JPH11167002A - Plastic lens and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain a plastic lens having a scratching resistance, wear resistance, adhesion property to a lens base material and further impact resistance by forming a primer layer between the plastic lens base material and a hard-coating layer. SOLUTION: This plastic lens has the formed primer layer 12 on the surface of the plastic lens base material and is formed with hard-coating layer 13 thereon. The primer layer 12 includes polyvinyl acetal. The polyvinyl acetal of 0 to 20 in the carbon atoms of the satd. hydrocarbon group of the acetal part is usable and preferably has the carbon atoms from 0 to 10. The hard-coating layer 13 is deposited by applying an active energy ray curing type hard-coating liquid on the primer layer 12 formed on the base material 11, then curing the coating only by the irradiation with active energy rays or making combination use of the irradiation with the UV rays and heat treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to abrasion resistance, abrasion resistance,
The present invention relates to a plastic lens having excellent shock absorption and high durability and excellent practicality, and a method for producing the same.

[0002]

2. Description of the Related Art Plastic lenses have advantages such as light weight, easy workability, and easy dyeing, and are rapidly spreading in optical materials, particularly in the field of eyeglass lenses. However, plastic lenses generally have the disadvantage that they are easily damaged. Therefore, usually, a hard coat layer is formed on the surface of the plastic lens substrate to improve the scratch resistance and the wear resistance.

As a material for the hard coat layer, a material mainly containing an organic silicon compound is generally used.
In addition, a plastic lens substrate having a relatively low refractive index, in which the refractive index of the plastic lens substrate is about 1.5, contains fine particles of silica or the like in a coating liquid containing an organosilicon compound as a main component to be a hard coat layer. The added one is used. When using a high-refractive-index plastic lens substrate having a refractive index of 1.6 or more, titanium oxide, tin oxide,
What contains fine particles having a relatively high refractive index such as tungsten oxide is used.

[0004] In general, as a material of a hard coat layer formed on a plastic lens, a thermosetting type material has been often used. The thermosetting hard coat layer has been formed by applying a coating liquid to the surface of a plastic lens substrate and then performing a heat treatment for several hours to cure the coating liquid. on the other hand,
Recently, an ultraviolet-curable hard coat layer has been developed and is becoming popular. The ultraviolet-curable hard coat layer is disclosed in, for example, JP-A-6-279705 and JP-A-6-41468. These documents disclose that a coating liquid is applied on a plastic substrate to form a coating film, and then the coating film is cured by irradiating ultraviolet rays. The curing time is usually about several seconds to several minutes, and can be cured in a very short time as compared with the conventional thermosetting type, and is excellent in productivity.

[0005]

The present inventors formed a hard coat layer on the surface of a plastic lens substrate by using a thermosetting coating solution containing an organic silicon compound as a main component. As a result, as described above, the use of the thermosetting coating liquid has a problem that the curing time is long and the production efficiency is low.

Next, the durability of a plastic lens having a hard coat layer formed using a thermosetting coating solution was examined. As a result, abrasion resistance and abrasion resistance were improved, but there was a problem that impact resistance was significantly reduced. In order to solve this problem, the present inventors have tried to improve the impact resistance by increasing the center thickness of the plastic lens substrate. However, there has been a problem that the weight becomes heavy. In the case of a minus degree, there is a problem that the edge thickness is increased.

[0007] In order to solve these problems, the present inventors have replaced the conventional thermosetting hard coat layer with an ultraviolet curable hard coat layer. Then, the durability and the like were examined. As a result, it was found that the ultraviolet-curable hard coat layer formed on the plastic lens substrate had poor adhesion to the plastic lens substrate. In order to solve this problem, the present inventors performed a pretreatment such as a saponification treatment with an aqueous alkaline solution or a plasma treatment on the surface of the plastic substrate. However, although this method was effective for specific plastic materials, it was not possible to obtain sufficient adhesion to many types of plastic substrates. In order to solve this new problem, the composition of the coating solution was examined, but good results could not be obtained. Further, as a result of research, it was found that a hard coat layer having excellent adhesion to a plastic substrate had poor scratch resistance.

From the above research results, it is an object of the present invention to easily obtain a plastic lens having abrasion resistance, abrasion resistance, adhesion to a plastic lens substrate and impact resistance. .

