JPH09274116A - Optical waveguide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical waveguide with which a waveguide forming stage is simplified, flattening is easy and optical wiring of multiple layers is possible by not using solvent. SOLUTION: The core part or clad part of this optical waveguide is formed of a liquid UV curing resin which is controllable in a range of a refractive index 1.51 to 1.74 and allows solventless application. This resin compsn. consists of 100 pts.wt. vinyl compd. contg. at least one kinds of sulfur and <=500 pts.wt. vinyl compd. without contg. the sulfur.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical waveguide which can be used in an optical circuit or the like, has excellent flatness, and is easily processed.

[0002]

2. Description of the Related Art Quartz is often used as a material for optical waveguides, but it has a problem that it has a high processing temperature and is difficult to manufacture in a large area. Recently, research on plastic waveguides using polymethylmethacrylate, etc. has progressed from the viewpoint of ease of processing. Even when such a resin is used, the resin is applied to the substrate in a state of being dissolved in a solvent. After that, in order to remove the solvent to form the core portion and the like, the solvent must be removed at an appropriate rate when removing the solvent. When the removal rate is high, bubbles or voids are generated or internal strain is generated. Further, there is a drawback that it takes a long time when the removal rate is low. When the removal temperature is increased, bubbles or voids may be generated and internal strain may occur due to the difference in coefficient of thermal expansion between the resin and the substrate. Further, when a soluble resin is used for the optical waveguide, it is necessary to prevent the resin portion already formed when the clad portion and the core portion are formed from melting. Therefore, it has been necessary to introduce a cross-linking component into the resin or change the resin components in the core and clad portions. The optical transmission loss factor in the optical waveguide is the intrinsic factor,
Absorption loss such as ultraviolet absorption due to electronic transition, scattering loss due to Rayleigh scattering due to density and concentration fluctuations,
External factors include absorption loss due to transition metals, OH groups, and other impurities, impurities such as dust and bubbles, irregularities in the core / cladding interface, core diameter fluctuations, and microbending.
Scattering loss due to structural imperfections such as orientation birefringence is included. Regarding Rayleigh scattering, the coexistence of regions with different refractive indices is not preferable, and the crystalline polymer,
Those exhibiting a micro phase separation structure such as block copolymerization and graft copolymerization are not preferable. Further, in order to suppress fluctuations in the solid due to thermal motion, a resin that is three-dimensionally cured by ultraviolet rays or the like is desired rather than a linear polymer. Further, peeling at the core / clad interface also causes a transmission loss, so that the clad resin is required to have good adhesion and adhesiveness to the core material. Therefore, it is desired that the core part and the clad part have similar components. The refractive index of the core of the optical waveguide is required to be higher than that of the cladding.
It is preferable that the cladding material of a general multimode waveguide has a refractive index difference of 2 to 3% or more of that of the core material. Further, in the case of optical waveguide in a single mode, when the cross section of the core part is a square having a side of 8 μm, a clad having a refractive index as small as 0.3% is required. The refractive index fluctuation of the material is 1/1000
Accuracy is required.

Therefore, it is necessary that the refractive index controllability of the waveguide material can be controlled by 1/1000.
Conventionally, there have been few resins having such a good refractive index controllability, and there have been few resins having a high refractive index in the vicinity of 1.60 that are easily controlled. Therefore, in a transmission system based on an optical device based on a polymer material having a refractive index of around 1.60, for example, a plastic optical fiber (a fiber whose main material is polystyrene or polycarbonate), the signal of the optical fiber is Since the refractive index matching between the peripheral device to be processed and the plastic optical fiber is not so good, there are problems that the reflection loss increases and the signal waveform is distorted. Furthermore, a non-linear material has been attracting attention as a functional polymer material. In order to make this non-linear material highly efficient, it is possible to achieve high efficiency by forming a waveguide structure and effectively increasing the optical power density by confining light, but materials that exhibit high efficiency are generally π Since it contains many components such as aromatic rings composed of electrons, its refractive index is often at least 1.6 or more. For this reason, it is necessary to use a polymer material having a refractive index of 1.6 or more as a clad material for producing a waveguide using a nonlinear material as a core. However, in general, there are few polymer materials for cladding that have optical characteristics of 1.6 or more, particularly excellent transparency and excellent processability. For example,
Polyimide or the like is mentioned as a typical polymer material having a refractive index of 1.6 or more, but it is often not applicable as a clad material because of its large birefringence or the need for a processing temperature of 300 ° C. or higher. From the above, there has been a demand for a material that can be controlled in a relatively high refractive index range (1.52 to 1.74) and is easy to process and easy to handle.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide an optical waveguide excellent in workability.

