JP2017052869A - Photochromic curable composition, cured product thereof, and laminate including said cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic curable composition in which a photochromic cured product (including a photochromic laminate) that has a good photochromic property and scratch resistance, and in addition hardly causes poor appearance such as cracks, can be produced.SOLUTION: Provided is a photochromic curable composition characterized in comprising (A1) a long-chain (meth)acrylic monomer component having a long molecular chain such as polyethylene glycol dimethacrylate, (A2) trimethylolpropane tri-methacrylate and/or a 3-functional or more (meth)acrylic monomer component having a silsesquioxane structure and containing 10 or more (meth) acryl groups, (B)a photochromic compound, and (C) an inorganic oxide fine particle.SELECTED DRAWING: None

Description

  The present invention relates to a novel photochromic curable composition, a novel photochromic cured product obtained by curing the composition, and a novel photochromic laminate obtained by laminating the photochromic cured product on a plastic substrate.

  Specifically, the present invention relates to a novel photochromic curable composition having a hard surface hardness and capable of forming a photochromic coat layer having excellent photochromic properties. And this invention relates to the photochromic laminated body which laminated | stacked this hardening body on the novel hardening body containing this composition and a plastic base material.

  Photochromism is a reversible action that quickly changes color when a compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, and returns to its original color when light is turned off and placed in a dark place. It is applied to various uses. As photochromic compounds having such properties, fulgimide compounds, spirooxazine compounds, chromene compounds and the like have been found. Since these compounds can be made into optical articles having photochromic properties by being compounded with plastics, many studies have been made on compounding.

  For example, photochromism is also applied in the field of spectacle lenses. Photochromic eyeglass lenses that use photochromic compounds function as sunglasses by rapidly coloring the lens outdoors when exposed to light containing ultraviolet rays such as sunlight, and fading indoors where there is no such light irradiation. It functions as normal transparent glasses, and its demand has increased in recent years.

  As photochromic eyeglass lenses, those obtained by imparting photochromic performance to a plastic lens are widely used from the viewpoint of lightness and safety. In order to impart photochromic performance to a plastic lens, generally, an organic photochromic compound is used, and photochromic properties are imparted to the plastic lens by various methods. For example, photochromic eyeglass lenses are manufactured by a method called a coating method. Specifically, a photochromic coating (photochromic laminate) having a photochromic coating layer (photochromic cured body) is obtained by applying a photopolymeric coating agent containing a radical polymerizable component and a photochromic compound to the surface of a plastic lens substrate and curing it. It is a method of manufacturing.

  This coating method is an excellent method in that photochromic performance can be imparted regardless of the material of the plastic lens. In this method, in order to improve photochromic properties such as color density and fading speed, it is necessary to determine the types and blending amounts of various radical polymerizable monomers.

  Various improvements have been made to the photochromic curable composition for forming the photochromic coating layer. For example, a method is known in which the ratio of an acrylic monomer and a methacrylic monomer in a photochromic curable composition is limited to improve the photochromic properties and the adhesion of the hard coat layer (Patent Document 1). Moreover, the method of improving the surface hardness of the photochromic layer obtained by mix | blending a silsesquioxane monomer with a photochromic curable composition is also examined (patent document 2). According to these methods, a photochromic laminate having excellent performance can be produced.

  In recent years, the demand for photochromic laminates has been further increased. For example, in a photochromic lens (photochromic laminate) having a photochromic coating layer, a photochromic coating layer having a higher surface hardness is desired from the viewpoint of preventing scratching of the photochromic coating layer (hereinafter also referred to as scratch resistance). ing. If the surface hardness of the photochromic coating layer itself can be further increased, then the scratch resistance of the optical material on which the hard coating layer and the antireflection film are formed can be improved. In order to satisfy the recent high demands as described above, the methods described in Patent Documents 1 and 2 have been desired to be improved in the following points.

  For example, according to the study by the present inventors, the method described in Patent Document 1 tends to reduce the surface hardness of the resulting photochromic coat layer when attempting to improve the photochromic characteristics. On the contrary, when the surface hardness was improved, the photochromic characteristics tended to decrease.

  On the other hand, in the method described in Patent Document 2, the surface hardness of the photochromic coating layer can be improved by using a silsesquioxane monomer. However, although it is considered that the resulting photochromic coat layer is caused by a decrease in flexibility, appearance defects such as cracks occur after the formation of the photochromic coat layer or in a hard coat forming process which is a subsequent process. There was a case. This tendency was remarkable when a photochromic coat layer was formed on a plastic lens having a strength of several plastic lenses and / or a plastic lens having an inclined edge. Among them, particularly when the primer coat layer is formed on the plastic lens and the photochromic coat layer is formed on the primer coat layer, the problem of poor appearance is particularly remarkable. For this reason, when forming a photochromic coat layer on the above plastic lenses, it was necessary to limit the blending amount of the silsesquioxane monomer in the curable composition in order to suppress poor appearance. In order to improve the surface hardness while limiting the blending amount of the silsesquioxane monomer, a polyfunctional (having a plurality of polymerizable groups in the molecule) monomer in the curable composition instead of the silsesquioxane monomer It is necessary to increase the blending amount. In this case, the photochromic characteristics tended to decrease.

International Publication No. 2011-125156 Pamphlet International Publication No. 2013/008825 Pamphlet

As described above, in the conventional photochromic curable composition,
The effect of providing a photochromic coating layer (photochromic cured product) having more excellent photochromic properties while maintaining excellent scratch resistance, and that appearance defects such as cracks are less likely to occur when the photochromic coating layer is formed. It was difficult to be highly satisfied. Therefore, it has been desired to develop a photochromic curable composition, a cured product thereof, and a photochromic laminate having the cured product that highly satisfy all these characteristics.

  Therefore, an object of the present invention is to provide a photochromic curable composition capable of producing a photochromic cured body (including a photochromic laminate) that has good photochromic properties and scratch resistance and is less likely to cause appearance defects such as cracks. There is to do.

  The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, it has been found that by adding inorganic oxide fine particles to the photochromic curable composition, the surface hardness can be improved while maintaining the photochromic properties of the resulting photochromic coat layer (photochromic cured product). As a result of further examination, a photochromic compound and inorganic oxide fine particles were added to a polymerizable composition containing a specific polyfunctional (meth) acrylic monomer component having a long molecular chain and other polyfunctional (meth) acrylic monomer components. By blending, it has been found that the photochromic curable composition has a sufficient surface hardness while being greatly improved in photochromic properties, and is less prone to cracking when the photochromic coat layer is formed, and the present invention has been completed. .

That is, the first aspect of the present invention is
(A1) At least one long-chain (meth) acrylic monomer component selected from the group consisting of the following component (A1a), component (A1b), component (A1c), and component (A1d) (hereinafter simply referred to as component (A1)) In some cases)
(A2) The following (A2a) component, and at least one multi-functional (meth) acrylic monomer component selected from the group consisting of (A2b) component (hereinafter sometimes simply referred to as (A2) component),
(B) a photochromic compound (hereinafter sometimes simply referred to as component (B)), and (C) inorganic oxide fine particles (hereinafter sometimes simply referred to as component (C)).
A photochromic curable composition comprising:

(A1) monomer used for component;
(A1a) component: a polyalkylene glycol di (meth) acryl monomer component having a molecular weight of 600 to 2000,
(A1b) component: (meth) acrylic monomer component represented by the following general formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a is an average value of 8 to 15, and b is an integer of 3 to 6. ),
(A1c) component: (meth) acrylic monomer component represented by the following general formula (2)

(Where
R ⁴ and R ⁵ are each a hydrogen atom or a methyl group,
R ⁶ and R ⁷ are each a hydrogen atom or a methyl group,
A is the following formula

Any of the groups shown in
c and d are each independently an integer of 1 or more, and c + d is an average value of more than 15 and 40 or less. ),
(A1d) component: (meth) acrylic monomer component represented by the following general formula (3)

(Where
B and B ′ are each a linear or branched alkylene group having 2 to 15 carbon atoms, e is an average value of 2 to 20,
When a plurality of B are present, B may be the same group or different groups,
R ⁸ and R ⁹ are a hydrogen atom or a methyl group. ).

(A2) monomer used for component;
(A2a) component: (meth) acrylic monomer component represented by the following general formula (4)

(Wherein preferably
R ¹¹ is a hydrogen atom or a methyl group,
R ²¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³¹ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a ′ is an average value of 0 to 3, and b ′ is an integer of 3 to 6. ),
(A2b) component: (meth) acrylic monomer component represented by the following general formula (5)

(Where
A plurality of R ¹⁰ may be the same or different from each other,
At least 10 R ¹⁰ are organic groups containing a (meth) acryl group,
f is a polymerization degree and is an integer of 15-50. ).

  As a matter of course, in the present invention, the (meth) acrylic monomer refers to a methacrylic monomer and / or an acrylic monomer, and the (meth) acrylic group refers to a methacrylic group and / or an acrylic group. .

  In 1st this invention, it is preferable that 10-100 mass parts of said (C) component is included per 100 mass parts of total of said (A1) component and said (A2) component. By satisfying this blending amount, the surface hardness of the photochromic cured product can be further improved. Furthermore, since the dispersion stability of the component (C) can be improved and the solubility of the component (B) can also be improved, the storage stability of the photochromic curable composition itself can be improved, and the photochromic properties are also improved. Can be improved.

  Moreover, in 1st this invention, it is preferable that 30-85 mass parts of said (A1) components are included per 100 mass parts of total of said (A1) component and said (A2) component. By satisfying this blending amount, the effect of suppressing photochromic properties, surface hardness, and crack generation is further enhanced.

  In the first aspect of the present invention, in order to enhance the photochromic properties and further improve the storage stability of the photochromic curable composition itself, when the total amount of the component (A1) is 100% by mass, (A1 ) Component contains (A1a) 40-40% by mass, (A1b) 0-40% by mass, (A1c) 0-40% by mass, and (A1d) 0-40% by mass. Is preferred.

  Furthermore, in the first aspect of the present invention, the component (C) is a photochromic compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton, the component (A1), and the (A2) When 0.1-10 mass parts is contained per 100 mass parts of total of a component, it can be conveniently used as a photochromic coat layer.

  In the first aspect of the present invention, (A3) includes a monofunctional (meth) acrylic monomer component having one (meth) acrylic group in the molecule (hereinafter sometimes simply referred to as (A3) component), It is preferable that 0.1-50 mass parts of said (A3) components are contained per 100 mass parts of total of said (A1) component and said (A2) component. By including the component (A3), the durability of the resulting photochromic cured product can be improved, and the adhesion with the other layer of the cured product can be further enhanced.

