JP3531192B2 - Optical article having antireflection layer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical article having an antireflection layer provided with an antireflection property by light interference of a thin film. 2. Description of the Related Art In recent years, the size of transparent members such as windows, doors, and show windows of buildings and vehicles has been further increased, but with the increase in size, reflection and reflection of sunlight, lighting, and the like have occurred. The number of problem cases is increasing. Solar cells and solar water heaters utilizing sunlight are also widely used, but it is necessary to reduce the reflection loss of the light receiving unit. Furthermore, with the spread of portable personal computers, televisions, video players, video recorders, etc., and the development of large displays, LCDs, CRTs, plasma displays, and other displays may be used outdoors or in brightly lit spaces. It has increased. [0003] Optical articles such as plates or windows made of a material such as glass or resin used for these are desirably antireflective in order to reduce unnecessary reflection of light rays and improve transmittance. . Conventionally, in order to impart anti-reflection properties, the surfaces of these optical articles are subjected to anti-reflection processing of thin films by a vapor deposition method or the like. However, there are many optical articles that have not been subjected to antireflection processing, mainly for cost reasons. In particular, when the size of the optical article is large, the antireflection processing cost is enormous, so that it is usual that the antireflection processing is not performed. In order to solve these disadvantages, a polymer having a fluorinated aliphatic ring structure disclosed in JP-A-2-19801 has been proposed as an antireflection processing agent.
Since this polymer has a low refractive index and is soluble in a specific fluorine-based solvent, an antireflection process can be applied to a plate, a film, or the like with high productivity. However, when a polymer having a fluorinated aliphatic ring structure is used alone, the antireflection effect is limited. SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of antireflection processing, and is superior in productivity and antireflection as compared with the conventional vapor deposition method. It is an object to provide an optical article having a layer. According to the present invention, a transparent layer made of a phenoxy resin or a bromide thereof having a higher refractive index than that of a substrate is provided on one surface of a sheet or film substrate. Amorphous fluorinated aliphatic ring on the transparent layer
An optical article having an antireflection layer provided with a fluoropolymer layer made of a polymer having a structure . The optical article of the present invention has an antireflection layer having excellent productivity and an excellent antireflection effect. As the fluorine-containing polymer, tetrafluoroethylene resin, perfluoro (ethylene-propylene) resin, tetrafluoroethylene-perfluoro (alkyl vinyl ether) resin, vinylidene fluoride resin, ethylene-tetrafluoroethylene resin, chlorotrifluoro resin Although ethylene resins and the like are widely known, many of these fluoropolymers have crystallinity, so that light scattering occurs and transparency is not good. The non-crystalline fluorine-containing polymer is excellent in transparency because light is not scattered by crystals. Examples of the non-crystalline fluorine-containing polymer include a terpolymer having units of tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene of 37 to 48% by weight, 15 to 35% by weight and 26 to 44% by weight, respectively. And a polymer having a fluorinated aliphatic ring structure. In particular, a polymer having a fluorinated aliphatic ring structure is preferably employed because of its excellent mechanical properties such as creep resistance. The polymer having a fluorinated alicyclic structure includes a polymer having a fluorinated alicyclic structure in a main chain obtained by polymerizing a monomer having a fluorinated alicyclic structure, and a polymer having at least two polymers. Polymers having a fluorinated aliphatic ring structure in the main chain obtained by cyclopolymerization of a fluorinated monomer having an acidic double bond are preferred. A polymer having a fluorinated alicyclic structure in the main chain obtained by polymerizing a monomer having a fluorinated alicyclic structure is known from JP-B-63-18964. That is, by homopolymerizing a monomer having a fluorinated aliphatic ring structure such as perfluoro (2,2-dimethyl-1,3-dioxole), or by polymerizing the monomer with a radical polymerizable monomer such as tetrafluoroethylene. It is obtained by copolymerization. A polymer having a fluorinated aliphatic ring structure in the main chain obtained by cyclopolymerization of a fluorinated monomer having at least two polymerizable double bonds is disclosed in
238111 and JP-A-63-238115. That is, it can be obtained by cyclopolymerizing a monomer such as perfluoro (allyl vinyl ether) or perfluoro (butenyl vinyl ether), or by copolymerizing the monomer with a radical polymerizable monomer such as tetrafluoroethylene. Further, perfluoro (2,2-dimethyl-
Monomers having a fluorinated aliphatic ring structure such as 1,3-dioxole) and perfluoro (allyl vinyl ether)
Or a polymer obtained by copolymerizing a fluorine-containing monomer having at least two polymerizable double bonds such as perfluoro (butenyl vinyl ether) or the like. The polymer having a fluorinated aliphatic ring structure is
Polymers having a fluorinated aliphatic ring structure in the main chain are preferred. It is preferable that a monomer unit having a fluorinated aliphatic ring structure be contained in a monomer unit forming a polymer in an amount of 20 mol% or more in terms of transparency, mechanical properties, and the like. The substrate in the present invention is not particularly limited, and a wide range is used. For example, glass, polymethyl methacrylate (acrylic resin), polycarbonate,
Examples thereof include transparent sheets and films of urethanes and the like. The sheet-like or film-like base material may have a smooth surface, the surface of which has been subjected to prism processing, Fresnel lens processing, lenticular processing, etc., a polarizing function, a light diffusing function, a phase difference function, etc. Those having the various functions described above can also be used. The material of the transparent layer (hereinafter abbreviated as high refractive index film) having a higher refractive index than the substrate used in the present invention includes :
Phenoxy resins or bromide is used. [0016] In terms of increasing the adhesion between the substrate and the fluorine-containing polymer layer, such as phenoxy resins is not good. In the present invention, the antireflection layer comprising the high refractive index film and the fluoropolymer layer is applied to one surface of the substrate. The antireflection layer is preferably two layers of a high-refractive-index film and a fluoropolymer layer, but if necessary to enhance the adhesion between the high-refractive-index film and the substrate or the fluoropolymer layer in addition to the two layers. An intermediate layer may be provided. The thickness of the layer in the antireflection layer utilizing the light interference of the thin film is strictly designed optically. Thickness d ₁ of the fluoropolymer layer, using the wavelength lambda of the light to be refractive index n ₁ and the subject of the _{polymer, d 1 = (2m 1 -1} ) · λ /
(4n ₁ ). Although m ₁ is a positive integer, m ₁ = 1 to reduce reflection at a wide band of wavelengths.
