JP2007070326A - Bis(hydroxyphenyl)alkane derivative having oxetane ring, method for producing the same and optical waveguide using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound capable of producing a polymer excellent in thick membrane-forming property, curing property, heat resistance, etc., a method for producing the same and an optical waveguide using the same. <P>SOLUTION: This bis(hydroxyphenyl)alkane derivative having a specific oxetane ring is produced by cesium-phenolating specific phenols with cesium salts, and then reacting with a sulfonic acid ester. Further, an optical wave guide comprising a substrate plate 1 and a cladding layer 2 formed on the substrate plate 1, and formed with a core part 3 having a prescribed pattern and transmitting light signals, in the cladding layer 2 is provided with that at least one of the cladding layer 2 and core part 3 is formed by a resin composition containing the bis(hydroxyphenyl)alkane derivative having the oxetane ring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a bis (hydroxyphenyl) alkane derivative having an oxetane ring capable of cationic polymerization, a process for producing the same, and an optical waveguide using the same. Specifically, a bis (hydroxyphenyl) alkane having an oxetane ring in which a photocurable resin and a thermosetting resin using the compound have excellent heat resistance, mechanical properties, low water absorption, coating flatness, adhesion, and the like The present invention relates to a derivative, a manufacturing method thereof, and an optical waveguide using the same.

  Oxetane compounds are recently attracting attention as monomers capable of photoinitiated cationic polymerization or curing, and many monofunctional and polyfunctional oxetane compounds have been developed, and accordingly, methods for synthesizing various oxetane compounds. Has been proposed.

  As said oxetane compound, the oxetane compound represented by following General formula (4) is proposed also in the patent document, for example (refer patent document 1).

  Furthermore, biphenyl derivatives having an oxetane ring represented by the following general formula (5) and general formula (6) have also been proposed (see Patent Documents 2 and 3).

The above compounds are usually obtained by synthesizing an oxetane sulfonic acid ester and a corresponding dihydric phenol compound in the presence of an alkali metal such as sodium hydroxide or potassium hydroxide as a base. can get. In the synthesis, a phase transfer catalyst such as a quaternary ammonium salt is also used as necessary to increase the yield of the compound. Furthermore, the oxetane compound has been conventionally used for materials such as paints and adhesives in order to improve heat resistance, adhesion, etc. In recent years, it has also been proposed to use it as a material for forming optical waveguides. (See Patent Documents 4 and 5). Optical waveguides are incorporated in optical waveguide devices, optical integrated circuits, and optical wiring boards, and are widely used in the fields of optical communication, optical information processing, and other general optics.
JP-A-6-16804 JP-A-11-106380 JP 2001-31665 A JP 2000-356720 A JP 2003-147045 A

  However, among the oxetane compounds, the biphenyl derivative is a compound having a low molecular weight, and thus has a low viscosity. For example, when a film is formed on a substrate, it has a difficulty in forming a thick film. Moreover, since it is bifunctional, there also exists a fault that hardening requires time. Further, other oxetane compounds have a problem that it is difficult to obtain desired thick film formability and curability.

  In addition, when such a conventional oxetane compound is used, for example, as a material for forming an optical waveguide, it is difficult to stably cure and produce the same shape. There are also problems such as inability to form.

  Furthermore, the conventional method for synthesizing an oxetane compound also has a problem that the introduction of an oxetanyl group does not proceed quantitatively and the yield of the target oxetane compound is low. In addition, since a compound having an unreacted hydroxyl group is generated as a by-product, a complicated operation is often involved before obtaining the target oxetane compound.

  The present invention has been made in view of such circumstances, and a bis (hydroxyphenyl) alkane derivative having a novel oxetane ring that makes it possible to produce a polymer excellent in thick film formability, curability, heat resistance, and the like, and An object of the present invention is to provide a manufacturing method thereof and an optical waveguide using the manufacturing method.

In order to achieve the above object, the first gist of the present invention is a bis (hydroxyphenyl) alkane derivative having an oxetane ring represented by the following general formula (1).

The present invention also provides a process for producing a bis (hydroxyphenyl) alkane derivative having an oxetane ring as defined in the first aspect, wherein a phenol represented by the following general formula (2) is converted to cesium phenolate with a cesium salt. Then, the second gist is a method for producing a bis (hydroxyphenyl) alkane derivative having an oxetane ring that is reacted with a sulfonic acid ester represented by the following general formula (3).

