JP2002055202A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic lens with a primer layer of an aqueous resin composition which imparts superior shock, water and weather resistance. SOLUTION: In the plastic lens with a plastic lens substrate, a primer layer formed on the substrate and a hard coat layer formed on the primer layer, the primer layer is based on a water-based acrylic-urethane resin which is a copolymer of an acrylic polyol and a polyfunctional isocyanate compound or a composite of an acrylic polyol and a water-based polyurethane resin and has been dispersed in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic lens, and more particularly, to a plastic lens having excellent impact resistance, water resistance, light resistance, and the like.

[0002]

2. Description of the Related Art Plastic lenses are widely used in the field of spectacle lenses because they are lighter in weight, have better moldability, workability, dyeability, are less likely to break, and have higher safety than glass lenses.

However, since plastic lenses are soft and very easily damaged, a hard coat layer having high hardness is provided on the surface of the plastic lens to improve abrasion resistance. Further, an anti-reflection film in which an inorganic substance is vapor-deposited may be provided on the surface of the hard coat layer in order to prevent surface reflection. The quality of the plastic lens is high due to the surface treatment layer of the plastic lens.

[0004] However, a plastic lens having a hard coat layer or an anti-reflection film surface treated is compared with a plastic lens having no surface treated layer.
There is a disadvantage that the impact resistance is reduced. Particularly, in the case of a minus power lens having a small center thickness of the lens, there is a disadvantage that the impact resistance is significantly reduced and the lens is easily broken. If the center thickness is increased to improve this, the thickness (edge thickness) at the peripheral portion of the lens becomes extremely large, which is not preferable in appearance. In addition, the weight of the lens has also increased, and the usability of the glasses has increased. Drop,
Not practically preferable. In recent years, the development of plastic lens substrates with a high refractive index has progressed.
Although the edge thickness can be reduced, a plastic lens substrate having a high refractive index has a drawback that it has low impact resistance and is easily broken.

To solve this problem, Japanese Patent Application Laid-Open No.
No. 114203 discloses that by applying a primer composition comprising an acrylic polyol and a polyfunctional organic isocyanate compound on a substrate, the adhesion of the surface treatment layer to the substrate is improved, and the impact resistance, weather resistance, and heat resistance are improved. It is disclosed that the aqueous properties can be improved. Also, JP-A-63-
87223 and JP-A-63-141001 disclose a method in which a urethane resin primer layer comprising a specific polyalcohol and an isocyanate is provided between a lens substrate and a hard coat layer. Similarly, Japanese Patent Application Laid-Open No. 3-109502 discloses a method using a urethane resin primer layer comprising a polyalcohol and a blocked isocyanate. Originally, the primer layer is a layer intended to improve the adhesion between the plastic lens substrate and the hard coat layer, but by selecting a specific urethane resin for this primer layer,
The impact resistance of the plastic lens can be improved.

[0006]

However, organic solvent-based resins have hitherto been mainly used as a coating liquid for forming a primer layer. However, in recent years, water-based resins have been replaced with water-based resins because of problems such as air pollution and improvement of working environment. It is currently being done. An aqueous resin is also desirable in the primer solution for forming the primer layer.

When a conventional urethane resin is used for the primer layer, the impact resistance can be improved, but the water resistance,
The plastic lens using such a urethane resin as a primer layer may be inferior in weather resistance, and has a problem that the appearance of the plastic lens is deteriorated due to yellowing or clouding as it is used.

The present invention has been made in view of the above circumstances, and has as its object to provide a plastic lens having a primer layer of a water-based resin that provides excellent impact resistance, water resistance, and weather resistance.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that aqueous acrylic
A plastic lens having a primer layer containing a urethane resin as a main component is an excellent plastic lens that has good water resistance and weather resistance in addition to the effect of improving the impact resistance of the urethane resin, and has little change over time in appearance. I found

Here, the water-based acryl-urethane resin is a copolymer of an acrylic polyol and a polyfunctional isocyanate compound or a composite of an acrylic polyol and a water-based polyurethane resin, which is dispersed in water. It is. The acrylic polyol is a copolymerized acrylic resin of an acrylic monomer having a hydroxyl group and a monomer copolymerizable with the acrylic monomer having the hydroxyl group.
Further, the aqueous polyurethane resin is a polyurethane resin in which a urethane resin obtained by a reaction between a polyfunctional isocyanate compound and a polyol is dispersed as an emulsion in an aqueous solution.

Further, since the refractive index of the water-based acrylic-urethane resin itself is about 1.5, if it is used as it is as a primer layer on a plastic lens substrate having a high refractive index, interference fringes may occur. Therefore, by blending metal oxide fine particles or composite fine particles in the primer layer, the refractive index of the primer layer containing water-based acryl-urethane resin as a main component can be improved, and the occurrence of interference fringes can be prevented.

