JP4532371B2 - Bonding method of glass material - Google Patents

Description

The present invention relates to adhesive how the glass material together.

As an adhesive method for optical parts, there are balsam, epoxy resin, methacrylic resin, polyester resin, ultraviolet curable resin, heat fusion and the like as an adhesive. However, these adhesives are all for visible light and cannot be used in the ultraviolet region below 250 nm. On the other hand, in thermal fusion, thermal strain remains in the optical material and it cannot be used as an optical waveguide. For this reason, there is no method other than air contact for joining optical components.

Regarding bonding of optical materials, Patent Document 1 “Method of manufacturing optical element” describes a method of bonding two lenses, and after dropping a tetraisocyanate compound or a chlorosilane compound on a glass lens, it is rotated at a high speed. The solution is uniformly diffused, heated by an infrared heater from above the uniformly diffused solution to form a SiO ₂ film having a three-dimensional crosslinked structure by hydrolysis, and then slowly cooled to room temperature. Then, after applying an acrylate-based ultraviolet curable transparent resin adhesive on the SiO ₂ film, another glass lens is pressed on the SiO ₂ film, and ultraviolet rays are irradiated from above the glass lens to cure the resin. A complex is formed. The SiO ₂ film formation by this method is based only on hydrolysis by overheating with infrared rays. In this method, a tetraisocyanate compound or chlorosilane compound is applied to the surface of one optical material, and then a flat surface that is completely vitrified by thermal hydrolysis is formed. An ultraviolet curable resin is applied to this surface, and the other optical material surface is applied. Joining is disclosed. However, this is only a means for shaping the first optical system, not a joint with the second lens. An acrylate-based UV curable transparent resin adhesive is used for bonding between the two lenses and is cured by photoexcitation with UV rays of 350 to 380 nm, but the cured adhesive layer has almost no transmission of 250 nm or less, and a wavelength of 250 nm or less. It cannot be used in the area. On the other hand, no light transmission of 250 nm or less is required for the direct bonding portion, but there is no strong adhesive other than heat fusion that requires resistance to 300 ° C. or higher and does not generate gas in a vacuum. However, thermal fusion leaves thermal strain on the material surface.

Regarding the formation of SiO ₂ in an oxygen atmosphere by ultraviolet rays of silicone oil, “Glass substrate coated with dimethylsiloxane silicone monomer (SiO (CH ₃ ) ₂ ) n (dimethylsiloxane silicone oil)” in Non-Patent Document 1 by the present inventors. On top of this, ArF excimer laser light is irradiated in an oxygen atmosphere to photodissociate the methyl group from the siloxane bond, and the oxygen atom O (3P) in the ground state generated by photoexcitation of oxygen binds to the dangling bond of Si. In other words, a transparent SiO ₂ hard film having a thickness of 2 μm was formed ”.

Large-diameter telescopes, large-diameter laser mirrors, and mirrors used in outer space use honeycomb structure mirrors to reduce the weight of materials. However, when an adhesive is used to join these mirrors and the honeycomb structure, curing distortion occurs, and gas is generated from the adhesive when the mirror is vacuum-deposited, which hinders the deposition. At present, heat fusion is performed to eliminate this gas generation, but this heat fusion requires heating near the melting point of the material. However, due to this high temperature, thermal distortion remains on the mirror surface, and the wavefront after vacuum deposition is distorted, resulting in problems in the observation results and the laser wavefront.
Japanese Patent Application No. 2-410824 (Japanese Patent Laid-Open No. 4-219349) Japanese Patent Application No. 5-238349 Japanese Patent Application 2002-350311 Japanese Patent Application 2001-14687 Japanese Patent Application 2002-119578 Masataka Murahara Plasticity and Processing (Journal of the Japan Society for Technology of Plasticity) Vol. 27, No. 307, 934-942 (1986) Shin-Etsu Chemical Co., Ltd. Technical data KF96 silicone oil performance test results (2003)

Optical materials that can be transmitted in the ultraviolet range include quartz glass, crystallized glass, low expansion glass, fluororesin, plastic, silicone rubber, sapphire, crystals, nonlinear crystals, and solid laser rods. If an adhesive is used, it cannot be used in a wavelength range of 250 nm or less. Further, even when heat fusion is used, thermal distortion remains on the material surface, which causes distortion in the wavefront. For this reason, air contacts are often used for joining different types of materials. However, depending on the materials, there are various drawbacks such as difficulty in air contact and weak joining strength.

On the other hand, a strong adhesive which does not require light transmission of 250 nm or less but has resistance to 300 ° C. or more and does not generate gas in a vacuum is only the heat fusion method. However, this method leaves thermal strain on the material surface. In addition, an intermediate glass was required for the thermal fusion between quartz glass and dissimilar glass.

Therefore, in the present invention, optical materials are bonded to each other by photochemical bonding with an organic silicone oil, and then changed to SiO ₂ that is an inorganic material by photooxidation, so that it can be used at a wavelength of 250 nm or less, and the bonding strength is also strong. And it aims at providing the optical material which has tolerance even 500 degreeC or more.