It is preferable that Further, the thickness d ₂ of the high refractive index film is determined by using the refractive index n ₂ of the high refractive index film as d ₂ = (2m ₂ -1) .lambda. /
(4n ₂ ). m ₂ is a positive integer, m ₂ = 1 is preferred also same reason as m _1. At this time, the wavelength λ
Has the highest anti-reflection effect with respect to the light of the following, but in order to cope with a wider wavelength range, d ₂ = (2m ₂ −1) · λ /
A method of (2n ₂ ) or another intermediate thickness design is also conceivable. The deviation of the actual film thickness from the design value is preferably within ± 10%, and more preferably within ± 5%, in order to exhibit a predetermined antireflection performance. Further, the thickness deviation in the same plane is preferably within ± 5%, more preferably within ± 3%, because if the deviation is large, the color of reflected light becomes uneven and the appearance is impaired. In the present invention, the method for forming the antireflection layer is not particularly limited, and any processing method can be selected. For example, non-crystalline fluoropolymers include perfluorooctane, CF ₃ (CF ₂ ) _n CH ＝ CH ₂ (n;
1) It is soluble in a specific fluorine-based solvent such as CF ₃ (CF ₂ ) _m CH ₂ CH ₃ (m; 5 to 11), and can be easily determined by applying a solution of this polymer and drying it. Can be formed. As the coating method, for example, a dip coating method, a roll coating method, a spray coating method, a gravure coating method, a comma coating method, a die coating method, and the like can be selected. These coating methods are capable of continuous processing, and are superior in productivity as compared with a batch type evaporation method or the like. Although the productivity is slightly inferior, a spin coating method or the like can also be employed. When a high refractive index film made of a polymer is provided, a method in which a polymer is dissolved in a solvent and applied can be used in exactly the same manner as the above-mentioned method for forming a fluoropolymer layer except that the solvent is different. When a high refractive index film made of an inorganic oxide is provided, a method of applying a dispersion of inorganic oxide fine particles, condensation, a compound that gives a desired high refractive index inorganic oxide by a reaction such as polymerization, and the like, is applied on a substrate. Then, the reaction can be advanced to form a high refractive index film. As the compound giving the high refractive index inorganic oxide, an alkoxide such as Ti is particularly preferably used. In any case, various additives and binders may be added to improve adhesion and improve physical properties. Further, in order to enhance the adhesion between the substrate and the high refractive index film, the surface of the substrate may be previously subjected to an active energy ray treatment such as a corona discharge treatment or an ultraviolet treatment, or a primer treatment. Even when a fluoropolymer layer is provided on the high-refractive-index film, the high-refractive-index film may be subjected to an active energy ray treatment such as a corona discharge treatment or an ultraviolet treatment or a primer treatment to enhance adhesion. . In order to increase the adhesion between the base material and the high refractive index film, and to increase the adhesion between the fluoropolymer layer and the high refractive index film, a material containing a high refractive index film and an amorphous material are used. It is effective to add a silane coupling agent to at least one of the fluoropolymers. In particular, the effect is high when added to a non-crystalline fluoropolymer. The silane coupling agent can be exemplified in a wide range including those conventionally known or known. For example, monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, dimethylvinylmethoxysilane, and dimethylvinylethoxysilane are exemplified. Also, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane,
Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyl methyl diethoxy silane, 3-methacryloyloxypropyl methyl dimethoxysilane, di methyl diethoxy silane, methyl vinyl dimethoxy silane, methyl vinyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, 3,3,3 -Trifluoropropylmethyldimethoxysilane, 3,3,4,4
5,5,6,6,7,7,8,8,8-tridecafluorooctylmethyldimethoxysilane, 3,3,4,4
5,5,6,6,7,7,8,8,9,9,10,1
Dialkoxysilanes such as 0,10-heptadecafluorodecylmethyldimethoxysilane; Further, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-
Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3
-Mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,
7,8,8,8-tridecafluorooctyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-heptadecafluorodecyltrimethoxysilane, tetramethoxysilane,
