JPS62178901A - Optical parts having multi-layered antireflection film - Google Patents

Abstract

PURPOSE:To improve adhesive strength and durability by providing a hard coat layer having scratching resistance on a transparent plastic base material and providing specific multi-layered antireflection films on the front layer thereof. CONSTITUTION:The hard coat layer 11 having the scratching resistance is provided on the transparent plastic base material 10. A layer 1 essentially consisting of zirconium oxide, a layer 2 essentially consisting of silicon oxide, a layer 3 essentially consisting of titanium oxide and a layer 4 essentially consisting of silicon dioxide are provided successively from the surface from the base material side on the front layer thereof; at the same time, the 1st layer and the 2nd layer are made of the equiv. films. The 1st layer and 2nd layer are formed as the layer having a middle refractive index as a while and the layer essentially consisting of the titanium oxide is then provided as the 3rd layer thereon. The layer essentially consisting of the silicon dioxide is provided as the 4th layer thereon. The film having the excellent antireflective function as a whole is attained coupled by the middle refractive index layer of the 1st and 2nd layer if a high refractive index layer is provided on the 3rd layer and a low refractive index is provided on the 4th layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an optical article having a multilayer antireflection film with excellent adhesion strength. More specifically, we offer multilayer anti-reflection coatings useful for optical lenses such as eyeglass lenses and camera lenses, optical filters attached to displays such as word processors and cathode ray tubes of televisions, and window glass of automobiles. The present invention relates to an optical article having the following.

[Prior art] Plastic molded products, such as plastic lenses, have extremely high impact resistance and transparency, are light nails, and can be easily dyed, so the demand for them has been increasing in recent years. . However, plastic optical products have a disadvantage in that their surface hardness is lower than that of inorganic glass and they are easily scratched.

Many attempts have already been made to improve the vulnerability of the former. For example, a method of coating the surface of a plastic substrate with an inorganic substance such as 3i02 by vacuum deposition (Japanese Patent Laid-Open No. 58-204031), a method of coating the surface of a plastic substrate with a polyorganosilane hard coat film or an acrylic Bartco-1~ Method of providing a membrane (USP 3.
986,997, USP4,211,823, Japanese Patent Publication No. 5
7-168922, JP 59-38262, JP 59-51908, JP 59-51
954, JP 59-78240, JP 59-89368, JP 59-102964, JP 59-109528, JP 59-
120663M, JP 59-155437, JP 59-174629, JP 59-19
No. 3969, Japanese Unexamined Patent Application Publication No. 59-204669, etc.) are disclosed.

Improvement of surface hardness by vacuum deposition of an inorganic material such as S i 02, which is the conventional technique described above, has high hardness, but on the other hand, it has large effects that reduce adhesion to the base material, heat resistance, impact resistance, hot water resistance, light resistance, etc. There are bound to be problems.

In addition, in order to improve both the surface hardness and anti-reflection properties of plastics, 5102 of approximately 1 micron is coated on the plastic substrate by vacuum deposition, and a multilayer anti-reflection film is roughly coated on top of this. is disclosed.

(Japanese Unexamined Patent Publication No. 113101/1983).

Furthermore, JP-A-59-48702, JP-A-59-
No. 78301 and JP-A-59-78304 disclose a method in which a polyorganosilane Bartco-1 film or a cured epoxy resin film is applied to the surface of a plastic base material, and then an antireflection film made of an inorganic substance is coated. A method is disclosed.

Furthermore, although the technology disclosed in JP-A-56-113101 has high hardness and antireflection properties, it deteriorates adhesion, heat resistance, impact resistance, hot water resistance, weather resistance, etc. There's a problem.

Also, Japanese Patent Publication No. 45-6193, Japanese Patent Publication No. 59-487
02 Tan Publication, JP-A No. 59-78301, JP-A-Sho 5
Although the technique disclosed in Japanese Patent Publication No. 9-78304 has antireflection properties, it has insufficient adhesion to the substrate and causes deep and thick scratches, which is a major disadvantage in use. Furthermore, it is easily immersed in water, alcohol, etc., and has major problems such as adhesion after immersion in hot water and weather resistance.

We have reviewed the conventional technologies above, but all of these technologies have problems with the adhesion between the hard coat layer on the base material and the vapor deposited film (antireflection layer) on the surface layer, and if used for a long period of time, the vapor deposited film ( The problem was that the antireflection layer (antireflection layer) peeled off in the form of scales.

