JP2013072000A - Photochromic curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic curable composition capable of obtaining a photochromic eyeglasses lens which can obtain a coating layer having enough hardness without generation of a scratch during a step of processing a lens, and which has excellent photochromic properties such as high color-developing density, high fading rate and high repeating durability.SOLUTION: This photochromic curable composition includes a polymerizable monomer (I), which has a silsesquioxane backbone of a cage structure; at least one bonding group selected from among a urethane bond, a thiourethane bond and a urea bond; and a radical polymerizable group within a molecule, as well as a photochromic compound (II).

Description

  The present invention relates to a novel curable composition useful in producing an optical article having photochromic properties.

  Photochromic glasses are ordinary glasses that are colored and function as sunglasses when they are exposed to light containing ultraviolet rays such as sunlight, and the lenses quickly color and function as sunglasses. In recent years, the demand has increased.

  As for the photochromic lens, a plastic lens is particularly preferred from the viewpoint of lightness and safety. Such a photochromic property is generally imparted to a plastic lens by combining it with an organic photochromic compound. As a composite method, a method of impregnating a photochromic compound on the surface of a lens that does not have photochromic properties (hereinafter referred to as an impregnation method), or by dissolving a photochromic compound in a polymerizable monomer and polymerizing it, A method for directly obtaining a photochromic lens (hereinafter referred to as a kneading method) is known.

  In addition to these methods, a method of providing a coating layer having photochromic properties (hereinafter also referred to as a photochromic coating layer) on the surface of a plastic lens using a coating agent containing a photochromic compound (hereinafter also referred to as a photochromic coating agent). (Hereinafter referred to as a coating method) is also known.

  In general, in order to obtain good photochromic properties, it is necessary to soften the lens substrate or the coating layer so that the conformational change of the photochromic compound occurs smoothly in the lens substrate or in the coating layer. In particular, when a compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton that exhibits excellent performance as a photochromic compound is used, the tendency is remarkable. Therefore, compared with plastic lenses that do not have photochromic properties, in the process of processing the lens, such as the process of polishing the back surface of the lens to obtain the desired power and the process of trimming the outer periphery to match the frame mold The photochromic lens has a problem that the lens substrate or the coating layer is easily damaged.

  In order to solve the above problem, a technique for increasing the hardness of a lens using a silsesquioxane compound is known. For example, a method for producing a photochromic lens by polymerizing and curing a composition in which a silsesquioxane compound having a radical polymerizable group, a polyurethane prepolymer represented by urethane (meth) acrylate, and a photochromic compound are mixed (Patent Document 1). See).

  However, according to the study by the present inventors, it is considered that it depends on the type and ratio of the monomer to be blended, but the cured product obtained from the polyurethane prepolymer and the silsesquioxane compound having a radical polymerizable group is Some have not reached a level that can simultaneously exhibit hardness that can prevent scratches and high photochromic properties. Furthermore, this is also considered to be due to the type and ratio of the monomer to be blended, but many of the polyurethane prepolymer and the silsesquioxane compound having a radical polymerizable group are incompatible with each other. Even in a composition that seems to have melted, a cured product obtained by polymerizing and curing the composition was cloudy.

US Publication No. 2010/0249264

  Therefore, an object of the present invention is to have sufficient hardness to prevent the occurrence of scratches in the lens processing step, such as the step of polishing the back surface of the lens and the step of trimming the outer peripheral portion according to the frame mold. The present invention also provides a photochromic curable composition capable of forming a cured product having excellent photochromic properties such as a high color density, a high color fading speed, and a high repetition durability.

  The inventor has intensively studied this problem. As a result, in the molecule, (I-1) at least one linking group selected from a silsesquioxane skeleton having a cage structure, (I-2) a urethane bond, a thiourethane bond, and a urea bond, and (I- 3) A cured product obtained by curing a photochromic curable composition containing a (I) silsesquioxane derivative having a radical polymerizable group and a photochromic compound only exhibits high hardness that can prevent scratches. And found that high photochromic properties can be exhibited. Furthermore, the above-mentioned (I) silsesquioxane derivative does not have the problem of white turbidity of the cured product itself, and has good compatibility with other radical polymerizable monomers. It has been found that the white turbidity of the cured product is reduced, and the present invention has been completed.

That is, the first aspect of the present invention is
In the molecule,
(I-1) a silsesquioxane skeleton having a cage structure;
(I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond;
(I-3) A photochromic curable composition comprising a (I) silsesquioxane derivative having a radically polymerizable group and (II) a photochromic compound.

  The (I-3) radical polymerizable group is preferably any of a (meth) acryl group, a vinyl group, and an allyl group.

  Furthermore, the (II) photochromic compound preferably includes a compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton.

  2nd this invention is a coating agent containing the said photochromic curable composition.

  The third aspect of the present invention is an optical material having a photochromic coating layer obtained by curing the coating agent on at least one surface of an optical substrate.

  The fourth aspect of the present invention is a photochromic cured product obtained by curing the photochromic curable composition.

  In the molecule, the present invention includes (I-1) a silsesquioxane skeleton having a cage structure, (I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond, and ( I-3) A photochromic curable composition comprising (I) a silsesquioxane derivative having a radically polymerizable group and (II) a photochromic compound. The cured product obtained from this composition exhibits excellent photochromic properties such as high hardness, high color density, high fading speed, and high repeated durability. Therefore, it has a high hardness both when a coated photochromic lens is produced using the curable composition as a coating agent and when a kneaded photochromic lens is produced using the curable composition. A photochromic lens can be obtained and scratches can be made difficult to occur in the lens processing step.

  In the molecule, (I-1) a silsesquioxane skeleton having a cage structure, (I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond, and (I-3) The (I) silsesquioxane derivative having a radical polymerizable group is cured (polymerized) so that at least one linking group selected from a silsesquioxane skeleton, a urethane bond, a thiourethane bond, and a urea bond is present. A cured body in which a hydrogen bonding site to be formed is present in an appropriate positional relationship is provided. As a result, high hardness can be obtained, and at the same time, “free space” in which the conformational change of the photochromic compound can smoothly occur is constructed, so that excellent photochromic properties such as high color density and fast fading speed can be exhibited. it is conceivable that.

  According to the present invention, it is possible to provide a cured product having higher hardness and excellent photochromic characteristics, which is difficult to achieve with the conventional method. Further, the obtained cured product does not cause white turbidity.

The present invention provides the following:
(I-1) a silsesquioxane skeleton having a cage structure;
(I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond;
(I-3) A photochromic curable composition comprising a (I) silsesquioxane derivative having a radically polymerizable group and (II) a photochromic compound. Each component will be described.

<(I) Silsesquioxane Derivative: Component (I)>
First, the (I) silsesquioxane derivative (hereinafter sometimes referred to as component (I)) used in the present invention will be described.

This component (I) is in the molecule,
(I-1) a silsesquioxane skeleton having a cage structure;
(I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond;
(I-3) A compound having a radical polymerizable group. These structures and groups will be described.

(I-1) Silsesquioxane skeleton having a cage structure In the present invention, the silsesquioxane skeleton having a cage structure in component (I) is represented by the following formulas (1) -A, (1) -B, (1 -C

It has the structure shown by either. The (I) silsesquioxane derivative used in the present invention may contain two or more skeletons represented by the above formula alone.

  In addition, what has the structure of (1) -A is especially preferable from a viewpoint that the acquisition of the silsesquioxane compound which is a raw material is easy, and the hardening body which has especially high hardness is obtained.

(I-2) At least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond. The urethane bond and the thiourethane bond as the linking group in component (I) are represented by the following formula (2).

It has the structure shown by. Here, X and Y represent an oxygen atom or a sulfur atom.

  Moreover, the urea bond which is a bonding group in component (I) is represented by the following formula (3)

It has the structure shown by.

(I-3) Radical polymerizable group The radical polymerizable group in component (I) is not particularly limited, and examples thereof include known groups. Among these, any of a (meth) acryl group, a vinyl group, and an allyl group is preferable.

The (I) silsesquioxane derivative used in the present invention comprises the above (I-1) silsesquioxane skeleton having a cage structure,
(I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond;
If it is a compound which has (I-3) radical polymerizable group in a molecule | numerator, the number in particular of the said frame | skeleton, a coupling group, and a radical polymerizable group will not be restrict | limited. Further, the production method is not particularly limited, but it is preferably produced by the following method.

