JPH1036511A - Optical material of polymer and beam guiding path using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polysilsesquioxane low in loss, high in heat resistance and moisture resistance and excellent in cracking resistance by using a copolymer comprising specific four kinds of repeating units. SOLUTION: This beam guiding path suitable as various optical parts, optical integrated circuits, optical circuit boards or cores and clads useful in fields such as general optics, fine optics fields, optical communication and optical information treatment is obtained by using a copolymer comprising a repeating unit of formula I and formula II (R1 is cyclohexyl or cyclopentyl) and a repeating unit of formula III and formula TV [R2 is a phenyl of the formula C6 Y5 (Y is H or deuterium) or a deuterated phenyl], preferably a mixture of the copolymer and a polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material and an optical waveguide using the same, which are used in the fields of general optics and micro-optics, and in the fields of optical communication and optical information processing. For optical components, optical integrated circuits or optical wiring boards.

[0002]

2. Description of the Related Art A polymer material is easy to form a thin film by a spin coating method or a dipping method, and is suitable for producing a large-area optical component. In addition, since a heat treatment step at a high temperature is not included during film formation, an optical waveguide is manufactured on a substrate that is difficult to heat at a high temperature, such as a semiconductor substrate or a plastic substrate, as compared with a case where an inorganic glass material such as quartz is used. There is an advantage that you can. Further, a flexible optical waveguide utilizing the flexibility and toughness of a polymer can be produced. Therefore, it is expected that optical waveguide components such as an optical integrated circuit used in the field of optical communication and an optical wiring board used in the field of optical information processing can be manufactured in large quantities and at low cost using polymer optical materials. ing. Conventionally, polymer optical materials have been considered to have problems in terms of environmental resistance such as heat resistance or moisture resistance, or transparency in the optical communication wavelength band (from the visible region to the near infrared region). Significantly improved materials have been invented and reported (e.g.,
JP-A-3-43423]. Since the material is a polymer material having a silsesquioxane structure as a molecular skeleton, the material has excellent heat resistance. Further, since the phenyl group and the alkyl group in the side chain are hydrophobic, the moisture resistance is high. Furthermore, since the hydrogen of the C—H bond contained in the side chain is replaced by halogen or deuterium, absorption in the near-infrared region caused by the overtone or the combined sound of the stretching or bending vibration of the C—H bond or the bending vibration. , Has been greatly reduced. When an optical waveguide having a core / clad structure is manufactured using such a polymer optical material, at least two types of materials having a precisely controlled refractive index difference are required as the core / clad material. This is because the guided light is confined and propagated in the core part having a higher refractive index than the surrounding clad part. The magnitude of the refractive index difference is determined according to the mode of light to be guided and the size of the core, but is generally in the range of 0.1% to 5%. For example, when matching the mode diameter of the single mode optical fiber with that of the guided light, it is desirable that the shape of the core portion be a square of 8 μm square and the refractive index difference be 0.3%. In the polymer optical material according to the invention, the refractive index is controlled by copolymerizing repeating units having different side chains. For example, a phenyl group is known as a side chain having a high refractive index, and a linear alkyl group such as a methyl group is known as a side chain having a low refractive index. That is, when polyphenylsilsesquioxane having a phenyl group side chain is used as the core material, a copolymer of phenylsilsesquioxane and methylsilsesquioxane can be used as the cladding material. An optical waveguide is manufactured by laminating the core / cladding materials obtained in this way, and at this time, it is necessary to prevent intermixing. Here, intermixing means that when another polymer solution is applied on a polymer thin film to form a film, the surface of the lower layer is dissolved in the coating solution for forming the upper layer and the interface becomes non-uniform. Say. In order to avoid such intermixing, a high molecular weight optical material in which a low molecular weight oligomer or prepolymer is cured by thermal crosslinking or photocrosslinking can be used. After being cured by crosslinking, such a thermally crosslinkable material has excellent solvent resistance and is generally insoluble in organic solvents. A problem in producing an optical waveguide using such a crosslinked material is the occurrence of cracks. Since the cross-linkable material involves a volume change during cross-linking, internal stress may be generated to cause cracks. Although the cracking probability increases as the film thickness increases, it is essential to form a thin film having a certain thickness or more when manufacturing an optical waveguide.
For example, when a single-mode optical waveguide having a square 8 μm square core portion is formed on a silicon substrate, a film thickness of about 15 μm or more is required as a lower clad to avoid the influence of metal cladding. here,
Metal cladding means that when the thickness of the lower cladding is small, light guided through the core is drawn into the silicon substrate, and the waveguide loss is significantly increased. Also, in order to prevent the influence of dust or dirt on the surface, stress from the outside, etc. from affecting the light guided through the core, the upper clad should have a thickness of about 8 μm or more from the upper surface of the core. Required. In fact, when polyphenylsilsesquioxane whose side chains are all phenyl groups is used, the cured thin film is hard and easily cracks.
It was difficult to reliably obtain a film thickness of about 15 μm or more. However, by introducing a side chain other than a phenyl group, the flexibility of the cured thin film can be improved, and the incidence of cracks can be significantly reduced. Conventionally, a linear alkyl group such as a methyl group has been known as a side chain. That is, when a linear alkyl group such as a methyl group is introduced into a part of the side chain instead of the phenyl group, as the content of the alkyl group in the side chain increases, the cured thin film becomes more flexible and cracks are generated. The rate is greatly reduced. That is, introducing a linear alkyl group such as a methyl group into the side chain gives the above-mentioned refractive index controllability to the polysilsesquioxane-based crosslinked polymer optical material, and at the same time, provides crack resistance. Is to give.