Problems to be Solved by the Invention] The present inventors have conducted intensive studies to solve the above problems, and as a result, have arrived at the present invention described below.

In other words, the present invention has particularly excellent adhesion strength and durability, and also has excellent abrasion resistance, abrasion resistance, impact resistance, chemical resistance, flexibility, heat resistance, light resistance, weather resistance, antistatic properties, etc. An object of the present invention is to provide an optical article having an excellent multilayer antireflection film.

[Means to solve problems] That is, the present invention consists of the following configuration.

"A hard coat layer having abrasion resistance is provided on a plastic transparent base material, and on the surface thereof, in order from the base material side toward the surface: a first layer; a second layer containing zirconium oxide as a main component; A third layer containing silicon dioxide as a main component; A fourth layer containing titanium oxide as a main component; At the same time as providing a layer containing silicon dioxide as a main component, the first layer and the second layer are equivalent films. An optical article having a multilayer anti-fouling film characterized by the following: In the present invention, it is first necessary to provide Bartco-1 to layers having abrasion resistance on a transparent plastic substrate. Here, the plastic may be any known material. Moreover, the transparent base material may be any material as long as light can pass therethrough. For items used on the front of displays such as word processors, the visible light transmittance should be increased to 25~25 by sprinkling or dyeing.
Preferably it is 70%. This is to reduce eye fatigue. In addition, the Hedoco 1 layer has abrasion resistance.
A coating layer with high hardness such as polyorganosiloxane, silica, alumina, or a layer containing an acrylic component. This is to improve the surface of plastic products, which are generally easily scratched, and to improve adhesion by undercoating the surface with a multilayer anti-reflection film that is vapor-deposited or sputtered. Particularly preferably, the Bartco-1 layer is a polyorganosiloxane coated with methyl-1-rimethoxysilane, vinyl-1-ethoxysilane, or a hydrolyzate thereof, and then crosslinked and thermally condensed.

The preferred thickness of the hard coat layer is 1 to 10 μm.
That's about it.

Further, the acrylic hard coat layer refers to a layer obtained by crosslinking an ester compound of an acrylic compound such as methacrylic acid and a polyfunctional glycol such as pentaerythryl or glycerin.

Next, in the present invention, a layer containing zirconium oxide as a main component is provided as a first layer on the surface layer of the Bartco-1 layer. The layer mainly composed of zirconium oxide works as a binder to improve the adhesion strength to both the lower hard coat layer and the upper layer mainly composed of silicon dioxide. This is because by combining it with a layer whose main component is to form an equivalent film, the refractive index is set to be intermediate compared to the third layer and the fourth layer.

Next, in the present invention, a layer containing silicon dioxide as a main component is provided as a second layer on the surface layer of the first layer. It exhibits the effect of improving the adhesion strength to both the first layer and the third layer, and at the same time, by combining the first layer with the layer mainly composed of zirconium oxide to form an equivalent film, the third layer , to have a medium refractive index compared to the fourth layer.

The first layer and the second layer as a whole have a medium refractive index.

Next, a layer containing titanium oxide as a main component is provided as a third layer, and a layer containing silicon dioxide as a main component is provided thereon as a fourth layer. By providing a high refractive index layer in the third layer and a low refractive index layer in the fourth layer, together with the medium refractive index layer in the first and second layers, a film with excellent antireflection function as a whole can be achieved. This is because that.

In the present invention, the first to fourth layers can be provided by vacuum deposition or sputtering. More preferred is vacuum deposition. Methods such as ion beam assist may also be applied as appropriate. Further, titanium oxide or the like may be added to the first layer of zirconium oxide within a range that does not reduce the effect of the present invention, and similarly, Ta205 or the like may be mixed into the third layer of titanium oxide. .

The film may have any thickness as long as it can prevent reflection of visible light. Preferred optical film thicknesses are, when the design wavelength is λ0, in the range of 450 to 550ru++.First layer: 0.05 to 0.15λO Second layer: 0.05 to 0.15λO Third layer: 0.36 to 0.49λ0 Fourth layer: 0.15 to 0.35λ0. Among these, it is particularly preferable that the fourth layer has a thickness of 0.25λ0.

