JPH09241040A - Production of composite optical parts and composite optical parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain enough adhesion strength of a joining face between a glass and a resin in the processes of treating the surface of a glass substrate with a silane coupling agent and polymerizing an energy ray-hardening type resin thereon, by adding a process to directly irradiate the substrate with UV rays from a light source before the process of surface treatment. SOLUTION: The surface of a glass lens 1 where a resin is to be formed is irradiated with UV rays from a low pressure mercury lamp (184.9nm and 253.7nm main wavelength) for 3min (shown in Fig.2). The distance from the lamp to the lens 1 is 20mm and the output of the mercury lamp is 20W/mm. A silane coupling agent diluted with ethanol is applied by spin coating on the surface of the lens 1 and dried (Fig.3). A liquid UV-curing urethane acrylate resin 5 is applied in a proper amt. on the center part of the lens (Fig.4). A die 6 is pressed downward on the resin 5 till the die is 100nm above the center (Fig.5). The resin 5 is hardened by irradiating with UV rays from a high pressure mercury lamp (356nm wavelength) through the lower part of the lens 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite optical component manufacturing method and a composite optical component, which are formed by bonding glass and resin together.

[0002]

2. Description of the Related Art In recent years, in optical equipment such as cameras,
By using an aspherical lens having the same effect as a compound lens composed of a plurality of lenses, reduction in the number of lenses of an optical device, reduction in size and weight, and reduction in cost have been achieved. As an optical component having such an aspherical surface, a composite optical component in which a resin layer is formed on a glass surface has been proposed.

Generally, in such a composite type optical component, a stress is generated due to the curing shrinkage of the resin and the difference in the linear expansion coefficient between the glass and the resin, so that a sufficient bonding strength is required on the bonding surface between the glass and the resin. Is.

Conventionally, as a method of ensuring the adhesive strength of such a joint surface, as disclosed in, for example, Japanese Patent Application Laid-Open No. 54-6006, a glass surface is treated with a silane coupling agent and then the resin is treated. Methods of forming layers have been proposed.

[0005]

However, in general, a silane coupling agent has an effect of increasing the adhesive strength with an inorganic substance by chemically bonding with a hydroxyl group (OH group) on the surface of the inorganic substance. For this reason, OH is naturally formed on the surface.
It is said that SiO _{2 which} is easy to generate a group is most effective among inorganic substances. On the other hand, there are many types of optical glass, and there are many glasses having a low SiO ₂ content. In such glass, since there are not enough bonds for the silane coupling agent to chemically bond, sufficient adhesive strength cannot be obtained at the bonding surface between the glass and the resin, and the resin layer peels from the glass. There is a problem above.

Further, depending on the design of the optical product, it may be necessary to perform processing such as cutting after forming the resin layer on the composite type optical component. In such a case, in addition to the above-mentioned stress, a large force is required during processing. On the resin layer,
Even with glass having a sufficiently high O ₂ content, the resin layer may peel off.

[0007] The present invention has been made in view of the above conventional problems, apply glass content of SiO ₂ is low, after the resin layer is formed even when the content of SiO ₂ is applied a high glass An object of the present invention is to provide a method for manufacturing a composite optical component and a composite optical component that can obtain sufficient adhesive strength on a bonding surface between a glass and a resin when processing such as cutting.

[0008]

Means for Solving the Problems In order to solve the above problems, the present invention is configured as follows. The invention according to claim 1 is a method for producing a composite optical component, comprising a step of treating the surface of a glass substrate with a silane coupling agent, and a step of polymerizing an energy-curable resin on the treated surface. Before the step of surface treatment with the agent, the surface of the glass substrate was directly irradiated with ultraviolet rays from a light source.

According to the invention of claim 2, in the manufacturing method of claim 1, a low-pressure mercury lamp is used as a light source.

According to a third aspect of the present invention, there is provided a method for producing a composite optical component, comprising: a step of treating the surface of a glass substrate with a silane coupling agent; and a step of polymerizing an energy curable resin on the treated surface. Before the step of surface-treating with the silane coupling agent, the gas discharge was brought into direct contact with the surface of the glass substrate.

According to the invention of claim 4, in the manufacturing method of claim 3, the gas is a gas containing at least oxygen (O) and / or hydrogen (H).

According to the fifth and sixth aspects of the invention, there is provided a composite type optical component manufactured by the manufacturing method according to the first to fourth aspects.

