JP6346183B2 - Photochromic laminate containing cured product of photocurable primer composition for optical article, and method for producing the laminate - Google Patents

Description

  The present invention relates to a novel photocurable primer composition for optical articles and a photochromic laminate including a cured product of the primer composition. Specifically, a photo-curable primer composition for optical articles for forming a primer coat layer that exhibits excellent adhesion, and thus forming a laminate having high surface hardness, less scratches, and excellent photochromic properties. And a photochromic laminate including a cured product of the photocurable primer composition for optical articles.

  Photochromic glasses are lenses that quickly color and function as sunglasses when exposed to light containing ultraviolet rays such as sunlight, and fade and become transparent when indoors where ultraviolet light is not irradiated. Function. In recent years, the demand for photochromic glasses has increased.

  As a method for producing a plastic lens having photochromic properties, a method of impregnating a surface of a lens having no photochromic properties with a photochromic compound (hereinafter referred to as “impregnation method”) is known. Further, a resin layer having photochromic properties is applied by applying a coating agent (hereinafter sometimes referred to as “photochromic curable composition”) made of a curable composition having photochromic properties to the surface of the plastic lens. There is also known a method (hereinafter referred to as “coating method”) for providing (hereinafter also referred to as “photochromic coating layer”). Furthermore, a method of directly obtaining a photochromic lens by dissolving a photochromic compound in a monomer and polymerizing it (hereinafter referred to as “kneading method”) is also known. Among these manufacturing methods, the coating method is an excellent method in that photochromic performance can be imparted regardless of the material of the plastic lens.

  In order to use a photochromic lens manufactured by a coating method (hereinafter sometimes referred to as “photochromic laminate”) for a long time, it is necessary to firmly adhere the photochromic coating layer to the surface of various plastic lens substrates. is there. It is also important that the photochromic coat layer has a sufficient surface hardness in order to prevent scratching of the photochromic coat layer. Furthermore, even in an article in which a hard coat layer or an antireflection film is laminated on the photochromic coat layer, it is necessary to prevent scratches on the surface, and for that purpose, the article has a sufficient surface hardness in the state of the photochromic laminate. This is very important.

  Various improvements have been made so far in order to improve the adhesion of the photochromic coating layer to the plastic lens. For example, a method for improving adhesion to a plastic lens substrate by adding a radically polymerizable monomer or amine compound having a silanol group or a group that generates a silanol group by hydrolysis to a photochromic coating composition is known. (Patent Document 1). Also known is a method of using a moisture curable polyurethane resin and / or a polyurethane resin composed of a cured product of a precursor thereof as a primer coat layer and laminating a photochromic coat layer thereon (Patent Document 2). Furthermore, a method is also known in which a primer composition composed of an emulsion containing a urethane resin is applied to form a primer coat layer, and a photochromic coat layer is laminated thereon (Patent Document 3).

WO03 / 011967 Japanese Patent Laid-Open No. 2005-199683 WO2008 / 001875

  However, these conventional methods have room for improvement in the following points. That is, the method of Patent Document 1 is a method of improving adhesion to a plastic lens substrate by adding a composition having a bonding group to the surface of a plastic lens to the photochromic coating composition. Although the photochromic coating layer obtained by this method has initial adhesion, it has been found that if it is used repeatedly under high temperature and high humidity conditions, depending on the type of substrate, the adhesion may decrease and peeling may occur. It was.

  Further, the method of Patent Document 2 using a moisture-curable polyurethane resin can withstand repeated use under high temperature and high humidity conditions, and the surface hardness of the photochromic coat layer is sufficient. However, depending on the type of plastic lens substrate, the surface of the substrate may be affected by the primer composition. Therefore, before applying the primer composition, the substrate surface should be coated with a crosslinked film such as a hard coat layer in advance. It was necessary to keep. In addition, even after the primer coat layer is formed, the primer coat layer is not easily wetted by the photochromic coat composition, so when the photochromic coat composition is applied by a method such as a spin coat method, the uncoated photochromic coat composition is left uncoated. It was found that poor appearance may occur.

  On the other hand, the method of Patent Document 3 in which an emulsion containing a urethane resin is used as a primer has good wettability between the primer coat layer and the photochromic coat layer, adhesion between the photochromic coat layer and the plastic lens, and photochromic properties. However, it was revealed that the surface hardness of the photochromic coat layer was insufficient and the photochromic coat layer was easily scratched.

As mentioned above, the photochromic layer has a sufficient surface hardness that keeps the photochromic coat layer from scratching while maintaining high photochromic properties and high adhesion between the photochromic coat layer and the plastic lens under high temperature and high humidity. There is no laminate, and it has been desired to develop a photochromic laminate having all these characteristics.
Accordingly, an object of the present invention is to provide a photocurable primer composition for optical articles that can be used even under high temperature and high humidity conditions, is excellent in photochromic properties, and is used to obtain a photochromic laminate that does not easily scratch the photochromic coating layer. To provide things.

  The present inventors have made extensive studies to solve the above problems. First, it has been found that when the surface hardness of the photochromic coat layer is increased in order to prevent scratching of the photochromic laminate, appearance defects (cracks) occur in the photochromic coat layer. Further examination of the photochromic coating layer in detail revealed that the photochromic properties deteriorated when both the suppression of the appearance defect and the improvement of the surface hardness are achieved.

  The inventors of the present invention do not affect the surface hardness of the primer coat layer serving as the foundation of the photochromic coating layer on the surface hardness of the photochromic coating layer in the photochromic laminate and the scratch prevention of the photochromic laminate. Therefore, a primer composition for forming a primer coat layer was examined. As a result, by using a cured product of a specific urethane (meth) acrylate excellent in water dispersibility as a primer coat layer, while maintaining good adhesion between the photochromic coat layer and the plastic lens, and photochromic characteristics, The present inventors have found that the photochromic coat layer can be prevented from being scratched and have completed the present invention.

  That is, according to the present invention, there is provided a photocurable primer composition for an optical article comprising an aqueous dispersion containing urethane (meth) acrylate and a photopolymerization initiator, and the elongation of a single cured product of the urethane (meth) acrylate. A photocurable primer composition for optical articles is provided, wherein the rate (25 ° C.) is 0.1 to 10%.

In the photocurable primer composition for optical articles of the present invention,
(1) The tensile strength (25 ° C.) of the urethane (meth) acrylate single cured body is 10 to 50 MPa,
(2) The Vickers hardness when cured is 8 to 30,
Is preferred.

  Further, according to the present invention, a lens substrate, a primer coat layer, and a photochromic coat layer are laminated in this order, and the primer coat layer is a cured photocurable primer composition for optical articles. The photochromic laminated body characterized by being a body is provided.

In the photochromic laminate of the present invention,
(3) The Vickers hardness of the photochromic coat layer on the primer coat layer is preferably greater than 8 and 12 or less.

  Furthermore, according to the present invention, the step of applying the photocurable primer composition for an optical article on a lens substrate to form a first precursor provided with a primer precursor layer before curing, A step of applying a photochromic curable composition containing a photopolymerization initiator on the primer precursor layer, providing a photochromic precursor layer before curing to form a second precursor, and light on the second precursor Is provided, and the method includes the step of curing the primer precursor layer and the photochromic precursor layer.

  ADVANTAGE OF THE INVENTION According to this invention, the photochromic laminated body which maintains the adhesiveness under high temperature, high humidity, and also has the surface hardness which is hard to be damaged, maintaining a high photochromic characteristic. In the obtained photochromic laminate, appearance defects such as cracks do not occur in the photochromic coating layer. Moreover, since the dispersion medium in the photocurable primer composition for optical articles of the present invention is aqueous, the surface of the lens base material is not affected by the primer composition, and is used directly on various lens base materials. It is possible.

  When the photocurable primer composition for optical articles and the photochromic curable composition of the present invention are applied to a lens substrate and cured, the curing step can be completed in one step. Since the adhesion between the primer coat layer and the photochromic coat layer thus obtained is particularly high, it is particularly suitable from the viewpoint of workability.

FIG. 1 is a conceptual diagram showing a beveled plastic lens.

<Photocurable primer composition for optical articles>
The photocurable primer composition for optical articles of the present invention (hereinafter sometimes referred to as the primer composition of the present invention) comprises an aqueous dispersion containing urethane (meth) acrylate and a photopolymerization initiator.
When the primer composition of the present invention is applied on a lens substrate and cured, a primer coat layer having a high surface hardness can be obtained. Moreover, the photochromic laminated body which has this primer coat layer has surface hardness higher than before, and is hard to be damaged.
Hereinafter, each component which comprises the primer composition of this invention is demonstrated.

