JP2021107909A - Polymerizable composition for forming protective layer of photochromic article, photochromic article and spectacles - Google Patents

Abstract

To provide a photochromic article with a protective layer having high hardness and excellent solvent resistance.SOLUTION: A polymerizable composition for forming a protective layer of a photochromic article contains one or more (meth)acrylates, and contains 70.0 mass% or more of alicyclic bifunctional (meth)acrylate with respect to the total amount of the (meth)acrylates.SELECTED DRAWING: None

Description

The present invention relates to a polymerizable composition for forming a protective layer of a photochromic article, a photochromic article and eyeglasses.

The photochromic compound is a compound having a property of developing color under irradiation with light in a wavelength range having photoresponsiveness and fading under non-irradiation (photochromic property). Hereinafter, an article containing a photochromic compound will be referred to as a photochromic article. For example, Patent Document 1 discloses a photochromic article in which a layer containing a photochromic compound (photochromic layer) is provided on a substrate.

WO2003 / 011967

The present inventor has studied providing a protective layer on a photochromic article with the aim of improving the performance of the photochromic article. With respect to such a protective layer, the present inventor has come to believe that the following performance is desired.
First, it has high hardness. This is because the durability of the photochromic article can be enhanced by providing the protective layer having high hardness.
Second, it has excellent solvent resistance. In the manufacturing process of a photochromic article, usually, after forming a layer, a wiping treatment with a solvent is performed to clean the surface of the formed layer. This is because if the protective layer is damaged in this wiping process, it causes fogging and optical defects in the photochromic article.

In view of the above, one aspect of the present invention is to provide a photochromic article having a protective layer having both high hardness and excellent solvent resistance.

One aspect of the present invention is
Polymerization for forming a protective layer of a photochromic article containing one or more kinds of (meth) acrylates and containing 70.0% by mass or more of alicyclic bifunctional (meth) acrylates with respect to the total amount of (meth) acrylates. Composition (hereinafter, also simply referred to as "polymerizable composition for forming a protective layer" or "composition"),
Regarding.

The composition contains 70.0% by mass or more of alicyclic bifunctional (meth) acrylate with respect to the total amount of (meth) acrylate. This makes it possible to provide the photochromic article with a protective layer having high hardness and excellent solvent resistance as a cured layer obtained by curing the composition.

According to one aspect of the present invention, it is possible to provide a polymerizable composition for forming a protective layer of a photochromic article, which can form a protective layer having high hardness and excellent solvent resistance on the photochromic article. Further, according to one aspect of the present invention, it is possible to provide a photochromic article having a protective layer formed from such a composition.

[Polymerizable composition for forming a protective layer for photochromic articles]
Hereinafter, the above composition will be described in more detail.

The above composition is a polymerizable composition for forming a protective layer of a photochromic article. In the present invention and the present specification, the "photochromic article" is an article containing a photochromic compound. In the photochromic article, the photochromic compound is contained in, for example, a layer (photochromic layer) provided on the base material. The details of the photochromic layer will be described later. The protective layer formed from the above composition can be provided, for example, on the photochromic layer, which can contribute to improving the durability of the photochromic article.

<(Meta) acrylate>
The composition is a polymerizable composition and contains one or more polymerizable compounds. In the present invention and the present specification, the "polymerizable compound" is a compound having one or more polymerizable groups in one molecule. The above composition contains one or more kinds of (meth) acrylates as a polymerizable compound, and the total amount of the (meth) acrylates is 100% by mass, and the alicyclic bifunctional (meth) acrylate is 70.0% by mass. Including the above.

In the present invention and the present specification, the term "(meth) acrylate" is used to include acrylate and methacrylate. "Acrylate" is a compound having one or more acryloyl groups in one molecule. A "methacrylate" is a compound having one or more methacryloyl groups in one molecule. For (meth) acrylate, the functional number is the number of groups selected from the group consisting of acryloyl groups and methacryloyl groups contained in one molecule. In the present invention and the present specification, "methacrylate" means a (meth) acryloyl group containing only a methacryloyl group, and a (meth) acryloyl group containing both an acryloyl group and a methacryloyl group is an acrylate. Call. The acryloyl group may be contained in the form of an acryloyloxy group, and the methacryloyl group may be contained in the form of a methacryloyloxy group. The "(meth) acryloyl group" described below is used in the sense of including an acryloyl group and a methacryloyl group, and the "(meth) acryloyloxy group" includes an acryloyloxy group and a methacryloyloxy group. Used in the sense. Further, unless otherwise specified, the described groups may have a substituent or may be unsubstituted. When a group has a substituent, the substituents include an alkyl group (for example, an alkyl group having 1 to 6 carbon atoms), a hydroxyl group, an alkoxy group (for example, an alkoxy group having 1 to 6 carbon atoms), and a halogen atom (for example, a fluorine atom). , Chlorine atom, bromine atom), cyano group, amino group, nitro group, acyl group, carboxyl group and the like. Regarding a group having a substituent, the "carbon number" shall mean the carbon number of the portion not containing the substituent.