Tri or tetraalkoxysilanes, such as tetraethoxysilane, may be mentioned. These alkoxysilanes can be used alone or in combination. Among these, 3-aminopropyltriethoxysilane having an amino group, 3-aminopropylmethyldiethoxysilane, as one that improves the adhesiveness of the fluoropolymer without impairing the transparency of the fluoropolymer, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane,
N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane or the like, or 3 having an epoxy group
Glycidyloxypropyltrimethoxysilane, 3-
Glycidyloxypropylmethyldimethoxysilane, 3
Glycidyloxypropyltriethoxysilane, 3-
Glycidyloxypropylmethyldiethoxysilane and the like can be exemplified as particularly suitable. The optical article of the present invention can be used by attaching it to an article requiring antireflection, for example, a polarizing sheet or film, a display, or another article. Examples of the display include a CRT, a VDT (visual display terminal), a liquid crystal display, a projection display, a plasma display, and the like. The attachment of the optical article of the present invention can contribute to prevention of reflection of external light, improvement of luminance, improvement of contrast, and the like. The method of attaching the optical article of the present invention to another article is not particularly limited, and a method such as adhesion, adhesion or heat fusion can be selected. The surface on which no layer is formed may have an adhesive layer or an adhesive layer. Further, a protective film for protecting the adhesive layer, the adhesive layer or the antireflection layer may be provided. The article to which the optical article of the present invention is attached is CR
When placed on the front of the display as a T filter, an LCD protection panel, or a front panel of a projection screen, it can contribute to the improvement of visibility as described above,
It is also useful as a touch panel. Next, examples of the present invention will be described more specifically, but this description does not limit the present invention. Synthesis Example 1 35 g of perfluoro (butenyl vinyl ether), 150 g of ion-exchanged water and ((CH
₃ ) 90 mg of ₂ CHOCOO) ₂ in 200 ml internal volume
In a pressure-resistant glass autoclave. After purging the system with nitrogen three times, suspension polymerization was performed at 40 ° C. for 22 hours.
As a result, 28 g of polymer A was obtained. The intrinsic viscosity [η] of this polymer was 0.50 at 30 ° C. in perfluoro (2-butyltetrahydrofuran). The glass transition point of the polymer was 108 ° C., and it was a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature was 465 ° C., the refractive index was as low as 1.34, and the light transmittance was as high as 95% or more. Solution A was prepared by dissolving this polymer in perfluorooctane at 1.5% by weight. ## STR1 ## Formulation Example 1 Brominated phenoxy resin (Phenotote YPB manufactured by Toto Kasei)
A solution F was prepared by dissolving -43C, molecular weight of about 60,000) in 1,1,2,2-tetrachloroethane at 1.5% by weight. The refractive index of the brominated phenoxy resin was 1.63. Example 1 A solution F was spin-coated on a glass plate at 3000 rpm.
One side of the substrate was coated with a thin film of a brominated phenoxy resin by heating at 70 ° C. for 10 minutes. Furthermore this
After immersing the glass plate in the solution A, the glass plate is vertically moved at a speed of 200 mm / min.
By heating at 120 ° C for 10 minutes.
Thus, both surfaces of the glass plate were coated with a thin film of the polymer A. Continued
And wipe the coat on the back using perfluorooctane
Take brominated phenoxy resin and polymer A only on the surface
A glass plate coated with a two-layer thin film was obtained. The single-sided reflectance of this glass plate was 0.25%, and almost no reflection of the background was visually observed. Comparative Example 1 The single-sided reflectance of the glass plate used in Example 1 was 4.1%, and the reflection of the background was observed. According to the present invention, it is possible to obtain an optical article having an antireflection layer capable of performing antireflection processing with high productivity and exhibiting extremely high antireflection properties. it can.

Continuation of the front page (56) References JP-A-3-90345 (JP, A) JP-A-2-19801 (JP, A) JP-A-6-18705 (JP, A) JP-A-6-115023 (JP) JP-A-7-168005 (JP, A) JP-A-1-191852 (JP, A) JP-A-1-191852 (JP, A) JP-A-6-18704 (JP, A) 59-115840 (JP, A) JP-A-63-238115 (JP, A) JP-A-63-238111 (JP, A) JP-B-63-18964 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02B 1/11

Claims (1)

(57) [Claim 1] A phenoxy resin or a phenoxy resin having a refractive index higher than that of a base material on one side of a sheet or film base material.
An optical article having an antireflection layer comprising a transparent layer comprising a bromide and a fluoropolymer layer comprising a polymer having a non-crystalline fluorinated alicyclic structure on the transparent layer .