Further, by using a primer layer containing a water-based acryl-urethane resin as a main component, the impact resistance when an antireflection film is formed on the hard coat layer can be improved.

[0013] Further, by forming a primer layer using a water-based acryl-urethane resin obtained by reacting an isocyanate group-containing urethane prepolymer with a chain extender in an aqueous phase to increase the molecular weight, a particularly excellent resistance can be obtained. It has been found that impact resistance, water resistance and weather resistance can be imparted.

Furthermore, it has been found that by using a self-emulsifying urethane prepolymer having a carboxyl group, it is not necessary to use a surfactant when dispersing in water, so that the water resistance is further improved.

Accordingly, the present invention provides a plastic lens having a plastic lens substrate, a primer layer formed on the plastic lens substrate, and a hard coat layer formed on the primer layer. And a plastic lens characterized in that the primer layer contains a water-based acryl-urethane resin as a main component.

According to a second aspect of the present invention, in the plastic lens according to the first aspect, the primer layer is made of S
i, Al, Sn, Sb, Ta, Ce, La, Fe, Z
A plastic lens characterized by containing one or more oxide fine particles or composite fine particles of a metal selected from n, W, Zr, In and Ti.

According to a third aspect of the present invention, there is provided the plastic lens according to the first or second aspect, further comprising an antireflection film on the hard coat layer.

According to a fourth aspect of the present invention, in the plastic lens according to any one of the first to third aspects, the aqueous acryl-urethane resin reacts an isocyanate group-containing urethane prepolymer with a chain extender in an aqueous phase. To provide a plastic lens characterized by having a high molecular weight.

According to a fifth aspect of the present invention, there is provided the plastic lens according to the fourth aspect, wherein the isocyanate group-containing urethane prepolymer is a carboxyl group-containing self-emulsifying type.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the plastic lens of the present invention will be described, but the present invention is not limited to the following embodiments.

As described above, the plastic lens of the present invention comprises a plastic lens substrate, a primer layer mainly composed of an aqueous acrylic-urethane resin formed on the plastic lens substrate, and a plastic layer formed on the primer layer. Hard coat layer.

The plastic lens substrate is not particularly limited, but includes (meth) acrylic resin, styrene resin, carbonate resin, allyl resin, diethylene glycol bisallyl carbonate resin (CR-3).
9) an allyl carbonate resin, a vinyl resin, a polyester resin, a polyether resin, a urethane resin obtained by reacting an isocyanate compound with a hydroxy compound such as diethylene glycol, a thiourethane resin obtained by reacting an isocyanate compound with a polythiol compound, A transparent resin obtained by curing a polymerizable composition containing a (thio) epoxy compound having one or more disulfide bonds in a molecule can be exemplified.

The primer layer in the plastic lens of the present invention is characterized in that it contains a water-based acryl-urethane resin as a main component. Aqueous acrylic-urethane resin is a copolymer obtained by copolymerizing a polyol compound using acrylic polyol as a main component and a polyfunctional isocyanate compound, or a composite of acrylic polyol and aqueous polyurethane resin. Yes, dispersed in water. The acrylic polyol is a copolymerized acrylic resin of an acrylic monomer having a hydroxyl group and a copolymerizable monomer such as an acrylic ester having the hydroxyl group and an acrylic ester. The aqueous polyurethane resin is also called an aqueous urethane resin or a water-dispersible polyurethane, and is a urethane resin obtained by a reaction between a polyfunctional isocyanate compound and a polyol, which is dispersed as an emulsion in an aqueous solution.

Examples of the acrylic monomer having a hydroxyl group as a raw material of the acrylic polyol include 2-hydroxyethyl acrylate, 3-chloro-2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, and 2-hydroxyethyl methacrylate. , 2-hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, 5,6-
Dihydroxyhexyl methacrylate and the like,
These may be used alone or in combination of two or more.

The monomers copolymerizable with the acrylic monomer having a hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth)
Acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, isoamyl (meth) acrylate, trifluoroethyl (meth) Acrylate, benzyl (meth)
Acrylate, 2-n-butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, cinnamyl (meth) acrylate , Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, furfuryl (meth)
Acrylate, hexafluoroisopropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-
Methoxybutyl (meth) acrylate, 2-nitro-2-
Methylpropyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, tetrapyranyl (meth) acrylate, acrylic acid,
Examples include acrylic monomers such as methacrylic acid, and ethylenic monomers such as acrylonitrile, vinyl acetate, vinylpyridine, vinylpyrrolidone, methylcrotonate, maleic anhydride, styrene, and α-methylstyrene. In addition, (meth) acrylate means acrylate or methacrylate.

