JP2009157304A - Lens and manufacturing method of the lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lens having high contact for hard coating layer and an antireflection layer, and to provide a manufacturing method therefor. <P>SOLUTION: The lens 1 comprises a lens base material 11, the hard coating layer 12 formed on the lens base material 11, the antireflection layer 14 formed on the hard coating layer 12, and a contact layer 13 provided in between the hard coat layer 12 and the antireflection layer 14, and the contact layer 13 has the same or substantially the same refractive index as that of the harding coat layer 12. It is preferable that the thickness of the contact layer 13 be 0.5 μm or larger and 5 μm or smaller. Also, it is preferable that the contact layer 13 be formed from a composition, containing silica sol at 5 mass% or higher, and at 20 mass% or lower by solid content weight ratio. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a lens having a hard coat layer and an antireflection layer, and a method for producing the same.

Plastic lenses are lighter than glass lenses, have excellent moldability, processability, dyeability, etc., and are highly resistant to breakage. For this reason, it has spread rapidly in the eyeglass lens field, and occupies most of it.
However, since plastic lenses are more easily damaged than glass lenses, generally, a hard coat layer is formed on a lens substrate to improve surface hardness. An antireflection layer is provided on the hard coat layer for the purpose of preventing surface reflection. Furthermore, an antifouling layer is often formed on the antireflection layer.

Here, if the hardness of the hard coat layer is insufficient, the lens is easily damaged, and the hard coat layer may be peeled off from the lens substrate. Therefore, a harder hard coat layer is required.
For example, a method using an acetylacetone Al (III) salt catalyst is known as a method for obtaining a hard coat layer with high hardness.
However, there is a problem that the unreacted groups are reduced and the adhesion between the hard coat layer and the antireflection layer is deteriorated by increasing the degree of crosslinking by the acetylacetone Al (III) salt catalyst.

  Here, in the antireflection film described in Patent Document 1, adhesion between the hardcoat layer and the antireflection layer is improved by providing a primer layer between the hardcoat layer and the antireflection layer.

Japanese Patent Laid-Open No. 2002-6103

However, the antireflection film described in Patent Document 1 intends to suppress the refractive index of the primer layer and also use the primer layer as a part of the antireflection layer. For this reason, it was necessary to make the thickness of a primer layer thin, and there existed a possibility that adhesiveness with a hard-coat layer might fall.
Moreover, even if the dual use as an antireflection layer was given up and the primer layer was thickened, interference fringes might be generated due to the difference in refractive index from the hard coat layer.

  Therefore, an object of the present invention is to solve the above-described problems and provide a lens having high adhesion between a hard coat layer and an antireflection layer, and a method for producing the same.

  The lens of the present invention comprises a lens substrate, a hard coat layer formed on the lens substrate, an antireflection layer formed on the hard coat layer, the hard coat layer, and the antireflection layer. An adhesive layer provided therebetween, wherein the adhesive layer has the same or substantially the same refractive index as the hard coat layer.

According to the present invention, since the adhesion layer is provided between the hard coat layer and the antireflection layer, the adhesion between the hard coat layer and the antireflection layer can be improved.
Here, since the refractive index of the adhesion layer and the refractive index of the hard coat layer are the same or substantially the same, the generation of interference fringes can be prevented. This makes it possible to increase the thickness of the adhesion layer and further improve the adhesion between the hard coat layer and the antireflection layer.
Further, due to the presence of the adhesion layer, it is possible to employ a hard coating layer having a high hardness, which has been a problem of insufficient adhesion. By adopting a hard coating layer with high hardness, it is possible to provide a high-quality lens that is less susceptible to scratches and peeling.

In the lens of the present invention, the thickness of the adhesion layer is preferably 0.5 μm or more and 5 μm or less.
According to such a configuration, sufficient adhesion between the hard coat layer and the antireflection layer can be obtained with an appropriate thickness of the adhesion layer.
Here, when the thickness of the adhesion layer is less than 0.5 μm, it is not preferable because sufficient adhesion cannot be obtained. On the other hand, if the thickness of the adhesion layer exceeds 5 μm, the smoothness of the lens surface may be impaired or optical distortion may occur, which is not preferable.

In the lens of the present invention, it is preferable that a primer layer is provided between the lens substrate and the hard coat layer.
According to such a configuration, the adhesion between the lens substrate and the hard coat layer can be improved by the primer layer.
Not only between the hard coat layer and the anti-reflection layer by the adhesion layer, but also the adhesion between the lens substrate and the hard coat layer can be improved. A quality lens can be provided.

In the lens of the present invention, it is preferable that the adhesion layer is formed of a composition containing silica sol having a solid content weight ratio of 5% by mass or more and 20% by mass or less.
According to such a configuration, sufficient adhesion between the hard coat layer and the antireflection layer can be obtained.

  The method for producing a lens of the present invention is a method for producing the above-described lens, wherein the hard coat layer is formed on the lens substrate, and the adhesion is performed after the hard coat layer formation step. An adhesive layer forming step for forming a layer, wherein the hard coat layer forming step and the adhesive layer forming step are performed in the same or substantially the same procedure except for the material used.

