JP2003195003A - Plastic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plastic lens by using a transparent resin prepared by curing a polymerizable composition containing sulfur and to provide a plastic lens having a primer layer giving excellent weather resistance and adhesion property with surface treatment layers, a hard coat layer and an antireflection film. <P>SOLUTION: The primer layer consists of a polyester resin and specified metal oxide fine particles The hard coat layer formed on the primer layer comprises specified metal oxide fine particles, a specified organic silicon compound and acetylacetonate having Fe (III) as the center metal atom. Further, the antireflection film has a specified film structure. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens, more specifically, a primer layer, a hard coat layer, and an inorganic antireflection film on the surface of a transparent resin obtained by curing a polymerizable composition containing sulfur. Various quality (appearance, scratch resistance,
The present invention relates to a plastic lens having excellent heat resistance, humidity resistance, impact resistance, weather resistance, adhesion between transparent resin and surface treatment layer, durability, etc.).

The following description will be made by taking a plastic lens for eyeglasses as an example, but the present invention is not limited to this.

[0003]

Plastic lenses are widely used in the field of spectacle lenses because they are lighter in weight than glass lenses, have good moldability, workability, dyeability, are hard to break and have high safety. However, since the plastic lens is soft and very easily damaged, a hard coat layer with high hardness is provided on the surface of the plastic lens to improve scratch resistance.
Further, in some cases, an antireflection film formed by depositing an inorganic substance is provided on the surface of the hard coat layer for the purpose of preventing surface reflection. In recent years, development of plastic lens base materials with high refractive index has progressed, and it is possible to reduce the center thickness and edge thickness of the lens, but plastic lenses with high refractive index have low impact resistance and are easily cracked. Has drawbacks,
In particular, in the case of a lens having a minus power with a thin center thickness, the impact resistance is remarkably reduced, and the lens is liable to break. If the central thickness is increased to improve this, the peripheral portion of the lens (edge thickness) becomes extremely thick, which is not desirable in appearance. In addition, the weight of the lens becomes heavy, and the usability of the eyeglasses deteriorates, which is not preferable in practice. In order to improve the impact resistance of a lens having a high refractive index, there is a method of providing a primer layer between the plastic lens substrate and the hard coat layer. 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 resin for this primer layer, the impact resistance of the plastic lens can be improved. . By such surface treatment of the plastic lens, the quality of the plastic lens is high. In recent years, as the development of plastic lens base materials having a high refractive index has progressed, the surface treatment technology for plastic lenses corresponding thereto has become important.

[0004]

A thiourethane resin (having a refractive index of 1.
60 or more), thioepoxy resin (refractive index 1.70 or more)
Etc., but these contain sulfur in the molecule to increase the refractive index. The transparent resin obtained by curing the polymerizable composition containing these sulfur is generally inferior in weather resistance, and the lens substrate turns yellow with the passage of time,
Further, the adhesion of the surface treatment layer is lowered, the surface treatment layer is peeled off, and the appearance tends to be unfavorable. Therefore, the present invention has various qualities (appearance, scratch resistance, heat resistance, moisture resistance, impact resistance, weather resistance, adhesion between the lens substrate and the surface treatment layer,
Durable plastic lens, especially weather resistance,
The purpose of the invention is to provide a plastic lens having excellent adhesion.

[0005]

The present invention provides a primer layer formed on a transparent resin obtained by curing a polymerizable composition containing sulfur, and a hard coat layer formed on the primer layer. It was found that this object was achieved by using specific components in the primer layer and the hard coat layer in the plastic lens.

