JPH06166550A - Production of optical element joined product - Google Patents

Abstract

PURPOSE:To inexpensively produce an optical element joined product having high peeling durability by installing a layer having a high adhesivity to a glass optical element on the glass optical element. CONSTITUTION:A lens 1 is immersed in at least one of an acidic solution, an Alkaline solution and water to enhance the contents of metal oxides on the surface of the glass lens. A silyl isocyanate compound, a chlorosilane compound, a perhydropolysilazane, an organoaluminum compound, an alumina sol, a titanate compound, a Zn alcolate compound, or the like, is coated on the surface of the lens 1 to be adhered to a resin such as an adhesive 3, and subsequently heated to form the film of at least one of silicon dioxide, aluminum trioxide, and titanium dioxide. An energy-curable transparent resin is further formed on the film 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bonded body of optical elements made of glass-glass and glass-resin, and a method of manufacturing a composite optical element having an energy-curable resin provided on glass.

[0002]

2. Description of the Related Art Generally, in the alignment of optical elements, a plurality of optical elements are bonded with an adhesive to form one optical element system. As the adhesive used here, a hot melt type adhesive such as balsam or an epoxy type reactive adhesive is used. Various optical glasses are used as materials for the optical elements to be joined. Generally, glass is Si
It contains a large amount of O ₂ and Al ₂ O ₃ . SiO ₂ and Al ₂
O ₃ is known to have a hydroxyl group on the surface, and therefore has good adhesiveness. However, among optical glasses, there are glasses with a low SiO ₂ or Al ₂ O ₃ content and very poor adhesiveness (eg LaK011, FK03, etc.). In a test or the like, peeling of the bonding layer occurs and the optical performance is impaired. This is not only for optical element bonding but also for glass-
The same phenomenon is observed in the resin composite type optical element.

Particularly, in a glass-resin composite type optical element, since a resin having low adhesiveness is sometimes used, the glass surface may be surface-treated with a silane coupling agent. SiO ₂ and Al ₂ O ₃ are also involved in the bonding on the glass surface.

On the other hand, in the one disclosed in Japanese Patent Laid-Open No. 63-89343, the bonding surface of the glass substrate is coated with a metal oxide film such as SiO ₂ or Al ₂ O ₃ by the vacuum deposition method. Generally, such SiO ₂ and Al ₂
Since O ₃ has a hydroxyl group on the surface and is polar, it has good adhesiveness to the resin. Therefore, S at the interface with the resin
By providing a layer of iO ₂ , Al ₂ O ₃ or the like, the adhesiveness of the resin to the optical element is increased, and the durability against peeling in the glass-resin composite type optical element is improved.

[0005]

However, JP-A-63-
As disclosed in Japanese Patent No. 893430, in order to improve the adhesiveness of optical glass having low adhesiveness, S is formed by a vacuum deposition method.
When forming an iO ₂ or Al ₂ O ₃ layer, an expensive vacuum vapor deposition apparatus is required, and a large investment must be made in manufacturing an expensive element.

Further, since the film is only physically placed in the vapor deposition, even if the adhesive force between the SiO ₂ or Al ₂ O ₃ layer and the adhesive can be secured, the SiO ₂ or Al ₂ O ₃ layer and the glass are adhered. There is a problem in that the adhesion with the is not so high and peeling occurs at that portion.

The present invention has been made in view of the above conventional problems, and by providing a layer having high adhesion to an optical element on the optical element at low cost, the optical element bonding having high durability against peeling is provided. It is an object to provide a method for manufacturing a body.

[0008]

In order to solve the above problems, the present invention produces an optical element assembly having a structure in which a glass optical element and an energy curable transparent resin are in contact with each other to form an interface. In so doing, the glass optical element is immersed in at least one liquid of acid, alkali and water,
A step of increasing the metal oxide content on the glass surface, the surface of the glass optical element, a silyl isocyanate compound,
A chlorosilane compound, a perhydropolysilazane, an aluminum alcoholate compound, an aluminum chelate compound, an aluminum organic compound such as a cyclic aluminum oligomer, an alumina sol, a titanate compound, at least one kind of a Zr alcoholate compound, and a diluted solution containing the substance. Apply, heat, silicon oxide,
At least one of aluminum oxide and titanium oxide
It has been decided to include a step of providing a first layer of a kind and a step of forming a second layer formed by polymerizing an energy-curable transparent resin on the first layer.