[0003]

However, in the above-mentioned crosslinked polymer optical material containing a linear alkyl group side chain, the 1.3 μm wavelength band of the wavelength band used for optical communication is guided. Although the loss is low, there is a problem that the waveguide loss is large in the 1.55 μm wavelength band. This is because the combined sound of the second harmonic of the stretching vibration of the C—H bond contained in the linear alkyl group and the bending vibration appears in the 1.55 μm wavelength band. The wavelength at which the stretching vibration or the bending vibration of the C—H bond appears differs depending on the molecular structure. Fortunately, with respect to the 1.3 μm wavelength band, almost no organic polymer material exhibits light absorption due to the overtones or combined sounds of the C—H bond stretching or bending vibration. However, for the 1.55 μm wavelength band, C
In some cases, light absorption due to an overtone or a combined sound of the expansion and contraction of the -H bond or the bending vibration may appear, which has a great influence on the waveguide loss. For example, in the case of a methyl group, the combined sound of the second harmonic of the stretching vibration of the C—H bond and the transverse bending vibration has a wavelength of 1.
It appears at 52 μm and has a significant effect on the waveguide loss in the 1.55 μm wavelength band. In fact, a copolymer of deuterated phenylsilsesquioxane and methylsilsesquioxane (molar ratio 1: 1) has a waveguide loss as low as about 0.2 dB / cm at a wavelength of 1.3 μm. 1.55μm wavelength
, The waveguide loss is as large as about 0.6 dB / cm.
Even when an ethyl group is used in place of a methyl group, a combined sound of the second harmonic of the stretching vibration of the C—H bond and the bending deformation vibration appears at a wavelength of 1.57 μm, and the wavelength of 1.55 μm in the 1.55 μm wavelength band. The waveguide loss is about the same as that of the methyl group. Also,
Even when hydrogen of the methyl group is replaced with deuterium, 1.55
Also in the μm wavelength band, the third harmonic of the stretching vibration of the CD bond appears, and the disadvantage that the waveguide loss is large in the 1.55 μm wavelength band could not be solved. Further, there is a method of fluorinating a part of the hydrogen of the alkyl group. However, since the surface energy is reduced by the fluorination of the side chain, there is a problem that the adhesion between the core and the clad is reduced. Replacing all the hydrogens of the alkyl group with fluorine causes a decrease in the thermal stability of the molecule due to the high electronegativity of the fluorine atom. Therefore, hydrogen of at least two methylene groups adjacent to silicon in the skeleton is Difficult to fluorinate. The present invention has been made in view of such circumstances, and its object is to provide not only a 1.3 μm wavelength band,
An object of the present invention is to provide a polymer optical material which has low loss even in a wavelength band of 1.55 μm and is excellent in heat resistance, moisture resistance, solvent resistance and crack resistance, and an optical waveguide using the same.

