JP2008310005A - Optical article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical article that has high abrasion resistance, adhesiveness, weatherability, moisture resistance, and coloring property, and has high refractive index. <P>SOLUTION: A glass lens 10 comprises a lens substrate 11, a primer layer 12, a hard coat layer 13, and a reflection preventing layer 14. The hard coat layer 13 is made of coating composition mainly containing the component (A) and component (B). (A) A particulate mainly made of at least one of a titanic oxide particulate and a compound particulate containing titanic oxide. (B) A particulate mainly made of one oxide of antimony and zirconium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical article such as a plastic lens.

In general, a hard coat layer and an antireflection layer are formed on the surface of an optical article such as an eyeglass lens. The hard coat layer is required to have a refractive index as high as that of a lens substrate having a high refractive index for the purpose of suppressing interference fringes. In order to cope with the increase in the refractive index of the hard coat layer, a method using inorganic oxide fine particles having a high refractive index is generally used. Specifically, Al, Sn, Sb, Ta, CE, La, Fe, Colorless and transparent inorganic oxide fine particles composed of oxides such as Zn, W, Zr, In, Ti, and complex oxides thereof are used. Among these, inorganic oxide fine particles containing titanium oxide are generally used from the viewpoints of refractive index, transparency, dispersion stability, and the like.
However, titanium oxide has a problem that it undergoes a valence change (Ti ⁴⁺ → Ti ³⁺ ) by receiving ultraviolet rays (<380 nm) and exhibits a blue color (blue discoloration phenomenon). In addition, when the antireflection layer is disposed on the surface of the hard coat layer, there is a problem that a colored color remains and is not easily faded.
As a method for suppressing the blue discoloration phenomenon, it is conceivable to improve the material. For example, Patent Document 1 discloses a technique in which titanium oxide having a rutile structure is coated with a coating composition containing a silicon oxide and an oxide of zirconium and / or aluminum and doped with a compound containing Fe atoms or V atoms. Is described.
On the other hand, as another method for suppressing the blue discoloration phenomenon, countermeasures by a film configuration such as catalyst dope and density control of the inorganic antireflection layer are being promoted.

JP 2005-281430 A

However, with the technique of Patent Document 1, although the blue discoloration phenomenon due to ultraviolet rays has been solved, the scratch resistance, weather resistance, moisture resistance and the like are not sufficient.
Further, when trying to suppress the blue discoloration phenomenon by measures such as catalyst dope and density control of the inorganic antireflection layer, problems such as coloring and deterioration of scratch resistance have occurred.

  Accordingly, an object of the present invention is to provide an optical article that is excellent in scratch resistance, adhesion, weather resistance, moisture resistance and color developability and has a high refractive index.

The optical article of the present invention is an optical article in which a hard coat layer and an antireflection layer are formed on the surface of a plastic substrate, and the hard coat layer contains the following component (A) and component (B): It is formed of a coating composition, and the component (A) and the component (B) are each dispersed in the coating composition.
(A) Titanium oxide fine particles and / or composite fine particles containing titanium oxide.
(B) Fine particles containing antimony oxide and / or fine particles containing zirconium oxide.

According to this invention, the hard-coat layer is formed with the coating composition which has the said component (A) and the component (B) as a main component.
Accordingly, an optical article having a high refractive index can be obtained by the titanium oxide of the component (A), and the valence change of the titanium oxide by the antimony oxide or zirconium oxide of the component (B) (blue discoloration phenomenon). Can be suppressed.
In the coating composition, the component (A) and the component (B) are dispersed. Therefore, the antimony oxide or zirconium oxide of the component (B) does not hinder the functions such as scratch resistance, weather resistance and moisture resistance.
That is, it is possible to provide an optical article that has excellent scratch resistance, weather resistance, and moisture resistance, has a high refractive index, and does not cause a blue discoloration phenomenon.