[0009]

The optical glass contains various components. As a basic structure, LiO ₂ , Na, etc. are contained in the metal oxide network capable of forming a three-dimensional network structure represented by SiO _{2 and the} like.
Alkali oxides such as ₂ O and K ₂ O, MgO, CaO,
The alkaline earth oxide such as BaO is in the form of existing as a network modifier. Therefore, when such a glass is immersed in an acid, an alkaline solution, water or the like, the components near the surface of the glass selectively dissolve and dissolve, and the composition changes only near the surface.

Further, the roughness of the surface changes accordingly, and many microscopic irregularities are generated. For example, glass material L
AH66 is composed of B ₂ O ₃ , La ₂ O ₃ , SiO _2, etc., but when this is immersed in an acidic solution, B ₂ O ₃ , L ₂
a ₂ O ₃ elutes. As a result, Si near the surface
The O ₂ concentration will increase.

Actually, the behavior of elution and dissolution varies depending on the composition of the glass, but by selecting the solution to be dipped, the concentration of SiO ₂ or Al ₂ O _{3 on} the glass surface can be increased and chemically A rough surface can be obtained. However, the surface thus obtained has a large amount of hydroxyl (O
Although it has H) group and has good adhesiveness, it becomes a porous surface having microscopic irregularities (defects), and the mechanical strength of the glass optical element itself is significantly reduced.

Then, on the surface thus obtained,
Silyl isocyanate compounds, chlorosilane compounds, perhydropolysilazanes, aluminum alcoholate compounds, aluminum chelate compounds, aluminum organic compounds such as cyclic aluminum oligomers, alumina sol,
A titanate compound, a Zr alcoholate compound, etc. are applied and heated.

Then, since water is usually present on the surface of the optical element, or in the diluting solvent and the atmosphere, the silylisocyanate compound solution coated on the surface of the optical element and the optical solution are reacted by the reaction shown in Chemical formula 1. Hydrolysis reaction occurs with water adhering to the element surface and water present in the diluting solvent or in the atmosphere, so that SiO ₂ , Al
_A film made of ₂ O ₃ , TiO _2, etc. is formed.

[0014]

[Chemical 1]

At this time, the surface of the optical element is made of SiO ₂ , A
Since many metal oxides such as l ₂ O ₃ are present, a hydroxyl group is formed on the surface of the optical element and reacts with this hydroxyl group to form a covalent bond, so that Si which is extremely strongly adhered to the optical element is formed.
A film made of O ₂ , Al ₂ O ₃ , TiO ₂ or the like is formed.

Since these films are formed so as to fill the fine irregularities on the glass surface, they physically adhere strongly to the glass surface (anchor effect), and further the irregularities (defects) are formed. Improves mechanical strength to reduce.

As described above, since the film made of SiO ₂ , Al ₂ O ₃ , TiO ₂ or the like is formed on the side of the surface of the optical element that is to be joined with the resin such as the adhesive, the optical element is joined with the adhesive. At this time, SiO ₂ , Al ₂ O ₃ , TiO on the surface of the optical element
_The film composed of ₂ or the like has a hydroxyl group on the surface, so that the adhesive is improved and the durability against peeling can be improved. That is, by providing a film having excellent adhesion to the glass surface and excellent adhesiveness on the glass surface, an optical element bonded body excellent in peeling durability can be obtained. Furthermore, since the equipment required for forming the film made of SiO ₂ , Al ₂ O ₃ , TiO _{2 and the} like is only a heating device and a coating device, the present invention can be realized with relatively inexpensive equipment. .

The present invention is not limited to the materials described in the examples below, but tetraisocyanate silane (Si (NCO) ₄ ), methyltrichlorosilane (CH ₃ SiCl ₃ ), aluminum sec-butyrate. , Aluminum ethylate, aluminum tris (ethyl acetate), aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, and other aluminum organic compounds, and alumina sol produced therefrom, As a commercially available material, "Tonen Polysilazane" manufactured by Tonen Co., Ltd., Nissan Chemical "NT Series", Kawaken Fine Chemicals Co., Ltd. alumina sol series (aluminum sol-10, aluminum sol-
CSA55, aluminum sol-SH5, etc.) can be applied, and the coating method can be spin coating, spraying, dipping, etc.