  According to the present invention, since the hard coat layer forming step and the adhesion layer forming step are performed in the same or substantially the same procedure except for the materials to be used, it is possible to simplify the manufacturing process and efficiently manufacture the lens. .

In the lens manufacturing method of the present invention, the hard coat layer forming step and the adhesion layer forming step are preferably performed by dipping.
According to such a configuration, since the hard coat layer forming step and the adhesion layer forming step are performed by dipping, which is a simple and general method, the lens can be manufactured more efficiently.

According to the present invention, the adhesion between the hard coat layer and the antireflection layer can be improved by the adhesion layer.
Since the refractive index of the adhesion layer and the refractive index of the hard coat layer are the same or substantially the same, the generation of interference fringes can be prevented, and the adhesion can be further improved by thickening the adhesion layer. .
Further, by improving the adhesion, a hard coating layer having a high hardness can be adopted, and a high-quality lens that hardly causes scratches or peeling can be provided.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The optical article and the manufacturing method thereof according to the present invention are not limited to the following embodiments.

[Lens configuration]
In FIG. 1, the outline of the laminated structure of the lens 1 of this embodiment is shown. 1A shows a schematic laminated structure of the lens 1, and FIG. 1B shows a schematic laminated structure of the antireflection layer 14.
Note that the lens 1 of the present embodiment is a spectacle lens.

  As shown in FIG. 1A, the lens 1 includes a lens substrate 11, a hard coat layer 12 formed on the lens substrate 11, an antireflection layer 14 formed on the hard coat layer 12, An adhesion layer 13 provided between the hard coat layer 12 and the antireflection layer 14 and an antifouling layer 15 provided on the antireflection layer 14 are provided.

The lens substrate 11 may be made of plastic and is not particularly limited, but it is preferable to use a transparent material having a refractive index of 1.6 or more.
For example, it is produced by polymerizing and curing a polythiourethane plastic produced by reacting a compound having an isocyanate group or isothiocyanate group with a compound having a mercapto group, or a raw material monomer containing a compound having an episulfide group. An episulfide plastic or the like can be used as a material for the lens substrate 11.

The hard coat layer 12 is formed on the lens substrate 11 and improves the scratch resistance of the lens 1.
The thickness of the hard coat layer 12 is preferably in the range of 1.5 μm or more and 10 μm or less.
Here, when the thickness of the hard coat layer 12 is less than 1.5 μm, the strength of the lens 1 cannot be sufficiently increased, which is not preferable.

The adhesion layer 13 is provided between the hard coat layer 12 and the antireflection layer 14 and improves the adhesion between them.
The refractive index of the adhesion layer 13 is the same as or substantially the same as the refractive index of the hard coat layer 12.
The thickness of the adhesion layer 13 is preferably 0.5 μm or more and 5 μm or less.
Here, it is not preferable that the thickness of the adhesion layer 13 is less than 0.5 μm because sufficient adhesion cannot be obtained. On the other hand, if the thickness of the adhesion layer 13 exceeds 5 μm, the smoothness of the surface of the lens 1 may be impaired or optical distortion may occur, which is not preferable.

The antireflection layer 14 has a single-layer or multi-layer structure composed of an inorganic composition. The antireflection layer 14 can reduce the light reflectance and improve the light transmittance. As the inorganic material constituting the anti-reflection layer _{14, SiO 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 or the like can be used. These inorganic materials can be used alone or as a mixture of two or more.
The antireflection layer 14 of this embodiment has five inorganic composition layers 14A to 14E as shown in FIG. In the antireflection layer 14, an inorganic composition having a high refractive index and an inorganic composition having a low refractive index are alternately laminated. For example, inorganic composition layer 14A, 14C, 14E are formed with SiO _2, the inorganic composition layer 14B, 14D may be formed of ZrO _2.
The antifouling layer 15 is, for example, a water repellent layer for repelling water droplets. As the water repellent for forming the water repellent layer, for example, a fluorine-based water repellent is preferably used.

[Lens manufacturing method]
FIG. 2 shows a flowchart of the manufacturing method of the lens 1 of the present embodiment.
As shown in FIG. 2, the manufacturing method of the lens 1 of the present embodiment includes a hard coat layer forming step S12 for forming the hard coat layer 12 on the lens substrate 11, and the adhesion layer 13 after the hard coat layer forming step. An adhesion layer forming step S13 to be formed, an antireflection layer forming step S14 for forming an antireflection layer, and an antifouling layer forming step S15 for forming an antifouling layer are provided.

[1. Hard coat layer forming step S12 and adhesion layer forming step S13]
The hard coat layer forming step S12 includes a first applying step S121 for applying a hard coat layer forming composition to be described later to the lens substrate 11, and a drying step S122 for drying the applied hard coat layer forming composition. Have.
The adhesion layer forming step S13 includes a second coating step S131 for applying a composition for forming an adhesion layer, which will be described later, to the lens base material 11 on which the composition for forming a hard coat layer after the drying step S122 is applied, and the applied adhesion layer. A main firing step S132 for drying the forming composition and heating the lens substrate 11 to complete the hard coat layer and the adhesion layer.
Thus, the hard coat layer forming step S12 and the adhesion layer forming step S13 are performed in the same or substantially the same procedure except for the materials used.