[0004]

SUMMARY OF THE INVENTION In summary, the first invention of the present invention relates to a polymer optical material, wherein each unit of the formulas (I) and (II) is a component. The following general formula (Formula 1):

[0005]

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(Wherein R ₁ is a cyclohexyl group or a cyclopentyl group), and each of the units of the formulas (III) and (IV) is represented by the following general formula (2) :

[0007]

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Wherein R ₂ is a phenyl group or a deuterated phenyl group represented by C ₆ Y ₅ (Y represents hydrogen or deuterium). It is characterized by being. A second invention of the present invention relates to another polymer optical material, and is characterized in that it is a mixture containing the copolymer of the first invention and a polyisocyanate. A third invention of the present invention relates to a polymer optical waveguide, wherein the polymer optical material according to the first or second invention is used as a core or a clad.

The present inventors have proposed that the side chain introduced for controlling the refractive index and suppressing the occurrence of cracks is not a straight-chain alkyl group as in the prior art, but a cyclic cyclohexyl group as described later. Or by improving the cyclopentyl group without impairing the transparency in the 1.55 μm wavelength band,
It has been found that controllability of the refractive index can be given and crack resistance can be improved. Further, the optical waveguide manufactured using the material has a wavelength of 1.55 μm as well as a wavelength of 1.3 μm.
The present inventors have found that the waveguide has a low waveguide loss even in the μm wavelength band, and has high heat resistance and moisture resistance, and has completed the present invention. In other words, the present invention relates to a conventional crosslinked polysilsesquioxane-based polymer optical material, which controls the refractive index and suppresses the occurrence of cracks by using a linear polymer that causes a loss of transparency in a 1.55 μm wavelength band. By introducing a cyclic alkyl group into the side chain while introducing a cyclic cyclohexyl group or cyclopentyl group without impairing the transparency in the 1.55 μm wavelength band,
The purpose is to provide controllability of the refractive index and improve crack resistance. Here, the reason why the cyclic cyclohexyl group or cyclopentyl group does not impair the transparency in the 1.55 μm wavelength band is as follows. The cyclohexyl group or the cyclopentyl group has a different spatial symmetry from the methylene group contained in the linear alkyl group. Therefore, roll bending vibration of C-H bond contained in the methylene group, whereas appear in a wave number region of 600cm ^-1 ~800cm ^-1, next to the C-H bond contained in the cyclohexyl or cyclopentyl group Shaking bending vibration is 850cm
^Appears on the higher wavenumber side than ^-1 . Therefore, the combined sound of the transverse bending vibration and the second harmonic of the C—H bond stretching vibration is
It appears on the shorter wavelength side than the 1.55 μm wavelength band. For this reason, the cyclic cyclohexyl group or cyclopentyl group does not impair the transparency in the 1.55 μm wavelength band. Also, in order to improve the transparency in the near infrared region,
There is also a method of replacing hydrogen of a straight-chain alkyl group with deuterium or a halogen, whereas the method of the present invention using a cyclohexyl group or a cyclopentyl group does not require a substitution reaction, so that a material is easily obtained, An optical material can be supplied at low cost.

