JP2006072020A - Optical article having polyolefin synthetic resin base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical article which is provided with a polyolefin synthetic resin base material and which can be fully fixed to a holding member. <P>SOLUTION: The optical article 100 has the polyolefin synthetic resin base material 1 and is adhered to the holding member 5. A fluorinated resin-containing layer 2 is formed on an optical surface 11 of the polyolefin synthetic resin base material 1 and a part to be adhered 101 and the fluorinated resin-containing layer 2 has UV curing nature and a refractive index of ≤1.45. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical article having a polyolefin-based synthetic resin substrate, and particularly relates to an optical article having an optical film that is difficult to peel and exhibiting excellent adhesion to a member to be held.

  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.

  However, since the polyolefin-based synthetic resin does not have a polar group such as a hydroxyl group, it has a property that it is difficult to adhere to various adhesives and resin-based coating agents. Therefore, there is a problem that sufficient adhesive strength cannot be obtained when bonding to a lens frame or the like.

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. The dielectric material located in the lowermost layer has adhesion to the polyolefin-based synthetic resin, and silicon dioxide located in the uppermost layer also has great adhesion to the adhesive. It shows a large adhesive strength with other members.

  However, when an optical film is formed by a physical film forming method, the film can be formed only on one surface of the substrate in one step because of the straightness of particles to be deposited. Therefore, since the surface to be bonded is limited to the same surface as the optical film, there is a problem that the synthetic resin optical member cannot be sufficiently fixed even if the adhesive force between the optical film and the lens frame is sufficient. is there. Further, these physical film forming methods require a vacuum apparatus, and thus have a problem of high cost.

Japanese Patent No. 3439227

  Accordingly, an object of the present invention is to provide an optical article comprising a polyolefin-based synthetic resin substrate, which can be sufficiently fixed to a frame.

  As a result of diligent research in view of the above object, the present inventors have discovered that a layer containing an ultraviolet curable fluororesin has sufficient adhesion to a polyolefin-based synthetic resin base material. I came up with it.

  That is, the optical article of the present invention has a polyolefin-based synthetic resin base material and is bonded to a holding member, and a fluorine-based resin-containing layer is provided on the optical surface of the polyolefin-based synthetic resin base material and the bonded portion. The fluorine-containing resin-containing layer is ultraviolet curable and has a refractive index of 1.45 or less.

  The fluororesin-containing layer is preferably an ethylenic fluorine-containing copolymer having a carboxyl group and / or a hydroxyl group in the side chain. The fluororesin-containing layer is preferably formed by a liquid coating method. The liquid coating method is preferably at least one selected from the group consisting of dip coating, spray coating, spin coating and flow coating.

  It is preferable that the optical surface has an ultraviolet curable resin layer other than the fluororesin-containing layer, and the ultraviolet curable resin layer other than the fluororesin-containing layer has a refractive index of 1.6 or more. In a preferred embodiment of the present invention, the polyolefin-based synthetic resin substrate is a lens, and the adherend is the edge of the lens.

  The optical article of the present invention has a polyolefin-based synthetic resin base material and is bonded to a holding member such as a lens barrel, and has a fluorine-based resin-containing layer on the optical surface and the bonded portion. Since the fluororesin-containing layer has good adhesion to the polyolefin synthetic resin substrate, optical film and adhesive, the optical film is difficult to peel off from the polyolefin synthetic resin substrate, and the optical article adheres firmly to the holding member. Is done. Further, since the preferred fluorine-containing resin-containing layer is an ethylenic fluorine-containing copolymer having a carboxyl group and / or a hydroxyl group in the side chain, it has even better adhesion to optical films and adhesives. Indicates. Furthermore, since the fluororesin-containing layer can be formed on any part of the surface of the polyolefin-based synthetic resin substrate, the position of the adherend is not limited. Furthermore, since the fluororesin-containing layer can be formed by a liquid coating method, the cost is low.

[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, a fluororesin-containing layer 2 that covers the substrate 1, a high refractive index layer 3, and a low refractive index layer 4.

