JP2004295114A - Photochromic layered product and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photochromic layered product which has a photochromic coating layer having high adhesibility provided on a thermoplastic resin substrate having a light translucencies like a plastic lens and has satisfactory optical characteristics, photochromic characteristics, and durability. <P>SOLUTION: The photochromic layered product comprises; the substrate made of a thermoplastic resin having a light transmission property like polycarbonate resin; a crosslinking resin layer which is formed on the surface of the substrate and contains 20 to 40 mass% inorganic colloid particles; and a photochromic coating layer formed on the surface of the crosslinking resin layer. Though this layered product has the layer showing photochromic properties formed by a coating method, whitening or swelling of the surface of the substrate made of the thermoplastic resin are suppressed not to damage excellent optical characteristics of the substrate, and adhesibility of the photochromic coating layer is high and the layered product is superior in durability. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photochromic laminate in which a coating layer having photochromic properties is provided on the surface of a substrate such as a plastic lens.

  With photochromic glasses, the lens is quickly colored and functions as sunglasses outdoors when light containing ultraviolet rays such as sunlight is irradiated, and it fades and clears indoors where there is no such light irradiation. The eyeglasses function as eyeglasses, and their demand has been increasing in recent years.

  As a method for producing a plastic lens having photochromic properties, an impregnation method, a coating method, and a kneading method are known. The impregnation method is to impregnate the surface of a plastic lens with a photochromic compound, and the coating method is to form a resin layer containing a photochromic compound (photochromic coating layer) on the surface of a plastic lens by coating. The kneading method is to obtain a lens having photochromic properties directly by dissolving a photochromic compound in a monomer and polymerizing the monomer in this state. Among these methods, the coating method has an advantage that it can easily impart photochromic properties to any substrate (lens) in principle, compared to the other two methods. For example, in the impregnation method, the lens as the base material needs to be a soft material in which the photochromic compound is easily diffused, and in the kneading method, a special monomer composition is required to express good photochromic properties. In the coating method, there is no restriction on such a substrate.

  Conventionally, the following methods (i) to (iv) have been known as coating methods. In addition, the photochromic compound-containing curable resin composition used as a coating composition in this method is hereinafter referred to as a “photochromic coating agent”.

  (i) A method in which a photochromic compound prepared by dissolving a photochromic compound in a urethane oligomer is applied to the lens surface and cured (for example, see Patent Document 1).

  (ii) A photochromic compound prepared by dissolving a photochromic compound in a polymerizable monomer composition combining monofunctional, bifunctional and polyfunctional radical polymerizable monomers is applied to the lens surface and cured. (See, for example, Patent Document 2).

  (iii) A method of applying and curing a photochromic coating agent prepared by dissolving a photochromic compound in a monomer composition composed of only two or more types of bifunctional (meth) acrylic monomers on a lens surface (for example, a patent Reference 3).

  (Iv) A method of applying a photochromic coating agent comprising an N-alkoxymethyl (meth) acrylamide, a catalyst (preferably an acidic catalyst) and a photochromic compound to the lens surface and thermally curing (for example, see Patent Document 4).

  Since these photochromic coating agents generally contain an organic solvent or a (meth) acrylic monomer, they can be applied to a substrate made of a three-dimensional crosslinkable resin having relatively strong organic solvent resistance without any problem. However, when applied to a substrate made of a thermoplastic resin having no three-dimensional crosslinking (for example, a substrate made of polycarbonate), there arises a problem that the optical characteristics of the substrate are reduced. That is, the application of such a photochromic coating agent causes whitening, swelling, or partial dissolution of the thermoplastic resin base material, thereby deteriorating the surface condition of the base material.

  In order to solve the above-mentioned problems, a protective layer (for example, a thermosetting silicon-based hard coat layer containing inorganic particles) that does not deteriorate the optical characteristics of the thermoplastic resin substrate is provided on the surface of the thermoplastic resin substrate. ) And applying a photochromic coating agent to the surface of such a protective layer. However, in this case, although it is possible to prevent a decrease in optical characteristics, the adhesion between the photochromic coating layer formed by applying the photochromic coating agent and the protective layer is low, and the durability becomes unsatisfactory. That is the current situation.

See WO 98/37115 pamphlet U.S. Pat. No. 5,914,174 See WO 01/02449 pamphlet See WO 00/36047 pamphlet

  Therefore, an object of the present invention is to provide a photochromic coating layer having good adhesion on a substrate made of a transparent thermoplastic resin such as a plastic lens, and having good optical properties, photochromic properties and durability. An object of the present invention is to provide a laminate and a method for producing the laminate.

  The present inventors have intensively studied to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by interposing a specific crosslinked resin layer between the substrate and the photochromic coating layer, and have completed the present invention.

  That is, according to the present invention, there is provided a substrate made of a thermoplastic resin having a light-transmitting property, and a crosslinked resin layer formed on the surface of the substrate and containing the inorganic colloid particles in an amount of 20 to 40% by mass. And a photochromic coating layer formed on the surface of the crosslinked resin layer.

In the photochromic laminate of the present invention,
(1) After immersing the photochromic laminate in boiling water at 100 ° C. for 1 hour and holding it in an atmosphere at 20 ° C. for 30 minutes, the photochromic coating determined by a cross-cut tape peel test (JIS D 0202-1988) The peel strength between the layer and the crosslinked resin layer is 95/100 or more,
(2) the thermoplastic resin is polycarbonate;
(3) the base material is a lens;
Is preferred.