[1-1. First application step S121 and second application step S131]
FIG. 3 shows the dipping apparatus 100 used for the first coating step S121 and the second coating step S131.
The first coating step S121 and the second coating step S131 are performed by dipping using the dipping apparatus 100.
As shown in FIG. 3, the dipping device 100 includes a first liquid storage tank 101 for storing a hard coat layer forming composition or an adhesion layer forming composition (hereinafter abbreviated as a coating composition), In order to return the coating composition from the third storage tank 103 to the first storage tank 101, the second storage tank 102 and the third storage tank 103 that receive the coating composition overflowing from the first storage tank 101. Pump 104, a filter 105 for filtering out foreign substances, and a holding jig 106 that holds the lens substrate 11 and moves up and down.

The liquid level of the first liquid storage tank 101 is always kept at a constant height.
Moreover, the 2nd liquid storage tank 102 and the 3rd liquid storage tank 103 are connected, and the coating composition collected in the 2nd liquid storage tank 102 flows into the 3rd liquid storage tank 103 by inclination. The coating composition accumulated in the third liquid storage tank 103 is forcibly returned to the first liquid storage tank 101 by the pump 104. At that time, the filter 105 filters out foreign substances such as dust that cause coating defects. Since the foreign matter mainly collects on the liquid surface of the coating composition, the foreign matter can be effectively removed by filtering the overflowed coating composition.

The lens substrate 11 is held at three locations by the holding jig 106 so that the plate surface is substantially perpendicular to the liquid surface of the first liquid storage tank 101.
The holding jig 106 is supported by a support unit that can be moved up and down (not shown), and the lifting speed of the support unit can be appropriately set by a control device (not shown).
A preferable pulling speed is about 50 to 500 mm / min, and more preferably about 100 to 400 mm / min.
The lens substrate 11 is immersed in the coating composition stored in the first liquid storage tank 101 and left for a while, and then lifted to form a coating film. A preferable immersion time is about 10 to 60 seconds.

  In addition, with respect to the lens base material 11 to be applied, the surface is previously treated with an alkali treatment, an acid treatment, a surfactant treatment, an inorganic or an inorganic material for the purpose of improving the adhesion with the coating film before dipping. It is preferable to carry out polishing treatment, primer treatment or plasma treatment with organic fine particles. Further, it is preferable to perform cleaning with ultrapure water.

[1-2. Drying step S122 and main firing step S132]
The drying of the coating film in the drying step S122 and the main baking step S132 can be performed by appropriate means such as natural drying or a dryer. The coating film can be appropriately dried by drying at a temperature of 40 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower for 30 minutes or longer and 8 hours or shorter.
The main baking step S132 can be performed using a general heating device such as a heating furnace.
The firing temperature is preferably 50 to 250 ° C, more preferably 80 to 150 ° C.

[2. Antireflection layer film forming step S14 and antifouling layer film forming step S15]
In the antireflection layer film forming step S14, the above-described inorganic composition layers 14A to 14E are formed by a vacuum deposition method, an ion plating method, a sputtering method, or the like. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used.
In the antifouling layer film forming step S15, the antifouling layer 15 as a water repellent layer made of a fluorine-based water repellent is formed on the antireflection layer 14 by vacuum deposition or the like.

[3. Hard coat layer forming composition and adhesion layer forming composition]
The composition for forming a hard coat layer and the composition for forming an adhesion layer (hereinafter abbreviated as coating composition) of the present invention are (A) an organic silica containing a polymerizable group and a hydrolyzable group in one molecule. An elemental compound, (B) metal oxide fine particles, (C) a low-viscosity organic solvent, and (D) a curing catalyst and disilane as necessary.

The component (A) is a so-called binder in the coating composition.
Examples of the polymerizable group contained in the component (A) include a vinyl group, an allyl group, an acrylic group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group.
Examples of the hydrolyzable group contained in the component (A) include alkoxy groups such as methoxy group, ethoxy group and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.

  Examples of the component (A) include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, and methacryloxypropyl. Dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (amino And ethyl) -γ-aminopropylmethyl dialkoxysilane.

The blending amount of the component (A) is 10% by weight to 90% by weight, particularly 20% by weight to 80% by weight, and most preferably 30% by weight to 70% by weight, based on the solid content. Is preferred.
If the blending amount is too small, the adhesion to the lens 1 and the antireflection layer 14 may be deteriorated. On the other hand, if the blending amount is too large, cracks may occur in the cured film.