[0009]

Means for Solving the Problems The present inventors first studied means for improving impact resistance. As a result, a primer layer was formed on the surface of the plastic substrate. Then, a material having good adhesion to the hard coat layer and various plastic materials was found. Accordingly, the present invention provides a plastic lens substrate, a primer layer containing polyvinyl acetal provided on the plastic lens substrate, and irradiation with only active energy rays provided on the primer layer, or irradiation with active energy rays. And a hard coat layer cured by heat treatment. Secondly, the present invention provides "the plastic lens according to claim 1, wherein the hard coat layer contains a photoinitiator (claim 2)." Thirdly, there is provided "a plastic lens according to claim 2, wherein the polyvinyl acetal contains polyvinyl butyral (claim 3)." Fourthly, the present invention provides “a plastic lens according to claim 1, wherein the breaking energy is 0.2 J or more (claim 4)”. Fifth, “a step of forming a primer layer containing an organic compound as a main component on a plastic lens substrate, an application step of applying a hard coat liquid on the primer layer, and a hard coat liquid applied by the application step” A step of irradiating active energy rays or irradiating with active energy rays and heating to cure the applied hard coat liquid to form a hard coat layer (claim 5). " provide.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A plastic lens according to the present invention has a structure as shown in FIG. In FIG. 1, reference numeral 11 denotes a plastic lens substrate. As the material of the plastic lens substrate, any type of resin such as a thermosetting resin, an ultraviolet curing resin, and a radiation curing resin can be used. Specifically, diethylene glycol bisallyl carbonate (CR-39), styrene, α-methylstyrene, chlorostyrene, phenyl methacrylate, phenyl acrylate, benzyl methacrylate, benzyl acrylate, naphthyl methacrylate, naphthyl acrylate,
Examples thereof include tetrabromobisphenol derivative (di) acrylate, tetrabromobisphenol derivative diallyl carbonate, methyl methacrylate, (di) ethylene glycol acrylate, vinylnaphthalene, and divinylbenzene. Also, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 2,3-
A reaction product of hydroxymethacrylate such as hydroxypropyl acrylate and polyfunctional (poly) isocyanate such as xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and cyclic trimer of hexamethylene diisocyanate, and di (2-mercaptoethyl) ether and pentane Reaction products of thiol compounds such as erythritol tetrakis-3-mercaptopropionate and 4-mercaptomethyl-3,6-dithia-1,8-octanediol with polyfunctional (poly) isocyanate or polyfunctional (poly) ene and these But not limited thereto.
In addition, the plastic lens substrate may be placed in a matrix after adding a polymerization initiator to the monomer, and may be polymerized by adding an initiator of heat or active energy ray or both.

The polymerization initiator which can be used in the present invention is not limited. For example, potassium peroxodisulfate, ammonium peroxodisulfate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, acetyl peroxide, Benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, diisopropylperoxycarbonate, t-butylperoxyneodecanoate, dimethyltin dichloride, biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoid, benzoin isobutyl ether, Benzyl dimethyl ketal, benzoyl peroxide, 1-hydroxycyclohexyl phenyl ketone, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, etc. Can be mentioned.

In FIG. 1, reference numeral 12 denotes a primer layer. Hereinafter, the present invention will be described in more detail. As the polyvinyl acetal represented by the general formula (I), which is a main component of the primer composition of the present invention, those having 0 to 20 carbon atoms in a saturated hydrocarbon group in the acetal portion can be used, and preferably 0 to 20.
To 10 and the carbon chain of the saturated hydrocarbon portion may not have a linear structure and may be branched. Particularly preferred is polyvinyl butyral in which the alkyl group has 3 carbon atoms.

[0013]

Embedded image

A polyvinyl acetal having a degree of acetalization of 10 to 90% can be used, and a polyvinyl acetal having a degree of acetalization of 20 to 80% is preferable. When the degree of acetalization of the polyvinyl acetal is less than 10%, the weather resistance is reduced, and the improvement of the impact strength is insufficient. Further, it is difficult to synthesize polyvinyl acetal having a degree of acetalization of 90% or more, and even if synthesized, a decrease in adhesion to a plastic substrate is expected.

The degree of polymerization of the polyvinyl acetal is preferably 5,000 or less, more preferably 10 or less.
0 to 3,000. When the average degree of polymerization of the polyvinyl acetal is more than 5,000, it is difficult to dissolve in a solvent, and it is difficult to synthesize a polyvinyl acetal having an optimum degree of acetalization. When the average degree of polymerization of the polyvinyl acetal is less than 100, the improvement of the impact strength becomes insufficient. The acetyl group in the polyvinyl acetal described in the formula (I) is not an essential component in the present invention, but a small amount remains because polyvinyl alcohol, which is a raw material of the polyvinyl acetal, is synthesized by hydrolysis of polyvinyl acetate. It is.