  2nd this invention is the photochromic hardened | cured material which hardened | cured the photochromic curable composition which is 1st this invention. In the present invention, a relatively thin film may be used as a photochromic coating layer. The cured product of the present invention obtained by curing the photochromic curable composition exhibits an excellent effect.

  3rd this invention is a photochromic laminated body which has the photochromic hardening body of 2nd this invention on a plastic base material. In particular, the present invention is effective when a primer layer made of a urethane resin is formed on a plastic substrate and the photochromic cured product is formed on the primer layer.

  According to the present invention, a photochromic cured product that has excellent photochromic properties while maintaining good surface hardness with good scratch resistance and that does not cause appearance defects such as cracks when forming a photochromic coating layer, and the cured product The photochromic laminated body which has can be manufactured. Moreover, according to this invention, the photochromic curable composition excellent in storage stability can be manufactured.

The photochromic curable composition of the present invention is
(A1) at least one long-chain (meth) acrylic monomer component selected from the group consisting of (A1a) component, (A1b) component, (A1c) component, and (A1d) component described in detail below,
(A2) At least one multi-functional (meth) acrylic monomer component selected from the group consisting of (A2a) component and (A2b) component described in detail below,
A photochromic curable composition comprising (B) a photochromic compound and (C) inorganic oxide fine particle particles. Each of these components will be described in detail.

(A1) component: long-chain (meth) acrylic monomer component In the present invention, at least selected from the group consisting of (A1a) component, (A1b) component, (A1c) component, and (A1d) component, which will be described in detail below. It contains one kind of long chain (meth) acryl monomer component. By blending this component (A1), a photochromic coating layer having excellent photochromic properties, less cracking, and good appearance can be formed. Hereinafter, the specific component (A1) will be described.

(A1a) Component In the present invention, the (A1) component includes a polyalkylene glycol di (meth) acryl monomer component ((A1a) component) having a molecular weight of 600 to 2000. As the component (A1a), a polyalkylene glycol di (meth) acrylate monomer having a molecular weight of 600 to 2000 is obtained from polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and a mixture of polypropylene glycol and polyethylene glycol. Examples include (meth) acryl monomer components such as di (meth) acrylate and polytetramethylene glycol di (meth) acrylate. Specifically, polyethylene glycol dimethacrylate having an average molecular weight of 736 ((meth) acryl equivalent 368), polyethylene glycol dimethacrylate having an average molecular weight of 1136 ((meth) acryl equivalent 568), polyethylene glycol diacrylate having an average molecular weight of 708 ((meth) ) Acrylic equivalent 354), polyethylene glycol diacrylate having an average molecular weight of 1108 ((meth) acrylic equivalent 554), dimethacrylate having an average molecular weight of 1114 obtained from a mixture of polypropylene glycol and polyethylene glycol ((meth) acrylic equivalent 557), average molecular weight 808 propylene glycol diacrylate ((meth) acrylic equivalent 404), polytetramethylene glycol diacrylate ((meth) acrylic) having an average molecular weight of 758 Mention may be made of the amount 378), and the like.

  In (A1a) component, the molecular weight employ | adopts the theoretical molecular weight computed from the raw material preparation ratio at the time of manufacture. However, since these (meth) acrylic monomers are not a single component but a mixture, they are expressed as an average molecular weight. The component (A1a) needs to have a molecular weight of 600 to 2000. When the molecular weight is less than 600, the photochromic properties, particularly the fading speed, are lowered, and when it exceeds 2000, the surface hardness is lowered, which is not preferable.

  As the component (A1a), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A1a).

(A1b) Component Next, the (A1b) component represented by the following general formula (1) will be described.
The component (A1b) has the following general formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a is an average value of 8 to 15, and b is an integer of 3 to 6. )
R ² in Formula (1) is a hydrogen atom, a methyl group, or an ethyl group. R ¹ is preferably a methyl group from the viewpoint of surface hardness.

R ³ in Formula (1) is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms. Specific examples include a group derived from a polyol or an organic group containing a trivalent to hexavalent hydrocarbon group.

  In the above formula (1), a is an average value of 8-15. Among these, from the viewpoint of photochromic properties, a is more preferably an average value of 8-12. In addition, since the polyfunctional (meth) acryl monomer shown by Formula (1) is normally obtained with the mixture from which the value of a differs, a was made into the average value.

  B in the above formula (1) is an integer of 3 to 6. Among these, 3 or 4 is preferable from the viewpoint of photochromic characteristics and appearance.

  Specific examples of the monomer (A1b) component represented by the formula (1) are trimethylolpropane polyethylene glycol triacrylate having an average molecular weight of 1616 (a = 10, b = 3, (meth) acryl equivalent 539), average molecular weight 1892. Pentaerythritol polyethylene glycol tetraacrylate (a = 9, b = 4, (meth) acryl equivalent 473), glycerin polyethylene glycol triacrylate (a = 9, b = 3, (meth) acryl equivalent 481) having an average molecular weight of 1442 and the like Is mentioned.

  As the component (A1b), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A1b).

(A1c) Component Next, the (A1c) component represented by the following general formula (2) will be described.

  The component (A1c) has the following general formula (2)

(Where
R ⁴ and R ⁵ are each a hydrogen atom or a methyl group,
R ⁶ and R ⁷ are each a hydrogen atom or a methyl group,
A is the following formula

Any of the groups shown in
c and d are each independently an integer of 1 or more, and c + d is an average value of more than 15 and 40 or less. ).

  Usually, since the bifunctional (meth) acrylic monomer (A1c) component represented by the formula (2) is obtained from a mixture having different values of c and d, c + d is an average value.

R ⁴ and R ⁵ in the formula (2) are each a hydrogen atom or a methyl group. Among these, a methyl group is preferable from the viewpoint of photochromic properties (particularly weather resistance) and surface hardness.

R ⁶ and R ⁷ in the formula (2) are each a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of photochromic properties.

A in the above formula (2) may be selected from the divalent groups shown above. Among them, ease of availability of raw materials in the production of (A1c) component, and from the viewpoint of the photochromic properties of the photochromic cured product, -C (CH ₃₎ 2 _- and most preferably a group.

  Specific examples of the component (A1c) include 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (c + d = 17, (meth) acrylic equivalent 556), 2,2-bis [4- Methacryloxy (polyethoxy) phenyl] propane (c + d = 20, (meth) acryl equivalent 622), 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (c + d = 30, (meth) acryl equivalent 842), 2, 2-bis [4-acryloxy (polyethoxy) phenyl] propane (c + d = 20, (meth) acrylic equivalent 608), 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (c + d = 30, (meth) acrylic Equivalent 828).

  As the component (A1c), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the blending amount of the component (A1c).

(A1d) Component Next, the (A1d) component represented by the following general formula (3) will be described.

  The component (A1d) has the following general formula (3)

(Where
B and B ′ are each a linear or branched alkylene group having 2 to 15 carbon atoms, e is an average value of 2 to 20,
When a plurality of B are present, B may be the same group or different groups,
R ⁸ and R ⁹ are a hydrogen atom or a methyl group. ).

  B and B ′ in the general formula (3) are each a linear or branched alkylene group having 2 to 15 carbon atoms. Among these, from the viewpoint of the moldability of the photochromic curable composition and the photochromic properties (color density, fading speed) of the obtained cured product, a linear or branched alkylene group having 3 to 9 carbon atoms is preferable. A linear or branched alkylene group having 4 to 7 carbon atoms is preferable. Examples of specific alkylene groups include trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, nonamethylene group, dodecamethylene group, pentadecamethylene group, 1-methyltriethylene group, Examples thereof include 1-ethyltriethylene group and 1-isopropyltriethylene group.

  In the said General formula (3), e is 2-20 by an average value. In other words, the component (A1d) represented by the formula (3) may be composed only of those having the same bond length (both having the same molecular weight) of -B-O- (C = O)-or different. It may be a mixture of materials (with different molecular weights). Usually, since the component (A1d) represented by the formula (3) is obtained as a mixture having different molecular weights, e is an average value. Among these, from the viewpoint of moldability and photochromic properties (color density, fading speed), e is preferably an average value of 2 to 8, and e is preferably an average value of 2 to 5.

  As described above, a plurality of B may exist. In this case, B may be the same group or different groups. Among these, from the viewpoint of compatibility with other monomers, it is preferable that different groups of B are mixed. When B is a different group, it is preferable that 10 to 90 mol% of alkylene groups having 3 to 5 carbon atoms and 10 to 90 mol% of alkylene groups having 6 to 9 carbon atoms are included in all groups B, Among the groups B, it is most preferable that 10 to 90 mol% of the alkylene group having 4 to 5 carbon atoms and 10 to 90 mol% of the alkylene group having 6 to 7 carbon atoms are contained. By using such B, the compatibility with other polymerizable monomers is improved, and a photochromic curable composition having good dispersibility can be obtained.

R ⁸ and R ⁹ in the general formula (3) are a hydrogen atom or a methyl group. Among these, a hydrogen atom is preferable from the viewpoint of photochromic properties (color density, fading speed).

  The component (A1d) represented by the general formula (3) can be produced by reacting polycarbonate diol with (meth) acrylic acid. Examples of the polycarbonate diol as a raw material include polycarbonate diol (number average molecular weight 500 to 2000) obtained by phosgenation of trimethylene glycol, polycarbonate diol (number average molecular weight 500 to 2000) obtained by phosgenation of tetramethylene glycol, Polycarbonate diol (number average molecular weight 500 to 2000) obtained by phosgenation of pentamethylene glycol, polycarbonate diol (number average molecular weight 500 to 2000) obtained by phosgenation of hexamethylene glycol, polycarbonate obtained by phosgenation of octamethylene glycol Diol (number average molecular weight 500-2000), polycarbonate diol (number average molecular weight 500-2000) obtained by phosgenation with nonamethylene glycol Polycarbonate diol obtained by phosgenation of triethylene glycol and tetramethylene glycol (number average molecular weight 500 to 2000), polycarbonate diol obtained by phosgenation of tetramethylene glycol and hexamethylene diglycol (number average molecular weight 500 to 2000) ), Polycarbonate diol obtained by phosgenation of pentamethylene glycol and hexamethylene glycol (number average molecular weight 500-2000), polycarbonate diol obtained by phosgenation of tetramethylene glycol and octamethylene glycol (number average molecular weight 500) -2000), polycarbonate diol (number average molecular weight 500-2000) obtained by phosgenation of hexamethylene glycol and octamethylene glycol, 1-methyl Polycarbonate diols obtained by the phosgenation of trimethylene glycol (number average molecular weight 500 to 2000) can be mentioned. In addition, as above-mentioned, it is preferable to use the polycarbonate diol used for a raw material whose number average molecular weight is 500-2000.