(Urethane (meth) acrylate)
The urethane (meth) acrylate used in the present invention has a (meth) acryl group at the end of the polyurethane skeleton, and further has an anionic group. Due to having an anionic group, the urethane (meth) acrylate used in the present invention exhibits good water dispersibility. Thus, by using urethane (meth) acrylate excellent in water dispersibility, an aqueous dispersion medium can be used in the primer composition of the present invention. As a result, the adverse effect of the primer composition on the surface of the lens substrate can be effectively avoided, and the primer composition can be used directly on various lens substrates.

  The number of (meth) acrylic groups is preferably 2 or more, more preferably 4 to 30 in one molecule of urethane (meth) acrylate, from the viewpoint of forming a cured product by polymerization.

  Examples of the anionic group possessed by urethane (meth) acrylate include carboxyl group; sulfonyl group; phosphate group; betaine structure-containing group such as sulfobetaine; and the like. From the viewpoint, a carboxyl group is preferable.

  In consideration of water dispersibility, the number of anionic groups is preferably 1 or more per molecule of urethane (meth) acrylate. Moreover, it is preferable that the average molecular weights of urethane (meth) acrylate are 1,000-30,000.

  In the present invention, as urethane (meth) acrylate, it is an important feature to use urethane (meth) acrylate having an elongation (25 ° C.) of 0.1 to 10% when a single cured product is formed. . By curing such urethane (meth) acrylate, it is presumed that a three-dimensional highly crosslinked cured body can be obtained, and as a result, a primer coat layer having a high surface hardness can be obtained. In addition, since the primer composition does not adversely affect the lens base material, and further has the above-described elongation characteristics, the primer coat layer obtained by the primer composition of the present invention is an adjacent layer (lens base material, photochromic). It can be firmly adhered to the coating layer), and the adhesion can be maintained even in a severe environment of high temperature and high humidity. In particular, urethane (meth) acrylate having a single cured body elongation (25 ° C.) of 0.5 to 5.0% is less likely to cause appearance defects such as cracks in the resulting photochromic laminate, and has a particularly high surface hardness. Therefore, it is preferable.

  The tensile strength (25 ° C.) of the urethane (meth) acrylate single cured body is 10 to 50 MPa from the viewpoint that appearance defects such as cracks are hardly generated in the resulting photochromic laminate, and that high surface hardness can be obtained. Particularly preferred is 15 to 30 MPa.

  The urethane (meth) acrylate single cured product is an urethane (meth) acrylate aqueous dispersion to which a predetermined photopolymerization initiator is added, separated into containers so that the film thickness after drying is about 500 μm, and then It means a polyurethane (meth) acrylate film obtained by drying and irradiating the aqueous dispersion under predetermined conditions. Components other than polyurethane (meth) acrylate and water may be blended in the aqueous dispersion for obtaining a single cured product as long as the solid content concentration is 10 to 70% by mass. And 0.3 parts by mass per 100 parts by mass of urethane (meth) acrylate. The details of the conditions for obtaining the single cured product are as described in the examples described later.

Specifically, the method for measuring the elongation percentage and tensile strength of the single cured product is as follows. The obtained urethane (meth) acrylate single cured body (polyurethane (meth) acrylate film) was cut into a size of 15 mm in width and 200 mm in length, and then marked at intervals of 50 mm in the center, and a measurement sample. Create The sample is attached to a tensile tester, and the tensile strength and the elongation rate are measured in an environment of 25 ° C. with the interval between the grips of the tester set to 100 mm until the sample breaks at a speed of 200 mm / min. The stress when the sample breaks is defined as the tensile strength. The elongation percentage is obtained by the following formula.
Elongation rate (%) = {(L−L ₀ ) / L ₀ } × 100
Where
L represents the distance between the gauge points at the time of breakage,
L ₀ represents the distance between the gauge points before the test.
Details of the measurement conditions are as described in Examples described later.

  The urethane (meth) acrylate used in the present invention can be quickly photopolymerized and cured. For example, when performing photopolymerization and curing under predetermined conditions to obtain a single cured product, 95 mol% or more (polymerization rate of 95% or more) of the (meth) acryl group is polymerized. Thus, by using urethane (meth) acrylate that can be easily polymerized and the elongation percentage of the single cured product can satisfy the above value, in the present invention, a good photochromic coating layer and a plastic lens A photochromic laminate that can prevent the photochromic coating layer from being scratched while maintaining adhesion and photochromic characteristics can be obtained.

  Known urethane (meth) acrylates can be used. Specifically, a known urethane (meth) acrylate obtained by reacting a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth) acrylate compound by a known method such as a one-shot method or a prepolymer method can be used. . From the viewpoint of ease of polymerization, a known urethane (meth) acrylate obtained by further reacting an anionic group-active hydrogen group-containing compound with a polyisocyanate compound, a polyol compound and a hydroxyl group-containing (meth) acrylate compound is used. Is preferred.

The polyisocyanate compound suitably used as a raw material for urethane (meth) acrylate is a compound having two or more isocyanate groups in one molecule. Specific examples of the polyisocyanate compound include the following compounds.
Aliphatic diisocyanate compounds, such as
Tetramethylene-1,4-diisocyanate,
Hexamethylene-1,6-diisocyanate,
Octamethylene-1,8-diisocyanate,
2,2,4-trimethylhexane-1,6-diisocyanate;
Alicyclic diisocyanate compounds, such as
Cyclobutane-1,3-diisocyanate,
Cyclohexane-1,3-diisocyanate,
Cyclohexane-1,4-diisocyanate,
2,4-methylcyclohexyl diisocyanate,
2,6-methylcyclohexyl diisocyanate,
Isophorone diisocyanate,
Norbornene diisocyanate,
An isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate),
Hexahydrotoluene-2,4-diisocyanate,
Hexahydrotoluene-2,6-diisocyanate,
Hexahydrophenylene-1,3-diisocyanate,
Hexahydrophenylene-1,4-diisocyanate,
1,9-diisocyanato-5-methylnonane,
1,1-bis (isocyanatomethyl) cyclohexane,
2-isocyanato-4-[(4-isocyanatocyclohexyl) methyl] -1-methylcyclohexane,
2- (3-isocyanatopropyl) cyclohexyl isocyanate;
Aromatic diisocyanate compounds, for example
Phenylcyclohexylmethane diisocyanate,
Isomer mixture of 4,4′-methylenebis (phenylisocyanate),
Toluene-2,3-diisocyanate,
Toluene-2,4-diisocyanate,
Toluene-2,6-diisocyanate,
Phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate,
1,3-bis (isocyanatomethyl) benzene,
Xylylene diisocyanate,
Tetramethylxylylene diisocyanate,
Naphthalene diisocyanate,
Diphenyl ether diisocyanate,
1,3-diisocyanatomethylbenzene,
4,4′-diisocyanato-3,3′-dimethoxy (1,1′-biphenyl),
4,4′-diisocyanato-3,3′-dimethylbiphenyl,
1,2-diisocyanatobenzene,
1,4-bis (isocyanatomethyl) -2,3,5,6-tetrachlorobenzene,
2-dodecyl-1,3-diisocyanatobenzene,
1-isocyanato-4-[(2-isocyanatocyclohexyl) methyl] 2-methylbenzene,
1-isocyanato-3-[(4-isocyanatophenyl) methyl)-
2-methylbenzene,
4-[(2-isocyanatophenyl) oxy] phenyl isocyanate,
Diphenylmethane diisocyanate;

further,
Multimers of the above polyisocyanate compounds (for example, dimers, trimers, etc.);
Modified biuret produced by the reaction of a polymer with a polyisocyanate compound and water;
Allophanate modified products and polyol modified products produced by the reaction of polyisocyanate compound multimers with alcohols or low molecular weight polyols described below;
An oxadiazinetrione-modified product produced by the reaction of a polyisocyanate compound multimer and carbon dioxide, and a multimer of these modified products;
Etc. may be used as raw materials. Polyisocyanate compounds can be used alone or in combination of two or more.

  Among the polyisocyanate compounds, it is preferable to use an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound from the viewpoint of weather resistance.

A polyol compound suitably used as a raw material is a compound containing two or more hydroxy groups in one molecule. Specific examples of the polyol compound include the following compounds.
Alkylene glycols such as
ethylene glycol,
1,2-propylene glycol,
1,3-butanediol,
1,4-butanediol,
1,6-hexanediol,
Neopentyl glycol,
Dipropylene glycol,
Diethylene glycol;
Polyalkylene glycols such as
Polypropylene glycol,
Polyethylene glycol,
Polytetramethylene glycol;
Poly (alkylene adipates), for example
Poly (diethylene adipate),
Poly (tetramethylene adipate),
Poly (hexamethylene adipate),
Poly (neopentylene adipate);
Polycaprolactone polyols, for example,
Poly-ε-caprolactone,
Polycaprolactone diol,
Polycaprolactone tolyl;
Polybutadiene glycols such as
Poly (1,4-butanediene) glycol,
Poly (1,2-butanediene) glycol;
Poly (alkylene carbonates), for example
Poly (hexamethylene carbonate);
Polyester polyols;
Polyols containing 3 or more hydroxy groups in one molecule, such as
Trimethylolethane,
Trimethylolpropane,
1,2,4-butanetriol,
1,2,6-hexanetriol,
Pentaerythritol;
Silicone polyols;
Polyol compounds can be used alone or in combination of two or more.