  Furthermore, the present invention is an optical waveguide comprising a substrate and a clad layer formed on the substrate, wherein a core portion that propagates an optical signal in a predetermined pattern is formed in the clad layer, A third gist is an optical waveguide in which at least one of the cladding layer and the core part is formed of a resin composition containing a bis (hydroxyphenyl) alkane derivative having an oxetane ring of the first gist.

  That is, the present inventors have developed an oxetane compound that is excellent in heat resistance, mechanical properties, etc., and can produce a polymer that can be effectively used as a material for paints, coating materials, adhesives, lenses, optical waveguides, and the like. We sought and intensively studied. As a result of synthesizing various compounds having a special structure and repeating experiments, when a bis (hydroxyphenyl) alkane derivative having a novel oxetane ring represented by the general formula (1) is used, As a result, the present invention has been achieved. That is, since the above novel compound has two oxetane rings in one molecule, it has fast curability and has excellent heat resistance because the cured product forms a high-density network structure. It becomes. In addition, the above novel compound has a high molecular weight to some extent rather than a low molecular weight like existing compounds, so it has a high viscosity, which is advantageous when forming a thick film, and particularly for optical waveguides (cladding layer and core part). When used as a forming material, it becomes easy to stably produce a cured material in the same shape, so that effects such as stabilization of waveguide characteristics can be obtained. On the other hand, the present inventors have also conducted research on a synthesis method capable of synthesizing the novel compound with high yield. As a result, the phenol represented by the general formula (2) and the sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by the general formula (3), in particular, a cesium salt as a base. As a result of using and reacting under predetermined conditions, it was also found that the target novel compound can be synthesized in high yield.

  Thus, the present invention relates to a bis (hydroxyphenyl) alkane derivative having a novel oxetane ring represented by the general formula (1). This derivative has a high molecular weight to some extent rather than a low molecular weight like existing oxetane compounds, and thus has a high viscosity and can easily form a thick film. Moreover, since it contains two oxetane rings in one molecule, it has the property of being rapidly cured by light or heat. Therefore, the photocurable resin composition and thermosetting resin composition using the bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention are excellent in curability, heat resistance, toughness and mechanical properties, and have low water absorption. High transparency, high film flatness and adhesion, and because of its high reactivity, the use of polymerization initiators can be reduced, so transparency is also high. For example, paints, coating materials, adhesives, optical lenses It is useful as a material for forming optical waveguides.

  And when synthesize | combining the bis (hydroxyphenyl) alkane derivative which has the said oxetane ring, by making a specific oxetanesulfonic acid ester and specific phenols react on a predetermined condition using a cesium salt as a base. The above compound can be synthesized in high yield without complicated operations.

  Furthermore, when at least one of the cladding layer and the core part in the optical waveguide is formed of a resin composition containing a bis (hydroxyphenyl) alkane derivative having an oxetane ring represented by the general formula (1), Thus, it is easy to cure and form the same shape, and stable waveguide characteristics can be obtained.

  Next, an embodiment of the present invention will be described.

The bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention is a compound represented by the following general formula (1), and has a structure having two oxetane rings in one molecule. In the general formula (1), R ₁ and R ₃ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms as shown below, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. Among them, a methyl group and an ethyl group are preferable. R ₂ is a fluorine atom or a monovalent aromatic group. For example, examples of the monovalent aromatic group include a phenyl group, and R ₂ is preferably a fluorine atom or a phenyl group.

  The bis (hydroxyphenyl) alkane derivative having an oxetane ring represented by the above general formula (1) is a phenol represented by the following general formula (2) and 3 represented by the following general formula (3). It can be produced by reacting a sulfonic acid ester of alkyl-3-hydroxymethyloxetane with a base as a synthetic raw material.