The operation of claims 1 and 5 will be described. Normally, O generated naturally on the surface of SiO ₂ contained in glass
The H group is limited. Here, when the surface of the glass substrate is directly irradiated with ultraviolet rays from a light source as in the present invention, the SiO ₂ bond is broken by the high energy of the ultraviolet rays, and at the same time O ₂ and H ₂ O in the air are decomposed. Then, chemically active O and H are generated, so that a large amount of OH groups are generated in the cut bond. Therefore, even if the glass has a low SiO ₂ content, the number of bonding hands for bonding with the silane coupling agent is remarkably increased, so that practically sufficient adhesive strength can be obtained on the bonding surface between the glass substrate and the resin. It is a thing. At this time, as a light source that emits ultraviolet rays, a high pressure mercury lamp, a low pressure mercury lamp, a microwave discharge lamp,
A xenon short arc lamp, a mercury / xenon short arc lamp, an excimer laser, a plasma light source, etc. can be used.

The operation of claims 2 and 5 will be described. Among the above light sources, for example, a low-pressure mercury lamp efficiently generates vacuum ultraviolet rays having a main wavelength of 184.9 nm and deep ultraviolet rays having a main wavelength of 253.7 nm, and is particularly effective for generating an OH group in SiO _2. Is. For this reason, it is possible to obtain sufficient adhesive strength particularly on the joint surface with the resin. Further, the low-pressure mercury lamp is excellent among the above light sources in that it is easily available and easy to handle.

The operation of claims 3 and 6 will be described. Further, as in the present invention, even if a gas discharge is brought into direct contact with the surface of the glass substrate, a large amount of OH groups can be generated on the surface of SiO ₂ . This is because the SiO ₂ bond is broken by the collision of gas ions and electrons having high energy during discharge, and at the same time, H ₂ O, which is usually a residual gas, is decomposed during discharge to generate chemically active O and H. Therefore, a large amount of OH groups are generated in the broken bond. Therefore, even with a glass having a low SiO ₂ content, the number of bonds for bonding with the silane coupling agent is significantly increased, so that sufficient bonding strength can be obtained on the bonding surface between the glass substrate and the resin. is there. The types of gas discharge include
There are glow discharges, corona discharges, spark discharges, arc discharges and the like, but there is no particular limitation, and the means for generating discharges may be direct current, high frequency, low frequency, microwave, or the like.

The operation of claims 4 and 6 will be described. As the above-mentioned discharge gas, in particular oxygen (O) and / or hydrogen (H)
When a gas containing is used, decomposed chemically active O
Since a large amount of H and H is generated, it is particularly effective for generating OH groups in SiO ₂ . For this reason, it is possible to obtain sufficient adhesive strength particularly on the joint surface with the resin. As the gas containing O, O ₂ , CO, CO ₂ , NOX, etc.
As the gas containing H, H ₂ , CH 4, NH 3, etc.
As the gas containing O and H, there are H ₂ O, H ₂ O _{2 and the} like, and these gases can be used alone, or two or more kinds can be mixed, or other gas such as a rare gas can be mixed and used. The gas pressure may be any pressure from atmospheric pressure to low pressure in a high vacuum region, and is not particularly limited.

[0017] As items common to Claim 1 to 6, SiO ₂ content of the glass required when the content of SiO ₂ in the glass is low, categorically differs depending thermal shock resistance required Although it cannot be specified, in general, if it is at least about 5% by weight, preferably about 10% by weight or more, sufficient OH groups, which are bond hands, are generated, and sufficient adhesive strength is obtained on the bonding surface between the glass substrate and the resin. can get. In addition, when processing such as cutting after forming the resin layer,
Because what is effective to increase the bonding strength of the joint surface of the glass substrate and the resin even at a content of SiO _2, SiO ₂ content is not particularly limited. In addition, the energy curable resin of the present invention includes an ultraviolet curable resin, a visible light curable resin, a thermosetting resin, an electron beam curable resin and the like, and any resin may be used.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION

[First Embodiment of the Invention] FIGS. 1 to 5 show a first embodiment of the present invention, FIG. 1 is a sectional view showing a manufactured composite optical component, and FIGS. 2 to 5 are manufacturing of the composite optical element. It is sectional drawing which shows a process.

Reference numeral 1 is a glass lens, and the glass material of this glass is LAH60 (manufactured by OHARA INC.). Si of this glass material
The content of O ₂ is about 10% by weight. Glass lens 1
In order to qualitatively evaluate the OH groups present on the surface of the glass, pure water of 3 μm was applied to the surface of the dummy flat glass made of the same glass material.
About 1 l was dropped and the contact angle of pure water was examined. As a result, it was as large as 50 °. It should be noted that the presence of the OH group, which is a hydrophilic group, tends to wet pure water and reduce the contact angle.