The plastic lens of claim 1 is a plastic having a primer layer formed on a transparent resin obtained by curing a polymerizable composition containing sulfur and a hard coat layer formed on the primer layer. In the lens, the primer layer comprises at least the following component (A),
A coating composition comprising (B) as a main component, wherein the hard coat layer contains at least the following components (B), (C) and (D) as main components. A plastic lens comprising a coating composition. (A). Polyester resin (B). Al, Sn, S with a particle size of 1-100 mm
b, Ta, Ce, La, Fe, Zn, W, Zr, In,
Fine particles composed of one or more metal oxides selected from Ti and / or Si, Al, Sn, Sb, Ta, Ce,
Composite fine particles composed of two or more metal oxides selected from La, Fe, Zn, W, Zr, In and Ti

(C). General formula

[Chemical 2] (Wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolyzable group, and n is Is 0 or 1.) (D). Acetylacetonate containing Fe (III) as the central metal atom

By using the component (A) as the component of the primer layer, it is possible to improve the adhesion of the entire surface-treated layer and also improve the impact resistance of the high refractive index plastic lens. Further, by using the component (B) in the primer layer and the hard coat layer, it is possible to suppress the yellowing of the plastic base material, the refractive index difference between the plastic base material and the primer layer, and the primer layer and the hard coat layer. The difference in the refractive index of the layers can be adjusted, and there is an effect of improving the deterioration of the appearance due to the generation of interference fringes. The component (C) as a component of the hard coat layer is a component for forming a matrix of the hard coat layer, and the scratch resistance can be adjusted by the type and amount thereof. Further, it is possible to improve the adhesion of the entire surface treatment layer. By using the component (D) as the component of the hard coat layer, it is possible to improve the adhesiveness of the entire surface treatment layer, and it also functions as a curing catalyst for the hard coat.

The plastic lens of claim 2 is the same as that of claim 1.
In the plastic lens described in (1), further, a low-refractive index layer and a high-refractive index layer are alternately laminated, and an antireflection film consisting of 7 layers is laminated. λ ₀ is 480 nm or more 56
Within the range of 0 nm or less, the low refractive index layer is composed of a SiO ₂ layer and the high refractive index layer is composed of a TiO ₂ layer. The outer layer is the seventh layer, the refractive index at the design dominant wavelength of each layer is nk (k is each layer number), and the optical film thickness is λk (k
Is the layer number), the refractive index of each layer is 1.43 ≦ n1, n3, n5, n7 ≦ 1.48 2.24 ≦ n2, n4, n6 ≦ 2.45, and the optical index of each layer is When the design dominant wavelength is λ ₀ , the film thickness is 0.05λ ₀ ≦ λ ₁ ≦ 0.10 λ ₀ 0.05λ ₀ ≦ λ ₂ ≦ 0.09λ ₀ 0.08λ ₀ ≦ λ ₃ ≦ 0.11λ ₀ 0 14λ ₀ ≦ λ ₄ ≦ 0.24λ ₀ 0.04λ ₀ ≦ λ ₅ ≦ 0.09λ ₀ 0.11λ ₀ ≦ λ ₆ ≦ 0.18λ ₀ 0.24λ ₀ ≦ λ ₇ ≦ 0.29λ ₀ A plastic lens for spectacles having a certain antireflection film.

By using a TiO ₂ layer as the high refractive index layer of the antireflection film, it is possible to suppress yellowing of the plastic substrate and also to improve scratch resistance. As the antireflection film, the optical film thickness (λ ₁
~ Λ ₇ ) is preferably within the above range. If the optical film thickness (λ _{1 to} λ ₇ ) of each layer deviates from the above range, the interference color of the antireflection film changes and a good appearance cannot be obtained. Function is impaired. Also in terms of durability, the internal stress balance of the film is lost, so that the adhesion of the entire surface treatment layer is reduced.

