JPS5949501A - Transparent material having antireflection film - Google Patents

Abstract

PURPOSE:To improve the resistance to heat and impact by coating three-layered antireflection films having prescribed refractive indices and thicknesses on the surface of a transparent base material. CONSTITUTION:Three-layered antireflection films having prescribed refractive indices and thicknesses are coated in a liquid form on the surface of a transparent base material of glass, plastics, etc. having transparency of >=80% cloudiness and are cured. The film having the refractive index higher by >=0.03 than either of the base material or the 3rd layer is used for the 1st layer among the antireflection films, and the film having the refractive index higher by >=0.03 than the 1st layer is used for the film to be coated as the 2nd layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transparent material having an antireflection 1F film that can be easily applied to various transparent materials and has good durability, heat resistance, and impact resistance.

A table for viewing objects through a transparent material 2 The reflected light is strong 9 The clarity of the reflected image is troublesome 9 For example, lenses for eyeglasses produce reflected images called ghosts and flares, which are unpleasant to the eyes. to give. Furthermore, with a looking glass, etc., there is a problem in that the contents are not clearly visible due to the reflection on the glass surface.

Conventionally, in order to prevent reflection, a method has been used in which a film of a substance whose refractive index meets that of the base material is formed on the base port by vacuum evaporation or the like. It is known that in order to achieve this high anti-reflection effect, it is important to select the thickness of the material that covers the base material at tθ. For example, in a single-layer coating, selecting a material with a lower oil refraction index than the base material with an optical film thickness of 1 to an odd multiple of the target light wavelength provides the minimum reflectance, that is, the maximum transmittance. It is known.

The optical film thickness here is given by the product of the refractive index of the coating forming material and the film thickness of the coating. Furthermore, it is possible to form a multi-layer anti-reflection layer, and several proposals have been made regarding the selection of film thickness in this case ("OFT Engineering C8OF
TH Engineering FILMS” p, 159-P, 283
A, VASICEK (NORTH-HOLLANDP
UBL EIH NG COMPANY ) AMBT
BRDAM (1960)).

The antireflection film formed by this vapor deposition method has the following problems depending on the application.

(1) Requires a high degree of vacuum/limits the size and material of the substrate to be treated. Also, the manufacturing time will be longer,
Productivity and economic efficiency decline.

(2) Usually requires intense heating, and depending on the base material, deformation 2
This causes problems such as decomposition.

(3) Monthly rate of film formation used - 1 Mainly made of inorganic oxide and forms a dense film, but on the other hand, in the case of a glass base material, it has heat resistance due to the difference in d-line expansion coefficient.

May cause reduced adhesion.

(4) The dye permeability necessary for dyeing, which is an effective means for packaging transparent substrates, is completely lost.

(5) Similar loss of dyeability, loss of heat resistance, and deterioration of adhesion occur in glass where dyeable materials are destroyed.

To the inventors: 1. We have previously proposed a transparent material having two layers, each coated in liquid form, upon reflection. However, the tl and tl reflection film formed from these two layers has the following problems depending on the application.

(1) To achieve high anti-reflection effect
Thickness control must be performed with high precision, and manufacturing variations are large.

(2) It is difficult to obtain a greenish reflected light color, which is particularly desired for eyeglass lenses.

The inventors of the present invention have made extensive studies to solve the numerous problems and have arrived at the present invention described below.

That is, the present invention provides an anti-reflection film obtained by coating each of three layers in liquid form on at least a portion of the surface of a transparent substrate, drying and curing or curing, and wherein the anti-reflection film The refractive index of the layer on the transparent base material side (first layer) is higher than that of the transparent base material layer in contact with this layer, and
A layer (sixth layer) having a lower refractive index than a layer provided above the layer (second layer) and further provided below the second layer (sixth layer)
has a lower refractive index than the first and second layers;

The present invention relates to a transparent material having a film at the time of reflection in which the film thicknesses of the second layer and the third layer each satisfy the following conditions.

El! 1st layer −λx O,7< nla+ < −J x
1.34 2nd layer −λx O,7< n2a2 <−λ×134 6th layer −λX (17< n3d, <−λ×1.5
4 (where nI+ n2+ ”S are the first layer and the 21st layer, respectively.
%.