The acrylic polyol can be obtained by polymerizing the acrylic monomer having a hydroxyl group and a monomer copolymerizable therewith by a known polymerization method such as a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method. . In particular, the emulsion polymerization method is preferable in that it can directly produce an aqueous acrylic polyol, and also obtains a macromolecular weight material which is difficult to produce by solution polymerization.

Further, in order to obtain a self-emulsifying aqueous polyurethane resin, it is preferable to use a compound having a carboxyl group and at least two active hydrogens in the molecule together with the acrylic polyol. Such compounds include, for example, 2,2-dimethylolpropionic acid,
Examples include dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, and 2,2-dimethylolbutanoic acid. These may be used alone or in combination of two or more.

On the other hand, polyfunctional isocyanate compounds include toluene diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. , Dicyclohexylmethane diisocyanate, norborane diisocyanate, p-phenylene diisocyanate, t-
Diisocyanates such as cyclohexane-1,4-diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, trimethylhexamethylene diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane; Triphenylmethane triisocyanate,
Tris (isocyanatephenyl) thiophosphate,
Lysine ester triisocyanate, 2-isocyanateethyl-2,6-diisocyanate hexanoate,
1,6,11-undecane triisocyanate, 1,8
-Diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate,
And triisocyanates such as bicycloheptane triisocyanate. Furthermore, these diisocyanates,
A urethane modified product obtained from a triisocyanate can be used. Examples of the urethane-modified product include an adduct, a uretdione (a dimer), an isocyanurate (a trimer), a carbodiimide, an allohanate-modified, a urea-modified polyisocyanate, a buret-modified polyisocyanate, and an isocyanate prepolymer (semi-prepolymer). Is raised. Further, blocked isocyanates obtained by blocking these polyisocyanates with a blocking agent such as acetylacetone, dimethylmalonate, diethylmalonate, 2,4-hexanedione, 3,5-heptanedione, acetoxime, methylethylketoxime, pukunone oxime, and caprolactam are also used. can give.

Among these, an aliphatic diisocyanate compound and an alicyclic diisocyanate are preferable from the viewpoint of weather resistance. For example, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norborane diisocyanate, and hexamethylene diisocyanate are preferable.

As a method for obtaining an aqueous acrylic-urethane resin, for example, acrylic polyol, other polyol if necessary,
Having a carboxyl group by reacting a compound having two active hydrogens, a polyfunctional isocyanate compound and a catalyst in an organic solvent using a stoichiometric excess of the polyfunctional isocyanate compound with respect to the hydroxyl group, and having a carboxyl group, After producing an acrylic-modified urethane prepolymer having a group, it is neutralized and neutralized with a neutralizing agent, and the aqueous urethane prepolymer is dispersed in water, and further polymerized with a chain extender to form a self-emulsifying aqueous solution. There is a method of obtaining a fluorinated acrylic-urethane copolymer composition.

Examples of the polyol other than the acrylic polyol include polyester polyols, polycarbonate polyols and polyether polyols, and one of these polyols can be used alone or in combination of two or more. .

Examples of the polyester polyol include polyethylene adipate, polyethylene propylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene adipate, polydiethylene adipate, polyethylene terephthalate, polyhexamethylene isophthalate adipate, polyethylene succinate, and polybutylene. Succinate,
Polyethylene sebacate, polybutylene sebacate, poly-ε-caprolactone diol, poly-3-methyl-
Examples include 1,5-pentylene adipate, a polycondensate of 1,6-hexanediol and dimer acid, and the like.

[0033] Examples of the polycarbonate polyol include polyhexamethylene carbonate diol.

Further, examples of the polyether polyol include homopolymers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, block copolymers, and random copolymers.

As the above catalyst, one or more of dibutyltin dilaurate, stannasoctoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine and the like can be used.

Examples of the neutralizing agent include amines such as trimethylamine, triethylamine, tri-n-propylamine, tributylamine and triethanolamine, potassium hydroxide, sodium hydroxide and ammonia.

Examples of the chain extender include low molecular weight polyfunctional alcohols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and sorbitol;
Furthermore, ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, low-molecular-weight polyamines such as triethylenetetramine, and the like, and these alone or in combination of two or more. They can be used in combination.

The compounding amount of the compound having a carboxyl group and at least two active hydrogens is such that the content of the carboxyl group in the resin is 0.3 to 5% by weight, particularly 0.5 to 1.5% by weight. A range is preferred.

