JP3068252B2 - 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 An antireflection film is provided on the surface of a synthetic resin in order to improve the surface reflection characteristics of an optical member made of the synthetic resin, and a synthetic resin is used in order to improve the scratch resistance of the antireflection film. It is well known that an underlayer is interposed between the antireflection film and the antireflection film. As examples in which the underlayer is interposed, for example, JP-A-56-160003 (hereinafter, referred to as “publication 1”) and JP-A-2-291502 (hereinafter, referred to as “publication 2”). An underlayer consisting only of SiO ₂ is disclosed in JP-A-56-66802 (hereinafter referred to as “publication 3”).
There is disclosed an optical member made of a synthetic resin provided with an underlayer made of a mixture of iO ₂ and Al ₂ O ₃ .

[0003]

THE INVENTION to be solved problems were subjected to a base layer composed only of SiO ₂ which is disclosed in Japanese 1,2 plastic optical member, SiO ₂ in refractive index as disclosed in JP 3 1.54 and because Al ₂ O ₃ was applied an undercoat layer formed by mixing a synthetic resin optical member can not be formed by increasing the substrate temperature during deposition as a glass substrate, the underlayer over time It has the characteristic that the degree to which the heat resistance temperature decreases is large. Due to this influence, the antireflection film applied on the underlayer also has a problem that the heat-resistant temperature decreases over time. This problem has, for example, the following disadvantages. Glasses wearers often wear glasses in the sauna or go out of the car with the glasses left in the car. When the optical member disclosed in Publications 1 to 3 is used as a spectacle lens under such a high temperature condition, the antireflection film tends to crack in about four months after the optical member is manufactured. The present invention has been made to solve the above-described disadvantages, and its purpose is to reduce the degree to which the heat-resistant temperature decreases over time, even when the substrate temperature must be lowered during deposition, such as a synthetic resin. An object of the present invention is to provide an optical member having an antireflection film.

[0004]

The above objects have been achieved by the inventions described below. The invention is an optical member having a base layer and an antireflection film on a synthetic resin, wherein the base layer contains SiO ₂ and Al ₂ O ₃ as essential components,
a ₂ O ₅ , Y ₂ O ₃ , TiO ₂ , and ZrO ₂ , which are composed only of a mixture containing optional components, and wherein the refractive index of the underlayer ranges from 1.48 to 1.52. It is an optical member having an antireflection film.

Hereinafter, the present invention will be described in detail. By setting the range of the refractive index of the underlayer to 1.48 to 1.52 and specifying the essential components of the film material as SiO ₂ and Al ₂ O ₃ , the heat resistance temperature of the underlayer is improved without impairing the conventional characteristics. However, the degree of decrease in the heat-resistant temperature over time is reduced.
Furthermore, even when the substrate temperature at the time of vapor deposition must be lowered, such as a synthetic resin, by applying this underlayer, the heat resistance temperature of the entire antireflection film applied on the surface of the underlayer is improved. The present inventor has found that the heat resistance is improved over time and the degree of decrease in the heat-resistant temperature over time is reduced.

If the refractive index of the underlayer is out of the above range, for example, less than 1.48 or more than 1.52, or if the essential component of the underlayer is not a mixture of SiO ₂ and Al ₂ O ₃ , It is not preferable because the heat resistant temperature is not improved and the degree of decrease in the heat resistant temperature with time is not reduced.

The underlayer according to the present invention is made of Ta ₂ O ₅ , Y ₂ O ₃ , TiO ₂ , Z so as not to impair the effects described above.
rO ₂ can be mixed as an optional component . The range of the thickness of the underlayer is not particularly limited, but is particularly preferably 0.125λ to 0.8λ (λ = 500 nm) in order to increase the temperature at which cracks occur in the antireflection film.