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be specifically described below. When the optical material according to the first aspect of the present invention is used, a solvent or a catalyst can be contained as a component other than the copolymers represented by the general formulas (1) and (2). By containing a solvent, the optical material becomes a fluid having an appropriate viscosity corresponding to the process of forming a thin film.
Solvents used at this time include aromatics such as toluene, xylene, mesitylene and chlorobenzene, alcohols such as ethanol, n-propyl alcohol, i-propyl alcohol and butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl isoamyl. Ketones such as ketones, esters such as ethyl acetate, butyl acetate and ethyl lactate, 2-ethoxyethanol,
Cellosolves such as butoxyethanol, 2-ethoxyethyl acetate, cellosolve acetates such as 2-butoxyethyl acetate, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; and heterocycles such as tetrahydrofuran, N-methylpyrrolidone, and γ-butyrolactone. The optical material can obtain an appropriate viscosity corresponding to the thin film forming step by selecting the type of the solvent and adjusting the solution concentration. Furthermore, in order to produce a thin film having high uniformity and flatness, it is desirable to use a solvent having good compatibility with the copolymers represented by the general formulas (1) and (2) and having a high boiling point. .

The curing of the optical material is carried out three-dimensionally by a condensation reaction of hydroxyl terminals contained in the components represented by the formulas (II) and (IV) in the general formulas (1) and (2). This is performed by forming a crosslinked structure. The curing temperature and curing time depend on the type of the side chain or terminal, but are generally 150 ° C.
The heating is performed in an electric furnace at a temperature of about 300 ° C. for about 1 hour to several hours. When the optical material contains a solvent, a temperature lower than the curing temperature, for example, 60
It is desirable to remove the solvent in advance at a temperature of from 100C to 100C. Furthermore, when using the optical material, a catalyst for accelerating the curing reaction can be added. For example, the addition of tetramethylammonium hydroxide or the like can lower the curing temperature or shorten the curing time. The optical material thus obtained contains not only a side chain of a linear alkyl group but also a side chain of a cyclohexyl group or a cyclopentyl group.
It has low waveguide loss even in the wavelength band, and is excellent in heat resistance, moisture resistance, solvent resistance, and crack resistance.

The mixture constituting the optical material according to the second aspect of the present invention may contain a solvent or a catalyst as other components. In this case, the solvent described in the description of the first invention can be used. However, in order to produce a uniform and highly flat thin film, a solvent having good compatibility with the copolymers represented by the general formulas (1) and (2) and a polyisocyanate and having a high boiling point is used. It is desirable. Curing of the optical material,
Formula (II) in the general formula (Chemical Formula 1) and Formula (IV) in the (Chemical Formula 2)
This is carried out by forming a three-dimensional crosslinked structure via a urethane bond by an addition reaction between a hydroxyl group contained in the component represented by the formula (1) and an isocyanate group of the polyisocyanate. As the polyisocyanate, an aromatic polyisocyanate or an aliphatic polyisocyanate can be used. However, since aromatic polyisocyanates are relatively easily yellowed, it is more desirable to use aliphatic polyisocyanates. In addition, since the aliphatic polyisocyanate has a flexible molecular chain as compared with the aromatic polyisocyanate, it has an effect of suppressing generation of cracks when used as a crosslinking agent for polysilsesquioxane. Further, among the aliphatic polyisocyanates, isophorone diisocyanate, a polyisocyanate containing a large number of alkyl groups such as hexamethylene diisocyanate,
1,3-bis (isocyanatomethyl) cyclohexane,
It is more preferable to use a polyisocyanate containing a cyclohexyl group such as dicyclohexylmethane-4,4'-diisocyanate. This is because, as described above, the C—H bond contained in the alkyl group affects the transparency in the 1.55 μm wavelength band. Although the curing temperature and curing time of the optical material also depend on the type of polyisocyanate, the curing is generally performed by heating in an electric furnace at a temperature of 100 ° C. to 200 ° C. for about 1 hour to several hours. When the optical material contains a solvent, it is desirable to remove the solvent at a temperature lower than the curing temperature, for example, at a temperature of 60C to 100C before the curing reaction. It is also possible to cure by leaving it at room temperature for several days, but it is desirable to further heat and dry to completely remove the solvent and unreacted components. Further, the optical material can include a catalyst for promoting a curing reaction. For example, the addition of dibutyltin dilaurate or the like can lower the curing temperature or shorten the curing time. The optical material thus obtained has a content of linear alkyl groups smaller than that of the conventional material, so that not only the 1.3 μm wavelength band but also the 1.55 μm
It has low waveguide loss even in the wavelength band, and is excellent in heat resistance, moisture resistance, solvent resistance, and crack resistance.