Refractive index of the sixth layer, dl, d2. d3 are the first layer and the second layer, respectively.
layer, the thickness of the sixth layer (in nm degrees), e is a positive integer, 2m is a positive integer, n is an odd positive integer, λ is an arbitrary reference wavelength (in nm) chosen within the visible peripheral region) where The transparent base material is a transparent base material having a transparency with a haze value of 80% or less as determined by the following formula.

If necessary, this may include those colored with dyes or the like, and those colored in patterns. A transparent substrate that is coated with a coating phase to impart scratch resistance, for example, is included in the transparent substrate of the present invention if the haze value determined by the following formula is 80% F or less. I can do it.

In order to more effectively exhibit the effects of lowering the light reflectance and improving light transmittance as intended by the present invention, it is preferable to use a material that is as transparent as possible. If only one side of the substrate is sufficient, 2. Even if the opposite side is covered with an opaque material, it can be used as the lucky transparent substrate in the present invention. In this case, The haze value must be defined by removing the opaque material on the opposite side.

Examples of the above-mentioned transparent substrate include glass, molded products such as plastic articles, sheets, films, and the like. In particular, when a plastic article is used as a transparent substrate, a coating material is applied on the substrate in advance to improve and impart various physical properties such as adhesion, hardness, chemical resistance, durability, and dyeability. You can also use something. However, it is necessary that the substrate (transparent substrate) coated with these coating materials has the same transparency as that given for the transparent substrate.

The liquid composition for forming the coating that imparts the antireflection properties may be composed only of a film-forming substance, or may contain various volatile solvents to impart the necessary coating workability. can.

Here, the liquid composition is a composition having a viscosity within a range to which ordinary coating operations can be applied, and is 10 poise or less, preferably 1 poise or less at the application temperature. That is, it is difficult to obtain a uniform coating film with a liquid composition having a viscosity higher than this. The coating method used in normal coating work is possible, but from the viewpoint of controlling the thickness of the thin film, curtain flow coating,
Dip coating, spin coating, etc. are preferred.

Among the anti-reflection coatings, the coating that is first applied as the first layer has a coating that is 0.0.
A material having a refractive index as high as 0.03 or higher, preferably 0.005 or higher is used. The film applied as the second layer has a refractive index higher by 0.06 or more, preferably by 0.05 or more, than the first layer in contact with the second layer. When applying the first layer, second layer, and filtration layer, adhesion can be improved by applying various chemical treatments and physical treatments to the layers in contact with each other.

The above-mentioned first layer, second layer and sixth layer are separately and Dry and/or cure at once.

Such a film-forming material is such that the film formed therefrom satisfies the requirements regarding refractive index.

Any material may be used as long as it forms a liquid composition by itself or by dispersing or dissolving it in a solvent, but in particular, it may be an organic material, or inorganic fine particles dispersed in an organic material to an extent that does not impair transparency. Inorganic materials with film-forming properties that can be dispersed or dissolved in solvents, or that are liquid themselves.

Alternatively, a mixture of such an inorganic material and an organic material is used.

When these materials are used as the first layer and the second layer,
Film-forming substance 9 with a relatively high refractive index as an organic material
For example, polystyrene, polystyrene copolymers, polycarbonates, various polymer compositions containing aromatic rings other than polystyrene, heterocycles, alicyclic groups, and halogen groups other than fluorine, melamine resins, phenolic resins, or epoxy resins. Introducing type 2 packing into various thermosetting resin-forming compositions using as a curing agent, urethane-forming compositions consisting of alicyclic or aromatic inocyanates and polyols, and the above-mentioned compounds. Accordingly, compositions containing various modified resins or prepolymers that can be radically cured are preferably used.

Since inorganic particles generally have a high refractive index, an organic material with dispersed inorganic particles may also have a lower refractive index than when an organic material is used alone. Vinyl copolymers including curved acrylics, polyester (including alkyd) polymers, lp of the organic materials mentioned in 2.
Fibrous polymer.

Various organic materials that are transparent and can stably disperse inorganic fine particles can be used, such as urethane polymers, various curing agents for curing these polymers, and compositions having curable functional groups. Additionally, organically substituted silicon-based compounds can be submerged therein. These silicon-based compounds are compounds with the general formula (%) or their hydrolyzable properties.
2 It is a thing. Here, R is an alkyl group, an alkenyl group, an allyl group, respectively. or a hydrolyzable substituent selected from a halogen group, an epoxy group, an amine group, a mercapto group, a hydrocarbon group having a methacryloxy group or a cyano group, an alkoxyl group, an alkoxyalkoxyl group, a halogen group or an acyloxy group, a, b are each hO21 or 2 and a+b is 1 or 2. As the inorganic compound dispersed in this, oxides of metal elements such as aluminum, titanium, zirconium, and antimony are preferably used. These are provided in the form of fine particles or as a colloid or dispersion in water and/or other solvents. These are mixed and dispersed in the above organic material or organosilicon compound.