  Here, as the base, it is conceivable to use a conventionally known alkali metal (sodium hydroxide, potassium hydroxide, etc.). In the present invention, when the cesium salt is used as the base, the general Since the compound represented by the formula (1) can be synthesized in a high yield without complicated operations, the above cesium salt is used. In this case, the synthesis reaction using each raw material includes, for example, (i) a reaction in which phenols are converted to cesium phenolate with a cesium salt and then reacted with an oxetane sulfonate ester. Further, (ii) a reaction performed by reacting an oxetanesulfonic acid ester with a phenol in the presence of a cesium salt. Of these, the procedure (i) is preferably performed. The above synthesis is usually carried out in an organic solvent (reaction solvent), and after the reaction is completed, water or the like is added to the reaction solution to form an aqueous phase and an organic phase, and extraction from the organic phase is performed for the purpose. A bis (hydroxyphenyl) alkane derivative having an oxetane ring can be obtained.

  Examples of the cesium salt include cesium carbonate, cesium hydroxide, cesium fluoride, cesium formate, and the like. Among these, cesium carbonate is preferably used because the desired bis (hydroxyphenyl) alkane derivative having an oxetane ring can be obtained in a higher yield.

  And it is preferable to set the usage-amount of the said cesium salt to 0.8-2.0 mol with respect to 1 mol of phenolic hydroxyl groups of the phenols represented by the said General formula (2), More preferably, 1 The range is from 0.0 to 1.5 mol.

  Examples of the phenols represented by the general formula (2) include 1,1-bis (4-hydroxy-3-fluorophenyl) methane and 2,2-bis (4-hydroxy-3-fluorophenyl) ethane. 2,2-bis (4-hydroxy-3-fluorophenyl) propane, 2,2-bis (4-hydroxy-2-fluorophenyl) propane, 2,2-bis (4-hydroxy-3-fluorophenyl) Examples include propane and 2,2-bis (4-hydroxybiphenyl) propane. These may be used alone or in combination of two or more.

In the sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by the general formula (3) used together with the phenols as described above, R ₄ in the formula (3) has 1 carbon atom. -7 alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group and the like, preferably methyl group and ethyl group. Specific examples thereof include 2- (3-oxetanyl) propyl mesylate, 2- (3-oxetanyl) propylphenylsulfonylate, 2- (3-oxetanyl) propyl tosylate, 2- (3-oxetanyl). Examples thereof include butyl mesylate and 2- (3-oxetanyl) butyl tosylate. These may be used alone or in combination of two or more.

  The sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by the general formula (3) is, for example, organic synthesis vol. 1 [Organic Synthesis, Collective vol. 1, pp. 145 (1941)]. It can be synthesized according to the method described in 1.

  And the usage-amount of the sulfonic acid ester of 3-alkyl-3-hydroxymethyl oxetane represented by the said General formula (3) is 1 mol of phenolic hydroxyl groups of the phenol represented by the said General formula (2). Is preferably set to 1.5 to 2.0 mol, and more preferably in the range of 1.0 to 1.5 mol.

  And at the time of manufacture of the bis (hydroxyphenyl) alkane derivative which has the oxetane ring of this invention, it is preferable to set the reaction temperature in the case of the synthesis | combination to 0-120 degreeC, More preferably, it is the range of 60-100 degreeC. It is. Moreover, when phenols are cesium phenolated in advance with a cesium salt, the reaction temperature in the cesium phenolate is preferably set to 0 to 120 ° C, more preferably in the range of 40 to 100 ° C. . And the pressure in these reactions is not specifically limited, Any of a normal pressure, pressurization, and pressure reduction may be sufficient. Also, the reaction atmosphere is not particularly limited, such as under an inert gas atmosphere such as nitrogen gas.

  In addition, when synthesizing the bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention, an alkali metal such as sodium or potassium, an alkali metal hydride such as lithium hydride or sodium hydride, An alkali metal hydroxide such as sodium oxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate, or the like may be appropriately added as a synthetic raw material.

  Moreover, you may add a quaternary ammonium salt, a quaternary phosphonium salt, etc. as a phase transfer catalyst between an aqueous phase and an organic phase as needed. The quaternary ammonium salt is not particularly limited, and examples thereof include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and tetraethylammonium bromide, and aralkyltrialkylammonium halides such as benzyltrimethylammonium chloride. can give. The quaternary phosphonium salt is not particularly limited, and examples thereof include tetraarylphosphonium halides such as tetraphenylphosphonium bromide.