  As the component (A1d), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A1d).

(Preferable (A1) component amount of each component)
In the present invention, the component (A1) is at least one long-chain (meth) acrylic monomer component selected from the group consisting of the component (A1a), the component (A1b), the component (A1c), and the component (A1d). Is included. These (A1) components are polyfunctional monomers having two or more (meth) acryl groups in the molecule. Especially, from a viewpoint of coexistence of a photochromic characteristic and surface hardness, it is preferable that the number of (meth) acryl groups in a molecule | numerator is 2-6, and it is more preferable that it is 2-3. Among the components (A1) as described above, those having a (meth) acryl equivalent of 300 to 1000 are preferable.

  The component (A1) can be used alone (for example, only the component (A1a)), or a plurality of types (for example, both the component (A1a) and the component (A1b)) are mixed and used. You can also In the case of a plurality of types, the total mass thereof is regarded as the blending amount of the component (A1).

  The component (A1) is not particularly limited, but in order to enhance the photochromic properties and to further improve the storage stability of the photochromic curable composition itself, the total amount of the component (A1) is 100% by mass. When the component (A1a) is 40 to 100% by mass, the component (A1b) is 0 to 40% by mass, the component (A1c) is 0 to 40% by mass, and the component (A1d) is preferably 0 to 40% by mass. . Among these, considering dispersion stability in a photochromic cured product such as an additive blended as necessary, the component (A1a) is 40 to 80% by mass, the component (A1b) is 0 to 40% by mass, and (A1c It is preferable that 0-40 mass% of a component and 10-40 mass% of (A1d) components are included.

  Furthermore, considering the productivity of the photochromic curable composition itself, recovery of the photochromic curable composition, dispersion stability of the additive in the photochromic cured product, the component (A1) is the component (A1a), and (A1d) ) Component. In this case, when the total amount of the component (A1) is 100% by mass, it is preferable that the component (A1a) contains 60 to 80% by mass and the component (A1d) contains 20 to 40% by mass.

Component (A2) In the present invention, the component (A2) is at least one multi-functional (meth) acrylic monomer component selected from the group consisting of the component (A2a) and the component (A2b), which will be described in detail below. is there.

(A2a) component In this invention, (A2a) component is a polyfunctional (meth) acryl monomer shown by following formula (4).

(Wherein preferably
R ¹¹ is a hydrogen atom or a methyl group,
R ²¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³¹ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a ′ is an average value of 0 to 3, and b ′ is an integer of 3 to 6. )
By blending the component (A2a) represented by the general formula (4), the surface hardness of the photochromic laminate (photochromic coat layer) can be improved, and the photochromic properties, particularly the color density, can be improved.

R ³¹ in the general formula (4) is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms. . Specific examples include a group derived from a polyol or an organic group containing a trivalent to hexavalent hydrocarbon group.

R ¹¹ or R ²¹ in the general formula (4) is a hydrogen atom or a methyl group. Among them, R ^11, from the viewpoint of surface hardness of the obtained photochromic cured product is preferably a methyl group.

  In the general formula (4), a 'is preferably an average value of 0 to 3, more preferably 0 or 1 from the viewpoint of surface hardness. Usually, since the component (A2a) is also obtained from a mixture, a 'is shown as an average value.

  In the above formula (1), b ′ is an integer of 3 to 6, and is preferably 3 or 4 from the viewpoint of photochromic properties, surface hardness, and appearance.

  Specific examples of the component (A2a) include trimethylolpropane trimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane tripropylene glycol trimethacrylate, tetramethylol. Multifunctional methacrylic monomers having a methacrylic group such as methanetetraethylene glycol tetramethacrylate, tetramethylolmethane tetrapropylene glycol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, Tetramethylo Methane tetraacrylate, trimethylolpropane triethylene glycol triacrylate, trimethylolpropane tripropylene glycol triacrylate, tetramethylol methane tetraethylene glycol tetraacrylate, tetramethylol methane tetrapropylene glycol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa The polyfunctional acrylic monomer which has acrylic groups, such as an acrylate, can be mentioned. Two or more of these polyfunctional (meth) acrylic monomers may be used in combination. As the component (A2a), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A2a).

  Among these polyfunctional (meth) acrylic monomers, trimethylolpropane trimethacrylate and ditrimethylolpropane tetramethacrylate are preferred from the viewpoint of photochromic properties (particularly fading speed) and surface hardness.

(A2b) Component In the present invention, the component (A2b) is a silsesquioxane monomer represented by the following formula (5).

(Where
A plurality of R ¹⁰ may be the same or different from each other,
At least 10 R ¹⁰ are organic groups containing a (meth) acryl group,
f is a polymerization degree and is an integer of 15-50. )
The weight average molecular weight of the component (A2b) is preferably 3,000 to 8,000, and the (meth) acryl equivalent is preferably 150 to 800. The average molecular weight of the component (A2d) is a value measured by a gel permeation chromatography method (GPC method).

Here, the organic group containing a (meth) acryl group in R ¹⁰ includes only a (meth) acryl group (a polymerizable group (for example, a (meth) acryl group or the like) is bonded directly to a silicon atom). Including things). Specifically, a (meth) acryl group, a (meth) acryloxypropyl group, a (3- (meth) acryloxypropyl) dimethylsiloxy group, and the like can be given. Among them, the (meth) acryloxypropyl group is particularly preferable because it is easy to obtain the raw material when the component (A2b) is produced, and high film strength can be obtained while exhibiting excellent photochromic properties.

R ¹⁰ in the general formula (6) is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a phenyl group when it is not an organic group containing a (meth) acryl group.

  As an alkyl group, a C1-C10 alkyl group is preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, An n-octyl group, an isooctyl group, etc. are mentioned.

  As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable. 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.

  The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. 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.

  In general, the silsesquioxane compound can have various structures such as a cage shape, a ladder shape, and a random shape, but the component (A2d) used in the present invention is preferably a mixture having a plurality of structures. As the component (A2b), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A2b).

(Preferable (A2) component amount of each component)
In the present invention, the component (A2) includes at least one (meth) acryl monomer component selected from the group consisting of the component (A2a) and the component (A2b).

  The component (A2) can be used alone (for example, only the component (A2a)), or a plurality of types (for example, both the component (A2a) and the component (A2b)) can be used in combination. You can also In the case of a plurality of types, the total mass thereof is regarded as the blending amount of the component (A2).

  The component (A2) is not particularly limited, but in order to enhance the photochromic properties and to increase the surface hardness of the resulting cured product, when the total amount of the component (A2) is 100% by mass, The component (A2a) preferably contains 50 to 100% by mass, the component (A2b) 0 to 50% by mass, the component (A2a) 60 to 100% by mass, and the component (A2b) 0 to 40% by mass. preferable. In particular, in order to reduce cracks in the photochromic cured product and increase the fading speed, it is preferable that the component (A2a) contains 85 to 95% by mass and the component (A2b) contains 5 to 15% by mass. However, in consideration of the productivity of the photochromic curable composition itself, only the component (A2a) (100% by mass of the component (A2a)) may be used.

In the present invention, a matrix in which the photochromic compound (component (B)) and inorganic particles (component (C)) are dispersed is used as the component (A1) and component (A2). ) Component. By using this (A1) component in combination with (A2), it is possible to exhibit photochromic properties, surface hardness, cracking suppression effects, or other effects. The component (A1) is a main component necessary for exhibiting excellent photochromic properties, and the component (A2) is a mechanical property of the photochromic cured product (for example, properties such as scratch resistance, tensile / bending strength). It is a necessary main component.

  The blending ratio of the component (A1) and the component (A2) preferably includes 30 to 85 parts by mass of the component (A1) per 100 parts by mass in total of the component (A1) and the component (A2) ((A2) The component is 15 to 70 parts by mass.) Hereinafter, the total mass of the component (A1) and the component (A2) may be simply used as a reference mass. By setting the component (A1) and the component (A2) to the above amounts, high film (cured body) strength can be obtained while expressing more excellent photochromic characteristics. In order to exhibit the more excellent effect, it is preferable to contain 50-80 mass parts (A1) component (20-50 mass parts of (A2) component) per 100 mass parts of reference | standard mass.

(A1) component, polymerizable monomer component other than component (A2) (other monomer)
In this invention, if (A1) component and (A2) component are contained as an essential component, it will not restrict | limit in particular, Another polymerizable monomer component can be included. Specifically, (A3) a monofunctional (meth) acryl monomer component having one (meth) acryl group in the molecule, and / or
(A4) The (meth) acryl monomer component which has two or more (meth) acryl groups in a molecule | numerator which does not correspond to (A1) component and (A2) component is mentioned. However, in the present invention, since the (A1) component and the (A2) component are the main components, the blending amounts of the (A3) component and the (A4) component are less than 100 parts by mass per 100 masses of the reference mass. Preferably, it is 50 parts by mass or less, and more preferably 45 parts by mass or less. Next, other monomers that can be suitably blended will be described.

(A3) Component In the present invention, (A3) a monofunctional (meth) acrylic monomer component having one (meth) acrylic group in the molecule (hereinafter sometimes simply referred to as the (A3) component) is blended. You can also. Especially, it is preferable that (A3) component is a monomer component which has an epoxy group and an alkoxy silyl group. The component (A3a) having an epoxy group will be described.

(A3a) Component In the present invention, as the (A3) component that can be suitably blended, a (meth) acrylic monomer component represented by the following formula (6) (hereinafter sometimes simply referred to as the (A3a) component) is blended. It is preferable to do.

(Where
R ¹² and R ¹³ are each a hydrogen atom or a methyl group,
R ¹⁴ and R ¹⁵ are each an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxy group, or the following formula (7):

A group represented by
j and k are numbers of 0 to 20 on average. The (meth) acryl monomer component ((A3a) component) which has an epoxy group shown by this is mentioned. By including the component (A3a), good photochromic characteristics can be obtained over a long period of time.

In R ¹⁴ and R ¹⁵ of the general formula (7), examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, and a tetramethylene group. The component (A3a) may be obtained in the form of a mixture of molecules having different molecular weights. Therefore, j and k are shown as average values.