The resin (adhesive) is also an epoxy type, epoxy acrylate type, silicone type, urethane type, urethane acrylate type, acrylic type, polyester type,
It is also possible to use an ester acrylate-based resin or the like or a combination thereof, and it is also possible to use an energy curable resin (adhesive) such as ultraviolet (light), heat, or electron beam for curing.

Further, applicable glass materials are not limited to the materials used in the embodiments described later, and various glass materials can be applied.

As described above, there are no restrictions on the applicable materials,
Since it is possible to manufacture a resin optical element bonded body, there is an effect that the degree of freedom in optical design is greatly expanded. Furthermore, the refractive index of each material is
When the film <glass material or glass material <film <resin (adhesive) is satisfied, it is possible to significantly reduce the reflectance around an arbitrary wavelength by controlling the film thickness, and also to improve the optical performance. It can be expected.

[0022]

EXAMPLE 1 FIG. 2 shows a lens assembly according to the present invention. Lens 1 is made of glass material FK01 (manufactured by OHARA INC.)
Is created by. Lens 2 is a glass material KZFS40
It is made by (Ohara Co., Ltd.). Adhesive 3
Is an acrylate-based ultraviolet curing adhesive.

First, as shown in FIG. 1 (1), the lens 1
The surface of the joining side 1A was dipped in sulfuric acid (H ₂ SO ₄ ) 7 for 12 hours. Next, the monoSEC butoxyaluminum diisopropylate ((CH ₃ ) ₂ CHC is formed on the center of the lens 1.
_{H 2 -O-Al (O-} CH (CH 3) 2) of n- a 10% solution was dropped onto with hexane (see FIG. 1 (2)). Next, as shown in FIG. 1C, the entire lens 1 was rotated at a high speed, and monoSEC butoxyaluminum diisopropylate was uniformly applied to the surface of the lens 1. After this,
The lens 1 was heated with an infrared heater from above the mono-SEC butoxyl urinium diisopropylate application surface. The heating temperature of the surface of the lens 1 at this time is 15
The temperature is adjusted to 0 to 200 ° C. By this heating, the chemical reaction shown in the above chemical formula 1 occurs, and Al is formed on the surface of the lens 1.
_{A 2} O ₃ film 6 is formed. After heating, the lens 1 was gradually cooled to room temperature. After that, an appropriate amount of liquid adhesive 3 is applied to the central portion of the lens 1 (FIG. 1 (4)), and the lens 2 is gently pressed onto the adhesive 3 from above to prevent bubbles from entering the adhesive layer. The thickness was 10 μm. Next, the optical core was adjusted by a predetermined method, and ultraviolet rays were irradiated from above the lens 2 to cure the adhesive 3 (FIG. 1 (5)). The lens assembly is manufactured through the above steps.

A thermal shock test (-50 to
Five cycles were carried out (+ 90 ° C .: 2 hours / 1 cycle), but no peeling was observed at the joint portion of the lens. As a comparative example, when a similar test was performed on a lens joined body in which the Al ₂ O ₃ film 6 was not formed on the lens 1, peeling of the joining layer was observed near the lens outer peripheral portion. Moreover, when the same test was performed on the joined body joined without forming the Al ₂ O ₃ film 6 after the immersion in sulfuric acid, the glass lens itself was cracked.

[0025]

Example 2 The same glass lens and adhesive as in Example 1,
A lens conjugate was prepared in the same manner as in Example 1 using hydrochloric acid (HCl) and alkyl acetoacetate aluminum diisopropylate (structural formula 2) (trade name Planeact AL-M: Ajinomoto Co., Inc.).

[0026]

[Chemical 2]

A thermal shock test (-50 to
After 5 cycles (+ 90 ° C.), no peeling was observed at the joint portion of the lens. As a comparative example, lens 1
When a similar test was performed on the lens joined body in which the Al ₂ O ₃ film 6 was not formed, peeling of the joining layer was observed near the lens outer peripheral portion.

Although an ultraviolet curable adhesive was used as the adhesive in the present embodiment and the embodiment 1, a thermosetting adhesive such as an epoxy adhesive or an electron beam curable adhesive may be used.

