JP2006072019A - Optical article having optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical article which is provided with an optical film having excellent adhesion to a polyolefin synthetic resin base material and which has excellent optical performance. <P>SOLUTION: The optical article comprises the polyolefin synthetic resin base material 1 and the optical film 2 which is composed of a plurality of layers and is formed on the polyolefin synthetic resin base material 1. A fluorinated resin-containing layer 21 coming into contact with the polyolefin synthetic resin base material 1 contains a UV curing fluorinated resin and has refractive index of ≤1.45. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical article comprising a polyolefin-based synthetic resin substrate and an optical film, and more particularly to an optical article having an optical film having excellent adhesion to a polyolefin-based synthetic resin substrate.

  In recent years, resin-made optical articles have been used for the purpose of reducing the size and / or weight of an optical system and reducing the manufacturing cost of the optical system. Resins commonly used in optical articles include methacrylic resin (PMMA), polycarbonate (PC) and polyolefin resins. Among these, PMMA and PC do not have sufficient heat resistance and / or moisture resistance, and are known to have the disadvantage of causing birefringence, while polyolefin resins have such problems. Not. For this reason, recently, polyolefin-based resins are particularly promising for optical article substrates.

  In order to obtain sufficient optical performance, an optical film is often formed on the surface of an optical article. For example, an antireflection film is formed on the surface of the objective lens in order to efficiently transmit incident light. Conventionally, physical vapor deposition methods such as sputtering and ion plating, and chemical vapor deposition such as CVD have been mainstream as methods for forming an optical film.

Japanese Patent No. 3439227 (Patent Document 1) is a composite in which an optical film is formed on the optical surface of an optical component made of a polyolefin-based synthetic resin and the surface of the adherend in the same direction as the optical surface and on the outer periphery of the optical surface. A resin optical member in which the uppermost layer of the optical film is made of silicon dioxide and the lowermost layer is made of a dielectric material such as Al ₂ O ₃ , TiO ₂ , or SiO ₂ is described. Each layer of the optical film is formed by a physical film forming method such as vacuum deposition, ion plating, or sputtering. However, in recent years, optical films having functions such as conductivity, water repellency, and antibacterial properties in addition to the general optical performance of optical films have been desired. According to physical vapor deposition or chemical vapor deposition, It is difficult to form an optical film made of resin that can have these functions. These methods also have a problem of high cost because they require vacuum equipment.

  On the other hand, wet methods such as a spray coating method, a spin coating method, a dip method, a flow coating method, and a screen printing method are low cost and are also suitable for forming a film having various functions as described above. For this reason, it has been put into practical use for optical films such as flat panel displays and automobile glass. However, when the substrate of the optical article is made of a polyolefin-based resin, there is a problem that the optical film formed by the wet method is easily peeled off. This is considered to be because the polyolefin-based resin does not have a bonding functional group such as a hydroxyl group at the terminal, and thus it is difficult to bond with a chemical species.

Japanese Patent No. 3439227

  Accordingly, an object of the present invention is to provide an optical article having an optical film having excellent adhesion to a polyolefin-based synthetic resin substrate, and having excellent optical performance.

  As a result of diligent research in view of the above object, the present inventors have found that a layer made of an ultraviolet curable fluorine-based resin has sufficient adhesion to a polyolefin-based synthetic resin substrate, and arrived at the present invention. did.

  That is, the optical article of the present invention includes a polyolefin-based synthetic resin base material and an optical film formed of a plurality of layers and formed on the polyolefin-based synthetic resin base material, and the optical film is the polyolefin-based synthetic resin. It has a fluorine-containing resin-containing layer in contact with a substrate, and the fluorine-containing resin-containing layer is ultraviolet curable and has a refractive index of 1.45 or less.

  The physical film thickness of the fluororesin-containing layer is preferably 10 to 400 nm. The fluororesin-containing layer is preferably made of a fluorocopolymer.

  Each of the plurality of layers constituting the optical film preferably contains an ultraviolet curable resin. A layer formed by a liquid coating method is preferred. The optical film is preferably an antireflection film.

  The optical article of the present invention comprises a polyolefin-based synthetic resin base material and a multilayer optical film, and among the layers of the optical film, the fluororesin-containing layer that comes into contact with the base material contains an ultraviolet curable fluororesin. The layer made of a fluorine-based resin has excellent adhesion to the polyolefin-based synthetic resin substrate and is difficult to peel from the substrate. For this reason, the entire optical film is also difficult to peel off from the substrate and has excellent durability. Moreover, since it is ultraviolet curable, it can be produced without the need to heat the polyolefin-based synthetic resin substrate. Furthermore, since the fluororesin-containing layer of the preferred optical article has a physical film thickness of 10 to 400 nm, it has excellent optical performance even if it has a refractive index of 1.45 or less.