  Among the above-mentioned polyol compounds, polyalkylene glycols, polyols containing 3 or more hydroxy groups, polyalkylene adipates, polyalkylene carbonates, polycaprolactone polyols or polyester polyols have a higher heating temperature when cured. This is preferable because it can be lowered, and thermal deformation and discoloration of the substrate can be more reliably prevented.

The anionic group active hydrogen group-containing compound that can be used as a raw material contains one or more anionic groups in one molecule and two or more active hydrogen groups. Examples of the anionic group include a carboxyl group; a sulfonyl group; a phosphate group; a betaine structure-containing group such as sulfobetaine; The active hydrogen group is a group that can react with an isocyanate group, and examples thereof include a hydroxyl group and an amino group. Specific examples of the anionic group-active hydrogen group-containing compound include the following compounds.
Dihydroxylcarboxylic acids such as 2,2-dimethylolacetic acid,
2,2-dimethylol lactic acid,
2,2-dimethylolpropionic acid,
2,2-dimethylolbutanoic acid,
2,2-dimethylolbutyric acid,
2,2-dimethylolvaleric acid;
Diaminocarboxylic acids, for example
lysine,
Cystine,
Arginine;
The anionic group active hydrogen group-containing compound can be used alone or in combination of two or more.

The hydroxyl group-containing (meth) acrylate compound as a raw material is a (meth) acrylate compound having one or more hydroxyl groups in the molecule. As such a hydroxyl group-containing (meth) acrylate compound, specifically,
2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate,
3-hydroxybutyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate,
2,2-dihydroxymethylbutyl (meth) acrylate,
Hydroxyhexyl (meth) acrylate,
2-hydroxy-3-chloropropyl (meth) acrylate,
2-hydroxy-3-phenoxypropyl (meth) acrylate,
1,4-butylene glycol mono (meth) acrylate,
Glycerin mono (meth) acrylate,
Propylene glycol mono (meth) acrylate,
Polycaprolactone glycol mono (meth) acrylate,
Trimethylolpropane di (meth) acrylate,
Pentaerythritol tri (meth) acrylate,
Ditrimethylolpropane tri (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Polyhydroxyalkyl maleate,
Mention may be made of polyhydroxyalkyl fumarate. The hydroxyl group-containing (meth) acrylate compound can be used alone or in combination of two or more.

  What is necessary is just to determine suitably the compounding quantity of each said component at the time of manufacturing the urethane (meth) acrylate used by this invention according to the structure of the target urethane (meth) acrylate, but urethane (meth) acrylate is easy. From the viewpoint of being easily obtained, the total equivalent of isocyanate groups of the polyisocyanate compound is a hydroxyl group in the polyol compound, a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound, and an anionic group active hydrogen used as necessary. It is preferably determined to be 0.95 to 2.0 equivalents relative to the total equivalent of active hydrogen groups (hydroxyl group, amino group, etc.) in the group-containing compound, and particularly 1.0 to 1.5 equivalents. It is preferable to determine such that

In addition, the total equivalent of the isocyanate group of the polyisocyanate compound is 1 with respect to the total equivalent of the hydroxyl group in the polyol compound, the active hydrogen group in the anionic group active hydrogen group-containing compound, and the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound. In the case of exceeding 0.0, chain extension can be performed using a chain extender after water dispersion. As the chain extender, a known chain extender can be used. Specifically, such chain extenders include:
water;
ethylene glycol;
Short chain diols such as 1,4-butanediol;
Hydrazine;
Ethylenediamine;
Diethyltriamine;
Triethylenetetramine;
Tetraethylenepentamine;
Pentaethylenehexamine;
Propylenediamine;
Hexamethylenediamine;
Cyclohexylenediamine;
Piperazine;
2-methylpiperazine;
Phenylenediamine;
Tolylenediamine;
Xylenediamine;
α, α'-methylenebis (2-chloroaniline);
3,3′-dichloro-α, α′-biphenylamine;
m-xylenediamine;
Isophoronediamine;
Polyamines such as N-methyl-3,3′-diaminopropylamine;
Is mentioned. The chain extender can be used alone or in combination of two or more.

(Aqueous dispersion of urethane (meth) acrylate)
In the present invention, the urethane (meth) acrylate aqueous dispersion is obtained by dispersing the urethane (meth) acrylate in water, and water such as an emulsion, dispersion, colloidal dispersion of the urethane (meth) acrylate. It is a dispersion.

If necessary, a neutralizing agent may be added to the urethane (meth) acrylate aqueous dispersion. Examples of the neutralizing agent include the following.
Trialkylamines such as trimethylamine, triethylamine;
N, N-dialkylalkanolamines such as N, N-dimethylethanolamine;
Trialkanolamines such as triethanolamine;
Sodium hydroxide;
Potassium hydroxide;
Lithium hydroxide;
ammonia;
Trimethylammonium hydroxide;
The neutralizing agent can be used alone or in combination of two or more.

  Moreover, the average particle diameter of urethane (meth) acrylate in the aqueous dispersion of urethane (meth) acrylate is the viewpoint of preventing the viscosity of the aqueous dispersion from becoming high, the viewpoint of maintaining the smoothness of the resulting coating film, and water. From the viewpoint of maintaining good dispersion stability and storage stability, the thickness is preferably 30 to 250 nm, and particularly preferably 50 to 200 nm. The average particle diameter of urethane (meth) acrylate in the aqueous dispersion can be confirmed, for example, by a laser diffraction scattering method.

  In the aqueous dispersion of urethane (meth) acrylate, the amount of the solid content is not particularly limited, but is preferably 10 to 70% by weight in order to improve the coating property of the aqueous dispersion. More preferably, it is 50% by weight.

  In the aqueous dispersion of urethane (meth) acrylate, components other than urethane (meth) acrylate and water may be blended on condition that the concentration of the solid content is in the above range. For example, the aqueous dispersion of urethane (meth) acrylate may further contain an emulsifier for the purpose of improving the wettability of the primer composition with respect to the lens substrate. Examples of the emulsifier include nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers. The emulsifier can be used in any amount as necessary, but it is preferably added in an amount of 0.01 to 10% by weight based on the urethane (meth) acrylate.

  As an aqueous dispersion of urethane (meth) acrylate used in the present invention, Ucecoat manufactured by Daicel Ornex Co., Ltd. is suitable.

(Photopolymerization initiator)
The primer composition of the present invention contains a photopolymerization initiator. By applying and curing the primer composition of the present invention on a lens substrate, a primer coat layer having a high surface hardness can be obtained. Moreover, the photochromic laminated body which has this primer coat layer has a surface hardness higher than before, and can obtain the photochromic laminated body which is hard to be damaged.

Known photopolymerization initiators can be used. Specific examples of the photopolymerization initiator include the following.
Benzophenone;
Acetophenone compounds such as 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-morpholinopropan-1-one,
2-Benzyl-2dimethylamino-1- (4-morpholinophenyl) -butanone-1,1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one;
α-dicarbonyl compounds such as 1,2-diphenylethanedione,
Methylphenylglycoxylate;
Acylphosphine oxide compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide,
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-
Pentylphosphine oxide,
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
2,4,6-trimethylbenzoyldiphenylphosphinic acid methyl ester,
2,6-dichlorobenzoyldiphenylphosphine oxide,
2,6-dimethoxybenzoyldiphenylphosphine oxide;
1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)];
Oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester;
Oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester;

Among the photopolymerization initiators, it is preferable to use a liquid or water-soluble photopolymerization initiator from the viewpoint of easy mixing with an aqueous dispersion of urethane (meth) acrylate. As a liquid or water-soluble photopolymerization initiator, specifically,
2-hydroxy-2-methyl-1-phenylpropan-1-one (BA
SF DAROCUR1173);
A mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (IRGACURE500 manufactured by BASF);
Mixture of oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester (IRGACURE754 made by BASF);
An aqueous dispersion of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819DW manufactured by BASF);
A mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR4265 manufactured by BASF);
Etc.

  You may use a photoinitiator 1 type or in mixture of 2 or more types. In addition, a known polymerization accelerator such as a tertiary amine can be used in combination.