  Furthermore, when producing the bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention, a reaction solvent is usually used as described above. The reaction solvent is not particularly limited. For example, aromatic hydrocarbons (toluene, xylene, etc.), ethers (tetrahydrofuran, dibutyl ether, etc.), aprotic polar solvents (N-methylpyrrolidone, N-methyl-2- Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) are preferably used. These may be used alone or in combination of two or more.

  As described above, bis (hydroxyphenyl) alkane derivatives having an oxetane ring synthesized from each of these raw materials are usually separated into an aqueous phase and an organic phase by adding water or ethyl acetate to the reaction solution. The organic phase extracted from the liquid can be recovered by drying over anhydrous magnesium sulfate or the like.

  The bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention thus obtained is a photocurable resin and a thermosetting resin that constitute paints, coating materials, adhesives, lenses, optical waveguides, and the like. It can be used effectively as a material.

  Among them, an optical waveguide, specifically, as shown in FIG. 1, includes a substrate 1 and a cladding layer 2 formed on the substrate 1, and propagates an optical signal in a predetermined pattern in the cladding layer 2. In the optical waveguide in which the core portion 3 is formed, when at least one of the cladding layer 2 and the core portion 3 is formed of a resin composition containing the bis (hydroxyphenyl) alkane derivative having the oxetane ring, Since the derivative has a high molecular weight, it has a high viscosity, which is advantageous when forming a thick film. In addition, it is possible to obtain an effect such as that the waveguide characteristics can be stably stabilized by being easily cured in the same shape. The clad layer 2 needs to have a refractive index smaller than that of the core portion 3.

  Further, at least one of the cladding layer 2 and the core portion 3 is formed of a resin composition containing a compound having an epoxy group or a vinyl ether group together with a bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention. If it is, a cured product having excellent heat resistance and moisture resistance can be obtained, and exposure sensitivity can be improved, which is preferable. Here, as the compound having an epoxy group, any compound can be used as long as it is compatible with the compound represented by the formula (1) of the present invention. Specifically, examples of the epoxy compound having one epoxy group include phenyl glycidyl ether and butyl glycidyl ether, and examples of the epoxy compound having two or more epoxy groups include bisphenol A diglycidyl ether, bisphenoxyethanol full orange glycidyl. Ether, trimethylolpropane triglycidyl ether, bisphenolfluorene tetraglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate, 2,2-bis ( An adduct of 1,2-epoxy-4- (2-oxiranyl) cyclohexane with hydroxymethyl) -1-butanol is preferably used. Moreover, as a compound which has the said vinyl ether group, all can be used if it shows compatibility with the compound represented by Formula (1) of this invention. Specifically, examples of the compound having one vinyl ether group include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether and the like. As the compound having two or more vinyl ether groups, cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, novolak type divinyl ether and the like are preferably used. And these compounds are used individually or in combination of 2 or more types.

  And the said optical waveguide can be manufactured by a process as shown in FIG. 2, for example. That is, as shown in FIG. 2A, first, a substrate 1 is prepared, and as shown in FIG. 2B, an under cladding layer 2a (a lower portion of the cladding layer 2) is formed on the surface of the substrate 1. Next, as shown in (c), a layer 3 ′ made of a resin composition for forming the core portion 3 is formed on the under cladding layer 2 a. Then, as shown in (d), a photomask 9 for exposing a predetermined pattern (optical waveguide pattern) is disposed on the surface of the resin composition layer 3 ′, and ultraviolet rays are emitted through the photomask 9. Irradiation and further heat treatment. Thereafter, the unexposed portion of the resin composition layer 3 ′ is dissolved and removed using a developer to form the core portion 3 as shown in FIG. Then, as shown in (f), the over clad layer 2b (the upper portion of the clad layer 2) is formed on the core portion 3. Thereby, the target optical waveguide can be obtained.

  Each layer on the substrate 1 can be formed by a conventionally known method such as spin coating or coater. The optical waveguide can also be made into a film-like optical waveguide by peeling off the substrate 1. In such a configuration, the flexibility becomes excellent.