According to the present invention,
Non-solvent curable primer composition containing 20 to 40% by mass of inorganic colloid particles having a radical polymerizable group introduced on the surface in terms of inorganic metal oxide, and further containing a polyfunctional radical polymerizable monomer Preparing the process,
A step of forming a primer coating layer by applying the curable primer composition on a substrate surface made of a thermoplastic resin having a light-transmitting property,
Semi-curing the primer coating layer,
Step of applying a polymerizable photochromic composition containing a photochromic compound and a radical polymerizable monomer on the semi-cured primer coating layer,
as well as,
Performing a complete curing of the primer coating layer in the semi-cured state and polymerization of the polymerizable photochromic composition to form a photochromic coating layer on the surface of the substrate via a crosslinked resin layer,
And a method for producing a photochromic laminate characterized by comprising:

In the production method of the present invention,
The curable primer contains 5 to 60% by mass of a urethane oligomer;
Is preferred.

  The photochromic laminate of the present invention has a photochromic coating layer formed via a crosslinked resin layer containing a specific amount of inorganic colloid particles. Shows good photochromic properties without impairing the optical properties of

  Further, in the production method of the present invention, a non-solvent-based curable primer composition containing a certain amount of inorganic colloid particles having a radical polymerizable group introduced on the surface thereof and containing no organic solvent is used. Since the crosslinked resin layer is formed on the surface of the material, a decrease in the optical characteristics of the thermoplastic resin base material can be effectively avoided. Furthermore, a polymerizable photochromic composition (hereinafter sometimes simply referred to as a photochromic composition) is applied in a state where the curable primer composition is semi-cured, and the curable primer composition is completely cured and the photochromic composition is cured. Since the polymerization is performed at a time, the photochromic coating layer can be formed with good adhesion. That is, when the photochromic laminate of the present invention obtained by such a production method is immersed in boiling water at 100 ° C. for 1 hour and then kept in an atmosphere at 20 ° C. for 30 minutes, a cross cut tape peeling test (JIS D0202-1988), the peel strength between the photochromic coating layer and the crosslinked resin layer is 95/100 or more, particularly 98/100 or more, and the photochromic coating layer has high adhesion and excellent durability. Have the property.

  The peel strength determined by the cross-cut peel test is indicated by the number of squares that were not peeled off by the adhesive tape, out of 100 square squares engraved on the surface of the laminate. The strength of 95/100 indicates that 95 squares remain without peeling.

  The photochromic laminate of the present invention is extremely useful as, for example, a photochromic spectacle lens, particularly a photochromic spectacle lens whose lens substrate is made of polycarbonate.

(Production of photochromic laminate)
Briefly, the photochromic laminate of the present invention is prepared by preparing a curable primer composition for forming a crosslinked resin layer (curable primer preparation step), and coating the curable primer composition on the surface of a translucent thermoplastic resin substrate. (Primer coating layer forming step), semi-curing the primer coating layer (semi-curing step), and applying the photochromic composition on the semi-cured primer coating layer (photochromic agent applying step) Then, it is manufactured by performing final curing (final curing step). Hereinafter, each step will be sequentially described.
-Curable primer preparation process-
The curable primer composition used to form the crosslinked resin layer is a non-solvent system and is prepared without using any organic solvent. That is, by using a curable primer composition containing no organic solvent, deterioration of the surface of the thermoplastic resin base material can be avoided, and a decrease in optical characteristics can be prevented.

(A) a polyfunctional radically polymerizable monomer;
The curable primer contains a bifunctional or trifunctional or higher polyfunctional radical polymerizable monomer. Examples of the polyfunctional radical polymerizable monomer include the following formulas:
_{{H 2 C = C (-R} ') - COO-} n -R
Wherein R is an n-valent organic residue;
R ′ is a hydrogen atom or a methyl group,
n is an integer of 2 to 4,
A polyfunctional (meth) acrylate represented by the following formula is preferable. Here, examples of groups suitable as R include an n-valent aliphatic hydrocarbon group and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and these hydrocarbon groups include a halogen atom, a hydroxyl group, a carboxyl group and a carboxyl group. And a substituent such as an acyloxy group. Specific examples of the polyfunctional (meth) acrylate include the following compounds.

  Trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane triacrylate, trimethylol propane triethylene glycol triacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, urethane oligomer tetraacrylate, urethane Oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, bisphenol A dimethacrylate, 2 2- bis (4-methacryloyloxy) propane, hexanediol di (meth) acrylate, 2,2-bis (4-acryloyloxy polyethylene glycol phenyl) propane.

  Such a polyfunctional (meth) acrylic acid ester can be used alone or in combination of two or more, but the thermoplastic resin base material and the photochromic coating layer It is preferable to use two or more of them in view of securing high adhesion to both. Specifically, the following mixture is suitably used as the polyfunctional radically polymerizable monomer.

Mixture of hexanediol di (meth) acrylate and pentaerythritol tri (meth) acrylate (weight ratio 30 / 70-70 / 30)
Mixture of hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate (weight ratio 30/70 to 70/30)
Mixture of diethylene glycol di (meth) acrylate and pentaerythritol tri (meth) acrylate (weight ratio 30/70 to 70/30)
Mixture of diethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate (weight ratio 30/70 to 70/30)
In the present invention, the above-mentioned polyfunctional radical polymerizable monomer is preferably contained in the curable primer composition in an amount of 10 to 80% by mass.

(B) inorganic colloid particles;
Further, the curable primer composition contains inorganic colloid particles. Such inorganic colloid particles are not particularly limited as long as they are inorganic particles having a colloidal size and do not reduce the light transmittance of a crosslinked resin layer formed by curing the curable primer composition. Since it is possible to obtain a cross-linked resin layer having a high transparency and a desired refractive index, it is preferable to be colloidal particles of a single or composite oxide of silicon, titanium, tin, tungsten, antimony, zirconium, or the like, Colloidal silica is most preferably used.

  Further, it is necessary that a radical polymerizable group is introduced on the surface of the above-mentioned inorganic colloid particles. By introducing a radical polymerizable group onto the surface of the inorganic colloid particles, the inorganic colloid particles can be uniformly and stably dispersed in the curable primer composition, and the curable primer composition can be cured. In the cross-linked resin layer formed by the above, the inorganic colloid particles function as cross-linking points and will be present in a state chemically bonded to the matrix resin having a cross-linked structure, which is excellent for a thermoplastic resin base material. Shows a protective effect.

