JPH04243936A - Optical element and production thereof - Google Patents

Abstract

PURPOSE:To improve the adhesiveness of a resin layer to a glass matrix by successively forming the first layer containing silicon oxide and a specific component of the glass matrix, the second layer comprising a silane coupling agent- cured film, and the third layer comprising an organic polymeric compound on the glass matrix. CONSTITUTION:A deposited film 5 comprising a mixture of 20-95wt.% of silicon oxide and 5-80wt.% of a component contained in a glass matrix, such as B2O3, is vacuum-deposited on the glass matrix 1 containing <=25wt.% of silicon oxide such as SiO2 to form the first layer. The first layer is treated with a silane coupling agent to form the second layer comprising a silane coupling agent-cured film 2. An organic polymeric compound is coated on a flat plate mold 4, and the silane coupling agent-treated glass matrix is placed on the coated flat plate mold 4, followed by irradiating the coated organic polymeric compound with UV rays to perfectly cure the organic polymeric compound to form the third layer comprising the cured resin 3. The flat plate mold 4 is removed to provide an optical element comprising the matrix plate 1 and the resin layer 3 both being tightly bonded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical element having a resin layer made of an ultraviolet curable resin on a glass base material, and a method for manufacturing the same.

0002

[Prior Art] Conventionally, aspherical lenses have been known that have a structure in which resin is laminated on a glass base material, but since the bonding surface between glass and resin has poor adhesion, peeling occurs under the usage environment. It had the disadvantage of being easy. In order to overcome this drawback, efforts have been made to improve adhesion, for example, by applying a silane coupling agent to the glass surface. However, the surface treatment effect of silane coupling agents cannot be obtained for all glass base materials.
Among the more than 200 types of optical glasses, there are many glass materials with low SiO2 content, and the surface treatment effect of silane coupling agents is often small for these materials.

[0003] Therefore, for such types of glass, there is a method of increasing adhesion by forming a layer made of silicon oxide, metal oxide, or a mixture thereof on the glass surface in advance, and then treating it with a silane coupling agent. has been proposed (Japanese Unexamined Patent Publication No. 89343/1983).

0004

[Problems to be Solved by the Invention] However, the above conventional example is based on the premise that a thin film of silicon oxide, metal oxide, or a mixture thereof is completely adhered to the glass base material, and the thin film of silicon oxide, metal oxide, or a mixture thereof is completely adhered to the glass base material. In glass base materials, the main components are often La2 O3 and B2 O3, and in thin films simply made of silicon oxides, metal oxides, or mixtures thereof, the base material components and thin film components may be different. There is a drawback that adhesion is insufficient due to the low affinity between the glass base material and the thin film, and the glass and resin layer peel off due to peeling between the glass base material and the thin film in the usage environment. Ta.

[0005] Accordingly, an object of the present invention is to provide an optical element in which a resin layer is formed that has excellent adhesion even to a glass base material with a low SiO2 content, and a method for manufacturing the same.

[0006]

[Means and effects for solving the problem] According to the present invention, silicon oxide and metal oxide are excluded from the glass base material and the silicon oxide and glass base material-containing components sequentially formed thereon. An optical element consisting of a first layer containing at least one type of component, a second layer consisting of a silane coupling agent cured film, and a third layer consisting of an organic polymer compound, and silicon on a glass base material. Forming a first layer containing at least one type of component excluding silicon oxide and metal oxide from the oxide and glass matrix-containing components, and then forming a second layer consisting of a silane coupling agent cured film. Then, a method for manufacturing an optical element is provided by forming a third layer made of an organic polymer compound.

The present invention also provides the above optical element, wherein the glass base material contains silicon oxide in an amount of 25% by weight or less. Further, the present invention provides the above-mentioned optical element, wherein one of the components excluding silicon oxide and metal oxide from among the components containing silicon oxide and glass matrix material is boron oxide.

[0008] The reason why SiO2 is contained in the first layer is as follows.
When coating with a silane coupling agent and adhering the resin, the silanol groups (-Si-OH) generated during the coupling reaction treatment and the -Si-OH groups appearing on the surface of SiO2 in the first layer are -Si-O-S by dehydration condensation
This is to create a chemical bond of i and firmly adhere the resin and the film. The SiO2 content in the first layer is preferably 95
-20% by weight, more preferably 85-50% by weight. If it exceeds 95% by weight, the proportion of other components contained in the base material will be less than 5% by weight, which tends to reduce the adhesion due to affinity with the base material, and if it is less than 20% by weight, the effect of the silane coupling agent will weaken. Therefore, the adhesion with the resin tends to deteriorate.

The reason for including B2 O3 in the first layer is, firstly, to increase affinity and improve adhesion by including components of the same type as those contained in the base material, and secondly, to improve adhesion. By making a mixture of and B2 O3,
This is to make the coefficient of thermal expansion of the first layer close to that of the base material to prevent peeling of the first layer film due to the difference in coefficient of thermal expansion. The content of B2 O3 in the first layer is preferably 80
-5% by weight, more preferably 50-15% by weight. If it exceeds 80% by weight, it is difficult to vitrify and transparency is easily lost, and the film becomes brittle and adhesion failure due to film cracking is likely to occur. If it is less than 5% by weight, the adhesion due to affinity with the base material tends to deteriorate, and the coefficient of linear expansion approaches that of quartz (SiO2), which tends to increase the difference from the base material.