In the optical article of the present invention, the mass ratio of the component (A) to the component (B) is preferably 99.9 / 0.1 to 50/50.
In this invention, a component (A) and a component (B) are mixed within the range of mass ratio 99.9 / 0.1-50 / 50. If the mass ratio of component (B) is less than 0.1, the blue discoloration phenomenon cannot be suppressed. On the other hand, when the mass ratio of the component (B) is larger than 50, the refractive index is lowered.

In the optical article of the present invention, the mass ratio of the component (A) to the component (B) is preferably 99/1 to 80/20.
According to the present invention, an optical article having a high refractive index and a blue discoloration suppressing function in a well-balanced manner by setting the mass ratio of the component (A) and the component (B) to 99/1 to 80/20. Can be provided.

In the optical article of the present invention, the antireflection layer is preferably formed of an inorganic oxide.
According to this invention, the antireflection layer is formed of an inorganic oxide. The antireflection layer is composed of a single layer or multiple layers of an inorganic oxide. Examples of the inorganic oxide include 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 and the} like, and these can be used alone or in combination of two or more.
When a multilayer structure is formed using these inorganic oxides, a structure in which a low refractive index layer and a high refractive index layer are alternately stacked is preferable. For example, SiO _{2 is used} for the low refractive index layer and ZrO _{2 is used for the} high refractive index layer. A configuration using can be illustrated. With such a configuration, an optical article having excellent scratch resistance and antireflection properties can be provided.

The optical article of the present invention is preferably an optical lens.
In the present invention, an optical lens having the above-described effects can be provided. In particular, when a color lens or the like is used, coloration due to the blue discoloration phenomenon does not occur, so that it is possible to provide a color lens with excellent color development.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The optical article used in this embodiment is a spectacle lens.
FIG. 1 is a cross-sectional view of the eyeglass lens of the present embodiment.

[Configuration of Glasses Lens 10]
In FIG. 1, the eyeglass lens 10 includes a lens substrate 11, a primer layer 12, a hard coat layer 13, and an antireflection layer 14.

[Lens substrate 11]
The lens substrate 11 has a function for maintaining basic characteristics of glasses or optical articles such as refractive power, mechanical strength, and transmittance.
The lens substrate 11 is not particularly limited, but includes (meth) acrylic resin, styrene resin, polycarbonate resin, allyl resin, allyl carbonate resin such as diethylene glycol bisallyl carbonate resin (CR-39), vinyl resin, polyester resin, poly Ether resin, urethane resin obtained by reaction of isocyanate compound and hydroxy compound such as diethylene glycol, thiourethane resin obtained by reacting isocyanate compound and polythiol compound, (thio) epoxy having one or more disulfide bonds in the molecule Examples thereof include a transparent plastic resin obtained by curing a polymerizable composition containing a compound.

  When manufacturing the lens substrate 11, raw materials are prepared as a polymerizable composition, and additives such as a polymerization catalyst, a light stabilizer, and an antioxidant are mixed as necessary, and heat treatment, ultraviolet irradiation, etc. Can be manufactured. One example is cast polymerization. In casting polymerization, the side surfaces of two circular glass molds arranged opposite to each other are fixed with an adhesive tape or a gasket to assemble a mold that seals the gap between the glass molds, and the polymerizable composition is put into this mold. The plastic substrate can be manufactured by injection filling, polymerizing and curing by heat energy or light energy, and finally releasing from the glass mold.

[Primer layer 12]
The primer layer 12 is formed on the surface of the lens substrate 11 and is present at the interface between both the lens substrate 11 and a hard coat layer 13 described later, and exhibits adhesion to both the lens substrate 11 and the hard coat layer 13. It plays the role of improving the durability of the entire surface treatment film. Furthermore, it also has the property as an external shock absorbing layer and has the property of improving impact resistance.
The primer layer 12 is preferably formed using a composition containing a polar organic resin polymer and metal oxide fine particles (single oxide or composite oxide) containing titanium oxide.

The organic resin polymer expresses adhesion to both the lens substrate 11 and the hard coat layer 13. The metal oxide fine particles act as a filler to improve the crosslinking density of the primer layer 12 and can improve water resistance, weather resistance and light resistance. As the organic resin polymer, 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 a sulfur atom and dispersibility of metal oxide fine particles serving as a filler.
On the other hand, as the metal oxide fine particles containing titanium oxide, it is preferable from the viewpoint of light resistance to use titanium oxide having a rutile-type crystal structure without photoactivity. The average particle diameter of the metal oxide fine particles is preferably 1 to 200 nm, more preferably 5 to 30 nm.