The component (B) functions as a so-called filler in the hard coat layer 12 and the adhesion layer 13.
As the component (B), those having a particle size of about 1 μm to 100 μm are generally used.
As the component (B), specifically, fine particles of one kind of metal oxide selected from Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti, or 2 Examples include composite fine particles of more than one kind of metal oxide. Specific examples of the metal oxide include SiO ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe ₂ O ₃ , ZnO, WO ₃ and ZrO _2. In ₂ O ₃ and TiO ₂ can be exemplified.

In addition, in order to improve the dispersion stability of the component (B) in the coating composition, it is also possible to use a component obtained by treating the surface of the fine particles of the component (B) with an organosilicon compound or an amine compound.
Examples of the organosilicon compound used for the surface treatment include monofunctional silane, trifunctional silane, and tetrafunctional silane.
In the treatment, a state in which the hydrolyzable group reacts with the hydroxyl group of the fine particles is preferable, but there is no problem in stability even in a state in which a part remains.
Examples of amine compounds include ammonium, ethylamine, triethylamine, isopropylamine, alkylamines such as n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine, etc. Can be illustrated.
The addition amount of these organosilicon compounds and amine compounds is preferably in the range of about 1% by mass to 15% by mass with respect to the weight of component (B).

  The metal oxide fine particles used as the component (B) are generally supplied in a colloidal dispersion in a dispersion medium such as water, alcohol, cellosolve or the like. Since the selection of the dispersion medium affects the viscosity of the coating composition of the present invention, the type thereof will be described later together with the description of the organic solvent.

The blending amount of the component (B) in the coating composition is 20% by mass or more and 80% by mass or less, particularly 30% by mass or more and 70% by mass or less, and most preferably 40% by mass or more and 60% by mass or less. preferable.
If the blending amount is reduced, the viscosity of the composition is lowered, but it may not be possible to secure a film thickness sufficient to form the hard coat layer and the adhesion layer coating, while the blending amount is large. If too much, cracks may occur in the coating.

Component (C) is for reducing the viscosity of the coating composition.
As the component (C), specifically, alcohols such as methanol (viscosity 0.59) and ethanol (viscosity 1.17), acetone (viscosity 0.316), MEK (viscosity 0.423 ( 15)), 2-pentanone (viscosity 0.473 (25 ° C)), MIBK (viscosity 0.542 (25 ° C)), 2-heptanone (viscosity 0.80), ketones, methyl acetate (Viscosity 0.385), ethyl acetate (viscosity 0.449), propyl acetate (viscosity 0.585), isopropyl acetate (viscosity 0.569), butyl acetate (viscosity 0.697), isobutyl acetate (Viscosity 0.697), sec butyl acetate, isopentyl acetate (viscosity 0.87), methyl propionate (viscosity 0.50 (25 ° C)), butyl propionate (viscosity 0.76 (25 ° C)) ), 3-me Examples thereof include esters such as xylbutyl acetate (viscosity 0.96), 1,4-dioxane (viscosity 1.31), and the like. One of these may be used alone or in combination of two or more. it can.

  As the high viscosity solvent to be diluted, cellosolves such as methyl cellosolve (viscosity 1.72), ethyl cellosolve (viscosity 2.05), butyl cellosolve (viscosity 3.15 (15 ° C.)), isopropyl cellosolve, etc. It is preferable from the viewpoint of coating film performance. These low-viscosity solvent and high-viscosity solvent are used as a dispersion medium for the colloidal metal oxide fine particles described above or as a diluent for the coating composition.

Further, the amount of the component (C) in the coating composition is 60% by mass or more and 90% by mass or less, particularly 70% by mass or more and 80% by mass or less, in order to ensure the film thickness necessary for the hard coat layer 12 and the adhesion layer 13 The following are appropriate.
If the amount of the solid content is reduced, the viscosity of the coating composition can be lowered even with a conventional high-viscosity solvent. However, in this case, it becomes impossible to secure the film thickness necessary for the hard coat layer 12 and the adhesion layer 13. Therefore, in the coating composition, the amount of solid content in the whole is suitably in the range of 10% by mass to 40% by mass, particularly 20% by mass to 30% by mass.

Examples of the component (D) include the following groups (1) to (4).
That is,
(1) acetylacetonate having a central atom of a metal element of Fe (III), Al (III), Sn (IV) or Ti (IV),
(2) Magnesium perchlorate or ammonium perchlorate,
(3) Saturated or unsaturated carboxylic acids of fatty acids, aromatic carboxylic acids, or anhydrides of these acids,
(4) acetylacetonate having a central atom of a metal atom of LI (I), Cu (II), Mn (II) or Mn (III),
One or more selected from the above can be used in combination.
In particular, a combined catalyst of the curing catalyst of the group (1) to (3) and the curing catalyst of the group (4) is preferable as the component (D) because the pot life is improved.

The blending amount of the component (D) is preferably in the range of 0.2 mass% to 10 mass%, particularly 0.5 mass% to 3 mass% of the coating composition in terms of solid content weight ratio.
If the blending amount is too small, the blending effect may not appear. On the other hand, even if the blending amount is increased, the curing rate does not improve any more, which may be uneconomical.