Commercially available self-emulsifying water-based acryl-urethane resins include, for example, Neo Sticker 400, Neo Sticker 700, and X-7200 (all trade names, manufactured by Nikka Chemical Co., Ltd.). This water-dispersible polyurethane is further improved in water resistance by adding a crosslinking agent such as an aqueous oxazoline-based crosslinking agent that reacts with a carboxyl group, an aqueous (poly) carbodiimide-based crosslinking agent, and an aqueous epoxy resin-based crosslinking agent.

Also, without using a compound having a carboxyl group and at least two active hydrogens, an acrylic polyol, if necessary, other polyols, a polyfunctional isocyanate compound and a catalyst are added in stoichiometric excess with respect to the hydroxyl group. After producing an acrylic-modified urethane prepolymer having an isocyanate group at a terminal by reacting in an organic solvent using a functional isocyanate compound, the urethane prepolymer is dispersed in water using a surfactant, and further dispersed with a chain extender. There is a method of obtaining a water-based acrylic-urethane copolymer composition of a forced emulsification type by polymerizing.

Further, as another method for obtaining an aqueous acrylic-urethane resin, an acrylic polyol containing the above-mentioned compound having a carboxyl group and at least two active hydrogens in the above-mentioned ratio and a polyfunctional isocyanate compound are reacted with an isocyanate group and an active group. Equivalent ratio of hydrogen group is 0.8 / 1 to 1.2
After neutralizing the carboxyl groups with the above neutralizing agent, the polyurethane is dispersed in water.

Further, the acrylic polyol and the polyfunctional isocyanate compound can be used in an equivalent ratio of isocyanate group to active hydrogen group of 0.8 / 1 to 1.2 without using a compound having a carboxyl group and at least two active hydrogen groups. After reacting at a ratio of / 1, the resulting polyurethane resin is dispersed in water using a surfactant to obtain an aqueous acrylic-urethane resin.

Further, for example, an acrylic monomer is emulsion-polymerized in the presence of an aqueous polyurethane resin to form a core.
There is a method of obtaining a composite emulsion which is a composite of an acrylic polyol having a shell structure and an aqueous polyurethane resin.

In this method, for example, a polyol containing the above-mentioned compound having a carboxyl group and at least two active hydrogens in the above-mentioned ratio and a polyfunctional isocyanate compound are prepared by adjusting the equivalent ratio of the isocyanate group to the active hydrogen group to 0.8 / 1 to 1. 1.
After reacting at a ratio of 2/1 and neutralizing the carboxyl group with the above neutralizing agent, the polyurethane is dispersed in water. An acrylic monomer is mixed in an aqueous medium in which the water-dispersed polyurethane is present, and is polymerized by a polymerization initiator to obtain an aqueous acrylic-urethane resin having a core-shell structure.

Further, an aqueous acrylic-urethane resin can also be obtained by simply mixing the aqueous polyurethane resin and the acrylic polyol emulsion obtained by the emulsion polymerization method.

Since the refractive index of the water-based acryl-urethane resin is about 1.5, a recent increase in the refractive index of the plastic lens substrate has resulted in a primer on the plastic lens substrate having a refractive index of around 1.7. When the aqueous acryl-urethane resin is applied as it is as a layer, interference fringes are generated by the primer layer. Therefore, it is preferable to adjust the refractive index by mixing metal oxide fine particles in the primer layer.

As such metal oxide fine particles,
Si, Al, Sn, Sb, Ta, Ce, La, Fe, Z
One or more oxide fine particles or composite fine particles of a metal selected from n, W, Zr, In, and Ti can be exemplified. Specifically, SiO ₂ , SnO ₂ , Sb ₂ O ₅ ,
Fine particles of inorganic oxides of CeO ₂ , ZrO ₂ and TiO ₂ colloidally dispersed in a dispersion medium such as water, alcohol or other organic solvent, or Si, A
1, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Examples thereof include those in which composite fine particles composed of two or more kinds of inorganic oxides of Zr, In, and Ti are colloidally dispersed in water, an alcohol, or another organic solvent. In any case, the particle diameter is preferably about 1 to 300 mμ.

Further, in order to enhance the dispersion stability in the coating liquid, it is possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound or an amine compound.

The organosilicon compound used at this time includes monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. After the treatment, the hydrolyzable group is-
A state in which it has reacted with an OH group is preferable, but there is no problem in stability even in a state where a part remains.

Examples of the amine compound include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, monoethanolamine, triethanolamine and the like. Alkanolamines.

It is preferable to add the organic silicon compound and the amine compound in an amount of about 1 to 15% based on the weight of the fine particles.