The plastic lens of the present invention is a plastic lens provided with a primer layer formed on a transparent resin obtained by curing a polymerizable composition containing sulfur, and a hard coat layer formed on the primer layer. In the lens, a specific component is used for the primer layer and the hard coat layer, but as the transparent resin obtained by curing the polymerizable composition containing sulfur, a conventionally known one can be used, Examples thereof include polythiourethane (thiourethane resin) and polythioepoxy (thioepoxy resin). The polyester resin as the component (A) contained in the primer layer formed on the transparent resin obtained by curing the polymerizable composition containing sulfur is composed of dicarboxylic acids and glycols. Is phthalic acid, 2,6-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid,
Linear saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, decamethylenedicarboxylic acid, and octadecanedicarboxylic acid; aliphatic oxocarboxylic acids such as ε-oxycaproic acid; and ester-forming derivatives thereof. To be Examples of glycols include aliphatic glycols such as ethylene glycol, trimethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butanediol and neopentyl glycol,
Examples thereof include aliphatic glycols such as 1,6-cyclohexanedimethanol, poly (1,2-butadiene glycol), poly (1,4-butadiene glycol) and hydrogenated products thereof, and ester-forming derivatives thereof.
Further, ε-caprolactone (C6), enanthlactone (C7) and caprolilolactone (C8) are also useful as the polyester component.

The primer layer and hard coat of the present invention
Particle size of component (B) commonly used in layers 1 to 100 mm
Micron Al, Sn, Sb, Ta, Ce, La, F
One or more selected from e, Zn, W, Zr, In and Ti
Of metal oxides of Si and / or Si, A
l, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
Two or more metal oxides selected from Zr, In and Ti
As a specific example of the composite fine particles composed of
₂O₃, SnO₂ , Sb₂O_Five, Ta₂O_Five, CeO₂ , La
₂O₃, Fe₂O₃, ZnO, WO₃ , ZrO₂ , In₂O₃
 , TiO₂ The inorganic oxide fine particles of
Colloid in water, alcohol or other organic solvent
It is dispersed in a shape. Or SiO₂ , Al₂
O₃, SnO₂ , Sb ₂O_Five, Ta₂O_Five, CeO₂ , La₂
O₃, Fe₂O₃, ZnO, WO₃ , ZrO₂ , In
₂O₃, TiO₂ Consisting of two or more inorganic oxides
If the composite fine particles are water, alcohol, or other
It is a colloidal dispersion in an organic solvent. Furthermore
In order to improve dispersion stability in the coating solution,
The particle surface is treated with an organosilicon compound or an amine compound.
It is also possible to use an intelligent one. Used at this time
There is a monofunctional silane as the organosilicon compound.
Ia bifunctional silane, trifunctional silane, tetrafunctional silane
Etc. Treat with no hydrolyzable groups
Alternatively, it may be hydrolyzed. After processing
Is a state in which the hydrolyzable group reacts with the -OH group of the fine particles.
It is preferable, but there is no stability problem even if it remains partially
There is no. As the amine compound, ammonium or
Is ethylamine, triethylamine, isopropylamine
Alkylamines such as amine and n-propylamine, benzyl
Aralkylamines such as amines and alicyclic amines such as piperidine
Min, monoethanolamine, triethanolamine, etc.
There are alkanolamines. These organosilicon compounds
And the amount of amine compound added is from 1 to the weight of fine particles.
It is necessary to add within the range of about 15%. All are particles
The diameter is preferably about 1 to 300 mμ, and the coater of the present invention is used.
The coating type and amount used in the coating composition is the desired coating performance.
However, the amount used is 10% of the solid content.
It is desirable to be 70% by weight. That is, 10 layers
If the amount is less than%, the adhesion to the inorganic vapor deposition film will be insufficient.
Or, the scratch resistance of the coating film becomes insufficient. Again 7
If it exceeds 0% by weight, cracks occur in the coating film. continue
In the component (C) used for the hard coat layer, R₁ Is
An organic group having a polymerizable reactive group, such as a vinyl group or an
Ryl group, acrylic group, methacrylic group, epoxy group, mel
Polymerization of capto group, cyano group, isocyano group, amino group, etc.
A silane compound having a possible reactive group, R₂ Is carbon
The hydrocarbon groups of the numbers 1 to 6, as specific examples thereof
Is a methyl group, ethyl group, butyl group, vinyl group, phenyl group
And the like. Also X₃ Is a hydrolyzable functional group
And specific examples thereof include a methoxy group and ethoxy.
Group, alkoxy group such as methoxyethoxy group, chloro group,
Examples include halogen groups such as bromo and acyloxy groups.
It

Specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane and methacryl. Oxypropyl dialkoxymethyl silane, γ-glycidoxy propyl trialkoxy silane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxy silane, mercapto propyl trialkoxy silane, γ-amino propyl trialkoxy silane, N-β (Aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like. You may use these in mixture of 2 or more types. The amount of component (C) used is
It is desirable to be 20 to 60% by weight of the total composition. That is, if it is less than 20% by weight, the adhesiveness to the inorganic vapor deposition film tends to be insufficient. If it exceeds 60% by weight,
It is not preferable because it causes cracks in the cured film. Component (D) Fe (II) used in the hard coat layer
Acetylacetonate containing I) as the central metal atom not only acts as a curing catalyst, but also improves the transparency and curability of the coating film obtained by thermosetting a composition containing high refractive index metal fine particles as a main component. It not only provides excellent performance but also has the function of extending the life of the coating liquid. In particular, when the high refractive index metal fine particles contain titanium oxide, the effect is further exhibited. Further, it also affects the adhesiveness, and in consideration of the adhesiveness, the range of 100 to 300 ppm is desirable.

In the plastic lens of the present invention, when an antireflection film is further laminated, it is desirable that the low-refractive index layers and the high-refractive index layers are alternately laminated to laminate the antireflection film of 7 layers. When forming the TiO ₂ layer, the pressure in the vacuum chamber is set to 3.0 × 10 ⁻³ Pa by vapor deposition while assisting oxygen ions and introducing oxygen gas or argon gas for adjusting the degree of vacuum. ~ 6.0 x 10 ^-3 P
It is desirable to keep it in the range of a. A stress is generated in the antireflection film due to the film thickness balance of the formed layers, which causes instability in adhesion and appearance. That is, when the internal stress of the antireflection film, which is the result of the combination of the stresses of the SiO ₂ layer and the TiO ₂ layer, is large, the adhesiveness varies and the appearance deteriorates. It is generally said that when formed by vacuum evaporation, the SiO ₂ film has a compressive stress and the TiO ₂ film has a tensile stress. However, since the film formed by the ion assisted vapor deposition method tends to have a small internal stress, the SiO ₂ film formed by the electron beam heating vapor deposition method and the TiO ₂ film formed by the ion assisted vapor deposition method. When combined with the film, most of the stress in the compression direction of the SiO ₂ film remains as the internal stress of the antireflection film. Regarding the adhesion and appearance of the anti-reflection film, when the stress in the compression direction becomes large, it causes the force to distort the film, causing fine irregularities on the surface to deteriorate the appearance and the force in the direction of peeling the film from the substrate. Causes a decrease in adhesion. Internal from these studies, adhesion and the to stabilize appearance make the TiO ₂ layer having a tensile stress can offset the compressive stress of the SiO ₂ layer, antireflection film by adjusting the thickness of each layer It was found that reducing the stress is effective. The cause of the stress in the film formed by the vacuum evaporation method is the thermal contraction that occurs when the evaporated atoms that reach the substrate are cooled and the volume change accompanying the phase transition from the gas phase to the solid phase. It is considered that it is because the atoms constituting the deposited film substance are stacked while the interatomic distance is deviated from the energetically stable state. The stress can be divided into two depending on the direction in which the force acts, the force acting in the direction in which the contracted one tries to spread is the compressive stress, and the force acting in the contracted one in the direction to contract the tensile stress. is there. Which stress the formed film has is largely determined by the material of the film, and the main materials having compressive stress include SiO ₂ and ZnS, and most other materials including TiO ₂ . The substance is a substance having tensile stress. In the case of a multilayer film such as an antireflection film, the internal stress is the sum of the effects of the internal stress of each layer. If this is extremely inclined in the direction of compressive stress or the direction of tensile stress, distortion or cracking of the film will occur, so it is important to balance the internal stress in order to improve the durability and appearance of the film. On the other hand, since the film formed by the ion assisted vapor deposition method has good crystallinity, the internal stress tends to be small. In view of the above, in the anti-reflection film formed by laminating alternately an SiO ₂ layer and the TiO ₂ layer, will be referred to as a tensile stress of the TiO ₂ layer being deposited by ion-assisted deposition is reduced, SiO ₂ Since the tensile stress that cancels the compressive stress of the layer is reduced, the internal stress of the antireflection film is greatly inclined in the compressive stress direction. This compressive stress is a cause of instability of adhesion and generation of fine irregularities on the surface. Hereinafter, further details will be described with reference to examples.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

