JPH02118077A - Manufacture of oxide molded body and oxide pattern formation - Google Patents

Abstract

PURPOSE:To easily manufacture an oxide molded body and an oxide pattern molding by irradiating a molded body of a composition composed principally of fine oxide grains and specific photosensitive resin or the above composition on which a mask of the prescribed pattern is placed with ultraviolet rays, removing an unexposed part and then carrying out solidification by heating. CONSTITUTION:A composition 3 prepared by adding photosensitive resin 2, such as polyester acrylate or methacrylate, to fine grains 1 of oxide, such as SiO2, ZrO2, TiO2, BaTiO3, LiNbO3, and SeO2, is put into a vessel 4 and irradiated with ultraviolet rays from a mercury lamp to undergo solidification and the resulting solid matter 5 is sintered so as to be formed into an oxide molded body 6, or, the above composition 3 is applied to a substrate 7, such as glass plate, to form a film 8 and a photomask 9 is allowed to adhere to the above film 8, and these are irradiated with ultraviolet rays, and then, an unexposed part is removed by means of organic solvent, etc., and an exposed part is solidified by heating and subjected to sintering, by which a pattern consisting of oxide can be easily formed.

Description

[Detailed description of the invention] Ru.

Example 1 A mixed solution of tetraethoxysilane, hydrochloric acid and ethanol was refluxed for 4 hours. Next, water and ethanol were added to this solution, and the mixture was further refluxed for 8 hours. After cooling to room temperature, an azide-based photoinitiator and ethylene glycol dimethacrylate (average molecular weight: 330) were added to the solution at predetermined ratios to form a composition.

Next, this composition was applied onto a glass substrate to a thickness of about 0.5 μm, and after removing the solvent, the applied composition was irradiated with ultraviolet rays using a high-pressure mercury lamp. Furthermore, an oxide molded body was obtained by gradually heating from room temperature to 800°C and vitrifying at 800°C. To form a pattern made of oxide, when irradiating ultraviolet rays, a mask with a predetermined pattern is placed on top of the applied composition, the unexposed areas are removed, and then heated to vitrify.

FIG. 3 shows the relationship between the heating temperature and the residual rate of the film in the composition comprising glass fine particles and polyethylene glycol diacrylate in this example. Here, the residual ratio of 1 thickness is the ratio between the thickness of the composition applied onto the substrate and the thickness after vitrification by heating. Curve A shows the case where the mixing ratio (weight ratio) of crow fine particles and polyethylene glycol dimethacrylate = +/+, and curve B shows the case where the mixing ratio (weight ratio) = +/+.
Weight ratio)=1/2. The remaining film thickness is at a mixing ratio of 1/1.
400℃-
At a heating temperature of 800° C., the remaining film thickness remains almost constant.

After mixing the tetraethoxysilane, ethanol, and dilute ammonia water, the mixture was reacted at 70° C. for one week. The obtained reaction solution was concentrated and the concentration of silica glass was adjusted to 70 zero (count value). Add silica glass to this solution.
0% by weight of polyethylene glycol diacrylate (average molecular weight: 536) and 3% of the acetophenone photoinitiator of polyethylene glycol diacrylate were added and thoroughly mixed.

This mixture was placed in a glass tube with a diameter of 70 m+ with one end closed, degassed, and then irradiated with ultraviolet rays using a high-pressure mercury lamp. After drying the obtained molded product at 11 high and 105°C, it was gradually heated from room temperature to 1350°C in a helium-oxygen mixed atmosphere.
and vitrified at 1350°C to obtain a transparent glass loft with a diameter of 400 m.

1 wide ± 1 silica glass fine particles (specific surface area approximately 200 m'/g, trade name: Orozil 10), 3% 2.2-dimethoxy-2
- 150 x 15 compositions of polypropylene glycol diacrylate containing phenylacetophenone
The mixture was placed in a 0 mm quartz glass container, dried, and then irradiated with ultraviolet rays to obtain a sheet of the composition. Next, this sheet was gradually heated from room temperature to 1350°C in a helium-oxygen mixed atmosphere, and vitrified at 1350°C to obtain a quartz glass plate.