The ratio of the metal oxide fine particles to the solid content in the primer solution is preferably 0 to 65% by weight, particularly preferably 55% by weight or less. If it exceeds 65% by weight,
The primer layer may become cloudy and the appearance may deteriorate.

A method for forming a primer layer on a plastic substrate is, for example, by mixing metal oxide fine particles as necessary with an aqueous solution containing an aqueous acrylic-urethane resin, and diluting it with a solvent as necessary to prepare a primer solution. Can be used. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used. The prepared primer solution is applied to a plastic substrate by a method such as spin coating and dipping, and after drying,
It can be performed by a curing method.

The thickness of the primer layer is 0.01 to 50 μm
Is preferred. If the primer layer is too thin, the effect of improving the impact resistance is small, while if it is too thick, the surface accuracy decreases. Further, the primer layer of the present invention can contain various conventionally known additives such as a leveling agent.

In the plastic lens of the present invention, a hard coat layer is formed on such a primer layer to impart abrasion resistance.

The hard coat film provided on the surface of the primer layer is obtained by applying and curing a composition containing the following inorganic fine particle component and silane compound component as main components.

Inorganic fine particle component: S having a particle size of 1 to 100 μm
fine particles of at least one metal oxide selected from i, Sn, Sb, Ce, Zr, Ti and / or Si, A
1, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Composite fine particles composed of two or more metal oxides selected from Zr, In, and Ti.

Silane compound component: A silane compound having at least one or more polymerizable reactive groups.

Specific examples of the inorganic fine particle component include Si
O ₂ , SnO ₂ , Sb ₂ O ₅ , CeO ₂ , ZrO ₂ , TiO ₂
Are dispersed in a colloidal form in a dispersion medium such as water, an alcoholic or other organic solvent. Or Si, A1, Sn, Sb, Ta, C
Composite fine particles composed of two or more inorganic oxides of e, La, Fe, Zn, W, Zr, In, and Ti are colloidally dispersed in water, an alcohol, or another organic solvent.

Further, in order to enhance the dispersion stability in the coating solution, it is possible to use those obtained by treating the surface of these fine particles with an organosilicon compound or an amine compound.

As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. After the treatment, the hydrolyzable group is-
A state in which it has reacted with an OH group is preferable, but there is no problem in stability even in a state where a part remains.

Examples of the amine compound include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, monoethanolamine, triethanolamine and the like. Alkanolamines. The addition amount of these organosilicon compounds and amine compounds is 1 to the weight of the fine particles.
It is preferable to add within the range of about 15%.

Specific examples of the silane compound component include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryl Oxypropyl dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, N-β (Aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like. This silane compound component may be used as a mixture of two or more kinds. It is also useful to add a disilane compound represented by the following general formula.

[0064]

Embedded image (Wherein, R ¹ and R ² are a hydrocarbon group having 1 to 6 carbon atoms).
X ¹ and X ² are hydrolyzable groups. Y is an organic group containing a carbonate group or an epoxy group;
Or 1. These disilane compounds can be synthesized by various conventionally known methods. For example, it can be obtained by performing an addition reaction between diallyl carbonate and trichlorosilane or the like, followed by alkoxylation. Alternatively, the compound can be obtained by adding a trichlorosilane or the like to a compound having an addable substituent at both ends and further containing an epoxy group or an epoxidizable functional group therein, followed by alkoxylation. It is more effective to use either of these disilane compounds after hydrolysis or to perform an acid treatment on the cured film.

It is also useful to add a polyfunctional epoxy compound. Polyfunctional epoxy compounds are widely used for paints, adhesives, casting, etc.
For example, polyolefin epoxy resins synthesized by the peroxidation method, alicyclic epoxy resins such as cyclopentadiene oxide and cyclohexene oxide or polyglycidyl esters obtained from hexahydrophthalic acid and epichlorohydrin, and polyfunctional compounds such as bisphenol A, catechol, and resorcinol Polyglycidyl ether obtained from phenol or polyfunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol and epichlorohydrin, epoxidized vegetable oil,
Epoxy novolak obtained from novolak phenol resin and epichlorohydrin, epoxy resin obtained from phenolphthalein and epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene, and further containing the above epoxy compound and monocarboxylic acid ( Epoxy acrylates obtained by a glycidyl group ring-opening reaction with (meth) acrylic acid are exemplified.

Specific examples of the polyfunctional epoxy compound include 1,6-hexanediol diglycidyl ether,
Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether,
Tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalic acid ester, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl Ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, Aliphatic epoxy compounds such as rubitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophorone diol diglycidyl ether, bis-2 Alicyclic epoxy compounds such as 1,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ortho phthalic acid diglycidyl ester, phenol novolak polyglycidyl And aromatic epoxy compounds such as ether and cresol novolak polyglycidyl ether. Among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) Aliphatic epoxy compounds such as triglycidyl ether of isocyanurate are particularly preferred.