As a result of diligent research to achieve the above-mentioned object, the present inventors have carried out photochemical bonding between the plastic material and the inorganic optical material surface, which are organic materials, in the joining of optical materials with silicone oil, which is an organic material. the specific photooxidation, by varying the silicone oil is an organic material to SiO ₂ is an inorganic material, can also be used in a wavelength 250 nm, and the bonding strength stronger, and an optical material having resistance even 500 ° C. or higher It was found that the intended purpose can be achieved by forming. At that time, the methods disclosed in the above-mentioned Patent Documents 2, 4, 5 and Non-Patent Document 1 by the inventors of the present application are used.

Regarding the adhesion between the solid material and the fluororesin, the inventors of the present application claimed in claim 23 of Patent Document 2 “Fluororesin via a thin liquid layer of an adhesive having a liquid compound or a functional group having a hydrogen atom on the top surface of the solid material to be treated. The plate is pressure-bonded, and the solid material to be treated and the fluororesin plate are directly bonded by irradiating ultraviolet light having a photon energy of 128 kcal or more through the fluororesin plate, A transparent window material is pressure-bonded through a thin liquid layer of an adhesive having a hydrogen atom in a functional group, and the processed solid material and the fluororesin plate are irradiated with ultraviolet rays having a photon energy of 128 kcal or more through the transparent window material. Are directly bonded to each other ”, and among the liquid compounds of claim 4, silicone oil is disclosed. However, in the above invention, even if ultraviolet rays are irradiated through the silicone oil between the fluororesin plate and the transparent window material, because of the presence of methyl groups in the silicone oil, ultraviolet rays of 250 nm or less are transmitted after completion of the bonding. I couldn't. When the photon energy density was further increased or the number of irradiation pulses was increased, the carbon atoms of the methyl group in the silicone oil were liberated and blackened to reduce the light transmittance. Therefore, in the present invention, an oxidant is interposed in silicone oil, and these are heated to 160 ° C. or more to promote the oxidation reaction by ultraviolet rays, thereby completely changing dimethylsiloxane or methylphenylsiloxane to SiO _2. , It can transmit ultraviolet rays of 250nm or less. Moreover, in order to improve the adhesion to the silicone oil on the fluororesin surface and the quartz glass surface to which the silicone oil is applied, Patent Document 3 “Activation by plasma treatment or the like of the surface of the solid material” by the inventors of the present application. Plasma treatment is applied to strengthen the adhesive strength of both optical materials with silicone oil.

Regarding the formation of SiO ₂ in an oxygen atmosphere by ultraviolet rays of silicone oil, a glass substrate coated with “dimethylsiloxane silicone monomer (SiO (CH ₃ ) ₂ ) n (dimethylsiloxane silicone oil)” in Non-Patent Document 1 by the present inventors. On top of this, ArF excimer laser light is irradiated in an oxygen atmosphere to photodissociate the methyl group from the siloxane bond, and the oxygen atom O (3P) in the ground state generated by photoexcitation of oxygen binds to the dangling bond of Si. A transparent SiO 2 hard film having a thickness of 2 μm was formed ”.

In general, when silicone oil is applied to the surface of a substance, it is said that a releasing action is exhibited, and other substances are prevented from sticking, and at the same time, stability against thermal oxidation is very excellent. However, it is the present invention to use these silicone oils as an adhesive photochemically by ultraviolet irradiation.

Non-patent by the inventors of the present application that the organic silicone oil is bonded to quartz by ultraviolet irradiation, and that the organic silicone oil itself is changed to quartz having a siloxane bond that is an inorganic glass by ultraviolet irradiation in the presence of an oxidizing agent. The glass substrate coated with “dimethylsiloxane silicone monomer (SiO (CH ₃ ) ₂ ) n (dimethylsiloxane silicone oil)” described in Reference 1 is irradiated with ArF excimer laser light in an oxygen atmosphere to form methyl groups from siloxane bonds. And a ground-state oxygen atom O (3P) generated by photoexcitation of oxygen bonded to a danglin bond of Si to form a transparent SiO ₂ hard film with a thickness of 2 μm. Yes.

In addition, honeycomb structures are used to reduce the weight of materials in large-aperture telescopes, large-diameter laser mirrors, and mirrors used in space. However, when an adhesive is used to join these mirrors and the honeycomb structure, curing distortion occurs, and gas is generated from the adhesive when the mirror is vacuum-deposited, which hinders the deposition. In order to eliminate this gas generation, heat fusion is performed. This heat fusion requires high-temperature heating close to the melting point. However, due to this high temperature, thermal distortion remains on the mirror surface, and the wave front after vacuum deposition is distorted, resulting in a distorted observation result and laser wave front. Crystallized glass such as Clear Serum (registered trademark), Zerojuwa (registered trademark), and ULE (Ultra Low Expansion) cannot be heat-sealed. Even if it reaches low expansion glass or ceramics such as Pyrex (registered trademark) or Tempax (registered trademark), heat fusion cannot be performed similarly. In order to avoid these problems, a bonding method can be provided in which the treatment can be carried out at a relatively low temperature overheating, and the adhesive is changed to SiO ₂ after bonding.