  Examples of the component (A3a) include glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl methacrylate, polyethylene glycol glycidyl methacrylate having an average molecular weight of 406, and an average molecular weight of 538. Polyethylene glycol glycidyl methacrylate, polyethylene glycol glycidyl methacrylate having an average molecular weight of 1022, polypropylene glycol glycidyl methacrylate having an average molecular weight of 664, bisphenol A-monoglycidyl ether-methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, Glycidyl acrylate, glycidyl oxy Methyl acrylate, 2-glycidyloxyethyl acrylate, 3-glycidyloxypropyl acrylate, 4-glycidyloxybutyl acrylate, polyethylene glycol glycidyl acrylate having an average molecular weight of 406, polyethylene glycol glycidyl acrylate having an average molecular weight of 538, polyethylene glycol glycidyl acrylate having an average molecular weight of 1022 , 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, and the like. Among these, glycidyl methacrylate, glycidyloxymethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, and glycidyl acrylate are preferable, and glycidyl methacrylate is particularly preferable.

  As the component (A3a), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A3a).

  (A3a) Although the compounding quantity of a component is not restrict | limited in particular, when stability of a long-term photochromic characteristic is considered, it may be 0.1-10 mass parts with respect to 100 mass parts of reference masses. Preferably, the content is further preferably 0.3 to 5 parts by mass, and particularly preferably 0.3 to 3 parts by mass.

(A3b) Component In the present invention, the (A3) component has one (meth) acryl group in the molecule and has an alkoxysilyl group (hereinafter sometimes referred to simply as the (A3b) component). It is preferable to contain. By mix | blending (A3b) component, in the photochromic hardened | cured body obtained, adhesiveness with the hard-coat layer formed on a photochromic hardened | cured body can be improved as needed.

  Specific examples of the component (A3b) include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane and the like.

  As the component (A3b), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A3b).

  The compounding amount of the component (A3b) is not particularly limited, but is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the reference mass in consideration of adhesion with the hard coat layer. It is preferable that it is 5-15 mass parts.

Other (A3) component (A3) component other than (A3a) component and (A3b component), specifically, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate with an average molecular weight of 293, methoxypolyethylene glycol methacrylate with an average molecular weight of 468 , Methoxy polyethylene glycol methacrylate, phenoxyethyl methacrylate, average molecular weight 218, methoxy polyethylene glycol acrylate, average molecular weight 454, methoxy polyethylene glycol acrylate, phenoxyethylene glycol acrylate, phenoxy diethylene glycol acrylate, average molecular weight 1054, Phenoxypolyethylene with an average molecular weight of 412 Unsaturated carboxylic acids such as lenglycol acrylate, 2-hydroxy methacrylate, 2-hydroxy acrylate, stearyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, acrylic acid, methacrylic acid, maleic anhydride Ester compounds of acrylic acid or methacrylic acid such as methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, urethane (meth) acrylate, 2-isocyanatoethyl methacrylate, methylthioacrylate, benzylthioacrylate, benzylthio; And ester compounds of thioacrylic acid or thiomethacrylic acid such as methacrylate, etc. . These (A3a) component and (A3b component) other than (A3b component) can be blended as long as the effects of the present invention are not impaired.

(A3) Compounding amount of component (A3) The component is 0 in order to exert an excellent effect per 100 parts by mass (reference mass: 100 parts by mass) of the component (A1) and the component (A2). It is preferable that 1-50 mass parts is contained, and it is preferable that 0.1-45 mass parts is contained. Among these, in order to exhibit a particularly excellent effect in the present invention, it is preferable that at least one of the (A3a) component and the (A3b) component is included as the (A3) component. And it is preferable that both (A3a) component and (A3b) component are contained especially. When both are contained, it is preferable that the total compounding quantity of (A3a) component and (A3b) component shall be 2.1-30 mass parts with respect to 100 mass parts of reference masses, 2.3- The amount is more preferably 25 parts by mass, further preferably 2.3 to 23 parts by mass, and most preferably 5.3 to 18 parts by mass.

(A4) Component In the present invention, a (meth) acrylic monomer component having two or more (meth) acrylic groups in the molecule that does not correspond to the (A1) component and the (A2) component can also be included ( Hereinafter, it may be simply referred to as component (A4).

  As the component (A4), a known monomer can be used. Specifically, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 536, 1,3-butanediol di Methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, 2-methyl-1,8-octanediol dimethacrylate , Tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, pentapropylene glycol dimethacrylate, Polypropylene glycol dimethacrylate having a molecular weight of 536, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 508, 1,3-butanediol Diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol diacrylate Acrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, pentapropylene glycol diacrylate 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane having an average molecular weight of 452, 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane having an average molecular weight of 478, 2,2 having an average molecular weight of 540 -Bis [4-methacryloxy (polyethoxy) phenyl] propane, 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane having an average molecular weight of 672, 2,2-bis [4-methacryloxy (polyethoxy) phenyl having an average molecular weight of 804 ], 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane having an average molecular weight of 466, 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane having an average molecular weight of 512, 2,2 having an average molecular weight of 644 -Bis [4-acryloxy (polyethoxy ) Phenyl] propane, 2,2-bis [4-acryloxy (polyethoxy) phenyl] propane having an average molecular weight of 776, neopentyl glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, glycerin dimethacrylate, tricyclodecane dimethanol diacrylate , Neopentyl glycol diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, polyester oligomer hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, average molecular weight of 2,500-3,500 Functional polyester oligomer (Daicel UCB, EB80, etc .: ((meth) acryl group number 4)), tetrafunctional polyester oligo having an average molecular weight of 6,000 to 8,000 -(Daicel UC Corporation, EB450, etc. ((meth) acryl group number 4)), 6-functional polyester oligomer having an average molecular weight of 45,000-55,000 (Daicel UC Corporation, EB1830, etc. ((meth) acryl group number 6)) , Tetrafunctional polyester oligomer having an average molecular weight of about 10,000 (Daiichi Kogyo Seiyaku Co., Ltd., GX8488B etc. ((meth) acryl group number 6)), 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- Acryloyloxy Tilthioethyl) sulfide, 1,2-bis (methacryloyloxyethylthioethylthio) ethane, 1,2-bis (acryloyloxyethylthioethylthio) ethane, 1,2-bis (methacryloyloxyisopropylthioisopropyl) sulfide, 1, 2-bis (acryloyloxyisopropylthioisopropyl) sulfide, polyfunctional urethane (meth) acrylate, etc. can be mentioned. The molecular weight of these (meth) acrylates was also expressed as an average molecular weight, similar to the molecular weight of the (meth) acrylic monomer.

  Specific examples of the polyfunctional urethane (meth) acrylate that can be used as the component (A4) include U-108A (average molecular weight of about 1600, (meth) acryl group number 2, (meth) acryl equivalent 800), UA 4200. (Average molecular weight of about 1300, (meth) acrylic group number 2, (meth) acrylic equivalent 650), UA4400 (average molecular weight of about 1300, (meth) acrylic group number 2, (meth) acrylic equivalent of 650), UA160TM (average molecular weight of about 1600, (Meth) acrylic group number 2, (meth) acrylic equivalent 800), U108 (average molecular weight about 1600, (meth) acrylic group number 2, (meth) acrylic equivalent 800), UA-122P (average molecular weight about 1100, (meth) acrylic Number of radicals 2, (meth) acrylic equivalent 550), UA-5201 (average molecular weight about 1) 00, (meth) acrylic equivalent 500), U-2THA (average molecular weight about 1300, (meth) acrylic group number 2, (meth) acrylic equivalent 650), U-4HA (average molecular weight 596, (meth) acrylic group number 4), U-6HA (molecular weight 1019, (meth) acryl group number 6), U-6LPA (average molecular weight 818, (meth) acryl group number 4), U-15HA (average molecular weight 2,300, (meth) acryl group number 415), ( All of them are manufactured by Shin-Nakamura Chemical Co., Ltd.), EB4858 (average molecular weight 454) (manufactured by Daicel UC Corporation), and other than those, the (meth) acrylic equivalent is less than 300 or more than 1000. U-200PA, UA-511, U-412A, UA-4100, UA-2235PE, UA-6100, UA 6200, UA-4000, UA-512 and Nippon Kayaku Co., Ltd. UX-3204, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, UXF-4002, DPHA-40H, UX -5000, UX-5003D, UX-5005 and the like. The molecular weight of the polyfunctional urethane (meth) acrylate was also expressed as an average molecular weight, similar to the molecular weight of the (meth) acrylic monomer.

  As the component (A4), one type of monomer can be used, or a mixture of a plurality of monomers can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (A4). (A4) The compounding quantity of a component can be mix | blended in the range by which the effect of this invention is not impaired.

Preferred component (A4) and preferred combination with component (A3) In the present invention, when component (A1a) is used, since component (A1a) tends to become a solid at low temperatures, the molecular weight is less than 600. Polyalkylene glycol di (meth) acrylic monomers, preferably polyalkylene glycol di (meth) acrylic monomers having a molecular weight of less than 500 to 600 can be used. Specifically, polyethylene glycol dimethacrylate (the average chain length of the ethylene glycol chain is 9, the average molecular weight is 536, and the (meth) acryl equivalent is 268). The polyalkylene glycol di (meth) acryl monomer having a molecular weight of less than 600 is not particularly limited, but it is particularly preferable to blend 5 to 15 parts by mass with respect to 100 parts by mass of the reference mass.

  Further, when a polyalkylene glycol di (meth) acrylic monomer having a molecular weight of less than 600 is used, an alkoxypolyalkylene glycol (meth) acrylic having a molecular weight of 200 to 1100 is used as the component (A3) in order to adjust the photochromic characteristics. It is preferable to use a monomer in combination. Specifically, methoxy polyethylene glycol methacrylate having an average molecular weight of 293, methoxy polyethylene glycol methacrylate having an average molecular weight of 468, methoxy polyethylene glycol methacrylate having an average molecular weight of 1068, phenoxyethyl methacrylate, methoxy polyethylene glycol acrylate having an average molecular weight of 218, methoxy having an average molecular weight of 454 Examples thereof include polyethylene glycol acrylate and methoxypolyethylene glycol acrylate having an average molecular weight of 1054.

  In the case of using a polyalkylene glycol di (meth) acrylic monomer having a molecular weight of less than 600 (component (A4)) and an alkoxypolyalkylene glycol (meth) acrylic monomer having a molecular weight of 200 to 1100 (component (A3)). Is a polyalkylene glycol di (meth) acrylic monomer ((A4) component having a molecular weight of less than 600 with respect to 100 parts by mass of the reference mass (A1a) component included in the component (A1) 10-30 mass parts, and it is preferable that 10-30 mass parts of alkoxy polyalkylene glycol (meth) acryl monomers ((A3) component) whose molecular weight is 200-1100 are contained.