[0005]

The present invention will be described in brief. The present invention relates to an optical waveguide, and the core portion or the cladding portion of the optical waveguide is controlled within the range of refractive index 1.52 to 1.74. It is characterized in that it is formed from a liquid ultraviolet curable resin composition or a thermosetting resin composition which can be applied without using a solvent.

As a result of intensive studies, the present inventors have found that the ultraviolet-curable resin or thermosetting resin containing a vinyl compound containing sulfur as a main component can freely control the refractive index by changing the sulfur content. The resin has a low viscosity before curing, is excellent in coating properties such as spin coating, and has a relatively small curing shrinkage ratio. Therefore, it has excellent optical transparency and flatness when applied to the core part or clad layer of an optical waveguide. They have found that they are extremely excellent and have completed the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In a preferred embodiment of the present invention, an ultraviolet curable resin composition comprising 100 parts by weight of a sulfur-containing vinyl compound and 500 parts by weight or less of a sulfur-free vinyl compound in a core portion or a clad portion of an optical waveguide. The present invention relates to an optical waveguide characterized by using a material or a thermosetting resin composition. More specifically, the following (A) to (C): (A) The following general formula (Formula 1):

[0008]

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(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents hydrogen, halogen or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 10). A vinyl sulfide compound represented by: (B) the following general formula (Formula 2):

[0010]

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A methacrylic acid derivative represented by the formula (wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and each represents hydrogen, halogen or an alkyl group having 1 to 6 carbon atoms): ) A methacrylic acid derivative represented by the above general formula (Formula 2) and the following general formula (Formula 3):

[0012]

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A vinyl containing at least one sulfur selected from the group consisting of a prepolymer obtained by addition reaction with a thiol represented by the formula (wherein m represents an integer of 1 to 4). The present invention relates to an optical waveguide having a core part or a clad part formed of an ultraviolet curable resin composition or a thermosetting resin composition, which comprises 100 parts by weight of a compound and 500 parts by weight or less of a vinyl compound containing no sulfur.

R in the vinyl sulfide compound represented by the above general formula (Formula 1) of the component (A) in the present invention.
^{As the} halogen represented by ¹ , R ² , R ³ and R ⁴ ,
Examples of the alkyl group having 1 to 6 carbon atoms include chlorine, bromine, iodine, and the like, and linear and branched alkyl groups such as methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, pentyl,
Hexyl and the like. Preferably, R ^{1 to} R ⁴ are all hydrogen, and n is 0 to 10, preferably 0 to 5.

Examples of the vinyl sulfide compound include
For example, the following compounds may be mentioned. Bis (4-vinylthiophenyl) sulfide, bis (3-methyl-4-vinylthiophenyl) sulfide, bis (3,5-dimethyl-4-vinylthiophenyl) sulfide, bis (2,3,5,6- Tetramethyl-4-vinylthiophenyl) sulfide, bis (3-hexyl-4)
-Vinylthiophenyl) sulfide, bis (3,5-dihexyl-4-vinylthiophenyl) sulfide, bis (3-chloro-4-vinylthiophenyl) sulfide,
Bis (3,5-dichloro-4-vinylthiophenyl) sulfide, bis (2,3,5,6-tetrachloro-4-
Vinylthiophenyl) sulfide, bis (3-bromo-
4-vinylthiophenyl) sulfide, bis (3,5-
Dibromo-4-vinylthiophenyl) sulfide, bis (2,3,5,6-tetrabromo-4-vinylthiophenyl) sulfide. Preferably, bis (4-vinylthiophenyl) sulfide, bis (2,3,5,6-tetrachloro-4-vinylthiophenyl) sulfide, bis (2,3,5,6-tetrabromo-4-vinylthio) Examples thereof include phenyl) sulfide.

The method for producing the above vinyl sulfide compound is not particularly limited, and examples thereof include a method of reacting bis (4-mercaptophenyl) sulfide with dichloroethane in the presence of alkali, and then dehydrochlorinating with alkali. be able to. In this case, compounds having different numbers of n in the general formula (Formula 1) can be obtained by changing the reaction conditions such as the amount of dichloroethane used and the charging method.

As the halogen and the alkyl group having 1 to 6 carbon atoms represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ in the methacrylic acid derivative represented by the above general formula (Formula 2) of the component (B). May be the same as R ^{1 to} R ^{4 in the} general formula (Formula 1). Preferably, R ^{5 to} R ⁸ are all hydrogen.

