JPH0511101A - Optical member having antireflection film - Google Patents

Abstract

PURPOSE:To decrease the extent at which a heat resistant temp. lowers with lapse of time by forming a substrate layer of a mixture composed of SiO2 and Al2O3 and further, specifying the range of the refractive index of a substrate layer to a specific range. CONSTITUTION:This member has the substrate layer and an antireflection film on a synthetic resin. The substrate layer is formed of the mixture composed of the SiO2 and the Al2O3 in such a case and further, the range of the refractive index of the substrate layer is specified to 1.48 to 1.52. The antireflection film is formed by laminating, successively from the surface of the substrate layer, a low-refractive index layer constituted of a Ta2O5 layer and a layer mixture contg. the Ta2O5, Y2O3 and SiO2, a high-refractive index layer constituted of the Ta2O5 layer, the layer mixture contg. the Ta2O5, Y2O3 and SiO2 and the Ta2O5 layer, and a 2nd low-refractive index layer constituted of the SiO2 layer. The synthetic resin includes a homo polymer of methyl methacrylate, a copolymer consisting of methyl methacrylate and 1 kinds of other monomers as monomer components a homo polymer of diethylene glycol bisallyl carbonate, etc.

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 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. Examples of interposing this underlayer are disclosed, for example, in Japanese Patent Application Laid-Open No. 56-11003 (hereinafter referred to as “publication 1”) and Japanese Patent Application Laid-Open No. 2-291502 (hereinafter referred to as “publication 2”). An underlayer made of only SiO ₂ has a refractive index of 1.54 and S in JP-A-56-66802 (hereinafter referred to as “publication 3”).
There is disclosed a synthetic resin optical member provided with an underlayer formed by mixing iO ₂ and Al ₂ O ₃ .

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An optical member made of a synthetic resin provided with an underlayer made of only SiO ₂ disclosed in Japanese Patent Laid-Open Nos. 1 and 2, and a refractive index of 1.54 disclosed in Japanese Patent No. ₃ Since a synthetic resin optical member provided with an underlayer formed by mixing Al ₂ O ₃ and Al ₂ O ₃ cannot be formed by elevating the substrate temperature during vapor deposition like a glass substrate, the underlayer can be formed over time. It has the characteristic that the heat-resistant temperature is greatly reduced. Due to this influence, the antireflection film formed on the underlayer also has a problem that the heat-resistant temperature decreases with time. This problem has the following disadvantages, for example. A spectacle wearer often wears spectacles in a sauna or goes out of the car with the spectacles left in the car. When the optical members disclosed in JP-A Nos. 1 to 3 are used as eyeglass lenses under such a high temperature condition, the antireflection film is likely to crack in about 4 months after the optical member is manufactured. The present invention has been made to solve the above-mentioned inconvenience, and its object is to reduce the degree of lowering of the heat resistant temperature with time even when the substrate temperature during vapor deposition has to be lowered like a synthetic resin. An object is to provide an optical member having an antireflection film.

[0004]

The above-mentioned objects have been achieved by the invention described below. The invention is an optical member having a base layer and an antireflection film on a synthetic resin, wherein the base layer is made of a mixture of SiO ₂ and Al ₂ O ₃ .
Further, the range of the refractive index of the underlayer is 1.48 to 1.52.
Is an optical member having an antireflection film.

The present invention will be described in detail below. By setting the range of the refractive index of the underlayer to 1.48 to 1.52 and specifying SiO ₂ and Al ₂ O _{3 as} the essential components of the film material, the heat resistance temperature of the underlayer is improved without impairing the conventional characteristics. However, the degree of decrease in the heat resistant temperature with time becomes small.
Furthermore, even when the substrate temperature is required to be low during vapor deposition such as synthetic resin, by applying this underlayer, the heat-resistant temperature of the entire antireflection film applied on the surface of the underlayer is improved. The present inventor has found that the heat resistance temperature decreases with time and the degree of decrease in heat resistant temperature with time decreases.