(I) Manufacturing method of silsesquioxane derivative Although it does not restrict | limit especially about the manufacturing method of component (I) in this invention, For example, it can obtain by either of the four methods shown below.

(First method)
The first method is
(A1) Cage-structure silsesquioxane compound having active hydrogen group (A2) Diisocyanate compound (A3) Active hydrogen group and polymerizable monomer having radical polymerizable group are essential components, and each component is reacted. It is the method of manufacturing by making it.

  Here, the active hydrogen group is preferably any one of a hydroxyl group, a mercapto group, and an amino group. The radical polymerizable group is preferably any one of (meth) acrylic group, vinyl group and allyl group as described in the component (I).

(A1) A silsesquioxane compound having a cage structure having an active hydrogen group (component (A1))
The silsesquioxane compound having a cage structure having an active hydrogen group used as (A1) in the present invention is any one of the following formulas (4) -A, (4) -B, (4) -C, or A compound represented by a mixture thereof is preferable.

Here, R ⁵ is a group having at least one active hydrogen group, and the rest are alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, It is a group selected from a halogenated alkyl group having 1 to 6 carbon atoms, a phenyl group, and a phenyl group substituted with a halogen. If at least one of R ⁵ is a group having an active hydrogen group, the remaining groups may be the same group or different groups.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Is mentioned.

  Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group.

  Examples of the halogenated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

  Examples of the phenyl group substituted with halogen include 4-chlorophenyl group and 4-bromophenyl group.

  Among these, from the viewpoint of easy acquisition of raw materials and obtaining a cured product having high hardness, an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, Particularly preferred are isopropyl, n-butyl, sec-butyl and tert-butyl groups.

  Examples of the group having an active hydrogen group include a group having a hydroxyl group, a mercapto group, and an amino group.

  Among these, as the group having a hydroxyl group, for example, a group having 1 to 4 hydroxyl groups and 1 to 30 carbon atoms is preferable. A group containing 1 to 4 siloxane bonds is also preferred. Suitable groups having a hydroxyl group include (3- (2,2-bis (hydroxymethyl) butoxy) propyl) dimethylsiloxy group, 1- (2- (cyclohexyl-3,4-diol)) ethyl group, 1- (3- (2,3-dihydroxypropyl) oxy) propyl group, 3-hydroxy-3-methylbutyldimethylsiloxy group and the like can be mentioned.

  The group having a mercapto group is preferably a group having 1 to 4 mercapto groups and 1 to 30 carbon atoms, for example. A group containing 1 to 4 siloxane bonds is also preferred. Suitable groups having a mercapto group include 1- (3-mercapto) propyl group and the like.

  As the group having an amino group, for example, a group having 1 to 4 amino groups and 1 to 30 carbon atoms is preferable. A group containing 1 to 4 siloxane bonds is also preferred.

  Suitable groups having an amino group include aminopropyl group, aminoethylaminopropyl group, 1- (4-aminophenyl) group, N-methylaminopropyl group, 1- (3-aminophenyl) group and the like. .

Among them, the preferred (A1) cage-structure silsesquioxane compound having an active hydrogen group has a skeleton (having 8 Si) represented by (4) -A, and all of R ⁵ are active hydrogens. A group having a group, or (4) a group having a skeleton represented by -A, wherein one of R ⁵ has an active hydrogen group, and the other seven are alkyl groups having 1 to 6 carbon atoms Or what is a C3-C8 cycloalkyl group is mentioned. In particular, a preferable compound has a skeleton represented by (4) -A, one of R ⁵ is a group having an active hydrogen group, and the other seven are alkyl groups having 1 to 6 carbon atoms, or Specific examples thereof include those having a cycloalkyl group having 3 to 8 carbon atoms. Specifically, as a silsesquioxane compound having a cage structure having a hydroxyl group as an active hydrogen group,
“TMP diol isobutyl POSS (registered trademark)” (manufactured by Hybrid Plastics, AL0104; having 8 Si, one of R ⁵ being (3- (2,2-bis (hydroxymethyl) butoxy) propyl) dimethylsiloxy group And the other seven are isobutyl groups),
“Trans-cyclohexanediol isobutyl POSS (registered trademark)” (manufactured by the same company, AL0125; having 8 Si, one of R ⁵ is 1- (2- (cyclohexyl-3,4-diol)) ethyl group, and others 7 are isobutyl groups),
“1,2-propanediol isobutyl POSS (registered trademark)” (manufactured by the same company, AL0130; one of R ⁵ is a 1- (3- (2,3-dihydroxypropyl) oxy) propyl group and the other seven are isobutyl groups some stuff),
“Octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS (registered trademark)” (manufactured by the same company, AL0136; having 8 Si, 8 R ⁵ being 3-hydroxy-3-methylbutyldimethylsiloxy group) Some).

Moreover, as a silsesquioxane compound having a cage structure having a mercapto group as an active hydrogen group,
“Mercaptopropylisobutyl POSS®” (manufactured by Hybrid Plastics, TH1550; having 8 Si, one of R ⁵ is a 1- (3-mercapto) propyl group and the other 7 are isobutyl groups ),
“Mercaptopropylisooctyl POSS (registered trademark)” (manufactured by the same company, TH1555; having 8 Si, one of R ⁵ being a 1- (3-mercaptopropyl) group and the other 7 being an isooctyl group) Etc.

Furthermore, as a silsesquioxane compound having a cage structure having an amino group as an active hydrogen group,
“Aminopropylisobutyl POSS®” (from Hybrid Plastics, AM0265; having 8 Si, one of R ⁵ is an aminopropyl group and the other 7 are isopropyl groups),
“Aminopropylisooctyl POSS®” (manufactured by the same company, AM0270; having 8 Si, one of R ⁵ is an aminopropyl group and the other 7 is an isooctyl group),
“Aminoethylaminopropylisobutyl POSS®” (manufactured by the same company, AM0275; having 8 Si, one of R ⁵ is an aminoethylaminopropyl group and the other 7 is an isobutyl group),
“Octaaminophenyl POSS (registered trademark)” (manufactured by the same company, AM0280; having 8 Si, and 8 R ⁵ being a 1- (4-aminophenyl) group),
“N-methylaminopropylisobutyl POSS®” (manufactured by the same company, AM0282; having 8 Si, one in which R ⁵ is an N-methylaminopropyl group and the other 7 is an isobutyl group),
“P-aminophenylcyclohexyl POSS (registered trademark)” (manufactured by the same company, AM0290; having 8 Si, one of R ⁵ is a 1- (4-aminophenyl) group and the other 7 are cyclohexyl groups ),
“M-aminophenylcyclohexyl POSS (registered trademark)” (manufactured by the same company, AM0291; having 8 Si, one of R ⁵ is 1- (3-aminophenyl) group and the other 7 are cyclohexyl groups ) And the like.

These silsesquioxane compounds having a cage structure having an active hydrogen group may be used alone or in combination of two or more.

(A2) Diisocyanate compound (component (A2))
Next, the diisocyanate compound used as (A2) in the present invention has the following formula (5):

It is preferable that it is a compound shown by these. Here, R ¹ represents an aliphatic, alicyclic, or aromatic divalent organic group. Among these, from the viewpoint of weather resistance, it is preferable to use those in which R ¹ is aliphatic and / or alicyclic. In particular, it is preferable to use an aliphatic group having 6 to 15 carbon atoms and / or an alicyclic group.

  Examples of the diisocyanate compound that can be suitably used as the component (A2) include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, cyclobutane- 1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4'-methylenebis (Cyclohexyl isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrofuran Nylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, phenylcyclohexylmethane diisocyanate, isomer mixture of 4,4'-methylenebis (phenylisocyanate), toluene-2,4-diisocyanate, toluene-2, Examples include 6-diisocyanate, phenylene-1,3-diisocyanate, and phenylene-1,4-diisocyanate.

  Among these, from the viewpoint of the weather resistance of the obtained polyurethane-urea resin, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4 ′ Isomer mixtures of methylenebis (cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenol Ren-1,3-diisocyanate, it is preferable to use a hexa hydro-phenylene-1,4-diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.

(A3) A polymerizable monomer having an active hydrogen group and a radical polymerizable group (component (A3))
Next, a polymerizable monomer having an active hydrogen group and a radical polymerizable group used as (A3) in the present invention is represented by the following formula (6).

It is preferable that it is a compound shown by these.

Here, R ³ is a divalent organic group that is either aliphatic, alicyclic, or aromatic. Among these, an aliphatic divalent organic group having 2 to 20 carbon atoms is preferable.