In this embodiment, the surface of the glass lens 1 is directly irradiated with ultraviolet rays from a light source. A low pressure mercury lamp 3 is used as a light source, and a glass lens 1 is used in the atmosphere as shown in FIG.
The main wavelength of the resin molding surface of
Ultraviolet rays of 4.9 nm and 253.7 nm were irradiated for 3 minutes. The output of the low-pressure mercury lamp 3 was 20 W / mm, and the distance to the glass lens 1 was 20 mm. The composition of the atmosphere was 80% N ₂ , 18% O ₂ , and ₂ % H ₂ O in terms of partial pressure. Here, similarly, the contact angle of pure water with respect to the dummy glass irradiated with ultraviolet rays is 3 ° or less, which is very small.
A large amount of groups were produced.

Next, a resin layer 2 having an aspherical shape and made of an ultraviolet curable urethane acrylate is formed on the glass lens 1. Hereinafter, a method for producing the resin layer 2 will be described with reference to FIGS.

First, as shown in FIG. 3, a silane coupling agent 4 diluted with ethanol is formed on the surface of the glass lens 1.
After spin-coating (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), the glass lens 1 is surface-treated by drying at 100 ° C. for 20 minutes. After that, as shown in FIG. 4, an appropriate amount of liquid ultraviolet curable urethane acrylate resin 5 is applied to the central portion of the glass lens 1. Subsequently, as shown in FIG. 5, a die 6 having a desired aspherical shape is gently pressed from above the resin 5 so that air bubbles do not enter the applied resin 5, and the thickness of the resin 5 is centered. 100 μm
Then, the pressing of the mold 6 is stopped. Finally, from the bottom of the glass lens 1, the main wavelength is 35
After irradiating with ultraviolet rays of 6 nm to polymerize and cure the resin 5, the mold 6 is released to form the resin layer 2 on the glass lens 1. Through the steps described above, the composite optical component of the present embodiment shown in FIG. 1 is manufactured.

Next, the thermal shock resistance of the composite optical component of this embodiment was examined in order to evaluate the adhesion between the glass lens 1 and the resin layer 2. The thermal shock resistance was determined by a method in which the appearance was visually inspected after 30 cycles of alternating 30 minutes each in an environment of temperatures of −50 ° C. and 90 ° C. As a result, peeling of the glass lens 1 and the resin layer 2 did not occur, and there was no problem in practical use. As a glass material for the glass lens 1, the content of SiO ₂ is 10% by weight.
Even if LAL14 (manufactured by OHARA INC.) Is used,
The same good thermal shock resistance was obtained.

[Embodiment 2] In Embodiment 2 of the present invention, a mercury / xenon short arc lamp is used as the light source instead of the low-pressure mercury lamp 3 as the light source of Embodiment 1, and the surface of the glass lens 1 is used. , The wavelength is 230 than the light source
Directly irradiate with ultraviolet light of ˜250 nm. The output of the mercury / xenon short arc lamp was 200 W / mm, and the distance to the glass lens 1 was 30 mm. Similarly, the contact angle of pure water with respect to the dummy glass after being irradiated with ultraviolet rays is 3
It was very small at less than °, and a large amount of OH groups were formed.
Other steps and conditions were the same as in Embodiment 1 to obtain a composite optical component.

Next, when the thermal shock resistance of the composite type optical component of the second embodiment was examined by the same method as in the first embodiment, peeling of the glass lens 1 and the resin layer 2 did not occur, which was a practical problem. There was no. In addition, the light source is ArF (wavelength 193
(nm) or KrF (wavelength 248 nm) excimer laser or the like, the same good thermal shock resistance was obtained.

[Third Embodiment of the Invention] In the third embodiment of the present invention, LAL61 (manufactured by OHARA INC.) Having a SiO ₂ content of about 5% by weight is used as the glass material of the glass lens 1. When the contact angle of pure water with respect to a dummy flat glass plate made of the same glass material was examined in the same manner as in Embodiment 1, it was 60.
It was as big as °.

In this embodiment, on the surface of the glass lens 1,
Directly contact the discharge of gas. Hereinafter, the contact method for gas discharge will be described with reference to FIG. A coil-shaped electrode 8 is arranged in the vacuum chamber 7, and the electrode 8 has a width of 13.56.
A high frequency power supply 9 of MHz is connected. Further, gas inlets 10 and 11 are provided on the side surface of the vacuum chamber 7.