(Alicyclic bifunctional (meth) acrylate)
The alicyclic bifunctional (meth) acrylate refers to a compound having an alicyclic structure and having two (meth) acryloyl groups contained in one molecule. The composition contains 70.0% by mass or more of alicyclic bifunctional (meth) acrylate with respect to the total amount of (meth) acrylate. The present inventor believes that this is the reason why the protective layer formed from the above composition can exhibit high hardness and excellent solvent resistance. From the viewpoint of making it possible to provide a protective layer capable of exhibiting higher hardness and better solvent resistance in a photochromic article, the above composition is alicyclic bifunctional with respect to the total amount of (meth) acrylate. The (meth) acrylate is preferably contained in an amount of 75.0% by mass or more, more preferably 80.0% by mass or more, further preferably 85.0% by mass or more, and further preferably 90.0% by mass or more. It is preferable, and it is even more preferable to contain 95.0% by mass or more. In one form, the composition may be an alicyclic bifunctional (meth) acrylate in which the total amount of the (meth) acrylate is. The composition may contain only one type of alicyclic bifunctional (meth) acrylate in one form, and may contain two or more types in the other form. When two or more kinds of alicyclic bifunctional (meth) acrylates are contained, the content of the above alicyclic bifunctional (meth) acrylate is the total content of two or more kinds. This point is the same for the content rate of other components.

Difunctional (meth) acrylates of cycloaliphatic, for ^{example, R 1 - (L 1)} n1-Q- (L 2) may be a compound having a structure represented by ^{n2-R 2.} Here, Q represents a divalent alicyclic group, R ¹ and R ² independently represent a (meth) acryloyl group or a (meth) acryloyloxy group, and L ¹ and L ² each independently represent a linking group. Represented, n1 and n2 independently represent 0 or 1, respectively. As the divalent alicyclic group represented by Q, an alicyclic hydrocarbon group having 3 to 20 carbon atoms is preferable, and for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, or a tri. Cyclodecanilen group, adamantylene group, isobornyl group and the like can be mentioned. Examples of the linking group represented by L ¹ and L ^{2 include an alkylene group.} The alkylene group can be, for example, an alkylene group having 1 to 6 carbon atoms.
Specific examples of the alicyclic bifunctional (meth) acrylate include, for example, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, propoxylated cyclohexanedimethanol di (meth) acrylate, and ethoxy. Propoxylated cyclohexanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, ethoxylated tricyclodecanedimethanol di (meth) acrylate, propoxylated tricyclohexanedimethanol di (meth) acrylate, ethoxy Propoxylated tricyclodecanedimethanol di (meth) acrylate and the like can be mentioned. The molecular weight of the alicyclic bifunctional (meth) acrylate can be, for example, in the range of 200 to 400, but is not limited to this range. In the present invention and the present specification, the molecular weight of the polymer adopts the structural formula determined by the structural analysis of the compound or the theoretical molecular weight calculated from the raw material charging ratio at the time of production. The alicyclic bifunctional (meth) acrylate may contain only an acryloyl group, may contain only a methacryloyl group, or may contain an acryloyl group and a methacryloyl group as the (meth) acryloyl group.

(Other (meth) acrylates)
In one form, the composition may contain one or more other (meth) acrylates in addition to the alicyclic bifunctional (meth) acrylate as the (meth) acrylate, and in the other form, ( Only the alicyclic bifunctional (meth) acrylate can be contained as the meta) acrylate. In the case of the former form, there is no particular limitation on other (meth) acrylates contained together with the alicyclic bifunctional (meth) acrylate, and one or more of various (meth) acrylates may be used. can. Examples of other (meth) acrylates include monofunctional, bifunctional, trifunctional, tetrafunctional and pentafunctional (meth) acrylates, which may be acyclic or cyclic. By "non-annular" is meant not to include a cyclic structure. On the other hand, "annular" means to include an annular structure. The (meth) acrylate containing a cyclic structure may have an alicyclic structure as the cyclic structure, or may have another cyclic structure. For the alicyclic structure, the above description regarding the alicyclic bifunctional (meth) acrylate can be referred to. In the above composition, the content of the other (meth) acrylate is 30.0% by mass or less, 25.0% by mass or less, 20.0% by mass or less, 15.0 with respect to the total amount of the (meth) acrylate. It can be less than or equal to mass%. Further, in the above composition, the content of the other (meth) acrylate is 0% by mass, 0% by mass or more, more than 0% by mass, 1.0% by mass or more, 5 by mass, based on the total amount of the (meth) acrylate. It can be 0.0% by mass or more or 10.0% by mass or more.