  ZH is an active hydrogen group selected from a hydroxyl group, a mercapto group, and an amino group. Among these, a hydroxyl group is preferable from the viewpoint of easy availability of raw materials.

  Q is a radical polymerizable group selected from a (meth) acryl group, an allyl group, and a vinyl group. Among these, a polymerizable monomer having a (meth) acryl group is preferable from the viewpoint that it is easily available and is relatively easy to cure by polymerization. Moreover, it is preferable that s is an integer of 1-3. Among them, s is preferably 1.

  Examples of the polymerizable monomer having an active hydrogen group and a radical polymerizable group that can be suitably used as the component (A3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, polyethylene Glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, nonap Pyrene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogencaprolactonate, 2- (meth) acryloyloxyethylhydrogen dicaprolactonate, 2- (meth) Acryloyloxyethyl hydrogen polycaprolactonate, 2- (meth) acryloyloxyethyl-2-hydroxy-6-hexanolactonate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, allyl alcohol, 2 -Hydroxyethyl allyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, diethylene glycol monoallyl ether Glycerol diallyl ether, trimethylolpropane diallyl ether, diglycerol triallyl ether.

  Examples of the polymerizable monomer having a particularly preferable active hydrogen group and radical polymerizable group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate , Dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, nonapropylene glycol mono ( Data) acrylate, polypropylene glycol mono (meth) acrylate.

  These polymerizable monomers having an active hydrogen group and a radical polymerizable group may be used alone or in combination of two or more.

(First method: manufacturing conditions)
As a method of obtaining the component (I) from the components (A1), (A2), and (A3), first, a prepolymer having an isocyanate group is obtained by reacting the component (A1) with the component (A2). Thereafter, the method of reacting the component (A3) is common.

  In the above method, the reaction between the component (A1) and the component (A2), that is, the reaction between the silsesquioxane compound having an active hydrogen group and the diisocyanate compound is carried out in the presence or absence of a solvent with nitrogen or argon. What is necessary is just to make it react at 25-120 degreeC for 0.5 to 24 hours in inert gas atmosphere. At this time, with respect to 1 mol of the component (A1), the component (A2) is charged so as to have the same number of moles as the number of active hydrogen groups in one molecule of the component (A1). As the solvent, organic solvents such as methyl ethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used. In the reaction, in order to avoid a reaction between an isocyanate group in the diisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried. In carrying out the above reaction, dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, 1,4-diazabicyclo [2,2, 2] A catalyst such as octane may be added. As an addition amount at the time of using a catalyst, it is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of a component (A1) and a component (A2).

  The reaction between the prepolymer thus obtained and the component (A3), that is, the reaction between the compound having an isocyanate group and the polymerizable monomer having an active hydrogen group and a radical polymerizable group is carried out in the presence of a solvent. The reaction may be carried out at 25 to 120 ° C. for 0.5 to 24 hours in an inert gas atmosphere such as nitrogen or argon under or in the absence. At this time, with respect to 1 mol of the prepolymer, the component (A3) is charged so as to have the same number of moles as the number of isocyanate groups in one molecule of the prepolymer. As the solvent, the same solvents as described above can be used. In the reaction, in order to avoid a reaction between the isocyanate group in the compound having an isocyanate group and water as an impurity, it is preferable that the various reaction reagents and the solvent are dehydrated in advance and sufficiently dried. In carrying out the above reaction, dibutyltin dilaurate, dimethylimidazole, triethylenediamine, tetramethyl-1,6-hexadiamine, tetramethyl-1,2-ethanediamine, 1,4-diazabicyclo [2,2, 2] A catalyst such as octane may be added. As an addition amount at the time of using a catalyst, it is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of a component (A1) and a component (A2). Furthermore, when performing the said reaction, you may add polymerization inhibitors, such as BHT and methoquinone. As addition amount at the time of using a polymerization inhibitor, it is preferable that it is 0.001-1 mass part with respect to a total of 100 mass parts of a component (A1), a component (A2), and a component (A3).

In the first method, as described above, the components (A1), (A2), and (A3) may be reacted. In this reaction, (A6) a compound having two active hydrogen groups is used. It can also be blended.

Optional component for producing component (I): (A6) Compound having two active hydrogen groups (component (A6))
Further, as an optional component, (A6) a compound having two active hydrogen groups can also be used. In the present invention, (A6) the compound having two active hydrogen groups is specifically a diol compound, a dithiol compound, a diamine compound, or a compound having two or more kinds of groups among a hydroxyl group, a mercapto group, and an amino group. Represents.

  Above all, the following formula (7)

It is preferable that it is a compound shown by these.

  Here, ZH represents any one of a hydroxyl group, a mercapto group, and an amino group, and may be the same as or different from each other.

R ² is a divalent organic group that is either aliphatic, alicyclic, or aromatic. Among these, an aliphatic divalent organic group having 2 to 20 carbon atoms is preferable.

  When this component (A6) is used, a prepolymer having an isocyanate group is obtained by reacting the component (A1) with the component (A2), and further, a prepolymer having an isocyanate group is obtained by reacting with the component (A6). After obtaining the polymer, component (A3) can be reacted.

  Moreover, after making the prepolymer which has an isocyanate group by making a component (A2) and a component (A6) react, and also obtaining the prepolymer which has an isocyanate group by making it react with a component (A1), a component (A3 ).

  Any of these reactions can be obtained by reacting in the same manner as described above.

  Of the components (A6), the diol compound is a compound having two hydroxyl groups in the molecule. As the diol compound, it is preferable to use at least one diol compound selected from polyether diol, polycarbonate diol, polycaprolactone diol, and polyester diol from the viewpoint of easy availability.

  The diol compounds such as polyether diol, polycarbonate diol, polycaprolactone diol, and polyester diol described above may be used alone or in combination of two or more. Hereinafter, various compounds used as the component (A6) will be described in detail.

  Examples of the polyether diol include ethylene glycol, propylene glycol, and butane diol. These may be used alone or in combination of two or more. In the polyether polyol, from the viewpoint of ensuring the hardness of the resulting cured product and photochromic properties (color density, fading speed, weather resistance, etc.), the molecular weight is preferably 60 to 2000, particularly 60 to 1500, Most preferably, it is 60-1000.

  Examples of the polycarbonate diol include a polycarbonate polyol obtained by phosgenation of a polyol, a polycarbonate polyol obtained by a transesterification method using diphenyl carbonate, and the like. In the polycarbonate diol, for the same reason as in the polyether diol, the number average molecular weight is preferably 500 to 2000, particularly preferably 500 to 1500, and most preferably 500 to 1000.

  As the polycaprolactone diol, a compound obtained by ring-opening polymerization of ε-caprolactone can be used. In the polycaprolactone diol, for the same reason as in the polyether diol, the number average molecular weight is preferably 100 to 2000, particularly preferably 100 to 1500, and most preferably 100 to 1000.

  Examples of the polyester diol include a polyester diol obtained by a condensation reaction of “polyhydric alcohol” and “polybasic acid”. Here, as the “polyhydric alcohol”, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 3,3'-dimethylol heptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis (hydroxymethyl) heptane, diethylene glycol, dipropylene glycol, etc. It may be used, or two or more kinds may be mixed and used. Examples of the “polybasic acid” include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination of two or more. In the polyester diol as the A6 component, for the same reason as in the polyether polyol, the number average molecular weight is preferably 200 to 2000, particularly preferably 200 to 1500, and most preferably 200 to 1000.

  Of the components (A6), the dithiol compound is a compound having two mercapto groups in the molecule. Examples of compounds suitably used as the polythiol compound include ethanedithiol and cyclohexanedithiol.

  Further, among the components (A6), the diamine compound is a compound having two amino groups in the molecule. Examples of the compound suitably used as the diamine compound include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4. -Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- (4-aminocyclohexyl) methane, bis- (4-amino -3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornene diamine, hydrazine, dihydrazine adipate, phenylene diamine, 4,4'-diphenylmethane diamine, N, N ' -Diethylethylenediamine, N, N'-dimethylethylenediamine, N N'- dipropyl ethylenediamine, N, N'- dibutyl diamine and the like.

  Further, among the compounds (A6), as a compound having two or more groups among a hydroxyl group, a mercapto group, and an amino group, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, Examples include 6-aminohexanol, 1-aminothiol, and 2-aminoethanethiol.