[0008] The film configuration of the antireflection film in the present invention is not particularly limited, and a two-layer film of λ / 4-λ / 4, λ / 4-λ / 4.
A three-layer film of -λ / 4 or λ / 4-λ / 2-λ / 4, or a multilayer film of four or more layers can be used. Particularly preferred film configurations include the two antireflection films described below. The first anti-reflection film (corresponding to claim 2 in the claims section) is formed of T in order from the surface of the underlayer.
a first low refractive index layer composed of an a ₂ O ₅ layer and a mixed layer containing Ta ₂ O ₅ , Y ₂ O ₃ and SiO ₂ ; Ta ₂
O ₅ layer _{and, Ta 2 O 5, Y 2} O 3 , and a mixed layer containing a SiO _2, Ta ₂ O ₅ layer than configured high refractive index layer;
It is configured by laminating a second refractive index layer composed of a SiO ₂ layer. Further, the second antireflection film (corresponding to claim 3 in the claims section) includes a mixed layer containing Ta ₂ O ₅ , Y ₂ O _3, and SiO _{2 in} order from the surface of the underlayer; Ta ₂ O ₅ layer first low refractive index layer composed of; a mixed layer containing a _{Ta 2 O 5, Y 2 O} 3 and SiO _2, and Ta ₂ O ₅ layer, Ta ₂ O _5, Y ₂ O ₃ and S
High refractive index layer composed of a mixed layer containing iO ₂ ; Si
It is formed by laminating a second low refractive index layer composed of an O ₂ layer.

The reason why these antireflection films are particularly preferable is that these antireflection films themselves have good heat resistance, and furthermore, have the property that the degree of decrease in heat resistance over time is small. is there. Excellent heat resistance by applying these antireflection films on the underlayer in the present invention,
Further, it is possible to obtain an optical member having an antireflection film in which the degree of decrease in the heat-resistant temperature with time is extremely small.

Another particularly preferred example of the antireflection film is a film in which a layer made of the same film material and the same refractive index as the underlayer described above is provided in the antireflection film.
By providing this layer in the anti-reflection film, the heat resistance of the anti-reflection film is further improved, and the degree of decrease in the heat-resistant temperature over time is reduced. Become smaller.

Examples of the synthetic resin used in the optical member of the present invention include 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. Polymer.

When an underlayer and an antireflection film are 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 a base layer and an antireflection film on the hard coat layer. In forming the antireflection film of the present invention, in addition to the vacuum evaporation method,
A method such as a sputtering method or an ion plating method using a similar sintered body as a target material can also be used.

The optical member having the antireflection film according to 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.

[0014]

EXAMPLES The present invention will be described in detail below 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 1 times 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 According to JIS-Z-1522, 10 × 10 squares were formed, and a peeling test was performed three times with a cellophane adhesive tape, and the number of remaining squares was counted.

(C) Luminous reflectance (single-sided) 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 vapor deposition was exposed outdoors for 4 months, and then evaluated by the same method as the heat resistance test described above.

(F) Acid Resistance Test After immersion in a 10% hydrochloric acid aqueous solution at 20 ° C. for 1 hour, the acid resistance was determined as follows. ○: No change from before immersion ×: Peeling occurs on the antireflection film

(G) Alkali Resistance Test After immersion in a 10% aqueous solution of sodium hydroxide at 20 ° C. for 1 hour, the alkali resistance was determined as follows. ○: No change from before immersion ×: Peeling occurs on the antireflection film

Example 1 First, as a synthetic resin for forming an antireflection film, diethylene glycol bisallyl carbonate was used as a main component, and as a UV absorber, 2-hydroxy-4-n-optoxybenzophenone was used. 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 in a coating liquid containing 80 mol% of colloidal silica and 20 mol% of γ-glycidoxypropyltrimethoxysilane, After curing, a hard coat layer was provided.

(Ii) Formation of Underlayer and Antireflection Film The plastic lens having the hard coat layer
° C, and SiO ₂ and Al ₂ O ₃ were deposited on the hard coat layer by a vacuum deposition method (degree of vacuum: 2 × 10 ^-5 Torr).
Underlayer [refractive index 1.51, thickness 0.6λ (λ =
500 nm)]. Next, on the underlayer, T
a ₂ O ₅ layer (refractive index: 2.05, film thickness: 0.06λ);
A first low-refractive-index layer composed of a mixed layer (refractive index 1.61 and film thickness 0.11λ) composed of a ₂ O ₅ , Y ₂ O ₃ and SiO ₂ was formed. Ta ₂ O is applied on the first low refractive index layer.
₅ layers (refractive index 2.05, film thickness 0.05λ) and Ta ₂ O
₅ , a high refractive index composed of a mixed layer of Y ₂ O ₃ and SiO ₂ (refractive index 1.61, thickness 0.05λ) and a Ta ₂ O ₅ layer (refractive index 2.05, thickness 0.15λ) And a _second layer made of SiO ₂ on the high refractive index layer.
Was formed (refractive index: 1.46, film thickness: 0.25λ) to obtain a plastic lens with an antireflection film.
Note that the first low refractive index layer and the second low refractive index layer were formed by the same vacuum evaporation method that formed the underlayer.