  The blending ratio of the photopolymerization initiator in the primer composition of the present invention is sufficient to ensure sufficient surface hardness of the primer coat layer and adhesion between the primer coat layer and the lens base material. In order to prevent poor appearance, it is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of urethane (meth) acrylate. It is most preferable that it is 1-0.5 mass part.

(Other additives)
In the primer composition of the present invention, a known polyurethane resin is preferably mixed from the viewpoint of improving adhesion.

  Such a polyurethane resin preferably has good water dispersibility. This is because the primer composition of the present invention using an aqueous dispersion medium can be uniformly dispersed.

  The polyurethane resin having water dispersibility is preferably obtained by reacting at least a polyol compound and a polyisocyanate compound as a raw material, and obtained by reacting at least a polyol compound, a polyisocyanate compound and an anionic group active hydrogen group-containing compound. More preferably.

  Among them, in addition to the above raw materials, as described in Japanese Patent No. 5016266 or Patent Document 3, a polyurethane resin obtained by reacting a hydroxyl group-containing acrylate compound and / or an alkoxysilyl group-containing polyamine compound is provided. Particularly preferred.

As the polyol compound, the anionic group active hydrogen group-containing compound, the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound, which are raw materials for the polyurethane resin, the same materials as those for the aforementioned urethane (meth) acrylate can be used. . Examples of the alkoxysilyl group-containing polyamine compound include an alkoxysilyl compound 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] ethylenediamine and the like can be mentioned.

  The polyurethane resin comprises an active hydrogen group-containing component (that is, a polyol compound, a hydroxyl group-containing (meth) acrylate compound, an anionic group active hydrogen group-containing compound, an alkoxysilyl group-containing polyamine compound) and a polyisocyanate component (that is, a polyisocyanate compound). Can be synthesized in the same manner as urethane (meth) acrylate by a one-shot method or a prepolymer method. As the synthesis method, a prepolymer method is more preferable. A chain extender can also be used.

  The polyurethane resin suitably used in the present invention is a high-elongation polyurethane resin that stretches well after irradiation with light. Specifically, the elongation (25 ° C.) when a single cured product is 100 to 1000%, particularly 200 It is a polyurethane resin contained in a range of ˜800%. By using such a polyurethane resin, the adhesion of the primer coat layer finally obtained is further improved.

  Among the high elongation polyurethane resins, from the viewpoint of the appearance and adhesion of the photochromic laminate of the present invention, a polyurethane resin having a single cured body having a tensile strength (25 ° C.) of 20 to 70 MPa, particularly 30 to 60 MPa. It is preferable to use it.

  The single cured product of polyurethane resin is produced in the same manner as the single cured product of urethane (meth) acrylate. The tensile strength and elongation of the single cured product of polyurethane resin are also measured in the same manner as the tensile strength and elongation of the single cured product of urethane (meth) acrylate.

  Among the polyurethane resins, those having a Vickers hardness of 1 to less than 8, particularly 2 to 6 are preferable from the viewpoint of improving the appearance and adhesion of the obtained photochromic laminate. The Vickers hardness of the single cured product of the polyurethane resin can be measured in the same manner as the Vickers hardness of the cured film of the primer composition described later.

  The polyurethane resin may have a (meth) acrylate group, but the proportion of the (meth) acrylate group in the polyurethane resin varies depending on whether the polyurethane resin is irradiated with light or not. The ratio is preferably such that (elongation rate, tensile strength, Vickers hardness) does not change. That is, the various characteristics of the single cured body of polyurethane resin show the above-mentioned range, and the various characteristics of the dried body prepared in the same manner as the single cured body except for not irradiating light also show the above-mentioned range. It is preferable to adjust the proportion of the (meth) acrylate group.

  When a polyurethane resin is used in the primer composition of the present invention, the blending ratio of the polyurethane resin prevents a decrease in surface hardness after the photochromic layer is laminated due to a decrease in the surface hardness of the resulting primer coat layer, and improves adhesion. In order to obtain the effect sufficiently, it is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and more preferably 30 to 100 parts by mass with respect to 100 parts by mass of urethane (meth) acrylate. Is most preferred.

  The polyurethane resin can be blended as it is, or an aqueous dispersion in which the polyurethane resin is dispersed in water can be blended. When the polyurethane resin is used in the state of an aqueous dispersion, the solid content in the aqueous dispersion is preferably 10 to 70% by weight from the viewpoint of improving the coating properties of the aqueous dispersion. More preferably, it is 50% by weight.

  In the primer composition of the present invention, the Vickers hardness of the cured film of the primer composition is preferably 8-30, more preferably 8.5-30, from the viewpoint of the surface hardness of the resulting photochromic laminate. 13 to 25 is particularly preferable.

  For measurement of Vickers hardness, a primer composition is applied on a lens substrate under predetermined conditions, then dried and photocured, and then a cured film obtained by heating is used. The Vickers hardness of the obtained cured film can be measured using a micro Vickers hardness meter PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A square pyramid diamond indenter is used as the indenter, and evaluation is performed under the conditions of a load of 10 gf and an indenter holding time of 20 seconds. The measurement result is shown as an average value of a total of three times after performing a total of four measurements and excluding the first value with a large measurement error. Details of the measurement of the Vickers hardness when the primer composition is cured will be described in the examples described later.

<Method for producing primer composition of the present invention>
The primer composition of the present invention is produced by adding the above polyurethane resin or the like, if necessary, in addition to the aqueous dispersion containing the urethane (meth) acrylate and the photopolymerization initiator.

  Although the manufacturing method of the primer composition of this invention is not specifically limited, It is preferable to stir and mix in a dark place at the temperature range of 5-40 degreeC, Preferably it is 10-30 degreeC. The order of addition of the raw materials used is not particularly limited.

  The primer composition of the present invention produced as described above is used to improve the appearance of the primer coat layer obtained, and to stabilize the adhesion between the lens substrate and the primer coat layer and between the primer coat layer and the photochromic coat layer. From the viewpoint, it is preferable to use after filtering for the purpose of removing foreign matters before applying to the lens substrate.

<Photochromic curable composition>
The photochromic curable composition is one in which the primer composition of the present invention is applied onto a lens substrate and further applied thereon. The photochromic curable composition comprises a photochromic compound, a (meth) acryl monomer, and a polymerization initiator. As a photochromic curable composition, the photochromic curable composition which can be used by the conventional coating method can be used without limitation. However, from the viewpoint of photochromic properties, optical properties, solvent resistance of the photochromic layer, surface hardness and adhesion,
WO03 / 011967 (Patent Document 1),
WO 04/050775,
WO05 / 014717,
WO2011-12595,
WO2013 / 008825,
JP2013-072000A,
Japanese Patent Application No. 2013-155220,
It is preferable to use a photochromic curable composition described in Japanese Patent Application No. 2013-155590.

As the (meth) acrylic monomer used in the photochromic curable composition, a known (meth) acrylic monomer can be used without particular limitation. Specifically, the following can be mentioned.
Trimethylolpropane trimethacrylate;
Trimethylolpropane triacrylate;
Tetramethylol methane trimethacrylate;
Tetramethylol methane triacrylate;
Tetramethylol methane tetramethacrylate;
Tetramethylol methane tetraacrylate;
Trimethylolpropane triethylene glycol trimethacrylate;
Trimethylolpropane triethylene glycol triacrylate;
Ditrimethylolpropane tetramethacrylate;
Ditrimethylolpropane tetraacrylate;
Dipentaerythritol hexaacrylate;
Bisphenol A dimethacrylate;
2,2-bis (4-methacryloyloxyethoxyphenyl) propane;
2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane (average molecular weight 628);
2,2-bis (4-methacryloyloxypolyethylene glycol phenyl) propane (average molecular weight 804);
2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane (average molecular weight 776);
Methoxypolyethylene glycol methacrylate (average molecular weight 468)
;
Diethylene glycol dimethacrylate;
Triethylene glycol dimethacrylate;
Tetraethylene glycol dimethacrylate;
Pentaethylene glycol dimethacrylate;
Pentapropylene glycol dimethacrylate;
Diethylene glycol diacrylate;
Triethylene glycol diacrylate;
Tetraethylene glycol diacrylate;
Pentaethylene glycol diacrylate;
Tripropylene glycol diacrylate;
Tetrapropylene glycol diacrylate;
Pentapropylene glycol diacrylate;
Polyethylene glycol dimethacrylate (average molecular weight 330);
Polyethylene glycol dimethacrylate (average molecular weight 536);
Polytetramethylene glycol dimethacrylate (average molecular weight 736)
;
Tripropylene glycol dimethacrylate;
Tetrapropylene glycol dimethacrylate;
Polypropylene glycol dimethacrylate (average molecular weight 536);
Polyethylene glycol diacrylate (average molecular weight 258);
Polyethylene glycol diacrylate (average molecular weight 308);
Polyethylene glycol diacrylate (average molecular weight 508);
Polyethylene glycol diacrylate (average molecular weight 708);
Polycarbonate polyol diacrylate monomer;
Polycarbonate di (meth) acrylate, which is a reaction product of polycarbonate diol and (meth) acrylic acid;
Multifunctional urethane (meth) acrylates such as urethane oligomer tetraacrylate;
Urethane oligomer hexamethacrylate;
Urethane oligomer hexaacrylate;
Polyfunctional polyester (meth) acrylates such as polyester oligomer hexaacrylate;
A silsesquioxane monomer having a (meth) acrylic group and having various structures such as cage, ladder, and random;
2-isocyanatoethyl methacrylate;
γ-methacryloxypropyltrimethoxysilane;
γ-methacryloxypropylmethyldimethoxysilane;
Glycidyl methacrylate;

  Among these, photochromic curing described in Japanese Patent Application No. 2013-155590 or Japanese Patent Application No. 2013-155220 is required to obtain a photochromic coat layer having high surface hardness without causing appearance defects such as cracks. It is preferable to employ a sex composition.