  The optical waveguide thus obtained is, for example, a straight optical waveguide, a curved optical waveguide, a crossed optical waveguide, a Y-branch optical waveguide, a slab optical waveguide, a Mach-Zehnder optical waveguide, an AWG optical waveguide, a grating, or an optical waveguide lens. Etc. can be used. Optical devices using these optical waveguides include wavelength filters, optical switches, optical splitters, optical multiplexers, optical multiplexers / demultiplexers, optical amplifiers, wavelength converters, wavelength dividers, optical splitters, directional couplers. Furthermore, an optical transmission module in which laser diodes and photodiodes are integrated in a hybrid manner can be used.

  Next, the present invention will be described based on examples. However, the present invention is not limited to these examples.

  First, prior to Examples, 2- (3-oxetanyl) butyl tosylate, which is a sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane, was synthesized as follows.

[Synthesis of 2- (3-oxetanyl) butyl tosylate]
In a 2000 ml three-necked eggplant flask equipped with a thermometer, a condenser, a stirring device and a dropping funnel, 190.65 g (1.0 mol) of p-toluenesulfonic acid chloride and 32.24 g (0.1 mol) of tetramethylammonium bromide And 400 ml of toluene was added, and it cooled to 5 degreeC, stirring in an ice bath. After adding 116.16 g (1.0 mmol) of 3-ethyl-hydroxymethyloxetane to this, 130 ml of 35 wt% sodium hydroxide aqueous solution was dripped over 30 minutes with the dropping funnel. After completion of the dropping, the flask was stirred as it was at the same temperature for 1 hour, and further stirred at room temperature (25 ° C.) for 16 hours. After completion of the reaction, 800 ml of water was added to the flask and stirred vigorously, and then left to separate into an aqueous phase and an organic phase. This organic phase was further washed with 400 ml of water and dried over anhydrous magnesium sulfate overnight. Thereafter, magnesium sulfate was filtered off and the filtrate was concentrated. The crude product thus obtained was separated and purified by silica gel column chromatography (eluent: hexane / ethyl acetate) to give 2- (3-oxetanyl) butyl tosylate as a colorless liquid as the target product. 243.3 g (90% yield) was obtained.

  In a 200 ml three-necked flask equipped with a thermometer, a condenser and a stirrer, 2.64 g (10 mmol) of 2,2-bis (4-hydroxy-3-fluorophenyl) propane and N-methyl-2-pyrrolidone 15 ml was added and stirred until completely dissolved while heating to 80 ° C. in a nitrogen atmosphere. After dissolution, 7.82 g (24 mmol) of cesium carbonate was added, and the mixture was further stirred at 80 ° C. for 30 minutes in a nitrogen atmosphere. Thereto was added 5.95 g (22 mmol) of 2- (3-oxetanyl) butyl tosylate synthesized earlier, and the mixture was stirred at 80 ° C. for 20 hours in a nitrogen atmosphere. After the completion of the reaction, the reaction mixture was cooled to room temperature (25 ° C.), added with 100 ml of distilled water, stirred and filtered. The residue after filtration was further washed with water and dried to obtain a crude reaction product.

  The crude product thus obtained was analyzed by thin layer chromatography, and only one spot was confirmed. This was recrystallized and purified to obtain 4.11 g (yield 89%) of a white solid. When the purity of the compound was examined by liquid chromatography, it was 99% or more.

The compound thus obtained is represented by the following structural formula (7) from the following results obtained by analysis using ¹ H-NMR and ¹³ C-NMR (both manufactured by JEOL Ltd.). 2,2-bis (4- (2- (3-oxetanyl)) butoxy-3-fluorophenyl) propane.

¹ H-NMR (CDCl ₃ , 400 MHz): δ (ppm); 0.93 (t, J = 7.6 Hz, 6H, CH ₃ ), 1.61 (s, 6H, CH ₃ ), 1.89 ( q, J = 7.6 Hz, 4H, CH ₂ ), 4.13 (s, 4H, CH ₂ ), 4.48 (d, J = 6.4 Hz, 4H, CH ₂ ), 4.55 (d, J = 6.0 Hz, 4H, CH ₂ ), 6.91 (m, 6H, Ar)
¹³ C-NMR (CDCl ₃ , 100 MHz): δ (ppm); 8.23, 26.57, 30.74, 41.99, 43.48, 72.23, 78.19, 115.02, 115. 12, 115.14, 115.21, 122.07, 122.10, 144.33, 144.38, 144.90, 145.02, 151.27, 153.71