The first embodiment corresponds to the second embodiment of the present invention.
It corresponds to.

Table 2 shows the evaluation results of the obtained plastic lens with an antireflection film. As shown in Table 2, the plastic lens with an anti-reflection film of Example 1 has scratch resistance,
Excellent adhesion, acid resistance and alkali resistance, high crack generation temperature of 100 ° C, and low crack generation temperature of 95 ° C after 4 months of outdoor exposure. Was something.

Comparative Example 1-1, Comparative Example 1-2 Two comparative examples are given as a comparison of Example 1. As shown in Table 1, the refractive index of the underlayer was 1.47, which is out of the range of the present invention.
Except for (Comparative Example 1-1) and 1.54 (Comparative Example 1-2), an antireflection film was produced in the same manner as in Example 1. Table 2 shows the evaluation results. As shown in Table 2, the crack generation temperature of the plastic lens with the antireflection film of Comparative Example 1-1 was 90 ° C, and the crack generation temperature after outdoor exposure for 4 months was 70 ° C. The crack generation temperature of the plastic lens with an anti-reflection coating of No. 2 is 90
The temperature at which cracks occur after outdoor exposure for 4 months is 75 ° C., which is lower in heat resistance than that of the plastic lens with an antireflection film of Example 1 and the degree of decrease in the temperature at which cracks occur with time is large. there were.

Embodiment 2 Embodiment 2 will be described as an embodiment corresponding to claim 3 in the section of claims. The film configuration was as shown in Table 3, and the film forming conditions were the same as in Example 1 to obtain a plastic lens with an antireflection film. As shown in the evaluation results, as shown in Table 4, the crack initiation temperature was excellent at 100 ° C., and the crack initiation temperature after outdoor exposure for 4 months was 95 ° C., and the degree of decrease in the heat-resistant temperature over time was small. there were.

Comparative Examples 2-1 and 2-2 Comparative examples 2-1 and 2-2 will be given as comparisons of the second embodiment. The refractive index of the underlayer is out of the range of the present invention 1.47.
A plastic lens with an antireflection film was obtained in the same manner as in Example 2 except that (Comparative Example 2-1) and 1.54 (Comparative Example 2-2) were used. As shown in Table 4, the evaluation results showed that the heat resistance was lower than that of the plastic lens with the antireflection film of Example 2 and that the temperature at which cracks occurred with time decreased greatly.

Third Embodiment A third embodiment will be described as another embodiment corresponding to the second aspect of the present invention. The film configuration was as shown in Table 5, and the film forming conditions were the same as in Example 1 to obtain a plastic lens with an antireflection film. As shown in Table 6, as shown in Table 6, the crack generation temperature was 105 ° C., which is excellent in heat resistance, and the crack generation temperature after outdoor exposure for 4 months was 100 ° C., and the degree of decrease in the heat resistance temperature over time was as follows. It was small.

Comparative Examples 3-1 and 3-2 Comparative examples 3-1 and 3-2 are given as comparisons of the third embodiment. The refractive index of the underlayer is out of the range of the present invention 1.47.
A plastic lens with an antireflection film was obtained in the same manner as in Example 3 except that (Comparative Example 3-1) and 1.54 (Comparative Example 3-2) were used. As shown in Table 6, the evaluation results showed that the heat resistance was lower than that of the plastic lens with an antireflection film of Example 3 and that the temperature at which cracks occurred with time decreased significantly.

Embodiments 4 to 6-2 Four embodiments are given as embodiments corresponding to claim 4 in the claims section. Table 7 (Example 4), Table 9 (Example 5), Table 11 (Example 6-1 and Example 6)
A plastic lens with an antireflection film was obtained as described in 2), and the film formation conditions were the same as in Example 1. As shown in Table 8 (Example 4), Table 10 (Example 5), and Table 12 (Example 6-1 and Example 6-2), the evaluation results all show the degree of decrease in the crack generation temperature with time. Was small.