(Example 1) (1) Preparation of primer composition and coating curing Commercially available polyester resin ... "Peth Resin A-160P"
(Takamatsu Yushi Co., Ltd., water dispersion emulsion, solid content concentration
27%) 100 parts of titanium oxide composite fine particles
Lake 1130F-2 (A-8) "(Catalyst Chemical Co., Ltd.
Made by Shiki Company, Fe ₂ O₃ / TiO₂ = 0.02, SiO₂ 
/ TiO₂ = 0.11, particle size: 10 mμ, solid content concentration:
30%, dispersion solvent: methyl alcohol, surface treatment: Tet
Laethoxysilane) 84 parts, methylal as a diluent solvent
640 parts of call, silicone type interface as leveling agent
Activator ("SILWET L-77" made by Nippon Unicar)
Mix 1 part, stir until homogeneous and press well.
It was a composition for a limer. This primer composition is
Polyurethane lens base material of urethane resin (refractive index 1.
67 Seiko Super Sovereign (Seiko Epson Corporation
Dipping method (lifting speed 20 cm / mi)
n) was applied. The coated lens substrate is 1 at 100 ℃
Heat-curing treatment for 5 minutes and 0.8 μm primer on the substrate
Layer was formed.

(2) Preparation and Hardening of Hard Coat Composition 144 parts of butyl cellosolve, methanol-dispersed titanium dioxide-zirconium dioxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 20% by weight) 60
After mixing 3 parts, 170 parts of γ-glycidoxypropyltrimethoxysilane was mixed. 0.0 to this mixture
60 parts of 5N hydrochloric acid aqueous solution was added dropwise with stirring, and further 4
After stirring for one day and aging for one day and night, 0.2 part of Fe (III) acetylacetonate and 0.3 part of a silicon-based surfactant (Nippon Unicar Co., Ltd., trade name "L-7001") were added. After stirring for an hour, the mixture was aged overnight to give a coating liquid.

This composition was applied onto the plastic lens substrate having the primer layer obtained in (1) by the dipping method (withdrawing speed 20 cm / min). The coated plastic lens substrate was 120 ° C. for 120 minutes. A heat-curing treatment was performed to form a hard coat layer having a film thickness of 2.1 μm on the substrate. The pulling rate was 18 cm / min. After coating, it was air-dried at 80 ° C. for 20 minutes and then baked at 130 ° C. for 120 minutes.

(3) Formation of Antireflection Film An antireflection film was constructed on the plastic lens substrate having the primer layer and the hard coat layer obtained in (2). The SiO ₂ layer is formed by vacuum vapor deposition (vacuum degree 2.0 ×
It was performed at 10 ⁻⁴ Pa). The TiO ₂ layer was formed by the ion-assisted vapor deposition method (vacuum degree 4.0 × 10 ⁻³ Pa).
The ion assist conditions for forming the TiO ₂ layer by ion assist deposition are an acceleration voltage of 520 V and an acceleration current value of 270.
The degree of vacuum was set to mA and the pressure was maintained at 4.0 × 10 ⁻³ Pa by introducing oxygen. Counting from the base material side, the first layer is 0.
SiO ₂ layer having an optical thickness of 083λ ₀ (refractive index 1.4
5), the second layer is TiO ₂ with an optical thickness of 0.070λ ₀
Layer (refractive index 2.36), the third layer is a SiO ₂ layer having an optical thickness of 0.10λ ₀ , the fourth layer is a TiO ₂ layer having an optical thickness of 0.18λ ₀ , and the fifth layer is 0. The SiO ₂ layer having an optical thickness of 0.065λ ₀ , and the sixth layer T having an optical thickness of 0.14λ ₀
The SiO ₂ layer and the seventh layer are SiO 2 having an optical thickness of 0.26λ _0.
An antireflection film was constructed by sequentially stacking _two layers.