When the refractive index of the underlayer outside the above range, for example, less than 1.48 or more than 1.52, or when the essential component of the underlayer is not a mixture of SiO ₂ and Al ₂ O ₃ , This is not preferable because the heat resistant temperature does not improve and the degree of decrease in the heat resistant temperature with time does not decrease.

The underlayer in the present invention is made of Ta ₂ O ₅ , Y ₂ O ₃ , TiO ₂ , Z, to the extent that the above-mentioned effects are not impaired.
It is possible to mix metals such as rO ₂ and MgF ₂ . The range of the film thickness of the underlayer is not particularly limited, but 0.125λ to 0.8λ (λ = 500 nm) is particularly preferable in order to raise the crack generation temperature of the antireflection film.

The film constitution of the antireflection film in the present invention is not particularly limited, and it is 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, and a multilayer film of four or more layers can be used. Particularly preferable film configurations include the two antireflection films described below. The first antireflection film (corresponding to claim 2 in the scope of the claims) has a T layer 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 constructed by laminating a second refractive index layer composed of a SiO ₂ layer. The second antireflection film (corresponding to claim 3 in the section of the claims) is 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
A high refractive index layer composed of a mixed layer containing iO ₂ ; Si
It is constructed 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 further have a characteristic that the degree of decrease in heat resistant temperature with time is small. is there. By providing these antireflection films on the underlayer in the present invention, excellent heat resistance,
Furthermore, it is possible to obtain an optical member having an antireflection film whose degree of decrease in heat resistant temperature with time is extremely small.

Another example of another particularly preferable antireflection film is one in which a layer made of the same film material and having the same refractive index range as that of the underlayer is provided in the antireflection film.
(Corresponding to claim 4 in the scope of claims.) By providing this layer in the antireflection film, the heat resistance of the antireflection film is further improved, and the degree of decrease in the heat resistance temperature with time is reduced. Get smaller.

Examples of the synthetic resin used in the optical member of the present invention include a methyl methacrylate homopolymer, a copolymer containing methyl methacrylate and at least one other monomer as a monomer component, 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. Polymers of

When a base layer and an antireflection film are provided on a 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 a dipping method or a spin coating method. 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 vapor deposition method,
A sputtering method using a similar sintered body as a target material, an ion plating method, or the like can also be used.

The optical member having the antireflection film of the present invention is
In addition to eyeglass lenses, it can be used for camera lenses, automobile window glass, and optical filters attached to word processor displays.

[0014]

EXAMPLES The present invention is 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 film obtained in Examples and Comparative Examples were measured by the following test methods.

(A) Scratch resistance test # 0000 Steel wool with a number of reciprocations of 1 on the surface
The scratch resistance was evaluated by rubbing 0 times as follows. A: Slightly scratched B: Many scratches C: Film peeling occurs

(B) Adhesion Test In accordance with JIS-Z-1522, 10 × 10 goggles were made, and a peeling test was performed three times with a cellophane adhesive tape, and the number of remaining goggles 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 An optical member having an antireflection film immediately after formation of a vapor deposition film was placed in an oven for 1 hour to be heated and examined for the occurrence of cracks. The heating temperature was started from 50 ° C. and increased by 5 ° C., and the temperature at which cracks were generated was examined.

(E) Temporal heat resistance test An optical member having an antireflection film immediately after vapor deposition was exposed outdoors for 4 months, and then evaluated by the same method as the heat resistance test.

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

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

Example 1 First, as a synthetic resin for providing an antireflection film, diethylene glycol bisallyl carbonate was used as a main component, 2-hydroxy-4-n-optoxybenzophenone was used as an ultraviolet absorber, and the weight ratio of the former to the latter was adjusted. 99.97 / 0.
A plastic lens having a refractive index of 1.499, which is contained so as to have a value of 03, was prepared.

