JP2983329B2 - Optical member having antireflection film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical member having an antireflection film.

[0002]

2. Description of the Related Art It is well known that an antireflection film is formed on the surface of a synthetic resin in order to improve the surface reflection characteristics of an optical member made of the synthetic resin. As an optical member having the antireflection film, for example, Japanese Patent Application Laid-Open No.
(Diethylene glycol bisallyl carbonate) resin, a base layer made of SiO _{2 in} order from the substrate side and having a thickness of 1.5λ, a ZrO ₂ layer and a SiO
_{A first} layer having a total thickness of about 0.25λ, which is a two-layer equivalent film composed of two layers, a second layer of ZrO ₂ having a thickness of about 0.50λ, and a film thickness of SiO ₂ Is about 0.
An optical member provided with an antireflection film having a third layer of 25λ is disclosed. However, the optical member disclosed in Publication 1 cannot form an antireflection film by increasing the substrate temperature during vapor deposition like a glass substrate.
For example, a layer made of ZrO ₂ has insufficient heat resistance, and the heat resistance is significantly reduced with time. For example, there is a problem that it is practically insufficient for use as a spectacle lens. In order to solve this problem, for example, Japanese Unexamined Patent Publication No. 2-291502 (hereinafter, referred to as “publication 2”) discloses that a high refractive index film is made of Ta ₂ O.
₅ , an optical member having an antireflection film using a deposited film containing ZrO ₂ and Y ₂ O ₃ is disclosed.

[0003]

The optical member disclosed in Japanese Unexamined Patent Publication (Kokai) No. 2 (1994) has improved heat resistance in comparison with the optical member disclosed in Japanese Unexamined Patent Publication (Kokai) No. 1 (1995). However, there is a problem that the degree to which heat resistance is reduced is large. This problem has the following disadvantages. When a plastic lens is framed in a plastic spectacle frame, the plastic lens is inserted by heating and deforming the rim of the plastic spectacle frame. When the spectacle frame is heated, the plastic lens is also easily heated by heat conduction. Therefore, when the optical member disclosed in Japanese Patent Application Laid-Open Publication No. 2004-133873 is framed in a plastic spectacle frame after four months or more, cracks are likely to occur in the antireflection film of the optical member.

An object of the present invention is to provide an optical member having an antireflection film having good heat resistance and having a small decrease in heat resistance over time. is there.

[0005]

The above-mentioned object has been solved by the following invention. The first invention is an optical member having an anti-reflection film on a synthetic resin, wherein the anti-reflection film is formed by a vacuum evaporation method , and Ta ₂ O ₅ is formed from the synthetic resin side. An optical member having an antireflection film, comprising: a layer containing Y ₂ O _3; and a layer containing Ta ₂ O ₅ .

A second invention is an optical member having an antireflection film on a synthetic resin, wherein the antireflection film is formed by vacuum deposition.
A layer containing Y ₂ O ₃ , a layer containing Ta ₂ O _5, and a layer containing Y ₂ O ₃ , in that order from the synthetic resin side. An optical member having a characteristic antireflection film.

First, the first invention will be described. The first invention is characterized in that the following three layers are sequentially provided as a set. Layer containing Ta ₂ O ₅ (hereinafter, referred to as “A layer”) Layer containing Y ₂ O ₃ (hereinafter, referred to as “B layer”) Layer containing Ta ₂ O ₅ (hereinafter, referred to as “C layer”) )

[0008] The above three layers are A layer and B layer according to the synthetic resin side.
The layers are stacked in this order. The reason is as follows. The layer B has a substrate heating temperature of 70 to 85.
Even when formed at a temperature as low as ° C., a layer having excellent heat resistance can be formed. The A layer and the C layer have characteristics of good weather resistance and alkali resistance, and a small decrease in heat resistance over time. The inventor has found that when the layers A, B, and C are laminated in this order, the layer B sandwiched between the layers A and C prevents a decrease in heat resistance over time, and furthermore, the layer A in contact with the layer B Layer, C
It has been found that the layer has a complementary effect such that the heat resistance can be further improved.