That is,
1) Polycarbonate di (meth) acrylate,
2) Multifunctional (meth) acrylate, for example
Trimethylolpropane trimethacrylate,
Ditrimethylolpropane tetramethacrylate, and 3) di (meth) acrylates having a bisphenol A skeleton, such as
2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane (average chain length of ethylene glycol chain: 10, average molecular weight: 804),
A photochromic curable composition comprising, or
4) Multifunctional (meth) acrylate, for example
Trimethylolpropane trimethacrylate,
Ditrimethylolpropane tetramethacrylate,
5) Di (meth) acrylate having a bisphenol A skeleton, for example
2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane (average chain length of ethylene glycol chain: 10, average molecular weight: 804), and 6) polyalkylene glycol di (meth) acrylate having a molecular weight of 600 to 2000 And a photochromic curable composition comprising at least one long-chain (meth) acrylic monomer selected from the group consisting of urethane di (meth) acrylates having a molecular weight of 600 to 2,000.
Furthermore, 1) is 10 to 30% by mass, 2) is 35 to 50% by mass, and 3) is 10 to 65% by mass when the total of (meth) acrylate monomers of 1) to 3) is 100% by mass. % Of the photochromic curable composition or the total of the (meth) acrylate monomers of 4) to 6) is 100% by mass, 4) is 35 to 70% by mass, and 5) is 10 to 40% by mass. 6) is more preferably a photochromic curable composition of 10 to 40% by mass.

Moreover, the compound which shows a photochromic effect | action can be employ | adopted for a photochromic curable composition as a photochromic compound. As compounds showing a photochromic action, for example, photochromic compounds such as fulgide compounds, chromene compounds and spirooxazine compounds are well known. 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 include JP-A-2-28154,
JP-A-62-2288830,
WO94 / 22850,
Examples thereof include compounds described in WO96 / 14596.

Further, compounds newly found by the present inventors as compounds having excellent photochromic properties, such as JP-A-2001-114775,
JP 2001-031670,
JP 2001-011067,
JP2001-011066,
JP 2000-347346,
JP 2000-344762,
JP 2000-344761,
JP 2000-327676 A,
JP 2000-327675,
JP 2000-256347,
JP 2000-229976,
JP 2000-229975,
JP 2000-229974,
JP 2000-229773,
JP 2000-229972,
JP 2000-219687,
JP 2000-219686,
JP 2000-219865,
JP-A-11-322739,
JP-A-11-286484,
JP-A-11-279171,
JP-A-10-298176,
JP 09-218301,
JP 09-124645,
JP 08-295690,
JP 08-176139 A,
JP 08-157467,
US Pat. No. 5,645,767,
US Pat. No. 5,658,501,
US Pat. No. 5,961,892;
US Pat. No. 6,296,785,
Japanese Patent No. 4424981,
Japanese Patent No. 4424962,
WO2009 / 136668,
WO2008 / 023828,
Japanese Patent No. 4369754,
Japanese Patent No. 4301621,
Japanese Patent No. 4256985,
WO2007 / 086532,
JP 2009-120536 A,
JP 2009-67754 A,
JP2009-67680,
JP2009-57300,
Japanese Patent No. 4195615,
Japanese Patent No. 41588881,
Japanese Patent No. 4157245,
Japanese Patent No. 4157239,
Japanese Patent No. 4157227,
Japanese Patent No. 4118458,
JP 2008-74832 A,
Japanese Patent No. 3982770,
Japanese Patent No. 3801386,
WO 2005/028465,
WO2003 / 042203,
JP 2005-289812 A,
JP 2005-289870,
JP 2005-112772,
Japanese Patent No. 3522189,
WO2002 / 090342,
Japanese Patent No. 3471107,
JP2003-277181,
WO2001 / 060811,
WO2000 / 071544,
WO 2005/028465,
WO2011 / 16582,
WO2011 / 034202,
WO2012 / 121414,
The compounds disclosed in WO2013 / 042800 and the like can be suitably used.

  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 coloration, durability, and fading speed. It is more preferable to use more than one type. Among these chromene compounds, those having a molecular weight of 540 or more are preferable because they are particularly excellent in color density and fading speed.

  Although the usage-amount in particular of a photochromic compound is not restrict | limited, It is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of (meth) acryl monomers, and it is more preferable that it is 1-10 mass parts.

  Moreover, the usage-amount of a polymerization initiator is although it does not restrict | limit in particular, Preferably it is 0.001-10 mass parts with respect to 100 mass parts of (meth) acryl monomers, More preferably, it is the range of 0.01-5 mass parts. is there.

  When a photochromic curable composition is applied by a spin coating method described later, the viscosity (25 ° C.) of the photochromic curable composition is 50 to 1 because it is easy to obtain a photochromic coating layer having a uniform thickness. It is preferable to adjust to a range of 1,000,000 cP, particularly 100 to 500 cP.

  In addition to the aforementioned components, the photochromic curable composition includes, for example, a surfactant, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, Various stabilizers such as pigments and fragrances and additives can be mixed as required.

  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. Can be used without By adding a surfactant, it is possible to improve the wettability with respect to the primer and to prevent appearance defects without adversely affecting the photochromic properties and adhesion of the resulting photochromic coating layer.

Examples of silicone surfactants and fluorosurfactants that can be suitably used in the present invention include:
Toray Dow Corning L-7001, L-7002, L-7
604, FZ-2123;
MegaFuck F-470, MegaFack F-1405, MegaFuck F-479 manufactured by Dainippon Ink & Chemicals, Inc .;
Florad FC-430 manufactured by Sumitomo 3M;
Etc. Two or more surfactants may be mixed and used.

  Although the usage-amount of surfactant is not restrict | limited in particular, It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of said (meth) acryl monomers.

From the viewpoint of further improving the durability of the photochromic compound, it is preferable to mix and use an ultraviolet stabilizer in the photochromic curable composition. As a UV stabilizer,
Hindered amine light stabilizers,
Hindered phenol oxidation prevention,
A sulfur-based antioxidant or the like can be suitably used. As a suitable example,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, ADK STAB LA-52, LA-57, LA-6 manufactured by Asahi Denka Kogyo Co., Ltd.
2, LA-63, LA-67, LA-77, LA-82, LA-87,
2,6-di-tert-butyl-4-methyl-phenol,
2,6-ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], IRGANOX 1010, 1035, 1075, 1 manufactured by Ciba Specialty Chemicals
098, 1135, 1141, 1222, 1330, 1425, 1520
259, 3114, 3790, 5057, 565
Etc. Although the usage-amount of a ultraviolet stabilizer is not restrict | limited in particular, It is preferable that the compounding quantity of each ultraviolet stabilizer is 0.1-10 mass parts with respect to 100 mass parts of the above-mentioned (meth) acrylic monomers. Two or more kinds of ultraviolet stabilizers may be mixed and used.

<Lens substrate>
The lens base material used in the present invention is not particularly limited as long as it is a light-transmitting base material, and includes known lens base materials such as glass lenses, plastic lenses, house and automobile window glass, plastics A lens is particularly suitable.

  Plastic lenses include thermoplastic resin lenses such as (meth) acrylic resins and polycarbonate resins; crosslinkable resins such as polyfunctional (meth) acrylic resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins A known lens used as a plastic lens can be used.

  The primer composition of the present invention has excellent adhesion to such plastic lenses. In addition, when the primer composition of the present invention is laminated on a plastic lens and a photochromic curable composition is further laminated thereon, not only excellent adhesion but also surface hardness is excellent.