  In the present invention, the introduction of the radical polymerizable group onto the surface of the inorganic colloid particles is performed by a radical polymerizable group (specifically, a radical polymerizable group copolymerizable with the polyfunctional radical polymerizable monomer, It is easily performed by surface-treating the inorganic colloid particles using a coupling agent having a (meth) acryloyl group or a vinyl group). Such a coupling agent is an alkoxide of a metal constituting the inorganic colloid particles, which binds to the surface of the inorganic colloid particles by hydrolysis and condensation reaction.For example, when colloidal silica is used as the inorganic colloid particles, The following silane compounds (silyl acrylates) having a (meth) acrylate group are preferably used.

_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 -Si (OC 2 H 5) 3
_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 -Si (OCH 3) 3
_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 CH 2 -Si (OC 2 H 5) 3
_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 CH 2 -Si (OCH 3) 3
_{CH 2 = CHCO 2 -CH 2 CH} 2 CH 2 -Si (OC 2 H 5) 3
_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 CH 2 CH 2 -Si (OC 2 H 5) 3
_{CH 2 = CCH 3 CO 2 -CH} 2 CH 2 CH 2 CH 2 -Si (OCH 3) 3
The coupling agent is usually used in an amount of 5 to 50 parts by mass, especially 15 to 35 parts by mass, per 100 parts by mass of the inorganic colloid particles to be surface-treated. Further, the surface treatment (introduction of a radical polymerizable group) of the surface of the inorganic colloid particles with such a coupling agent may be performed in a semi-curing step described later. In this case, the curable primer composition contains The coupling agent and the inorganic colloid particles are present in the form of a mixture.

  In the present invention, the inorganic colloid particles having the above-mentioned radical polymerizable groups introduced into the surface are 20 to 40% by mass in terms of oxides of metal elements (including metal elements in the coupling agent) constituting the colloid particles. , Especially 25 to 35% by weight in the curable primer composition. If the amount of the inorganic colloid particles is less than this range, the protective effect of the formed crosslinked resin layer will be reduced, causing inconveniences such as deterioration of the optical characteristics of the thermoplastic resin base material. Also, if the inorganic colloid particles are added in a larger amount than the above range, it is considered that the chemical stability of the crosslinked resin layer is unnecessarily enhanced, but the crosslinked resin layer and the photochromic coating formed thereon Adhesion with the layer is impaired. For example, even when a treatment or the like for introducing an active group is performed on the surface of the crosslinked resin layer, the adhesion with the photochromic coating layer cannot be improved.

(C) other compounding agents;
In the curable primer composition, a photopolymerization initiator is blended in addition to the above components.

  Examples of the photopolymerization initiator include, but are not particularly limited to, ketone-type photopolymerization initiators such as benzophenone, diethoxyacetophenone, acetophenone, benzyl, benzaldehyde, o-chlorobenzaldehyde, xanthone, thioxanthone, and 9,10-phenanthrequinone. , A photopolymerization initiator containing a phosphorus atom such as acylphosphine, diacylphosphine and the like can be preferably used. Specific examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone, 4,4'-dichlorobenzophenone, diethoxyacetophenone, and 2-hydroxy-2-methyl-1-phenylpropane. -1-one, benzyl methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthiooxanthon, bis (2,6 -Dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - can be given butanone-1 and the like.

  The amount of such a photopolymerization initiator is preferably in the range of about 0.2 to 5% by mass based on the total weight of the curable primer composition.

  It is also a preferred embodiment to use a thermal polymerization initiator as described in the photochromic composition described later together with the photopolymerization initiator. The amount of the thermal polymerization initiator at that time is the same as in the case of the photopolymerization initiator.

  Further, in the present invention, by admixing a urethane oligomer into the curable primer composition, the adhesion between the crosslinked resin layer and the photochromic coating layer can be further increased. As the urethane oligomer, those used as a coating agent material for providing a flexible film can be used. In particular, a (meth) acrylate esterified fat having a urethane segment and a (meth) acryl segment can be used. Group urethanes, for example, polyurethanes obtained by reacting a polyurethane having a pendant hydroxyl group with isocyanatoethyl methacrylate; hydroxy-terminated polydimethylsiloxane, 2,4-toluene diisocyanate, 2-hydroxyethyl methacrylate, etc. Urethane acrylate obtained by the reaction; and the like can be suitably used. Such a urethane oligomer preferably has a number average molecular weight of about 200 to 50,000, and is preferably incorporated in the curable primer composition in a range of 5 to 60% by weight. When these urethane oligomers belong to the above-mentioned (A) polyfunctional radical polymerizable monomers of urethane acrylates such as urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, and urethane oligomer hexaacrylate, they are also used as the components. May be blended.

  In addition to the above components, an ultraviolet absorber or an antioxidant can be added to increase the durability of the crosslinked resin layer, and a leveling agent can be added to increase the smoothness of the coating film. it can. Examples of the UV absorber include a hydroxybenzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and benzylidene malonate. Usually, the UV absorber is incorporated in the curable primer composition in an amount of 5 to 10% by weight. can do. Known compounds such as hindered amine and hindered phenol can be used as the antioxidant. Further, as the leveling agent, known materials such as silicone, fluorine, acrylic, and vinyl can be used.