In order to further increase the curing rate, it is preferable to blend a disilane compound that functions as a curing accelerator together with a curing catalyst. By using the curing catalyst and the disilane compound in combination, the curing rate can be sufficiently increased even when the curing rate is slow due to a dye component such as an epoxy compound described later.
As a disilane compound, the compound represented by following formula (1) can be illustrated, for example.

In formula (1), R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms, X ² and X ³ are hydrolyzable groups, and Y is an organic group containing a carbonate group or an epoxy group. And k and m are 0 or 1.
Examples of the hydrocarbon group having 1 to 6 carbon atoms of R ³ and R ⁴ include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. Examples of the hydrolyzable group for X ² and X ³ include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups.
Moreover, the following can be illustrated as an organic group containing the carbonate group or epoxy group of Y.

These disilane compounds can be synthesized by a conventionally known method.
For example, it can be obtained by addition reaction of diallyl carbonate and trichlorosilane and then alkoxylation.
Alternatively, it can be obtained by addition-reacting trichlorosilane or the like to a compound having a substituent that can be added at both ends and further containing a functional group that can be epoxidized therein, followed by alkoxylation.

By blending the disilane compound, the curing rate can be improved, and defects such as wrinkles and fogging of the coating film can be prevented.
Further, if the curing speed is improved and the curing time is shortened, the yield can be improved by reducing the possibility of dust and impurities adhering to the coating film surface in the first coating step S121 and the second coating step S131. it can.
Furthermore, there is an effect of improving dyeability, an effect of reducing the blending amount of the polyfunctional epoxy compound described below, or an effect of making the presence of defective parts such as scratches present on the surface of the object to be applied inconspicuous. .

The blending amount of the disilane compound is preferably in the range of 3% by weight to 40% by weight, particularly 5% by weight to 20% by weight, based on the solid content.
If the blending amount is too small, the reaction promoting effect may not appear. On the other hand, if the blending amount is too large, the water resistance of the coating film may be deteriorated or the pot life of the coating composition may be shortened.

The coating composition may further contain a polyfunctional epoxy compound as a dyeing component and to improve water resistance and warm water resistance.
This polyfunctional epoxy compound is widely used for paints, adhesives, casting and the like.
As the polyfunctional epoxy compound, for example, a polyolefin-based epoxy resin synthesized by a peroxidation method, cyclopentadiene oxide or cyclohexene oxide, and an alicyclic epoxy resin such as polyglycidyl ester obtained from hexahydrophthalic acid and epichlorohydrin, From polyhydric phenols such as bisphenol A, catechol, and resorcinol, or polyhydric alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol and epichlorohydrin Polyglycidyl ether obtained, epoxidized vegetable oil, epoxy novolac obtained from novolac type phenolic resin and epichlorohydrin, phenol lid An epoxy resin obtained from in and epichlorohydrin, a copolymer of glycidyl methacrylate and a methyl methacrylate acrylic monomer or styrene, and a glycidyl group ring-opening reaction of the epoxy compound with a monocarboxylic acid-containing (meth) acrylic acid. An epoxy acrylate etc. are mentioned.

  The polyfunctional epoxy compounds 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, neopentyl glycol hydroxyhybalic acid ester Diglycidyl ether, trimethylolpropane Glycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, dipentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl Aliphatic epoxy compounds such as ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophoronediol glycidyl ether, bis-2, 2-hydroxycyclohexylpropane diglycidylate Such as alicyclic epoxy compounds, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, etc. An aromatic epoxy compound etc. can be illustrated.

  Among these, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, etc. Aliphatic epoxy compounds are preferred.

The blending amount of the polyfunctional epoxy compound is preferably in the range of 5% by mass to 40% by mass, particularly 5% by mass to 20% by mass of the coating composition in terms of solid content weight ratio.
If the blending amount is too small, the water resistance of the coating film may be insufficient. On the other hand, if the blending amount is too large, the adhesion with the antireflection layer 14 may be insufficient.

It is also useful to add a tetrafunctional silane compound whose general formula is represented by Si (OR) ₄ .
Specific examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2- Examples include methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, and the like. These may be used alone or in combination of two or more. These are preferably used after being hydrolyzed in the presence of an acid in the absence of a solvent or in an organic solvent such as alcohol.

  In addition to the above components, the coating composition may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil dye, a fluorescent dye, a pigment and other dyes, and a photochromic compound. Further, a light and heat resistant stabilizer such as a hindered amine / hindered phenol may be blended. Thereby, the applicability | paintability of a coating composition and the film performance after hardening can be improved.

The composition for forming a hard coat layer and the composition for forming an adhesion layer differ depending on the presence or absence of silica sol that improves the adhesion.
Here, for example, in the composition for forming the hard coat layer and the composition for forming the adhesion layer, by making the refractive index of the component (B) (filler) and the ratio of the component (A) and the component (B) common, The refractive indexes of the hard coat layer 12 and the adhesion layer 13 can be the same or substantially the same.