According to Non-Patent Document 2, a number of types of representative silicone oil KF96 (Shin-Etsu Chemical Co., Ltd.) are commercially available depending on the viscosity from a low viscosity of 1 cs to a high viscosity of 1 million cs. This viscosity means a molecular weight, and the viscosity is equivalent to 200 to 100,000 when expressed in terms of molecular weight. In the present invention, when these silicone oils having different molecular weights are sandwiched between two quartz glasses and irradiated with Xe ₂ excimer lamp light having a wavelength of 172 nm, both quartz glasses are bonded, and as the molecular weight of the silicone oil increases, the two are bonded. The strength is remarkably high, showing the highest strength at 60,000.

In general, optical materials that can be transmitted in the ultraviolet region include quartz glass, crystallized glass, low expansion glass, fluororesin, plastic, silicone rubber, sapphire, crystal, nonlinear crystal, and solid laser rod. If an adhesive is used for bonding, it cannot be used in a wavelength range of 250 nm or less. Further, even when heat fusion is used, thermal distortion remains on the material surface, which causes distortion in the wavefront. For this reason, air contacts are often used for joining different types of materials. However, depending on the material, there are many drawbacks such as difficulty in air contact and weak joining strength.

In the present invention, the glass material is a quartz glass such as synthetic quartz glass, synthetic fused silica glass, natural quartz glass, crystallized glass such as Clear Serum (registered trademark), Zerojuwa (registered trademark), ULE (Ultra Low Expansion), Pyrex (Registered trademark), low expansion glass such as Tempax (registered trademark), ceramic glass, white plate glass, crown glass, flint glass, lead glass and other optical glass, soda glass, laser glass, optical fiber, etc. Plasma treatment or ultraviolet treatment is performed on the surfaces of the materials to be joined, each of which has a planar, spherical, or aspherical shape composed of a combination, by the method disclosed in Patent Document 4 by the inventors of the present application, and the surfaces of the materials to be joined are subjected to the treatment. Improves affinity with silicone oil.

According to Non-Patent Document 2, silicone oil generally contains 200 ppm of water inside and outside, and can dissolve air, oxygen, carbon dioxide gas, and the like. Thermally stable up to 150 ° C, thermal oxidation starts when the temperature exceeds 200 ° C and combustion begins at 450 ° C. Furthermore, the viscosity of silicone oil is lowered by heating, and the molecular weight is reduced.

In the present invention, the organic silicone oil is photooxidized and converted into inorganic glass. For this reason, an oxygen source is required in the photoreaction process. This oxygen source is oxygen adsorbed on the sample surface, an oxygen source mixed in the silicone oil, or air or oxygen supplied during the reaction. Therefore, the sample surface is previously subjected to plasma treatment or ultraviolet treatment in an oxygen atmosphere to increase the oxygen atom density on the sample surface. This treatment greatly contributes to improving the ultraviolet transmittance after bonding. Further, after silicone oil is applied to the surfaces of the materials to be bonded, the subsequent photo-oxidation reaction is promoted by increasing the oxygen atom density by hot air from a dryer or oxygen plasma treatment on the silicone oil application surface. In addition, the silicone oil left in the atmosphere contains 200 ppm of water inside and outside. Oxygen generated by the photolysis of this water plays a role in oxidizing the silicone oil into SiO2. On the other hand, since silicone oil can dissolve air, oxygen, carbon dioxide gas, etc., in order not to lower the viscosity of the silicone oil, the silicone oil should be heated at room temperature, and when the viscosity should be lowered, it should be heated at 200 ° C or lower. After vacuum degassing, oxygen, ozone, etc. are dissolved again, or water, hydrogen peroxide solution, water vapor, etc. are mixed to promote SiO ₂ conversion of the adhesive layer. However, when these oxidizing agents are excessive, the adhesive layer may become cloudy. The transmittance below 250 nm is somewhat lower, but there is no white turbidity, and when maintaining transparency from visible light to near-ultraviolet region, the viscosity of the silicone oil should be reduced at room temperature in order not to lower the viscosity of the silicone oil. In order to lower the temperature, it is only necessary to deaerate in a vacuum while heating at 200 ° C. or less, and apply to the surfaces to be joined excluding contaminants such as oxygen, carbon dioxide, and water. In addition, the light transmittance after bonding is limited, but overheated silicone oil, potassium permanganate, sodium peroxide, potassium peroxide, lithium peroxide, barium peroxide, lead peroxide, chromium peroxide, rubidium peroxide, By mixing peroxides such as cesium peroxide, benzoyl peroxide and lauroyl peroxide, the subsequent photooxidation reaction is promoted. However, in this case, the photochemical reaction is unlikely to occur because ultraviolet rays having a wavelength of 300 nm to 150 nm, which are the excitation sources of the photochemical reaction, inhibit the penetration into the adhesive layer. For this reason, it is necessary to make the adhesive layer very thin and to increase the amount of incident ultraviolet rays.

In general, in a large area or uniform joining, uniformity and thinness of the thickness of the adhesive layer are required. For this reason, an ultra-low viscosity UV curable adhesive of 8 cps has been developed compared to the conventional 10 cps. However, the viscosity showing the strongest adhesive strength with silicone oil is 10,000 cs, and their molecular weight is 60,000. Therefore, in order to reduce the thickness of the adhesive layer and improve uniformity, the surfaces of the materials to be bonded are overlapped in a high-temperature atmosphere and pressurized in the range of 0 to 30 kg / cm ² , or the bonded portion is evacuated. The joint surface is pressurized by atmospheric pressure or an external pressure by an inert gas. Alternatively, the container internal pressure is made higher than the external pressure, and a uniform load is applied with the differential pressure.