  Since the primer composition of the present invention hardly dissolves the thermoplastic resin as compared with the solvent-based primer, it can be suitably used for a plastic lens made of a thermoplastic resin such as a polycarbonate resin. As the lens substrate, a lens substrate having a silicone or acrylic hard coat layer formed thereon may be used. A lens substrate that has been subjected to etching treatment such as alkali treatment, acid treatment, polishing treatment, plasma etching, and corona discharge treatment can also be used.

  The shape of the plastic lens substrate used in the present invention is not particularly limited, and can be a known shape. The plastic lens substrate has various shapes depending on the visual acuity of the user, the shape of the glass mold at the time of molding the plastic lens substrate, or productivity. For example, a myopic lens is a minus lens having a thin center and a thickness at the edge, and a far vision lens is a plus lens having a thick center and a thin edge. Furthermore, the shape of the plastic lens substrate depends on a mold or the like when the plastic lens substrate is molded, and the vicinity of the outer edge of the upper surface of the plastic lens substrate may be inclined toward the lower surface toward the outer periphery. (Hereinafter, this shape of the edge portion may be referred to as “bevel shape”).

  The primer composition of the present invention can be applied to any of the plastic lens substrates described above. According to the study by the present inventors, in the case of a primer composition layer and a photochromic coating layer formed on a negative lens, a positive lens, and a lens having a beveled shape, particularly in the conventional primer composition, cracks occur. It tends to occur. On the other hand, the crack which arises in a photochromic laminated body can be suppressed by using the primer composition of this invention. Among them, although depending on the type of the base material, cracks are likely to occur. For example, a positive lens of +5.00 or higher and a negative lens of −3.00 or lower using an allyl resin composed of allyl diglycol carbonate. Even if the photochromic laminate is formed by using the above, it is possible to suppress appearance defects such as cracks (hereinafter, the positive lens and the negative lens may be collectively referred to as “intensity plastic lens”).

  The thickness of this strength plastic lens is 5 to 30 mm at the center and 1 to 5 mm at the edge in the case of a plus lens, and 1 to 15 mm at the center and 5 in the edge in the case of a minus lens. ~ 25 mm. Further, even when a photochromic laminate is formed using a plastic lens having an oblique shape, appearance defects such as cracks can be suppressed. An example of a plastic lens having a beveled shape is a beveled plastic lens 1 as shown in FIG. 1. The beveled shape portion 2 has a width of 0.1 to 2.0 mm and an angle 3 with respect to the edge surface of 30. ~ 60 °. The thickness is not particularly limited, but is 1 to 30 mm.

<Method for producing photochromic laminate>
A photochromic laminate can be obtained by applying the above-described primer composition and photochromic curable composition of the present invention on a lens substrate and irradiating with light (hereinafter referred to as the photochromic laminate of the present invention). There is.)

  The method for applying the primer composition and the photochromic curable composition of the present invention is not particularly limited, and any known coating method can be applied without any limitation. Specifically, the method of apply | coating this composition by methods, such as spin coating, spray coating, dip coating, dip-spin coating, is illustrated. Among these coating methods, it is preferable to employ spin coating because the film thickness can be easily controlled and a coating film having a good appearance can be obtained.

  When applying a primer composition and a photochromic curable composition by a coating method, for example, after applying the primer composition on a lens substrate by a spin coating method and placing it in an inert gas such as nitrogen, UV is applied. The photochromic laminate of the present invention can be obtained by irradiating, subsequently applying a photochromic curable composition and placing it in an inert gas such as nitrogen, followed by UV irradiation.

  However, in the present invention, a primer composition is applied onto a lens substrate by a spin coating method or the like to form a first precursor provided with a primer precursor layer before curing, and then on the primer precursor layer A photochromic curable composition is applied to a photochromic precursor layer before curing to form a second precursor, and then the second precursor is placed in an inert gas such as nitrogen before UV irradiation. A method of curing the primer precursor layer and the photochromic precursor layer is preferable. This is because the procedure can be simplified by completing the curing step in one step. According to the coating composition of the present invention, even if UV irradiation performed after applying the primer composition and before applying the photochromic curable composition is omitted, the adhesiveness, hardness, and appearance equivalent to those when not omitted are the same. The photochromic laminated body which has can be obtained. In particular, from the viewpoint of adhesion between the primer coat layer and the photochromic coat layer, after the primer composition is applied on the lens substrate, it is dried at 10 to 40 ° C. for 5 to 30 minutes, and then on the obtained primer coat layer. A method of applying a photochromic curable composition, placing it in an inert gas such as nitrogen, and simultaneously photocuring the primer coat layer and the photochromic coat layer by UV irradiation is preferable.

  When the primer composition is applied by spin coating, the viscosity (25 ° C.) of the primer composition is in the range of 5 to 200 cP, particularly 10 to 100 cP, because it is easy to obtain a primer coat layer having a uniform thickness. It is preferable to adjust. The viscosity can be adjusted by changing the type and amount of the dispersion medium. Moreover, when using a urethane resin etc. for the primer composition of this invention, it is also possible to adjust a viscosity with these mixing ratios.

  The thickness of the primer precursor layer is preferably 0.1 to 20 μm in a state after drying from the viewpoint of good optical properties and adhesion between the lens substrate and the primer coat layer and between the primer coat layer and the photochromic coat layer. , More preferably 1 to 10 μm, and particularly preferably 1 to 7.5 μm.

  The thickness of the photochromic coat layer is preferably 10 to 100 μm, and particularly preferably 20 to 50 μm, from the viewpoints of good optical properties, photochromic properties, and adhesion between the primer coat layer and the photochromic coat layer.

When photopolymerizing the primer composition and the photochromic curable composition of the present invention, UV intensity among the polymerization conditions affects the properties of the resulting photochromic laminate. This illuminance condition is affected by the type and amount of the photopolymerization initiator and the type of the (meth) acrylic monomer, and thus cannot be generally limited, but generally UV light of 50 to 500 mW / cm ² at a wavelength of 405 nm. Is preferably selected so that the light is irradiated for 0.5 to 5 minutes.

  In the photochromic laminate of the present invention, after the primer coat layer and the photochromic coat layer are laminated by UV curing, in order to improve the adhesion between the lens substrate and the primer coat layer and between the primer coat layer and the photochromic coat layer, 60 to It is preferable to heat-process in the temperature range of 120 degreeC for about 0.5 to 6 hours. This is because a photochromic laminate having good adhesion at all interfaces can be obtained.

<Characteristics and post-treatment of photochromic laminate>
The photochromic laminate produced by using the primer composition and the photochromic curable composition of the present invention, in which the lens base material, the primer coat layer, and the photochromic coat layer are in this order, has excellent surface hardness and poor appearance such as cracks. It is a photochromic plastic lens that does not occur, has good adhesion, and has excellent photochromic properties.

  In the photochromic laminate of the present invention, it is preferable that the Vickers hardness of the photochromic coat layer on the primer coat layer is greater than 8 and 12 or less from the viewpoint of preventing scratches.

The photochromic laminate of the present invention can be subjected to the following treatment depending on its application. That is, dyeing using a dye such as a disperse dye; a silane coupling agent, a hard coating agent mainly composed of a sol such as silicon, zirconium, antimony, aluminum, tin, and tungsten; and SiO ₂ , TiO ₂ , ZrO _2, etc. It is also possible to carry out processing and secondary treatment such as antireflection treatment by deposition of metal oxide thin film or coating of organic polymer thin film; antistatic treatment;

  Next, although this invention is demonstrated in detail using an experiment example, this invention is not limited to this experiment example.

<Primer composition>
Material A: Aqueous dispersion of urethane (meth) acrylate A1: A carboxyl group-containing aqueous dispersion urethane acrylate dispersion
Ucecoat 7655 manufactured by Daicel Ornex
Average particle size: 150 nm
Solid content concentration: 35%
Tensile strength: 25 MPa
Elongation rate: 1.5%
A2: carboxyl group-containing water-dispersed urethane acrylate dispersion
Ucecoat 7849 manufactured by Daicel Ornex
Average particle size: 150 nm
Solid content concentration: 35%
Tensile strength: 15 MPa
Elongation rate: 1.3%
A3: Water-dispersed urethane acrylate dispersion containing carboxyl group
Ucecoat 7684 manufactured by Daicel Ornex
Average particle size: 150 nm
Solid content concentration: 40%
Tensile strength: 24 MPa
Elongation rate: 18%

Material B: Photopolymerization initiator B1; Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide
Irgacure 819 manufactured by BASF
B2; 2-hydroxy-2-methyl-1-phenylpropan-1-one
DAROCUR1173 manufactured by BASF
B3: Mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone
IRGACURE500 manufactured by BASF
B4; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1-
ON mixture
BASF DAROCUR4265