<Other ingredients>
The composition contains at least one (meth) acrylate as a polymerizable compound, can contain one or more polymerizable compounds other than the (meth) acrylate in one form, and is polymerized in the other form. Only (meth) acrylate can be included as the sex compound. The other polymerizable compounds are not particularly limited, and one or more known polymerizable compounds can be used. The composition contains 80.0% by mass or more, 85.0% by mass or more, 90.0% by mass or more, or 95.0% by mass or more of (meth) acrylate, with the total amount of the polymerizable compound being 100% by mass. And the total amount of the polymerizable compound can be (meth) acrylate.

In one form, the composition has a (meth) acrylate content (in the case of containing two or more (meth) acrylates, the total content thereof) of 80. It is preferably 0% by mass or more, more preferably 85.0% by mass or more, further preferably 90.0% by mass or more, and even more preferably 95.0% by mass or more. In the present invention and the present specification, with respect to the content rate, the "total amount of the composition" means the total amount of all the components excluding the solvent for the composition containing the solvent. The composition may or may not contain a solvent. When a solvent is contained, any solvent can be used as a usable solvent as long as it does not hinder the progress of the polymerization reaction of the polymerizable composition.

The composition can contain one or more of various additives that can be contained in the polymerizable composition at an arbitrary content. Examples of such additives include various known additives such as a polymerization initiator for advancing the polymerization reaction and a leveling agent for improving the coating suitability of the composition.

For example, as the polymerization initiator, a known polymerization initiator capable of functioning as a polymerization initiator for (meth) acrylate can be used, a radical polymerization initiator is preferable, and a radical polymerization initiator is used as the polymerization initiator. It is more preferable to contain only the agent. Further, as the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used, and the photopolymerization initiator is preferable from the viewpoint of advancing the polymerization reaction in a short time. Examples of the photoradical polymerization initiator include benzoyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-. Α-Hydroxyketones such as 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one; 2-benzyl-2-dimethylamino-1 Α-Aminoketones such as − (4-morpholinophenyl) -butane-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; 1-[ (4-Phenylthio) phenyl] -1,2-octadion-2- (benzoyl) oxime and other oxime esters; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Phenyl oxides such as 2,4,4-trimethylpentylphosphenyl oxide, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-) Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 4,5-diphenyl 2,4,5-Triarylimidazole dimer such as imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N'-tetramethyl-4, Benzoyl compounds such as 4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone; 2-ethylanthraquinone, phenylanthrenquinone, 2-tert-butylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10 -Kinone compounds such as phenanthraquinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin aids such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether Tell; benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; benzyl compounds such as benzyldimethylketal; aclysine compounds such as 9-phenylaclysine and 1,7-bis (9,9'-acridinylheptane): N- Examples thereof include phenylglycine and coumarin. Further, in the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups of the two triarylimidazole sites may give the same and symmetric compound, and give different and asymmetric compounds. May be good. Further, a thioxanthone compound and a tertiary amine may be combined, such as a combination of diethyl thioxanthone and dimethylaminobenzoic acid. Among these, α-hydroxyketone and phosphine oxide are preferable from the viewpoint of curability, transparency and heat resistance. The content of the polymerization initiator can be in the range of, for example, 0.1 to 5.0% by mass, assuming that the total amount of the composition is 100% by mass.

Also, in one form, the composition may include an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -s-triazine and 2,4,6-tris (2,4,6-tris). 2-Hydroxy-4-hexyloxy-3-methylphenyl) -s-triazine, 2- [2-hydroxy-4- (2-ethylhexyloxy) phenyl] -4,6-dibiphenyl-s-triazine, 2- [[2-Hydroxy-4- [1- (2-ethylhexyloxycarbonyl) ethyloxy] phenyl]] A hydroxyphenyltriazine compound such as -4,6-diphenyl-s-triazine, 2- (5-chloro-2H-benzo) Benzotriazole-based UV absorption such as triazole-2-yl) -6-tert-butyl-4-methylphenol and 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol One or more of various ultraviolet absorbers such as agents can be used. The inclusion of the ultraviolet absorber in the composition may contribute to the improvement of the weather resistance of the photochromic article having the protective layer formed from the composition. When the composition contains an ultraviolet absorber, the content of the ultraviolet absorber can be in the range of, for example, 0.1 to 1.0% by mass, with the total amount of the composition being 100% by mass.

The above composition can be prepared by sequentially mixing the various components described above at the same time or in any order.

[Photochromic goods]
One aspect of the present invention relates to a photochromic article having a photochromic layer containing a photochromic compound and a protective layer which is a cured layer obtained by curing the above composition.
Hereinafter, the above photochromic article will be described in more detail.

<Photochromic layer>
(Photochromic compound)
As the photochromic compound, a known compound exhibiting photochromic properties can be used. The photochromic compound can exhibit photochromic properties to, for example, ultraviolet rays. For example, examples of the photochromic compound include compounds having a known skeleton exhibiting photochromic properties, such as a flugimid compound, a spirooxazine compound, a chromene compound, and an indeno-condensed naphthopyrane compound. The photochromic compound can be used alone or in combination of two or more. The content of the photochromic compound in the above composition can be, for example, about 0.1 to 15% by mass, with the mass of the photochromic layer being 100% by mass, but is not limited to this range.