[0029]

Third Embodiment FIG. 3 shows a glass-resin composite type lens according to the present invention. The lens 4 is made of glass material LaK011.
(Made by OHARA INC.) (Nd = 1.74). The resin 5 is a urethane acrylate-based ultraviolet curable resin.

First, as shown in FIG. 4A, the lens 4
The resin molding surface 4A of No. 2 was immersed in sulfuric acid for 12 hours. Next, aluminum triisopropoxide (Al ₂ (OCH (CH
₃ ) ₂ ) ₃ ) and distilled water were mixed at a molar ratio of 1: 100, and hydrolyzed while stirring at a temperature of 75 to 85 ° C for 2 hours. These operations are particularly effective in increasing transparency.

Thereafter, hydrochloric acid was added dropwise to allow it to dissolve, and 8
Aging was performed for a time to obtain a translucent alumina sol. Next, an appropriate amount of the above-mentioned alumina sol was dropped on the central portion of the lens 4, and Example 1
Similarly to, as shown in FIG. 4B, the entire lens 4 was rotated at high speed, and alumina sol was uniformly applied to the surface of the lens 4. After that, heating was performed from above the alumina sol-coated surface of the lens 4 with an infrared heater. The heating temperature of the surface of the lens 4 at this time is adjusted to 150 ° C. By this heating, the Al ₂ O ₃ film 6 is formed on the surface of the lens 4. After heating, the lens 4 was gradually cooled to room temperature. further,
As shown in FIG. 4C, a surface treatment was performed on the Al ₂ O ₃ film 6 of the lens 4 with a silane coupling agent “KBM-503” (Shin-Etsu Chemical Co., Ltd.).

After that, the liquid UV curable resin 5 (nd =
1.52) is applied to the center of the lens 4 in an appropriate amount (Fig. 4).
(4)), from above, gently press the mold 8 formed in a desired shape such as an aspherical surface so that air bubbles do not enter the resin 5,
The thickness of the resin layer was 100 μm at the center. Next, FIG.
As shown in (5), ultraviolet rays were irradiated from the lower part of the lens 4 to cure the resin 5. After the resin 5 hardens, the mold 8
Was released. The glass-resin composite lens is manufactured through the above steps.

When the glass-resin composite lens was subjected to a thermal shock test (-50 to + 90 ° C.) for 5 cycles, no crack or peeling of the resin layer was observed. As a comparative example, the same test was performed on a glass-resin composite lens in which the Al ₂ O ₃ film 6 was not formed on the lens 4,
Peeling of the resin layer was observed near the outer periphery of the lens.

[0034] In this embodiment, the refractive index of the Al ₂ O ₃ film 6 (nd = 1.64), becomes substantially midway between the refractive index of the glass material of the resin, the Al ₂ O ₃ film 6 By controlling the film thickness, it is possible to significantly reduce the reflectance of the joint surface. Specifically, in the case of reducing the reflectance around 550 nm, λ / 4 = 1375Å, Al ₂ O
_{3 The} film thickness may be set to 1375Å.

[0035]

Embodiment 4 FIG. 3 shows a glass-resin composite lens according to the present invention. The lens 4 is made of glass material LaK011.
It is made by (Ohara Co., Ltd.). Resin 5 is
It is a urethane acrylate type UV curable resin.

First, as shown in FIG. 4, the molding surface side 4A of the lens 4 was immersed in hydrochloric acid for 12 hours. Next, an appropriate amount of alumina clear sol (Kawaken Fine Chemical Co., Ltd.) (Al ₂ O ₃ : 5 wt% product) was dropped on the center of the molding surface side 4A of the lens 4, and the entire lens 4 was prepared in the same manner as in Example 1. The surface was rotated at high speed, and the alumina sol was uniformly applied to the surface of the lens 4.
After that, heating was performed from above the alumina sol-coated surface of the lens 4 with an infrared heater. The heating temperature of the surface of the lens 4 at this time is adjusted to 150 ° C. By this heating, the Al ₂ O ₃ film 6 is formed on the surface of the lens 4. After heating, the lens 4 was gradually cooled to room temperature. Furthermore, the silane coupling agent “K” is formed on the Al ₂ O ₃ film 6 of the lens 4.
The surface treatment was performed by "BM-503" (Shin-Etsu Chemical Co., Ltd.).