Material C: Water dispersion of polyurethane resin C1; Water dispersible urethane resin dispersion
Daiichi Kogyo Seiyaku Co., Ltd. Superflex 420
Solid content concentration: 32%
Tensile strength: 30 MPa
Elongation rate: 280%
C2: Water dispersible urethane resin dispersion
NJ-321A manufactured by Tokuyama Corporation
Solid content concentration: 35%
Tensile strength: 50 MPa
Elongation rate: 400%

(Measurement of tensile strength and elongation of single cured product)
The tensile strength and elongation of the urethane (meth) acrylate and polyurethane resin are both the tensile strength and elongation of the single cured product. The tensile strength and elongation of the single cured product were measured by the following methods. First, 2-hydroxy-2-methyl-1-phenylpropan-1-one (photopolymerization initiator) is added to an aqueous dispersion containing urethane (meth) acrylate or urethane resin (the solid concentration is as described above). The material B2) was added in an amount of 0.3 parts by mass with respect to 100 parts by mass of urethane (meth) acrylate or urethane resin. The mixture was placed in a petri dish or the like so that the film thickness after drying was 500 μm, dried at room temperature in the dark (20-25 ° C.) for 24 hours, then in the dark at 80 ° C. for 6 hours, and further in the dark at 120 ° C. And dried for 20 minutes. Then, using a F3000SQ (manufactured by Fusion UV Systems) equipped with a D bulb, which was adjusted so that the output at 405 nm on the sample surface was 200 mW / cm ² in a nitrogen gas atmosphere, light was irradiated for 90 seconds, A film was prepared. The polymerization rate of this urethane (meth) acrylate or urethane resin was 95% or more.

Next, this film was cut into a size of 15 mm in width and 200 mm in length, and then a mark was written in the center at an interval of 50 mm to prepare a measurement sample. The sample was attached to a tensile tester, and the elongation rate was measured by pulling the sample at a speed of 200 mm / min until the sample broke at an interval of 100 mm in a 25 ° C. environment. The stress when the sample broke was regarded as the tensile strength, and the elongation was obtained from the following formula.
Elongation rate (%) = {(L−L ₀ ) / L ₀ } × 100
Where
L represents the distance between the gauge points at the time of breakage,
L ₀ represents the distance between the gauge points before the test.

(Preparation of primer composition (P1))
The following materials:
Aqueous dispersion of urethane acrylate (Material A1)
100 parts by mass and 0.1 part by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one (material B2) were mixed thoroughly and filtered through a filter paper made of cellulose acetate (eyes: 0.8 μm). As a result, a primer composition (P1) was obtained.

The Vickers (Hv) hardness of the primer coat layer obtained from this primer composition (P1) was 20.1.
The Vickers hardness of the primer coat layer was measured by the following method.

(Measurement of Vickers hardness after curing of primer composition)
The sample used for Vickers hardness measurement was produced by the following method regardless of the presence or absence of a photopolymerization initiator.
An allyl plastic lens having a center thickness of 2 mm and a refractive index of 1.50 was prepared as an optical substrate. This 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), the surface of the plastic lens was coated with the primer composition at a rotation speed of 70 rpm for 15 seconds and then at 700 rpm for 5 to 20 seconds. Then, after drying for 10 minutes at room temperature (20 to 25 ° C.), F3000SQ (Fusion) equipped with a D-valve adjusted so that the output at 405 nm on the optical substrate surface is 200 mW / cm ² in a nitrogen gas atmosphere. UV coating was used for 90 seconds to cure the coating film. Thereafter, the sample was further heated at 100 ° C. for 1 hour to obtain a sample for measuring Vickers hardness. The obtained primer layer had a thickness of 6.5 to 7.5 μm.

  The Vickers hardness was measured using a micro Vickers hardness meter PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A square pyramid diamond indenter was used as the indenter, and evaluation was performed under the conditions of a load of 10 gf and an indenter holding time of 20 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.

(Preparation of primer compositions (P2) to (P18))
Primer compositions (P2) to (P18) were prepared in the same manner as the primer composition (P1) except that the materials shown in Table 1 were used. In addition, when using a urethane resin, when mixing a urethane (meth) acrylate aqueous dispersion and a photoinitiator, the urethane resin was also mixed together. The composition is shown in Table 1. Primer compositions (P1) to (P2) and (P4) to (P15) correspond to the compositions of the examples. The primer compositions (P3) and (P16) to (P18) correspond to the composition of the comparative example.

<Photochromic curable composition>
(Material D: (Meth) acrylic monomer)
D1; trimethylolpropane trimethacrylate (TMPT)
D2: Ditrimethylolpropane tetramethacrylate (D-TMP)
D3; 2,2-bis [4- (methacryloxy polyethoxy) phenyl]
Propane (average chain length of ethylene glycol chain: 10, average molecular weight:
804) (BPE500)
D4; polyethylene glycol dimethacrylate (average chain length of ethylene glycol chain: 14, average molecular weight: 736) (14G)
D5: Glycidyl methacrylate (GMA)
D6; γ-methacryloxypropyltrimethoxysilane (MA1)
D7: Silsesquioxane monomer (MA2)
D8: Polycarbonate polyol diacrylate monomer (MA3)

(D7; Synthesis of Silsesquioxane Monomer (MA2))
The following materials:
3-Trimethoxysilylpropyl methacrylate
248 g (1.0 mol),
248 ml of ethanol and 54 g (3.0 mol) of water
As a catalyst, 0.20 g (0.005 mol) of sodium hydroxide was added and reacted at 30 ° C. for 3 hours. After confirming the disappearance of the raw materials, neutralize with dilute hydrochloric acid,
174 ml of toluene,
174 ml of heptane and 174 g of water
Was 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 (MA2). In addition, it confirmed that the raw material was consumed completely from 1H-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 (MA2) was measured by a gel permeation chromatography method (GPC method), the weight average molecular weight was 4,800.

(D8: Synthesis of polycarbonate polyol diacrylate monomer (MA3))
The following materials:
600 g (0.6 mol) of polycarbonate diol (number average molecular weight 1000) obtained by phosgenation of hexamethylene glycol (50 mol%) and pentamethylene glycol (50 mol%),
108 g (2.5 mol) of acrylic acid,
300g of benzene,
11 g (0.06 mol) of p-toluenesulfonic acid,
0.3 g of p-methoxyphenol (700 ppm with respect to polycarbonate dial)
And reacted under reflux. Water produced by the reaction was azeotroped with the solvent, and only water was removed from the system with a separator, and the solvent was returned to the reaction vessel. The conversion rate of the reaction was confirmed by the amount of water removed from the reaction system, and it was confirmed that the amount of water was removed from the 21.6 g reaction system, and the reaction was stopped. Thereafter, the product was dissolved in 600 g of benzene, neutralized with 5% sodium hydrogen carbonate, and then washed 5 times with 300 g of 20% saline to obtain 430 g of MA3 which is a transparent liquid.

(Material PC: Photochromic compound)

(Material E: UV stabilizer)
E1; Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight 508) (HALS)
E2; ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245 manufactured by Ciba Specialty Chemicals) (HP)

(Preparation of photochromic curable composition (F1))
The following materials:
TMPT (material D1) 20 parts by mass,
D-TMP (material D2) 30 parts by mass,
BPE500 (material D3) 30 parts by mass,
14G (Material D4) 17 parts by mass,
MA1 (material D6) 3 parts by mass,
1.2 parts by mass of material PC1
Material PC2 0.4 part by mass,
1.2 parts by mass of material PC3,
HALS (material E1) 3 parts by mass,
HP (material E2) 3 parts by mass,
Phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (material B1) 0.3 part by mass and L7001 (leveling agent) (L) manufactured by Toray Dow Corning Co., Ltd.
0.1 part by mass was added and mixed with stirring at 70 ° C. for 15 minutes to obtain a photochromic curable composition (F1). Each blending amount is shown in Table 2.

(Preparation of photochromic curable compositions (F2) to (F3))
As shown in Table 2, the photochromic curable compositions (F2) to (F3) were prepared in the same manner as the photochromic curable composition (F1) except that the composition of the (meth) acrylic monomer was changed. . The composition is shown in Table 2.

<Experimental example 1>
The lens base material is an allyl plastic lens (PL1) having a center thickness of 2 mm and a refractive index of 1.50, or an allyl plastic lens having a power of +8.00, a center thickness of 15 mm, an edge thickness of 1.5 mm, and a refractive index of 1.50. (PL2) was prepared. In addition, PL1 and PL2 performed alkali etching for 5 minutes at 50 degreeC beforehand using 10% sodium hydroxide aqueous solution, and were fully wash | cleaned with distilled water after that. PL1 was used for evaluations 1) to 5), and PL2 was used only for evaluation 5).