(Ingredients for forming a photochromic layer)
The photochromic layer can be a cured layer obtained by curing a polymerizable composition containing one or more photochromic compounds. Known techniques for photochromic articles can be applied to various components such as polymerizable compounds contained in the polymerizable composition for forming the photochromic layer. From the viewpoint of adhesion to the protective layer, the photochromic layer is preferably a cured layer obtained by curing a polymerizable composition containing (meth) acrylate as a polymerizable compound.

In one form, the photochromic layer cures a coating layer formed by directly applying a polymerizable composition containing one or more photochromic compounds to the surface of a base material or applying it to the surface of a layer provided on the base material. It can be a cured layer. As the coating method, a known coating method such as a spin coating method or a dip coating method can be adopted, and the spin coating method is preferable from the viewpoint of coating uniformity. The polymerization treatment can be light irradiation and / or heat treatment, and light irradiation is preferable from the viewpoint of allowing the polymerization reaction to proceed in a short time. The polymerization conditions may be determined according to the type and composition of various components contained in the polymerizable composition. The above description of the coating method and the polymerization treatment also applies to the polymerizable composition for forming a protective layer. The thickness of the photochromic layer is preferably in the range of, for example, 5 to 80 μm, and more preferably in the range of 20 to 60 μm.

<Protective layer>
The photochromic article has a protective layer which is a cured layer obtained by curing the polymerizable composition for forming a protective layer. The protective layer can be provided directly on the surface of the photochromic layer, or can be provided on the surface of a layer located above the photochromic layer. Examples of the layer that can be located between the photochromic layer and the protective layer include a primer layer and the like. The thickness of the protective layer is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, and even more preferably 25 μm or more. The thickness of the protective layer is preferably 45 μm or less, more preferably 40 μm or less. The protective layer can contribute to improving the durability of the photochromic article. Further, it is possible to protect the photochromic layer and prevent the photochromic layer from being scratched until further treatment (for example, formation of a cured layer described later) is performed.

<Base material>
The photochromic article can, in one form, be an optical article. Optical articles include various articles such as spectacle lenses, goggle lenses, visor parts of sun visors, and shield members of helmets. For example, the photochromic article can have a photochromic layer and a protective layer on a base material selected according to the type of the optical article. As an example of the base material, the spectacle lens base material can be a plastic lens base material or a glass lens base material. The glass lens base material can be, for example, a lens base material made of inorganic glass. As the lens base material, a plastic lens base material is preferable from the viewpoint of being lightweight, hard to break, and easy to handle. Examples of the plastic lens base material include styrene resins such as (meth) acrylic resins, polycarbonate resins, allyl resins, allyl carbonate resins such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resins, polyester resins, and polyether resins. , Urethane resin obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, and a (thio) epoxy compound having one or more disulfide bonds in the molecule. Examples thereof include a cured product (generally referred to as a transparent resin) obtained by curing the curable composition contained therein. As the lens base material, an undyed lens (colorless lens) may be used, or a dyed lens (dyed lens) may be used. The refractive index of the lens base material can be, for example, about 1.60 to 1.75. However, the refractive index of the lens base material is not limited to the above range, and may be within the above range or may be vertically separated from the above range. In the present invention and the present specification, the refractive index means the refractive index for light having a wavelength of 500 nm. Further, the lens base material may be a lens having a refractive power (so-called prescription lens) or a lens without refractive power (so-called prescription lens).

The spectacle lens can be various lenses such as a single focus lens, a multifocal lens, and a progressive power lens. The type of lens is determined by the surface shapes of both sides of the lens base material. Further, the surface of the lens base material may be a convex surface, a concave surface, or a flat surface. In ordinary lens substrates and spectacle lenses, the surface on the object side is convex and the surface on the eyeball side is concave. However, the present invention is not limited to this. The photochromic layer can usually be provided on the object-side surface of the lens base material, but may be provided on the eyeball-side surface.

The photochromic layer may be provided directly on the surface of the base material, or may be provided indirectly via one or more other layers. Examples of the other layer include a primer layer for improving the adhesion between the photochromic layer and the base material. Such primer layers are known.

<Layer that can be provided arbitrarily>
The photochromic article can have a layer structure of "base material / photochromic layer / protective layer". With respect to the layer structure, "/" is used to include a form in which it is in direct contact with each other without interposing another layer and a form in which it is provided through one or more layers of another layer. For example, a primer layer may exist between the base material and the photochromic layer as described above, but the base material and the photochromic layer may be in direct contact with each other. Further, in one form, the photochromic article can have a layer structure of "base material / photochromic layer / protective layer / other cured layer". In such a layer structure, the other hardened layer can be a hardened layer generally called a hard coat layer. By providing a hard coat layer in addition to the protective layer, the durability of the photochromic article can be further enhanced. Further, in one form, the impact resistance of the photochromic article can be enhanced by providing the hard coat layer. In one form, the other cured layer can be in direct contact with the protective layer without interposing another layer.