According to a third aspect of the present invention, when an optical waveguide is manufactured using the polymer optical material according to the first or second aspect, the steps can be performed as follows. First, the refractive index of the material is adjusted according to the waveguide mode condition required for the optical waveguide, and at least two materials having a precisely controlled refractive index difference are prepared as the core / cladding material. The magnitude of the refractive index difference is determined according to the mode of light to be guided and the size of the core, but is generally in the range of 0.1% to 5%. For example, when matching the mode diameter of the single mode optical fiber with that of the guided light, it is desirable that the shape of the core portion be a square of 8 μm square and the refractive index difference be 0.3%. In the optical material, since the component represented by the general formula (Chemical Formula 1) has a lower refractive index than the component represented by the general formula (Chemical Formula 2), the refractive index is changed by changing the copolymerization ratio. Adjustment of the rate is possible. Next, a clad material whose refractive index has been adjusted is applied as a lower clad on the substrate by a spin coating method or the like, and is cured by the above method. Next, a core material whose refractive index has been adjusted is applied thereon by spin coating or the like, and cured by the above method. Here, since the lower cladding layer is cured, no intermixing occurs when the core material is applied. Subsequently, a layer serving as an etching mask is formed on the core layer, and processed into a waveguide pattern by photolithography or the like. As a material for the etching mask, an organic photoresist or a metal is used. Further, the core layer is processed into a desired waveguide pattern by reactive ion etching, and finally, an upper clad layer is applied and cured. Here, since the lower clad layer and the core layer are hardened, no intermixing occurs when the upper clad material is applied. The optical waveguide thus manufactured has a wavelength of 1.55 μm as well as a wavelength of 1.3 μm because the material used includes a cyclohexyl group or a cyclopentyl group instead of an alkyl group.
It has low waveguide loss even in the wavelength band, and is excellent in heat resistance and moisture resistance.

[0014]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Phenyltrichlorosilane (236.9 g) and cyclohexyltrichlorosilane (191.4 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) were added thereto so that the liquid temperature did not rise. Was slowly dropped. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto.
After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Furthermore, the polymer A was obtained by vacuum-drying this liquid. GPC of the molecular weight of this material
Was Mw = 3300 and Mn = 1500. Composition B consisting of 50 g of the above polymer A and 50 g of solvent methyl isobutyl ketone (MIBK) was prepared. This composition was cured by heating at 200 ° C. for 1 hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5100 at a wavelength of 1.3 μm. Also, phenyltrichlorosilane (211.5 g)
And cyclohexyltrichlorosilane (217.5 g) were dissolved in 1 liter of dehydrated tetrahydrofuran,
Here, 3 equivalents of water (108 g) were slowly added dropwise so that the liquid temperature did not rise. Subsequently, while stirring the reaction solution, 3 equivalents of sodium hydrogen carbonate (504 g) were added thereto.
Was added. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Further, this liquid was vacuum-dried to obtain a polymer C. When the molecular weight of this material was measured by GPC, Mw = 3300, Mn =
1500. 50 g of the above polymer C and solvent MI
Composition D consisting of 50 g of BK was prepared. The composition is 2
The resin was cured by heat treatment at 00 ° C. for 1 hour and became insoluble in the solvent. The refractive index of the cured composition was 1.5055 at a wavelength of 1.3 μm.