Examples of the methacrylic acid derivative include the following compounds. Bis (4-
Methacryloylthiophenyl) sulfide, bis (3-
Methyl-4-methacryloylthiophenyl) sulfide, bis (3,5-dimethyl-4-methacryloylthiophenyl) sulfide, bis (2,3,5,6-tetramethyl-4-methacryloylthiophenyl) sulfide, bis (3 -Hexyl-4-methacryloylthiophenyl) sulfide, bis (3,5-dihexyl-4-methacryloylthiophenyl) sulfide, bis (3-chloro-4-methacryloylthiophenyl) sulfide,
Bis (3,5-dichloro-4-methacryloylthiophenyl) sulfide, bis (2,3,5,6-tetrachloro-4-methacryloylthiophenyl) sulfide, bis (3-bromo-4-methacryloylthiophenyl) sulfide , Bis (3,5-dibromo-4-methacryloylthiophenyl) sulfide, bis (2,3,5,6-
Tetrabromo-4-methacryloylthiophenyl) sulfide. Preferably, bis (4-methacryloylthiophenyl) sulfide, bis (2,3,5,6-tetrachloro-4-methacryloylthiophenyl) sulfide,
Examples thereof include bis (2,3,5,6-tetrabromo-4-methacryloylthiophenyl) sulfide.

The method for producing the above methacrylic acid derivative is not particularly limited, and for example, bis (4-
Examples include a method of reacting mercaptophenyl) sulfide with methacrylic acid chloride.

The method for producing the component (C) is not particularly limited. For example, it is represented by the methacrylic acid derivative represented by the general formula (Formula 2) and the general formula (Formula 3) in the presence of a base catalyst. Examples of the method include adding reaction of thiols.
The ratio of mercapto group of thiol to methacryloyl group of methacrylic acid derivative is 0.05 in terms of functional group equivalent ratio.
The range of -1.0 is preferable, and 0.2-0.6 is particularly preferable. When the functional group equivalent ratio is greater than 1.0, unreacted mercapto groups remain in the obtained prepolymer, resulting in poor stability of the prepolymer. The reaction temperature is 0 to 8
0 degreeC is preferable and 20-60 degreeC is especially preferable. Especially,
Bis (4-methacryloylthiophenyl) sulfide,
Bis (2,3,5,6-tetrachloro-4-methacryloylthiophenyl) sulfide, bis (2,3,5,6)
Good results are obtained with prepolymers obtained from -tetrabromo-4-methacryloylthiophenyl) sulfide and thiols.

The sulfur-free vinyl compound in the present invention is not particularly limited, and examples thereof include (meth) acrylic acid derivatives, aromatic vinyl compounds, alicyclic vinyl compounds and vinyl ethers. These may be used alone or in combination of two or more. Further, not only a monofunctional compound but also a polyfunctional compound can be selected according to the purpose of use.

Examples of such a sulfur-free vinyl compound include the following compounds.
In the present specification, both acrylic acid and methacrylic acid are collectively represented by the term “(meth) acrylic acid”, and similarly, by the term “(meth) acrylate”,
It shall represent both acrylate and methacrylate. Further, "EO" means ethylene oxide. Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, dodecyl (meth) acrylate, n
-Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, glycidyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) Acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, cyanophenyl (meth) acrylate, chloromethyl (meth) acrylate, bromoethyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid polyethylene glycol ester, N, N-dimethyl (meth) acrylamide,
Monofunctional (meth) acrylates such as N, N-diethyl (meth) acrylamide and (meth) acrylic acid. Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth)
Acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (or tetra) (meth)
Acrylate, dibromoneopentyl glycol dimethacrylate, tetrabromobisphenol A EO adduct di (meth) acrylate, EO-modified bisphenol A
Unsaturated fatty acid such as polyol (poly (meth) acrylate) such as di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate and derivatives thereof. Aromatic vinyl compounds such as styrene, α-methylstyrene, α-methylstyrene dimer, vinyltoluene, chlorostyrene, bromostyrene, chloromethylstyrene, methoxystyrene and divinylstyrene. Cyclohexene, 4-vinylcyclohexane, 1,5-cyclooctadiene, 5-vinylcyclo [2,2,1] hept-2-
Alicyclic vinyl compounds such as ene. Vinyl acetate, ethyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-amyl vinyl ether, isoamyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, n-octadecyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, ethylene glycol Monovinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, butanediol monovinyl ether, butanediol divinyl ether, hexanediol monovinyl ether, Sanji ol divinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, vinyl compounds such as phenyl vinyl ether. Preferably glycidyl (meta)
Acrylate, 1,3-butylene glycol di (meth)
(Meth) acrylic acid esters such as acrylate, tetrahydrofurfuryl (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, and EO-modified bisphenol F di (meth) acrylate.

In the present invention, 500 parts by weight or less, preferably 300 parts by weight or less, of a vinyl compound containing no sulfur is added to 100 parts by weight of a vinyl compound containing sulfur.
More preferably, if 200 parts by weight or less is used, good results can be obtained.