The thickness of the other cured layer can be, for example, in the range of 1 to 10 μm, preferably in the range of 1 to 8 μm, and more preferably in the range of 1 to 5 μm. In one form, the other cured layer can be thinner than the protective layer. As an example of the above-mentioned other hardened layer, an organosilicon-based hardened layer can be mentioned. The organosilicon-based cured layer is generally preferable because it has excellent impact resistance. Further, for example, when an antireflection film is further provided, the organosilicon-based cured layer is generally preferable from the viewpoint of excellent adhesion to the antireflection film.

The organosilicon-based cured layer is a cured layer obtained by curing a polymerizable composition containing an organosilicon compound. Examples of the organosilicon compound include an organosilicon compound capable of producing a silanol group by being subjected to a polymerization treatment, an organopolysiloxane having a reactive group such as a halogen atom or an amino group that condenses with the silanol group, and the like. can. Examples of the organic silicon compound include a silane coupling agent having a polymerizable group such as a vinyl group, an allyl group, a (meth) acryloyl group and a (meth) acryloyloxy group and a hydrolyzable group such as an alkoxy group. You can also. The polymerizable composition containing an organosilicon compound may contain particles of an inorganic substance such as a silicon oxide or a titanium oxide in order to adjust the refractive index or the like. For details of the polymerizable composition containing an organosilicon compound, a known technique regarding an organosilicon-based cured layer capable of functioning as a hard coat layer can be applied. Such a polymerizable composition can be cured by advancing the polymerization reaction by light irradiation and / or heat treatment, depending on the type of the component contained in the composition.

A protective layer to which a polymerizable composition for forming the other cured layer is applied by wiping the surface of the protective layer with a solvent before providing the other cured layer on the protective layer. The cleanliness of the surface can be improved. It is preferable to perform the wiping treatment with a solvent in this way from the viewpoint of preventing foreign matter from interposing between the protective layer and the other cured layer. However, if the protective layer is inferior in solvent resistance, the protective layer will be damaged by the solvent wiping treatment (for example, surface roughness will occur). The occurrence of such damage causes fogging and optical defects in the photochromic article containing this protective layer. On the other hand, the protective layer formed from the polymerizable composition for forming a protective layer having the composition described above can exhibit excellent solvent resistance.

The wiping treatment with a solvent can be performed by a known method. For example, by wiping the surface of the protective layer with a cloth soaked with a solvent, the wiping process with the solvent can be performed. Examples of the solvent include a ketone solvent such as acetone and an alcohol solvent such as ethanol and isopropyl alcohol. In one form, the protective layer preferably has high resistance to a ketone solvent commonly used as a solvent for wiping during the manufacture of optical articles.

The photochromic article may further have one or more layers in addition to the various layers described above. Examples of such a layer include a layer known as a functional layer of an optical article such as an antireflection layer, a water-repellent or hydrophilic antifouling layer, and an antifogging layer.

One form of the photochromic article is a spectacle lens. Further, as one form of the above-mentioned photochromic article, a lens for goggles, a visor (eaves) portion of a sun visor, a shield member of a helmet, and the like can be mentioned. The photochromic article can be suitably used as an optical article having an antiglare function.

[glasses]
One aspect of the present invention relates to spectacles provided with the above photochromic article, which is a spectacle lens. The details of the spectacle lens included in the spectacles are as described above. By providing the above-mentioned spectacle lens, for example, the photochromic compound contained in the photochromic layer can exert an antiglare effect like sunglasses by being irradiated with sunlight to develop a color indoors. When it returns, the photochromic compound fades and the permeability can be restored. A known technique can be applied to the structure of the frame and the like for the above-mentioned eyeglasses.

Hereinafter, the present invention will be further described with reference to Examples. However, the present invention is not limited to the embodiments shown in the examples. Unless otherwise specified, the steps and evaluations described below were performed in the air at room temperature (20 ° C ± 5 ° C).

[Example 1]
<Making spectacle lenses (photochromic articles)>
A plastic lens base material (trade name EYAS manufactured by HOYA Corporation; center wall thickness 2.5 mm, radius 75 mm, S-4.00) is immersed in a 10 mass% sodium hydroxide aqueous solution (liquid temperature 60 ° C.) for 5 minutes and then pure. It was washed with water and dried. Then, a primer layer was formed on the convex surface (object side surface) of this plastic lens base material. Specifically, a water-based polyurethane resin solution (polycarbonate polyol-based polyurethane emulsion; viscosity 100 CPS, solid content concentration 38% by mass) is applied to the convex surface of a plastic lens base material by a spin coating method in an environment of a temperature of 25 ° C. and a relative humidity of 50%. By air-drying for 15 minutes, a primer layer having a thickness of 5.5 μm was formed.
A polymerizable composition for forming a photochromic layer prepared as follows was applied onto the primer layer by a spin coating method to form a coating layer. The surface of the coating layer was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration of 500 ppm or less), and the coating layer was cured to form a photochromic layer. The thickness of the formed photochromic layer was 45 μm.
A polymerizable composition for forming a protective layer prepared as follows was applied onto the photochromic layer by a spin coating method to form a coating layer. The surface of the coating layer was irradiated with ultraviolet rays (wavelength 405 nm) in a nitrogen atmosphere (oxygen concentration of 500 ppm or less), and the coating layer was cured to form a protective layer. The thickness of the protective layer formed was 15 μm.