The content of polyvinyl acetal in the primer composition is preferably from 1 to 30% by weight, more preferably from 2 to 20% by weight. Polyvinyl acetal content of 3
If it is more than 0% by weight, the viscosity of the polyvinyl acetal resin solution becomes too high, making it difficult to apply the solution to a plastic lens, increasing the thickness of the applied primer layer or losing the uniformity of the applied surface. When the content of polyvinyl acetal is less than 1% by weight, the impact resistance becomes insufficient because the applied primer layer is thin.

[0017]

Embedded image

[0018]

Embedded image

The organosilane compound represented by the formula (II) or (III) is used as a crosslinking agent. A hydrolyzable group in the organosilane compound is hydrolyzed to generate a silanol group, which is dehydrated and condensed with a hydroxyl group in the polyvinyl acetal by the action of a catalyst and heat, thereby performing cross-linking between molecules or within a molecule. The molecule participating in the crosslinking is a hydrolyzate of an organosilane compound or a condensate thereof. The organosilane compound may be added as it is, or a compound that has been hydrolyzed in advance may be added. Further, one kind of organosilane compound may be used alone, or two or more kinds of organosilane compounds may be used in combination. Examples of the organosilane compound include a halosilane compound in which the hydrolyzing group is a halogen atom, an alkoxysilane compound in which the hydrolyzing group is an alkoxy group, a carboxysilane compound in which the hydrolyzing group is a carboxy group, or a ketoxime in which the hydrolyzing group is a ketoxime. Preferred are ketoxime silane compounds, which are groups, and more preferred are alkoxysilane compounds. Examples of the hydrolyzable organosilane compound represented by the general formula (II) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, γ-chloro Propylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, γ-
Methacryloxypropylmethyldimethoxysilane, γ-
Methacryloxypropylmethyldiethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltrisilane Ethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyltris (2-methoxyethoxy) silane, propyltrimethoxysilane, propyltrie Toxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane , Γ
-Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane Silane, (3,4-epoxycyclohexylmethyl) trimethoxysilane, (3,4-epoxycyclohexylmethyl) triethoxysilane, β- (3,4-epoxycyclohexylethyl) trimethoxysilane, β
-(3,4-epoxycyclohexylethyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Further, when the hydrolyzable organosilane compound represented by the general formula (III) is exemplified,
1-bis (trimethoxysilyl) ethane, 1,1-bis (triethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,3- Bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 2,2-bis (trimethoxysilyl) propane,
2,2-bis (triethoxysilyl) propane, and the like. The addition amount of the organosilane compound in the primer composition is preferably 0.01 to 30% by weight,
0.1-20% by weight is more preferred.

[0020]

Embedded image

The dialdehyde compound of the general formula (IV) or the acetal compound of the dialdehyde of the general formula (V) is also used as a crosslinking agent. In the case of a dialdehyde compound, an aldehyde group reacts with a hydroxyl group in polyvinyl acetal by the action of a catalyst or forms an acetal bond by an acetal exchange reaction with an alkyl acetal group. Since the dialdehyde compound has two aldehyde groups in the molecule, cross-linking between or within the molecules of the polyvinyl acetal is performed. That is, it is possible to crosslink three-dimensionally. In the case of an acetal compound of dialdehyde, it is considered that the cross-linking reaction mechanism is exactly the same as that of the dialdehyde, since it is in equilibrium with the corresponding dialdehyde in the presence of water and an acidic catalyst. The dialdehyde compound or the acetal compound of dialdehyde may be used alone, or two or more compounds may be used as a mixture. Specific examples of the dialdehyde compound represented by the general formula (IV) include glutaraldehyde, hexanedial, 2-hydroxyhexanedial, and the like.

[0022]

Embedded image

Examples of the dialdehyde acetal compound represented by the general formula (V) include malonaldehyde tetramethyl acetal, malonaldehyde tetraethyl acetal, glutaraldehyde tetramethyl acetal, glutaraldehyde tetraethyl acetal, and the like. The addition amount of the dialdehyde compound or acetal compound in the primer composition is 0.01 to
30% by weight is preferred, and 0.1-20% by weight is preferred.

In the case of a mixed system of a hydrolyzable organosilane compound and a dialdehyde compound, or a mixed system of a hydrolyzable organosilane compound and an acetal compound of dialdehyde, the mixture of the above-described dialdehyde compound or acetal compound of dialdehyde is used. A reaction similar to that of the hydrolyzable organosilane occurs in the mixed system. The amount of the dialdehyde compound or the acetal compound of the dialdehyde in the primer composition is 0.01 to 30% by weight.
However, it is preferably 50 mol% or less of the organosilane compound. When the addition amount of the dialdehyde compound or the acetal compound of the dialdehyde exceeds 50 mol% of the addition amount of the organosilane compound, the impact resistance decreases.