  Using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens is spin-coated with the primer composition (P1) of the present invention and dried at room temperature (20 to 25 ° C.) for 10 minutes. A lens substrate having a precursor layer was obtained. The obtained primer precursor layer had a thickness of 6.5 to 7.5 μm.

Thereafter, about 2 g of the photochromic curable composition (F1) was spin-coated on the primer precursor layer. The lens base material whose surface was coated with the photochromic curable composition coating film was equipped with a D-valve adjusted so that the output at 405 nm of the lens base material surface was 200 mW / cm ² in a nitrogen gas atmosphere. Using F3000SQ (manufactured by Fusion UV Systems), light was irradiated for 90 seconds to cure the coating film. Then, the photochromic laminated body was obtained by performing the heat processing for 1 hour with a 100 degreeC thermostat further. The film thickness of the obtained photochromic coat layer was 40 ± 1 μm.

The evaluation shown to following 1) -5) was implemented about the obtained photochromic laminated body. As a result, the photochromic laminate exhibited the following characteristics.
1) Vickers hardness 12.0
2-1) Maximum absorption wavelength: 588 nm
2-2) Color density 1.0
2-3) Fading speed 58 seconds 3) Initial adhesion 100
4) Adhesion after boiling 2 hours 5) Appearance evaluation (when the lens is PL1) 1
5) Appearance evaluation (when the lens is PL2) 1

[Sample evaluation method]
1) Vickers hardness Vickers hardness was measured using a micro Vickers hardness meter PMT-X7A (manufactured by Matsuzawa Co., Ltd.). A square pyramid diamond indenter was used as the indenter, and 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.

2) Photochromic properties (maximum absorption wavelength, color density, fading density)
The obtained photochromic laminate (photochromic layer thickness 40 ± 1 μm) was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 (manufactured by Hamamatsu Photonics) was passed through an aeromass filter (manufactured by Corning). The photochromic properties were measured by irradiating for 120 seconds at 20 ° C. ± 1 ° C. with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the polymer surface. Each photochromic characteristic was evaluated by the following method.
2-1) Maximum absorption wavelength (λmax)
The maximum absorption wavelength after color development was determined using a spectrophotometer (instant multichannel photo detector MCPD1000, manufactured by Otsuka Electronics Co., Ltd.). The maximum absorption wavelength is an index related to the color tone at the time of color development.
2-2) Color density {ε (120) −ε (0)}
The difference between the absorbance {ε (120)} after light irradiation for 120 seconds and the absorbance {ε (0)} before light irradiation at the maximum absorption wavelength was determined as the color density. The higher this value, the better the photochromic properties.
2-3) Fading speed [t1 / 2 (sec.)]:
After light irradiation for 120 seconds, when the light irradiation is stopped, the time required for the absorbance at the maximum wavelength of the sample to decrease to half of {ε (120) −ε (0)} is measured, and fading occurs. It was speed. The shorter this time, the better the photochromic properties.

3) Initial adhesion The adhesion was measured by a cross-cut tape test in accordance with JISD-0202. That is, using a cutter knife, cuts having a spacing of about 1 mm were made on the surface of the photochromic layer of the obtained photochromic laminate, and 100 squares were formed. A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., cello tape (registered trademark)) was strongly pasted thereon. Next, the cellophane adhesive tape was pulled at a stretch from the surface in the direction of 90 ° and peeled, and then the number of cells in which the photochromic layer remained was counted.

4) Adhesiveness after boiling The photochromic laminate as a test piece was immersed in boiling distilled water every hour. Thereafter, the photochromic laminate was taken out, water droplets were wiped off, and left at room temperature for 1 hour. About the obtained photochromic laminated body, 3) Adhesiveness was measured like the initial stage adhesiveness test. A photochromic laminate in which 95 or more of 100 squares remain is considered to maintain adhesiveness, and such a photochromic laminate is in contact with the photochromic laminate until the adhesiveness is not maintained (that is, the remaining mass is 94 squares). Boiled (until below). The boiling time was up to 5 hours in total.

5) Appearance evaluation The number of two types of photochromic laminates obtained using the lens substrates PL1 and PL2 were visually observed, and the number of appearance defects such as cracks in the photopolymerization step or the subsequent heating step. I counted. The appearance was evaluated based on the number of appearance defects.

<Experimental Examples 2-17 and 19-21>
A photochromic laminate was prepared and evaluated in the same manner as in Experimental Example 1 except that the primer composition and the photochromic curable composition shown in Table 3 were used. The results are shown in Table 3. Since the initial adhesion of the photochromic laminate of Experimental Example 19 was less than 95 masses, the adhesion after boiling could not be measured.

<Experimental example 18>
As the lens substrate, the same lenses (PL1, PL2) used in Experimental Example 1 were used. PL1 was used in evaluations 1) to 5), and PL2 was used only in evaluation 5).

The photochromic laminate was prepared in the same manner as in Experimental Example 1, except that after the primer composition (P8) was applied to the surface of the lens substrate, photocuring was performed before the photochromic curable composition (F1) was applied. Obtained. That is, using a spin coater (1H-DX2, manufactured by MIKASA), the surface of the plastic lens is spin-coated with the primer composition (P8) of the present invention and dried at room temperature (20 to 25 ° C.) for 10 minutes. It was. Next, in a nitrogen gas atmosphere, light irradiation was performed for 90 seconds using an F3000SQ (manufactured by Fusion UV Systems) equipped with a D bulb adjusted so that the output at 405 nm on the surface of the lens substrate was 200 mW / cm ^2. The coating film was cured to obtain a lens substrate having a primer coat layer. The resulting primer coat layer had a thickness of 6.5 to 7.5 μm.

Thereafter, about 2 g of the photochromic curable composition (F1) was spin-coated on the surface of the lens substrate having the primer coat layer. The lens base material whose surface was coated with the photochromic curable composition coating film was equipped with a D-valve adjusted so that the output at 405 nm of the lens base material surface was 200 mW / cm ² in a nitrogen gas atmosphere. Using F3000SQ (manufactured by Fusion UV Systems), light was irradiated for 90 seconds to cure the coating film. Then, the photochromic laminated body was obtained by performing the heat processing for 1 hour with a 100 degreeC thermostat further. The film thickness of the obtained photochromic coat layer was 40 ± 1 μm. The obtained photochromic laminate was evaluated in the same manner as in Experimental Example 1. The results are shown in Table 3.

  As is clear from Experimental Examples 1, 2, and 4-18, the photochromic laminate obtained using the primer composition of the present invention is not only excellent in photochromic properties but also excellent in surface hardness, adhesion, and appearance. . However, in Experimental Example 3 and Experimental Example 19-21, at least one of the physical properties of adhesion, appearance, and surface hardness was insufficient, and none of the physical properties was satisfied at the same time.

DESCRIPTION OF SYMBOLS 1 Plastic lens base material which has bevel shape 2 Bevel shape part 3 Angle of bevel shape

Claims (7)

A lens substrate, a primer coat layer and a photochromic coat layer are laminated in this order,
It said primer coating layer is made of cured product of the optical Science article photocurable primer composition,
The photocurable primer composition for optical articles comprises an aqueous dispersion containing urethane (meth) acrylate and a photopolymerization initiator, and the elongation percentage at 25 ° C. of the urethane (meth) acrylate single-cured product is 0.1 to 0.1. A photochromic laminate characterized by 10% . 2. The photochromic laminate according to claim 1, wherein the urethane (meth) acrylate single cured body has a tensile strength (25 ° C.) of 10 to 50 MPa. The photochromic laminate according to claim 1 or 2, wherein the cured product of the photocurable primer composition for optical articles has a Vickers hardness of 8 to 30. The photochromic laminate according to any one of claims 1 to 3, wherein the photochromic coat layer on the primer coat layer has a Vickers hardness of more than 8 and 12 or less . Step of applying a light Science article photocurable primer composition onto a lens substrate to form a first precursor primer precursor layer before curing is provided,
A step of applying a photochromic curable composition containing a photopolymerization initiator on the primer precursor layer, providing a photochromic precursor layer before curing to form a second precursor, and the second precursor is irradiated with light, it viewed including the step of curing the primer precursor layer and the photochromic precursor layer,
The photocurable primer composition for optical articles is a photocurable primer composition for optical articles comprising an aqueous dispersion containing urethane (meth) acrylate and a photopolymerization initiator, wherein the urethane (meth) acrylate is cured alone. The manufacturing method of the photochromic laminated body characterized by the elongation rate in 25 degreeC of a body being 0.1 to 10% . The manufacturing method of the photochromic laminated body of Claim 5 whose tensile strength (25 degreeC) of the single hardening body of the said urethane (meth) acrylate is 10-50 Mpa. The method for producing a photochromic laminate according to claim 5 or 6, wherein the cured product of the photocurable primer composition for optical articles has a Vickers hardness of 8 to 30.