In order to adjust the refractive index of the coating or to further improve the durability of the coating, it is also useful to add a tetrafunctional silane compound represented by the general formula Si (OR) ₄ . Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis ( 2-ethylbutoxy) silane, tetrakis (2
-Ethylhexyloxy) silane and the like. These may be used alone or as a mixture of two or more.

Further, it is preferable to use them after hydrolysis in the presence of an acid in the absence of a solvent or in an organic solvent such as an alcohol. It is also useful to add a curing catalyst for silanol or epoxy compound.

Preferred curing catalysts include perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate, Cu (II), Zn (II), Co (II), N
i (II), Be (II), Ce (III), Ta (I
II), Ti (III), Mn (III), La (II
I), Cr (III), V (III), Co (II
I), Fe (III), Al (III), Ce (I
V), Zr (IV), V (IV) and the like as central metal atoms such as amino acids such as acetylacetonate, amine and glycine, Lewis acids, and organic acid metal salts. Among these, the most preferred curing catalysts include magnesium acetylacetonate of magnesium perchlorate, Al (III) and Fe (III).

The composition for hard coat obtained in this way can be used after being diluted with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used.

The composition for hard coat is applied on the primer layer by a method such as spin coating and dipping.
After drying, a hard coat film can be formed by a method of curing.

The antireflection film can be formed by a vacuum deposition method, an ion plating method, a sputtering method, or the like. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. As the film configuration, either a single-layer antireflection film or a multilayer antireflection film may be used.

Examples of usable inorganic substances include, for example, Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be exemplified, and these inorganic substances can be used alone or in combination of two or more. In particular, for plastic lenses, ZrO ₂ , Si which can lower the deposition temperature
O ₂ and TiO ₂ can be preferably used.

As described above, the plastic lens in which the above-mentioned primer layer, hard coat layer and antireflection film are formed on the plastic substrate is provided with scratch resistance by the hard coat layer and has a light transmittance of the antireflection film. The primer layer improves the adhesion of the hard coat layer and the anti-reflection film to the plastic substrate, and lowers due to the provision of the hard coat layer and the anti-reflection film. Since the impact resistance is remarkably improved and the primer layer itself has good weather resistance and water resistance, it is a high quality plastic lens with little change over time in appearance.

Further, since the primer layer is mainly composed of water-soluble acryl-urethane resin, it is possible to eliminate the need for an organic solvent in the step of forming the primer layer, thereby improving the working environment. Furthermore, since the inorganic oxide fine particles dispersed in water or alcohol used in the hard coat layer forming step can be used as they are, there is an advantage that the materials can be shared.

[0076]

EXAMPLES (Example 1) (1) Preparation and application and curing of a composition for a primer Commercially available aqueous emulsion polyurethane "Neo Sticker 700" (manufactured by Nichika Chemical Co., Ltd., solid content concentration 37%, non-yellowing type, acrylic) 165 g of modified polyurethane) and 330 g of methanol are added to dilute the solid content to 10%. This primer composition was applied to a plastic lens substrate CR-3.
9 (refractive index 1.50) by dipping (pulling speed 10c)
m / min). The coated base lens is 10
Heat-curing treatment at 0 ° C for 10 minutes to give a film thickness of 1.0μ on the substrate
m of primer layers were formed.

(2) Formation of Hard Coat Layer 157 g of isopropyl cellosolve and SiO ₂ fine particle sol dispersed with methyl cellosolve (manufactured by Catalyst Chemical Industry Co., Ltd.)
Brand name "Oscar 1832" solid content concentration 30wt%) 2
54 g and 69 g of γ-glycidoxypropyltrimethoxysilane were mixed. 19 g of a 0.1N aqueous hydrochloric acid solution was added dropwise to this mixture with stirring. After stirring for another 5 hours, 0.7 g of Fe (C ₅ H ₇ O ₂ ) ₃ and Mn (C ₅ H ₇
0.5 g of O ₂ ) ₃ and 0.15 g of a silicone-based surfactant (trade name “L-7604” manufactured by Nippon Unicar Co., Ltd.) were added, and the mixture was stirred for 4 hours and then aged all day and night.
Immersion method (pulling speed 20 cm / mi) on the plastic lens substrate on which the primer layer obtained in (1) is formed
n). The applied plastic lens substrate was heat-cured at 120 ° C. for 180 minutes to form a 2.5 μm-thick hard coat layer on the substrate.

Example 2 An antireflection film was formed on the plastic lens obtained in Example 1 as follows.