In applying the primer layer-forming composition (coating solution), the surface of the lens substrate is previously treated with alkali, acid, surfactant, inorganic or inorganic for the purpose of improving the adhesion between the lens substrate and the primer film. It is effective to perform peeling / polishing treatment and plasma treatment with organic fine particles. As a coating liquid application / curing method, a coating liquid is applied by a dipping method (dipping method), a spin coating method, a spray coating method, a roll coating method, a flow coating method, or the like. The primer layer can be formed by heating / drying at a temperature for several hours.
Moreover, the film thickness of a primer layer is 0.01-50 micrometers, Especially the range of 0.1-30 micrometers is preferable. If the primer layer is too thin, basic performance such as water resistance and impact resistance cannot be realized. Conversely, if the primer layer is too thick, the smoothness of the surface may be impaired, or appearance defects such as optical distortion, white turbidity, and cloudiness may occur. There is a case. In addition, in order to avoid generation | occurrence | production of an interference fringe, it is preferable to match | combine the refractive index of a primer layer with the refractive index of a lens base material.

[Hard coat layer 13]
The hard coat layer 13 is formed of a coating composition mainly composed of the following component (A) and component (B).
(A) Fine particles mainly composed of at least one of titanium oxide fine particles and composite fine particles containing titanium oxide.
(B) Fine particles mainly composed of at least one of antimony and zirconium.
As the component (A), titanium oxide fine particles may be used alone, but in addition to titanium oxide, composite fine particles in which fine particles such as tin oxide and silicon oxide are combined can be used.
Component (B) is fine particles mainly composed of at least one of antimony oxide and zirconium oxide.
The particle size of the fine particles of component (A) and component (B) is preferably 5 to 50 μm, more preferably 10 to 40 μm, and still more preferably 10 to 20 μm. When the particle diameter of the fine particles exceeds 50 μm, light is scattered and the characteristics as an optical article cannot be obtained. Further, if the particle diameter of the fine particles is smaller than 5 μm, the scratch resistance may be lowered.

As the components (A) and (B), those dispersed in a colloidal form in a dispersion medium such as water, alcohols or other organic solvents are used.
In order to disperse the component (A) and the component (B), the mass ratio is preferably within a range of 99.9 / 0.1 to 50/50, more preferably 99/1 to 80/20. is there. When the content of the component (B) exceeds 50 in terms of mass ratio, the refractive index decreases, which is not preferable. Moreover, when content of a component (B) becomes smaller than 0.1 by mass ratio, the blue discoloration phenomenon of a titanium oxide cannot be suppressed.

In addition, an organosilicon compound is added to the coating composition in which component (A) and component (B) are dispersed for the purpose of improving dispersion stability.
Examples of the organosilicon compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, and γ-glycid. Examples include xylpropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, and the like. Two or more types of organosilicon compounds may be mixed and used.

  The addition amount of the organosilicon compound is in a mass ratio with the component (A), and is in the range of organosilicon compound / component (A) = 30/70 to 70/30, more preferably 60/40 to 40/60. Like that. If the organosilicon compound exceeds 70 by mass ratio, cracks may occur. On the other hand, when the organosilicon compound is smaller than 30 by mass ratio, the adhesion with the antireflection layer 14 described later is lowered, and the scratch resistance is lowered, which is not preferable.

  Moreover, it is useful to mix | blend a polyfunctional epoxy compound with the composition for hard-coat layers. By using a polyfunctional epoxy compound in combination, the water resistance can be improved and the adhesion to the primer layer 12 as a base can be further stabilized. In particular, when a hydroxyl group is present in the molecule of the polyfunctional epoxy compound, it is recognized that the adhesion with the primer layer is improved. Therefore, by using a polyfunctional epoxy compound containing one or more hydroxyl groups in one molecule, it is possible to reduce the blending amount of this polyfunctional epoxy compound as a whole, without causing a decrease in scratch resistance, It is possible to improve durability.