The curing catalyst is not particularly limited in a system using a hydrolyzable organosilane compound as a cross-linking agent, as long as it promotes the dehydration-condensation of the hydrolyzed silanol groups with the hydroxyl groups in the polyvinyl acetal. There is no. In a system using a dialdehyde compound or an acetal compound of dialdehyde as a crosslinking agent, there is no particular limitation as long as it accelerates an acetalization reaction between an aldehyde group and a hydroxyl group in polyvinyl acetal.

In a mixed system of a hydrolyzable organosilane compound and a dialdehyde compound or a mixed system of a hydrolyzable organosilane compound and an acetal compound of a dialdehyde, silanol formed by hydrolysis of the hydrolyzable organosilane compound is used. There is no particular limitation as long as it promotes the dehydration condensation between the group and the hydroxyl group in the polyvinyl acetal, and the acetalization reaction between the dialdehyde compound or the acetal compound of the dialdehyde and the hydroxyl group in the polyvinyl acetal.

An acidic catalyst is effective in any of the crosslinking agent systems. For example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, formic acid, acetic acid, benzoic acid, phthalic acid, methanesulfonic acid, benzenesulfonic acid, and alkyl groups having 1 carbon atom
And organic tin compounds such as dibutyltin laurate, dibutyltin octate, and dibutyltin acetate. Particularly preferred are inorganic acids such as hydrochloric acid and nitric acid, methanesulfonic acid, benzenesulfonic acid, p
Organic acids such as toluenesulfonic acid, and organic tin compounds. These may be used alone or as a mixture of two or more kinds of catalysts. The addition amount of the curing catalyst in the primer composition is 0.002 to 10% by weight.
Is preferable, and 0.005 to 5% by weight is more preferable.

As the organic solvent in the primer composition,
There are hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, and ethers, and other known solvents that dissolve polyvinyl acetal well are preferable. Especially methanol, ethanol, propanol, butanol, hexanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, tetrahydrofuran, dioxane, acetic acid, methyl acetate, ethyl acetate, and these are preferable. They may be used alone or as a mixture of two or more.

The thickness required for the primer layer is 0.0
5 to 5 μm. If the thickness is less than 0.05 μm, the impact resistance is remarkably poor, and if the thickness is more than 5 μm, the surface accuracy decreases. For the plastic lens provided with the primer layer, a hard coat layer can be formed by a known method to improve the surface hardness. In the method of forming the hard coat layer, a hydrolyzate of an organoalkoxysilane, a metal oxide fine particle, and a hard coat solution in which a metal complex catalyst is dissolved are applied by dipping or spin coating a lens, Then a wet method of heating and curing,
There is a dry method such as plasma CVD.

As the metal oxide fine particles, a commercially available sol of metal oxide fine particles dispersed in water or an organic solvent is used. Examples of the metal oxide fine particle sol include sols such as zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, and cerium oxide. These sols can be used by mixing at least one kind or more.

The thickness of the primer layer is about 0.05 μm to 10 μm. The primer layer can impart impact resistance to the plastic lens substrate. At the same time, since the plastic lens substrate made of various materials and the active energy ray-curable hard coat layer have excellent adhesion, good adhesion can be imparted to the active energy ray-curable hard coat layer. .

The adhesion of the primer layer of the present invention can be further improved by pre-treating the surface of the plastic lens substrate in advance. Examples of the pretreatment include saponification treatment with an aqueous alkali solution such as an aqueous sodium hydroxide solution, plasma irradiation, ultraviolet irradiation, and a combination thereof. If necessary, a particulate inorganic substance can be added to the primer layer. The addition of the finely divided inorganic substance makes it possible to control the refractive index of the layer. For example, when the refractive index is increased, particulate inorganic substances such as zinc oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, and cerium oxide can be used. These inorganic substances can be used alone or as a mixture, in the form of a complex compound of a plurality of compounds, or in the form of a solid solution. The primer layer of the present invention exhibits excellent adhesion to many types of active energy ray-curable resins.

Further, the plastic lens may be colored yellow when used for a long time. This is due to the fact that the plastic material is deteriorated by receiving ultraviolet rays. If an ultraviolet absorber is added to a plastic substrate to solve this deterioration, and a primer layer according to the present invention is formed, a lens having excellent shock absorption, adhesion, and high durability with little deterioration of the plastic can be obtained. Obtainable. It is also possible to add an ultraviolet absorber to the primer layer of the present invention. Examples of the ultraviolet absorber usable in the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
Benzotriazoles such as benzophenones such as 2,2'-hydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-allyloxybenzophenone, and ethyl And diphenyl acrylates such as -2-cyano-3,3-diphenyl acrylate; inorganic oxides such as zinc oxide, titanium oxide and cerium oxide; and mixtures thereof.