  Component (A6) is a component based on the premise that the number of isocyanate groups in one molecule of the prepolymer to be reacted with component (A3) is the same as the number of active hydrogen groups in one molecule of component (A1). (A1) 1 to 20 mol, preferably 1 to 10 mol, and more preferably 1 to 5 mol can be charged per 1 mol. If it exceeds 20 mol, sufficient hardness cannot be expressed in the cured product.

(Second method)
The second method is
(A1) A cage-structured silsesquioxane compound having an active hydrogen group (A4) A method for producing an isocyanate group and a polymerizable monomer having a radical polymerizable group as essential components and reacting each component It is.

  Here, the component (A1) is the same as that described in the first method.

(A4) A polymerizable monomer having an isocyanate group and a radical polymerizable group (component (A4))
The polymerizable monomer having an isocyanate group and a radical polymerizable group used as the component (A4) is represented by the following formula (8).

It is preferable that it is a compound shown by these. Or it is preferable that it is a compound shown by (OCN-Q) which the isocyanate group and group Q couple | bonded directly.

Here, R ⁴ represents a divalent organic group selected from aliphatic, alicyclic, and aromatic. Among these, an aliphatic divalent organic group having 2 to 20 carbon atoms is preferable.

  Q is a radical polymerizable group selected from a (meth) acryl group, an allyl group, and a vinyl group. s is an integer of 1 to 3, and is particularly preferably 1.

  Examples of the polymerizable monomer having an isocyanate group and a radical polymerizable group that can be suitably used include 2-isocyanatoethyl (meth) acrylate, 1,1- (bis (meth) acryloyloxymethyl) ethyl cyanate, vinyl Isocyanate, propenyl-α, α-dimethylbenzyl isocyanate, allyl isocyanate, and the like.

  As a method of obtaining component (I) from the above essential components, a method of simply reacting component (A1) and component (A4) by the method described in the first method is general.

  Moreover, the said component (A2) and a component (A6) can also be used as an arbitrary component. In this case, in this case, after obtaining a prepolymer having an active hydrogen group at the terminal, (A4) can be finally reacted.

  At this time, with respect to 1 mol of the component (A1), the component (A4) is charged so as to have the same number of moles as the number of active hydrogen groups of the component (A1).

  In the component (A2) and the component (A6), the number of active hydrogen groups in one molecule of the prepolymer to be reacted with the component (4) is the same as the number of active hydrogen groups in one molecule of the component (A1). As a premise, 1 to 20 moles, preferably 1 to 10 moles, and more preferably 1 to 5 moles can be added to 1 mole of component (A1). If it exceeds 20 mol, sufficient hardness cannot be expressed in the cured product.

(Third method)
The third method is
(A5) A silsesquioxane compound having a cage structure having an isocyanate group (A3) A method of producing by reacting each component with an active hydrogen group and a polymerizable monomer having a radical polymerizable group as essential components. is there.

(A5) Silsesquioxane compound having a cage structure having an isocyanate group The silsesquioxane compound having a cage structure having an isocyanate group used as (A5) in the present invention has the following formula (9) -A, ( 9) A compound represented by any one of -B and (9) -C or a mixture thereof.

Here, R ⁶ is a group having at least one isocyanate group, and the rest are alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, carbon It is a group selected from a halogenated alkyl group of formulas 1 to 6, a phenyl group, and a phenyl group substituted with a halogen. If at least one of R ⁶ is a group having an isocyanate group, the remaining groups may be the same group or different groups. Specific examples of R ⁶ include the same groups as those described for R ⁵ in formula (4), and preferred groups are also the same.

  As the group having an isocyanate group, for example, a group having 1 to 4 isocyanate groups and having 1 to 30 carbon atoms is preferable. A group containing 1 to 4 siloxane bonds is also preferred.

  Suitable groups having an isocyanate group include isocyanatopropyldimethylsilyloxy group and isocyanatopropyl group.

Examples of the compound represented by the formula (11) that can be suitably used include “isocyanatopropyldimethylsilyloxycyclopentyl POSS (registered trademark)” (manufactured by Aldrich, having 8 Si, and one of R ³ is isocyanato Propyldimethylsiloxy group and the other seven are cyclopentyl groups).

  The component (A3) is the same as that described in the first method.

  As a method for obtaining component (I) from the above essential components, a method of simply reacting component (A5) and component (A3) by the method described in the first method is general.

  Moreover, the said component (A2) and a component (A6) can also be used as an arbitrary component. In this case, after obtaining the prepolymer having an isocyanate group at the terminal, the component (A3) can be finally reacted.

  At this time, with respect to 1 mol of the component (A5), the component (A3) is charged so as to have the same number of moles as the number of isocyanate groups in the component (A5).

  In addition, in the component (A2) and the component (A6), the number of isocyanate groups in one molecule of the prepolymer to be reacted with the component (A3) is the same as the number of isocyanate groups in one molecule of the component (A5). As a premise, 1 to 20 mol, preferably 1 to 10 mol, and more preferably 1 to 5 mol can be charged with respect to 1 mol of component (A5). If it exceeds 20 mol, sufficient hardness cannot be expressed in the cured product.

(Fourth method)
The fourth method is
(A5) Silsesquioxane compound having a cage structure having an isocyanate group (A6) Compound having two active hydrogen groups (A4) An isocyanate group and a polymerizable monomer having a radical polymerization group as essential components, It is a method of manufacturing by reacting components.

  Here, components (A5), (A6), and (A4) are the same as those described in the first to third methods.

  As a method of obtaining the component (I) from the component (A5), the component (A6), and the component (A4), first, a prepolymer having an active hydrogen group is obtained by reacting the component (A5) with the component (A6). A method of reacting the component (A4) after obtaining is common.

  Moreover, the said component (A2) can also be used as an arbitrary component. In this case, in this case, after obtaining the prepolymer having an active hydrogen group at the terminal, the component (A4) can be finally reacted.

  At this time, with respect to 1 mol of the component (A5), the component (A6) is charged so as to have the same number of moles as the number of isocyanate groups in one molecule of the component (A1). Furthermore, with respect to 1 mol of prepolymers obtained, the component (A4) is charged so as to have the same number of moles as the number of active hydrogen groups in one molecule of the prepolymer.

  In addition, the component (A2) is based on the premise that the number of active hydrogen groups in one molecule of the prepolymer to be reacted with the component (A4) is the same as the number of isocyanate groups in one molecule of the component (A5). (A5) 1 to 20 moles, preferably 1 to 10 moles, and more preferably 1 to 5 moles can be charged per 1 mole. If it exceeds 20 mol, sufficient hardness cannot be expressed in the cured product.

Preferred (I) Silsesquioxane Derivative Structure Component (I) is composed of the above-mentioned (I-1) cage-structure silsesquioxane skeleton in the molecule, (I-2) urethane bond, thiourethane bond And at least one linking group selected from urea bonds and (I-3) a radical polymerizable group are not particularly limited. As a preferred structure,
Following formula (10)

(here,
A ^{1 to} A ⁷ may be the same as or different from each other, and each represents a urethane bond, a thiourethane bond, or a urea bond;
P represents a divalent organic group obtained by removing the active hydrogen group and the isocyanate group from the silsesquioxane compound having the cage structure described above,
R ¹ has the same meaning as that of the diisocyanate compound described above,
R ² has the same meaning as that of the compound having two active hydrogen groups described above,
R ³ has the same meaning as that of the radically polymerizable monomer having the active hydrogen group and the radically polymerizable group described above,
R ⁴ has the same meaning as that described above for the isocyanate group and the radical polymerizable monomer having a radical polymerizable group,
Q represents a radical polymerizable group,
a, b, c, d, h and i are each independently 0 or 1,
d, f and g are each independently an integer of 0 to 20,
h represents an integer of 1 to 3,
One of a and b and one of h and i are always 0. )
Or the following formula (11)

(here,
A ^{1 to} A ⁷ , R ¹ , R ² , R ³ , R ⁴ , Q are as defined in the formula (10),
P represents a monovalent or 3-12 valent organic group obtained by removing the active hydrogen group and the isocyanate group from the silsesquioxane compound having the cage structure described above,
k, l, m, and o are each independently 0 or 1,
n and p are each independently an integer of 0 to 20,
t represents 1 or an integer of 3 to 12, s represents an integer of 1 to 3,
One of k and l and one of q and r are always 0. )
The thing shown by is mentioned.