The curable primer composition used in the present invention is prepared by uniformly mixing the above-described components, and includes an inorganic colloid particle having a radical polymerizable group on the surface, and a polyfunctional radical polymerizable monomer. And a non-solvent-based substrate disclosed in Japanese Patent Publication No. 6-99577, U.S. Pat. No. 4,486,504, U.S. Pat. No. 4,478,876, etc. Curing a coating agent to improve the abrasion resistance and weather resistance of the film, and a photo-curable hard coating agent "UVHC8558", "UVHC1105", etc., manufactured by GE Toshiba Silicone Co., Ltd. It can also be used as a hydrophilic primer composition. When the above-mentioned urethane oligomer is not blended in these commercially available products and the coating agents shown in the prior art documents, it is desirable to use it additionally. The above-mentioned prior arts (Japanese Patent Publication No. 6-99577, U.S. Pat. No. 4,486,504, and U.S. Pat. No. 4,478,876) describe layers formed by these coating agents. There is no description on the formation of a photochromic coating layer thereon and the adhesiveness at that time.
-Primer coating layer forming process-
In the present invention, the above-mentioned curable primer composition is applied to the surface of a transparent thermoplastic resin base material to form a primer coating layer.

  The application means is not particularly limited, and known methods such as dipping, spin coating, and dip spin coating can be employed.However, since this curable primer composition has photocurability, light In order to avoid long-term storage under the conditions, it is preferable to adopt a coating method by spin coating. That is, in the spin coating method, coating can be performed using only a necessary amount of the curable primer composition, and the use of a large amount of the curable primer more than the necessary amount can be avoided.

  The transparent thermoplastic resin substrate to which the curable primer composition is applied is a substrate composed of a transparent thermoplastic resin such as a (meth) acrylic resin and a polycarbonate resin. There is no particular limitation as long as it is used, and optical materials such as plastic spectacle lenses and windows of houses and automobiles can be used without any limitation. Among these, a lens made of a (meth) acrylic resin or a polycarbonate resin, particularly a lens made of a polycarbonate resin is preferably used from the viewpoint of a high demand for imparting photochromic properties.

  The application amount of the curable primer composition (the thickness of the primer coating layer) is adjusted so that the thickness of the crosslinked resin layer formed by completely curing the composition falls within a predetermined range described later. You.

Prior to the application of the curable primer composition, if necessary, the surface of the substrate is pre-treated to form a crosslinked resin layer formed by curing the curable primer composition (primer coating layer). And the adhesiveness with the film. Examples of such pretreatment include chemical treatment with a basic aqueous solution or an acidic aqueous solution, plasma treatment using atmospheric pressure plasma and low pressure plasma, corona discharge treatment, flame treatment, UV ozone treatment, and the like. The pretreatment is to enhance the adhesion to the crosslinked resin layer by introducing an active group such as a carbonyl group into the surface of the base material. Further, such a pretreatment can be performed by physical etching (for example, polishing treatment using an abrasive). Thereby, the surface area of the substrate surface is increased, and the anchoring effect is increased by making the substrate surface rough, thereby improving the adhesion to the crosslinked resin layer.
-Semi-curing process-
Next, the primer coating layer is semi-cured by photopolymerization in an environment where dust, humidity or temperature is controlled, and if necessary, in an environment where the atmosphere is replaced with an inert gas. The degree of semi-curing is such that the polymerization rate of the monomer in the primer coating layer is in the range of 70 to 97%, preferably 80% to 95%. Here, the measurement of the polymerization rate in the primer coating layer after performing the semi-curing step was performed by immersing a polycarbonate lens having a crosslinked resin layer in methylene chloride for 2 days to extract unreacted monomers from the crosslinked resin layer, The extracted monomer can be identified and quantified by using gas chromatography and liquid high-performance chromatography, and the total of unreacted monomers is determined, and calculated by the following formula.

  That is, if the curing is advanced more than necessary, the adhesion between the crosslinked resin layer and the photochromic coating layer formed thereon is impaired, and if the curing is insufficient, the protective effect is reduced. Becomes insufficient, and when the photochromic composition is applied on this layer in the following steps, whitening or swelling of the substrate surface occurs, and optical characteristics are impaired. Further, it becomes difficult to uniformly apply the photochromic composition, and the thickness of the photochromic coating layer tends to vary.

The light irradiation for semi-curing the primer coating layer is performed using a metal halide lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a germicidal lamp, a xenon lamp, a carbon arc, a tungsten lamp, etc. Alternatively, this is performed using an electrodeless lamp or the like. The intensity of the irradiation light is not particularly limited, but from the viewpoint of preventing deformation and discoloration of the base material due to radiant heat, the light intensity at 405 nm on the base material surface is 150 mW / cm ² or less, particularly 30 to 130 mW / cm ² , Is preferably in the range of 40 to 120 mW / cm ² , and the curing time is not particularly limited, but is usually in the range of 5 seconds to 3 minutes.

The primer coating layer in the semi-cured state thus formed has high solvent resistance, and effectively suppresses whitening and swelling of the thermoplastic resin base material surface during application of the photochromic coating agent, and It shows excellent adhesion to the photochromic coating layer obtained by curing the photochromic composition.
-Photochromic agent application process-
In the present invention, the polymerizable photochromic composition (photochromic composition) is applied on the semi-cured primer coating layer. Prior to the application of the photochromic composition, if necessary, the surface of the semi-cured primer coating layer may be coated. Can be pre-processed. This pretreatment is the same as the above-described pretreatment of the substrate surface, chemical treatment with a basic aqueous solution or an acidic aqueous solution, plasma treatment using atmospheric pressure plasma, low pressure plasma, etc., corona discharge treatment, flame treatment, UV ozone treatment An active group is introduced into the surface by, for example, or the anchor effect is enhanced by physical etching such as a polishing treatment using an abrasive.