Reference numeral 13 in FIG. 1 is a hard coat layer.
In the present invention, the hard coat layer is coated with an active energy ray-curable hard coat liquid on a primer layer formed on a plastic substrate, and then cured only by irradiation with active energy rays, or irradiated with ultraviolet rays. The film is cured and formed into a film by using heat treatment together. The active energy rays in the present invention are visible light, ultraviolet light, infrared light, electron beam, X-ray, radiation and the like.

As an active energy ray source used for curing the hard coat layer, a light source such as a xenon lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a laser, and other electron beam sources, an X-ray source, and a radiation source can be used. It is.
The irradiation time of the active energy ray may be about several seconds to about 10 minutes, and is preferably within 5 minutes. If it is shorter than this, problems such as a decrease in abrasion resistance due to insufficient curing occur,
If it is longer than this, problems such as cracks will occur.

For hardening the hard coat layer, it is also possible to use heating together with the irradiation of the active energy ray as described above. In this case, heating can be performed before or after the irradiation of the active energy ray, or at any time during the irradiation. The heating temperature is preferably from room temperature to about 150 ° C, more preferably from room temperature to about 120 ° C.
If the temperature is lower than this, problems such as the inability to obtain a curing acceleration effect occur. If the temperature is higher than this, problems occur such as cracking and yellowing of the coating film. In this case, the heating time is preferably about several seconds to 10 minutes, and more preferably 5 minutes or less.

In the present invention, as the active energy ray-curable hard coat liquid, those which are generally used as a hard coat liquid composed of a photo-curable resin can be used. Specifically, acrylic resin, urethane acrylate resin ,
Epoxy acrylate resin, unsaturated polyester resin,
A phosphazene resin, a melamine resin, an acrylic silane resin, or the like can be used.

In the present invention, when curing by light, a photopolymerization initiator is added. When heating is used in combination, a thermal polymerization initiator is added. When curing is performed using an electron beam or radiation, these initiators may not be added. Also, when curing by the combination of light and heat,
The addition amount of the thermosetting catalyst is preferably the same as in the case of the thermosetting resin alone (conventional), but is not limited thereto, and the amount of the thermosetting catalyst is slightly smaller than in the conventional case. Is also good.

The photo-curing catalyst is used in an amount of about 0.01 to 5% with respect to a conventional hard coat liquid containing a thermosetting resin as a main component.
Although it is added, it is preferable to add 0.1 to 3%. Fine particles can also be added to the hard coat layer. Addition of fine particles to the hard coat layer has an effect of adjusting the refractive index of the hard coat layer and an effect of improving scratch resistance. Examples of usable fine particles include inorganic oxide fine particles such as zinc oxide, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, and cerium oxide. These inorganic oxide fine particles can be used alone or in a mixed state of a plurality of fine particles. Further, a composite state of a plurality of fine particles or a solid solution state can also be used.

An antireflection film or a water-repellent film on the hard coat layer,
It is possible to form a hydrophilic film. In general, a single-layer or multilayer anti-reflection film made of an inorganic oxide such as silicon oxide, titanium oxide, aluminum oxide, or zirconium oxide can be formed as the anti-reflection film. As a forming method, it can be formed by a dry method such as a vacuum evaporation method, a sputtering method, and a CVD method. By forming the antireflection film in this manner, an optical member having improved wear resistance, impact resistance, and antireflection performance can be easily manufactured.

As the water-repellent film, a fluorine-containing organic silicon compound can be used. Further, as the functional group of the organic compound, one having 1 to 3 functions can be used.
Those having a functional group such as an alkoxy group and an amino group can be preferably used. The water-repellent film is formed by a dipping method in which a substrate is immersed in a liquid water-repellent material, a wet method such as a spin coating method, a spray method, or a dry method such as a vacuum evaporation method, a sputtering method, or a CVD method. It is possible to By forming the water-repellent film, it becomes possible to easily manufacture an optical member having improved abrasion resistance, impact resistance and drainage prevention effect.

The hydrophilic film can be formed of a surfactant-coated film or a material containing a photocatalytic substance such as titanium oxide. As the formation method, the above-mentioned wet method and dry method can be used. The breaking energy in the present invention is based on the US FDA standard. That is, a plastic lens is set horizontally, and a steel ball having a mass of 16 g is freely dropped on the plastic lens from a position of a height of 127 cm, and whether or not the base material is cracked or cracked is determined. Also, the impact resistance is determined based on the fact that fragments do not scatter. In the present invention,
As a product using a material that hardens the hard coat layer by irradiation with active energy rays, a breaking energy of 0.2 J or more could be achieved.