An optical waveguide using the polymer A as a core and the polymer C as a clad was prepared as follows. First, the composition D was applied on a silicon substrate by spin coating to form a film. At this time, the rotation speed of the spin coater was adjusted so that the film thickness became 15 μm. After the formed thin film was heated at 60 ° C. for 2 hours to remove the solvent,
It was cured by heating at 0 ° C. for 1 hour to form a lower clad layer. Next, a core layer was formed thereon by spin coating using the composition B. The rotation speed of the spin coater was adjusted so that the thickness of the core layer was 8 μm. At this time, no intermixing was observed between the lower cladding layer and the core layer. The formed core layer is at 60 ° C.
After heating for 2 hours to remove the solvent, the composition was cured by heating at 200 ° C. for 1 hour. Subsequently, a photoresist was applied thereon, and a linear waveguide mask pattern was formed by photolithography. Further, the core layer other than the mask pattern was removed by reactive ion etching to form a rectangular core ridge having a width of 8 μm and a height of 8 μm. The composition D was applied thereon and cured as in the case of forming the lower clad to produce a buried channel optical waveguide having a core / clad structure. The thickness of the upper clad was 8 μm from the upper surface of the core.
No crack was observed in the above optical waveguide manufacturing process. This optical waveguide was cut into a length of 5 cm with a dicing saw, and the waveguide loss was measured.
0.3 not only at 1.3 μm wavelength but also at 1.55 μm wavelength
It was less than dB / cm. The loss of the optical waveguide did not fluctuate for more than one month even under the condition of 75 ° C./90% RH.

Example 2 Deuterated phenyltrichlorosilane (346.4 g) and cyclohexyltrichlorosilane (87.0 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) was added thereto. It was dropped slowly so as not to rise. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator.
A clear, colorless, viscous liquid was obtained. Further, this liquid was vacuum-dried to obtain a polymer E. When the molecular weight of this material was measured by GPC, Mw = 2400, Mn = 12
00. 50 g of the above polymer E and solvent MIBK
Composition F consisting of 50 g was prepared. The composition comprises 200
The composition was cured by heat treatment at 1 ° C. for 1 hour and became insoluble in the solvent. The cured composition has a refractive index of 1.3 wavelength.
It was 1.5282 in μm. Also, deuterated phenyltrichlorosilane (320.4 g) and cyclohexyltrichlorosilane (113.1 g) are dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) are added thereto so that the liquid temperature does not rise. It was dripped slowly. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Further, this liquid was vacuum-dried to obtain a polymer G. GPC of the molecular weight of this material
As a result, Mw = 2400 and Mn = 1200. 50 g of the above polymer G and 50 g of solvent MIBK
A composition H was prepared. The composition is 1 at 200 ° C.
The resin was cured by heat treatment for an hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5236 at a wavelength of 1.3 μm. A core comprising the above polymer E;
An optical waveguide using the polymer G as a clad was manufactured according to Example 1. This optical waveguide was cut into a length of 5 cm by a dicing saw, and the waveguide loss was measured. As a result, it was 0.2 dB / cm or less not only at the wavelength of 1.3 μm but also at the wavelength of 1.55 μm. The loss of the optical waveguide did not fluctuate for more than one month even at 120 ° C.

Example 3 Deuterated phenyltrichlorosilane (277.1 g) and cyclohexyltrichlorosilane (156.6 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) was added thereto. It was dropped slowly so as not to rise. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator.
A clear, colorless, viscous liquid was obtained. Further, this liquid was vacuum-dried to obtain a polymer I. When the molecular weight of this material was measured by GPC, Mw = 2400, Mn = 12
00. Composition J consisting of 35 g of the above polymer I, 15 g of 1,3-bis (isocyanatomethyl) cyclohexane, and 50 g of solvent MIBK was prepared. The composition is cured by heating at 150 ° C. for 1 hour,
It became insoluble in the solvent. The refractive index of the cured composition was 1.5240 at a wavelength of 1.3 μm. An optical waveguide using the polymer E described in Example 2 as a core and the composition J as a clad was manufactured according to Example 1. No crack was found in the process of manufacturing the optical waveguide. The fabricated optical waveguide is cut with a dicing saw to 5c.
When the waveguide loss was measured at a wavelength of 1.3 μm and a wavelength of 1.55 μm, it was 0.2 dB.
/ Cm or less. The loss of this optical waveguide is 75
It did not fluctuate for more than one month under the conditions of ° C / 90% RH.