Fire 5 ■4 200 g of polypropylene glycol diacrylate containing 6 g of 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator, 200 g of silica glass fine particles obtained by hydrolysis/polycondensation of tetraethoxysilane, and 50 g of polyethylene glycol. - minutes and spread the mixture onto a quartz glass substrate to a thickness of I mm1. After coating, this pattern was transferred to the composition using a mold in which a pattern with a groove width of 2 μm, a depth of approximately 500 mm, and a hitch of 5 μm was drawn, and then ultraviolet rays were irradiated to solidify the composition. Next, the solidified product was vitrified at 1200°C by gradually heating from room temperature to 1200°C in a helium-oxygen mixed atmosphere. A glass molded body with a pattern almost the same as that of the mold was obtained.

Further, after the mixture was applied to a thickness of 200 μm on a quartz glass substrate, ultraviolet rays were irradiated with a high-pressure mercury lamp using a photomask on which a pattern with a groove width of 2 μm and a pitch of 5 μm was drawn. After removing the unexposed area with methyl ethyl and ketone, it was heated gradually from room temperature to 1200°C in a helium-oxygen mixed atmosphere and vitrified at 1200°C. The pattern obtained was almost equivalent to the pattern of the photomask.

Example 5 Tetraethoxysilane, tributoxyboron.

Ethanol and an aqueous hydrochloric acid solution were mixed (molar ratio of tetraethoxysilane to tributoxyboron=872). After reacting for a predetermined period of time, the same method as in Example 4 was used to obtain a glass molded body and an oxide pattern onto which the pattern was transferred. Note that on the nut layer side, the maximum heating temperature, that is, the temperature reached when the temperature was gradually raised from room temperature was 600°C.

After mixing tetraethoxysilane, ethanol and dilute ammonia water, the mixture was reacted at 70°C for two weeks. The obtained reaction mixture was concentrated and adjusted to have a perilla concentration of 70 to (count value). Add 50% by weight of silica to this solution of polyethylene glycol diacrylate (average molecular weight: 53).
B) An acetophenone photoinitiator containing 3% by weight of polyethylene glycoldiacrylate was added and thoroughly mixed.

This mixture was placed in a glass tube with a diameter of 70 mm with one end closed, degassed, and then irradiated with ultraviolet rays using a high-pressure mercury lamp. The temperature of the obtained molded product was gradually raised from room temperature to 105°C, dried at 105°C, and then heated gradually from room temperature to 1350°C in a mixed atmosphere of helium, oxygen, chlorine, and silicon tetrafluoride. A 40m+n fluorine-doped quartz glass hollow lot was obtained.

Next, this hollow glass rod was heated from the outside with an oxyhydrogen burner to make it solid, thereby obtaining a single mode optical fiber preform. This base material was drawn using a wire drawing machine using a carbon resistance heating element as a heat source. The transmission loss at a wavelength of 1.3 μm was 0.4 dB/ka+.

Example 7 Equimolar L! 0C2Hs and Nb (OC2H51) were added to ethanol and refluxed for 24 hours to prepare a double alkoxide solution. To this double alkoxide was added an ethanol solution containing water in an equimolar amount to the double alkoxide.
After reacting at room temperature for 12 hours, the reactor was turned on at 24 hours.

After concentrating the solution, an azide photoinitiator containing 30% by weight of LiNbO3 polyethylene glycol dimethacrylate (average molecular fi: 560) and 3% polyethylene glycol dimethacrylate was added and thoroughly mixed.

Next, after immersing the sapphire substrate in the mixed solution and drying it,
The pattern was transferred to the composition using a mold in which a pattern with a groove width of 2 μm, a depth of approximately 500 mm, and a pitch of 5 μm was drawn, and then solidified by ultraviolet irradiation. Next, it was heated at 400°C in a mixed atmosphere of oxygen-helium-steam. A ceramic molded body with a pattern almost the same as that of the mold was obtained.