When forming the A and C layers, ZrO ₂ , TiO
₂ , Y ₂ O ₃ , SiO ₂ and other metal oxides are converted to Ta ₂ O ₅
Can be mixed. The proportion is preferably in the range of 0.05 mol to 5 mol of the metal oxide per 1 mol of Ta ₂ O ₅ .

Similarly, when forming the B layer, ZrO ₂ , Ti
Metal oxides such as O ₂ , Ta ₂ O ₅ and SiO ₂ are converted to Y ₂ O
₃ can be mixed. The ratio is preferably in the range of 0.05 mol to 1 mol of the metal oxide per 1 mol of Y ₂ O ₃ .

The preferred range of the film thickness of the A to C layers is as follows. (Λ = 500 nm). 0.01λ ≦ A layer ≦ 0.20λ 0.01λ ≦ B layer ≦ 0.23λ 0.01λ ≦ C layer ≦ 0.20λ

The reason is that the heat resistance of the antireflection film of the present invention depends on the thickness of the B layer, and the thickness of the B layer is 0.01λ.
When the thickness is smaller, the effect is reduced, and when the film thickness is less than 0.1.
If it is larger than 23λ, the effect of preventing a decrease in heat resistance over time tends to decrease. When the film thickness is smaller than 0.01λ, the effect of preventing the heat resistance from lowering with time is small, and when the film thickness is larger than 0.20λ, the material of the layer A and C, Ta ₂ , is used. This is because the characteristics of O ₅ appear strongly, and the effect of complementing the B layer with Y ₂ O ₃ , that is, it is difficult to obtain an antireflection film having sufficient heat resistance.

The position where the A to C layers are formed as a set is not particularly limited. The A to C layers may be formed on one of the low-refractive-index films or the high-refractive-index films, or may be formed between the low-refractive-index films and the high-refractive-index films. Good. Further, two or more sets of a set of layers A to C may be formed.

The film configuration of the antireflection film in the present invention is λ
/ 4-λ / 4 two-layer film, λ / 4-λ / 4-λ / 4 or λ / 4-λ / 2-λ / 4 three-layer film. It may be.

The synthetic resin used in the optical member of the present invention includes methyl methacrylate homopolymer, a copolymer containing methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol Copolymers containing bisallyl carbonate and one or more other monomers as monomer components, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, etc. Is mentioned.

When an antireflection film is provided on the synthetic resin, a hard coat layer containing an organosilicon polymer is formed on the surface of the synthetic resin by a coating method such as dipping or spin coating. It is preferable to provide an antireflection film thereon. Further, in order to improve the adhesion between the synthetic resin and the anti-reflection film, the abrasion resistance, etc., a hard coat layer and an anti-reflection film formed between the synthetic resin and the anti-reflection film or on the surface of the synthetic resin. Preferably, an underlayer is interposed between the layers. As such an underlayer, for example, a deposited film of silicon oxide or the like can be used.

In forming the antireflection film of the present invention, a vacuum evaporation method is used.

Next, the second invention will be described. However,
Here, the description of the overlapping part described in the first invention is omitted. The second invention is characterized by having the following three layers in order. Layer containing Y ₂ O ₃ (hereinafter, referred to as “D layer”) Layer containing Ta ₂ O ₅ (hereinafter, referred to as “E layer”) Layer containing Y ₂ O ₃ (hereinafter, referred to as “F layer”) The three layers described above are laminated in the order of D layer, E layer, and F layer from the synthetic resin side. The reason is that the complementary effect described in the first invention is provided, and the first layer is further provided by the D layer and the F layer.
This is for further improving the heat resistance as compared with the optical member according to the invention of (1).

When forming the D and F layers, ZrO ₂ , TiO
_2, Ta ₂ O _5, a metal oxide such as SiO ₂ Y ₂ O ₃
Can be mixed. The ratio is preferably in the range of 0.05 mol to 1 mol of the metal oxide per 1 mol of Y ₂ O ₃ .