  Examples of the multifunctional epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and 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, trimethylolpropa Diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether , Pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanate, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, etc. Group epoxy compounds, isophoronediol diglycidyl Ether, alicyclic epoxy compounds such as bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether And aromatic epoxy compounds such as phenol novolac polyglycidyl ether and cresol novolac polyglycidyl ether.

  Of these, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl) isocyanate An aliphatic epoxy compound such as triglycidyl ether of nate can be preferably used.

Furthermore, a curing catalyst may be added to the coating composition for the hard coat layer 13. Examples of the curing catalyst include perchloric acids such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), and Be (II). Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III) Acetylacetonate having a central metal atom such as Ce (IV), Zr (IV), V (IV), amino acids such as amine and glycine, Lewis acid, organic acid metal salts and the like.
Among these, preferable curing catalysts include acetylacetonate having magnesium perchlorate, Al (III), and Fe (III) as a central metal atom. In particular, it is most preferable to use acetylacetonate having Fe (III) as a central metal atom. The addition amount of the curing catalyst is desirably in the range of 0.01 to 5% by mass of the solid content of the hard coat liquid.

  The coating composition for the hard coat layer 13 obtained in this way can be used after diluted with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used. Moreover, the coating composition for the hard coat layer 13 may contain a small amount of metal chelate compound, surfactant, antistatic agent, ultraviolet absorber, antioxidant, disperse dye, oil-soluble dye, pigment, photochromic as required. A compound, a hindered amine, a light-resistant heat stabilizer such as a hindered phenol, and the like can be added to improve the coating property of the coating liquid, the curing speed, and the film performance after curing.

The coating composition is applied and cured by dipping, spin coating, spray coating, roll coating, or flow coating, and the coating composition is applied at 40 to 200 ° C. A hard coat film can be formed by heating and drying at a temperature for several hours.
In addition, it is preferable that the film thickness of the hard-coat layer 13 is 0.05-30 micrometers. If the film thickness is less than 0.05 μm, the basic performance cannot be realized. On the other hand, if the film thickness exceeds 30 μm, the surface smoothness may be impaired, or optical distortion may occur.

[About the antireflection layer 14]
The antireflection layer 14 is formed on the hard coat layer 13. The antireflection layer 14 has a refractive index lower by 0.10 or more than the refractive index of the hard coat layer 13 and is composed of a single inorganic thin layer or multiple layers having a thickness of 50 nm to 150 nm. The material of the inorganic thin _{layer, 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 and the} like, and these can be used alone or in combination of two or more. In the case of a plastic lens, SiO ₂ , ZrO ₂ , TiO ₂ , and Ta ₂ O ₅ that can be vacuum-deposited at a low temperature are preferable. When it is a multilayer film structure, the outermost layer is preferably a SiO _2.

In this embodiment, a multilayer film structure made of an inorganic oxide is used. As the antireflection layer 14 in the present embodiment, a multilayer structure including a low refractive index layer (L) and a high refractive index layer (H) is disclosed. Specifically, the antireflective layer 14 has a low refractive index layer 14L1 first laminated from the side in contact with the hard coat layer 13, and a high refractive index layer 14H1 laminated on the top surface. 14L2, 14H2, and 14L3 are laminated to form a total of five antireflection layers 14.
The antireflection layer 14 includes, for example, a low refractive index layer made of a low refractive index material such as SiO ₂ or fluoride, and a high refractive index such as ZrO ₂ , TiO ₂ , Nb ₂ O ₂ , or Ta ₂ O _2. Although five high refractive index layers made of a substance are alternately stacked, the number of stacked layers may be at least more than this. For example, the antireflection layer may be formed by laminating about 4 to 7 layers.

Further, when forming the antireflection layer, it is desirable to perform a surface treatment of the hard coat layer. Specific examples of the surface treatment include acid treatment, alkali treatment, ultraviolet irradiation treatment, plasma treatment by high frequency discharge in an argon or oxygen atmosphere, and ion beam irradiation treatment of argon, oxygen or nitrogen.
As a method for forming the antireflection layer 14, for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed. 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.