Further, a sapphire substrate was immersed in the mixed solution, dried, and then irradiated with ultraviolet rays using a photomask on which a pattern with a groove width of 2 μm and a pitch of 5 μm was drawn. N the unexposed area
, N-dimethylformamide, and then heated at 400°C in a mixed atmosphere of oxygen, helium, and water vapor to form a LiNb0. I got the pattern.

Friend A ■ Barium isopropoxide isopropanol (FG liquid and titanium isopropoxide isopropanol i8
Fj, the molar ratio of these two types of alkoxides is 1:!
mixed so that

Next, this mixed solution was passed through a nitrogen stream for 6 hours, and then water was added and reflux was continued for 3 hours. Cool to room temperature and leave for 24 hours.
After 11 hours, the solution was concentrated, and 20% by weight of BaTiO3 polyethylene glycol dimethacrylate (average molecular plate approximately 560) and an azide-based photoinitiator of 3% by weight of polyethylene glycol dimethacrylate were added and mixed thoroughly. .

Mixed next? 8? After immersing the quartz substrate in rIi and drying it, the pattern was transferred to the composition using a mold in which a pattern with a groove width of 2 μm, a depth of approximately 500 mm, and a pitch of 5 μm was drawn, and then ultraviolet rays were irradiated with a high-pressure mercury lamp. and solidified. Then, in a mixed atmosphere of oxygen-helium-water vapor, 800
Heated at ℃. In this way, a ceramic molded body having a pattern almost identical to that of the mold was obtained.

Also, after immersing a quartz substrate in the mixed solution to form a layer on the quartz substrate and drying it, a photomask on which a pattern with a groove width of 2 μm and a pitch of 5 μm is formed is placed on the above layer. , ultraviolet rays were irradiated with a high-pressure mercury lamp. After removing the unexposed area, it is heated at 800°C in a mixed atmosphere of oxygen, helium, and water vapor to make Ba almost equivalent to the photomask.
A pattern of Ti0* was obtained.

Although this example mainly deals with the SiO□ glass film, in order to form a leading wave circuit, a SiO□ glass film doped with F (fluorine) was used on the substrate using the method described in Example 1.
Then, by the method of Example 4, for example, a Y-branch circuit pattern of a Sin layer is formed, and an F-Sin2 glass layer as a crat is formed on top of the Sin layer, for example, a Y-branch leading wave. Methods of combining such embodiments to form circuits are also contemplated by the present invention.

[Effects of the Invention] As explained above, the present invention uses a composition consisting of oxide fine particles and a photosensitive resin to form a pattern by light irradiation, so it is possible to form a pattern on large glass or precision glass bodies or ceramics. The body can be molded, the manufacturing process is extremely simple, and... 311 has the advantage that a rough pattern can be easily formed.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram showing the manufacturing process of the oxide molded body of the present invention, Fig. 2 is a schematic diagram showing the pattern forming process according to the present invention, and Fig. 3 is the glass powder and polyethylene glycol diacrylate in Example 1. It is a figure showing the relationship between the mixing ratio (weight ratio) and film thickness. DESCRIPTION OF SYMBOLS 1... Oxide fine particles, 2... Photosensitive resin, 3... Composition, 4...-Container, 5... Solidified product, 6... Oxide molded body, 7... Substrate , 8...Monday Mo, 9...Photomask. lO: Oxide fine particle film.

Claims (1)

[Claims] 1) An oxide characterized by comprising the steps of: irradiating a composition containing oxide fine particles and a photosensitive resin with light to produce a solidified body; and heating the solidified body. Method for manufacturing a molded object. 2) A step of placing a mask with a predetermined pattern on a composition containing oxide fine particles and a photosensitive resin and irradiating it with light; A method for forming an oxide pattern, comprising the steps of: removing the exposed portion; and heating the exposed portion.