(B) Photochromic compound and blending amount thereof The photochromic compound (hereinafter sometimes simply referred to as component (B)) will be described. The photochromic compound is used in an amount that provides desired photochromic properties. It is preferable to use 0.1 to 10 parts by mass with respect to 100 parts by mass of the reference mass. Especially, the photochromic curable composition of this invention is used suitably for the plastics lens (photochromic laminated body) of the lamination method manufactured by a coating method, a two-stage polymerization method, etc. Therefore, when used as a plastic lens (photochromic laminate) of a lamination method, the blending amount of the photochromic compound is more preferably 0.1 to 7 parts by mass, further preferably 100 parts by mass of the reference mass. 1 to 5 parts by mass.

  As the photochromic compound, a compound exhibiting a photochromic action can be employed. For example, photochromic compounds such as fulgide compounds, chromene compounds, and spirooxazine compounds are well known, and in the present invention, these photochromic compounds can be used without any limitation. These may be used alone or in combination of two or more. Examples of the fulgide compound, the chromene compound, and the spirooxazine compound are described in JP-A-2-28154, JP-A-62-228830, WO94 / 22850, WO96 / 14596, and the like. Compounds.

  Further, compounds newly found by the present inventors as compounds having excellent photochromic properties, such as JP 2001-114775, JP 2001-031670, JP 2001-011067, JP 2001-011066, JP 2000-347346, JP 2000-344762, JP 2000-347476, JP 2000-327676, JP 2000-327675, JP 2000-256347, JP 2000-229976, Special JP 2000-229975, JP 2000-229974, JP 2000-229993, JP 2000-229972, JP 2000-219687, JP 2000-219686, JP 2000-219865, JP 11-322739, JP-A-1 -286484, JP-A-11-279171, JP-A-10-298176, JP-A-09-218301, JP-A-09-124645, JP-A-08-295690, JP-A-08-176139, JP-A-08- No. 157467, US Pat. No. 5,645,767, US Pat. No. 5,658,501, US Pat. No. 5,961,892, US Pat. No. 6,296,785, Japanese Patent No. 42494981, Japanese Patent No. 4424962, WO2009 / 136668, WO2008 No. 0238828, Japanese Patent No. 4369754, Japanese Patent No. 4301621, Japanese Patent No. 4256985, WO 2007/086532, Pamphlet No. 2009-120536, Special 2009-67754, JP-A-2009-67680, JP-A-2009-57300, Japanese Patent No. 4195615, Japanese Patent No. 41588881, Japanese Patent No. 4157245, Japanese Patent No. 4157239, Japanese Patent Japanese Patent No. 4157227, Japanese Patent No. 4118458, Japanese Patent Laid-Open No. 2008-74832, Japanese Patent No. 3984770, Japanese Patent No. 3801386, WO 2005/028465, WO 2003/042203, JP 2005-289812. JP-A-2005-289870, JP-A-2005-112772, JP-A-3522189, WO2002 / 090342 pamphlet, JP-A-3471107, JP-A-2003-277. 381, WO2001 / 060811, pamphlet WO2000 / 071544, WO2005 / 028465 pamphlet, WO2011 / 16582 pamphlet, WO2011 / 034202 pamphlet, WO2012 / 121414 pamphlet, WO2013 / 042800 pamphlet and the like.

  Among these photochromic compounds, 1 is a chromene compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton from the viewpoint of photochromic properties such as color density, initial coloring, 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.

(C) Inorganic oxide fine particles and blending amount thereof The photochromic curable composition of the present invention is characterized by containing inorganic oxide fine particles (hereinafter sometimes referred to simply as component (C)). By blending the inorganic oxide fine particles, the surface hardness can be improved while maintaining excellent photochromic properties.

  Conventionally, in order to improve the surface hardness of the photochromic coating layer, a method of increasing the crosslinking density by increasing the blending amount of the low molecular weight polyfunctional (meth) acrylate monomer, a monomer having a rigid structure in the molecule is used. Methods such as a method of blending, a method of blending a monomer having a functional group capable of forming a hydrogen bond such as a urethane group, and the like are used. However, in any of these methods, if the amount of such a monomer is increased too much, the matrix in which the photochromic dye is present becomes rigid, so that the structural change accompanying the ring-opening / ring-closing reaction of the photochromic dye is suppressed. It becomes a factor which reduces a characteristic.

  In addition, when the crosslink density is increased, the shrinkage rate of the photochromic coat layer at the time of polymerization increases, so that the residual stress increases and the toughness of the cured film tends to decrease. Therefore, there is a possibility that appearance defects such as cracks are likely to occur.

  In contrast to these methods, if the method of the present invention, that is, a method of blending inorganic oxide fine particles, microscopically, an environment (resin) where photochromic dye molecules exist depending on the presence or absence of inorganic oxide fine particles. The matrix) itself does not change. For this reason, no deterioration in photochromic characteristics is observed. Further, by adding inorganic oxide fine particles, the shrinkage rate of the entire photochromic coat layer is lowered, so that the residual stress is reduced. For this reason, the risk of appearance defects such as cracks accompanying an increase in surface hardness can be minimized.

  Component (C) used in the present invention is an oxide or composite inorganic oxide fine particle containing at least one element selected from Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W and Ce. It is preferable to use fine particles comprising, in particular, oxide or composite inorganic oxide fine particles containing at least one element selected from the group consisting of Si, Al, Ti, Fe, Zr, Sn, Sb and W. The inorganic oxide fine particles need only contain one or more oxides of elements selected from the above element group, and may include composite oxide fine particles containing the above elements, or a plurality of the above inorganic oxide fine particles. Fine particle particles may be mixed and used. Among these, silica is most preferable from the viewpoint of availability and dispersion stability in the (meth) acrylic monomer.

  As the particle size of the component (C), those having a primary particle size of about 1 to 100 nm observed with an electron microscope (TEM) can be suitably used. From the viewpoint of easy availability and transparency (low haze) of the obtained photochromic layer, those of about 5 to 30 nm are particularly preferable.

  The component (C) used in the present invention is preferably hydrophobized for the purpose of improving wettability and dispersion stability to the (meth) acrylic monomer component, which is generally hydrophobic. For example, when the inorganic oxide fine particles are silica, the surface is hydrophobized by reacting a hydrophobizing agent such as a silane coupling agent or a silylating agent with a silanol group on the silica surface to form a chemical bond. be able to. Suitable hydrophobizing agents include silazane, siloxane or alkoxysilane and partial hydrolysates thereof or dimers in which they are condensed. The hydrophobizing agent has a functional group for imparting hydrophobicity, and examples of the functional group include an alkyl group, a phenyl group, a vinyl group, a (meth) acryloyl group, a glycidyl group, and a styryl group. It is done. Among these, those containing a (meth) acryloyl group as a hydrophobizing agent are preferable from the viewpoint of dispersion stability in a (meth) acrylic monomer and adhesion to a resin component after curing.

  Specific examples of the component (C) that can be suitably used in the present invention include MEK-AC-2140Z, MEK-AC-4130Y, MEK-EC-2130Y, TOL-ST, MIBK-AC-2140Z, MIBK-SD. -L (all manufactured by Nissan Chemical Industries, Ltd.), YA010C-SM1, YA010C-SV1, YA010C-SP3 (all manufactured by Admatechs Co., Ltd.) and the like. As the component (C), one kind of inorganic oxide fine particles can be used, or a mixture of a plurality of inorganic oxide fine particles can be used. In the case of a mixture, the total mass of the mixture is regarded as the amount of component (C).

  In this invention, it is preferable that the compounding quantity of (C) component is 10-100 mass parts per 100 mass parts of reference masses. When the blending ratio of the component (C) satisfies the above range, the surface hardness of the obtained cured product, the dispersion stability of the component (C), the solubility of the photochromic compound, the storage stability of the photochromic curable compound, etc. are improved. To do. Considering the balance between film hardness and storage stability of the photochromic curable composition from the above viewpoint, the blending amount of the inorganic oxide fine particles (C) is 20 to 85 parts by mass per 100 parts by mass of the standard mass. Is more preferable, and it is more preferable to set it as 20-70 mass parts.

  Moreover, the storage stability of the photochromic curable composition of the present invention may vary depending on the blending ratio of the component (C) and the component (A1). In order to further improve the storage stability, the component (C) is preferably 20 to 100 parts by mass per 100 parts by mass of the component (A1).

  In addition to powder, the inorganic oxide fine particles used in the present invention are usually provided in a state dispersed in an organic solvent (hereinafter also referred to as organosol) in many cases. Even when the organosol is used, the blending amount of the component (C) is converted by the amount excluding the organic solvent.

The manufacturing method of a photochromic curable composition, and another compounding agent The photochromic curable composition of this invention mixes the said (A1) component, (A2) component, (B) component, and (C) component. Can be manufactured. In the case of using an organosol when blending the component (C), after mixing the organosol with the components (A1) and / or (A2), a method of concentrating and distilling the organic solvent with a rotary evaporator or the like. Can be adopted. At this time, the component (B) may be added and dissolved before the organic solvent is distilled off, or may be added and dissolved after the organic solvent is distilled off. In addition, after mixing (A1) component or a part of (A2) component and organosol and distilling off an organic solvent, you may add and mix the remaining (A1) component or (A2) component. In particular, when a component having a low boiling point is contained in the component (A1) or the component (A2), the high-boiling component in the component (A1) and / or the component (A2) and the organosol are mixed, and an organic solvent After distilling off, it is preferable to add the remaining low-boiling components. By carrying out like this, when distilling off an organic solvent, it can prevent that the low boiling point component in (A1) component or (A2) component will be distilled off. What is necessary is just to mix the (A3) component and (A4) component mix | blended as needed by the same method.

  In addition to the (A1) component, the (A2) component, the (B) component, the (C) component, and the (A3) component and the (A4) component blended as necessary, the photochromic curable composition of the present invention A known additive can be blended. For example, various stabilizers and additives such as surfactants, mold release agents, ultraviolet absorbers, infrared absorbers, ultraviolet stabilizers, antioxidants, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments and fragrances The polymerization regulator can be mixed as necessary.

  Among these, it is preferable to mix and use an ultraviolet stabilizer because the durability of the photochromic compound can be further improved. As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol antioxidant, and a sulfur-based antioxidant can be suitably used. The hindered amine light stabilizer is not particularly limited, but bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is particularly preferable from the viewpoint of preventing deterioration of the photochromic compound. Moreover, it is marketed by Asahi Denka Kogyo Co., Ltd. under the trade names such as ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-77, LA-82, LA-87. Hindered amine light stabilizers can also be suitably used.