(Example 2) (1) Preparation of composition for primer and coating curing The titanium oxide-based composite fine particles of Example 1 were converted to titanium oxide-based composite fine particles (Catalyst Kasei Kogyo Co., Ltd., Optraque 112).
0Z (S-7, G), ZrO ₂ / TiO ₂ = 0.02,
SiO ₂ / TiO ₂ = 0.22, particle size: 10 mμ, solid content concentration: 20%, dispersion solvent: methyl alcohol, surface treatment: γ-glycidoxypropyltrimethoxysilane) 5
A primer layer was formed in the same manner as in Example 1 except that the amount was changed to 7 parts.

(2) Preparation of Hard Coat Composition and Coating and Hardening The hard coat layer was formed in the same manner as in Example 1.

(3) Formation of antireflection film An antireflection film was formed in the same manner as in Example 1.

(Embodiment 3) In Embodiment 1, except that the plastic lens base material is changed to a plastic lens base material of thiourethane resin (Seiko Super Lucious (made by Seiko Epson Corporation) having a refractive index of 1.60). The same processing as in Example 1 was carried out to produce a plastic lens.

Example 4 (1) Preparation and Coating and Curing of Composition for Primer In Example 2, the plastic lens substrate was a plastic lens substrate of thioepoxy resin (Seiko Prestige with a refractive index of 1.74 (Seiko Epson Corporation). The same treatment as in Example 1 was carried out except that the product was changed to (made by the company)) to form a 0.8 μm primer layer on the plastic lens substrate.

(2) Preparation of hard coat composition and coating curing Methanol 94.1 parts, 1,4-dioxane 62.7
Parts, 590.4 parts of methylcellosolve-dispersed titanium dioxide-iron trioxide-silicon dioxide composite fine particle sol (manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 20% by weight), and then γ-
170 parts of glycidoxypropyltrimethoxysilane and 21.9 parts of tetramethoxysilane were mixed. To this mixed solution, 59.2 parts of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight. 0.2 parts of Fe (III) acetylacetonate and a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-
7001 ") 0.3 part and hindered amine light stabilizer (manufactured by Sankyo Co., Ltd., trade name [Sanol LS-770])
0.5 part was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid. This composition was applied onto the plastic lens substrate having the primer layer obtained in (1) by the dipping method (pulling speed: 20 cm / min). The coated plastic lens substrate was heat-cured at 120 ° C. for 120 minutes. Then, a hard coat layer having a thickness of 2.4 μm was formed on the substrate. After coating, air dry at 80 ° C for 20 minutes and then at 130 ° C for 12 minutes.
Firing was performed for 0 minutes.

(3) Formation of antireflection film An antireflection film was formed in the same manner as in Example 1.

(Embodiment 5) In Embodiment 1, except that the plastic lens base material is changed to a plastic lens base material of thioepoxy resin (Seiko Prestige (manufactured by Seiko Epson Corporation) having a refractive index of 1.74). The same treatment as in 1 was performed to produce a plastic lens.