  As the photochromic composition, those known per se can be used without particular limitation. However, the photochromic properties, the optical properties, and the solvent resistance, scratch resistance, and adhesion of the photochromic coating layer formed by curing the photochromic properties are considered. From those containing a radical polymerizable monomer having a silanol group or a group capable of forming a silanol group by hydrolysis (hereinafter referred to as a silanol-radical polymerizable monomer), an amine compound and a photochromic compound are preferable Preferably, the photochromic composition further contains a radical polymerizable monomer containing a maleimide group (maleimide-radical polymerizable monomer). Adhesion can be further enhanced by blending the monomer

  Examples of the silanol-radical polymerizable monomer include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, (3-acryloyloxypropyl) dimethylmethoxysilane, 3-acryloyloxypropyl) methyldimethoxysilane, (3-acryloyloxypropyl) trimethoxysilane, (methacryloyloxymethyl) dimethylethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxypropyldimethylethoxysilane And methacryloyloxypropyldimethylmethoxysilane. The amount of the monomer used is not particularly limited, but it is preferably contained in the photochromic composition in an amount of 0.5 to 20% by mass, particularly 1 to 10% by mass.

  As the maleimide-radical polymerizable monomer, 4,4′-diphenylmethanebismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimide) Phenoxy) phenyl] propane, m-maleimidobenzoyl-N-hydroxysuccinimide ester, succinimidyl-4- (N-maleimidomethyl) cyclohexane-1-carboxylate and the like can be used. The amount of the monomer used is not particularly limited, but it is preferably contained in the photochromic composition in an amount of 0.05 to 15% by mass, particularly 0.1 to 10% by mass.

  Further, the above-mentioned silanol-radical polymerizable monomer and maleimide-radical polymerizable monomer may contain other radical polymerizable monomer other than the monomeric monomer. Are trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, trimethylolpropane triethylene glycol triacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, urethane oligomer tetraacrylate , Urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, diethylene glycol diacrylate Tacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, glycidyl methacrylate, 2,2 having an average molecular weight of 776 -Bis (4-acryloyloxy polyethylene glycol phenyl) propane, methyl ether polyethylene glycol methacrylate having an average molecular weight of 475, and the like. The use amount of these other radically polymerizable monomers is not particularly limited, but can be contained in the photochromic composition in an amount of 20 to 90% by mass, particularly 40 to 80% by mass.

  As the amine compound contained in the photochromic composition, triethanolamine, N-methyldiethanolamine, triisopropanolamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate and the like can be used. The amount of the amine compound used is not particularly limited, but is preferably 0.01 to 15% by mass, particularly 0.1 to 10% by mass in the photochromic composition. This amine compound is considered to play a role as a catalyst for generating the above-mentioned silanol group, and as a result, has a function of further improving the adhesion between the crosslinked resin layer and the photochromic layer.

  Further, as the photochromic compound, naphthopyran derivatives, chromene derivatives, spirooxazine derivatives, spiropyran derivatives, fulgimide derivatives, and the like can be used. The use amount of the photochromic compound is not particularly limited, but it is preferable that the photochromic compound is contained in the photochromic composition in a range of 0.1 to 30% by mass, particularly 1 to 10% by mass.

  Further, the photochromic composition contains a photopolymerization initiator or a thermal polymerization initiator depending on the type of the radical monomer used. As the photopolymerization initiator, those incorporated in the above-mentioned curable primer composition can be suitably used. As the thermal polymerization initiator, benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxide Peroxides such as oxy-2-ethylhexanoate, tert-butylperoxydicarbonate, tert-butylperoxyisobutyrate and diisopropylperoxydicarbonate; azides such as azobisisobutyronitrile; tributylborane And boron compounds such as tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate and potassium tetrakis (p-chlorophenyl) borate. These polymerization initiators vary depending on the type thereof, but are usually preferably contained in the photochromic composition in the range of 0.01 to 5% by mass, particularly 0.1 to 2% by mass.

  In the present invention, it is preferable that the photochromic composition further contains a coupling agent such as a silane coupling agent, whereby the adhesion between the crosslinked resin layer and the photochromic coating layer can be further improved. . That is, at the interface between the crosslinked resin layer and the photochromic coating layer, the inorganic colloid particles in the crosslinked resin layer and the coupling agent in the photochromic layer are chemically bonded, and as a result, the adhesion between the two layers is further improved. It is brought. Examples of such a coupling agent include an alkoxysilane compound having an epoxy group, specifically, γ-glucidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, or a curable primer composition. The exemplified ones can be used, and a silane coupling agent is particularly preferable. Further, the content of the coupling agent in the photochromic composition is preferably in the range of 0.1 to 20% by mass, particularly preferably 0.5 to 10% by mass.

The viscosity of the photochromic composition containing each component described above is adjusted by adjusting the content of each component within the above-described range. For example, the viscosity at 25 ° C is 20 to 1000 cP, particularly 50 to 800 cP, and more preferably 70 to 800 cP. It is preferable from the viewpoint of applicability that the viscosity is adjusted in the range of from 500 cP to 500 cP, and the thickness of the photochromic coating layer obtained by curing the photochromic composition is usually from 10 to
It is applied to a thickness of 100 μm, especially 20 to 50 μm. Incidentally, since the coating agent for hard coating and the like generally applied to plastic lenses contains a solvent or the like in order to obtain a uniform thin film, the viscosity at 25 ° C. is usually 5 cP or less. The thickness of the obtained coating layer is also several μm or less. Therefore, the photochromic composition used in the present invention has a higher viscosity than such a coating agent, and the thickness of the obtained photochromic coating layer is very large.

  The means for applying the photochromic composition is not particularly limited, and a known method can be applied without any limitation. For example, methods such as spin coating, spray coating, dip coating, and dip-spin coating can be employed.

In the present invention, the photochromic composition is applied on the semi-cured primer coating layer, so that the surface of the thermoplastic resin base material is protected by the primer coating layer. Therefore, whitening and swelling of the substrate surface due to the application of the photochromic composition are effectively suppressed.
-Final curing process-
After applying the photochromic composition on the semi-cured primer coating layer as described above, polymerization curing is performed again, and the semi-cured primer coating layer is finally cured to form a crosslinked resin layer, and at the same time, the photochromic composition is formed. A photochromic coating layer is formed by polymerization and curing of the product.