The composition for forming an adhesion layer preferably contains 5% by mass or more and 20% by mass or less of silica sol in terms of solid content weight ratio.
Here, when the content of the silica sol in the composition for forming an adhesion layer is less than 5% by mass, the effect of improving the adhesion is unfavorably low.

[Effects of Embodiment]
According to the present embodiment, the following excellent effects can be obtained.
(1) By providing the adhesion layer 13, the adhesion between the hard coat layer 12 and the antireflection layer 14 can be improved. In addition, since the refractive index of the adhesion layer 13 and the refractive index of the hard coat layer 12 are the same or substantially the same, the generation of interference fringes can be prevented, and the adhesion layer 13 can be made thicker. The adhesion between the layer 12 and the antireflection layer 14 can be further improved.
The presence of such an adhesion layer 13 makes it possible to employ the high-hardness hard coat layer 12 in which lack of adhesion has been a problem, and can provide a high-quality lens 1 that is less susceptible to scratches and peeling. .

(2) With an appropriate thickness of the adhesion layer 13, sufficient adhesion between the hard coat layer 12 and the antireflection layer 14 can be obtained.
(3) Since the adhesion layer 13 is formed from a composition for forming an adhesion layer containing a silica sol having a solid content weight ratio of 5% by mass or more and 20% by mass or less, between the hard coat layer 12 and the antireflection layer 14. Sufficient adhesion can be obtained.

(4) Since the hard coat layer forming step S12 and the adhesion layer forming step S13 are performed in substantially the same procedure except for the materials to be used, the manufacturing process can be simplified and the lens 1 can be manufactured efficiently.
(5) Since the hard coat layer forming step S12 and the adhesion layer forming step S13 are performed by dipping, which is a simple and general method, the lens 1 can be manufactured more efficiently.

[Modification]
In addition, this invention is not limited to the above-mentioned embodiment, Other modifications etc. which can achieve the objective of this invention are included, The deformation | transformation etc. which are shown below are also contained in this invention.
For example, in the lens 1 of the above-described embodiment, a primer layer may be provided between the lens substrate 11 and the hard coat layer 12.
Here, the primer layer is present at the interface between both the lens substrate 11 and the hard coat layer 12, and has the property of achieving both adhesion to both the lens substrate 11 and the hard coat layer 12. It plays a role of improving the durability of the upper layer structure. In addition, the primer layer also has properties as an impact absorbing layer from the outside, and improves the impact resistance of the lens 1.

Such a primer layer may contain, for example, an organic resin polymer having a polar group and metal oxide fine particles such as titanium oxide, zirconium oxide, tin oxide, and silicon oxide.
As the organic resin polymer having a polar group, various resins such as a polyester resin, a polyurethane resin, an epoxy resin, a melamine resin, a polyolefin resin, a urethane acrylate resin, and an epoxy acrylate resin can be used. Among these, a polyester resin can be preferably used from the viewpoint of adhesion to a lens substrate containing sulfur atoms and dispersibility of metal oxide fine particles serving as a filler.

In the polyester resin, an ester bond and a hydroxyl group or an epoxy group attached to the side chain in the resin are likely to interact with the lens base material 11 (surface molecule of the lens base material 11), and exhibit high adhesion. On the other hand, the pH of the polyester resin often shows weak acidity and often coincides with the pH at which the metal oxide fine particles serving as the filler can stably exist. Therefore, the metal oxide fine particles are uniformly dispersed in the primer resin without being localized, and the crosslinking density of the primer layer is stabilized or improved, thereby improving water resistance and light resistance.
For example, the primer layer can be formed by dipping similar to the first coating step S121 and the second coating step S131.

  Such a primer layer can improve not only the adhesion between the hard coat layer 12 and the antireflection layer 14 but also the adhesion between the lens substrate 11 and the hard coat layer 12, so that It is possible to provide a high-quality lens 1 that is less likely to be scratched or peeled off.

[Example]
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples and comparative examples.

[Example 1]
[1. Preparation of primer coating solution]
Into a reaction vessel equipped with a stirrer, 640 g of methanol and 100 g of a polyester resin (trade name “Pesresin A-160P”, solid content concentration 27%, manufactured by Takamatsu Yushi Co., Ltd.) are charged.
Here, 84 g of a composite sol of anatase type titanium oxide / silicon oxide / iron oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “Optlake 1130F-2 (A-8)”), silicone surfactant (manufactured by Nihon Unicar) , 1 g of trade name “SILWET L-77”) was mixed and sufficiently stirred to obtain a primer coating solution.

[2. Application of primer coating solution]
The obtained primer coating solution is applied to the lens base 11 (plastic eyeglass lens manufactured by Seiko Epson Corporation, lens fabric for Seiko Super Sovereign, refractive index 1.67) using the dipping device 100 shown in FIG. did. The film thickness was 0.8 μm.
After application, it was air-dried at 100 ° C. for 15 minutes.