Suitable examples of inorganic materials that have film-forming properties and can be dispersed in solvents or are liquid themselves include alkoxides of various elements, salts of organic acids, and coordination compounds combined with coordination compounds. Examples include titanium oxide, titanium tetran-
propoxide, titanium tetra-n-butoxide, titanium tetra-8θC-butoxide, titanium tetra-tert
-Butoxide.

Aluminum triethoxide, aluminum tri-
Globoxide, aluminum tributoxide, antimony triethoxide, antimony tributoxide, zirconium tetraethoxide, zirconium tetra-i-
Glopoxide, zirconium tetra-n-globoxide, zirconium tetra-n-butoxide, zirconium tetra-5ec-butoxide, zirconium tetra-t
metal alcoholate compounds such as ert-butoxide,
Furthermore, diisoglopoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, bisacetylacetone zirconium, and aluminum acetylacetonate.

Chelate compounds such as aluminum di-n-butoxide monoethyl acetoacetate, aluminum di-1-proboxoxide monomethyl acetoacetate, tri-0-butoxide zirconium monoethylacetoacetate, as well as zirconyl ammonium carbonate or zirconium as the main component. Examples include active inorganic polymers.

In addition to those mentioned above, various alkyl silicates or their hydrolysates, fine particulate silica, especially colloidally dispersed silica sol are used as compounds having a relatively low refractive index but which can be used in combination with the above compounds.

On the other hand, among the above-mentioned organic materials and/or inorganic compounds, relatively the first layer,
A material that forms a film with a refractive index lower than that of the second layer is used, and preferred examples include vinyl copolymers including acrylic copolymers that do not contain aromatic rings, and various fluorine-substituted polymers.

Polyester (including alkyd) polymers that do not contain aromatic rings, cellulose derivatives, and silicone polymers.

Among hydrocarbon polymers or prepolymers thereof, there are compositions comprising those having a curable functional group and a curing agent. As the inorganic material, organically substituted silicon compounds containing no aromatic rings, various alkyl silicates, and particulate silica, especially colloidally dispersed silica sol, are preferably used.

The above-mentioned various materials used in the first layer, the second layer, and the sixth layer can be used alone or in combination of two or more types within a range that does not reduce transparency.

These compositions are usually applied diluted in volatile solvents. The solvent to be used is not particularly limited, but the solvent should be determined by taking into consideration the stability of the composition, wettability to the transparent substrate, volatility, etc.

Moreover, it is also possible to use not only one type of solvent but also a mixture of two or more types.

It is also possible to use various surfactants in the coating compositions of the first, second and sixth layers of the present invention for the purpose of improving the flow during coating, especially dimethylsiloxane. Block or graft copolymers with alkylene oxide and fluorine-based surfactants are effective.

Furthermore, it is easily possible to add an ultraviolet absorber to each layer for the purpose of improving weather resistance, and an antioxidant to improve heat resistance to deterioration.

The coating composition of each layer applied in this manner can be thermally cured and/or dried in stages, or the second layer can be sheeted after the first layer coating has been precured and/or dried. death.

After pre-curing and/or drying, it is also possible to apply a sixth layer and heat-cure and/or dry. As a heating method, hot air, infrared rays, etc. can be used. Still the heating temperature should be determined by the applied transparent substrate and the coating composition used, but is usually 50-250°C, more preferably 60°C.
~200°C is used. If the temperature is lower than this, curing or drying will be insufficient, and if the temperature is higher than this, thermal decomposition will occur, causing problems such as yellowing.

Furthermore, it is also possible to cure using radiation such as ultraviolet rays, electron beams, and gamma rays by utilizing the curable functional group 1, for example, a double bond in a polymer or oligomer.

Further, the film thicknesses of the first layer, second layer and third layer of the present invention are controlled by the solid content of the coating composition, coating method, and coating conditions.

As the transparent base material of the present invention, any transparent material may be used as long as the purpose of the present invention is required, but from the viewpoint of liquid coating, glass and plastic materials give particularly effective results. The above plastic materials include polymethyl methacrylate and its copolymers, and polycarbonate.