  The substrate 1 is made of a polyolefin-based synthetic resin. The substrate 1 shown in FIG. 1 includes a lens part 110 having an optical surface 11 and an edge part 120 having an edge surface 12 extending from the optical surface 11. The edge surface 12 of the lens means a surface other than the back surface 13 that does not contribute to light collection, and includes a surface extending from the optical surface 11 and an end surface. 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, a light guide, a diffraction element, a polarizing element, a flat plate, a film, or the like.

  The fluororesin-containing layer 2 covers at least the optical surface 11 and the edge surface 12 of the substrate 1, but of course, as in the example shown in FIG. 1, the entire surface of the substrate 1 may be coated. The fluorine resin-containing layer 2 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 such as perfluoro (allyl vinyl ether) and perfluoro (butenyl vinyl ether). Examples thereof include those obtained by copolymerizing a fluorine-containing monomer 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 2 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 fluorine resin-containing layer 2 may contain a resin other than the fluorine resin. 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.

  The fluororesin-containing layer 2 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 layer thickness of the fluororesin-containing layer 2 is preferably 10 to 400 nm. The physical layer thickness represents the physical thickness of the layer. If the physical layer 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 bad.

  On the fluororesin-containing layer 2, a high refractive index layer 3 and a low refractive index layer 4 are formed in this order. The fluororesin-containing layer 2, the high refractive index layer 3 and the low refractive index layer 4 formed on the optical surface 11 function as an antireflection film.

  The high refractive index layer 3 preferably has a refractive index of 1.6 to 2.3. The high refractive index layer 3 may be a layer composed only of an inorganic material such as a metal oxide having a refractive index of 1.6 to 2.3, or 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 particles). -It may be referred to as a binder composite layer), but a composite layer composed of inorganic fine particles and an ultraviolet curable binder is preferable. 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 layer thickness of the high refractive index layer 3 is generally about 20 to 200 nm.

  The composition of the low refractive index layer 4 may be the same as or different from that of the fluororesin-containing layer 2. Examples of the low refractive index layer 4 having a composition different from that of the fluororesin-containing layer 2 include a layer made of inorganic fine particles having a refractive index of 1.3 to 1.5 and a binder. Specific examples of the 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 that is cured by ultraviolet rays. The physical layer thickness of the low refractive index layer 4 is generally about 50 to 500 nm.

  FIG. 2 shows an optical article 100 supported by the lens barrel 5. The lens barrel 5 is cylindrical and has an annular flange 51 protruding from the inner surface. The edge portion 120 of the optical article 100 is engaged with the annular flange 51, and the portion of the edge surface 12 that faces the annular flange 51 is the adherend portion 101. The adhesive 6 is applied to the adherend 101 and fixed to the annular flange 51.

  FIG. 3 shows another example of the optical article of the present invention. The optical article shown in FIG. 3 is the same as the example shown in FIG. 1 except that only the fluororesin-containing layer 2 is provided on the entire surface (optical surface 11, edge surface 12 and back surface 13) of the substrate 1. The fluororesin-containing layer 2 formed on the optical surface 11 functions as a single-layer antireflection film. The physical layer thickness of the fluororesin-containing layer 2 formed on the optical surface 11 is preferably 50 to 500 nm so as to exhibit a sufficient antireflection effect.

  FIG. 4 shows still another example of the optical article of the present invention. The optical article shown in FIG. 4 is substantially the same as the example shown in FIG. 1 except that the fluororesin-containing layer 2 is provided on the optical surface 11 and the edge surface 12 of the substrate 1, and only the differences will be described below. The high refractive index layer 3 and the low refractive index layer 4 are formed only on part of the optical surface 11 and the edge surface 12 (curved surface portion).

  In the example shown in FIGS. 1 to 4, the film formed on the optical surface 11 exhibits an antireflection effect, 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 what has a single layer optical film and an optical film of a 3 layer structure, The thing which has an optical film which consists of a layer of two layers and four 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 2, a solution of a composition containing (a) a fluorine-containing polymer and a crosslinkable compound was applied to a substrate or the like. It may be crosslinked later, or (b) 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%. Alternatively, a solution or dispersion containing a fluorine-containing olefin copolymer obtained by copolymerization to an extent having an average molecular weight of 1 million or less may be used. 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 a dehydration condensation polymerization reaction 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 dip coating method, a spin method, a spray method, a roll coating method, a screen printing method or the like. The coating of the fluorine-containing composition solution will be described by taking as an example the case where the fluororesin-containing layer 2 is formed on the surface of the substrate 1 by the dip coating method.