  In a 200 ml three-necked flask equipped with a thermometer, a condenser and a stirrer, 3.80 g (10 mmol) of 2,2-bis (4-hydroxybiphenyl) propane and 15 ml of N-methyl-2-pyrrolidone were placed. The mixture was stirred until it was completely dissolved while being heated to 80 ° C. in a nitrogen atmosphere. After dissolution, 7.82 g (24 mmol) of cesium carbonate was added, and the mixture was further stirred at 80 ° C. for 30 minutes in a nitrogen atmosphere. Thereto was added 5.95 g (22 mmol) of 2- (3-oxetanyl) butyl tosylate synthesized earlier, and the mixture was stirred at 80 ° C. for 20 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was cooled to room temperature (25 ° C.), 100 ml of ethyl acetate and 50 ml of distilled water were added, and the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The organic phase thus separated was extracted, further washed with water and saturated brine, and dried over anhydrous magnesium sulfate overnight. Thereafter, magnesium sulfate was filtered off, and the solvent was distilled off to obtain a crude reaction product.

  The crude product thus obtained was analyzed by thin layer chromatography, and only one spot was confirmed. This was recrystallized and purified to obtain 5.45 g (yield 95%) of a white solid. When the purity of the compound was examined by liquid chromatography, it was 99% or more.

The compound thus obtained is represented by the following structural formula (8) from the following results obtained by analysis using ¹ H-NMR and ¹³ C-NMR (both manufactured by JEOL Ltd.). 2,2-bis (4- (2- (3-oxetanyl)) butoxybiphenyl) propane.

¹ H-NMR (CDCl ₃ , 400 MHz): δ (ppm); 0.82 (t, J = 7.6 Hz, 6H, CH ₃ ), 1.73 (s, 6H, CH ₃ ), 1.74 ( q, J = 7.6 Hz, 4H, CH ₂ ), 4.06 (s, 4H, CH ₂ ), 4.35 (d, J = 6.0 Hz, 4H, CH ₂ ), 4.43 (d, J = 6.0 Hz, 4H, CH ₂ ), 6.93 (d, J = 8.8 Hz, 2H, Ar), 7.20 (dd, J = 2.4 Hz, J = 8.4 Hz, 2H, Ar) ), 7.27 (d, J = 2.4 Hz, 2H, Ar), 7.29 (t, J = 7.2 Hz, 2H, Ar), 7.36 (t, J = 7.2 Hz, 4H, Ar), 7.46 (d, J = 7.2 Hz, 4H, Ar)
¹³ C-NMR (CDCl ₃ , 100 MHz): δ (ppm); 8.14, 26.75, 31.18, 41.99, 43.36, 71.25, 78.40, 112.46, 126. 80, 126.86, 127.74, 129.46, 129.62, 130.73, 138.66, 143.72, 153.73

  In the following manner, an under cladding layer, a core portion, and an under cladding layer were formed to produce an optical waveguide (see FIG. 1). And the evaluation with respect to the optical waveguide was performed as follows.

[Formation of underclad layer]
First, 2,2-bis (4- (2- (3-oxetanyl)) butoxy-3-fluorophenyl) propane 70 parts by weight (hereinafter abbreviated as “part”) obtained in Example 1 and an alicyclic ring 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (Daicel Chemical Industries, Celoxide 2021P), which is an epoxy compound, and 4,4-bis [di (β-hydroxyethoxy) Phenylsulfinio] 1 part of a 50% propion carbide solution of phenyl sulfide-bis-hexafluoroantimonate was dissolved in cyclohexanone to prepare a polymerizable composition A as a precursor for forming a cladding layer.

Next, a glass substrate (5 cm × 5 cm × 2 mm in thickness) was prepared, and the polymerizable composition A was applied to the surface by a spin coating method and dried at 100 ° C. for 5 minutes. Then, the entire surface was irradiated with ultraviolet rays at a dose of 2000 mJ / cm ² , and subsequently heat-treated at 100 ° C. for 30 minutes to form an under cladding layer (see FIG. 2B). It was 30 micrometers when the thickness of this under clad layer was measured with the contact-type film thickness meter. The refractive index of the under cladding layer was 1.545 at a wavelength of 633 nm.