Diethylene glycol bisallyl carbonate (CR)
-39), polyesters, especially polyethylene terephthalate, and unsaturated polyesters, acrylonitrile-
Styrene copolymer, vinyl chloride.

Polyurethane, epoxy resin, etc. are preferred.

Moreover, it can also be preferably used for glass.

The plastic according to Jt further coated with a coating material.

It can also be preferably applied to transparent substrates such as glass.

In particular, the coating material underlying the antireflective thin film of the present invention improves adhesion, hardness, chemical resistance, and durability.

Physical properties such as dyeability can be improved.

However, in order to improve the hardness, it is possible to use various materials that have been known as coatings for increasing the surface hardness of plastics. (asp3.894,881,
Tokuko Showa 51-24!168. Japanese Patent Publication No. 52-112698
, USP 4,211,825), especially the U.S.
F 4,211,823 to which the anti-reflective multi-layer film of the present invention is applied to the dyeable highly hardened coating maximizes the effect of the present invention as an anti-reflective coating that is dye permeable. It can be preferably used if it is obtained.

Many combinations of the base material or coated base material and antireflection multilayer film can be considered to achieve the purpose of the present invention, and the optimal range should be determined experimentally depending on the purpose.

The transparent material having an antireflection film obtained by the present invention has the following characteristics in addition to the antireflection function.

(1) Can be dyed with disperse dyes, etc.

(2) Excellent heat resistance and hot water resistance.

(3) High surface hardness and scratch resistance.

(4) Excellent chemical resistance.

Furthermore, an antireflection film having a green reflected light color, which cannot be obtained with a two-layer film, can be obtained.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of first layer coating composition 164.9 g of acetylacetone was mixed with 17.2 g of tetra-n-butyl titanate under stirring, and colloidal silica dispersed in methanol (average particle size 1231 ml, solid content 60%) 20
．． 0 g and 0.11 g of a silicone surfactant were added to prepare a coating composition.

(2) Preparation of second layer coating compositions All compositions were prepared in the same manner as in the previous section (1) except that the amounts added were changed as shown below.

Acetylacetone 16200 g Tetra-n-butyl titanate 30.20 g Methanol-dispersed colloidal silica 10. OOg Silicone surfactant 0.11 g (3) Preparation of 6th layer coating composition (a) Preparation of silane hydrolyzate γ-glycidoxyprobyltrimethoxysilane 56.5
g, vinyltriethoxysilane 24.0g, n-propyl alcohol 100.3g K0.05N aqueous hydrochloric acid solution 1
98 g was added dropwise and mixed under stirring while controlling the temperature to 10°C. After the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour to obtain a silane hydrolyzate.

(b) Preparation of coating composition 150.5 g of n-globanol, 71.2 g of water, 23.9 g of ethyl cellosolve, and 23.9 g of ethyl cellosolve were mixed into 693 g of the silane hydrolyzate. 32.5 g of dispersed colloidal silica, 0.22 g of a silicone surfactant, and 0.98 g of aluminum acylacetonate were added and thoroughly stirred and mixed.

A coating composition was obtained.

(4) A diethylene glycol bisallyl carbonate polymer lens (diameter 75
The first layer coating composition prepared in () above was spin-coded onto a CR-Ro9 Praruns (2.1 mm thick, 2.1 mm thick) under the following conditions. The coated lens is 90'
Heat drying was performed in O for 0.75 hours.

Spin cord conditions Rotation speed: 3500 rpm Rotation time: 60 seconds After heating, it was immersed in hot water at 40-C for 1 hour, washed with water, and further immersed in acetone to remove water droplets attached to the surface. . Thereafter, it was heated and dried at 110'O for 1 hour to obtain a first layer.

On top of the obtained first layer, the second layer prepared in (2) above is further added.
The layer coating composition was spin-coded under the same conditions as the first layer, and after coating was subjected to the same heating and hot water treatment as the first layer to obtain the second layer.

Further, the sixth layer coating composition prepared in (3) above was spin-coated on the second layer obtained under the same conditions as the first layer except that the rotation time was changed to 60 seconds.

After coating, heat curing was performed for 2 hours in a hot air dryer at id9°C.

(5) Test results The total light transmittance of the obtained lens was 95.2%.

The reflected light color was reddish-purple. In addition, uncoated CR-69
The total light transmittance of the lens was 92.6%.