The plastic lens of the present invention can be used not only for spectacle lenses but also for optical members such as cameras, binoculars and telescopes, and optical equipment. Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the description of these examples.

[0044]

Example 1 (1-1) Preparation of Coating Solution to be a Primer Layer Polyvinyl Butyral (Wako Pure Chemical Industries, Ltd.) 700
After dissolving 630 parts by weight of n-butanol in parts by weight,
400 parts by weight of methanol, 100 parts by weight of water, and 4.2 parts by weight of tetramethoxysilane as a cross-linking agent were added and stirred until the mixture became uniform. Next, 1.2 parts by weight of p-toluenesulfonic acid as a curing catalyst and a surfactant FC-430 (manufactured by Sumitomo 3M Limited) 1 as a leveling agent
The mixture was further added with parts by weight, stirred, and filtered through a 3 μm membrane filter to obtain a coating liquid to be a primer layer.

(1-2) The film forming frequency of the primer layer is -3.00 diopter and the center thickness is 1.0 mm
The CR-39 (diethylene glycol bisallyl carbonate) plastic lens required for spectacles was immersed in a 10% sodium hydroxide solution at 60 ° C. for 5 minutes, washed and pretreated. The coating solution prepared in the section (1-1) was applied to both surfaces of the pretreated plastic lens by dip coating.

Next, the plastic lens coated with the coating solution was heated at 100 ° C. for 15 minutes to cure the primer layer. (1-3) Formation of Hard Coat Layer After UVH-600, a UV-curable hard coat layer solution manufactured by Sanyo Chemical Industries, Ltd., was filtered through a 1 μm membrane filter, a primer layer was formed in the above (1-2). Both surfaces of the filmed plastic lens were applied by spin coating. The rotation speed in the spin coating method is 1,000 r
pm for 5 seconds, then 2,000 rpm for 5 seconds.

Next, both surfaces of the plastic lens on which the coating film was formed by the spin coating method were irradiated with ultraviolet rays for 2 minutes using a metal halide lamp. The temperature of the irradiation chamber was set to be 80 ° C. (1-4) Characteristic evaluation of plastic lens The characteristic evaluation of the plastic lens on which the primer layer and the hard coat layer obtained in (1-3) were formed was performed in the following procedure. The evaluation results are shown in Table 1.

(1-4-1) Evaluation of abrasion resistance The abrasion resistance of the plastic lens prepared in the above (1-3) was determined by rubbing the surface of the hard coat layer 10 times with steel wool (# 0000). The degree of scratching was evaluated according to the following criteria. A: The ratio of the scratched area to the rubbed area is 10% or less.

B: The percentage of the scratched area in the rubbed area is 10% or more and 30% or less. C: The ratio of the scratched area in the rubbed area is 30% or more. (1-4-2) Evaluation of Adhesion of Hard Coat Layer The adhesion was evaluated by a cross hatch tape test as follows. 1 with a cutter knife on the coating layer surface
A square grid of 100 mm square was made, and a cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) was strongly adhered. Then, one end of the tape was held, and the tape was vigorously peeled off in the direction of 90 degrees. Then, the number of grids on the surface of the coating layer remaining without being peeled was counted, and the number was expressed as X / X / 100. In this case, the larger the value of X, the better the adhesion, and a value of 100/100 means that the film was not peeled at all.

(1-4-3) Impact Absorption The impact resistance of the plastic lens was evaluated by a steel ball drop test. In this method, a 16 g steel ball was dropped freely from a height of 127 cm toward the center of a plastic lens surface placed horizontally, and the number of times the plastic lens was cracked or cracked was measured up to five times. .

[0051]

Embodiment 2 (2-1) Formation of Primer Layer In the same manner as in (1-1) and (1-2) of Embodiment 1,
A plastic lens made of CR-39 having a primer layer was prepared. (2-2) Formation of Hard Coat Layer After UV-curable hard coat layer solution HARDICRC-5120 manufactured by Dainippon Ink and Chemicals, Inc. was filtered through a 1 μm membrane filter, the primer layer was formed in the above (2-1). Spin coating was performed on both sides of the formed plastic lens. Spin coating rotation speed is 1,000 rpm
For 5 seconds, and then at 2,000 rpm for 5 seconds.

Ultraviolet rays were irradiated from both sides of the plastic lens after the spin coating for 2 minutes using a high-pressure mercury lamp. The room temperature of the irradiation room was set to 80 ° C. Further, after the completion of the ultraviolet irradiation, the film was heated at 80 ° C. for 3 minutes to form a hard coat layer. (2-3) Formation of anti-reflection film In a manner such that four layers of silicon oxide and zirconium oxide are alternately laminated on the surface of the plastic lens on which the primer layer and the hard coat layer obtained in (2-2) are formed. A film was formed by vacuum evaporation to form an antireflection film.