(3) Formation of Antireflection Thin Film Ion beam irradiation treatment with oxygen gas (acceleration voltage 500
After performing (V × 60 seconds), an antireflection multilayer film composed of five layers of SiO ₂ , ZrO ₂ , SiO ₂ , TiO ₂ , and SiO ₂ is sequentially deposited from the substrate to the atmosphere by a vacuum deposition method (Vacuum Instrument Industry Co., Ltd. Co., Ltd .; BMC-1000).
At this time, a fourth layer of TiO ₂ was formed by ion beam assisted vapor deposition. The optical film thickness of each layer deposited is the first S
iO ₂ , the next equivalent film layer of ZrO ₂ and SiO ₂ is λ / 4, T
The iO ₂ layer was formed so as to have λ / 2, and the uppermost SiO ₂ layer was formed so as to have λ / 4. The design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

(Example 3) (1) Preparation of a composition for primer and coating and curing A commercially available aqueous emulsion polyurethane "Neo Sticker 700" (manufactured by Nika Chemical Co., Ltd., solid content concentration 37%, non-yellowing type, acrylic-modified) Polyurethane) 103 g, a commercially available metal oxide sol “OPT Lake 1120Z (S-7,
G) "(manufactured by Catalyst Co., Ltd., solid content concentration: 20%) 1
85 g and 212 g of methanol were mixed and stirred well.
This composition was applied to a plastic lens substrate (refractive index 1.6).
No. 7 Seiko Super Sovereign (manufactured by Seiko Epson Corporation)) (with a pulling speed of 15 cm / mi)
n). The applied plastic lens substrate was heat-cured at 100 ° C. for 15 minutes to form a film having a film thickness of 1.
A 2 μm primer layer was formed.

(2) Formation of Hard Coat Layer A hard coat liquid for Seiko Super Sovereign (refractive index.
1.67) was applied to the plastic lens substrate on which the primer layer was formed by a dipping method (pulling speed: 30 cm / min). 125 applied plastic lens substrate
Heat curing at 120 ° C for 120 minutes to form a film with a thickness of 2.2μ on the substrate
m of the hard coat layer was formed.

(3) Formation of anti-reflection thin film The lens was subjected to plasma treatment (argon plasma 400 W ×
60 seconds), and sequentially from the substrate to the atmosphere, Z
An antireflection multilayer film composed of four layers of rO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ was vacuum-deposited (BM, manufactured by Vacuum Equipment Co., Ltd .: BM
C-1000), a film was formed at a film forming temperature of 250 ° C. The optical film thickness of each layer is the first ZrO ₂ and Si
O ₂ equivalent film layer, next ZrO ₂ layer, uppermost layer SiO ₂
The layers were formed so as to have a wavelength of λ / 4. The design wavelength λ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98.5%.

(Example 4) (1) Preparation and application and curing of a composition for primer Commercially available aqueous emulsion polyurethane "Neo Sticker 700" (manufactured by Nichika Chemical Co., Ltd., solid content concentration 37%, non-yellowing type, acrylic modified) Polyurethane) 76 g, 159 g of metal oxide sol "Optreak 1130F-2" (manufactured by Catalyst Chemicals, Inc., solid content concentration: 30%), methanol 2
65 g were mixed and stirred well. This composition was applied on a plastic lens substrate (Seiko Prestige having a refractive index of 1.74 (manufactured by Seiko Epson Corporation)) by an immersion method (pulling speed: 15 cm / min). The applied plastic lens substrate was at 100 ° C. A heat-curing treatment was performed for 15 minutes to form a 1.2 μm-thick primer layer on the substrate.

(2) Formation of Hard Coat Layer A hard coat layer was formed in the same manner as in Example 3.

(3) Formation of Antireflection Film An antireflection thin film was formed in the same manner as in Example 3.

(Comparative Example 1) A plastic lens was manufactured in the same manner as in Example 1, except that the processing was performed without forming the primer layer.

Comparative Example 2 Example 3 was repeated except that a primer layer was formed by the following method.
A plastic lens was produced by performing the same treatment as in the above.

(1) Preparation of composition for primer and coating and curing Commercially available aqueous emulsion polyurethane “Superflex 150” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 30%, non-yellowing type, ether / ester type) 130 g,
Commercially available metal oxide sol “OPTLAKE 1120Z (S-
7, G) "(manufactured by Catalyst Chemicals, Inc., solid content concentration: 20
%) And 265 g of methanol were mixed and stirred well. This composition is immersed on a plastic lens substrate (Seiko Super Sovereign having a refractive index of 1.67 (manufactured by Seiko Epson Corporation)) (pulling speed: 20 cm /
min). The applied plastic lens substrate was heat-cured at 100 ° C. for 15 minutes to form a 1.3 μm-thick primer layer on the substrate.