Example 4 A composition K was prepared consisting of 35 g of the polymer I described in Example 3, 15 g of isophorone diisocyanate and 50 g of solvent MIBK. The composition was cured by heating at 150 ° C. for 1 hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5225 at a wavelength of 1.3 μm. An optical waveguide using the polymer E described in Example 2 as a core and the composition K as a clad was manufactured according to Example 1. No crack was found in the process of manufacturing the optical waveguide. The produced optical waveguide is cut out to a length of 5 cm with a dicing saw,
When the waveguide loss was measured, it was 0.2 dB / cm or less not only at the wavelength of 1.3 μm but also at the wavelength of 1.55 μm.
The loss of the optical waveguide did not fluctuate for more than one month even under the condition of 120 ° C.

Example 5 A composition L was prepared consisting of 35 g of the polymer I described in Example 3, 15 g of dicyclohexylmethane-4,4'-diisocyanate and 50 g of MIBK solvent. The composition is cured by heating at 150 ° C. for 1 hour,
It became insoluble in the solvent. The refractive index of the cured composition was 1.5226 at a wavelength of 1.3 μm. An optical waveguide using the polymer E described in Example 2 as a core and the composition L as a clad was manufactured according to Example 1. No crack was found in the process of manufacturing the optical waveguide. The fabricated optical waveguide is cut with a dicing saw to 5c.
When the waveguide loss was measured at a wavelength of 1.3 μm and a wavelength of 1.55 μm, it was 0.2 dB.
/ Cm or less. In addition, this optical waveguide showed no change in loss even after the heat treatment at 200 ° C. for 30 minutes.

Example 6 Phenyltrichlorosilane (236.9 g) and cyclohexyltrichlorosilane (179.2 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) were added so that the liquid temperature did not rise. Was slowly dropped. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto.
After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Further, the liquid was vacuum-dried to obtain a polymer M. GPC of the molecular weight of this material
As a result, Mw = 3000 and Mn = 1400. 50 g of the above polymer M and 50 g of solvent MIBK
A composition N was prepared. The composition is 1 at 200 ° C.
The resin was cured by heat treatment for an hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5070 at a wavelength of 1.3 μm. Further, phenyltrichlorosilane (211.5 g) and cyclopentyltrichlorosilane (203.6 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108
g) was slowly added dropwise so that the liquid temperature did not rise. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Furthermore, the polymer O was obtained by vacuum-drying this liquid. When the molecular weight of this material was measured by GPC, it was Mw = 3000 and Mn = 1400. Composition P consisting of 50 g of the above polymer O and 50 g of solvent MIBK was prepared. This composition was cured by heating at 200 ° C. for 1 hour, and became insoluble in the solvent. The refractive index of the cured composition is 1.5 at a wavelength of 1.3 μm.
021. The optical waveguide using the polymer M as a core and the polymer O as a clad was manufactured in accordance with Example 1. This optical waveguide is 5 cm by a dicing saw.
When the waveguide loss was measured, 0.3 dB was obtained not only at 1.3 μm but also at 1.55 μm.
/ Cm or less. The loss of this optical waveguide is 12
No change was observed for more than one month even at 0 ° C.

Example 7 Deuterated phenyltrichlorosilane (259.8 g) and cyclopentyltrichlorosilane (162.9 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) was added thereto. It was dropped slowly so as not to rise. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator.
A clear, colorless, viscous liquid was obtained. Further, this liquid was vacuum-dried to obtain a polymer Q. When the molecular weight of this material was measured by GPC, Mw = 2500, Mn = 12
00. 50 g of the above polymer Q and solvent MIBK
Composition R consisting of 50 g was prepared. The composition comprises 200
The composition was cured by heat treatment at 1 ° C. for 1 hour and became insoluble in the solvent. The cured composition has a refractive index of 1.3 wavelength.
It was 1.5103 in μm. Also, deuterated phenyltrichlorosilane (233.8 g) and cyclopentyltrichlorosilane (187.3 g) are dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) are added thereto so that the liquid temperature does not rise. It was dripped slowly. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Furthermore, the polymer S was obtained by vacuum-drying this liquid. GPC of the molecular weight of this material
Was Mw = 2500 and Mn = 1200. 50 g of the above polymer S and 50 g of solvent MIBK
Was prepared. The composition is 1 at 200 ° C.
The resin was cured by heat treatment for an hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5054 at a wavelength of 1.3 μm. The above polymer Q as a core,
An optical waveguide using the polymer S as a clad was manufactured in accordance with Example 1. This optical waveguide was cut into a length of 5 cm by a dicing saw, and the waveguide loss was measured. As a result, it was 0.2 dB / cm or less not only at the wavelength of 1.3 μm but also at the wavelength of 1.55 μm. The loss of the optical waveguide did not fluctuate for more than one month even under the condition of 75 ° C./90% RH.