In the present invention, the multilayer antireflection film described above is provided on one or two sides of a plastic substrate. When provided on one side, it is preferable to provide at least the hard coat described above in order to prevent damage to the opposite side. In addition, the multilayer antireflection coating of the present invention is provided on one side, and a bartcoat layer is provided on the opposite side.
~ layer, indium oxide/tin oxide@ (so-called ITO film), or a layer mainly composed of silicon dioxide is provided on this ITO film, with an antireflection layer on one side and an electromagnetic shielding layer on the other side. It can also be a layer with. In the above, when an ITO layer is provided as the outermost layer, a relatively thin film (about 100 to 500 layers) is preferable, and when a layer containing silicon dioxide as a main component is provided on the ITO film, a relatively thick film (for example, (approximately 500 to 1000 people) is preferable.

By the way, you may attach a ground to this product to remove static electricity. In this case, if the ITO film is present, it is preferable to connect the ground directly to the ITO film or to keep it in a conductive state. Alternatively, a metal frame may be placed around the product of the present invention to discharge static electricity. Also in this case, when the ITO film is present, the metal frame is
It is preferable to be in direct contact with the TO film or to be in a conductive state.

This will be explained below with reference to the drawings.

FIG. 1 shows a cross-section of one embodiment of an optical article having a preferred multilayer antireflection coating of the present invention. A hard coat layer 11 having abrasion resistance is provided on a plastic transparent base material 10, and the multilayer antireflection films 1 to 4 are sequentially provided on the surface layer thereof.

FIG. 2 is the closest example of the prior art.

That is, since the first layer of the multilayer antireflection film was made of yttrium oxide, it was likely to peel off at the interface of both the hard coat layer and the titanium oxide layer.

The optical article having the multilayer antireflection film of the present invention is particularly effective as a filter for a television or display screen (so-called optical filter).

It is also expected to be used as lenses for glasses, films, and molded products.

Note that the multilayer film of the present invention can be formed by "Auger electron spectroscopy." In this method, an electron beam is irradiated onto the surface of a sample placed in a high vacuum, and the energy of Auger electrons emitted from the surface is divided and detected using an analyzer. The measurement conditions are as follows.

Measuring device @2 "JAHP-103" manufactured by JEOL Ltd. When analyzing the outermost surface: 1X 10'Pa When analyzing in the depth direction: 6X 10'Pa (Ar atmosphere)
Sampling: Hold the edge of the sample with a copper plate and fix it to the sample stand.

Acceleration voltage: 3.0KV Sample current: 1X10'A Beam diameter: 1μm Slit: No. 5 Sample tilt angle: 40-70 degrees Ar ion etching conditions Acceleration voltage: 3. OKV Sample current: 3X10'A Etching speed: 200 people/min (SiO2
case) [Example] The following will be explained using an example.

Example 1 A commercially available polymethacrylate plate (manufactured by Mitsubishi Rayon Co., Ltd., trademark "Aqualite" LN-084, gray spun-dyed, thickness approximately 2 mm) was used as a base material. As the hard coat paint, as described in Example 1 of JP-A-59-114501, vinyltrie-1-xysilane hydrolyzed with glacial acetic acid and methyl-1-ethoxysilane hydrolyzed with glacial acetic acid were used. I used a mixture of things. A hardening agent, sodium acetate, was added to this mixed solution, and a silicone-based surface smoothing agent was added to the coating to form a paint.

This paint was applied to the surface (front and back) of the base material to a thickness of 2 μm, and heated and cured at 90'C for 3 hours.

Next, this hard-coated plastic substrate was set in a vacuum evaporation tank, and a 1 x 1 film was deposited at a set temperature of 60'C.
After evacuation to 0-5 TORR, an argon ion beam was generated using a Kaofman type ion beam generator, and the substrate was cleaned at an acceleration voltage of 500V. Subsequently, a four-layer intestine was formed on the front and back surfaces under the following conditions using an electron beam method starting from the substrate side.

(1) First layer: layer mainly composed of zirconium dioxide, optical thickness (nd) approximately 42 nm, degree of vacuum 3X10-''To
'RR (oxygen introduction) (2> 2nd layer; layer mainly composed of silicon dioxide, optical thickness (nd) approximately 42 nm, degree of vacuum 1 x 10-
"TO1?R (3) 3rd layer; layer mainly composed of titanium oxide, optical thickness (nd) approximately 2161 m, degree of vacuum 4
X 10 'TORR (Oxygen introduction) (4) Fourth layer; layer mainly composed of silicon dioxide, optical thickness (nd) approximately 1201 m, degree of vacuum 1 X 10-
"TORf? (However, in (1) to (4) above, the optical film thickness uses a design wavelength of 480 nm.) The product of the present invention produced by the above method and conditions has a blue-violet reflection interference color, and a wavelength of 550 nm. The surface reflectance per hole was about 0.2%, and it had extremely excellent anti-q dimension properties.