  As shown in FIG. 5, the edge portion 120 of the substrate 1 is sandwiched by a jig 210 and immersed in the fluorine-containing composition solution 200. Since the fluorine-containing composition solution 200 does not come into contact with the portion of the edge surface 12 held by the jig 210, the fluorine-based resin-containing layer 2 is not formed. However, the portion where the fluororesin-containing layer 2 is not formed is negligible on the edge surface 12, so that the fixing of the optical article 100 is hardly affected. The jig 210 is suspended by a hook that forms the lower end of the support member 220. The thickness of the fluorine-containing resin-containing layer 2 to be formed can be controlled by the concentration of the fluorine-containing composition solution 200, the dipping time, the pulling time, and the like.

(c) Polymerization The fluorine-containing composition is subjected to a crosslinking reaction or a polymerization reaction. The layer of the fluorine-containing composition solution is preferably irradiated with UV at about 50 to 3000 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 100 ° C.

(2) Formation of a high refractive index layer When the high refractive index layer 3 is made of only an inorganic material, physical vapor deposition methods such as vapor deposition, sputtering, and ion plating, chemical vapor deposition such as thermal CVD, plasma CVD, and photo-CVD. It can be formed by a method or the like. In the case of the inorganic fine particle-binder composite layer, it 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.

  A method for producing the high refractive index layer 3 will be described using 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 3 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 2. Since it is almost the same as the manufacturing method of the fluorine-type resin content layer 2 except doing, only a different point is demonstrated below. In the present specification, the “binder component” represents 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 0.7. If the mass ratio of the high refractive index fine particles / binder component is more than 0.7, 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. The preferred radical polymerization initiator and concentration are the same as those of the fluorine-containing composition solution. 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 on the fluorine-based resin-containing layer 2 or the substrate 1 formed with the fluorine-based resin-containing layer 2 is immersed in the high refractive index fine particle-containing slurry, and then the binder component is polymerized. When dried, the high refractive index layer 3 is formed.

(3) Formation of Low Refractive Index Layer The method for producing the low refractive index layer 4 is as follows. (A) When the low refractive index layer 4 has the same composition as the fluororesin-containing layer 2, (B) When the low refractive index layer 4 is a composite layer composed of low refractive index inorganic fine particles and a binder, a slurry containing low refractive index inorganic fine particles 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 3 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 layer thickness of the low refractive index layer 4 and the like.

(4) Adhesion to the holding member Adhesive 6 is applied to the adherend 101 and brought into contact with the flange 51 of the holding member 5 such as a lens barrel to cure the adhesive 6. In the case of the ultraviolet curable adhesive 6, the adhesive 6 can be cured by irradiating ultraviolet rays from the back surface 13 side of the substrate 1. The fluororesin-containing layer 2 has an affinity for the adhesive 6 and exhibits adhesion. For this reason, the optical article 100 is firmly fixed to the holding member 5.

  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) Coating liquid for fluorine resin-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. A fluorine-containing composition solution was obtained by uniformly dispersing in MIBK so that the concentrations shown in Table 1 were obtained. This fluororesin-containing liquid was used for producing the fluororesin-containing layer 2 and the low refractive index layer 4.

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) Coating liquid for high refractive index layer 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 The volume ratio of the mixed solvent consisting of butanol, methyl butyl ketone and i-propyl alcohol (butanol: methyl butyl ketone: i-propyl alcohol) is adjusted so that the initiator (1-hydroxycyclohexyl phenyl ketone) has the concentration shown in Table 2. 1: 1: 1) to obtain a dispersion for a high refractive index layer.

(c) Formation of fluororesin-containing layer (first layer) A jig is attached to the lens 1 having the structure shown in FIG. 1 and made of ZEONEX330R (manufactured by Nippon Zeon Co., Ltd.). It was immersed in the fluorine resin containing liquid obtained in Example 1 (a). Next, the lens was pulled up, and then irradiated with ultraviolet rays at 1500 mJ / cm ² using a UV irradiation apparatus (manufactured by Fusion Systems). As a result, the fluororesin-containing layer 2 (first layer) was formed not only on the optical surface 11 but also on the edge surface 12 and the back surface 13. The physical layer thickness of the fluororesin-containing layer 2 was 20.2 nm, and the refractive index was 1.36.