After that, a liquid UV curable resin 5 is applied on the central portion of the lens 4 in an appropriate amount, and a mold 8 having a desired shape such as an aspherical surface is quietly placed thereon so that no air bubbles enter the resin 5. Then, the thickness of the resin layer was set to 100 μm at the center. Next, the resin 5 was cured by irradiating ultraviolet rays from the lower part of the lens 4. After the resin was cured, the mold 8 was released. The glass-resin composite lens is manufactured through the above steps.

When this glass-resin composite lens was subjected to a thermal shock test (-50 to + 90 ° C.) for 5 cycles, no crack or peeling of the resin layer was observed. As a comparative example, the same test was performed on a glass-resin composite lens in which the Al ₂ O ₃ film 6 was not formed on the lens 4,
Peeling of the resin layer was observed near the outer periphery of the lens.

As a commercially available material, an alumina sol series (aluminum sol-1 manufactured by Kawaken Fine Chemicals Co., Ltd.)
0, aluminum sol-CSA55, aluminum sol-SH5, etc.)
Etc. are applicable.

[0040]

Embodiment 5 FIG. 2 shows a lens assembly according to the present invention. Lens 1 is made of glass material FK01 (manufactured by OHARA INC.)
Is created by. Lens 2 is a glass material KZFS40
It is made by (Ohara Co., Ltd.). Adhesive 3
Is an acrylate-based ultraviolet curing adhesive.

First, as shown in FIG. 1, the joint side 1A of the lens 1 was immersed in sulfuric acid for 12 hours. Next, tetraisocyanate silane (Si (NCO) ₄ ) was added to the center of the bonding side 1A.
Was added dropwise. Next, the entire lens 1 was rotated at high speed, and tetraisocyanate silane was uniformly applied to the surface of the lens 1. Then, heating was performed from above the tetraisocyanatesilane-coated surface of the lens 1 with an infrared heater.
The heating temperature of the surface of the lens 1 at this time is 200 to 250.
It is adjusted to ℃. By this heating, the chemical reaction shown in Chemical formula 3 occurs, and the surface of the lens 1 is three-dimensionally crosslinked with Si.
The O ₂ film 6 is formed. After heating, the lens 1 was gradually cooled to room temperature. Then, an appropriate amount of liquid adhesive 3 is applied to the central portion of the lens 1, and the lens 2 is gently pressed onto the adhesive 3 from above to prevent bubbles from entering, and the thickness of the adhesive layer is set to 10 μm.
m. Next, the optical core was adjusted by a predetermined method, and ultraviolet rays were irradiated from above the lens 2 to cure the adhesive 3. The lens assembly is manufactured through the above steps.

[0042]

[Chemical 3]

A thermal shock test (-50 to
After 5 cycles (+ 90 ° C.), no peeling was observed at the joint portion of the lens. As a comparative example, lens 1
When a similar test was performed on the lens joined body in which the SiO _{2 3} film 6 was not formed on the above, peeling of the joining layer was observed in the vicinity of the lens outer peripheral portion.

[0044]

[Sixth Embodiment] The same glass lens and adhesive as in the fifth embodiment are used.
A lens joined body was prepared in the same manner as in Example 5 using sulfuric acid and methyltrichlorosilane (CH ₃ SiCl ₃ ). The heating temperature at this time was 150 to 250 ° C.

A thermal shock test (-50 to
After 5 cycles (+ 90 ° C.), no peeling was observed at the joint portion of the lens. As a comparative example, lens 1
When a similar test was performed on the lens joined body in which the SiO _{2 3} film 6 was not formed on the above, peeling of the joining layer was observed in the vicinity of the lens outer peripheral portion. Although an ultraviolet curable adhesive is used as the adhesive in the present embodiment and the embodiment 5, a thermosetting adhesive such as an epoxy adhesive or an electron beam curable adhesive may be used.

[0046]

Embodiment 7 FIG. 3 shows a glass-resin composite lens according to the present invention. The lens 4 is made of glass material LaK011.
It is made by (Ohara Co., Ltd.). Resin 5 is
It is a urethane acrylate type UV curable resin.