[Method of manufacturing eyeglass lens 10]
Hereinafter, a manufacturing method of the eyeglass lens 10 according to the present embodiment will be described.
In order to manufacture the above-described spectacle lens 10 by forming each layer on the surface of the above-mentioned lens base material 11, first, the lens base material 11 is formed by heating and / or irradiating light with a liquid plastic raw material. The primer layer 12 and the hard coat layer 13 are formed on the lens substrate 11. The primer layer 12 and the hard coat layer 13 are formed by applying a coating solution by a dipping method and then drying by heating. Then, the surface of the hard coat layer 13 is subjected to surface modification treatment by plasma, and then the antireflection layer 14 is applied by a sputtering method. The primer layer 12 and the hard coat layer 13 may be formed by a wet method such as a spinner method, a spray method, a flow method, or a brush coating method in addition to the dipping method.
The antireflection layer 14 is formed by alternately laminating low refractive index layers and high refractive index layers on the surface of the hard coat layer 13. The low refractive index layers 14L1, 14L2, and 14L3 are formed by using a target made of SiO ₂ and applying a high-frequency voltage under an argon introduction pressure of ₂ to 5 Pa. The high refractive index layers 14H1 and 14H2 are formed by using a target made of ZrO ₂ and applying a high-frequency voltage under an argon introduction pressure of 5 to 10 Pa.
In this embodiment, the thickness of each layer of the antireflection layer 14 is 0.10λ for the low refractive index layer 14L1, 2.71λ for the high refractive index layer 14H1, and 0.13λ for the low refractive index layer 14L2 with respect to the design wavelength λ. The refractive index layer 14H2 is 0.62λ, and the low refractive index layer 14L3 is 1.24λ.
Thus, the spectacle lens 10 in which the primer layer 12, the hard coat layer 13, and the antireflection layer 14 are formed on the lens substrate 11 can be obtained.

According to this embodiment described above, the following effects can be obtained.
(1) In this embodiment, antimony oxide fine particles and zirconium oxide fine particles are dispersed in the coating composition forming the hard coat layer 13 in addition to the titanium oxide fine particles.
Therefore, the ultraviolet rays can be scattered by the antimony oxide fine particles and the zirconium oxide fine particles, and the titanium oxide whose valence has been changed by the ultraviolet rays is returned to the original valence. That is, the blue discoloration phenomenon due to the valence change of the titanium oxide can be suppressed.

(2) In this embodiment, the component (A) containing titanium oxide and the component (B) containing antimony oxide fine particles and zirconium oxide fine particles were dispersed. That is, the component (A) is not covered with the component (B), and each component is dispersed in the hard coat layer 13.
Therefore, since the binding between the titanium oxide and the organosilicon compound is not hindered, an eyeglass lens having excellent scratch resistance can be provided.

(3) In the present embodiment, the component (A) containing titanium oxide, the component (B) containing antimony oxide fine particles and zirconium oxide fine particles are in a mass ratio of 99.9 / 0.1 to 50/50. It was dispersed within the range. Thereby, it is possible to provide a spectacle lens that has a high refractive index and does not cause a blue discoloration phenomenon.

(4) In this embodiment, the antireflection layer 14 is formed on the surface of the hard coat layer 13. Conventionally, the problem of blue discoloration has frequently occurred when an antireflection layer is formed.
Therefore, it is possible to provide a spectacle lens that does not cause a blue discoloration phenomenon even in the spectacle lens 10 provided with the antireflection layer 14 as in this embodiment.

(5) In this embodiment, since the hard coat layer 13 is formed by a wet method, the film thickness can be easily controlled by adjusting the pulling speed, and the operability is good.