(I) Formation of Hard Coat Layer (nd 1.50) The above plastic lens was dipped in a coating solution containing 80 mol% of colloidal silica and 20 mol% of γ-glycidoxypropyltrimethoxysilane, Then, it was cured to form a hard coat layer.

(Ii) Formation of Underlayer and Antireflection Film A plastic lens having the above hard coat layer was formed into 80
Then, the SiO ₂ and Al ₂ O ₃ are heated on the hard coat layer by vacuum deposition (vacuum degree 2 × 10 ^-5 Torr).
An underlayer consisting of [refractive index 1.51, film thickness 0.6λ (λ =
500 nm)] was formed. Next, T on the underlayer
a ₂ O ₅ layer (refractive index 2.05, film thickness 0.06λ), T
A first low refractive index layer made of a mixed layer (refractive index 1.61, film thickness 0.11λ) made of a ₂ O ₅ , Y ₂ O ₃ and SiO ₂ was formed. Ta ₂ O is formed on the first low refractive index layer.
₅ layers (refractive index 2.05, film thickness 0.05λ) and Ta ₂ O
High refractive index composed of a mixed layer of ₅ , Y ₂ O ₃ and SiO ₂ (refractive index 1.61, film thickness 0.05λ) and Ta ₂ O ₅ layer (refractive index 2.05, film thickness 0.15λ) And forming a _second refractive index layer on the high refractive index layer.
A low refractive index layer (refractive index: 1.46, film thickness: 0.25λ) was formed to obtain a plastic lens with an antireflection film.
The first low refractive index layer to the second low refractive index layer were formed by the same vacuum vapor deposition method as that for forming the underlayer.

The first embodiment is claim 2 in the scope of claims.
It corresponds to.

Table 2 shows the evaluation results of the obtained anti-reflection coating plastic lens. As shown in Table 2, the plastic lens with the antireflection film of Example 1 had scratch resistance,
Excellent adhesion, acid resistance, alkali resistance, crack generation temperature as high as 100 ° C, and crack generation temperature after outdoor exposure for 4 months of 95 ° C, showing little decrease in heat resistant temperature over time. It was a thing.

COMPARATIVE EXAMPLE 1-1, COMPARATIVE EXAMPLE 1-2 As a comparison of Example 1, two comparative examples will be given. As shown in Table 1, the underlayer has a refractive index of 1.47 which is out of the range of the present invention.
An antireflection film was produced in the same manner as in Example 1 except that (Comparative Example 1-1) and 1.54 (Comparative Example 1-2) were used. The evaluation results are shown in Table 2. 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 was 70 ° C. after 4 months of outdoor exposure, and Comparative Example 1- The cracking temperature of the plastic lens with anti-reflection film of No. 2 is 90
Since the cracking temperature after outdoor exposure at 4 ° C for 4 months was 75 ° C, the heat resistance was lower than that of the plastic lens with the antireflection film of Example 1, and the degree of decrease in the cracking temperature with time was large. there were.

Example 2 Example 2 will be given as an example corresponding to claim 3 in the scope of claims. The film constitution 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 Table 4, the evaluation result shows that the cracking temperature is excellent at 100 ° C., and the cracking temperature after the outdoor exposure for 4 months is 95 ° C., which shows a small decrease in the heat resistant temperature with time. there were.

Comparative Example 2-1 and Comparative Example 2-2 As a comparison of Example 2, Comparative Example 2-1 and Comparative Example 2-2 will be given. The refractive index of the underlayer is 1.47, which is outside the range of the present invention.
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 were that the heat resistance was lower than that of the plastic lens with an antireflection film of Example 2, and the degree of decrease in crack generation temperature with time was large.

Example 3 Example 3 will be given as another example corresponding to claim 2 in the scope of claims. The film constitution 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, the evaluation results show that the cracking temperature is 105 ° C., which is excellent in heat resistance, and the cracking temperature after outdoor exposure for 4 months is 100 ° C. It was a small one.