Then, Xe excimer lamp light, ArF excimer laser light, KrF excimer laser light, XeCl laser light, F2 laser light, harmonic laser light by nonlinear element, KrCl excimer lamp light, XeCl excimer lamp light, Glass materials are bonded together by irradiating Hg lamp light, Hg-Xe lamp light, deuterium lamp light, halogen lamp light, or ultraviolet rays having a wavelength of 300 nm to 150 nm obtained by gas arc, corona or silent discharge, etc. Let

When both glass materials are quartz glass, a small amount of oxidizer or water is mixed with organic silicone oil for bonding a quartz glass container for transporting silicon wafers, a solution cell for UV measurement, or a lightweight mirror with a honeycomb structure. Excimer laser or excimer lamp light is incident from one quartz side to chemically bond between the end group of both optical materials and the end group of silicone oil, and at the same time, unreacted Organic silicone oil is photo-oxidized with ultraviolet rays and converted into inorganic material SiO ₂ for strong adhesion.

When the optical material is bonded to a honeycomb structure mirror, the shape of one optical material is a flat plate or a curved plate, and the other is a structure processed into a honeycomb shape made of the same kind of material. A structure in which a small amount of oxidant or water mixed in organic silicone oil is used as an adhesive in the gap of the mold, and an excimer laser or excimer lamp light is incident from one quartz mirror side, and processed into a honeycomb shape with the mirror side At the same time, the end group on the physical side and the end group of the silicone oil are chemically bonded, and at the same time, the unreacted organic silicone oil is photooxidized with ultraviolet rays to be changed into the inorganic material SiO ₂ and strongly bonded.

According to the present invention, quartz glass can be photochemically bonded using silicone oil as an adhesive, and an optical material excellent in ultraviolet transmittance can be provided.

Large-diameter astronomical telescopes, large-diameter laser mirrors, and mirrors used in space use a honeycomb structure to reduce the material weight. If the present invention is used for joining these mirrors to the honeycomb structure, it can be processed at a relatively low temperature, so that thermal distortion due to thermal fusion or wavefront after vacuum deposition is distorted, and the observation results and laser wavefront are distorted. Can be avoided.

By manufacturing a vacuum tube, a discharge tube or a lamp by bonding a round or square pipe made of the same or different material as a synthetic quartz glass flat window as an ultraviolet ray incident or irradiation window such as an ultraviolet imaging tube or a head-on excimer lamp, There is no thermal distortion and no surface sag of the flat window due to conventional heat fusion. Further, synthetic quartz is used for the ultraviolet transmission window portion, and Pyrex (registered trademark) or optical glass as a different material can be used for the pipe portion, which is advantageous in terms of workability and economy.

The feature of the present invention is that, in the joining of optical materials, a silicone oil having a molecular weight of 200 to 120,000 is changed to SiO ₂ that is an inorganic material by photooxidation, so that it can be used at a wavelength of 250 nm or less and has a strong joining strength. Forming an optical material.

Dimethylsiloxane silicone oil (SiO (CH ₃ ) ₂ ) n) has a methyl group (—CH ₃ ) in the side chain of the structural formula. When this oil is irradiated with ultraviolet rays, carbon (C) is liberated and blackened. This blackening inhibits light transmission. In order to prevent this blackening, oxygen must be introduced into the reaction system.

Therefore, in the present invention, the molecular weight is 2 on the bonded surface of a glass material made of a combination of the same or different types such as quartz glass, crystallized glass, low expansion glass, ceramic glass, optical glass, soda glass, laser glass, and optical fiber. Apply 100 to 120,000 silicone oil, pressurize with hydraulic pressure or water pressure, etc. or nitrogen gas, carbon dioxide gas, helium, air, oxygen, or mixed gas diluted with nitrogen gas or helium Pressurization is performed in the range of 0 to 30 kg / cm ² by gas pressurization, and Xe ₂ excimer lamp light, ArF excimer laser light, KrF excimer laser light, XeCl laser light, F ₂ laser light, harmonic laser light by nonlinear element, KrCl excimer lamp light, XeCl excimer lamp light, Hg lamp light, UV light with a wavelength of 300 nm to 150 nm obtained by Hg-Xe lamp light, deuterium lamp light, halogen lamp light, gas arc, corona or silent discharge, etc. is irradiated in an oxidant gas atmosphere and photochemically strong. Glue.