(Comparative Example 1) (1) Preparation of composition for primer and coating curing Commercially available polyester resin ... "Pethresin A-160P"
(Takamatsu Yushi Co., Ltd., water-dispersed emulsion, solid content concentration 27%) 150 parts, 640 parts of methyl alcohol as a diluting solvent, and 1 part of a silicone-based surfactant (“SILWET L-77” manufactured by Nippon Unicar) as a leveling agent. The mixture was mixed and stirred until a uniform state was obtained, which was used as a primer composition. This primer composition was applied onto a plastic lens substrate of thioepoxy resin (Seiko Prestige having a refractive index of 1.74 (manufactured by Seiko Epson Corporation)) by a dipping method (pulling speed: 20 cm / min). The applied lens substrate was heat-cured at 100 ° C. for 15 minutes to form a 1.0 μm primer layer on the substrate.

(2) Preparation and Coating and Hardening of Hard Coat Composition 144 parts of butyl cellosolve and 603 parts of colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd., solid content concentration 20% by weight) were mixed, and then γ-glycid 170 parts of xypropyltrimethoxysilane were mixed. To this mixed solution, 60 parts of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight. Then, 0.2 part of Al (III) acetylacetonate and a silicon-based surfactant (Nippon Unicar ( Co., Ltd., trade name "L-7001") (0.3 parts) was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid.

This composition was applied onto the plastic lens substrate having the primer layer obtained in (1) by the dipping method (withdrawing speed 20 cm / min). The coated plastic lens substrate was 120 ° C. for 120 minutes. A heat-curing treatment was performed to form a hard coat layer having a thickness of 2.4 μm on the substrate. After coating, it was air-dried at 80 ° C. for 20 minutes and then baked at 130 ° C. for 120 minutes.

(3) Formation of Antireflection Film An antireflection film was constructed on the plastic lens substrate having the primer layer and the hard coat layer obtained in (2). The SiO ₂ layer is formed by vacuum vapor deposition (vacuum degree 2.0 ×
It was performed at 10 ⁻⁴ Pa). The TiO ₂ layer was formed by an ion assisted vapor deposition method (vacuum degree 2.0 × 10 ⁻³ Pa).
The ion assist conditions for forming the TiO ₂ layer by ion assist deposition are an acceleration voltage of 520 V and an acceleration current value of 270.
The degree of vacuum was set to mA and maintained at 2.0 × 10 ⁻³ Pa by introducing oxygen. Counting from the base material side, the first layer is 0.
SiO ₂ layer having an optical thickness of 083λ ₀ (refractive index 1.4
5), the second layer is TiO ₂ with an optical thickness of 0.070λ ₀
Layer (refractive index 2.36), the third layer is a SiO ₂ layer having an optical thickness of 0.10λ ₀ , the fourth layer is a TiO ₂ layer having an optical thickness of 0.18λ ₀ , and the fifth layer is 0. The SiO ₂ layer having an optical thickness of 0.065λ ₀ , and the sixth layer T having an optical thickness of 0.14λ ₀
The SiO ₂ layer and the seventh layer are SiO 2 having an optical thickness of 0.26λ _0.
An antireflection film was constructed by sequentially stacking _two layers.

(Comparative Example 2) In Comparative Example 1, except that the plastic lens substrate was changed to a thiourethane resin plastic lens substrate (Seiko Super Lucious (made by Seiko Epson Corporation) having a refractive index of 1.60). The same processing as in Comparative Example 1 was performed to produce a plastic lens.

The following evaluation methods were performed on the plastic lenses obtained in these examples and comparative examples. (A) Appearance: White turbidity and interference fringes were observed in transmitted light and reflected light using a fluorescent lamp in a dark box with a black background. (B) Scratch resistance: A load of 1 kg was applied with Bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), the surface was rubbed for 10 reciprocations, and the degree of scratching was visually observed. (C) Weather resistance: A sample having no change in surface condition after being exposed to a sunshine weather meter with a xenon lamp for 250 hours was regarded as good. (D) Humidity resistance test: After being left in an atmosphere of 60 ° C. × 99% for 10 days, those having no change in surface condition were regarded as good. (E) Adhesion of surface-treated layer: The adhesion between the lens substrate and the surface-treated layer (primer layer, hard coat layer and antireflection film) is measured according to JISD for those tested in (c) and (d). A cross-cut tape test was conducted according to -0202. That is, 1 on the substrate surface using a knife
Make cuts at mm intervals and make 100 squares per square mm.
Form individually. Then, after strongly pressing a cellophane adhesive tape (trade name "Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) on the surface, the film was left to have a coat layer after being peeled off rapidly by 90 degrees from the surface. The cells were visually observed using the squares as an adhesion index. (F) Impact resistance test: 16.3 g of hard balls were naturally dropped from the height of 127 cm to the center of the convex surface of the lens, and cracking of the lens was confirmed, and those without cracking or cracking were evaluated as good. The center thickness of all lenses used in this test was 1.2 mm. The results are shown in Table 1.