  The hindered phenol antioxidant is not particularly limited, but 2,6-di-t-butyl-4-methyl-phenol, IRGANOX245 manufactured by Ciba Specialty Chemicals: ethylene bis in terms of preventing deterioration of the photochromic compound. (Oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate], IRGANOX 1076 manufactured by Ciba Specialty Chemicals: octadecyl-3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate, IRGANOX 1010 manufactured by Ciba Specialty Chemicals: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and other Ciba specialty products Karuzu Co. IRGANOX1035,1075,1098,1135,1141,1222,1330,1425,1520,259,3114,3790,5057,565, and the like can be given.

  Although the usage-amount of this ultraviolet stabilizer is not restrict | limited in particular, The compounding quantity of each ultraviolet stabilizer is 0.01-20 mass parts by making the total amount of (A1) component and (A2) component into 100 mass parts. More preferably, it is the range of 0.1-10 mass parts.

  Moreover, as a polymerization regulator, thiols, such as t-decyl mercaptan, can also be added.

  In addition to the (meth) acrylic monomer, a polymerizable monomer such as a vinyl monomer can also be added. As the vinyl monomer, known compounds can be used without any limitation, but among them, compounding a compound that acts as a polymerization regulator is suitable for improving the moldability of the photochromic curable composition. Specific examples of the vinyl monomer include α-methylstyrene and α-methylstyrene dimer, and it is particularly preferable to combine α-methylstyrene and α-methylstyrene dimer.

  The surfactants are not limited to known surfactants such as silicone surfactants having a silicone chain (polyalkylsiloxane unit) as a hydrophobic group and fluorine surfactants having a fluorocarbon chain. It can be used without. By adding a surfactant, when forming the photochromic coating layer of the present invention by the coating method, the adhesiveness on the optical substrate and the optical substrate is improved without adversely affecting the photochromic properties and adhesion. It is possible to improve the wettability with respect to the primer formed for the purpose of preventing the occurrence of poor appearance.

  Specific examples of silicone surfactants and fluorosurfactants that can be suitably used in the present invention include “L-7001”, “L-7002”, “L-7604”, manufactured by Toray Dow Corning Co., Ltd. "FZ-2123", Dainippon Ink & Chemicals, Inc. "Megafac F-470", "Megafac F-1405", "Megafac F-479", Sumitomo 3M "Florad FC-430", etc. Can be mentioned. In using the surfactant, two or more kinds may be mixed and used.

About the manufacturing method of a polymerization initiator and a photochromic hardened | cured material The method in particular of obtaining a laminated body from a photochromic curable composition is not restrict | limited, A well-known method is employable. Specifically, a layer made of a photochromic curable composition may be present on a plastic substrate, and the curable composition may be polymerized and cured. As a method for polymerizing the photochromic curable composition, it can be carried out by heat, irradiation with ultraviolet rays (UV rays), α rays, β rays, γ rays, or a combination of both. Under the present circumstances, it is preferable to mix | blend radical polymerization initiators, such as the following thermal polymerization initiator and a photoinitiator, with the photochromic curable composition of this invention.

  In this invention, when using a polymerization initiator, the usage-amount of the polymerization initiator is with respect to 100 mass parts of reference masses, Preferably it is 0.001-10 mass parts, More preferably, it is 0.01-5 mass parts. Range.

  When a typical polymerization initiator is exemplified, examples of the thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; t-butyl Peroxyesters such as peroxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropyl peroxydicarbonate, di-sec-butylperoxy Examples include percarbonates such as dicarbonates; azo compounds such as azobisisobutyronitrile.

  When the photochromic cured product composition of the present invention is thermally polymerized, among the polymerization conditions, particularly the temperature affects the properties of the resulting photochromic cured product / laminate. This temperature condition is affected by the type and amount of the thermal polymerization initiator and the type of monomer, so it cannot be limited in general, but in general, the polymerization is started at a relatively low temperature, and the temperature is slowly increased. It is preferable to perform so-called taper type polymerization, which is cured at a high temperature at the end. Since the polymerization time varies depending on various factors as well as the temperature, it is preferable to determine the optimal time according to these conditions in advance. The conditions are preferably selected so that the polymerization is completed in 2 to 24 hours.

  As the photopolymerization initiator of the present invention, compounds such as acetophenone and acylphosphine can be employed. Specifically, benzophenone; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenones such as 1-one, 2-benzyl-2dimethylamino-1- (4-morpholinophenyl) -butanone-1, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Compounds; α-dicarbonyl compounds such as 1,2-diphenylethanedione and methylphenylglycoxylate; 2,6-dimethylbenzoyldiph Nylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6 -Acylphosphine such as trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide Examples thereof include oxide compounds; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and the like. These polymerization initiators may be used alone or in combination of two or more.

When photopolymerizing the photochromic cured product composition of the present invention, among the polymerization conditions, particularly the UV intensity affects the properties of the resulting photochromic cured product / laminate. This illuminance condition is unconditionally limited because it is affected by the type and amount of the photopolymerization initiator and the type of monomer, but generally, UV light of 50 to 500 mW / cm ² at a wavelength of 365 nm is reduced to 0. It is preferable to select conditions so that light is irradiated in a time of 5 to 5 minutes.

  Moreover, a thermal polymerization initiator and a photopolymerization initiator can be used in combination. When a photopolymerization initiator is used, a known polymerization accelerator such as a tertiary amine can be used in combination. When employing a two-stage polymerization method, it is preferable to blend a thermal polymerization initiator, and when employing a coating method, it is preferable to blend a photopolymerization initiator.

  Since the photochromic curable composition of the present invention can increase the surface hardness of the resulting cured product, it can be particularly suitably used when a photochromic coating layer that is a thin film is formed. However, the photochromic curable composition of the present invention can be used only in a cured product obtained by curing itself.

  Next, the method for producing the photochromic laminate of the present invention will be specifically described. First, the plastic substrate used will be described.

(Plastic substrate)
The plastic substrate on which the photochromic coating layer (cured body) made of the photochromic curable composition of the present invention is laminated is not particularly limited, and a known substrate can be used.

  Specific examples of the plastic substrate include (meth) acrylic resins, polycarbonate resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins. It can also be applied to other plastic lens substrates. Further, the present invention can also be applied to a plastic lens substrate in which a hard coat layer or the like is laminated on these plastic lens substrates.

  The shape of the plastic substrate used in the present invention is not particularly limited, and can be applied to a known shape. The plastic substrate has various shapes according to the visual acuity of the user, the shape of the glass mold at the time of molding the plastic substrate, and productivity. For example, the lens is a minus lens having a thin center as a myopic lens and a thickness at the edge, and a plus lens having a thick center and a thin edge as a distance lens. Furthermore, depending on the mold when molding the plastic substrate, the shape of the edge of the plastic substrate is inclined downward (opposite to the side on which the photochromic coating layer is laminated) toward the outer periphery. (Hereinafter, this shape of the edge portion may be simply referred to as “bevel shape”). As an advantage of having an oblique angle shape, for example, there is a point that the liquid pool in the edge portion can be reduced in the coating method.

  The photochromic curable composition of the present invention can be applied to any of the above plastic substrates.

  In order to improve the adhesion of the resulting photochromic laminate, the plastic substrate may be one that has been subjected to a chemical treatment such as an alkali solution or an acid solution, a physical treatment such as corona discharge, plasma discharge, or polishing. . Among these, the photochromic curable composition of the present invention can be particularly suitably applied when a lens substrate having a primer coat layer as an adhesive layer is used in order to improve the adhesion between the plastic substrate and the photochromic coat layer.

  As the primer coat layer, a known polyurethane resin can be used. Among them, from the viewpoint of adhesion, a moisture curable polyurethane resin / precursor as described in Japanese Patent No. 4405833, or Japanese Patent No. 5016266, Japanese Patent No. 5084727 A primer coat layer made of a water-dispersed urethane emulsion as described above is preferable.

(Application to plastic substrate having primer coat layer made of moisture curable polyurethane resin)
Moisture curable polyurethane resin and / or its precursor (hereinafter simply referred to as moisture curable polyurethane resin) means that some of the isocyanate groups present in the molecule react with moisture in the atmosphere to react with carbamic acid, for example. An isocyanate group-containing compound or a compound or a combination of compounds that is a precursor of such a compound, which is decarboxylated to form an amine after it has been formed, and the amine and the remaining isocyanate group react to form a urea bond to form a urea bond. It is.

  Among these, the moisture-curable polyurethane resin has an isocyanate group remaining from the aliphatic isocyanate compound and / or the aliphatic isocyanate compound and a compound having active hydrogen from the viewpoint of exhibiting excellent adhesion at a relatively low temperature. Polyisocyanate compounds or polyisocyanate oligomer compounds bonded by various methods at various preparation ratios, particularly cycloaliphatic isocyanate compounds and / or cycloaliphatic isocyanate compounds and compounds having active hydrogen from the viewpoint of coating properties. A polyisocyanate compound or a polyisocyanate oligomer compound bonded by various methods at a charging ratio such that a group remains is preferable.

  In addition, the moisture curable polyurethane resin is an aromatic isocyanate compound and / or the aromatic isocyanate compound from the viewpoint that the resulting polyisocyanate compound or polyisocyanate oligomer compound is fastened by reaction with moisture in the air. A polyisocyanate compound or a polyisocyanate oligomer compound in which an isocyanate group and a compound having active hydrogen are combined by various methods at a charging ratio such that an isocyanate group remains can also be suitably used. In this case, a urea bond is generated as a result of the reaction between moisture and isocyanate, but such a urea bond may be included in the adhesive layer in the present invention.

  As the compound having active hydrogen, polyalkylene glycols, polyols containing three or more hydroxy groups, polyalkylene adipates, polyalkylene carbonates, polycaprolactones, and polyester polyols may be used. preferable. In addition, the above compound having active hydrogen may be used alone or in combination of two or more.

  The molecular weight of the moisture curable polyurethane resin and / or precursor thereof used in the present invention is preferably relatively high. As a technique for increasing the molecular weight, when the above-mentioned isocyanate compound and the compound having active hydrogen are combined by various methods at a charging ratio such that the isocyanate group remains, adjustment is made so as to reduce the remaining amount of the isocyanate group. There is a way. Alternatively, there is also a method in which a plurality of isocyanate groups present in the molecule of the moisture curable polyurethane resin and / or its precursor are combined with a chain extender or the like. Here, examples of the chain extender include compounds having active hydrogen as described above and diamine compounds such as ethylenediamine. Among these, from the viewpoint of easy control of the chain extension reaction, 1, 3- Alkylene glycols such as butanediol, 1,4-butanediol, propylene glycol, and 1,6-hexanediol, and polyalkylene glycols such as polypropylene glycol are preferably used.