  As a curing method, a photocuring method or a thermosetting method is appropriately adopted depending on the type of the radical polymerization initiator compounded in the photochromic composition. From the viewpoint of completely curing the physical properties and appearance of the obtained coat film and the primer coating layer, it is preferable to employ a method of curing by light irradiation using a photopolymerization initiator and further heating to complete the curing. It is suitable. Therefore, in this case, it is desirable to use a photopolymerization initiator and a thermal polymerization initiator together as the polymerization initiator in the photochromic composition.

  As a light source used for photocuring, an electrode lamp such as a metal halide lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a germicidal lamp, a xenon lamp, a carbon arc, a tungsten lamp, or an electrodeless lamp. Can be used. An electron beam may be used as a light source. In this case, the photochromic composition can be cured without adding a photopolymerization initiator.

  Examples of the thermosetting method include a method of applying heat in a polymerization furnace to perform thermal polymerization, and a method of irradiating infrared rays in a polymerization furnace to perform polymerization and curing. However, in the case of performing thermosetting, it is necessary to set the polymerization temperature to a temperature at which the base material does not thermally deform (for example, 130 ° C. or lower).

In this way, by performing the final curing of the primer coating layer in a semi-cured state and the polymerization curing of the photochromic composition at once, the entanglement and chemical bonding of polymer molecules between the crosslinked resin layer and the photochromic coating layer are reduced. As a result, the adhesion between the two layers can be significantly increased.
(Photochromic laminate)
In the photochromic laminate obtained by the above-described method, a photochromic coating layer is formed on the surface of a base material made of a translucent thermoplastic resin represented by a (meth) acrylic resin or a polycarbonate resin via a crosslinked resin layer. It has a laminated structure.

  The crosslinked resin layer interposed between the substrate and the photochromic layer contains 20 to 40% by mass, particularly 25 to 35% by mass of inorganic colloid particles, and usually has a thickness of 0.1 to 20 μm, Preferably it is in the range of 0.5 to 15 μm, more preferably 1 to 5 μm. By forming the photochromic coating layer with such a cross-linked resin layer interposed, whitening and swelling of the substrate surface are suppressed, and the optical properties of the substrate are prevented from deteriorating. It is not damaged at all. In particular, in the crosslinked resin layer, as described above, since the inorganic colloid particles are chemically bonded to the resin component serving as the matrix, the protective effect of the crosslinked resin layer is extremely high, and when the photochromic composition is applied. Deterioration of the resulting substrate surface is reliably suppressed. The chemical bond between the inorganic colloid particles and the resin component can be confirmed, for example, by observing the interface between the two at the fractured surface of the crosslinked resin layer with an electron microscope. When no chemical bond is formed, the surface of the inorganic colloid particles is exposed as it is and a phase-separated structure is observed, but when a chemical bond is formed, the surface of the inorganic colloid particles is coated with a resin. Thus, a structure compatible with other resin components without phase separation is observed.

  As described above, the photochromic coating layer formed on the crosslinked resin layer usually has a thickness of 10 to 100 μm, particularly 20 to 50 μm, and contains a photochromic compound. It exhibits photochromic properties such that a predetermined color is generated by irradiation with light such as ultraviolet light, and the color is faded when the irradiation of light is stopped. In particular, the photochromic laminate of the present invention has extremely high adhesion between the photochromic coating layer and the crosslinked resin layer as shown in Examples described later. After immersion for a period of time, when held in an atmosphere at 20 ° C. for 30 minutes, the peel strength between the photochromic coating layer and the crosslinked resin layer determined by a cross cut tape peel test (JIS D 0202-1988) is 95/100. Above, especially 98/100 or more. Therefore, this photochromic laminate has excellent durability and exhibits photochromic properties over a long period of time.

  The photochromic laminate of the present invention can be used for a photochromic spectacle lens or the like as it is, for example, using a lens as a base material. However, it is preferable that the photochromic laminate be coated with a hard coat layer if necessary. By covering with a hard coat layer, scratch resistance can be improved. As such a hard coat layer, known ones can be used without any limitation, and a silane coupling agent or a hard coat agent mainly containing a sol of an oxide such as silicon, zirconium, antimony, and aluminum is applied. Cured ones and hardened ones coated with a hard coat agent containing an organic polymer as a main component are exemplified. In particular, by using a hard coat agent containing a silyl monomer, sufficient adhesion can be obtained more firmly and easily.