[Formation of core part]
Next, 90 parts of 2,2-bis (4- (2- (3-oxetanyl)) butoxy-3-fluorophenyl) propane obtained in Example 1 and bisphenoxyethanol fluorenediglycidyl ether (epoxy equivalent 320) 10 parts and 1 part of 50% propion carbide solution of 4,4-bis [di (β-hydroxyethoxy) phenylsulfinio] phenyl sulfide-bis-hexafluoroantimonate are dissolved in cyclohexanone to form a core part A polymerizable composition B as a precursor was prepared. And the said polymeric composition B was apply | coated on the said under clad layer by the spin coat method, and the core part precursor layer was formed by making it dry at 150 degreeC for 20 minutes (refer FIG.2 (c)). Further, a synthetic quartz-based chrome mask (photomask) on which a 50 μm-wide linear optical waveguide pattern is drawn is disposed thereon (see FIG. 2D), and contact exposure is performed through this chrome mask. The sample was irradiated with ultraviolet rays having a dose of 2000 mJ / cm ² and further subjected to heat treatment at 150 ° C. for 30 minutes. Then, in order to remove an unirradiated part, development was performed using a γ-butyrolactone aqueous solution, and the core pattern was formed by further heating at 150 ° C. for 30 minutes (see FIG. 2E). When the core shape was measured with a length measuring microscope, the core pattern had a square cross-sectional shape with a width of 50 μm and a height of 50 μm. Further, the refractive index of the core portion formed in this way was 1.567 at a wavelength of 633 nm.

[Formation of overclad layer]
The same composition as the polymerizable composition A prepared at the time of forming the underclad layer was applied onto the core part and the underclad layer by a spin coating method. Next, as in the formation of the underclad layer, the film was dried at 100 ° C. for 5 minutes, irradiated with ultraviolet rays at an irradiation amount of 2000 mJ / cm ² , and subsequently heat-treated at 150 ° C. for 60 minutes, thereby overheating. A clad layer was formed (see FIG. 2F). In this way, a multimode optical waveguide having a relative refractive index Δ = 1.4% was produced.

[Evaluation]
The optical waveguide was cut into a length of 10 cm using a dicing apparatus (Model 522 manufactured by Disco Corporation) and subjected to end face processing. When the cross-sectional shape of the optical waveguide was observed with a length measuring microscope, it was found to be a buried multimode optical waveguide with an under cladding layer thickness of 30 μm, a core portion of 50 μm × 50 μm, and an over cladding layer thickness of 70 μm. It was confirmed. And when this optical waveguide was measured for light propagation loss by a conventional cutback method using laser light having a wavelength of 850 nm, it was 0.09 dB / cm. In addition, this optical waveguide can be made into a film-like waveguide by peeling from the substrate. And this film-form waveguide was good also in flexibility, such as a loss fall not being observed with respect to the bending of R = 20mm, and the bending of R = 5mm being possible.

  In the following manner, an under cladding layer, a core portion, and an under cladding layer were formed to produce an optical waveguide (see FIG. 1). And the evaluation with respect to the optical waveguide was performed as follows.

[Formation of underclad layer]
First, 70 parts of 2,2-bis (4- (2- (3-oxetanyl)) butoxybiphenyl) propane obtained in Example 2 and 3,4-epoxycyclohexenylmethyl-3, which is an alicyclic epoxy, were used. 30 parts of ', 4'-epoxycyclohexenecarboxylate (Daicel Chemical Industries, Celoxide 2021P) and 4,4-bis [di (β-hydroxyethoxy) phenylsulfinio] phenyl sulfide-bis-hexafluoroantimonate 1 part of a 50% propion carbide solution was dissolved in cyclohexanone to prepare a polymerizable composition C which was a precursor for forming a cladding layer.

  Next, an Si substrate (5 cm × 5 cm × 2 mm in thickness) was prepared, and an under cladding layer was formed on the surface in the same manner as in Example 3 using the polymerizable composition C (FIG. 2B). reference). It was 30 micrometers when the thickness of this under clad layer was measured with the contact-type film thickness meter. The refractive index of the under cladding layer was 1.565 at a wavelength of 633 nm.