  The moisture curable polyurethane resin as described above is diluted with an organic solvent such as toluene, xylene, ethyl acetate, and butyl acetate, and further blended with a leveling agent as necessary to obtain a primer coat composition, and then a plastic lens base. A primer coat layer is formed by applying and drying on the material. At this time, the thickness of the primer coat layer is preferably 1 to 10 μm.

(Application to plastic substrate with primer coat layer made of water-dispersed urethane emulsion)
The polyurethane resin contained in the water-dispersed urethane resin emulsion has at least a polyol compound, an anionic group-active hydrogen group compound, an active hydrogen group-containing acrylate compound, and / or an alkoxysilyl group-containing polyamine compound as the active hydrogen group-containing component. And a urethane resin obtained by reacting these active hydrogen group-containing components with a polyisocyanate component, including a polyisocyanate compound as a polyisocyanate component.

  As the polyol compound and the polyisocyanate compound, which are raw materials for the water-dispersed urethane resin, the same materials as those for the moisture-curable urethane resin described above can be used.

  An anionic group active hydrogen group combined compound which is a raw material of water-dispersed urethane resin has, for example, one or more anionic groups such as a carboxyl group, a sulfonyl group, a phosphate group, a betaine structure-containing group such as sulfobetaine. And a compound having two or more active hydrogen groups such as a hydroxyl group and an amino group that can react with an isocyanate group, for example, having one anionic group and two or more The compound which has an active hydrogen group is mentioned. For example, 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2 as an anionic group-active hydrogen group-containing compound having a carboxyl group , 2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid and the like, for example, diaminocarboxylic acids such as lysine and arginine.

  The active hydrogen group-containing acrylate compound, which is a raw material of the water-dispersed urethane resin, is a (meth) acrylate compound having one or more hydroxyl groups in the molecule, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl ( Examples include meth) acrylate, hydroxybutyl (methacrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate.

  Examples of the alkoxysilyl group-containing polyamine compound that is a raw material of the water-dispersed urethane resin include alkoxysilyl compounds having a primary amino group and a secondary amino group. Specifically, N-β (aminoethyl)- γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane , Γ- (2-aminoethyl aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyldiethoxysilane, N, N′- Bis [α- (trimethoxysilyl) propyl] ethylenedi Min and the like.

  The water-dispersed urethane resin emulsion includes an active hydrogen group-containing component (that is, at least a polyol compound, an anionic group-active hydrogen group-containing compound, an active hydrogen group-containing acrylate compound, and / or an alkoxysilyl group-containing polyamine compound), A polyisocyanate component (that is, a polyisocyanate compound) can be synthesized by reacting with a one-shot method or a prepolymer method, and the prepolymer method is more preferable. Chain extenders can also be used.

  As chain extenders, other amines and hydrazines (other amines and hydrazines are included in the active hydrogen group-containing component) other than alkoxysilyl group-containing polyamine compounds can also be used in combination. For example, such other amines include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexyl isocyanate (isophoronediamine), 4,4′-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- Examples include diamines such as bis (aminomethyl) cyclohexane, and polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

  The water-dispersed polyurethane resin emulsion as described above has a polyurethane resin finally dispersed in water. If necessary, water, a leveling agent, and further an organic solvent are blended to form a primer coat composition. Thereafter, it is applied on a plastic lens substrate and dried to form a primer coat layer. At this time, the thickness of the primer coat layer is preferably 1 to 10 μm.

  A photochromic composition comprising a photochromic curable composition on a primer coating layer comprising a polyurethane resin on the plastic substrate as described above, a plastic lens having a normal shape, a strength plastic lens, a plastic lens having an oblique shape, and a polyurethane resin on the lens surface. A coat layer is laminated (a photochromic laminate is produced). Next, a method for forming a photochromic coat layer on these plastic substrates will be specifically described.

(Coating method, two-stage polymerization method: photochromic laminate production method)
Specific methods for producing a laminate include a coating method and a two-stage polymerization method. Coating method When producing a photochromic laminate by a coating method, a photopolymerization initiator is mixed on a plastic substrate. The photochromic cured product composition of the present invention is applied by a spin coating method or the like, placed in an inert gas such as nitrogen, and then irradiated with UV to obtain a photochromic laminate by the coating method. And in order to improve the adhesiveness of a photochromic coat layer and a plastic base material, it is preferable to heat-process at a temperature range of 80-120 degreeC for about 0.5 to 5 hours. By carrying out like this, the photochromic laminated body by which the primer coating layer / photochromic coating layer laminated | stacked in this order in the plastic lens base material / as needed can be obtained. The thickness of the photochromic coating layer formed by the coating method is not particularly limited, but is preferably 10 to 70 μm.

Two-stage polymerization method When producing a photochromic laminate by a two-stage polymerization method, a thermal polymerization initiator is blended in the gap between the glass mold and the plastic substrate held by an elastomer gasket, spacer, or adhesive tape. The cast polymerization which removes a laminated body from a glass mold, after inject | pouring the photochromic hardened | cured material composition of this invention which was made and polymerizing and hardening in an air furnace is mentioned. In the case of using a photopolymerization initiator, UV irradiation may be performed for the entire glass mold, and then the cured body may be removed from the glass mold. The temperature at the time of polymerization and curing is not particularly limited, but in the case of thermal polymerization, it is preferable to change the temperature in the range of 20 to 120 ° C. Moreover, in the case of photopolymerization, it is preferable to heat-process for about 0.5 to 5 hours in the temperature range of 80-120 degreeC after photopolymerization. By carrying out like this, the photochromic laminated body by which the primer base layer / photochromic coating layer formed in order in this order can be obtained. The thickness of the photochromic coating layer formed by the two-stage polymerization method is not particularly limited, but is preferably 100 to 1000 μm.

  The photochromic curable composition of the present invention can be formed on a plastic substrate by the method described above and cured to form a photochromic laminate.

Characteristics and post-processing of the photochromic laminate The photochromic laminate obtained by polymerizing the photochromic cured product composition of the present invention by the above method has excellent surface hardness and suppresses appearance defects such as cracks generated in the photochromic coat layer. And a photochromic plastic lens having excellent photochromic properties.

Furthermore, the photochromic laminate obtained by the above-described method can be subjected to the following treatment depending on the application. That is, dyeing using dyes such as disperse dyes, silane coupling agents, hard coating agents mainly composed of sols such as silicon, zirconium, antimony, aluminum, tin, and tungsten, and SiO ₂ , TiO ₂ , ZrO _2, etc. It is also possible to perform processing and secondary treatment such as antireflection treatment and antistatic treatment by vapor deposition of a metal oxide thin film or application of an organic polymer thin film.

  Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples. In addition, the used compound used by the present Example is as follows.

Component (A1) Component (A1a) Component 14G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain is 14, average molecular weight is 736, (meth) acryl equivalent 368).

Component (A1b) AT30: Ethoxylated trimethylolpropane triacrylate (average molecular weight 1616, a = 10, b = 3, (meth) acryl equivalent 539).

Component (A1c) BPE900: 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (c + d = 17, (meth) acryl equivalent 556).

Component (A1d) A-PC: esterified product of polyalkylene carbonate diol and acrylic acid mainly composed of pentanediol and hexanediol (average molecular weight 640, (meth) acrylic equivalent 320).

(A2) Component (A2a) Component / TMPT: Trimethylolpropane trimethacrylate.
D-TMP: ditrimethylolpropane tetramethacrylate.

(A2b) Component <Synthesis of PMS1>
To 248 g (1.0 mol) of 3-trimethoxysilylpropyl methacrylate, 196 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 performed at 45 ° 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. Thereafter, the organic layer was washed with water until the aqueous layer became neutral, and the solvent was concentrated to obtain a silsesquioxane monomer (PMS1). In addition, it confirmed that the raw material was consumed completely from < ¹ > H-NMR. ²⁹ Si-NMR confirmed that the mixture was a mixture of a cage structure, a ladder structure, and a random structure. When the molecular weight of the silsesquioxane monomer (PMS1) was measured by a gel permeation chromatography method (GPC method), the weight average molecular weight was 3,800. The (meth) acryl equivalent was about 178.

(A3) Component (A3a) Component / GMA: Glycidyl methacrylate.

(A3b) component MA1: γ-methacryloxypropyltrimethoxysilane.

Other (A3) component M90G: “M90G” monofunctional methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) (average chain length of methoxypolyethylene glycol methacrylate ethylene glycol chain is 9, and average molecular weight is 496).

Component (A4) 9G: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain is 9, average molecular weight is 536, (meth) acryl equivalent 268).
BPE500: 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane (average chain length of ethylene glycol chain is 10 and average molecular weight is 804).

  (B) Photochromic compound

(C) Inorganic oxide fine particles / SO1: Organosilica sol MEK-AC-2140Z (manufactured by Nissan Chemical Industries, average particle size 10 to 15 nm, silica content: 40% by mass, solvent: methyl ethyl ketone).

Other compounding agents (additives)
Stabilizer HALS: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508).
HP: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by Ciba Specialty Chemicals).

Photopolymerization initiator PI: phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (trade name: Irgacure 819, manufactured by BASF).

Plastic substrate PL1: An allyl plastic lens having a center thickness of 2 mm, an oblique angle of 45 °, a refractive index of 1.50, and an oblique angle shape.
PL2: A thiourethane plastic lens having a center thickness of 10 mm, an oblique angle of 45 °, a refractive index of 1.67, and an oblique shape.
PL3: Refractive index 1.50, power +6.00, center thickness 12 mm, edge thickness 1 mm, allyl plastic lens.
PL4: Refractive index 1.50, power -4.00, center thickness 3 mm, edge thickness 10 mm, allylic plastic lens.
PL5: an allyl plastic lens having a center thickness of 2 mm, a refractive index of 1.50, and no beveled shape.

Primer composition PR1: Water-dispersed urethane emulsion (product name: NJ-321A, manufactured by Tokuyama Corporation).
PR2: Moisture curable urethane resin primer (product name: TR-SC-P, manufactured by Tokuyama Corporation).