In order to perform strong adhesion of silicone oil in a room temperature atmosphere, a molecular weight of 30,000 to 120,000 is required, and among these, 60,000 inside and outside has the highest adhesive strength. Therefore, in order to satisfy the uniformity and thinness of the thickness of the adhesive layer, the surfaces of the materials to be joined are superposed in a high temperature atmosphere and pressed in the range of 0 to 30 kg / cm ² . And Xe2 excimer lamp light, ArF excimer laser light, F2 laser light, harmonic laser light by nonlinear element, KrCl excimer lamp light, Hg lamp light, Hg-Xe lamp light, deuterium lamp light, halogen lamp light on the joint surface Or ultraviolet rays having a wavelength of 300 nm to 150 nm obtained by gas arc, corona or silent discharge. In addition, if methylphenyl silicone oil containing a small amount of hydrogen peroxide is used as the oxidizing agent, the absorption band peculiar to the phenyl group is in the vicinity of 250 nm, so KrF excimer laser, KrCl excimer lamp light, XeCl excimer lamp light, etc. are used as excitation light. Can be used. When the oxygen in these silicone oils is excited by ultraviolet rays, some of them are used as carbon abstraction atoms, and the products are diffused out of the reaction system as CO ₂ gas. Other remaining active oxygen atoms are substituted after the removal of the methyl group, forming SiO ₂ and vitrified by sequential reaction.

Prior to the bonding between the glass, the surface to be bonded is plasma or oxidant gas atmosphere such as air, oxygen, ozone, water vapor, or an inert gas such as argon, xenon or helium with a small amount of oxygen mixed. Silicone oil is applied after ultraviolet rays are irradiated and the surface to be bonded of the glass material is excessive in oxygen, and if ultraviolet rays are irradiated, the reaction between the silicone oil and oxygen is carried out efficiently, and it is transparent and strong in the ultraviolet region. Adhesive strength is obtained.

Prior to bonding between the glass, silicone oil is applied to both surfaces to be bonded, then a gap is created between the surfaces to be bonded, and a dielectric barrier discharge is performed in the gap in an oxidizing gas atmosphere such as air, oxygen or ozone. After the surface of the silicone oil is made excessive in active oxygen, the discharge is stopped, and then the pressure is applied in the range of 0 to 30 kg / cm ² . The formation of active oxygen and the oxidation reaction of the silicone oil proceed by the ultraviolet rays generated by the discharge between the glass materials, and the adhesion reaction is started. Here, if ultraviolet irradiation is used in combination, the reaction between the silicone oil and oxygen is further efficiently performed, and a transparent and strong adhesive strength can be obtained in the ultraviolet region.

Silicone oil decreases in viscosity when heated. For example, KF96-1000 (Shin-Etsu Silicone) has a viscosity of 1000cs at 25 ° C, but when heated at 200 ° C, it decreases to 100cs. On the other hand, the thinner the adhesive layer, the stronger the adhesion. Therefore, after applying silicone oil between the materials to be bonded heated to a temperature of 200 ° C. or lower, when the layers are overlapped and pressed, the adhesive layer becomes uniform and thin, so that it is transparent in the ultraviolet region and strong adhesive strength can be obtained.

Silicone oil was degassed under reduced pressure to remove a large amount of contaminants such as oxygen, carbon dioxide, and water, and then an appropriate amount of oxygen, ozone, carbon dioxide, water, water vapor, hydrogen peroxide, and other oxidizing agents were added again. If silicone oil is used as an adhesive, the photoreaction can be completed without an oxidant atmosphere. If silicone oil is heated and degassed in a state where the viscosity is lowered, more effective adhesion can be achieved.

If silicone oil is applied to the material to be adhered and ultraviolet irradiation is performed while applying pressure in a carbon dioxide atmosphere, the polymerization is remarkable and strong adhesion can be achieved in a short time. More effective adhesion can be achieved by using degassed silicone oil as an adhesive.

If one of the glass materials is a flat plate or curved quartz glass, and the other is a honeycomb or groove or hollow structure made of the same or different material, the inside is a male structure.・ Since silicone oil is applied to the surface to be joined in a female form, the inside of the structure processed into a honeycomb shape or groove or depression is evacuated, so that the inside is in a reduced pressure state. The part can be irradiated with ultraviolet rays in a state of being uniformly weighted by atmospheric pressure. If a small amount of the oxidant gas is sealed in the vacuum cavity, more effective bonding can be achieved.

After applying silicone oil to the end faces of round or square pipes or frames made of quartz glass window materials or liquid crystal panel plates such as phototubes, photomultiplier tubes, ultraviolet light emitting lamps, deuterium lamps, and laser tubes. By evacuating the inside, it is possible to irradiate ultraviolet rays in a state where the joint portion of both glass materials is uniformly loaded by atmospheric pressure. More effective adhesion can be achieved if a small amount of oxidant gas is sealed in the vacuum cavity.

A plastic or rubber bag or envelope having a synthetic quartz glass window is in contact with both quartz glasses coated with the silicone oil, or when non-bonding surfaces of both glasses are used together with plasma irradiation. Plasma is generated between the two quartz glasses that are coated with silicone oil with electrodes facing each other, and then air or oxygen inside the envelope or bag while irradiating the bonded interface with ultraviolet rays. By exhausting to a low pressure, photochemical bonding can be performed while uniformly applying a differential pressure between the atmospheric pressure and the internal pressure of the container to the joint portion of both glass materials. When the pressure is controlled by gas, a container such as a plastic film having a synthetic quartz glass window or a rubber envelope may be provided with a structure that can freely expand and contract such as a bellows or an O-ring.

If the vacuum vessel is covered with an outer box having a synthetic quartz glass window, and the outer box is pressurized with an inert gas such as nitrogen gas, argon gas, xenon, or helium gas, a uniform load is applied to the joint portion of the glass material. You can call.