Among these, in the formula (10), A ^{1 to} A ⁷ are preferably urethane bonds from the viewpoint that a raw material is easily available and a cured product having high hardness is obtained. 1 to 5, d and f are 0 to 5 and j is 1 from the viewpoint of obtaining a cured product having high hardness.

In the formula (11), A ^{1 to} A ⁷ are preferably urethane bonds from the viewpoint of easy availability of raw materials and obtaining a cured product having high hardness, and n and p 0 to 5 and s is 1 are preferable from the viewpoint of obtaining a cured product having high hardness, and t is preferably 8 from the viewpoint of easy availability of raw materials.

  Furthermore, since it is easy to synthesize and has an appropriate viscosity, it can be easily handled as a curable composition, and a cured product excellent in hardness and photochromic properties can be obtained.

(here,
P ′ represents a divalent organic group obtained by removing the active hydrogen group from the silsesquioxane compound having the cage structure described above,
R ¹ has the same meaning as that of the diisocyanate compound described above,
R ³ has the same meaning as that of the radically polymerizable monomer having the active hydrogen group and the radically polymerizable group described above,
R ⁷ each independently represents a hydrogen atom or a methyl group. )
And the following formula (13)

(Here, P ′, R ¹ , R ³ , and R ⁷ have the same meanings as those shown in the formula (12).)
Is particularly preferred.

<(II) Photochromic compound: Component (II)>
Next, the photochromic compound used suitably in this invention is demonstrated.

  As the photochromic compound used in the photochromic curable composition of the present invention, known photochromic compounds such as a chromene compound, a fulgimide compound, a spirooxazine compound, and a spiropyran compound can be used without any limitation. These may be used alone or in combination of two or more.

  Examples of the fulgimide compound, spirooxazine compound, spiropyran compound and chromene compound described in JP-A-2-28154, JP-A-62-2288830, WO94 / 22850 pamphlet, WO96 / 14596 pamphlet and the like. The compound which is mentioned.

  In particular, chromene compounds having excellent photochromic properties other than those described in the above-mentioned patent documents are known as chromene compounds and can be suitably used. Examples of such chromene compounds include JP2001-031670, JP2001-011067, JP2001-011066, JP2000-344761, JP2000-327675, JP2000-256347, JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229993, JP 2000-229972, JP 2000-219678, JP 2000-219686, Special Kaihei 11-322739, JP 11-286484, JP 11-279171, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139, JP 08-157467, US Pat. No. 56457 No. 7, U.S. Pat. No. 5,658,501, U.S. Pat. No. 5,961,892, U.S. Pat. No. 6,296,785, Japanese Patent No. 4424981, Japanese Patent No. 4424962, WO2009 / 136668, WO2008 / 023828, Japanese Patent No. 4369754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, WO2007 / 086532 Pamphlet, JP2009-120536A, JP2009-67754A, JP2009-67680A. JP-A-2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 41588881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent No. 4157227 Gazette, Japanese Patent No. 4118458, Japanese Patent Laid-Open No. 2008-74832, Japanese Patent No. 3984770, Japanese Patent No. 3801386, WO 2005/028465 pamphlet, WO 2003/042203 pamphlet, JP 2005-289812, JP No. 2005-289807, JP-A-2005-112772, Japanese Patent No. 3522189, WO2002 / 090342 pamphlet, Japanese Patent No. 3471703, JP-A-2003-277381, WO2001 / 060811 pamphlet, WO2000 / 071544 No., WO2005 / 028465 pamphlet, WO2011 / 16582 pamphlet, WO2011 / 034202 pamphlet and the like.

  Among these photochromic compounds, 1 is a chromene compound having an indenonaphtho “2,1-f” naphtho “1,2-b” pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloration, durability, and fading speed. It is more preferable to use more than one type. Further, among these chromene compounds, compounds having a molecular weight of 540 or more are preferable because they are particularly excellent in color density and fading speed. Specific examples thereof include the following.

＜その他のラジカル重合性単量体＞
本発明においては、成分（Ｉ）とは異なる、（ＩＩＩ）その他のラジカル重合性単量体（成分（ＩＩＩ））を配合することもできる。

<Other radical polymerizable monomers>
In the present invention, (III) other radical polymerizable monomer (component (III)) different from component (I) can be blended.

  Although it does not restrict | limit especially as another radically polymerizable monomer, For example, a monofunctional (meth) acrylate compound, a bifunctional (meth) acrylate compound, a trifunctional or more (meth) acrylate compound, a vinyl compound, an allyl compound Etc.

  Specifically, radically polymerizable monomers disclosed in WO2001 / 005854 pamphlet, WO2003 / 11967 pamphlet, WO2004 / 83268 pamphlet, WO2009 / 75388 pamphlet and the like can be suitably used.

  Among these, since excellent photochromic properties are obtained and the viscosity is low, the following formula (14) is obtained from the viewpoint that it is easy to adjust to an appropriate viscosity when mixed with the component (I).

(Where
R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group,
R ¹⁰ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms,
u is an average value of 0 to 3;
v is an integer of 3-6. )
It is preferable to use a tri- or higher functional (meth) acrylate compound represented by

  Specifically, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate, trimethylol propane triethylene glycol trimethacrylate, Trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, polyester oligomer having 4 (meth) acryl groups, polyester oligomer having 6 (meth) acryl groups, (meth) acryl group Polyurethane oligomer having 4 and 6 (meth) acrylic groups Polyurethane oligomer, and the like that.

  In addition, other polymerizable monomers as shown below can be used.

  Monofunctional (meth) acrylate compounds include methoxydiethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, isostearyl methacrylate, isobornyl methacrylate, phenoxyethylene glycol methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, naphthoxyethylene glycol acrylate, Stearyl acrylate, isobornyl acrylate, glycidyl methacrylate, methoxypolyethylene glycol methacrylate (with an average chain length of ethylene glycol chain of 9 and an average molecular weight of 468), methoxypolyethylene glycol methacrylate (with an average chain length of ethylene glycol chain of 23) With an average molecular weight of 1068 , Phenoxypolyethylene glycol acrylate (ethylene glycol chain having an average chain length of 6 and an average molecular weight of 412), γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyl Examples include dimethoxysilane.

  Among the bifunctional (meth) acrylate compounds, those in which the homopolymer gives a hardened product include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetra Propylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, 1,3-butanediol Dimethacrylate, 1,6-hexanediol dimeta Lilate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (the average chain length of the ethylene glycol chain is 2.3), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (ethylene glycol chain having an average chain length of 2.6), 2,2-bis [4-methacryloxy (polyethoxy) Phenyl] propane (ethylene glycol chain having an average chain length of 4), tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate Acrylate, neopentyl glycol di Acrylate, tricyclodecane dimethanol diacrylate, dioxane glycol diacrylate, ethoxylated cyclohexane dimethanol diacrylate (with an average ethylene glycol chain length of 4), 2,2-bis [4-acryloxy (polyethoxy) phenyl] Examples include propane (having an ethylene glycol chain having an average chain length of 3), 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (having an ethylene glycol chain having an average chain length of 4), and the like.

  Among the bifunctional (meth) acrylate compounds, those in which the homopolymer gives a soft cured product include polyethylene glycol dimethacrylate (ethylene glycol chain having an average chain length of 9 and an average molecular weight of 536), polyethylene glycol diacrylate Methacrylate (ethylene glycol chain having an average chain length of 14 and an average molecular weight of 736), polyethylene glycol dimethacrylate (ethylene glycol chain having an average chain length of 23 and an average molecular weight of 1136), polypropylene glycol di Methacrylate (average propylene glycol chain length of 9 and average molecular weight of 662), polyethylene glycol diacrylate (ethylene glycol chain average chain length of 9 and average molecular weight of 508), polyethylene glycol Diacrylate (with an average chain length of ethylene glycol chain of 14 and an average molecular weight of 708), polypropylene glycol diacrylate (with an average chain length of propylene glycol chain of 7 and an average molecular weight of 536), polypropylene glycol Diacrylate (with an average chain length of propylene glycol chain of 12 and an average molecular weight of 808), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (with an average chain length of ethylene glycol chain of 10) ), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (ethylene glycol chain having an average chain length of 20), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (ethylene glycol chain) With an average chain length of 30), 2, 2 Bis [4- acryloxy (polyethoxy) phenyl] propane (having an average chain length of ethylene glycol chains of 10), and the like.