[0034]

[Table 1]

The plastic lenses of Examples 1 to 5 are excellent in weather resistance and adhesiveness because the antireflection film has a well-balanced film structure by containing specific components in the primer layer and the hard coat layer. In contrast, Comparative Examples 1 and 2 are slightly inferior in weather resistance and adhesion to the Examples.

[0036]

The plastic lens of the present invention comprises a primer layer using a specific component on a transparent resin obtained by curing a polymerizable composition containing sulfur, and a specific layer formed on the primer layer. Since it has a hard coat layer containing components, it has excellent weather resistance and adhesion.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/10 G02B 1/10 A 1/11 Z F term (reference) 2K009 AA02 AA09 AA15 BB25 CC03 CC09 CC34 CC38 CC42 CC47 DD02 DD03 4J038 DD001 HA216 JC32 JC38

Claims (2)

[Claims] 1. A plastic lens comprising a primer layer formed on a transparent resin obtained by curing a sulfur-containing polymerizable composition and a hard coat layer formed on the primer layer. The layer comprises a coating composition characterized by containing at least the following components (A) and (B) as main components, and the hard coat layer further comprises at least the following components (B), (C) and (D): ) A plastic lens comprising a coating composition characterized by containing (4) as a main component. (A). Polyester resin (B). Al, Sn, S with a particle size of 1-100 mm
b, Ta, Ce, La, Fe, Zn, W, Zr, In,
Fine particles composed of one or more metal oxides selected from Ti and / or Si, Al, Sn, Sb, Ta, Ce,
Composite fine particles (C) composed of two or more kinds of metal oxides selected from La, Fe, Zn, W, Zr, In and Ti. General formula [Chemical formula 1] (Wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolyzable group, and n is Is 0 or 1.) (D). Acetylacetonate containing Fe (III) as the central metal atom 2. The plastic lens according to claim 1, further comprising a low-refractive index layer and a high-refractive index layer alternately laminated to form an antireflection film of 7 layers. The antireflection film has a designed main wavelength λ _0.
In the range of 480 nm to 560 nm, the low refractive index layer is composed of a SiO ₂ layer, and the high refractive index layer is Ti.
An O ₂ layer, the layer closest to the base material is numbered in order as the first layer, the outermost layer is the seventh layer, and the refractive index at the design dominant wavelength of each layer is nk (k is each layer number),
When the optical film thickness is λk (k is each layer number), the refractive index of each layer is 1.43 ≦ n1, n3, n5, n7 ≦ 1.48 2.24 ≦ n2, n4, n6 ≦ 2.45. There is a relationship, and the optical film thickness of each layer is 0.05λ ₀ ≦ λ ₁ ≦ 0.10 λ ₀ 0.05λ ₀ ≦ λ ₂ ≦ 0.09λ ₀ 0.08λ ₀ ≦ λ, where λ _{0 is the} design dominant wavelength. ₃ ≦ 0.11λ ₀ 0.14λ ₀ ≦ λ ₄ ≦ 0.24λ ₀ 0.04λ ₀ ≦ λ ₅ ≦ 0.09λ ₀ 0.11λ ₀ ≦ λ ₆ ≦ 0.18λ ₀ 0.24λ ₀ ≦ λ ₇ ≦ A plastic lens for spectacles, which has an antireflection film having a relationship of 0.29λ ₀ .