(d) Formation of High Refractive Index Layer and Low Refractive Index Layer (Second Layer and Third Layer) The obtained lens 1 with fluororesin-containing layer 2 is immersed in a high refractive index layer solution and pulled up. UV irradiation was performed at mJ / cm ² . Next, this was immersed in a low refractive index liquid, pulled up, and then irradiated with ultraviolet rays at 1500 mJ / cm ² . An optical article in which the fluororesin-containing layer 2, the high refractive index layer 3, and the low refractive index layer 4 were formed in this order on the optical surface 11, the edge surface 12, and the back surface 13 of the lens 1 was obtained. The refractive index of the high refractive index layer 3 (second layer) was 1.78, and the physical layer thickness was 140.4 nm. The low refractive index layer 4 (third layer) had a refractive index of 1.36 and a physical layer thickness of 91.9 nm. The spectral reflectance of the obtained optical article was measured at an incident angle of 0 °. The results are shown in FIG.

(e) Adhering to the holding member An ultraviolet curable adhesive (trade name: KZ2510, manufactured by JSR Corporation) is applied to the edge surface 12 of the optical article, and the flange of the lens barrel (made of PC) 5 as shown in FIG. It was made to contact 51. Next, using a UV irradiation device (USHIO INC.), UV irradiation was performed at 1500 mJ / cm ² from the back surface 13 side, the adhesive was cured, and the optical article was fixed.

Example 2
An optical article having the fluororesin-containing layer 2 was obtained in the same manner as in Example 1 (c) except that the physical layer thickness of the fluororesin-containing layer 2 was 96.5 nm. The spectral reflectance of the obtained optical article was measured at an incident angle of 0 °. The results are shown in FIG.

  Apply an immediately curable adhesive [jelly-like instant adhesive, Toa Gosei Co., Ltd.] to the edge 12 of the optical article so that it is in contact with the flange 51 of the lens barrel (made of PC) 5 as shown in FIG. Held for 3 minutes to cure the adhesive.

When the tensile strength of the optical articles of Examples 1 and 2 was measured, both were 28 kgf / cm ² or more. From this, it was found that the adhesive has sufficient durability for practical use.

It is sectional drawing which shows an example of the optical article of this invention. It is sectional drawing which shows the optical article fixed to the holding member. It is sectional drawing which shows another example of the optical article of this invention. It is sectional drawing which shows another example of the optical article of this invention. It is the schematic which shows the polyolefin-type synthetic resin base material immersed in the fluorine-type resin containing liquid. 4 is a graph showing the spectral reflectance of the optical article of Example 1. 6 is a graph showing the spectral reflectance of the optical article of Example 2.

Explanation of symbols

1. Base material
11 ... Optical surface
12 ... edge
13 ... back surface 2 ... fluorine-based resin-containing layer 3 ... high refractive index layer 4 ... low refractive index layer 5 ... lens barrel (holding member)
51 ・ ・ ・ Flange 6 ・ ・ ・ Adhesive
100 ・ ・ ・ Optical article
101 ・ ・ ・ Adhered part

Claims (6)

  In an optical article having a polyolefin-based synthetic resin substrate and bonded to a holding member, a fluorine-based resin-containing layer is formed on the optical surface of the polyolefin-based synthetic resin substrate and an adherend, and the fluorine An optical article, wherein the resin-containing layer is ultraviolet curable and has a refractive index of 1.45 or less.   The optical article according to claim 1, 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. Goods.   The optical article according to claim 1 or 2, wherein the fluorine-containing resin-containing layer is formed by a liquid coating method.   The optical article according to claim 3, wherein the liquid coating method is at least one selected from the group consisting of dip coating, spray coating, spin coating, and flow coating.   5. The optical article according to claim 1, wherein the optical surface has an ultraviolet curable resin layer other than the fluorine-based resin-containing layer, and an ultraviolet-curable resin layer other than the fluorine-based resin-containing layer is provided. An optical article having a refractive index of 1.6 or more. The optical article according to any one of claims 1 to 5, wherein the polyolefin-based synthetic resin base material is a lens, and the adherend is an edge surface of the lens.

Images