Similarly, when forming the E layer, ZrO ₂ , Ti
The O _2, Y ₂ O _3, metal oxides such as SiO ₂ Ta ₂ O
₅ can be mixed. The ratio is Ta ₂ O ₅ 1
The amount of the metal oxide is preferably in the range of 0.05 mol to 5 mol with respect to the mol.

The preferred thickness range of the DF layer is as follows. (Λ = 500 nm.) 0.01λ ≦ D layer ≦ 0.23λ 0.01λ ≦ E layer ≦ 0.20λ 0.01λ ≦ F layer ≦ 0.23λ The reason is that the above-described AC layers are formed. For the same reason as described above, the description is omitted.

The positions at which the DF layers are formed are the same as the positions at which the A to C layers are formed.

According to the first and second aspects of the present invention, the above-described complementary effect is produced even when a film must be formed at a low heating temperature of 70 to 85 ° C., such as a synthetic resin. Accordingly, it is possible to obtain an optical member having an antireflection film having good heat resistance and hardly reducing heat resistance over time.

The optical member having the antireflection film of the present invention comprises:
In addition to spectacle lenses, it can be used for camera lenses, automobile window glasses, optical filters attached to word processor displays, and the like.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The physical properties of the optical members having the antireflection films obtained in Examples and Comparative Examples were measured by the following test methods.

(A) Scratch resistance test The surface was reciprocated one time with # 0000 steel wool.
Rubbing was performed 0 times and the scratch resistance was determined as follows. A: Slightly damaged B: Severely damaged C: Peeling of film occurs

(B) Adhesion test In accordance with JIS-Z-1522, 10 × 10 gobangs were formed and a peeling test was carried out three times with a cellophane adhesive tape, and the number of remaining gobangs was counted.

(C) Luminous reflectance (one side) Luminous reflectance was determined using a U3410 type self-recording spectrophotometer manufactured by Hitachi, Ltd. (D) Heat resistance test The optical member having the antireflection film immediately after the formation of the vapor-deposited film was placed in an oven for 1 hour and heated to check for the occurrence of cracks. The heating temperature was started from 50 ° C. and increased in steps of 5 ° C., and the temperature at which cracks occurred was examined.

(E) Temporal heat resistance test The optical member having the antireflection film immediately after the formation of the vapor-deposited film was exposed outdoors for 4 months, and then evaluated by the same method as the heat resistance test described above.

[0031]

EXAMPLE 1 First, as a synthetic resin for forming an antireflection film, diethylene glycol bisallyl carbonate was used as a main component, and 2-hydroxy-4-n-optoxybenzophenone was used as an ultraviolet absorber. 99.97 / 0.
A plastic lens having a refractive index of 1.499 was prepared so as to be 03.

(I) Formation of Hard Coat Layer (nd 1.50) The plastic lens is immersed and cured in a coating liquid containing 80 mol% of colloidal silica and 20 mol% of γ-glycidoxypropyltrimethoxysilane. To provide a hard coat layer.

(Ii) Formation of an antireflection film The plastic lens having the hard coat layer
C., and a base layer made of SiO ₂ [refractive index: 1.46, film thickness: 0.6λ (λ is 500 nm) on the hard coat layer by a vacuum deposition method (degree of vacuum: 2 × 10 ⁻⁵ Torr). )] Was formed. Next, a first layer composed of a Ta ₂ O ₅ layer (refractive index 2.05, film thickness 0.04λ) and a Y ₂ O ₃ layer (refractive index 1.75, film thickness 0.18λ) is formed on the underlayer. A low refractive index film [refractive index 1.80, film thickness 0.22λ] was formed. Next, a Ta ₂ O ₅ layer (thickness: 0.05) is formed on the first layer.
λ), a Y ₂ O ₃ layer (thickness 0.05 λ) and a Ta ₂ O ₅ layer (thickness 0.15 λ), a second high refractive index film [refractive index 1.99, thickness 0.25 λ] ] Was formed. Next, a third-layer low-refractive-index film made of SiO ₂ (refractive index: 1.46, film thickness: 0.25λ) was formed on the second layer to obtain a plastic lens with an antireflection film. The first to third layers
The layer was formed by the same vacuum evaporation method as that for forming the underlayer. This embodiment is directed to the first invention, that is, Ta ₂ O
_Two layers, each of which includes _five layers, a Y ₂ O ₃ layer, and a Ta ₂ O ₅ layer, are continuously formed.