Production Example Preparation of Photochromic Curable Composition (Z1) (A1a) Component: Polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain is 14, average molecular weight is 736) 55.6 parts by mass, (A1d) component: Esterified product of polyalkylene carbonate diol and acrylic acid mainly composed of pentanediol and hexanediol (average molecular weight 640, (meth) acrylic equivalent 320) 20.2 parts by mass, (A2a) component: trimethylolpropane trimethacrylate 24 .2 parts by mass and (C) component: organosilica sol MEK-AC-2140Z (manufactured by Nissan Chemical Industries, average particle size 10-15 nm, silica content: 40% by weight, solvent: methyl ethyl ketone) 108.3 parts by mass ( 43.3 parts by mass as silica) Concentrated under reduced pressure at bath temperature of 40 ° C. at over evaporator to distill off methyl ethyl ketone as a solvent. (A3a) component: 1.0 part by mass of glycidyl methacrylate and (B) component: 2.9 parts by mass of PC1 are added to the mixture after evaporation of the solvent, and the mixture is stirred and mixed at 70 ° C. for 15 minutes to dissolve PC1. It was. After cooling to room temperature, the component (A3b): γ-methacryloxypropyltrimethoxysilane 9.4 parts by mass, other compounding agents (additives) stabilizer: HALS 4.3 parts by mass, HP 4.3 parts by mass In addition, 0.26 parts by mass of PI as a polymerization initiator and 0.1 part by mass of L7001 manufactured by Toray Dow Corning Co., Ltd. were added as a leveling agent to obtain a photochromic curable composition (Z1) used in the coating method. Each blending amount is shown in Table 1.

Preparation of photochromic curable composition (Z2) to (Z18) Photochromic curable composition (Z2) was prepared in the same manner as the photochromic curable composition (Z1) except that the materials shown in Table 1 were used. -(Z17) was adjusted. The composition is shown in Table 1. The photochromic curable compositions (Z1) to (Z13) correspond to the compositions of the examples. Photochromic curable compositions (Z14) to (Z18) correspond to compositions of comparative examples.

Example 1
An allyl plastic lens having a center thickness of 2 mm, an oblique angle of 45 °, a refractive index of 1.50, and an oblique angle shape was prepared as a plastic substrate. The allylic plastic lens was previously subjected to alkali etching at 50 ° C. for 5 minutes using a 10% aqueous sodium hydroxide solution, and then thoroughly washed with distilled water.

Using a spin coater (1H-DX2, manufactured by MIKASA), a water-dispersed urethane emulsion (product name: NJ-321A, manufactured by Tokuyama Co., Ltd., pure water is added to the surface of the plastic lens to obtain a solid content concentration. Was adjusted at 35 rpm for 15 seconds, followed by spin coating at 1500 to 2000 rpm for 4 seconds and dried at room temperature for 15 minutes. At this time, the spin conditions were adjusted so that the thickness of the dried primer layer was 4 μm. Thereafter, about 2 g of the photochromic curable composition (Z1) obtained above is applied at a rotation speed of 100 rpm for 40 seconds, and then at 1000 rpm for 3 to 15 seconds. The film thickness of the cured photochromic coating layer is 40 μm. Spin coat as follows. The lens having the coating agent coated on the surface was irradiated with light for 90 seconds in a nitrogen gas atmosphere using a metal halide lamp with an output of 200 mW / cm ² to cure the coating film. Thereafter, the mixture was further heated at 100 ° C. for 1 hour to produce a photochromic laminate having a photochromic coating layer.

  The obtained photochromic laminate had photochromic properties of a maximum absorption wavelength of 458 nm, a color density of 1.1, and a fading speed of 59 seconds, an appearance evaluation of 0, an adhesion property of A, and a surface hardness of 5.0. These evaluations were performed as follows.

Photochromic characteristics Using the obtained photochromic laminate (photochromic layer thickness of 40 micrometers) as a sample, a xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics Co., Ltd., and an aeromass filter (manufactured by Corning). Then, color development was performed by irradiating at a temperature of 23 ° C. ± 1 ° C. and a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the polymer surface for 300 seconds, and the photochromic characteristics of the laminate were measured. Each photochromic characteristic was evaluated by the following method.

  1) Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development determined by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (instant multichannel photodetector MCPD3000). The maximum absorption wavelength is related to the color tone at the time of color development.

  2) Color density {ε (300) −ε (0)}: between the absorbance {ε (300)} after light irradiation for 300 seconds and the absorbance {ε (0)} before light irradiation at the maximum absorption wavelength. difference. It can be said that the higher this value, the better the photochromic characteristics.

  3) Fading speed [t1 / 2 (sec.)]: When light irradiation is stopped after 300 seconds of light irradiation, the absorbance at the maximum wavelength of the sample is {ε (300) −ε (0)} 1 Time required to drop to / 2. The shorter this time, the quicker the color disappears, and it can be said that the photochromic properties are excellent.

Appearance Evaluation Ten photochromic laminates were prepared and evaluated by the number of photochromic laminates in which cracks occurred in the photochromic coat layer.

Adhesion The adhesion of the obtained photochromic laminate was evaluated. Evaluation of adhesion was performed by a cross-cut tape test according to JISD-0202 for adhesion of the photochromic coat layer, the adhesive layer, and the plastic lens. That is, using a cutter knife, cuts are made at intervals of about 1 mm on the lens surface to form 100 squares. A cellophane adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) was firmly attached thereon, and then pulled and peeled away from the surface in a 90 ° direction at a stretch, and the remaining squares of the photochromic coating layer were counted. That is, the evaluation result is expressed as (number of remaining cells) / 100. The adhesion here is evaluating the adhesion of all the layers laminated on the lens substrate. The evaluation criteria are shown below.
A; 100/100.
B: 99/100 to 95/100.
C: Less than 95/100.

Surface Hardness The surface hardness in the present invention was evaluated by Vickers hardness. The measurement was carried out using a micro Vickers hardness meter PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A square pyramid diamond indenter was used as the indenter, and the evaluation was performed under the conditions of a load of 10 gf and an indenter holding time of 30 seconds. The measurement results were shown as an average value of a total of 3 times after performing a total of 4 measurements and excluding the first value with a large measurement error.

Example 2-18, Comparative Example 1-5
A photochromic laminate was prepared and evaluated in the same manner as in Example 1 except that the photochromic curable composition, plastic lens and primer shown in Table 2 were used. The evaluation results are shown in Table 2.

  As is clear from the above Examples 1-18, the photochromic laminate obtained by polymerizing the photochromic curable composition of the present invention is not only excellent in photochromic properties but also excellent in surface hardness, adhesion, and appearance. ing. However, in Comparative Examples 1 to 5, at least one physical property is insufficient among photochromic properties, surface hardness, adhesion, or appearance, and none of the physical properties satisfy all the physical properties at the same time.

Example 19
Evaluation of Storage Stability of Photochromic Curable Composition The photochromic curable composition (Z1) produced in the above production example was placed in a light-tight sealed container and stored at 25 ° C. for 1 week. The state of the photochromic curable composition after storage was observed and evaluated according to the following criteria.
No change before storage: ○
Thickening was observed compared to before storage: △
Gelation or precipitation occurred: x
The evaluation results are shown in Table 3.

Examples 20-31
Except that the photochromic curable composition shown in Table 3 was used, a storage test was carried out in the same manner as in Example 18 for evaluation. Table 3 shows the results.

Claims (9)

(A1) At least one long-chain (meth) acrylic monomer component selected from the group consisting of the following (A1a) component, (A1b) component, (A1c) component, and (A1d) component,
(A2) at least one multi-functional (meth) acrylic monomer component selected from the group consisting of the following (A2a) component and (A2b) component;
A photochromic curable composition comprising (B) a photochromic compound, and (C) inorganic oxide fine particles.

(A1a) component: a polyalkylene glycol di (meth) acryl monomer component having a molecular weight of 600 to 2000,
(A1b) component: (meth) acrylic monomer component represented by the following general formula (1)

(Where
R ¹ is a hydrogen atom or a methyl group,
R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a is an average value of 8 to 15, and b is an integer of 3 to 6. ),
(A1c) component: (meth) acrylic monomer component represented by the following general formula (2)

(Where
R ⁴ and R ⁵ are each a hydrogen atom or a methyl group,
R ⁶ and R ⁷ are each a hydrogen atom or a methyl group,
A is the following formula

Any of the groups shown in
c and d are each independently an integer of 1 or more, and c + d is an average value of more than 15 and 40 or less. ),
(A1d) component: (meth) acrylic monomer component represented by the following general formula (3)

(Where
B and B ′ are each a linear or branched alkylene group having 2 to 15 carbon atoms, e is an average value of 2 to 20,
When a plurality of B are present, B may be the same group or different groups,
R ⁸ and R ⁹ are a hydrogen atom or a methyl group. ).

(A2a) component: (meth) acrylic monomer component represented by the following general formula (4)

(Wherein preferably
R ¹¹ is a hydrogen atom or a methyl group,
R ²¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms,
R ³¹ is a 3 to 6 valent hydrocarbon group having 1 to 10 carbon atoms, or a 3 to 6 valent group containing an oxygen atom in a chain having 1 to 10 carbon atoms,
a ′ is an average value of 0 to 3, and b ′ is an integer of 3 to 6. ),
(A2b) component: (meth) acrylic monomer component represented by the following general formula (5)

(Where
A plurality of R ¹⁰ may be the same or different from each other,
At least 10 R ¹⁰ are organic groups containing a (meth) acryl group,
f is a polymerization degree and is an integer of 15-50. ).   The photochromic curable composition according to claim 1, comprising 10 to 100 parts by mass of the component (C) per 100 parts by mass of the total of the component (A1) and the component (A2).   3. The photochromic curable composition according to claim 1, comprising 30 to 85 parts by mass of the (A1) component per 100 parts by mass in total of the (A1) component and the (A2) component.   When the total amount of the component (A1) is 100% by mass, the component (A1) is 40 to 100% by mass of the component (A1a), 0 to 40% by mass of the component (A1b), and 0 to 0% of the component (A1c). The photochromic curable composition according to claim 1, comprising 40% by mass and 0 to 40% by mass of the component (A1d). The component (B) is a photochromic compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton,
The photochromic curable composition according to any one of claims 1 to 4, wherein 0.1 to 10 parts by mass is contained per 100 parts by mass in total of the component (A1) and the component (A2). And (A3) a monofunctional (meth) acryl monomer component having one (meth) acryl group in the molecule,
The component (A3) is contained in an amount of 0.1 to 50 parts by mass per 100 parts by mass in total of the component (A1) and the component (A2). Photochromic curable composition.   The photochromic hardening body which hardened | cured the photochromic curable composition in any one of Claims 1-6.   The photochromic laminated body which has a photochromic hardening body of Claim 7 on a plastic base material.   The photochromic laminated body which has a primer layer which consists of urethane resin on a plastic base material, and has the photochromic hardened | cured material of Claim 7 on this primer layer.