[1] Optical Article FIG. 1 shows an example of the optical article of the present invention. The optical article shown in FIG. 1 includes a substrate 1 and an antireflection film 2 provided on the surface 11 of the substrate 1. The antireflection film 2 has a multilayer structure, and includes a fluorine-based resin-containing layer 21 formed on the substrate 1, and a high refractive index layer 22 and a low refractive index layer 23 formed thereon.

  The substrate 1 is made of a polyolefin-based synthetic resin. In the example shown in FIG. 1, the substrate 1 is a lens, but the substrate of the optical article of the present invention is not limited to this. The substrate 1 of the optical article may be a prism, light guide, diffraction element, polarizing element, flat plate, fiber, film, or the like.

  The fluorine resin-containing layer 21 contains an ultraviolet curable fluorine resin. The fluororesin is preferably amorphous. A layer made of an amorphous fluororesin has excellent transparency. Specific examples of the amorphous fluorine-based resin include a fluoroolefin copolymer, a polymer having a fluorine-containing aliphatic ring structure, and a fluorinated acrylate copolymer. The fluororesin is an ethylenic fluorine-containing copolymer, and preferably has a carboxyl group and / or a hydroxyl group in the side chain. The ethylenic fluorine-containing copolymer having a carboxyl group and / or a hydroxyl group in the side chain has great adhesion to the substrate 1 made of a polyolefin-based synthetic resin.

  Examples of the fluoroolefin copolymer include those obtained by copolymerization of 37 to 48% by mass of tetrafluoroethylene, 15 to 35% by mass of vinylidene fluoride, and 26 to 44% by mass of hexafluoropropylene. .

  Examples of the polymer having a fluorinated alicyclic structure include those obtained by polymerizing a monomer having a fluorinated alicyclic structure, and those obtained by cyclopolymerizing a fluorinated monomer having at least two polymerizable double bonds. A polymer obtained by polymerization of a monomer having a fluorine-containing ring structure is described in JP-B-63-18964. This polymer is obtained by homopolymerization of a polymer having a fluorine-containing ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole) or copolymerization with a radical polymerizable monomer such as tetrafluoroethylene. .

  Polymers obtained by cyclopolymerization of fluorine-containing monomers having at least two polymerizable double bonds are described in JP-A Nos. 63-238111 and 63-238115. This polymer is obtained by cyclopolymerization of monomers such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether), or copolymerization with a radical polymerizable monomer such as tetrafluoroethylene. Examples of the copolymer include a monomer having a fluorine-containing ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole) and at least two such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether). Examples thereof include those obtained by copolymerizing fluorine-containing monomers having two polymerizable double bonds.

  When a copolymerization is carried out after adding a carboxyl group and / or a hydroxyl group to a copolymerizable fluorine-containing monomer, a fluorine-containing copolymer having a carboxyl group and / or a hydroxyl group in the side chain can be obtained.

  The fluororesin-containing layer 21 of the optical film that does not require transparency may contain a fluororesin having crystallinity. Examples of the fluororesin having crystallinity include polytetrafluoroethylene resin, perfluoroethylenepropylene resin, perfluoroalkoxy resin, polyvinylidene fluoride resin, ethylene-tetrafluoroethylene resin, and polychlorotrifluoroethylene resin.

  The fluororesin-containing layer 21 may contain a resin other than the fluororesin. Examples of resins other than fluorine-based resins include acrylic resins, silicone resins, epoxy resins, and urethane resins. Resins other than the fluororesin are also preferably UV curable. In order to improve durability and / or hardness, a filler may be added to the fluororesin-containing layer 21. Examples of the filler include colloidal silica and hollow silica.

  The fluororesin-containing layer 21 has a refractive index of 1.45 or less. The layer having a refractive index of more than 1.45 has a fluorine resin content that is too small and does not have sufficient adhesion to the substrate 1 made of a polyolefin synthetic resin. The physical film thickness of the fluororesin-containing layer 21 is preferably 10 to 400 nm. If the physical film thickness is less than 10 nm, the adhesion between the substrate 1 and the antireflection film 2 is not sufficient. If it exceeds 400 nm, the optical properties are too low.