[3. Preparation of composition for forming hard coat layer]
In a reaction vessel equipped with a stir bar, (A) 123.65 g of γ-glycidoxypropyltrimethoxysilane, (C) 200.0 g of methanol, and epoxy resin (trade name “Denacol EX421” manufactured by Nagase Chemical Industries, Ltd.) ) 50.00 g and 0.1N hydrochloric acid aqueous solution 56.63 g were added and stirred for 60 minutes.
Thereafter, (B) anatase-type titanium oxide / zirconium oxide / silicon oxide composite sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “Optlake 1820Z (U-25 / A8)”) 562.50 g, (D) acetylacetone Al (III) 3.0 g of salt and 3.00 g of a silicone surfactant (manufactured by Nihon Unicar Co., Ltd., trade name “L-7604”) are added and sufficiently stirred to form a hard coat layer forming composition. did.

[4. Hard coat layer forming step S12]
The obtained hard coat liquid was applied to the lens base material 11 to which the primer coat liquid was applied using the dipping apparatus 100 shown in FIG. 3 (first application step S121). The film thickness was 2 μm.
In addition, as the filter 105 of the dipping apparatus 100, a polypropylene cartridge type filter (manufactured by Japan Millipore Corporation, trade name “CN12”, pore diameter 1.2 μm) was used.
After the application, it was air-dried at 80 ° C. for 20 minutes (drying step S122).

[5. Preparation of composition for adhesion layer formation]
In a reaction vessel equipped with a stir bar, (A) γ-glycidoxypropyltrimethoxysilane 158.98 g, (C) methanol 117.11 g, and (E) methanol-dispersed colloidal silica (manufactured by Catalyst Kasei Kogyo Co., Ltd.) (Product name “Oscar 1432”) 83.33 g and (F) 0.1 N aqueous hydrochloric acid solution 72.82 g were added and stirred for 60 minutes.
Then, (B) a composite sol of rutile-type titanium oxide / zirconium oxide / silicon oxide / tin oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIK 1120Z (11RU-7 / A8)”) 562.50 g, (D ) 2.26 g of acetylacetone Fe (III) salt and 3.00 g of (G) silicone surfactant (product name “L-7604” manufactured by Nihon Unicar Co., Ltd.) were added and stirred sufficiently to form an adhesion layer. A composition was obtained.

[6. Adhesion layer forming step S13]
The obtained adhesion layer forming composition was applied to the lens substrate 11 coated with the primer coat liquid and the hard coat layer forming composition using the dipping apparatus 100 shown in FIG. 3 (second coating step S131). ). The film thickness was 1.5 μm.
After the application, air drying was performed at 80 ° C. for 20 minutes, and baking was performed at 130 ° C. for 60 minutes (main baking step S132).
As a result, the primer layer, the hard coat layer 12 and the adhesion layer 13 were formed on the lens substrate 11.

[7. Antireflection Layer Film Formation Step S14]
Plasma treatment (argon plasma 400 W × 60 seconds) was performed on the surface of the lens substrate 11 on which the layers up to the adhesion layer 13 were formed.
Thereafter, the antireflection layer 14 made of silicon oxide and zirconium oxide was multilayer-coated by a vacuum deposition method (manufactured by Vacuum Instrument Industry Co., Ltd., BMC-1000).
The layer structure is five layers in the order of silicon oxide, zirconium oxide, silicon oxide, zirconium oxide, and silicon oxide.
As a result, the primer layer, the hard coat layer 12, the adhesion layer 13, and the antireflection layer 14 were formed on the lens substrate 11.

[8. Antifouling layer forming step S15]
A fluorine-containing organosilicon compound (trade name “KY-130” manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
This KY-130 was diluted in a fluorine-based solvent (manufactured by Sumitomo 3M Limited, trade name “Novec HFE-7200”) to prepare a solution having a solid content concentration of 3%. This was impregnated with 1 g of porous ceramic pellets and dried to obtain a deposition source for forming an antifouling layer.
Using this antifouling layer deposition source, vacuum deposition was performed on the lens substrate 11 on which the layers up to the antireflection layer 14 were formed.
Thus, the lens 1 provided with the primer layer, the hard coat layer 12, the adhesion layer 13, the antireflection layer 14, and the antifouling layer 15 was obtained.

[Examples 2 to 9, Comparative Examples 1 to 3]
A lens 1 was produced in the same manner as in Example 1 except that the composition of the adhesion layer forming composition and the film thickness of the adhesion layer 13 were changed as shown in Table 1 below.
In Example 8 and Comparative Example 2, in order to reduce the film thickness, the adhesion layer 13 was formed by the microgravure method regardless of dipping.
In Comparative Example 2 and Comparative Example 3, since the component (B) was omitted, the refractive index of the adhesion layer 13 was 1.50, and the difference from the refractive index of the hard coat layer 12 was large.

[Test and evaluation results]
The obtained lens 1 was tested by the method described below.

[Abrasion resistance]
A load of 1 kg was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), and the surface was rubbed 10 times. The degree of scratches was visually evaluated in the following five stages.
A: There is no scratch at all in the range of 1 cm × 3 cm.
B: 1 to 10 scratches are attached within the above range.
C: There are 10 to 100 scratches within the above range.
D: There are countless scratches, but a smooth surface remains.
E: A smooth surface does not remain because of scratches on the surface.