(2-4) Evaluation of Characteristics of Plastic Lens The characteristics of the plastic lens obtained in (2-3) were evaluated in the same procedure as in (1-4) of Example 1. The evaluation results are shown in Table 1.

[0054]

Example 3 (3-1) Preparation of Coating Solution to be Primer Layer Commercially available polyvinyl butyral resin having a butyralization degree of about 70% and an average polymerization degree of 700 (70 parts by weight of Wako Pure Chemical Industries, Ltd. -Dissolved in 250 parts by weight of butanol, and gradually added 150 parts by weight of a composite sol of a particulate inorganic substance composed of tin oxide and a particulate inorganic substance composed of tungsten oxide (manufactured by Nissan Chemical Industries, Ltd., methanol solvent dispersion).
Further, 100 parts by weight of water, 8.5 parts by weight of methyltrimethoxysilane as a crosslinking agent and 1 part by weight of glutaraldehyde,
1.2 parts by weight of p-toluenesulfonic acid as a curing catalyst and 1 part by weight of Florad FC-430, which is a fluorine-based surfactant as a leveling agent, are sequentially added, and the mixture is sufficiently stirred until the mixture becomes homogeneous. The solution was filtered through a 0.2 μm membrane filter to prepare a coating solution to be a primer layer.

(3-2) Formation of a Primer Layer A plastic lens for spectacles (Nikon NLIII) having a frequency of -2.00 diopter and a center thickness of 1.0 mm
Saponification treatment was performed for the purpose of enhancing the adhesion of the primer layer. The saponification treatment was performed by immersing the plastic lens in a 10% aqueous sodium hydroxide solution heated to 60 ° C. for 5 minutes and then washing the plastic lens. Thereafter, a coating solution to be a primer layer prepared in the above (3-1) was applied to both surfaces of the plastic lens by a dip coating method at a pulling rate of 8 mm / sec. The coated plastic lens was placed in a heating furnace and heated at 80 ° C. for 30 minutes to form a primer layer.

(3-3) Film formation of hard coat layer UV-curable hard coat liquid PPZ manufactured by Kyoeisha Chemical Co., Ltd.
-U-1000 was weighed in an amount of 45 g, and a 10% methanol solution 5 of a fluorine-based surfactant Florard FC-430 was added thereto.
g, and the mixture was stirred and filtered through a 1 μm membrane filter, and then spin-coated on both surfaces of the plastic lens on which the primer layer was formed in (3-2). The rotation speed of the spin coat is first performed at 1,000 rpm for 5 seconds,
Next, it was set to 2,000 rpm for 5 seconds. The plastic lens after the spin coating was heated at 100 ° C. for 3 minutes. Next, ultraviolet rays were irradiated from both sides for 2 minutes using a metal halide lamp. The temperature of the irradiation chamber is 100
° C.

(3-4) Evaluation of Characteristics of Plastic Lens The characteristics of the plastic lens obtained in (3-3) were evaluated in the same procedure as in (1-4) of Example 1. The evaluation results are shown in Table 1.

[0058]

Example 4 (4-1) Preparation of Coating Solution to be a Primer Layer A coating solution for a primer layer was prepared in the same procedure as in (3-1) of Example 3. (4-2) The film formation frequency of the primer layer is -4.00 diopter, and the center thickness is 1.0 mm.
Plastic lenses for eyeglasses (Nikon N manufactured by Nikon Corporation)
LIII) First, to enhance the adhesion of the primer layer, a plasma reactor PR501 manufactured by Yamato Scientific Co., Ltd.
Using A, plasma irradiation was performed for 20 seconds under the conditions of an oxygen gas pressure of 0.4 Torr and an output of 100 W. Thereafter, the coating liquid to be a primer layer prepared in the above (4-1) was applied to both surfaces of the plastic lens by a dip coating method. The lifting speed of the plastic lens at this time is 8
The measurement was performed at a speed of mm / sec. Thereafter, the plastic lens was placed in a heating furnace and heat-treated at 80 ° C. for 30 minutes to cure the primer layer.

(4-3) Formation of Hard Coat Layer UV-curable hard coat liquid KZ manufactured by Nippon Synthetic Rubber Co., Ltd.
2510 was filtered through a membrane filter having a 1 μm mesh, and then applied to both surfaces of the plastic lens on which the primer layer was formed in (4-2) by a dipping method. Then, using a low-pressure mercury lamp, the hard coat layer was cured by irradiating ultraviolet rays for 3 minutes from both sides of the plastic lens after dip coating.