0010

[Examples] The present invention will be specifically explained below with reference to Examples. The following tests were conducted to evaluate adhesion. As shown in FIG. 1(A), SiO2 is placed on the base glass plate 1.
Alternatively, a deposited film 5 made of Al2O3 was vacuum deposited. Then, as shown in FIG. 1(B), the surface is treated with a silane coupling agent to form a silane coupling agent cured film layer 2.
was formed. Next, as shown in FIG. 1(C), a flat plate mold 4
An appropriate amount of photocurable resin (urethane acrylate composition) is dropped onto the top, and the silane coupling agent treated base glass plate is superimposed on top of the photocurable resin (urethane acrylate composition), and then ultraviolet light is irradiated to completely cover the resin layer 3. hardened. Then, the mold was released and Figure 1 (D)
Test pieces were prepared by bonding the base glass plate 1 and the resin layer 3 shown in (Nos. 5 to 8).

In FIG. 1(A), the deposited film 5 is SiO2
70%, B2 O3 30% or SiO2 60%, B
2 Test pieces in which the base material glass plate 1 and the resin layer 3 shown in FIG. 1(D) were bonded were created in the same manner as above except that 40% O3 was used (Nos. 9 to 12). . In addition,
Test pieces were created in exactly the same manner as above except that the vapor deposited film 5 in FIG. 1(A) was not formed (Nos. 1 to 4).

Test piece preparation conditions Base material glass plate...Dimensions: 35 x 35 x 2.5 mm Surface accuracy:
Double-sided polishing within 10 Newtons Silane coupling agent treatment...Coupling agent: γ-methacryloxypropyltrimethoxysilane (product name: A-174, manufactured by Nippon Unicar) Solution: Ethanol/Water/A-174=9/1/ 1 spin coating conditions: 500 rpm x 5 seconds → 3000 rpm x 3
0 second bake conditions: 100°C, 20 minutes Photocurable resin...Urethane acrylate composition Thickness: 1
00μm Irradiation conditions: 30mW/cm2 (365nm) x 10 minutes Flat plate type... Aluminum base material/KN plating surface polished finish Deposited film 5... Film material: (1) SiO2 100% (2) A
l2 O3 100% (3) SiO2 70%, B2 O3 30%; SiO
2 60%, B2 O3 40% Next, the test specimens prepared were: ■ Immediately after preparation (initial stage), ■ 80°C, 60% RH, 500
After leaving for a time (high temperature and humidity), -30℃ (1 hour) ←→70
℃ and 85% RH (1 hour) 30 times (temperature cycle), and then cut each piece into a 10 x 10 grid pattern with a cutter knife as shown in Figure 2 to obtain 100 pieces of resin. After adhering Sellotape (manufactured by Nichiban) to the surface, the Sellotape was peeled off at once, and the number of resin pieces remaining in close contact on the remaining glass base material excluding the part peeled off by the tape was counted. A score of 1 or more was considered "good." The results are shown in Table 1.

The compositions of the glass materials A, B, C, and D used are as follows. Glass material A: B2 O3 38%, La2 O3 38%,
SiO2 7%, other 17% Glass material B: La2 O3 46%, B2 O3 30%,
La2 O3 11%, SiO2 3%, others 10%
Glass material C: La2 O3 41%, B2 O3 40%,
CaO 6%, SiO2 2%, other 11% Glass material D: TiO2 28%, SiO2 25%, B2
O3 15%, BaO 7%, other 25%
Table 1 No. Glass material Vapor deposited film Adhesion test Judgment

Initial high temperature/humidity temperature cycle
1 A None
23 1 0
× 2 B
None 11
0 2 ×
3 C None
1 0
0 × 4D
None 5
4 15 23 ×
5 A SiO2 100%
86 63 2
3 × 6B
SiO2 100%
92 55 10 ×
7C Al2O3 100%
76 48
15 x 8D
SiO2 100%
99 78 51 ×
9 A SiO2 70%,
B2O3 30% 100 98 10
0 ○ 10B
SiO2 70%, B2O3 30% 100
98 98 ○
11C SiO2 70%, B2O3
30% 100 95 92
○ 12D SiO
2 60%, B2O3 40% 100 1
00 99 ○ As is clear from Table 1, test piece No. without vapor deposited film. In samples 1 to 4, the adhesion was poor. In addition, test piece No. with a vapor deposited film. 5～
In No. 8, the vapor deposition film material was 100% SiO2. 5,
Nos. 6 and 8 had insufficient adhesion, and the deposited film material was replaced with Al2O.
3 No. 100%. No. 7 also had insufficient adhesion.