First, as shown in FIG. 4, the molding surface side 4A of the lens 4 was immersed in sulfuric acid for 12 hours. Next, molding surface side 4A
Tetraisocyanate silane (Si (NCO)) in the center
₄ ) was added dropwise. Next, similarly to the fifth embodiment, the lens 4
The whole was rotated at high speed, and tetraisocyanate silane was uniformly applied to the surface of the lens 4. After that, heating was performed by an infrared heater from above the tetraisocyanate silane-coated surface of the lens 4. The heating temperature of the surface of the lens 4 at this time is adjusted to 200 to 250 ° C. By this heating, the chemical reaction shown in Chemical formula 3 above occurs and the lens 4
A three-dimensionally crosslinked SiO ₂ film 6 is formed on the surface of the. After heating, the lens 4 was gradually cooled to room temperature. Furthermore, lens 4
Silane coupling agents on SiO ₂ film 6 of "KBM-5
03 ”(Shin-Etsu Chemical Co., Ltd.).

After that, a liquid UV curable resin 5 is applied to the central portion of the lens 4 in an appropriate amount, and a mold 8 having a desired shape such as an aspherical surface is quietly placed thereon so that air bubbles do not enter the resin 5. Then, the thickness of the resin layer was set to 100 μm at the center. Next, the resin 5 was cured by irradiating ultraviolet rays from the lower part of the lens 4. After the resin was cured, the mold 8 was released. The glass-resin composite lens is manufactured through the above steps.

When this glass-resin composite lens was subjected to a thermal shock test (-50 to + 90 ° C.) for 5 cycles, no crack or peeling of the resin layer was observed. As a comparative example, the same test was conducted on the glass-resin composite lens in which the SiO _{2 3} film 6 was not formed on the lens 4,
Peeling of the bonding layer was observed near the outer peripheral portion of the lens.

[0050]

Embodiment 8 FIG. 2 shows a lens assembly according to the present invention. The lens 1 is made of a glass material FPL51 (manufactured by OHARA INC .; former name: FK01). Lens 2
Is a glass material BPH40 (manufactured by OHARA INC .; former name KZFS)
40). The adhesive 3 is an acrylate-based ultraviolet curable adhesive.

First, as shown in FIG. 1, the joint surface side 1A of the lens 1 was immersed in hydrochloric acid for 12 hours. Next, the joining surface side 1A
An appropriate amount of a 20% xylene solution of perhydropolysilazane (trade name: "Tonen polysilazane", manufactured by Tonen Corporation) was dropped in the central part of the. Next, the entire lens 1 was rotated at high speed, and perhydropolysilazane was uniformly applied to the surface of the lens 1.
After that, heating was performed by an infrared heater from above the surface of the lens 1 on which the perhydropolysilazane was applied. The heating temperature of the surface of the lens 1 at this time is adjusted to 200 to 250 ° C. By this heating, hydrogen in the perhydropolysilazane is replaced with oxygen in the atmosphere, so that the surface of the lens 1 is
A dimensionally crosslinked silicon oxide and a silicon nitride film 6 are formed. After heating, the lens 1 was gradually cooled to room temperature. After that, an appropriate amount of liquid adhesive 3 was applied to the central portion of the lens 1, and the lens 2 was gently pressed onto the adhesive 3 so that air bubbles did not enter the adhesive 3, and the thickness of the adhesive layer was set to 10 μm. Next, the optical core was adjusted by a predetermined method, and ultraviolet rays were irradiated from above the lens 2 to cure the adhesive 3. The lens assembly is manufactured through the above steps.

A thermal shock test (-50 to
After 5 cycles (+ 90 ° C.), no peeling was observed at the joint portion of the lens. As a comparative example, lens 1
When a similar test was conducted on the lens bonded body in which the silicon oxide and silicon nitride films 6 were not formed, peeling of the bonding layer was observed in the vicinity of the outer peripheral portion of the lens.

[0053]

[Example 9] A glass material YGH51 (manufactured by OHARA INC .; former name: LaSK01) was used for the lens 1, and the same adhesive bonding, sulfuric acid, and perhydropolysilazane as in Example 1 were used to bond the lens in the same manner as in Example 1. Created the body. The heating temperature at this time was 300 to 350 ° C.