First, after the glass lens 1 is placed in the vacuum chamber 7, the vacuum chamber 7 is evacuated to a pressure of 1.times.10@-3 Pa by a vacuum pump (not shown). 80 of residual gas at this time
% (Partial pressure) and above was H ₂ O. After that, O ₂ gas (purity 99.9%) was introduced into the vacuum chamber 7 through the gas inlet 10 until the pressure reached 1 Pa, and then a high-frequency power source 9 supplied 500 W of power to the electrode 8 for high-frequency glow discharge. Generate. After this discharge is brought into direct contact with the resin molding surface of the glass lens 1 for 5 minutes, the supply of electric power and the introduction of gas are stopped, the discharge is stopped, and then the glass lens 1 is taken out into the atmosphere. Similarly, the contact angle of pure water with respect to the dummy glass after contacting the discharge of gas is very small at 3 ° or less.
A large amount of groups were produced.

Subsequently, a resin layer 2 made of an ultraviolet curable urethane acrylate having an aspherical shape is formed on the glass lens 1 by the same method as in the first embodiment, and the composite optical component of the third embodiment is formed. To manufacture.

Next, the thermal shock resistance of the composite type optical component of this embodiment was examined by the same method as in Embodiment 1. As a result, peeling of the glass lens 1 and the resin layer 2 did not occur, and there was no practical problem. There was no.

[Fourth Embodiment of the Invention] In the fourth embodiment of the present invention, instead of the gas of the third embodiment, the gas discharge is brought into direct contact with the surface of the glass lens 1. Is introduced from a gas inlet 10 in the present embodiment 4 O ₂ gas is introduced to a pressure of 0.8 Pa, and the gas inlet port 11 to the H ₂ gas to a pressure of 0.2 Pa, O ₂ into the vacuum chamber 7 And a mixed gas of H ₂ was introduced. The contact angle of pure water with respect to the dummy glass after contacting the discharge of gas is very small at 3 ° or less.
A large amount of groups were produced. Other steps and conditions were the same as in the third embodiment, and a composite optical component was obtained.

Next, the thermal shock resistance of the composite optical component of this embodiment was examined by the same method as in Embodiment 1. As a result, peeling of the glass lens 1 and the resin layer 2 did not occur, and there was no practical problem. There was no. In addition, when the gas introduced into the vacuum chamber 7 was changed to the gas shown in Table 1 or the like, the same good thermal shock resistance was obtained.

[0033]

[Table 1]

[Embodiment 5] In Embodiment 5 of the present invention, as a glass material for the glass lens 1, BSL7 (manufactured by OHARA INC.) Having a SiO ₂ content of about 75% by weight.
Was used. When the contact angle of pure water with respect to a flat glass (dummy glass) made of the same glass material was examined in the same manner as in Embodiment 1, it was as large as 45 °.

Also in this embodiment, on the surface of the glass lens 1,
Directly contact the discharge of gas. Hereinafter, the contact method for gas discharge will be described with reference to FIG. The spherical electrode 12 and the plate-shaped electrode 13 are installed at a distance of 10 mm.
Is connected to a low frequency power source 14 of 20 Hz, and the electrode 13 is grounded.

First, after placing the glass lens 1 between the electrodes 12 and 13 with the resin molding surface facing upward, 50 W of electric power is supplied from the low frequency power source 14 to the electrode 12 in the atmosphere to generate corona discharge. Let This discharge is brought into direct contact with the resin molding surface of the glass lens 1 for 30 seconds. The composition of the atmosphere is partial pressure, N ₂ is 80%, O ₂ is 18%, and H ₂ O is 2%.
It was weak. Similarly, the contact angle of pure water with respect to the dummy glass after contacting the discharge of gas was very small at 3 ° or less, and a large amount of OH groups were generated.

Then, by the same method as in the first embodiment,
A resin layer 2 made of an ultraviolet curable urethane acrylate having an aspherical shape was formed on the glass lens 1 to manufacture a composite optical component of this embodiment.

Next, in order to evaluate the adhesion between the glass lens 1 and the resin layer 2 in the composite type optical component of this embodiment,
When the composite optical component was cut using a diamond cutter, peeling of the glass lens 1 and the resin layer 2 did not occur, and there was no practical problem.

COMPARATIVE EXAMPLE 1 As Comparative Example 1, the same glass lens 1 as in the first and third embodiments was used, and the same method as in the first embodiment was carried out without irradiation of ultraviolet rays or contact with gas discharge. A resin layer 2 made of an ultraviolet curable urethane acrylate having an aspherical shape on the glass lens 1.
Then, the composite optical component of Comparative Example 1 was manufactured.

Next, the thermal shock resistance of the composite optical component of Comparative Example 1 was examined by the same method as in Embodiment 1. As a result, peeling occurred between the glass lens 1 and the resin layer 2 in any of the glasses. It was a problem in practice.