[Initial adhesion]
The adhesion of the lens substrate 11, the hard coat layer 12, and the antireflection layer 14 was evaluated by a cross-cut tape test according to JIS D-0202.
That is, using a knife, the surface of the lens 1 is cut at intervals of 1 mm, and 100 squares of 1 mm 2 are formed. Next, after strongly pressing a cellophane adhesive tape (trade name “Cellotape (registered trademark)” manufactured by Nichiban Co., Ltd.) onto it, it is suddenly pulled and peeled 90 degrees from the surface. At this time, the remaining grid of each layer from the hard coat layer 12 to the antifouling layer 15 was used as an index of adhesion.

[Weather resistance, moisture resistance, optical characteristics, appearance]
There was no change in the surface condition after exposure to a sunshine weather meter with a xenon lamp for 250 hours, and a cross-cut tape test was conducted after the exposure. Further, a case where some peeling occurred was indicated by Δ, and a case where half or more peeling occurred was indicated by ×.
There was no change in the surface condition after 10 days exposure to an atmosphere of 60 ° C. × 99% RH, and a cross-cut tape test was conducted after the exposure. Further, a case where some peeling occurred was indicated by Δ, and a case where half or more peeling occurred was indicated by ×.
The reflectance in the visible light wavelength region was measured using a U-4100 type spectrophotometer (manufactured by Hitachi High-Technologies Corporation). At that time, the one having a low visible light reflectance was defined as a good optical property (◯). Those having a high reflectance in the visible light region were evaluated as x.
The appearance of the lens 1 was evaluated. Those that cannot be used as spectacle lenses, such as those with severe interference fringes and cracks, were rated as x. Interference fringes are somewhat observed, or cracks are slightly observed on the outer periphery, but those that can be used as spectacle lenses are indicated by Δ. Those with no particular problems in appearance were marked with ◯.
The results of these evaluations are shown in Table 2 below.

As is apparent from Table 2, the lenses 1 of Examples 1 to 9 having the configuration of the present invention are excellent in all of abrasion resistance, initial adhesion, weather resistance, moisture resistance, optical properties, and appearance. I understand.
In contrast, Comparative Example 1 that does not include the adhesion layer 13 is inferior in wear resistance, initial adhesion, weather resistance, and moisture resistance.
In Example 6 in which the blending amount of the component (E) (silica sol) is less than 5% by mass, the abrasion resistance, initial adhesion, weather resistance, and moisture resistance are slightly low. On the other hand, in Example 7 in which the blending amount of the component (E) exceeds 20% by mass, an appearance defect was observed.
In Example 8 in which the thickness of the adhesion layer is less than 0.5 μm and Example 9 in which the thickness of the adhesion layer is more than 5 μm, the initial adhesion, weather resistance, and moisture resistance are slightly low. In Example 8, the abrasion resistance was slightly low, and in Example 9, an appearance defect was also observed.
In Comparative Examples 2 and 3, in which the refractive index of the adhesion layer 13 is 1.50 and the difference between the refractive index of the hard coat layer 12 is large, the optical characteristics and the appearance are poor. In particular, Comparative Example 2 in which the film thickness of the adhesion layer 12 was less than 0.5 μm was inferior in wear resistance, initial adhesion, weather resistance, and moisture resistance.

Schematic which shows the laminated structure of the lens which concerns on embodiment of this invention. The flowchart of the manufacturing method of the lens which concerns on embodiment of this invention. Schematic of the dipping apparatus used for the 1st application process and the 2nd application process of the embodiment concerning the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Lens, 11 ... Lens base material, 12 ... Hard-coat layer, 13 ... Adhesion layer, 14 ... Antireflection layer

Claims (6)

A lens substrate;
A hard coat layer formed on the lens substrate;
An antireflection layer formed on the hard coat layer;
An adhesion layer provided between the hard coat layer and the antireflection layer,
The lens according to claim 1, wherein the adhesion layer has the same or substantially the same refractive index as the hard coat layer. The lens of claim 1, wherein
The thickness of the adhesion layer is not less than 0.5 μm and not more than 5 μm. The lens according to claim 1 or 2,
A lens comprising a primer layer between the lens substrate and the hard coat layer. In the lens according to any one of claims 1 to 3,
The adhesion layer is formed of a composition containing a silica sol having a solid content weight ratio of 5% by mass or more and 20% by mass or less. A method for manufacturing the lens according to any one of claims 1 to 4,
A hard coat layer forming step of forming the hard coat layer on the lens substrate;
An adhesion layer forming step of forming the adhesion layer after the hard coat layer forming step,
The method for manufacturing a lens, wherein the hard coat layer forming step and the adhesion layer forming step are performed in the same or substantially the same procedure except for a material to be used. In the manufacturing method of the lens of Claim 5,
The method for manufacturing a lens, wherein the hard coat layer forming step and the adhesion layer forming step are performed by dipping.