It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that modifications and improvements within the scope of achieving the objects and effects of the present invention are included in the contents of the present invention. Nor.
For example, in the present embodiment, the lens substrate 11, the primer layer 12, the hard coat layer 13, and the antireflection layer 14 are configured. For the purpose of improving the water and oil repellency on the upper surface of the antireflection layer, An antifouling layer made of an organosilicon compound containing fluorine may be formed. The antifouling layer can be formed by a known method such as a dipping method, a spinner method, a spray method, or a flow method.

Next, examples of the present invention will be described, but the present invention is not limited to the description of these examples.
Glasses lenses were produced by the methods shown in the following Examples 1 to 4 and Comparative Examples 1 to 3, and evaluated by the methods described later.

[Example 1]
(1) Production of plastic lens substrate In a nitrogen atmosphere, 90 parts by mass of bis (β-epithiopropyl) disulfide and 10 parts by mass of sulfur were mixed and stirred at 100 ° C. for 1 hour. After cooling, 0.05 parts by mass of tetrabutylammonium bromide as a catalyst was mixed to obtain a uniform solution. This was then filtered through a 0.5 μm PTFE filter, poured into a 1.2 mm thick glass mold for molding a lens, heated in an oven from 10 ° C. to 120 ° C. over 22 hours, and cured to produce a lens. . The obtained lens had a refractive index of 1.76, an Abbe number of 33, was transparent, and had a good surface condition.

(2) Preparation of primer composition In a stainless steel container, 3700 parts by mass of methyl alcohol, 250 parts by mass of pure water, and 1000 parts by mass of propylene glycol monomethyl ether were added and stirred sufficiently, followed by titanium oxide, tin oxide, and oxidation. 2800 mass of composite fine particle sol mainly composed of silicon (rutile crystal structure, methanol dispersion, total solid concentration 20% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIK 1120Z (8RS-7 · G)”) Part was added and mixed with stirring. Next, after adding 2200 parts by mass of a polyester resin and stirring and mixing, 2 parts by mass of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., trade name L-7604) was added and stirring was continued for a whole day and night. Filtration was performed with a 2 μm filter to obtain a primer composition.

(3) Preparation of hard coat composition 1000 parts by weight of butyl cellosolve was put into a stainless steel container, 1200 parts by weight of γ-glycidoxypropyltrimethoxysilane was added and stirred sufficiently, and then 0.1 mol / liter hydrochloric acid aqueous solution was added. 300 mass parts was added and stirring was continued all day and night to obtain a silane hydrolyzate. After adding 30 parts by mass of a silicone-based surfactant (trade name FZ-2164, manufactured by Toray Dow Corning Co., Ltd.) to this silane hydrolyzate, the mixture was stirred for 1 hour, and then mainly composed of titanium oxide, tin oxide, and silicon oxide. Composite fine particle sol (rutile type crystal structure, methanol dispersion, manufactured by Catalytic Chemical Industry Co., Ltd., trade name “Optlake 1120Z (8RS-25 • A17)”), zirconium oxide, tin oxide, antimony oxide, silicon oxide Composite particles (concentration 30% by weight, methanol dispersion, manufactured by Nissan Chemical Industries, Ltd., trade name “Sun Colloid HZ-307M6”) at a mass ratio of 100: 10, a total of 7300 parts by mass was added and stirred for 2 hours. Mixed. Next, 250 parts by mass of an epoxy resin (manufactured by Nagase Kasei Co., Ltd., trade name “EX-313”) was added and stirred for 2 hours, and then 20 parts by mass of iron (III) acetylacetonate was added and stirred for 1 hour. Filtration was performed with a 2 μm filter to obtain a hard coat composition.