Comparative Example 2 Furthermore, as Comparative Example 2, the same glass lens 1 as that of the fifth embodiment was used, and the same method as that of the first embodiment was carried out without irradiation of ultraviolet rays or contact of gas discharge. A resin layer 2 made of an ultraviolet curable urethane acrylate having an aspherical shape was formed on the glass lens 1 to manufacture a composite optical component of Comparative Example 2.

Next, when the composite optical component of Comparative Example 2 was cut by the same method as in Embodiment 5, partial peeling occurred between the glass lens 1 and the resin layer 2, which was a practical problem. .

[0043]

As described above, according to the present invention,
The following effects can be obtained. According to the first and fifth aspects of the present invention, there is provided a method for producing a composite optical component, comprising: a step of treating the surface of a glass substrate with a silane coupling agent; and a step of polymerizing an energy curable resin on the treated surface. Before the step of treating with the silane coupling agent, the surface of the glass substrate was directly irradiated with ultraviolet rays from a light source, so that even if the glass has a low SiO ₂ content, it is bonded to the silane coupling agent. Since the number of OH groups serving as a bonding hand for increasing the number is significantly increased, it is possible to provide a method for manufacturing a composite-type optical component and a composite-type optical component in which sufficient adhesive strength can be obtained on a bonding surface between a glass and a resin.

According to the second and fifth aspects of the invention, since the low-pressure mercury lamp is used as the light source in the manufacturing method of the first aspect, the OH group is particularly increased, so that the glass substrate and the resin are combined. It is possible to provide a method for manufacturing a composite-type optical component and a composite-type optical component in which sufficient bonding strength can be obtained on the bonding surface.

Further, according to the third and sixth aspects of the invention, since the gas discharge is brought into direct contact with the surface of the glass substrate before the step of treating with the silane coupling agent, the SiO ₂ content is increased. OH, which is a bond for bonding with the silane coupling agent, even if the glass has a low ratio
Since the number of bases is remarkably increased, it is possible to provide a method for producing a composite optical component and a composite optical component in which sufficient bonding strength can be obtained at the bonding surface between glass and resin.

According to the inventions of claims 4 and 6, in the manufacturing method of claim 3, the gas is at least oxygen (O).
Since the gas contains hydrogen and / or hydrogen (H), the OH group is remarkably increased, and therefore, a method for producing a composite optical component and a composite optical component capable of obtaining a sufficient adhesive strength on a bonding surface between a glass and a resin. A mold optical component can be provided.

[Brief description of drawings]

FIG. 1 is a sectional view showing a composite optical component according to a first embodiment of the present invention.

FIG. 2 is an explanatory diagram showing a manufacturing process according to the first embodiment of the present invention.

FIG. 3 is an explanatory view showing one manufacturing process of the first embodiment of the present invention.

FIG. 4 is an explanatory diagram showing a manufacturing step according to the first embodiment of the present invention.

FIG. 5 is an explanatory view showing one manufacturing process of the first embodiment of the present invention.

FIG. 6 is a schematic configuration diagram showing a gas discharge device used in Embodiments 3 and 4 of the present invention.

FIG. 7 is a schematic configuration diagram showing a gas discharge device used in a fifth embodiment of the present invention.

[Explanation of symbols]

 1 Glass Lens 2 Resin Layer 3 Low Pressure Mercury Lamp (Light Source) 4 Silane Coupling Agent 5 Resin 6 Mold 7 Vacuum Tank 8 Coiled Electrode 9 High Frequency Power Supply 10, 11 Gas Inlet 12 Spherical Electrode 13 Flat Electrode 14 Low Frequency power supply

Claims (6)

[Claims] 1. A method for producing a composite optical component, comprising: a step of treating the surface of a glass substrate with a silane coupling agent; and a step of polymerizing an energy-curable resin on the treated surface. A method for manufacturing a composite optical component, comprising a step of directly irradiating the surface of a glass substrate with ultraviolet rays from a light source before the step of surface-treating. 2. The method for manufacturing a composite optical component according to claim 1, wherein the light source is a low pressure mercury lamp. 3. A method for producing a composite optical component, comprising: a step of treating the surface of a glass substrate with a silane coupling agent; and a step of polymerizing an energy curable resin on the treated surface. A method for producing a composite-type optical component, characterized in that a gas discharge is brought into direct contact with the surface of a glass substrate before the surface treatment step. 4. The method for manufacturing a composite optical component according to claim 3, wherein the gas contains at least oxygen (O) and / or hydrogen (H). 5. A composite optical component manufactured by the manufacturing method according to claim 1. 6. A composite optical component manufactured by the manufacturing method according to claim 3.