Further, if necessary, SiO ₂ , TiO ₂ ,
Of course, it is also possible to carry out processing such as antireflection treatment and antistatic treatment by vapor deposition of a thin film made of a metal oxide such as ZrO ₂ or application of an organic polymer, and secondary treatment.
EXAMPLES Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The various polymerizable compounds used in the examples are as follows.
<Polymerizable compound>
MACO: Acrylated colloidal silica (16.6 g of colloidal silica in 50 g of t-butanol, 1 g of γ-methacryloyloxypropyltrimethoxysilane according to the method described in Example 1 of US Pat. No. 4,455,205) Was added, and the mixture was reacted at 83 ° C. for 5 minutes. After the completion of the reaction, the mixture was cooled and the solvent was distilled off to obtain the desired product.)
U4HA: tetrafunctional urethane acrylate (molecular weight 496, manufactured by Shin-Nakamura Chemical)
UA4100: Bifunctional urethane acrylate (Molecular weight 1200 manufactured by Shin-Nakamura Chemical)
TSL8370: γ-methacryloyloxypropyltrimethoxysilane A-200: ethylene glycol diacrylate (average molecular weight 308)
BPE10: 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane A-400: polyethylene glycol diacrylate (average molecular weight 532)
TMPT: Trimethylolpropane trimethacrylate EB1830: Polyester oligomer hexaacrylate (manufactured by Daicel UCB)
GMA: glycidyl methacrylate BMI: 4,4'-diphenylmethane bismaleimide PFR: aromatic isocyanate polyether polyol urethane oligomer (molecular weight 5000)
34EN: aliphatic isocyanate polyether polyol urethane oligomer (molecular weight 3000)
<Amine compound>
NMDEA: N-methyldiethanolamine <photopolymerization initiator>
CGI 1800: a mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4'-trimethyl-pentylphosphine oxide (weight ratio 3: 1)
<Thermal polymerization initiator>
-Perbutyl IB: t-butyl peroxyisobutyrate (Perbutyl IB (trade name) manufactured by NOF Corporation)
Example 1
<Formation of primer coating layer>
A polycarbonate lens substrate was used as a lens substrate. A photocurable hard coat agent “UVHC1105” (colloidal silica content: 30% by weight) manufactured by GE Toshiba Silicone Co., Ltd. was used as a curable primer composition (primer solution) on the surface of the base material, and this was applied to a film thickness of 2 μm. Was spin-coated using a spin coater 1H-DX2 manufactured by MIKASA. Thereafter, a metal halide lamp of 120 W was irradiated for 2 minutes in a nitrogen atmosphere to be semi-cured, thereby producing a lens substrate having a semi-cured primer coating layer having a colloidal silica content of 30% by mass, and the obtained primer coating layer Was evaluated by the following methods.
<Evaluation of physical properties of primer coating layer>
(A) Evaluation of polymerization rate A lens substrate having a primer coating layer in a semi-cured state was immersed in methylene chloride for 2 days, and unreacted monomers were extracted from the primer coating layer. The extracted monomers were identified and quantified using gas chromatography and liquid high performance chromatography, the total of unreacted monomers was determined, and the polymerization rate was calculated from the following equation.

As a result, the polymerization rate was 90%.
(B) Evaluation of Adhesion of Primer Coating Layer to Substrate After immersing the lens substrate having the primer coating layer in boiling water at 100 ° C. for 1 hour, the substrate was kept in an atmosphere at room temperature (20 ° C.) for 30 minutes. A cross cut tape peeling test was performed. The crosscut tape peel test was based on JIS D0202-1988. Using a cellophane tape ("CT24", manufactured by Nichiban Co., Ltd.), the tape was adhered to the surface of the primer coating layer with the pad of a finger, and then peeled off. Judgment was expressed by the number of squares that did not peel out of 100 squares. That is, when the primer coating layer is not peeled at all, the ratio is 100/100, and when the primer coating layer is completely peeled, the ratio is 0/100.

The adhesion between the primer coating layer prepared by the method described above and the lens substrate was 100/100.
<Formation of photochromic coating layer>
In order to prepare a photochromic coating layer, as a pretreatment of the primer coating layer, the surface was treated using a corona treatment device Multidyne manufactured by Navitas.

Then, the radical polymerizable monomer BPE10 / A-400 / TMPT /
EB1830 / GMA was blended at a blending ratio of 50 parts by weight / 15 parts by weight / 15 parts by weight / 10 parts by weight / 10 parts by weight to prepare a mixture of radically polymerizable monomers, and 100 parts by weight of this mixture On the other hand, 2.35 parts by weight of the photochromic compound (A) having the structure represented by the following formula, 0.6 parts by weight of the photochromic compound (B) having the structure represented by the following formula, and the structure represented by the following formula 0.4 parts by weight of the photochromic compound (C) having the formula (1) was added and mixed well.
Photochromic compound (A):

Photochromic compound (B)

Photochromic compound (C)

  Next, 0.5 parts by weight of CGI1800 as a polymerization initiator, 5 parts by weight of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer were added to the obtained mixture. 7 parts by weight of γ-methacryloyloxypropyltrimethoxysilane as a coupling agent, 1.5 parts by weight of 4,4′-diphenylmethanebismaleimide and 3 parts by weight of N-methyldiethanolamine were added, mixed well, and polymerized. A photochromic composition (photochromic composition) was prepared.

About 2 g of the photochromic composition thus obtained was spin-coated on the surface of a lens substrate having a semi-cured primer coating layer using a spin coater 1H-DX2 manufactured by MIKASA. The lens substrate coated with this surface was irradiated for 3 minutes in a nitrogen gas atmosphere using a metal halide lamp with an output of 120 mW / cm ² , and after the coating film was cured, it was further heated in a thermostat at 130 ° C. for 2 hours. By performing the treatment, a photochromic coating layer was obtained. By the above curing treatment, the primer coating layer in a semi-cured state was also finally cured to form a crosslinked resin layer, and a photochromic laminate was produced. The thickness of the obtained photochromic coating layer can be adjusted by the conditions of spin coating. In this example, the thickness of the photochromic coating layer was adjusted to be 40 ± 1 μm.

The physical properties (appearance, turbidity and adhesion) of the photochromic coating layer on the photochromic laminate surface (crosslinked resin layer surface) thus obtained were evaluated by the following methods.
<Evaluation of physical properties of photochromic coating layer>
(A) Evaluation of appearance To evaluate the appearance of a photochromic laminate in which a photochromic coating layer is formed on the surface of a polycarbonate lens substrate via a crosslinked resin layer, the lens substrate is irradiated with a projector and the projected surface is observed. evaluated. The evaluation criteria are shown below.

  ：: Flat and no irregularities were observed.

  ：: Very slight unevenness is observed.

  Δ: Irregularities are partially visible.

  ×: Irregularities are seen uniformly or the substrate is affected.

The evaluation of the appearance of the lens substrate produced by the method described above was ◎.
(B) Evaluation of turbidity Turbidity of the lens substrate was visually inspected using a projector. The evaluation criteria were classified into the following items.

  ：: No cloudiness.

  Δ: Cloudiness is partially observed.