Example 8 Deuterated phenyltrichlorosilane (190.5 g) and cyclopentyltrichlorosilane (228.0 g) were dissolved in 1 liter of dehydrated tetrahydrofuran, and 3 equivalents of water (108 g) was added thereto. It was dropped slowly so as not to rise. Subsequently, while the reaction solution was stirred, 3 equivalents of sodium hydrogen carbonate (504 g) was added thereto. After the generation of carbon dioxide was completed, stirring was continued for another hour. Next, the reaction solution was filtered, and tetrahydrofuran in the filtrate was distilled off with a rotary evaporator to obtain a colorless, transparent and viscous liquid. Furthermore, the polymer U was obtained by vacuum-drying this liquid. When the molecular weight of this material was measured by GPC, Mw = 2500, Mn =
1200. Composition V consisting of 35 g of the above polymer U, 15 g of 1,3-bis (isocyanatomethyl) cyclohexane, and 50 g of solvent MIBK was prepared. The composition was cured by heating at 150 ° C. for 1 hour, and became insoluble in the solvent. The refractive index of the cured composition was 1.5050 at a wavelength of 1.3 μm. The optical waveguide using the polymer Q described in Example 7 as a core and the composition V as a clad was manufactured according to Example 1.
No crack was found in the process of manufacturing the optical waveguide. The prepared optical waveguide was cut out to a length of 5 cm by a dicing saw, and the waveguide loss was measured.
0.2 not only at 1.3 μm wavelength but also at 1.55 μm wavelength
It was less than dB / cm. The loss of this optical waveguide did not change even after the heat treatment at 200 ° C. for 30 minutes.

[0024]

As described above, by using the optical material according to the present invention, low loss, high heat resistance, high moisture resistance, and high resistance are obtained not only in the 1.3 μm wavelength band but also in the 1.55 μm wavelength band. Polysilsesquioxane having excellent cracking properties can be realized. Further, an optical component using the optical material according to the present invention has high heat resistance and moisture resistance, and has a light resistance of 1.3 μm.
Since the loss is low not only in the m wavelength band but also in the 1.55 μm wavelength band, application to an optical waveguide type component is particularly advantageous. Therefore, the present invention can be applied to fields such as general optics, micro optics, optical communication, and optical information processing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication G02B 6/12 G02B 6/12 N (72) Inventor Saburo Imamura 3-19 Nishishinjuku, Shinjuku-ku, Tokyo No. 2 Nippon Telegraph and Telephone Corporation

Claims (3)

[Claims] 1. A compound represented by the following general formula (Chemical Formula 1) in which each unit of the formulas (I) and (II) is a constituent: (Wherein R ₁ is a cyclohexyl group or a cyclopentyl group), and the following general formula (Chemical Formula 2) in which each unit of the formulas (III) and (IV) is a constituent: 2] [Wherein, R ₂ is C ₆ Y ₅ (Y represents hydrogen or deuterium)
A phenyl group or a deuterated phenyl group represented by
A polymer optical material, which is a copolymer comprising a repeating unit represented by the formula: 2. A polymer optical material, which is a mixture containing the copolymer according to claim 1 and a polyisocyanate. 3. A polymer optical waveguide using the polymer optical material according to claim 1 as a core or a clad.