The reaction vessel with a quartz glass window is separated into two chambers with rubber plates. One synthetic quartz glass window is a sample chamber, the other is a mechanical pressurization chamber using hydraulic pressure or water pressure, and the sample chamber is heated with a vacuum exhaust valve. A heater is provided, and an adherend glass material coated with silicone oil is brought into contact with the quartz glass window side of the sample chamber, and UV irradiation is performed while mechanically pressing through a rubber plate to perform photochemical bonding. After removing contaminants such as oxygen, carbon dioxide, and water in the silicone oil applied to the surface of the glass to be adhered with the vacuum exhaust valve provided in the sample chamber, carbon dioxide is sealed in to enhance the adhesion effect. it can. Furthermore, the adhesive layer can be made extremely thin by reducing the viscosity of the silicone oil by heating a film heater attached on the rubber plate.

In a room temperature atmosphere, each molecular weight (200 to 140,000) silicone oil (KF96-1cs to 500,000cs manufactured by Shin-Etsu Chemical Co., Ltd.) is applied between two synthetic quartz glasses and a pressure of 10 kg / cm ² is applied. The quartz glass was covered on it and irradiated with Xe ₂ excimer lamp light for 0 to 120 minutes. FIG. 1 shows the relationship between the lamp irradiation time and the tensile shear strength (adhesion strength) of the sample at each molecular weight. From this measurement, it is clear that the adhesive strength increases as the irradiation time of Xe ₂ excimer lamp light increases. In terms of the relationship between each molecular weight and the adhesive strength, the highest adhesive strength is obtained when the silicone oil having a molecular weight of 60,000 is irradiated with Xe ₂ excimer lamp light for 90 minutes, and the adhesive strength is low even when the molecular weight is lower or lower. It shows a tendency to become. FIG. 2 shows the relationship between the tensile shear strength and the molecular weight (200 to 140,000) for each irradiation time (0 to 120 minutes). From this graph, Xe ₂ excimer lamp light irradiation of 30 minutes or more is necessary to effectively perform the photoadhesion reaction, and silicone oil having a molecular weight of 60,000 has high adhesive strength at any irradiation time.

In a room temperature atmosphere, a silicone oil with a molecular weight of 60,000 (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.) is applied between two pieces of synthetic quartz glass, pressurized at a pressure of 15 kg / cm ² , and quartz glass is applied on top of it. Then, Xe ₂ excimer lamp light having an emission wavelength of 172 nm and 222 nm KrCl excimer lamp light were irradiated at respective wavelengths for 90 minutes, and the excitation wavelength dependence of the silicone lamp was measured. As shown in FIG. 3, the tensile shear strength (adhesion strength) is low at 10 kg / cm ² even when irradiated with 222 nm light for 60 minutes, but the Xe ₂ excimer lamp light at 172 nm has a high adhesive strength of 180 kg / cm ² . It can be seen that the shorter wavelength has higher adhesive strength.

In a room temperature atmosphere, a silicone oil with a molecular weight of 60,000 (KF96-10000, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied between two pieces of synthetic quartz glass and pressurized at a pressure of 1 to 30 kg / cm ^2. The relationship between the adhesive strength and the pressure when the quartz glass was covered and irradiated with Xe ₂ excimer lamp light for 90 minutes was examined. As a result, it became clear that the pressure became stronger as the adhesive force increased at 2 kg / cm ² or more.

In a room temperature atmosphere, a silicone oil with a molecular weight of 60,000 (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.) is applied between synthetic quartz glass and soda glass, pressurized at a pressure of 10 kg / cm ² , and quartz glass is applied thereon. And the adhesive strength when irradiated with Xe ₂ excimer lamp light for 90 minutes was 50 kg / cm ² .

The surface to be bonded of two synthetic quartz glasses was subjected to ultraviolet transmittance (200 nm) comparison before and after plasma treatment and before and after ultraviolet irradiation treatment in an oxygen atmosphere. The transmittance was 70% without treatment, but 80% with UV treatment and 85% with plasma pretreatment. Furthermore, it was 90% with plasma treatment and infrared lamp combined irradiation.

Two pieces of synthetic quartz glass are separated by about 1 mm, and after applying silicone oil to both surfaces to be bonded, dielectric barrier discharge is performed, and a pressure of 10 kg / cm ² is applied with the silicone oil surface having excessive active oxygen. Then, when quartz glass was put on it and irradiated with Xe ₂ excimer lamp light for 90 minutes and before and after ultraviolet irradiation treatment, ultraviolet transmittance (200 nm) was measured. The transmittance was 85% and the adhesive strength was 160 kg / cm ² .

While heating two synthetic quartz substrates at 110 ° C, apply silicone oil with a molecular weight of 60,000 (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.), pressurize 10 kg / cm ² , and apply quartz on it. The glass was covered and irradiated with Xe ₂ excimer lamp light for 90 minutes. The adhesive strength at this time was 190 kg / cm ² .

Xe ₂ excimer with a molecular weight of 60,000 silicone oil (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.) is vacuum degassed in an oil bath at 180 ° C, and under a pressure of 10 kg / cm ^{2 in} a carbon dioxide atmosphere. The adhesive strength when irradiated with lamp light for 90 minutes was 200 kg / cm ² .