Comparative Example 3 The procedure of Example 4 was repeated except that the primer layer was formed in the following manner.
A plastic lens was produced by performing the same treatment as in the above.

(1) Preparation of primer composition and coating and curing Commercially available aqueous emulsion polyurethane "Superflex 150" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 30%, non-yellowing type, ether / ester type) 90 g, 154 g of a metal oxide sol "OPT Lake 1130F-2" (manufactured by Catalyst Chemicals, Inc., solid content concentration: 30%), and 256 g of methanol were mixed and thoroughly stirred. This composition,
It was applied on a plastic lens substrate (Seiko Prestige having a refractive index of 1.74 (manufactured by Seiko Epson Corporation)) by an immersion method (pulling speed: 15 cm / min). The applied plastic lens substrate was heat-cured at 100 ° C. for 15 minutes to form a 1.3 μm-thick primer layer on the substrate.

The following evaluation methods were performed on the plastic lenses obtained in these examples and comparative examples.

(A) Appearance: In a dark box, opacity, interference fringes and color tone (color unevenness) were observed with transmitted light and reflected light using a fluorescent lamp against a black background.

(B) Scratch resistance: 1 kg of Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
Was applied, and the surface of 10 reciprocations was rubbed, and the degree of damage was visually observed.

(C) Weather resistance: A sample having no change in the surface condition after exposure to a sunshine weather meter using a xenon lamp for 250 hours was evaluated as good.

(D) Moisture resistance: 1 in an atmosphere of 60 ° C. × 99%
After being left for 0 days, those having no change in the surface state were evaluated as good.

(E) Adhesion of surface-treated layer: The adhesion between the lens substrate and the surface-treated layer (hard coat layer and antireflection film) was determined in accordance with (c) and (d).
A cross cut tape test was performed according to ISD-0202. That is, cuts are made at 1 mm intervals on the base material surface using a knife, and 100 squares of 1 square mm are formed. Next, after strongly pressing a heserophan adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.), it was suddenly pulled away from the surface in the direction of 90 degrees, and then the remaining squares of the coating layer were adhered. It was visually observed as a sex index.

(F) Impact resistance: 16.3 g of hard spheres
The lens was naturally dropped from the height of 7 cm to the center of the convex surface of the lens, and cracking of the lens was confirmed. The center thickness of all lenses used in this test was 1.
It was 1 mm.

Table 1 shows the results.

[0099]

[Table 1]

Since the plastic lenses of Examples 1 to 4 have a primer layer using an aqueous acrylic-urethane resin, they are excellent in weather resistance, moisture resistance (water resistance) and impact resistance.

On the other hand, in Comparative Example 1 in which the primer layer was not formed, the weather resistance and the moisture resistance were excellent, but the impact resistance was poor. Further, in Comparative Examples 2 and 3 in which an ether / ester aqueous emulsion polyurethane was used as the primer composition, the weather resistance and the moisture resistance were slightly inferior to those of Examples.

[0102]

Since the plastic lens of the present invention has a primer layer using a specific urethane resin, it has excellent impact resistance, weather resistance and moisture resistance.

Continued on front page F-term (reference) 2K009 AA02 AA15 BB14 BB23 BB24 BB25 CC03 CC42 DD02 DD03 DD04 DD05 DD07 DD08 EE00 EE04 4J038 DG191 DG271 DG281 DG291 DG301 GA06 GA11 HA066 HA216 HA446 KA20 LA02 MA08 MA10 NA08

Claims (5)

[Claims] 1. A plastic lens having a plastic lens substrate, a primer layer formed on the plastic lens substrate, and a hard coat layer formed on the primer layer, wherein the primer layer is made to be aqueous. A plastic lens comprising an acrylic-urethane resin as a main component. 2. The plastic lens according to claim 1, wherein said primer layer is made of Si, Al, Sn, Sb, Ta,
A plastic lens comprising one or more oxide fine particles or composite fine particles of a metal selected from Ce, La, Fe, Zn, W, Zr, In, and Ti. 3. The plastic lens according to claim 1, further comprising an antireflection film on the hard coat layer. 4. The plastic lens according to claim 1, wherein the aqueous acryl-urethane resin is obtained by reacting an isocyanate group-containing urethane prepolymer with a chain extender in an aqueous phase to increase the molecular weight. A plastic lens, characterized in that: 5. The plastic lens according to claim 4, wherein the isocyanate group-containing urethane prepolymer is a self-emulsifying type containing a carboxyl group.