(4) Formation of primer layer, hard coat layer and antireflection film The plastic lens substrate having a diameter of 80 mm obtained in the above (1) was subjected to alkali treatment (into a 2 mol / liter potassium hydroxide aqueous solution kept at 50 ° C). After soaking for 5 minutes, wash with pure water, then soak in 1.0 mol / liter sulfuric acid kept at 25 ° C. for 1 minute to neutralize), wash with pure water, dry and allow to cool It was. Next, it was immersed in the primer composition prepared in (2) above, dip-coated at a pulling rate of 200 mm / min, and baked at 80 ° C. for 20 minutes to form a primer layer on the surface of the plastic substrate. Next, it is immersed in the hard coat composition prepared in (3) on the surface of the plastic lens on which the primer layer is formed, dip-coated at a pulling rate of 400 mm / min, and baked at 80 ° C. for 30 minutes. A hard coat layer was formed. Then, it heated for 3 hours in the oven maintained at 125 degreeC, and obtained the plastic lens in which the primer layer and the hard-coat layer were formed.
Then, plasma treatment (argon plasma 400 W × 60 seconds) is performed on the plastic lens on which the surface treatment layer is formed, and five layers of SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ , and SiO ₂ are sequentially formed from the substrate toward the atmosphere. Was formed with a vacuum vapor deposition machine (manufactured by Syncron Co., Ltd.). The optical film thickness of each layer is λ / 4 for the first SiO ₂ layer, the next ZrO ₂ and SiO ₂ equivalent film layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer with a design wavelength λ of 520 nm. It was formed to become.

[Example 2]
In the preparation of the hard coat composition of Example 1, a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIQUE 1120Z (8RS-25 · A17) ”) and composite fine particles mainly composed of zirconium oxide, tin oxide, antimony oxide, and silicon oxide (concentration 30% by weight, methanol dispersion, manufactured by Nissan Chemical Industries, Ltd., trade name“ Sun Colloid ” A hard coat layer was formed in the same manner as in Example 1 except that the mass ratio with HZ-307M6 ") was 100: 0.5.

[Example 3]
In the preparation of the hard coat composition of Example 1, a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIQUE 1120Z (8RS-25 · A17) ”) and composite fine particles mainly composed of zirconium oxide, tin oxide, antimony oxide, and silicon oxide (concentration 30% by weight, methanol dispersion, manufactured by Nissan Chemical Industries, Ltd., trade name“ Sun Colloid ” A hard coat layer was formed in the same manner as in Example 1 except that the mass ratio with HZ-307M6 ") was 100: 40.

[Example 4]
In the preparation of the hard coat composition of Example 1, a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIQUE 1120Z (8RS-25 · A17) ”), a composite fine particle sol mainly composed of titanium oxide, iron oxide, and silicon oxide (anatase type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name“ OPTRAIQUE ” A hard coat layer was formed in the same manner as in Example 1 except that 1120F ") was used.

[Comparative Example 1]
In the preparation of the hard coat composition of Example 1, composite fine particles mainly composed of zirconium oxide, tin oxide, antimony oxide, and silicon oxide (concentration 30 mass%, methanol dispersion, manufactured by Nissan Chemical Industries, Ltd., trade name “Sun”) Colloidal HZ-307M6 ”), a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name“ OPTRAIQUE 1120Z ( 8RS-25 · A17) ”) A hard coat film was formed in the same manner as in Example 1 except that 7300 parts by mass were added.

[Comparative Example 2]
In the preparation of the hard coat composition of Example 1, a composite fine particle sol mainly composed of titanium oxide, tin oxide, and silicon oxide (rutile type crystal structure, methanol dispersion, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “OPTRAIQUE 1120Z (8RS-25 · A17) ”) and composite fine particles mainly composed of zirconium oxide, tin oxide, antimony oxide, and silicon oxide (concentration 30% by weight, methanol dispersion, manufactured by Nissan Chemical Industries, Ltd., trade name“ Sun Colloid ” A hard coat film was formed in the same manner as in Example 1 except that the mass ratio with HZ-307M6 ") was 100: 80.

[Comparative Example 3]
In the preparation of the hard coat composition of Example 1, a composite fine particle sol (anatase type crystal structure, methanol dispersion, catalyst formation) in which composite fine particles mainly composed of titanium oxide, zirconium oxide and silicon oxide are used as core particles and coated with antimony oxide. A hard coat layer was formed in the same manner as in Example 1 except that the trade name “Hinex DC-20” manufactured by Kogyo Co., Ltd. was used.