×: Whitened as a whole.
(C) Evaluation of adhesion between photochromic coating layer and crosslinked resin layer This adhesion was evaluated by the same method as the evaluation of the adhesion between the lens substrate and the primer coating layer. As a result, the adhesion between the photochromic coating layer and the crosslinked resin layer was 100/100.

  In Example 1, the composition of the curable primer composition (primer liquid) and the semi-curing conditions used for forming the crosslinked resin layer are shown in Table 1, and the composition of the photochromic composition and the pretreatment conditions used are shown in Table 2. Further, Table 3 shows the polymerization rate of the primer coating layer and the results of evaluation of physical properties of the primer coating layer and the photochromic coating layer (photochromic layer).

Example 2
In the same manner as in Example 1 except that the primer liquid was changed to a photocurable hard coat agent “UVHC8558” manufactured by GE Toshiba Silicone Co., Ltd. to form a crosslinked resin layer having a colloidal silica content of 30% by weight in Example 1, A photochromic coating layer was formed on the lens substrate surface via a crosslinked resin layer to produce a photochromic laminate. The same physical property evaluation as in Example 1 was performed on this laminate.

  The composition of the curable primer composition and the semi-curing conditions are shown in Table 1, the composition of the photochromic composition and the pretreatment conditions are shown in Table 2, and the polymerization rate of the primer coating layer, the primer coating layer and the photochromic layer Are shown in Table 3.

Examples 3 to 18
A photochromic laminate was prepared in the same manner as in Example 1 except that the curable primer composition and the curing conditions were as shown in Table 1 and the photochromic agent was as shown in Table 2. did. The same physical property evaluation as in Example 1 was performed on this laminate.

  The composition of the curable primer composition and the semi-curing conditions are shown in Table 1, the composition of the photochromic composition and the pretreatment conditions are shown in Table 2, and the polymerization rate of the primer coating layer, the primer coating layer and the photochromic layer Are shown in Table 3.

Comparative Example 1
As a primer liquid, a thermosetting hard coat agent “NSC1274” (silica content: 50% by weight) manufactured by Nippon Seika Co., Ltd. containing silica colloidal sol and alkoxysilane was used. The primer was applied to the surface of the used polycarbonate lens substrate and cured at 110 ° C. for 1 hour to form a primer coating layer having a colloidal silica content of 50% by weight. Next, a photochromic coating layer was formed in the same manner as in Example 1 to form a photochromic laminate, and various physical properties were evaluated in the same manner as in Example 1. (For the photochromic coating layer, the appearance evaluation was x and the adhesion evaluation was x.)
The composition of the curable primer composition and the semi-curing conditions are shown in Table 1, the composition of the photochromic composition and the pretreatment conditions are shown in Table 2, and the polymerization rate of the primer coating layer, the primer coating layer and the photochromic layer Are shown in Table 3.

Comparative Example 2
In Example 1, without forming a primer coating layer, a photochromic coating layer was directly formed on the surface of the polycarbonate lens substrate in the same manner as in Example 1 to produce a photochromic laminate, and a photochromic coating layer (photochromic layer) was formed. ) Were evaluated, and the results are shown in Table 3. The appearance was white and the adhesion was poor.

Comparative Examples 3 and 4
A photochromic laminate was prepared in the same manner as in Example 1 except that the curable primer composition and the curing conditions were as shown in Table 1 and the photochromic agent was as shown in Table 2. did. The same physical property evaluation as in Example 1 was performed on this laminate.

  The composition of the curable primer composition and the semi-curing conditions are shown in Table 1, the composition of the photochromic composition and the pretreatment conditions are shown in Table 2, and the polymerization rate of the primer coating layer, the primer coating layer and the photochromic layer Are shown in Table 3.

  As is clear from the above examples, according to the present invention, a photochromic coating layer formed by a coating method on a substrate having a surface made of a translucent thermoplastic resin without deteriorating the optical characteristics of the substrate. Can be formed to impart photochromic properties. Moreover, the substrate and the photochromic coating layer can be firmly adhered. Further, the photochromic laminate of the present invention has excellent characteristics of good optical properties, photochromic properties, and good adhesion between layers, and can be suitably used as, for example, a photochromic spectacle lens.

Claims (6)

A substrate made of a thermoplastic resin having a light-transmitting property, a crosslinked resin layer formed on the surface of the substrate and containing inorganic colloid particles in an amount of 20 to 40% by mass, and formed on the surface of the crosslinked resin layer And a photochromic coating layer. After immersing the photochromic laminate in boiling water at 100 ° C. for 1 hour, and holding it in an atmosphere at 20 ° C. for 30 minutes, crosslinking with the photochromic coating layer determined by a grid tape peel test (JIS D 0202-1988) The photochromic laminate according to claim 1, wherein a peel strength between the resin layer and the resin layer is 95/100 or more. The photochromic laminate according to claim 1, wherein the thermoplastic resin is polycarbonate. The photochromic laminate according to any one of claims 1 to 3, wherein the substrate is a lens. Non-solvent curable primer composition containing 20 to 40% by mass of inorganic colloid particles having a radical polymerizable group introduced on the surface in terms of inorganic metal oxide, and further containing a polyfunctional radical polymerizable monomer Preparing the process,
A step of forming a primer coating layer by applying the curable primer composition on a substrate surface made of a thermoplastic resin having a light-transmitting property,
Semi-curing the primer coating layer,
Step of applying a polymerizable photochromic composition containing a photochromic compound and a radical polymerizable monomer on the semi-cured primer coating layer,
as well as,
Performing a complete curing of the primer coating layer in the semi-cured state and polymerization of the polymerizable photochromic composition to form a photochromic coating layer on the surface of the substrate via a crosslinked resin layer,
A method for producing a photochromic laminate, comprising: The method for producing a photochromic laminate according to claim 5, wherein the curable primer contains 5 to 60% by mass of a urethane oligomer.