In a state where the flat plate glass plates were adhered to both surfaces of the honeycomb structure having a hollow inside through silicone oil, the inside of the honeycomb structure was evacuated and then carbon dioxide gas at 0.2 atm was sealed inside. In this state, both sides were irradiated with Xe ₂ excimer lamp light for 90 minutes to produce a honeycomb mirror.

The quartz glass plate (10 × 10) with a 6 mm deep 1 mm groove in the center and a flat plate glass plate with a thickness of 5 mm are in close contact with each other through silicone oil. After carbon dioxide gas of 0.2 atm was sealed inside, Xe ₂ excimer lamp light irradiation was performed in the atmosphere for 60 minutes. After bonding, these samples were put in an electric furnace, and the relationship between the hysteresis temperature and the tensile shear strength is shown in FIG. Silicone oil (KF96-10000) had an adhesive strength of 180 kg / cm ² , but the strength decreased with increasing temperature and was 60 kg / cm ² at 500 ° C. Silicone oil (KF96-500) had the same strength.

Silicone oil (KF96-10000) was applied to a synthetic quartz round pipe (outer diameter 25φ, inner diameter 20φ) whose end face was polished, and then a synthetic quartz window plate having an outer diameter of 25φ was brought into close contact therewith. At the same time, after evacuating the inside of the pipe, carbon dioxide gas of 0.2 atm was sealed inside the pipe. Thereafter, Xe ₂ excimer lamp light was irradiated in the atmosphere for 90 minutes to bond the window to the pipe. The adhesive strength was 50 kg / cm ² .

A reaction vessel having a quartz glass window (100φ) was divided into two chambers with a silicone rubber plate, and an apparatus was prepared by separating one synthetic quartz glass window side into a sample chamber and the other into a hydraulic pressurizing chamber. A film heater (100φ × 2 mm) was attached between the silicone rubber plate and the sample, and the sample was heated to 110 ° C. Glass material to be bonded (90φ × 10) coated with silicone oil (KF96-10000 manufactured by Shin-Etsu Chemical Co., Ltd.) is placed on top of each other in the sample chamber, and the sample chamber is evacuated and filled with 0.5 atm carbon dioxide. did. Then, Xe ₂ excimer lamp light was irradiated from the synthetic quartz window side for 90 minutes in a state where hydraulic pressure (30 kg / cm ² ) was applied to the adherend material through a rubber plate. As a result of measuring the bonded sample with an interferometer, there was no change in surface wavefront distortion due to bonding. The transmittance of ultraviolet light (200 nm) was 91%.

Heat bonding at 1800 ° C inside and outside was indispensable for joining quartz glass that is resistant to high temperatures. However, this method is limited to optical applications because thermal strain remains on the workpiece. However, since the present invention can be bonded at room temperature or 200 ° C. or less, transmits ultraviolet light of 250 nm or less, and is resistant at 500 ° C. or higher, of course, as an optical material, crystallized glass other than quartz glass, low It contributes as an adhesive between materials such as expanded glass, ceramic glass, optical glass, soda glass, laser glass and optical fiber.

By joining the mirror and the honeycomb structure to reduce the weight, there is no thermal distortion of the large-diameter astronomical telescope, large-diameter laser mirror or mirror used in space, wavefront distortion after vacuum deposition, or laser wavefront distortion. A mirror can be supplied.

In the ultraviolet transmission measurement cell, the wall surface and the bottom surface of the quadrangular column are heat-sealed. However, since an adhesive is used in the present invention, it is possible not only to generate thermal distortion, but also to join different types of materials, so that the labor of glassworking and the range of material selection are expanded, thereby reducing the price of glassworking products. To contribute.

Couplers were indispensable for joining optical fibers made of quartz glass. However, in the present invention, since an adhesive is used, not only optical loss due to the coupler is extremely reduced, but also long-distance transmission without any coupler becomes possible. This contributes to economical and improved communication efficiency.

Thermal bonding between quartz glasses has been used to join pipe members with window materials such as head-on type vacuum tubes, photomultiplier tubes, deuterium lamps, excimer lamps, and discharge tubes having ultraviolet transmission windows. For this reason, the quartz window was thermally strained, and both members required the same type of quartz glass. However, since an adhesive is used in the present invention, it is possible not only to generate thermal distortion, but also to join different types of materials, so that the labor of glassworking and the range of material selection are expanded, thereby reducing the price of glassworking products. To contribute.