  The high refractive index layer 22 preferably has a refractive index of 1.6 to 2.3. The high refractive index layer 22 is preferably a composite layer composed of inorganic fine particles having a refractive index of 1.8 to 2.3 and a binder (hereinafter referred to as inorganic fine particle-binder composite layer), and is composed of inorganic fine particles and an ultraviolet curable binder. A composite layer is more preferred. A composite layer composed of inorganic fine particles and an ultraviolet curable binder can be formed by a liquid coating method.

  Examples of inorganic fine particles having a refractive index of 1.8 to 2.3 include the group consisting of zirconium oxide, cryolite, thiolite, titanium oxide, indium oxide, tin oxide, antimony oxide, cerium oxide, hafnium oxide, yttrium oxide, tantalum oxide and zinc oxide. There may be mentioned at least one kind of inorganic fine particles more selected. The refractive index of the inorganic fine particle-binder composite layer depends on the composition of the inorganic fine particles and the binder composition as well as the binder composition. Although depending on the shape and refractive index of the lens 1, the physical film thickness of the high refractive index layer 22 is generally about 20 to 200 nm.

  The composition of the low refractive index layer 23 may be the same as or different from that of the fluororesin-containing layer 21. An example of the low refractive index layer 23 having a composition different from that of the fluororesin-containing layer 21 is a layer composed of inorganic fine particles having a refractive index of 1.3 to 1.5 and a binder. Specific examples of inorganic fine particles having a refractive index of 1.3 to 1.5 are selected from the group consisting of magnesium fluoride, calcium fluoride, aluminum fluoride, sodium fluoride, lithium fluoride, cerium fluoride, silicon oxide, and barium fluoride. And at least one kind of inorganic fine particles. More preferable inorganic fine particles include colloidal silica fine particles. The colloidal silica fine particles are preferably surface-treated with a silane coupling agent or the like. The binder is preferably a resin cured by ultraviolet rays. The physical film thickness of the low refractive index layer 23 is generally about 50 to 500 nm.

  In the example shown in FIG. 1, the optical article is composed of the base material 1 and the antireflection film 2 having a three-layer structure formed thereon, but the present invention is not limited to this. For example, (a) having a hard coat film, antiglare film, antifogging film, antifouling film or antistatic film in addition to the antireflection film on the substrate 1, and (b) not having an antireflection film Those having a reflective film, a semipermeable film, a polarizing film, or an interference film are also within the scope of the present invention. Moreover, it is not limited to the optical film of 3 layer structure, The thing which consists of a layer of 2 layers and 4 layers or more is included.

[2] Manufacturing method of optical article
(1) Fluorine resin-containing layer
(a) Preparation of fluorine-containing composition solution To form the fluorine-containing resin-containing layer 21, after applying a solution of a composition containing (a) a fluorine-containing polymer and a crosslinkable compound to a substrate or the like Crosslinking may be carried out using (b), or a solution of a composition containing a fluorine-containing monomer and a monomer copolymerizable therewith may be applied and then polymerized. Methods for forming a fluorine-based resin-containing layer using a fluorine-containing composition are described in detail in JP-A Nos. 07-126552, 11-228631, 11-337706, and the like.

  For example, a fluorine-containing olefin compound, a compound copolymerized therewith, and a solvent are mixed to obtain a fluorine-containing composition solution. The mixing ratio of the fluorine-containing olefinic compound / copolymerization compound is appropriately determined according to the copolymerization ratio. Specifically, 7-allyloxycarbonyl-2,2,4,4,5,5,7,7-octa per 1 mol of 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate These are mixed so that fluoro-3,6-dioxaheptanoic acid is 1 to 99 mol%. Moreover, it is good also as a fluorine-containing composition solution containing the fluorine-containing olefin copolymer obtained by copolymerizing to the extent that it has an average molecular weight of 1 million or less. If the average molecular weight exceeds 1 million, it is too difficult to dissolve in a solvent. The concentration of the fluorine-containing olefin polymer is preferably 5 to 80% by mass.

  The preparation method of a fluorine-containing composition solution is demonstrated concretely. First, 2-propen-1-ol and substantially equimolar perfluoro-3,6-dioxaoctane-1,8-dioic acid are subjected to dehydration condensation polymerization in a mixed solvent of diethyl ether and MIBK. . The volume ratio of diethyl ether / MIBK is preferably 0.1 to 10, and more preferably 0.5 to 2. Next, a copolymer obtained by polymerization of the obtained ester compound with 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate, and a self-cleaving radical polymerization initiator Disperse uniformly in a polar solvent such as MIBK to obtain a fluorine-containing composition solution. The concentration of the copolymer of the fluorine-containing composition solution is preferably 0.5 to 10 g / L (for example, 4 g / L), and the concentration of the polymerization initiator is 0.001 to 0.1 g / L (for example, 0.01 g / L). It is preferable to do this.