<Preparation of polymerizable composition for forming a photochromic layer>
In a plastic container, 20 parts by mass of trimethylpropan trimethacrylate, 35 parts by mass of BPE oligomer (2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane), 10 parts by mass of EB6A (polyester oligomer hexaacrylate), average molecular weight A radically polymerizable composition consisting of 10 parts by mass of polyethylene glycol diacrylate and 10 parts by mass of glycidyl methacrylate of 532 was prepared. With respect to 100 parts by mass of this radically polymerizable composition, 3 parts by mass of the following chromane 1 as a photochromic compound, LS765 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl) as a light stabilizer (1,2,2,6,6-pentamethyl-4-piperidyl) sevacate) in 5 parts by mass, hindered phenolic antioxidant (Irgacure 245 manufactured by BASF) in 5 parts by mass, CGI- as an ultraviolet polymerization initiator 6 parts by mass of γ-methacryloyloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was added dropwise to the composition obtained by adding 0.6 parts by mass of 1870 (manufactured by BASF) and sufficiently stirring and mixing. .. Then, the foam was defoamed for 2 minutes with a rotation / revolution type stirring defoaming device to obtain a polymerizable composition for forming a photochromic layer.

<Preparation of polymerizable composition for forming protective layer>
In a plastic container, 86.7 parts by mass of tricyclodecanedimethanol diacrylate (alicyclic bifunctional (meth) acrylate), 4.3 parts by mass of pentaerythritol tetraacrylate, and 8.7 parts by mass of isobornyl acrylate. , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Omnilad 819 manufactured by IGM Resin BV) was mixed and sufficiently stirred, and then rotated and revolved with a stirring defoaming device. Defoamed. In this way, the polymerizable composition for forming the protective layer of Example 1 was prepared.
In the polymerizable composition for forming a protective layer of Example 1, the content of the alicyclic bifunctional (meth) acrylate is 87.0% by mass with respect to the total amount of the (meth) acrylate.

[Example 2]
An spectacle lens was produced by the same method as in Example 1 except that the composition for forming a protective layer was prepared by the following method.

<Preparation of polymerizable composition for forming protective layer>
In a plastic container, 99.0 parts by mass of tricyclodecanedimethanol diacrylate (alicyclic bifunctional (meth) acrylate) and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IGM Resin B. 1.0 part by mass of Omnirad 819) manufactured by V. Co., Ltd. was mixed and sufficiently stirred, and then defoamed with a rotation / revolution type stirring defoaming device. In this way, the polymerizable composition for forming the protective layer of Example 2 was prepared.
In the polymerizable composition for forming a protective layer of Example 2, since the (meth) acrylate is only an alicyclic bifunctional (meth) acrylate, the content of the alicyclic bifunctional (meth) acrylate is ( It is 100% by mass based on the total amount of the meta) acrylate.

[Comparative Example 1]
An spectacle lens was produced by the same method as in Example 1 except that the composition for forming a protective layer was prepared by the following method.

<Preparation of polymerizable composition for forming protective layer>
In a plastic container, 68.0 parts by mass of tricyclodecanedimethanol dimethacrylate (alicyclic bifunctional (meth) acrylate), 20.0 parts by mass of neopentyl glycol dimethacrylate, 12.0 parts by mass of trimethylolpropane trimethacrylate. 0.3 parts by mass and 0.3 parts by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819 manufactured by IGM Resin B.V.) were mixed and sufficiently stirred, and then the rotation and revolution method was stirred and defoamed. Defoamed with the device. In this way, the polymerizable composition for forming the protective layer of Comparative Example 1 was prepared.
In the polymerizable composition for forming a protective layer of Comparative Example 1, the content of the alicyclic bifunctional (meth) acrylate is 68.0% by mass with respect to the total amount of the (meth) acrylate.

In the above Examples and Comparative Examples, three spectacle lenses are produced, one is subjected to hardness evaluation, the other one is subjected to solvent resistance evaluation, and the remaining one is described later. A hard coat layer was formed by the method.

[Evaluation method]
(1) Evaluation of Hardness For each of the above spectacle lenses, an indenter was pressed by applying a load of 100 mgf to the surface of the protective layer using an ultra-fine indentation hardness tester ENT-2100 manufactured by Elionix Inc. At this time, the surface area invaded by the indenter was measured from the indentation depth, and the Martens hardness was determined as "load / surface area invaded by the indenter". Martens hardness is defined as a value obtained by dividing the load F by the surface area invaded by the indenter when the indenter is pushed to a predetermined pushing amount h by applying the load F. It is the hardness measured when a test load is applied, and is obtained from the value of the load-push depth curve when the load increases.