  Moreover, in this invention, the radically polymerizable monomer which has a urethane bond in a molecule | numerator can also be used conveniently. For example, a known urethane (meth) acrylate can be used. The urethane (meth) acrylate can be broadly classified into those having an aromatic ring such as a benzene ring in the molecular structure and those not having an aromatic ring, and any of them can be used in the present invention. From the viewpoint of light resistance of the cured product, a non-yellowing type having no aromatic ring is preferred.

  Specific examples of the urethane (meth) acrylate include, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine isocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isopropylidenebis-4-cyclohexyl isocyanate, Polyalkylene glycols having repeating units of dicyclohexylmethane diisocyanate, norbornene diisocyanate or methylcyclohexane diisocyanate and ethylene oxide, propylene oxide, hexamethylene oxide having 2 to 4 carbon atoms, or polyester diols such as polycaprolactone diol, polycarbonate diol, polybutadiene diol Low molecular polyfunctional polyols such as Tol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,8-nonanediol, Reacted with known low molecular weight polyols such as neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol to obtain urethane prepolymers Is a reaction mixture obtained by further reacting with 2-hydroxyethyl (meth) acrylate or the like which may have an alkylene oxide chain, or the diisocyanate may have an alkylene oxide chain. Hydro A reaction mixture obtained by direct reaction with ethyl (meth) acrylate, the molecular weight of a urethane (meth) acrylate is less than 400 to 20,000.

  Furthermore, radically polymerizable monomers such as styrene, α-methylstyrene, α-methylstyrene dimer, divinylbenzene allyl diglycol carbonate can also be used.

<Blending ratio of photochromic curable composition>
In the present invention, the blending amount of the photochromic compound may be appropriately determined according to the intended use. Especially, when using the photochromic curable composition of this invention for a photochromic spectacle lens use, it is preferable to set it as the following compounding quantities.

  That is, when the total radical polymerizable monomer (component (I) and component (III) described above) contained in the photochromic curable composition is 100 parts by mass, component (II) is 0.01. It is preferable to set it as -20 mass parts. The total radical polymerizable monomer refers to the sum of component (I) and other radical polymerizable monomers (the component (III)) blended as necessary.

  Further, among the uses of the photochromic eyeglass lens, when the photochromic curable composition of the present invention is used as a coating agent, the component (II) is added in an amount of 0.05 with respect to 100 parts by mass of all radical polymerizable monomers. It is preferable to set it as -20 mass parts, and also it is preferable that component (II) shall be 0.1-15 mass parts. Especially, it is preferable to change the compounding quantity of component (II) according to the thickness of the coating layer formed. When the thickness of the coating layer is 10 to 30 μm, the component (II) is preferably 5 to 15 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers. Moreover, when the thickness of a coating layer is 30-50 micrometers, it is preferable that component (II) shall be 0.5-5 mass parts with respect to 100 mass parts of all radically polymerizable monomers.

  On the other hand, when the cured product itself is used as a lens as a kneading type, the component (II) is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers. Further, the component (II) is preferably 0.03 to 0.5 parts by mass.

  Moreover, although the ratio of the component (I) which occupies for all radically polymerizable monomers can be suitably determined in the range which does not impair an effect, it is preferable to set it as 10-100 mass%, and 25-100 mass% It is particularly preferable to do this.

  Next, the other component which can be mix | blended with the photochromic hardening composition of this invention is demonstrated.

(Other ingredients)
In the curable composition of the present invention, in order to improve the repetition durability of the photochromic compound, the color development speed, the fading speed and the moldability, a surfactant, an antioxidant, a radical scavenger, Additives such as ultraviolet stabilizers, ultraviolet absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers may be added. It is also very preferable to add a polymerization initiator described later in order to cure the curable composition. About a polymerization initiator, it describes in detail in description of the method of manufacturing a hardening body. As these additives to be added, known compounds are used without any limitation.

  As the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in a polymerizable monomer. Specific examples of nonionic correct surface active agents that can be suitably used include sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, and the like. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers.

  Antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, benzotriazole compounds, benzophenones A system compound etc. can be used conveniently. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. Furthermore, when using these non-polymerizable compounds, surfactants and antioxidants, radical scavengers, UV stabilizers, and UV absorbers may be used in combination. The addition amount of these antioxidants, radical scavengers, UV stabilizers, and UV absorbers is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers.

  Among the stabilizers, a hindered amine light stabilizer is exemplified from the viewpoint of preventing deterioration of the photochromic compound when the curable composition is cured or improving the repeated durability of the cured product. As the hindered amine light stabilizer, known compounds can be used without any limitation. Among them, when used for coating agents, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Asahi Denka Kogyo Co., Ltd., is particularly used as a compound that exhibits the effect of preventing deterioration of the photochromic compound. Examples include ADK STAB LA-52, LA-62, LA-77, LA-82 and the like. The addition amount may be in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the total radical polymerizable monomer, but when used as a coating agent, it is in the range of 0.1 to 10 parts by mass. It is preferable to use in the range of 1 to 10 parts by mass.

  In addition, as another particularly useful stabilizer when used as a coating agent, a hindered phenol antioxidant can be particularly preferably used from the viewpoint of improving the repeated durability of the cured product. As the hindered phenol antioxidant, known compounds can be used without any limitation. Among them, when used in coating agent applications, as a compound that expresses the effect of preventing deterioration of the photochromic compound, IRGANOX245: ethylenebis (oxyethylene) bis [3,5-tert-butyl-4 manufactured by Ciba Specialty Chemicals -Hydroxy-m-toluyl] propionate], IRGANOX 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, IRGANOX 1010: pentaerythritol tetrakis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate] and the like. The addition amount may be in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the total radical polymerizable monomer, but when used as a coating agent, it is in the range of 0.1 to 10 parts by mass. It is preferable to use in the range of 1 to 10 parts by mass.

  Next, the preparation method of the photochromic curable composition of this invention, the formation method of a hardening body, and an application are demonstrated.

(Preparation method, formation method of cured body, and use thereof)
The preparation of the photochromic curable composition of the present invention is not particularly limited, and a predetermined amount of each component may be weighed and mixed. The order of addition of each component is not particularly limited, and all components may be added at the same time, or only the polymerizable monomer component is mixed in advance, and then, for example, immediately before polymerization as described later, the photochromic compound Or other additives may be added and mixed. As will be described later, a polymerization initiator may be further added as necessary during the polymerization.

  The photochromic curable composition of the present invention preferably has a viscosity of 5 to 500 cPs. When used as a coating agent, the viscosity at 25 ° C. is preferably 20 to 500 cPs. Among these, 50 to 300 cPs is more preferable, and 60 to 200 cPs is particularly preferable. By setting it as this viscosity range, it becomes easy to adjust the thickness of the coat layer mentioned later to 10-100 micrometers thickly, and it becomes possible to fully exhibit a photochromic characteristic. On the other hand, when using as a kneading type | mold, it is preferable that the viscosity in 25 degreeC shall be 5-300 cPs. Among these, 10 to 100 cPs is more preferable. By setting the viscosity within this range, the operation of injecting into the lens mold can be easily performed.

  The method for obtaining the photochromic cured product by curing the photochromic curable composition of the present invention is not particularly limited, and a known polymerization method according to the type of the polymerizable monomer to be used can be employed. The polymerization initiating means can be carried out by using radical polymerization initiators such as various peroxides and azo compounds, or irradiating with ultraviolet rays, α rays, β rays, γ rays or the like or using both in combination.

  The radical polymerization initiator is not particularly limited, and publicly known ones can be used, but representative examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, Diacyl peroxides such as lauroyl peroxide and acetyl peroxide; peroxyl such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate Oxyesters; percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4- Methyl valeronitrile), 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexane-1 such azo compounds carbonitrile) and the like.

  The amount of these thermal polymerization initiators used varies depending on the polymerization conditions, the type of initiator, the type and composition of the polymerizable monomer, and cannot be unconditionally limited. On the other hand, it is preferable to use in the range of 0.01 to 10 parts by mass. The above thermal polymerization initiators may be used alone or in combination.

  In the case of polymerization by irradiation with light such as ultraviolet rays, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aethofenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2. -Methyl-1-phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthioo Xanthone, bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzo B Diphenyl - phosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - be used butanone -1 or the like.

  These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers. The said photoinitiator may be used independently and may be used in mixture of multiple. Moreover, you may use the said thermal polymerization initiator together with a photoinitiator.

  A particularly preferred method for obtaining a cured product from the photochromic curable composition of the present invention is to cure the photochromic curable composition of the present invention containing the photopolymerization initiator by irradiating it with ultraviolet rays or the like, and further heating as necessary. Thus, the polymerization is completed.