[Formation of core part]
Next, 90 parts of 2,2-bis (4- (2- (3-oxetanyl)) butoxybiphenyl) propane obtained in Example 2, 10 parts of bisphenoxyethanol fluorenediglycidyl ether (epoxy equivalent 320), 1 part of a 50% propion carbide solution of 4,4-bis [di (β-hydroxyethoxy) phenylsulfinio] phenyl sulfide-bis-hexafluoroantimonate is dissolved in cyclohexanone, and the precursor for forming the core part is dissolved. A polymerizable composition D was prepared. And the core pattern was formed like Example 3 using the said polymeric composition D (refer FIG.2 (e)). When the core shape was measured with a length measuring microscope, the core pattern had a square cross-sectional shape with a width of 50 μm and a height of 50 μm. Further, the refractive index of the core portion formed in this way was 1.587 at a wavelength of 633 nm.

[Formation of overclad layer]
An over clad layer was formed in the same manner as in Example 3 by using the same polymerizable composition C prepared during the formation of the under clad layer (see FIG. 2 (f)). In this way, a multimode optical waveguide having a relative refractive index Δ = 1.4% was produced.

[Evaluation]
The optical waveguide was cut into a length of 10 cm using a dicing apparatus (Model 522 manufactured by Disco Corporation) and subjected to end face processing. When the cross-sectional shape of the optical waveguide was observed with a length measuring microscope, it was found to be a buried multimode optical waveguide with an under cladding layer thickness of 30 μm, a core portion of 50 μm × 50 μm, and an over cladding layer thickness of 70 μm. It was confirmed. Then, the optical propagation loss of this optical waveguide was measured by a conventional cutback method using a laser beam having a wavelength of 850 nm, and found to be 0.08 dB / cm. In addition, this optical waveguide can be made into a film-like waveguide by peeling from the substrate. And this film-form waveguide was good also in flexibility, such as a loss fall not being observed with respect to the bending of R = 20mm, and the bending of R = 5mm being possible.

  The bis (hydroxyphenyl) alkane derivative having an oxetane ring of the present invention is used as a constituent of a photocurable resin composition or a thermosetting resin composition, and these resin compositions include, for example, paints, coating materials, and adhesives. It is used for various forming materials such as agents, optical lenses, and optical waveguides. Examples of the optical waveguide include a straight optical waveguide, a curved optical waveguide, a crossed optical waveguide, a Y-branch optical waveguide, a slab optical waveguide, a Mach-Zehnder optical waveguide, an AWG optical waveguide, a grating, and an optical waveguide lens. It is done. The optical device using the optical waveguide includes a wavelength filter, an optical switch, an optical splitter, an optical multiplexer, an optical multiplexer / demultiplexer, an optical amplifier, a wavelength converter, a wavelength divider, an optical splitter, and directional coupling. And an optical transmission module in which a laser diode and a photodiode are hybrid-integrated.

It is a cross-sectional view showing an example of the optical waveguide of the present invention. It is explanatory drawing which shows the manufacturing process of the optical waveguide of this invention.

Explanation of symbols

1 Substrate 2 Clad layer 3 Core part

Claims (5)

A bis (hydroxyphenyl) alkane derivative having an oxetane ring represented by the following general formula (1).
A process for producing a bis (hydroxyphenyl) alkane derivative having an oxetane ring according to claim 1, wherein the phenol represented by the following general formula (2) is cesium phenolated with a cesium salt, and then the following general formula A method for producing a bis (hydroxyphenyl) alkane derivative having an oxetane ring, characterized by reacting with a sulfonic acid ester of 3-alkyl-3-hydroxymethyloxetane represented by formula (3).
  The method for producing a bis (hydroxyphenyl) alkane derivative having an oxetane ring according to claim 2, wherein the cesium salt is cesium carbonate.   An optical waveguide comprising a substrate and a clad layer formed on the substrate, wherein a core portion that propagates an optical signal in a predetermined pattern is formed in the clad layer, wherein the clad layer and the core portion At least one is formed with the resin composition containing the bis (hydroxyphenyl) alkane derivative which has an oxetane ring of Claim 1, The optical waveguide characterized by the above-mentioned.   The at least one of the said clad layer and a core part is formed with the resin composition containing the bis (hydroxyphenyl) alkane derivative of Claim 1, and the compound which has an epoxy group or a vinyl ether group. Optical waveguide.