Relationship between molecular weight and tensile shear strength (adhesion strength) at each irradiation time. Example 1 Relationship between irradiation time and tensile shear strength (adhesion strength) at each molecular weight of silicone oil. Example 1 Relationship between irradiation time and tensile shear strength (adhesion strength) for the oscillation wavelength of various lamps. (Example 2) Relationship between heat resistance test (heated temperature of sample and tensile shear strength) of bonded sample. (Example 10)

Claims (15)

At the time of bonding between glass materials, the surfaces of the materials to be bonded are kept as they are or subjected to plasma treatment or ultraviolet treatment in advance, and one or both of the surfaces of the materials to be bonded have a molecular weight of from two hundred. While applying 120,000 silicone oil, and irradiating the applied surface with plasma or ultraviolet light in the same state or in an oxidant gas atmosphere, the surfaces of the materials to be joined are overlapped at room temperature or at a temperature of 200 ° C. or lower. Surface of material to be joined by mechanical pressurization or pressurization in the range of 0 to 30 kg / cm ² under a gas atmosphere, or by sucking the joint to a low pressure and making the joint surface atmospheric pressure or external pressure by inert gas A glass material characterized by pressurizing while controlling the differential pressure between them and irradiating ultraviolet rays in the bonding interface as it is or in an oxidizing gas atmosphere Bonding method of Judges. 2. The glass according to claim 1, wherein the glass material is made of quartz glass, crystallized glass, low expansion glass, ceramic glass , optical glass, soda glass, laser glass, optical fiber, or the like, or a combination of different kinds. Bonding method between materials. Before SL silicone oil oxygen, ozone, adhesion of the glass material together according to claim 1 or claim 2 carbon dioxide, water, and wherein the is obtained by steam containing the oxidizing agent such as hydrogen peroxide Method.   2. The glass materials according to claim 1, wherein the silicone oil is degassed under reduced pressure in a room temperature or a temperature atmosphere of 200 ° C. or less, and contaminants such as oxygen, carbon dioxide, and water are excluded. Bonding method. One shape of the glass material is a flat plate or a curved plate, and the other is a structure processed in the form of a honeycomb or a groove or a depression made of the same or different material, and alternately in a male or female state. 4. The method for adhering glass materials according to claim 1, wherein the glass material is a honeycomb structure mirror or a cavity structure to be joined. The one shape of the glass material is flat plate or curved plate and the other is round or square pipes made of same or different materials, claims, characterized in that bonding with alternating male-female state A method for bonding glass materials according to any one of 1, 2, and 3 .   The method for adhering glass materials according to claim 1, wherein the plasma treatment or ultraviolet treatment is performed in an oxygen gas, an inert gas, or a mixed gas atmosphere of an inert gas and oxygen.   The method of bonding glass materials according to claim 1, wherein the oxidant gas is air, oxygen, ozone, water vapor, or an inert gas such as argon, xenon, or helium mixed with a trace amount of oxygen. The ultraviolet light is Xe ₂ excimer lamp light, ArF excimer laser beam, KrF excimer laser beam, XeCl laser beam, F2 laser beam, harmonic laser beam by nonlinear element, KrCl excimer lamp beam, XeCl excimer lamp beam, Hg lamp beam, Hg-Xe lamp beam, deuterium lamp beam 2. The method for adhering glass materials according to claim 1, wherein the glass material is ultraviolet light having a wavelength of 300 nm to 150 nm obtained by halogen lamp light, gas arc, corona or silent discharge.   In a state where the glass material coated with the silicone oil is in contact with a plastic or rubber bag or envelope having a synthetic quartz glass window, or when plasma irradiation is used together, the surfaces to be joined of both glasses Plasma is generated between the two quartz glasses that are coated with silicone oil with electrodes facing each other, and then air or oxygen inside the envelope or bag while irradiating the bonded interface with ultraviolet rays. The internal pressure in the container is made to be higher than the external pressure by applying a pressure difference between the atmospheric pressure and the internal pressure of the container uniformly to the joint of both glass materials or by mechanical pressurization such as air pressure, hydraulic pressure or water pressure. The method for bonding glass materials according to claim 1, wherein the photochemical bonding is performed while increasing the pressure and applying a uniform load with the differential pressure. The synthetic quartz containers such as plastic or rubber bag or envelope having a glass window, the glass material with each other to that claimed in claim 10, characterized in that a vacuum vessel equipped with telescopic free structures such as bellows or O-ring Bonding method. The vacuum container is covered with an outer box having a synthetic quartz glass window, and the outer box is pressurized with an inert gas such as nitrogen gas, argon gas, xenon, or helium gas, and a vacuum container is connected to the joint of the glass material. bonding method of the glass material between the claim 11, wherein you characterized by applying a uniform load by controlling the pressure difference between the external pressure due to internal pressure and the outer box. In manufacturing the honeycomb structure mirror or the cavity structure, the honeycomb structure mirror or the cavity structure itself constitutes a vacuum container by providing an exhaust mechanism inside the structure processed into a honeycomb shape or a groove or a depression shape, The internal pressure is lowered, or a small amount of the oxidant gas is sealed, and the joint portion of both glass materials is made to have a uniform load due to atmospheric pressure . The adhesion method of the glass materials as described in 2. In producing a head-on type tube having an ultraviolet transmission window, the head or pipe forms a vacuum vessel by providing a vacuum exhaust mechanism in the round or square pipe inner tube, and a large joint is formed at the joint between both glass materials. The method for adhering glass materials according to claim 1, wherein a uniform load due to atmospheric pressure is applied. The glass material coated with the silicone oil is brought into contact with the synthetic quartz glass window side in a container having the synthetic quartz glass window in the oxidant gas atmosphere, and the lower surface is heated or left as it is, through a rubber plate. The method for bonding glass materials according to any one of claims 1, 2, 3, 8, and 13, wherein photochemical bonding is performed while mechanical pressure is applied by water pressure.

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