  When the polymerization is performed by irradiation with ultraviolet rays, a known light source can be used without any limitation. Specific examples of the light source include an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc, a germicidal lamp, a metal halide lamp, and an electrodeless lamp. The time of light irradiation using the light source may be appropriately determined depending on the kind of the photopolymerization initiator, the absorption wavelength and sensitivity, the film thickness of the photochromic layer, and the like. Moreover, when using an electron beam for a light source, a photochromic layer can also be hardened, without adding a photoinitiator.

  The cured product thus obtained can be used as a photochromic optical material as it is, but is usually coated with a hard coat layer for the purpose of preventing the occurrence of scratches during wearing. used. Thereby, the scratch resistance can be improved.

  As a coating agent (hard coat agent) for forming the hard coat layer, known ones can be used without any limitation. Specifically, a hard coat agent mainly composed of a silane coupling agent or an oxide sol such as silicon, zirconium, antimony, aluminum, titanium, or a hard coat agent mainly composed of an organic polymer can be used. .

Further, a cured product of the photochromic curable composition alone of the present invention, an optical material having a coating layer made of the curable composition (coating agent) on the surface of the optical substrate, or a hard coat layer on the coating layer. On the surface of the formed optical article, processing such as antireflection treatment and antistatic treatment by deposition of a thin film of metal oxide such as SiO ₂ , TiO ₂ , ZrO ₂ , application of a thin film of organic polymer, etc. and secondary It is also possible to perform processing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Synthesis example 1
<Synthesis of Component (I) Polymerizable Monomer A>
Under a nitrogen stream, 95 g (0.10 mol) of 1,2-propanediol isobutyl POSS and 42 g (0.20 mol) of 2,2,4-trimethylhexamethylene diisocyanate were charged in a 1 L four-necked flask at 3O <0> C. Stir for hours. Thereafter, 26 g (0.20 mol) of hydroxyethyl methacrylate and 0.08 g of methoquinone were added and stirred at 70 ° C. for 3 hours. After confirming that the reaction was completed by quantifying the amount of residual isocyanate, it was cooled to room temperature.

When the nuclear magnetic resonance spectrum of the proton was measured for the resulting viscous body, a peak for 126 protons at 1 to 5 ppm, and a proton content of 4 protons based on a double bond of a methacryl group which is a radical polymerizable group at 5 to 7 ppm. And 4 protons based on urethane were observed. The Measurement of the infrared absorption spectrum disappeared peak of 2260 cm ^-1 based on isocyanates, that appeared peak based on urethanes 1740 cm ^-1 was confirmed.

  From the above, this viscous body has the following formula (A)

It was confirmed that the compound represented by the structure shown by was included.

Synthesis example 2
<Synthesis of polymerizable monomer B of component (I)>
In a 1 L four-necked flask under nitrogen flow, 85 g (0.05 mol) of octa (3-hydroxy-3-methylbutyldimethylsiloxy) POSS and 81 g (0.40 mol) of 2,2,4-trimethylhexamethylene diisocyanate were added. The mixture was stirred and stirred at 70 ° C for 3 hours. To this was added 46 g (0.40 mol) of hydroxyethyl acrylate and 0.11 g of methoquinone, and the mixture was stirred at 70 ° C. for 3 hours. By confirming the amount of residual isocyanate, the reaction was confirmed to be complete, and cooled to room temperature. I got a sticky body.

When the nuclear magnetic resonance spectrum of proton was measured for the resulting viscous body, a peak corresponding to about 304 protons at 1 to 5 ppm and 24 protons based on a double bond of a methacryl group which is a radical polymerizable group at 5 to 7 ppm. A peak for 16 minutes and a peak for 16 protons based on urethane were observed. The Measurement of the infrared absorption spectrum disappeared peak of 2260 cm ^-1 based on isocyanates, that appeared peak based on urethanes 1740 cm ^-1 was confirmed. From the above, this viscous body has the following formula (B)

It was confirmed that the compound represented by the structure shown by was included. This is a compound in which the oxygen atom (—O—) at the left end of R is bonded to a Si atom of a silsesquioxane skeleton having a cage structure.

Synthesis example 3
<Synthesis of Component I Polymerizable Monomer C>
In a 1 L four-necked flask under nitrogen stream, 89 g (0.40 mol) of isophorone diisocyanate and 100 g (0.20 mol) of polycarbonate polyol having an average molecular weight of 500 were charged and reacted at 70 ° C. for 3 hours to prepare a prepolymer having an isocyanate group. A polymer was obtained. To this, 96 g (0.10 mol) of trans-cyclohexanediol isobutyl POSS was added and stirred at 70 ° C. for 3 hours. Furthermore, 41 g (0.20 mol) of triethylene glycol monoacrylate and 0.16 g of methoquinone were added and stirred at 70 ° C. for 3 hours. It was confirmed that the reaction was completed by quantifying the amount of residual isocyanate, and cooled to room temperature to obtain a viscous body.

When the nuclear magnetic resonance spectrum of the proton was measured for the resulting viscous body, a peak of about 250 protons at 1 to 5 ppm, and 6 protons based on a double bond of an acrylic group which is a radical polymerizable group at 5 to 7 ppm. And a peak corresponding to 8 protons based on urethane were observed. The Measurement of the infrared absorption spectrum disappeared peak based on isocyanate 2260 cm ^-1 based on isocyanates, that appeared peak based on urethanes 1740 cm ^-1 was confirmed. From the above, this viscous body has the following formula (C)

It was confirmed that the compound represented by the structure shown by was included. It is a compound in which the methylene group (—CH ₂ —) at the left end of R is bonded to the Si atom of the silsesquioxane skeleton having a cage structure.

Synthesis example 4
<Synthesis of Component I Polymerizable Monomer D>
Under a nitrogen stream, 84 g (0.40 mol) of 2,2,4-trimethylhexamethylene diisocyanate and 100 g (0.20 mol) of polycarbonate polyol having a molecular weight of 500 were charged into a 1 L four-necked flask and reacted at 70 ° C. for 3 hours. Thus, a prepolymer having an isocyanate group was obtained. To this, 92 g (0.10 mol) of aminoethylaminopropylisobutyl POSS was added and stirred at 70 ° C. for 3 hours. Furthermore, 41 g (0.20 mol) of triethylene glycol monoacrylate and 0.16 g of methoquinone were added and stirred at 70 ° C. for 3 hours. By quantifying the amount of residual isocyanate, it was confirmed that the reaction was complete, and then cooled to room temperature to obtain a polymerizable monomer D.

When the nuclear magnetic resonance spectrum of the proton was measured for the resulting viscous body, a peak of about 250 protons at 1 to 5 ppm, and 6 protons based on a double bond of an acrylic group which is a radical polymerizable group at 5 to 7 ppm. A peak for 9 minutes and a peak for 9 protons based on urethane and urea were observed. The Measurement of the infrared absorption spectrum disappeared peak based on isocyanate 2260 cm ^-1 based on isocyanate, the peak based on the urethane and urea 1740 cm ^-1 and ^{1600 cm} -1 cm appeared was confirmed. From the above, this viscous body has the following formula (D)

It was confirmed that the compound represented by the structure shown by was included. It is a compound in which the methylene group (—CH ₂ —) at the left end of R is bonded to the Si atom of the silsesquioxane skeleton having a cage structure.

  The abbreviations and names of the compounds used as component (II), component (III) and other components are shown below.

Component (II): Photochromic compound PC1:

Component (III): Other radical polymerizable monomer TMPT: Trimethylolpropane trimethacrylate.
BPE100: 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (having an average chain length of ethylene glycol chain of 2.6)
A400: Polyethylene glycol diacrylate (the average chain length of the ethylene glycol chain is 9 and the average molecular weight is 508).
U-2PHA: urethane acrylate obtained by reacting isophorone diisocyanate and hydroxyethyl acrylate in a molar ratio of 1: 2.
GMA: glycidyl methacrylate.
MSD: α-methylstyrene dimer.

Other components Photopolymerization initiator CGI1800: Mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide (mass ratio: 3 to 1).

Thermal polymerization initiator perbutyl ND: t-butyl peroxyneodecanoate.
Perocta O: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.

Hindered amine light stabilizer Tinuvin 765: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

Hindered phenol antioxidant IRGANOX245: ethylene bis (oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate].

-Moisture-curing primer TR-SC-P manufactured by Tokuyama Corporation.