Comparative Example 3-1 and Comparative Example 3-2 As a comparison of Example 3, Comparative Example 3-1 and Comparative Example 3-2 will be given. The refractive index of the underlayer is 1.47, which is outside the range of the present invention.
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 were that the heat resistance was lower than that of the plastic lens with an antireflection film of Example 3, and the degree of decrease in crack generation temperature with time was large.

Example 4 to Example 6-2 Four examples will be given as examples corresponding to claim 4 in the scope of claims. The film constitution is shown in Table 7 (Example 4), Table 9 (Example 5), and Table 11 (Example 6-1 and Example 6-).
As described in 2), the film forming conditions were the same as in Example 1 to obtain a plastic lens with an antireflection film. As shown in Table 8 (Example 4), Table 10 (Example 5), and Table 12 (Example 6-1 and Example 6-2), the evaluation results are all about the degree of decrease in crack generation temperature with time. Was small.

Comparative Example 4-1 to Comparative Example 6-2 Comparative Example 4-1 to Comparative Example 4-4 as a comparison of Example 4
As a comparison of Example 5, Comparative Examples 5-1 to 5-4,
Comparative Example 6-1 as a comparison between Example 6-1 and Example 6-2
-Comparative example 6-3 is given. The film constitution is shown in Table 7 (Comparative Example 4-1).
-Comparative Example 4-4), Table 9 (Comparative Example 5-1 to Comparative Example 5-)
4) and Table 11 (Comparative Examples 6-1 to 6-3), and the film forming conditions were the same as in Example 1 to obtain a plastic lens with an antireflection film. The evaluation results are shown in Table 8 (Comparative Example 4-1 to Comparative Example 4-4), Table 10 (Comparative Example 5-1 to Comparative Example 5-4), and Table 12 (Comparative Example 6-1 to Comparative Example 6-3). As shown in Comparative Example 4-1 to Comparative Example 4
The plastic lens with the antireflection film of Example No. -4 is a comparative example 5 rather than the plastic lens with the antireflection film of Example 4.
The plastic lens with the antireflection film of 1 to Comparative Example 5-4 is more than the plastic lens with the antireflection film of Example 5, and the plastic lens with the antireflection film of Comparative Example 6-1 to Comparative Example 6-3 is the example. The degree of decrease in crack generation temperature with time was larger than that of the plastic lenses with antireflection film of 6-1 and 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 not only has good scratch resistance, adhesion, acid resistance and alkali resistance even when formed at a low substrate temperature such as a plastic substrate. Small decrease in heat resistant temperature over time.
Therefore, the optical member of the present invention can be particularly preferably used for a spectacle lens that may be manufactured and stored for a long time.

Claims (6)

[Claims] 1. An optical member having a base layer and an antireflection film on a synthetic resin, wherein the base layer is SiO ₂ and Al _2.
An optical member having an antireflection film, which is made of a mixture with O _3, and in which the range of the refractive index of the underlayer is 1.48 to 1.52. 2. The antireflection film comprises a Ta ₂ O ₅ layer, Ta ₂ O ₅ , Y ₂ O ₃ and Si in this 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 and Ta ₂ O ₅ , Y ₂ O ₃ and SiO ₂
2. A mixed layer containing: 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 are laminated. An optical member having an antireflection film. 3. The first anti-reflection film comprising 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. Stratum;
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 mixed layer containing O ₂ ; SiO
_The optical member having an antireflection film according to claim 1, wherein a second low refractive index layer composed of two layers is laminated. 4. The antireflection film is formed of SiO ₂ and Al ₂ O ₃
2. The optical member having an antireflection film according to claim 1, wherein the optical layer has a mixed layer of and the refractive index of the mixed layer is 1.48 to 1.52. 5. An optical system having an antireflection film according to claim 1, wherein a hard coat layer containing an organic silicon polymer is interposed between the synthetic resin and the underlayer. Element. 6. The optical member having an antireflection film according to claim 1, wherein the optical member is an eyeglass lens.