In contrast, the embodiments of the present invention (Nos. 9 to 1)
In 2), the vapor deposition film material is SiO2 70%, B2 O3
30% or a mixture of 60% SiO2 and 40% B2 O3, and by incorporating the B2 O3 component contained in both base materials into the deposited film side, high adhesion strength can be obtained, which is a significant improvement over the comparative example. The effect was seen.

Comparative Example 1 As shown in FIG. 3A, a SiO2 vapor deposition film 5 of 1000 Å was deposited on a spherical polished base glass lens (φ25 mm, both sides R=55 mm, center thickness 7 mm) made of glass material C. Next, as shown in FIG. 3(B), a silane coupling agent cured film layer 2 was provided on the surface. Next, Figure 3(C)
As shown in the figure, an ultraviolet curable resin is dropped onto the aspherical mold (base material SUS/KN plated cutting, maximum thickness deviation 60 μm from reference R) 8, and the lens treated with the silane coupling agent is placed on top of the aspherical mold 8. The center thickness of the cured resin layer 3 is approximately 70 μm
After superimposing them so that The mold was then released to produce an aspherical lens shown in FIG. 3(D).

When the obtained aspherical lens was left in a temperature cycle environment in which -30°C (1 hour)←→70°C, 85%RH (1 hour) was repeated 30 times, the resin part from the base material lens It was defective due to peeling.

Example 1 In FIG. 3(A), the deposited film 5 was made of 70% SiO2, B2
Two aspherical lenses shown in FIG. 3(D) were prepared in the same manner as Comparative Example 1 except that the lens was replaced with one containing 30% O3. One of these was left under the same temperature cycle environment as in Comparative Example 1, and the other was left under a high temperature and humidity environment of 80° C. and 60% RH (500 hours). In both lenses, no peeling of the resin was observed, and the glass and resin were strongly adhered to each other.

In this example, the composition of the first layer of the vapor deposited film of the present invention was 70% SiO2 and 30% B2O3, but this ratio was determined to ensure good adhesion between the film and the base material and maintain transparency. Any material may be used as long as it falls within the range.

Furthermore, any non-metallic oxide other than B2O3 may be used as long as it has the same components as the base material.

Furthermore, the first layer may be mainly composed of silicon oxide and glass matrix containing components, and may be made of 70% SiO2.
, B2 O3 25%, Al2 O3 5%.
A component-based film may be used, and a metal oxide may be contained in a small amount as long as it is not the main component. Furthermore, in the embodiment, the first
Although the first layer is a vapor-deposited film, the first layer may be a fired coating film from a solution, for example, a film obtained by coating a mixed alcoholic solution of alkoxysilicate and B2 O3 and then baking it.

Further, although the present embodiment uses a flat plate and an aspherical lens, it can also be applied to a Fresnel optical element having a repeating chevron structure on the resin surface, a phase type diffraction grating having a repeating structure such as concavities and convexities, and the like.

[0022]

As described above, according to the present invention, a layer containing silicon oxide and at least one component other than silicon oxide and metal oxide from among the components contained in the glass base material is formed on the base material. Due to the introduced configuration, the glass type of the base material is 25% by weight or less of silicon oxide, so even if a silane coupling agent is used, there is little effect on improving adhesion, and even if silicon oxide or metal oxide is vapor-deposited, it is sufficient. Even when the present invention is applied to an optical element in which a strong adhesion force cannot be obtained, an optical element in which the base material and the resin layer are firmly adhered to each other has been made possible.

[Brief explanation of the drawing]

FIGS. 1A to 1C are schematic diagrams showing a method for manufacturing an optical element of the present invention, and FIG. 1D is a schematic cross-sectional view of the optical element of the present invention.

FIGS. 2A to 2C are schematic diagrams showing a method for manufacturing an optical element of the invention, and FIG. 2D is a schematic cross-sectional view of the optical element of the invention.

FIG. 3 is a schematic diagram of a tape peel test piece.

[Explanation of sign]

1 Base material glass plate 2 Silane coupling agent cured film layer 3 Resin layer 4　Flat type 5 Vapor deposited film 6 Cutting with a cutter knife 7 Base material glass lens 8 Aspherical type

Claims (4)

[Claims] [Claim 1] A first glass base material containing a glass base material and at least one type of component formed in order on the glass base material, excluding silicon oxide and metal oxide from among silicon oxide and glass base material-containing components. an optical element comprising a layer, a second layer made of a silane coupling agent cured film, and a third layer made of an organic polymer compound. 2. Forming on a glass base material a first layer containing at least one type of component excluding silicon oxide and metal oxide from silicon oxide and components contained in the glass base material, A method for manufacturing an optical element, which comprises then forming a second layer made of a silane coupling agent cured film, and then forming a third layer made of an organic polymer compound. [Claim 3] The glass base material contains 25 silicon oxides.
The optical element according to claim 1, wherein the optical element contains not more than % by weight. 4. The optical element according to claim 1, wherein one of the silicon oxide and glass matrix-containing components excluding the silicon oxide and the metal oxide is a boron oxide.