The plastic lenses obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the following evaluation methods.
(A) Scratch resistance The surface of 10 reciprocating surfaces was rubbed with a bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) under a load of 1 kg. Evaluation was divided into stages.
A: Not scratched at all.
B: 10 to 10 scratches.
C: 10 to 100 scratches are attached.
D: There are countless scratches, but a smooth surface remains.
E: A smooth surface does not remain because of scratches on the surface.

(B) Initial adhesion The adhesion between the base material and the hard coat film and between the hard coat film and the multi-coat film is a cross-cut tape test according to JIS K5400 8.5.1-2 cross cut method / cross cut tape method. Went by. That is, using a cutter knife, the substrate surface is cut at intervals of 1 mm to form 100 squares of 1 mm square. Next, after strongly pressing cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) onto it, it was pulled and peeled off 90 degrees from the surface. Classified.
A: No film peeling (remaining cell number 100)
B: Almost no peeling (remaining grid number 99.9 to 95)
C: Some peeling (remaining cell number 94.9-80)
D: Peeled (remaining cell number: 79.9-30)
E: Peeling of almost entire surface (remaining cell number: 29.9 to 0)

(C) Weather resistance After being exposed to a sunshine weather meter using a carbon arc for 300 hours, the cross-cut tape test described in (b) was performed, and the number of remaining squares of the coat film was used as a durability index.

(D) Moisture resistance After being left in a constant temperature and humidity chamber maintained at a temperature of 60 ° C. and a relative humidity of 98% for 10 days, the cross-cut tape test described in (b) above was performed to determine the number of remaining squares of the coat film. The durability index was used.

(E) Color development property After being left for 20 hours under an artificial sun lamp in a thermostatic chamber maintained at a temperature of 25 ° C., the following classification was made.
A: No change B: Some color development is observed, but there is no problem in use. C: Color development is observed and visibility is impaired.

(F) Interference fringes The interference fringes generated on the lens surface under a three-wavelength type fluorescent lamp (trade name “National Palook”) were visually observed with reflected light and evaluated as follows.
○: There is little color change as a whole, and interference fringes are hardly seen.
Δ: Several stripe patterns due to film thickness unevenness are seen, and interference fringes can be recognized.
X: A stripe pattern due to film thickness unevenness is seen on the entire lens, and the interference fringes can be clearly recognized.
The evaluation results are shown in Table 1 below.

Examples 1 and 4 were good in all of scratch resistance, initial adhesion, weather resistance, moisture resistance, color development and interference fringes. Example 2 was slightly inferior to Example 1 in weather resistance and color development, and Example 3 was slightly inferior to Example 1 in scratch resistance and interference fringes.
Comparative Example 1 had a problem in color development and weather resistance because zirconium or antimony was not contained in the hard coat layer. Although Comparative Example 2 had good color developability and weather resistance, there were problems with scratch resistance and interference fringes. Comparative Example 3 was inferior in scratch resistance, weather resistance and moisture resistance.

  The present invention can be used for plastic optical articles such as eyeglass lenses.

1 is a cross-sectional view of an eyeglass lens according to an embodiment of the present invention.

Explanation of symbols

    DESCRIPTION OF SYMBOLS 10 ... Glasses lens, 11 ... Lens base material, 12 ... Primer layer, 13 ... Hard-coat layer, 14 ... Antireflection layer

Claims (5)

An optical article in which a hard coat layer and an antireflection layer are formed on the surface of a plastic substrate,
The hard coat layer is formed of a coating composition containing the following components (A) and (B):
The optical article, wherein the component (A) and the component (B) are dispersed in the coating composition.
(A) Titanium oxide fine particles and / or composite fine particles containing titanium oxide.
(B) Fine particles containing antimony oxide and / or fine particles containing zirconium oxide. The optical article according to claim 1.
An optical article, wherein a mass ratio of the component (A) to the component (B) is 99.9 / 0.1 to 50/50. The optical article according to claim 2,
The optical article, wherein the mass ratio of the component (A) to the component (B) is 99/1 to 80/20. The optical article according to any one of claims 1 to 3,
The optical article, wherein the antireflection layer is formed of an inorganic oxide. The optical article according to any one of claims 1 to 4,
The optical article is an optical lens.

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