A thermal shock test (-50 to
After 5 cycles (+ 90 ° C.), no peeling was observed at the joint portion of the lens. As a comparative example, lens 1
When a similar test was conducted on the lens bonded body in which the silicon oxide and silicon nitride films 6 were not formed, peeling of the bonding layer was observed in the vicinity of the outer peripheral portion of the lens.

Although an ultraviolet curable adhesive was used as the adhesive in the present embodiment and the embodiment 1, a thermosetting adhesive such as an epoxy adhesive or an electronically curable adhesive may be used.

[0056]

Example 10 FIG. 3 shows a glass-resin composite type lens according to the present invention. Lens 4 is glass material LAL61
(Made by OHARA INC .; former name LaSK011). The resin 5 is a urethane acrylate type ultraviolet curable resin.

First, as shown in FIG. 4, the molding surface side 4A of the lens 4 was immersed in sulfuric acid for 12 hours. Next, molding surface side 4A
An appropriate amount of a 20% xylene solution of perhydropolysilazane (trade name: "Tonen Polysilazane", manufactured by Tonen KK) was dropped in the center. Next, the entire lens 4 was rotated at high speed, and the surface of the lens 4 was uniformly coated with perhydropolysilazane. After that, heating was performed by an infrared heater from above the surface of the lens 4 coated with perhydropolysilazane. The heating temperature of the surface of the lens 4 at this time is adjusted to 200 to 250 ° C. By this heating, three-dimensionally cross-linked silicon oxide and silicon nitride film 6 are formed on the surface of lens 4. After heating, the lens 4 was gradually cooled to room temperature. Furthermore, a silane coupling agent (trade name “K” is formed on the silicon oxide film 6 and the silicon nitride film 6 of the lens).
A 1% ethanol solution of "BM-503" manufactured by Shin-Etsu Chemical Co., Ltd. was applied and surface treatment was performed by heating at 100 ° C for 20 minutes.

After that, a liquid UV curable resin 5 is applied on the central portion of the lens 4 in an appropriate amount, and a mold 8 having a desired shape such as an aspherical surface is quietly applied thereon so that no bubbles enter the resin 5. Then, the thickness of the resin layer was set to 100 μm at the center. Next, the resin 5 was cured by irradiating ultraviolet rays from the lower part of the lens 4. After the resin 5 was cured, the mold 8 was released. The glass-resin composite lens is manufactured through the above steps.

A thermal shock test (-50 to
When the resin layer was subjected to 5 cycles (+ 90 ° C.), neither cracking nor peeling of the resin layer was observed. As a comparative example, the lens 4
When a similar test was performed on the glass-resin composite lens in which the silicon oxide and silicon nitride films 6 were not formed on the film, peeling of the bonding layer was observed near the outer peripheral portion of the lens.

[0060]

As described above, according to the method for manufacturing an optical element bonded body of the present invention, a lens bonded body excellent in peeling resistance can be manufactured with inexpensive equipment, and in particular, it has a high refractive index. It is more effective when using a low-dispersion glass material, when using an optical element having a large diameter, or when it is desired to increase the thickness of the resin (or adhesive).

[Brief description of drawings]

FIG. 1 is a process drawing showing a manufacturing process of Examples 1, 2, 5, 6, 8, and 9 of the present invention.

FIG. 2 is a vertical cross-sectional view of a lens assembly manufactured in the same example.

FIG. 3 is a vertical sectional view of a lens assembly manufactured in Examples 3, 4, 7, and 10 of the present invention.

FIG. 4 is a process drawing showing the manufacturing process of the example.

[Explanation of symbols]

 1,2,4 Lens 3 Adhesive 5 Resin 6 Film

Claims (1)

[Claims] 1. When manufacturing an optical element assembly having a structure in which a glass optical element and an energy curable transparent resin are in contact with each other to form an interface, the glass optical element is at least one of acid, alkali and water. Soak in one liquid,
A step of increasing the metal oxide content on the glass surface, the surface of the glass optical element, a silyl isocyanate compound,
Chlorosilane compound, perhydropolysilazane, aluminum organic compound, alumina sol, titanate compound,
Applying at least one kind of Zr alcoholate compound and a dilute solution containing the substance and heating to provide a first layer made of at least one kind of silicon oxide, aluminum oxide, and titanium oxide; A method of manufacturing an optical element assembly, comprising the step of forming a second layer formed by polymerizing an energy-curable transparent resin on the first layer.