Table 6 shows the test results of the obtained plastic lens with an antireflection film. The plastic lens with an antireflection film obtained in Example 1 not only had good scratch resistance and good adhesion, but also had excellent heat resistance of 95 ° C. and heat resistance of 80 ° C. after 4 months.

Example 2 Diethylene glycol bisallyl carbonate (30 parts by weight), benzyl methacrylate (20 parts by weight), diallyl isophthalate (45 parts by weight) and methyl methacrylate (5 parts by weight) as a synthetic resin had a refractive index of 1.549.
Was used.

(I) Formation of Hard Coat Layer (nd1.56) The plastic lens is immersed in a coating solution containing 50 mol% of antimony pentoxide sol and 50 mol% of γ-glycidylpropyltrimethoxysilane. Thus, a hard coat layer was provided.

Further, in the same manner as in Example 1, a plastic lens with an antireflection film having a film configuration shown in Table 1 was obtained. As shown in Table 6, the plastic lens with an antireflection film obtained in Example 2 was also excellent in heat resistance, and showed little decrease in heat resistance over time.

Examples 3 to 16 Using the plastic lens substrates shown in Tables 1 to 4,
A plastic lens with an antireflection film was obtained in the same manner as in Examples 1 and 2, except that the first, second, and third layers were configured as shown in Tables 1 to 4. As shown in Tables 6 to 9, the obtained plastic lens with an anti-reflection film has the same scratch resistance and adhesion as those of Examples 1 and 2, and further has heat resistance and heat resistance over time. The decrease was excellent as in Examples 1 and 2.

COMPARATIVE EXAMPLES 1-2 As a comparative example, an example of a plastic lens with an antireflection film disclosed in JP-A-2-291502 will be described. A plastic lens with an anti-reflection film was obtained in the same manner as in Examples 1 and 2, except that the first, second, and third layers were configured as shown in Table 5. The resulting antireflection-coated plastic lens had abrasion resistance, adhesion,
The same heat resistance as in Examples 1 and 2 was obtained, but the heat resistance after being exposed outdoors for 4 months was 55 ° C., and the decrease in heat resistance over time was larger than that of the lenses of Examples. Was.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

[0050]

The optical member having the antireflection film of the present invention has good scratch resistance, adhesion and heat resistance,
The decrease in heat resistance over time is small. Therefore, the optical member of the present invention can be particularly suitably used, for example, for a spectacle lens that may be manufactured and stored for a long time.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Koji Sato 2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Inside of Hoya Co., Ltd. (56) References JP-A-64-40878 (JP, A) JP-A-61-196201 (JP, A) JP-A-63-113401 (JP, A) JP-A-1-197701 (JP, A)

Claims (4)

(57) [Claims] 1. An optical member having an anti-reflection film on a synthetic resin, wherein the anti-reflection film is formed by a vacuum evaporation method.
A layer containing Ta ₂ O ₅ , a layer containing Y ₂ O _3, and a layer containing Ta ₂ O ₅ in that order from the synthetic resin side. An optical member having a protective film. 2. An optical member having an anti-reflection film on a synthetic resin, wherein the anti-reflection film is formed by a vacuum deposition method.
A layer including Y ₂ O ₃ , a layer including Ta ₂ O _5, and a layer including Y ₂ O ₃ , in that order from the synthetic resin side. An optical member having a protective film. 3. The optical member according to claim 1, wherein a hard coat layer containing an organosilicon compound is interposed between the synthetic resin and the anti-reflection film. Optical members. 4. The optical member according to claim 1, wherein
The optical member, wherein the optical member is a spectacle lens.