(2) Evaluation of solvent resistance The surface of the protective layer of each of the above spectacle lenses was wiped with a cloth impregnated with acetone. The surface of the protective layer after wiping was visually observed and evaluated according to the following criteria.
Good: No surface roughness Damaged: Surface roughness is observed.

The results of the above evaluation are shown in Table 1.

[Formation of hard coat layer]
To a glass container equipped with a magnetic stirrer, add 17 parts by mass of γ-glycidoxypropyltrimethoxysilane, 30 parts by mass of methanol, and 28 parts by mass of aqueous-dispersed colloidal silica (solid content 40% by mass, average particle size 15 nm). It was mixed well and stirred at 5 ° C. for 24 hours. Next, 15 parts by mass of propylene glycol monomethyl ether, 0.05 parts by mass of a silicone-based surfactant, and 1.5 parts by mass of aluminum acetylacetonate as a curing agent were added, and the mixture was sufficiently stirred and then filtered. A hard coating liquid (a polymerizable composition for forming a hard coat layer) was prepared.
The surface of the protective layer of each spectacle lens produced above was wiped with acetone, and then the hard coating liquid was coated by a dip coating method (pulling speed 20 cm / min). Then, a hard coat layer (organosilicon-based cured layer) having a thickness of 3 μm was formed by heating and curing in a heat treatment furnace at a furnace temperature of 100 ° C. for 60 minutes.
When each spectacle lens on which the hard coat layer was formed was visually observed, the spectacle lens of Example 1 and the spectacle lens of Example 2 were more transparent than the spectacle lens of Comparative Example 1. This is because, as shown in Table 1, the protective layer of the spectacle lens of Example 1 and the spectacle lens of Example 2 is superior in solvent resistance to the protective layer of the spectacle lens of Comparative Example 1. It is considered that this is because the surface roughness was less likely to occur in the solvent wiping treatment performed before the formation of the hard coat layer.

[Example 3]
0.3% by mass of an ultraviolet absorber (hydroxyphenyltriazine-based ultraviolet absorber, trade name: Tinubin479 (manufactured by BASF)) was added to the polymerizable composition for forming a protective layer, with the total amount of the composition being 100% by mass. Except for the points, a spectacle lens having a base material, a primer layer, a photochromic layer, a protective layer, and a hard coat layer in this order was produced in the same manner as in Example 1.

The spectacle lens of Example 1 and the spectacle lens of Example 3 were evaluated for color density by the following method according to JIS T7333: 2005.
The object-side surface of each spectacle lens was irradiated with light for 15 minutes (900 seconds) through an aeromas filter using a xenon lamp to develop a color of the photochromic compound in the photochromic layer. The transmittance (measurement wavelength: 550 nm) at the time of color development was measured by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The light irradiation was carried out so that the irradiance and the permissible difference of the irradiance became the values shown in Table 2 below as specified in JIS T7333: 2005.

The smaller the value of the transmittance measured above (hereinafter referred to as "transmittance at the time of color development"), the higher the concentration of the photochromic compound.

Then, in a QUV ultraviolet fluorescent tube type accelerated weathering tester (manufactured by Q-Lab), ultraviolet rays were irradiated ^{toward the object side surface of the spectacle lens under an irradiation condition of 0.2 W / m 2 for one week.}
The spectacle lens after the ultraviolet irradiation was once placed in a dark room to fade the photochromic compound, and then the transmittance at the time of color development was determined in the same manner as described above. It can be evaluated that the smaller the increase in the transmittance at the time of color development after the ultraviolet irradiation is, the more excellent the weather resistance is than before the ultraviolet irradiation. For the spectacle lens of Example 1, the value of "(transmittance at the time of color development after ultraviolet irradiation)-(transmittance at the time of color development before ultraviolet irradiation)" was 2.8%. On the other hand, when the same evaluation was performed on the spectacle lens of Example 3, the value of "(transmittance at the time of color development after ultraviolet irradiation)-(transmittance at the time of color development before ultraviolet irradiation)" was 0.3%. Met.

For the spectacle lens of Example 1 and the spectacle lens of Example 3, the YI value specified in JIS K 7373: 2006 was measured using a spectroscopic transmission measuring device DOT-3 manufactured by Murakami Color Technology Laboratory Co., Ltd. The YI value is an index indicating the degree of coloring, and the smaller the value, the less the coloring.
Then, in a QUV ultraviolet fluorescent tube type accelerated weathering tester (manufactured by Q-Lab), ultraviolet rays were irradiated ^{toward the object side surface of the spectacle lens under an irradiation condition of 0.2 W / m 2 for one week.}
The YI value of the spectacle lens after the ultraviolet irradiation was determined in the same manner as described above. It can be evaluated that the smaller the increase in the YI value after the ultraviolet irradiation is, the more excellent the weather resistance is than before the ultraviolet irradiation. For the spectacle lens of Example 1, the value of "(YI value after ultraviolet irradiation)-(YI value before ultraviolet irradiation)" was 9.9%. On the other hand, when the same evaluation was performed on the spectacle lens of Example 3, the value of "(YI value after ultraviolet irradiation)-(YI value before ultraviolet irradiation)" was 4.6%.