In addition, this anti-reflection lens was dyed at a 90°
Stained for 145 minutes. This lens has a total light transmittance of 6
It was stained up to 0.08%. Furthermore, the antireflection lens had the same reflected light color after dyeing as before dyeing.

Note that the refractive index and film thickness of each of the first layer, second layer, and sixth layer were as follows.

Refractive index Film Thickness 1st layer 1.60 1040A 2nd layer 1
．． 71 920A 6th layer 1.48 90OA Comparative Example 1 In Example 1, the first layer and the second layer are reversed.

That is, everything was carried out in the same manner except that the second layer coating composition was first coated on the substrate, and then the first layer coating composition was coated thereon. As a result, the total light transmittance of the obtained lens was 889%, and the C
It showed greater reflection than R-39.

Example 2 (1) Preparation of undercoating composition (a)
Preparation of silane hydrolyzate γ-glycidoxyglobyl methyljethoxysilane 1
06.8 g was cooled to 10° C., and without stirring, 155 g of 005N hydrochloric acid aqueous solution was gradually added dropwise. After 4 drops were added, stirring was continued for an additional hour at room temperature to obtain a silane hydrolyzate.

(b) Preparation of coating composition To the silane hydrolyzate, 25 g of epoxy resin ("Epicote 827", manufactured by Shell Chemical Co., Ltd.), 25 g of epoxy resin ("Evolite 3002", manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and Acetone alcohol 58.9g
, benzyl alcohol29. '5g.

610g methanol, 1.5g silicone surfactant
416.7 g of methanol-dispersed colloidal silica used in Example 1 and 12.5 g of aluminum acetylacetonate were added.

After sufficient stirring, the coating composition is prepared.

(2) Application, curing, and pretreatment of undercoat The coating composition described above was applied to the diethylene glycol bisallyl carbonate polymer lens used in Example 1 by a dipping method, and heated at 93° C. for 4 hours. The cured lens was pretreated using a surface treatment plasma device (PR501A manufactured by Yamato Rigaku Co., Ltd.).
Oxygen flow rate 100 mi? -/min.

The treatment was performed for 30 seconds at an output of 50W.

(3) Production of antireflection film An antireflection film was obtained in exactly the same manner as in Example 1 using the undercoated lens.

Note that the refractive index and film thickness of the first layer, second layer, and sixth layer were all the same as in Example 1. The refractive index of the base material layer (undercoat layer) in contact with the first layer was 1.50.

(4) Test results The total light transmittance of the obtained lens was 969%.

It had a yellowish-green reflected light color. In addition, this lens was dyed at a 90°
Stained for C945 minutes. This lens has a total light transmittance of 2
Up to 2.3% was stained. When the abrasion resistance of this lens was examined using ≠0000 steel wool before and after dyeing, no scratches were observed after abrasion. The reflection spectrum of the lens obtained in this example was measured. The results are shown in Figure 1.

EXAMPLE The same procedure as in Example 1 was carried out except that the transparent lens was replaced with an inorganic glass lens.

The total light transmittance of the obtained lens was 96.8%.

71 - It was an antireflection lens with seven reflected light colors.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the reflection spectrum of an antireflection lens having a yellowish-green reflected light color according to an embodiment of the present invention. Patent applicant Toshi Co., Ltd. Figure 1 66 EOθ 600 7〃 Pi starvation

Claims (1)

[Claims] (1) An antireflection film obtained by coating each of six layers in a liquid state on at least a part of the surface of a transparent profiteer, drying and curing, or curing, and on the transparent substrate side of the antireflection film. The refractive index of the layer (first layer) is higher than that of the transparent base material layer in contact with the stiffness, and lower than the layer (second layer) provided next to the first layer, and The second layer (third layer) is the second layer (third layer) of the second layer.
1. A transparent material comprising an antireflection film having a refractive index lower than that of the first layer, the second layer, and the second layer, and the thicknesses of the first layer, the second layer, and the sixth layer each satisfy the following conditions. l! / 1st N −λx O, 7< nod, <−λ×1.3
4 2nd layer -λxO17(n2d2<-λx1.34 6th layer -λx O,7<n, d4<-λx1.3
4 (where nl + n2 + "4 is the first layer and the second layer, respectively. The refractive index of the fifth layer! a, + a2+ dS is the film thickness of the first layer, the second layer, and the fifth layer, respectively. / is a positive integer 1m is a positive integer pl 1 is an odd positive integer, λ is an arbitrary reference wavelength selected within the visible peripheral region (nmQ' - (1))