(4-4) Formation of antireflection film On the surface of the plastic lens obtained in (4-3), four layers of silicon oxide and zirconium oxide were alternately vacuum-deposited to form an antireflection film. (4-5) Characteristic evaluation of plastic lens The characteristic evaluation of the plastic lens obtained in (4-4) was performed in the same procedure as (1-4) of Example 1. The evaluation results are shown in Table 1.

[0061]

Comparative Example 1 A plastic lens was manufactured in the same manner as in Example 1 except that the primer layer was not formed in the section (1-2). However, prior to the application of the coating liquid to be a hard coat layer, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 60 ° C. for 5 minutes and washed as a pretreatment for the purpose of improving the adhesion. All other steps were the same as in Example 1. The evaluation results are shown in Table 1.

[0062]

Comparative Example 2 A plastic lens was produced in the same manner as in Example 2 except that the primer layer was not formed in the item (2-1). However, prior to the application of the coating liquid to be a hard coat layer, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 60 ° C. for 5 minutes and washed as a pretreatment for the purpose of improving the adhesion. All other steps were the same as in Example 2. The evaluation results are shown in Table 1.

[0063]

Comparative Example 3 A plastic lens was manufactured in the same manner as in Example 3, except that the formation of the primer layer in the section (3-2) was not performed. However, prior to the application of the coating liquid to be a hard coat layer, the substrate was immersed in a 10% aqueous solution of sodium hydroxide at 60 ° C. for 5 minutes and washed as a pretreatment for the purpose of improving the adhesion. All other operations were the same as in Example 3. The evaluation results are shown in Table 1.

[0064]

Comparative Example 4 A plastic lens was produced in the same manner as in Example 4, except that the formation of the primer layer in the section (4-2) was not carried out. However, prior to the application of the coating liquid to be a hard coat layer, a plasma reactor PR501A manufactured by Yamato Scientific Co., Ltd. was used as a pretreatment for the purpose of improving the adhesiveness at an oxygen gas pressure of 0.4 Torr and an output of 100 W for 20 seconds. And plasma irradiation.
Otherwise, the procedure was the same as in Example 4. The evaluation results are shown in Table 1.

[0065]

Comparative Example 5 In Example 2, items (2-1) and (2)
-2) The plastic lens which does not perform the process of the item 2;
A plastic lens formed of only the antireflection film of item (2-3) of the plastic lens consisting of 39 was produced.
The characteristic evaluation was performed in the same manner as in Example 2. Table 1 shows the evaluation results.
Shown in

[0066]

[Table 1]

[0067]

As described above, according to the present invention, a primer layer is provided between a plastic lens substrate and a hard coat layer cured by irradiation with active energy rays or a combination of irradiation with active energy rays and heat treatment. By providing, a plastic lens having excellent scratch resistance, abrasion resistance and adhesion can be provided. In particular, the plastic lens of the present invention satisfies the US FDA impact resistance standard and has a breaking energy of about 0.2 J or more.
It has sufficient impact resistance for practical use, and can withstand severe use conditions and use environments.

Furthermore, the primer layer according to the present invention exhibits good adhesion to both various plastic materials and ultraviolet-curable hard coat layers. It has become possible to provide a plastic lens having a hard coat layer having good adhesion to various types of plastic substrates. Further, since the hard coat layer of the present invention is a hard coat layer cured by irradiation with active energy rays or a combination of irradiation with active energy rays and heat treatment, the hard coat layer is formed using a conventional thermosetting resin. Since it can be cured in a shorter time than the formation of a layer, a plastic lens having excellent scratch resistance, abrasion resistance and impact resistance can be efficiently and easily manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view of the plastic of the present invention.

[Explanation of symbols]

 11 ... Plastic base material 12 ... Primer layer 13 ... Active energy ray-curable hard coat layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoko Takehara 3-2-2 Marunouchi, Chiyoda-ku, Tokyo Nikon Corporation

Claims (5)

[Claims] 1. A plastic lens substrate, a polyvinyl acetal-containing primer layer provided on the plastic lens substrate, and irradiation with only active energy rays provided on the primer layer, or irradiation with active energy rays And a hard coat layer cured by heat treatment. 2. The plastic lens according to claim 1, wherein said hard coat layer contains a photoinitiator. 3. The plastic lens according to claim 2, wherein the polyvinyl acetal contains polyvinyl butyral. 4. The plastic lens according to claim 1, wherein the breaking energy is 0.2 J or more. 5. A step of forming a primer layer containing an organic compound as a main component on a plastic lens substrate, a step of applying a hard coat solution on the primer layer, and a step of applying a hard coat liquid by the applying step. Irradiating the liquid with an active energy ray or irradiating with an active energy ray and heating to cure the applied hard coat liquid to form a hard coat layer.