Finally, each of the above aspects will be summarized.

According to one aspect, a photochromic article containing one or more (meth) acrylates and containing 70.0% by mass or more of alicyclic bifunctional (meth) acrylates with respect to the total amount of (meth) acrylates. A polymerizable composition for forming a protective layer is provided.

According to the above-mentioned polymerizable composition for forming a protective layer, a protective layer having both high hardness and excellent solvent resistance can be formed in a photochromic article.

In one form, the polymerizable composition for forming a protective layer can contain 80.0% by mass or more of an alicyclic bifunctional (meth) acrylate with respect to the total amount of the (meth) acrylate.

In one form, the polymerizable composition for forming a protective layer can contain 90.0% by mass or more of an alicyclic bifunctional (meth) acrylate with respect to the total amount of the (meth) acrylate.

In one form, the polymerizable composition for forming a protective layer can contain 80.0% by mass or more of (meth) acrylate with respect to the total amount of the composition.

In one form, the polymerizable composition for forming a protective layer can contain 90.0% by mass or more of (meth) acrylate with respect to the total amount of the composition.

In one form, the polymerizable composition for forming a protective layer may further contain a radical polymerization initiator.

In one form, the polymerizable composition for forming a protective layer may further contain an ultraviolet absorber.

According to one aspect, there is provided a photochromic article having a photochromic layer containing a photochromic compound and a protective layer which is a cured layer obtained by curing the polymerizable composition for forming a protective layer.

In one form, the thickness of the protective layer can be in the range of 10-45 μm.

In one form, the photochromic article may further have a substrate.

In one form, the photochromic article can have the base material, the photochromic layer, the protective layer, and the organosilicon-based cured layer in this order.

In one form, the photochromic article can be a spectacle lens.

In one form, the photochromic article can be a goggle lens.

In one form, the photochromic article can be the visor portion of a sun visor.

In one form, the photochromic article can be a helmet shield member.

According to one aspect, spectacles provided with the above spectacle lens are provided.

Two or more of the various aspects and forms described herein can be combined in any combination.

It should be considered that the embodiments disclosed this time are exemplary in all respects and not restrictive. The scope of the present invention is shown by the scope of claims rather than the above description, and it is intended to include all modifications within the meaning and scope equivalent to the scope of claims.

The present invention is useful in the technical fields of eyeglasses, goggles, sun visors, helmets and the like.

Claims (16)

Polymerization for forming a protective layer of a photochromic article containing one or more kinds of (meth) acrylates and containing 70.0% by mass or more of alicyclic bifunctional (meth) acrylates with respect to the total amount of (meth) acrylates. Composition. The polymerizable composition for forming a protective layer of a photochromic article according to claim 1, which contains 80.0% by mass or more of an alicyclic bifunctional (meth) acrylate with respect to the total amount of the (meth) acrylate. The polymerizable composition for forming a protective layer of a photochromic article according to claim 1 or 2, which contains 90.0% by mass or more of an alicyclic bifunctional (meth) acrylate with respect to the total amount of the (meth) acrylate. The polymerizable composition for forming a protective layer of a photochromic article according to any one of claims 1 to 3, which contains 80.0% by mass or more of (meth) acrylate with respect to the total amount of the composition. The polymerizable composition for forming a protective layer of a photochromic article according to any one of claims 1 to 4, which contains 90.0% by mass or more of (meth) acrylate with respect to the total amount of the composition. The polymerizable composition for forming a protective layer of a photochromic article according to any one of claims 1 to 5, further comprising a radical polymerization initiator. The polymerizable composition for forming a protective layer of a photochromic article according to any one of claims 1 to 6, further comprising an ultraviolet absorber. A photochromic layer containing a photochromic compound and
A protective layer which is a cured layer obtained by curing the composition according to any one of claims 1 to 7.
Photochromic articles with. The photochromic article according to claim 8, wherein the thickness of the protective layer is in the range of 10 to 45 μm. The photochromic article of claim 8 or 9, further comprising a substrate. The photochromic article according to claim 10, further comprising the base material, the photochromic layer, the protective layer, and an organosilicon-based cured layer in this order. The photochromic article according to any one of claims 8 to 11, which is a spectacle lens. The photochromic article according to any one of claims 8 to 11, which is a lens for goggles. The photochromic article according to any one of claims 8 to 11, which is a visor portion of a sun visor. The photochromic article according to any one of claims 8 to 11, which is a shield member of a helmet. Eyeglasses comprising the spectacle lens according to claim 12.