  Depending on the type of fluorine-containing olefinic compound and the molecular weight of the copolymer, preferred solvents include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, methanol, ethanol And alcohols such as fluorinated solvents such as perfluorohexane and perfluorobenzene, and mixtures thereof.

  A radical polymerization initiator is blended in the fluorine-containing composition solution. As the radical polymerization initiator, a compound that generates radicals upon irradiation with ultraviolet rays is used. Examples of preferred radical polymerization initiators include benzoic acid esters, benzoin ethers, acetophenones, benzophenones and derivatives thereof, thioxanthones, benzyldimethylketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones and acylphosphine oxides. Is mentioned. The addition amount of the radical polymerization initiator is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the fluorine-containing composition.

(b) Coating A layer of a fluorine-containing composition solution is formed on a substrate by a dipping method, a spin method, a spray method, a roll coating method, a screen printing method, or the like. For example, when the dipping method is used, the thickness of the layer to be formed can be controlled by the concentration of the solution, the immersion time, the pulling time, and the like. In the case of the spin method, the thickness of the layer can be controlled by the initial rotation speed, the rotation speed, the rotation time, and the like.

(c) Polymerization The fluorine-containing composition is subjected to a crosslinking reaction or a polymerization reaction. It is preferable that the layer of the fluorine-containing composition solution is irradiated with UV at about 50 to 10,000 mJ / cm ² using a UV irradiation apparatus. Although depending on the thickness of the layer, the irradiation time is usually about 0.1 to 60 seconds. Next, the solvent of the fluorine-containing composition solution is volatilized. In order to volatilize the solvent, the solvent may be kept at room temperature or heated to about 30 to 110 ° C.

(2) Formation of high refractive index layer The inorganic fine particle-binder composite layer can be formed by a wet method (liquid coating method) such as a dip coating method, a spin method, a spray method, a roll coating method, or a screen printing method. it can.

  A method for producing the high refractive index layer 22 will be described by taking a composite layer composed of inorganic fine particles with a high refractive index and an ultraviolet curable binder as an example. The high refractive index layer 22 is prepared by preparing a slurry containing a binder component and high refractive index inorganic fine particles (hereinafter referred to as high refractive index fine particles), and applying this slurry onto the fluororesin containing layer 21. Except for this, it is almost the same as the method for producing the fluororesin-containing layer 21, and only the differences will be described below. In the present specification, the “binder component” refers to a monomer and / or oligomer that becomes a binder by polymerization.

  The average particle diameter of the high refractive index fine particles is preferably about 5 to 80 nm. If the average particle size exceeds 80 nm, the transparency of the antireflection film is too bad. Those having an average particle size of less than 5 nm are difficult to produce. The mass ratio of the high refractive index fine particles / binder component is preferably 0.05 to 0.2. If the mass ratio of the high refractive index fine particles / binder component is more than 0.2, it is difficult to apply uniformly and the layer to be formed is too brittle. If the mass ratio is less than 0.05, it is difficult to achieve a desired refractive index.

  As the ultraviolet curable binder component, an acrylic ester is preferable. Specific examples of acrylic esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, carboxypolycaprolactone acrylate, acrylic acid, methacrylic acid and acrylamide Monofunctional (meth) acrylates such as pentaerythritol triacrylate, diacrylates such as ethylene glycol diacrylate and pentaerythritol diacrylate monostearate, tri (meth) acrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate, penta Multifunctional (meth) acrylates such as erythritol tetraacrylate derivatives and dipentaerythritol pentaacrylate Over bets, and these include oligomers obtained by polymerizing.

  A radical polymerization initiator is blended with the high refractive index fine particle-containing slurry. As the radical polymerization initiator, a compound that generates radicals upon irradiation with ultraviolet rays is used. Examples of preferred radical polymerization initiators include benzoic acid esters, benzoin ethers, acetophenone, benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethylketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones and acylphosphines And oxides. The addition amount of the radical polymerization initiator is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the radical polymerizable compound.

  You may mix | blend 2 or more types of high refractive index microparticles | fine-particles and / or a binder component with a slurry. In addition, general additives such as a dispersant, a stabilizer, a viscosity modifier, and a colorant can be used as long as the physical properties are not impaired.