Comparative Example 4-1 to Comparative Example 6-2 As a comparison of Example 4, Comparative Example 4-1 to Comparative Example 4-4
Comparative Example 5-1 to Comparative Example 5-4 as a comparison of Example 5,
Comparative Example 6-1 as a comparison between Example 6-1 and Example 6-2
Comparative Examples 6-3 will be given. Table 7 (Comparative Example 4-1)
Comparative Example 4-4), Table 9 (Comparative Example 5-1 to Comparative Example 5)
4) As shown in Table 11 (Comparative Example 6-1 to Comparative Example 6-3), the film formation conditions were the same as in Example 1, and a plastic lens with an antireflection film was obtained. The evaluation results are shown in Table 8 (Comparative Examples 4-1 to 4-4), Table 10 (Comparative Examples 5-1 to 5-4), and Table 12 (Comparative Examples 6-1 to 6-3). As shown in Comparative Examples 4-1 to 4
The plastic lens with an anti-reflection film of No. -4 was higher than the plastic lens with an anti-reflection film of Example 4 in Comparative Example 5-
The plastic lenses with an anti-reflection film of Comparative Examples 1 to 5-4 are better than the plastic lenses with an anti-reflection film of Example 5, and the plastic lenses with an anti-reflection film of Comparative Examples 6-1 to 6-3 are examples. 6-1 The degree of decrease in the temperature at which cracks occur with time was greater than that of the plastic lens with an antireflection film of Example 6-2.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

[Table 8]

[0041]

[Table 9]

[0042]

[Table 10]

[0043]

[Table 11]

[0044]

[Table 12]

[0045]

The optical member having the antireflection film of the present invention has good scratch resistance, adhesion, acid resistance and alkali resistance even when formed at a low substrate temperature such as a plastic substrate. The decrease in heat-resistant temperature with 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 Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G02B 1/10

Claims (7)

(57) [Claims] 1. An optical member having a base layer and an antireflection film on a synthetic resin, wherein the base layer is made of SiO ₂ and Al ₂
O ₃ as an essential component, Ta ₂ O ₅ , Y ₂ O ₃ , Ti
O ₂ and ZrO ₂ consist only of a mixture containing optional components.
And the refractive index of the underlayer ranges from 1.48 to 1.
52. An optical member having an antireflection film, wherein: 2. The method according to claim 1, wherein the thickness of the underlayer ranges from 0.125.lambda.
8 .lambda. (.Lambda. = 500 nm).
2. The optical member according to 1. 3. The anti-reflection film includes a Ta ₂ O ₅ layer, Ta ₂ O ₅ , Y ₂ O ₃ and Si in order from the surface of the underlayer.
A first low refractive index layer composed of a mixed layer containing O ₂ ;
Ta ₂ O ₅ layer, Ta ₂ O ₅ , Y ₂ O ₃ and SiO ₂
And a high refractive index layer composed of a Ta ₂ O ₅ layer and a _second low refractive index layer composed of a SiO ₂ layer. An optical member having an antireflection film. 4. The first antireflection film is a first low-refractive layer composed of a mixed layer containing Ta ₂ O ₅ , Y ₂ O ₃ and SiO ₂ and a Ta ₂ O ₅ layer in order from the surface of the underlayer. Rate layer;
A mixed layer containing Ta ₂ O ₅ , Y ₂ O ₃ and SiO ₂ , a Ta ₂ O ₅ layer, Ta ₂ O ₅ , Y ₂ O ₃ and Si
High refractive index layer composed of a mixed layer containing O ₂ ; SiO
_{2. The} optical member having an antireflection film according to claim 1, wherein a second low refractive index layer composed of two layers is laminated. 5. The antireflection film is made of SiO ₂ and Al ₂ O _3.
The optical member having an anti-reflection film according to claim 1, further comprising a mixed layer having a refractive index of 1.48 to 1.52. 6. An optical with claim 1-5 antireflection film of any one of claims, characterized in that by interposing a hard coat layer containing an organosilicon polymer between the synthetic resin and the underlying layer Element. Wherein said optical member is an optical member having an antireflection film according to claim 1 to 6 any one of claims, which is a spectacle lens.