In addition, a test was conducted in which a square polyester knitted fabric with a hard surface and a side of 2 cm was soaked with water and rubbed 2,000 times under a load of 2 kg.
No damage was observed.

Furthermore, an exposure test was performed by leaving it outdoors for one month, but there was no damage to the surface such as peeling of the antifouling film.

Furthermore, when this was used as an optical filter for a word processor, it had excellent anti-reflection properties and had a remarkable effect in terms of not tiring the user's eyes.

It was also highly durable.

The antistatic performance was roughly measured as follows. In other words, the front 5 of a CRT (NEC-KD551K) connected to a personal computer (NEC Corporation\I!jPc-9801E)
Static meter at 3mm position (Shishido Static Electric Co., Ltd.)
Set Statyron M″) and turn on the computer.
As a result of measuring the electrostatic potential at t, the blank was 9K.
It was more than V. Next, between the CRT and the stationaryon M', the distance from the stationaryon M It is 130 mm.
The product of the present invention with a ground connection was installed at the position, and the electrostatic potential was measured when the switch was turned on. As a result, 3
The voltage decreased to 0.2 KV or less within 0 seconds, and the antistatic effect was extremely excellent.

Comparative Example In Example 1, instead of the four-layer film, a three-layer film was created under the following conditions.

(1) 1st layer: Layer mainly composed of 1 to 1 chloride, optical thickness (nd > approx. 12011 m, degree of vacuum 3X)
10-5 TORR (oxygen introduction) (2> 2nd layer; layer mainly composed of titanium oxide, optical thickness (nd) approximately 216 nm, degree of vacuum 4 x 10'
TORR (Oxygen introduction) (3) Third layer A layer mainly composed of silicon dioxide, optical thickness (nd) approximately 1201 m, degree of vacuum 1 x 10-
``TOR'' The antireflection properties of the comparative product obtained by the above method were slightly inferior to that of the product of the present invention.

However, in a cloth friction test evaluated in the same manner as the product of the present invention, partial peeling of the antireflection film occurred after about 100 times. In addition, in an outdoor exposure test, a spot-like appearance or more appeared after about 1 week.

When antistatic performance was roughly measured in the same manner as in Example 1, the electrostatic potential was approximately 1V even after 10 minutes after turning on the switch.
It only went down to.

[Effects of the Invention] Since the present invention is a technology as described above, the multilayer anti-reflection film has particularly excellent adhesion strength and durability, and has excellent scratch resistance, abrasion resistance, impact resistance, chemical resistance, and flexibility. An optical article having a multilayer antireflection film with excellent flexibility, heat resistance, light resistance, weather resistance, antistatic property, etc. could be obtained.

In terms of durability in particular, it has shown remarkable longevity and can now be used in a stable manner for a long period of time.

Furthermore, as an unexpected effect, it showed extremely excellent antistatic effect.

[Brief explanation of drawings]

FIG. 1 shows a cross-section of one embodiment of an optical article having a preferred multilayer antireflection coating of the present invention. FIG. 2 is a known example that is the closest to the prior art. 1 to 4; Multilayer antireflection coating 10 Niblast transparent base material 11; Bartco-1 to layer

Claims (4)

[Claims] (1) A hard coat layer with abrasion resistance is provided on the plastic transparent base material, and the surface layer is coated with the following layers in order from the base material side to the surface: 1st layer; 2nd layer mainly composed of zirconium oxide. Layer: layer whose main component is silicon dioxide Third layer; layer whose main component is titanium oxide Fourth layer; at the same time as providing a layer whose main component is silicon dioxide, the first layer and the second layer are made equivalent An optical article having a multilayer antireflection film, characterized in that it is a film. (2) The optical thickness of the first to fourth layers is the design wavelength λ_0
In the range of 450 to 550 nm, first layer: 0.05 to 0.15λ_0 Second layer: 0.05 to 0.15λ_0 Third layer: 0.36 to 0.49λ_0 Fourth layer: 0.15 An optical article having a multilayer antireflection film according to claim (1), characterized in that the multilayer antireflection film has a multilayer antireflection coating of ˜0.35λ_0. (3) An optical article having a multilayer antireflection film according to claim (1), wherein the first to fourth layers are vapor deposited films or sputtered films. (4) An optical article having a multilayer antireflection film according to claim (1), wherein the hard coat layer is a layer containing organic polysiloxane.