  The concentration of the slurry affects the thickness of the thin film to be formed. Examples of solvents include alcohols such as methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, 2-butyl alcohol, i-butyl alcohol, t-butyl alcohol, 2-ethoxyethanol, 2-butoxy Alkoxy alcohols such as ethanol, 3-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ketols such as diacetone alcohol, ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, toluene And aromatic hydrocarbons such as xylene, and esters such as ethyl acetate and butyl acetate. The amount of the solvent used is about 20 to 10,000 parts by mass per 100 parts by mass in total of the high refractive index fine particles and the binder component.

  The obtained high refractive index fine particle-containing slurry is applied onto the fluorine-based resin-containing layer 21 to polymerize the binder component, and when dried, the high refractive index layer 22 is formed.

(3) Formation of the low refractive index layer The method for producing the low refractive index layer 23 is as follows. (A) When the low refractive index layer 23 has the same composition as the fluororesin-containing layer 21, the above-described fluororesin-containing layer 21 (B) When the low refractive index layer 23 is a composite layer composed of inorganic fine particles with a low refractive index and a binder, a slurry containing the inorganic fine particles with a low refractive index and a binder component is prepared, Except for applying the obtained low refractive index fine particle-containing slurry onto the high refractive index layer, the production method of the high refractive index layer 22 is almost the same. However, the concentration of the low refractive index fine particle-containing slurry and the ultraviolet irradiation time need to be appropriately adjusted according to the physical film thickness of the low refractive index layer 23 and the like.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
(a) Low refractive index coating liquid (coating liquid for forming fluororesin-containing layer and low refractive index layer)
0.5 mol of 2-propen-1-ol and 0.5 mol of perfluoro-3,6-dioxaoctane-1,8-dioic acid were mixed with diethyl ether and MIBK (diethyl ether: MIBK volume ratio). Were subjected to dehydration condensation polymerization reaction in 1: 1). The obtained ester compound was polymerized with 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol diacrylate, and the resulting copolymer and a self-cleaving radical polymerization initiator were used. It was uniformly dispersed in MIBK so that the concentrations shown in Table 1 were obtained. This dispersion was used as a coating solution for a fluorine-based resin-containing layer and a low refractive index layer.

注 共重合体は、2-プロペン-1-オール及びパーフルオロ-3,6-ジオキサオクタン-1,8-二酸のエステル化物と、1H,1H,6H,6H‐パーフルオロ‐1,6‐ヘキサンジオールジアクリレートとの共重合体を示す。

Note: The copolymer consists of esterified products of 2-propen-1-ol and perfluoro-3,6-dioxaoctane-1,8-dioic acid and 1H, 1H, 6H, 6H-perfluoro-1,6 -Shows a copolymer with hexanediol diacrylate.

(b) High refractive index coating solution Titanium oxide fine particles treated with silane coupling (average particle size 80 nm), silicone resin, acrylic resin (mass average molecular weight 300), self-cleaving radical polymerization initiator (1- The volume ratio of butanol, methyl butyl ketone and i-propyl alcohol (butanol: methyl butyl ketone: i-propyl alcohol) was 1: 1: 1), a coating solution for a high refractive index layer was obtained.

The low refractive index coating solution prepared in Example 1 (a) is applied to the lens 1 made of ZEONEX330R (manufactured by ZEON CORPORATION) by spray coating, and 1500 using a UV irradiation device (Fusion Systems). The fluorine resin-containing layer 21 was formed by irradiating with ultraviolet rays at mJ / cm ² . The physical layer thickness of the fluororesin-containing layer 21 was 10 nm.

On the fluororesin-containing layer 21, a high refractive index layer coating solution is applied by spray coating and irradiated with ultraviolet rays at 1500 mJ / cm ² , and then a low refractive index coating solution is applied and ultraviolet rays are applied at 1500 mJ / cm ² . Irradiated. The refractive index of the high refractive index layer 22 was 1.78, and the physical layer thickness was 36 nm. The low refractive index layer 23 had a refractive index of 1.36 and a physical layer thickness of 109 nm.

  The spectral reflectance of the obtained optical article was measured at an incident angle of 0 °. The measurement result of spectral reflectance is shown in FIG. As shown in FIG. 2, the reflectance was 1% or less at a wavelength of 430 to 590 nm.

Example 2
An acrylic hard coat liquid (manufactured by GE Toshiba Silicone, trade name UVHC8558) was diluted 10-fold with i-propyl alcohol to obtain a hard coat coating liquid.