Example 1
With respect to 100 parts by mass of the polymerizable monomer A produced in Synthesis Example 1, 0.05 part by mass of PC1 as a photochromic compound, 1 part by mass of perbutyl ND and 0.1 part by mass of perocta O as a polymerization initiator are sufficiently added. A photochromic curable composition was obtained by mixing. (The blending ratio of the photochromic curable composition is summarized in Table 1.) This mixed solution was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and the above-mentioned was performed by cast polymerization. The polymerizable monomer composition was polymerized. The polymerization was performed using an air furnace, gradually increasing the temperature from 30 ° C. to 90 ° C. over 18 hours, and maintaining at 90 ° C. for 2 hours. After the polymerization, the cured product was removed from the glass mold of the mold.

  The following evaluation was performed using the obtained photochromic hardened body (thickness 2 mm). The results are shown in Table 2.

  (1) Vickers hardness: Vickers hardness was obtained from the indentation by pushing the Vickers indenter into the obtained photochromic cured product using a hardness meter PMT-X7A with automatic measurement (reading) device manufactured by Matsuzawa Co., Ltd. at 10 gf for 30 seconds. . The Vickers hardness is an index as to whether or not a flaw is introduced in the lens processing process. As a guide, scratches are difficult to enter when the Vickers hardness exceeds 4.5, and scratches tend to occur when the hardness is 4.5 or less.

(2) Color density: To the obtained photochromic cured product, a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics was applied at 20 ° C. ± 1 ° C. through an aeromass filter (manufactured by Corning), a photochromic coating layer. The surface is irradiated with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² for 300 seconds to develop a color, and the maximum absorption wavelength at this time is a spectrophotometer (instant multimeter) manufactured by Otsuka Electronics Co., Ltd. Channel photo detector MCPD1000). The difference {ε (300) − between the absorbance {ε (300)} at the maximum absorption wavelength after irradiation with light for 300 seconds and the absorbance {ε (0)} at the wavelength of the cured product in a state where light is not irradiated ε (0)} was determined and used as the color density. It can be said that the higher this value, the better the photochromic characteristics.

  (3) Fading half-life: after irradiation with light for 300 seconds, the light irradiation is stopped, and the absorbance at the maximum wavelength of the cured product decreases to half of {ε (300) −ε (0)}. The time required {t1 / 2 (min)} was measured. It can be said that the shorter the time, the faster the fading speed and the better the photochromic characteristics.

(4) Repeated durability: The following deterioration acceleration test was conducted in order to evaluate the repeated durability of color development by light irradiation. That is, the obtained lens having the photochromic coating layer was accelerated and deteriorated for 200 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, and the color density (A ₀ ) before the test and the color density (A ₂₀₀ ) after the test were measured, and the value of {(A ₂₀₀ / A ₀ ) × 100} Was determined as a residual rate (%). It can be said that the higher the residual rate, the higher the repetition durability and the better the photochromic properties. The evaluation results obtained are summarized in Table 2.

Example 2
In Example 1, instead of 100 parts by mass of polymerizable monomer A, 40 parts by mass of polymerizable monomer B produced in Synthesis Example 2, 30 parts by mass of BPE500, 28 parts by mass of TMPT, 1 part by mass of GMA, and 1 part by mass of MSD were used. The same operation as in Example 1 was performed except that it was used. The blending ratio of the photochromic curable composition is shown in Table 1, and the obtained evaluation results are shown in Table 2.

Example 3
2 parts by mass of PC1 as a photochromic compound was added to 60 parts by mass of the polymerizable monomer C produced in Synthesis Example 3, 39 parts by mass of TMPT, and 1 part by mass of GMA, and mixed well. To this mixture, 5 parts by weight of tinuvin 765 as a light stabilizer, 3 parts by weight of IRGANOX245 as an antioxidant, and 0.5 parts by weight of CGI1800 as a polymerization initiator were added and mixed well to prepare a photochromic curable composition (coating Agent). (The blending ratio of the coating agent is shown in Table 3.) Using a spin coater 1H-DX2 manufactured by MIKASA, a plastic lens having a thickness of 2 mm (MR: thiourethane resin plastic lens; refractive index = 1.60) ) Was coated with a moisture-curing primer TR-SC-P at a rotational speed of 70 rpm for 15 seconds → 1000 rpm for 10 seconds. Thereafter, about 2 g of the coating agent obtained by the above method was spin-coated so that the film thickness of the photochromic coating layer became 40 μm under the conditions of 40 rpm at 60 rpm and 10 to 20 seconds at 600 rpm. The surface-coated lens was irradiated for 90 seconds using a metal halide lamp with an output of 200 mW / cm ^{2 in} a nitrogen gas atmosphere to cure the coating film. Thereafter, it was further heated at 110 ° C. for 1 hour (an optical material having a photochromic coating layer was produced).

  Evaluation similar to Example 1 was performed using the obtained optical material having a photochromic coating layer. The results are shown in Table 4.

Example 4
In Example 3, in place of 60 parts by mass of polymerizable monomer C, 39 parts by mass of TMPT, and 1 part by mass of GMA, Example 3 was used except that 100 parts by mass of polymerizable monomer D produced in Synthesis Example 4 was used. The same operation was performed. The blending ratio of the photochromic coating agent is shown in Table 3, and the obtained evaluation results are shown in Table 4.

Comparative Example 1
In Example 3, the same operation as Example 3 was performed except that the silsesquioxane derivative was not used and 60 parts by mass of A400, 39 parts by mass of TMPT, and 1 part by mass of GMA were used. Table 3 shows the blending ratio of the photochromic curable composition, and Table 4 shows the obtained evaluation results.

  An optical material having a photochromic coating layer produced using this photochromic curable composition had a low Vickers hardness.

Comparative Example 2
As a silsesquioxane compound having a radical polymerizable group and not having a urethane bond or urea bond, “methacryloylisobutyl POSS (registered trademark)” (manufactured by Hybrid Plastics, MA0702; having 8 Si, bonded to Si 90 parts by weight of U-2PHA is added to 10 parts by weight and mixed well, but MA0702 does not dissolve in urethane acrylate and is homogeneous. 10 parts by weight is a methacryloyloxypropyl group and the other 7 are isobutyl groups. Could not be obtained. Further, the mixture was heated to 70 ° C. and stirred while applying ultrasonic waves, but a uniform liquid could not be obtained. Therefore, it was not possible to dissolve the photochromic compound and to produce a cured product.

Claims (10)

In the molecule,
(I-1) a silsesquioxane skeleton having a cage structure;
(I-2) at least one linking group selected from a urethane bond, a thiourethane bond, and a urea bond;
(I-3) A photochromic curable composition comprising (I) a silsesquioxane derivative having a radical polymerizable group and (II) a photochromic compound. The (I) silsesquioxane derivative is
(A1) a silsesquioxane compound having a cage structure having an active hydrogen group;
(A2) a diisocyanate compound;
The photochromic curable composition according to claim 1, which is a reaction product obtained by reacting (A3) an active hydrogen group and a polymerizable monomer having a radical polymerizable group as essential components. The (I) silsesquioxane derivative is
(A1) a silsesquioxane compound having a cage structure having an active hydrogen group;
(A4) The photochromic curable composition according to claim 1, which is a reaction product obtained by reacting an isocyanate group and a polymerizable monomer having a radical polymerizable group as essential components. The (I) silsesquioxane derivative is
(A5) a silsesquioxane compound having a cage structure having an isocyanate group;
(A3) The photochromic curable composition according to claim 1, which is a reaction product obtained by reacting a polymerizable monomer having an active hydrogen group and a radical polymerizable group as essential components. The (I) silsesquioxane derivative is
(A5) a silsesquioxane compound having a cage structure having an isocyanate group;
(A6) a compound having two active hydrogen groups;
(A4) The photochromic curable composition according to claim 1, which is a reaction product obtained by reacting an isocyanate group and a polymerizable monomer having a radical polymerization group as essential components.   The photochromic curable composition according to claim 1, wherein the (I-3) radical polymerizable group is a group selected from a (meth) acryl group, a vinyl group, and an allyl group.   The photochromic curable composition according to claim 1, wherein the (II) photochromic compound comprises a compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton.   A coating agent comprising the photochromic curable composition according to claim 1.   An optical material having a photochromic coating layer obtained by curing the coating agent according to claim 8 on at least one surface of an optical substrate.   A photochromic cured product obtained by curing the photochromic curable composition according to claim 1.