hydroxyl group at the terminal introduced into the (A) polyrotaxane compound is introduced by a lactone-based compound. The photochromic curable composition according to claim 1, wherein the silsesquioxane has a weight average molecular weight of 1,500 to 20,000. Further, it is claimed that the compound (E) having an organic siloxane group is contained, and the compound having the (E) organic siloxane group is 0.0001 part by mass or more and 15 parts by mass or less in 100 parts by mass of the photochromic curable composition. Item 6. The photochromic composition according to any one of Items 1 to 8. The photochromic curable composition according to claim 11, wherein the compound having the organic siloxane group (E) is a compound having an alkyl group and / or a polymerizable group as an organic group. A photochromic cured product obtained by curing the photochromic curable composition according to any one of claims 1 to 9.
A photochromic laminate in which the cured product according to claim 10 is laminated on an optical substrate. (C) A photoclock curable composition containing a photochromic compound.
(I) The SP value of the photochromic curable composition is 8.0 to 12.0,
(II) The difference between the SP value of the adhesive for the scratch prevention protective film attached to the surface of the photochromic cured product obtained by curing the photochromic curable composition and the SP value of the photochromic curable composition is 0. .05-5,
(III) The contact angle of the photochromic cured product obtained by curing the photochromic curable composition with ethylene glycol is 50 degrees or more and less than 180 degrees.
(IV) The Vickers hardness of the photochromic cured product obtained by curing the photochromic curable composition is 3 or more and 8 or less.
A photochromic curable composition that is. Further, it is claimed that the compound (E) having an organic siloxane group is contained, and the compound having the (E) organic siloxane group is 0.0001 part by mass or more and 15 parts by mass or less in 100 parts by mass of the photochromic curable composition. Item 12. The photochromic curable composition according to Item 12. The photochromic curable composition according to claim 11, wherein the compound having the organic siloxane group (E) is a compound having an alkyl group and / or a polymerizable group as an organic group. A photochromic cured product obtained by curing the photochromic curable composition according to any one of claims 12 to 14. A photochromic laminate in which the cured product according to claim 15 is laminated on an optical substrate.

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