In the same manner as in Example 1 except that the physical layer thickness of the fluororesin-containing layer 21 is 202 nm and the physical layer thickness of the high refractive index layer 22 is 77 nm, a lens made of ZEONEX330R (manufactured by Nippon Zeon Co., Ltd.) is used. A fluorine resin-containing layer 21 and a high refractive index layer 22 were formed in this order. A hard coat coating solution is applied on the obtained high refractive index layer 22 by a spray coating method, and then irradiated with ultraviolet rays at 1500 mJ / cm ² using a UV irradiation device (manufactured by Fusion Systems) to form a hard coat layer. Formed. The refractive index of the hard coat layer was 1.49, and the physical layer thickness was 92 nm.

  The spectral reflectance of the obtained optical article was measured at an incident angle of 0 °. The measurement result of the spectral reflectance is shown in FIG. As shown in FIG. 3, the reflectance was 1% or less at a wavelength of 480 to 630 nm.

Example 3
The physical layer thickness of the fluororesin-containing layer 21 is 185 nm, the physical layer thickness of the high refractive index layer 22 is 142 nm, and the physical layer thickness of the low refractive index layer 23 is 92 nm. Then, the fluororesin-containing layer 21, the high refractive index layer 22, and the low refractive index layer 23 were formed in this order on the lens 1 made of ZEONEX330R (manufactured by Nippon Zeon Co., Ltd.). For the formation of the low refractive index layer 23, the same coating solution as that for the fluororesin-containing layer 21, that is, the low refractive index coating solution prepared in Example 1 (a) was used.

  The spectral reflectance of the obtained optical article was measured at an incident angle of 0 °. The measurement result of spectral reflectance is shown in FIG. As shown in FIG. 4, the reflectance was 1.2% or less at a wavelength of 380 to 750 nm.

Comparative Example 1
Using a low refractive index coating solution and a high refractive index coating solution having the same composition as in Example 1, a lens 1 made of ZEONEX330R (manufactured by Nippon Zeon Co., Ltd.) and a high refractive index layer 22 having a physical layer thickness of 33 nm A low refractive index layer 23 having a layer thickness of 110 nm was formed in this order.

  The spectral reflectance of the obtained optical article is shown in FIG. As shown in FIG. 5, the reflectance was 1% or less at a wavelength of 440 to 600 nm.

  Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was attached to a part of the antireflection film of the optical articles of Examples 1 to 3 and Comparative Example 2. Next, each tape was peeled off in a direction of 45 ° with respect to the surface of the lens 1, and the surface of the antireflection film was observed. The surface of the antireflection film of the optical articles of Examples 1 to 3 was in a smooth state as before the pasting, whereas in Comparative Example 1, the antireflection film was peeled off together with the tape, and a part of the lens 1 was removed. It was exposed.

It is sectional drawing which shows an example of the optical article of this invention. 6 is a graph showing the spectral reflectance of a lens with a multilayer antireflection film of Example 1. 6 is a graph showing the spectral reflectance of a lens with a multilayer antireflection film of Example 2. 6 is a graph showing the spectral reflectance of a lens with a multilayer antireflection film of Example 3. 6 is a graph showing the spectral reflectance of a lens with a multilayer antireflection film of Comparative Example 1.

Explanation of symbols

1. Base material
11 ... Surface 2 ... Anti-reflective coating
21 ... Fluorine resin layer
22 ... High refractive index layer
23 ... Low refractive index layer

Claims (6)

  An optical article comprising a polyolefin-based synthetic resin substrate and an optical film formed of a plurality of layers and formed on the polyolefin-based synthetic resin substrate, wherein the optical film is in contact with the polyolefin-based synthetic resin substrate An optical article comprising a fluororesin-containing layer, wherein the fluororesin-containing layer is ultraviolet curable and has a refractive index of 1.45 or less.   2. The optical article according to claim 1, wherein the fluororesin-containing layer has a physical film thickness of 10 to 400 nm.   The optical article according to claim 1 or 2, wherein the fluorine-containing resin-containing layer is an ethylenic fluorine-containing copolymer having a carboxyl group and / or a hydroxyl group in a side chain. Optical article to do.   The optical article according to any one of claims 1 to 3, wherein each of the plurality of layers constituting the optical film contains an ultraviolet curable resin.   The optical article according to any one of claims 1 to 4, wherein each layer constituting the optical film is a layer formed by a liquid coating method.   The optical article according to any one of claims 1 to 5, wherein the optical film has an antireflection function.

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