In the present invention, when the above polymerizable composition is polymerized, it is usually photopolymerized or thermally polymerized by using a radical polymerization initiator. Examples of the UV polymerization initiator for photopolymerization include 2,2-diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, benzophenone, and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 1-hydroxycyclohexyl phenyl ketone,
Carbonyl compounds such as 4,4-bisdimethylaminobenzophenone, methylbenzoisoformate, benzyldimethylketal and benzoylbenzoic acid, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4
-Thioxanthones such as dimethylthioxanthone. As the thermal polymerization initiator in the case of thermal polymerization, for example, 2,2′-azobisisobutyronitrile, 2,
Azo compounds such as 2'-azobisisovaleronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide, benzoyl peroxide, Diacyl peroxides such as 2,4-dichlorobenzoyl peroxide can be mentioned. The thermal polymerization temperature is in the range of 10 to 200 ° C, preferably 3
0-100 ° C. The amount of radical polymerization initiator used is
Since it varies depending on the type of radical polymerization initiator, the type of charged vinyl compound, and the composition ratio, it cannot be determined unconditionally, but normally for a composition comprising a sulfur-containing vinyl compound and / or a sulfur-free vinyl compound. 0.
It is in the range of 05 to 6% by weight, preferably in the range of 0.1 to 3% by weight.

In the present invention, if necessary, compounds such as a silane coupling agent, a titanium coupling agent, a flexibility imparting agent, a curing accelerator and a characteristic modifier can be added. The properties of the resin composition can be modified by adding these materials alone or in combination to the main component.

For example, as a silane coupling agent added to enhance the adhesiveness of the resin composition of the present invention, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane,
N-β- (aminoethyl) -β- (aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β- (N-vinyl Benzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-
Anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane , Trimethylchlorosilane, vinyltriethoxysilane, benzyltrimethylsilane, vinyltris (2-methoxyethoxy) silane,
γ-methacryloxypropyltris (2-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-isocyanurylpropyltriethoxysilane, n-octyltriethoxysilane Examples include silane.

If dust is present in the core or clad of the optical waveguide, it causes scattering loss. Therefore, at the stage of producing an ultraviolet curable resin or a thermosetting resin using the above-mentioned raw materials, even dust of a wavelength order of light is included. Need to be removed. Therefore, in the production of the core material and the clad material, production in a clean room or filtration step is desirable.

As a method for producing an optical waveguide according to the present invention, there are a case where an ordinary polymer resin is used for a clad and a case where an ultraviolet curable resin or a thermosetting resin similar to the core material is used. Examples thereof are shown below (Fig. 1). That is, FIG. 1 is a process diagram showing an example of a method of manufacturing an optical waveguide. In FIG. 1, reference numeral A is a substrate, B is a lower clad, C is a core layer,
D is a resist, E is a mask, and F is a side surface and an upper clad.

(1) A resin having a refractive index smaller than that of the core to be the lower clad is applied to an arbitrary substrate. After coating, the solvent is removed by heating and drying. When an ultraviolet curable resin or a thermosetting resin is used here, it suffices to cure the resin by applying ultraviolet rays or heating after applying the resin. By using these cured resins, the step of removing the solvent can be omitted.
(2) The resin of the present invention, which will be the core, is applied on this and cured by ultraviolet rays. (3) A photoresist is applied, (4) patterning is performed, and (5) a waveguide pattern is formed by reactive ion etching or the like. If the lower layer clad can be etched, (6) apply polymer resin for clad, UV curable resin or thermosetting resin, and (7)
It is cured by removing the solvent, ultraviolet rays or heating. Here, it is desirable that the lower clad and the clad on the side surface of the core and the upper clad to be finally formed have the same refractive index, and the same material is more preferable. Furthermore, when an ultraviolet curable resin or a thermosetting resin is used for the clad, the uppermost surface can be flattened. In this case, multi-layer optical wiring becomes possible,
When performing multi-layering, the above (2) to (7) may be repeated.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Prepolymer In a 1-liter four-necked flask, bis (4-methacryloylthiophenyl) sulfide in which R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen in the general formula (Formula 2) is used. 500g (1.2
9 mol), 220 g of dichloromethane and 0.08 g of p-methoxyphenol were charged, and the mixture was stirred at 40 ° C. until it became transparent. After adding 0.08 g of diethylamine as a catalyst, n was 2 in the general formula (Formula 3). A certain bis (2-mercaptoethyl) sulfide 60g (0.38
(9 mol) was added dropwise, and the mixture was stirred at 40 ° C. for 15 minutes.
In this case, the functional group equivalent ratio is 0.302. afterwards,
Dichloromethane was distilled off under reduced pressure to obtain 560 g of a methacrylic acid prepolymer as a pale yellow liquid. The refractive index of this liquid was 1.660. The result of gel permeation chromatography analysis of this liquid was a mixture of a prepolymer having an average molecular weight of 1000 and bis (4-methacryloylthiophenyl) sulfide.

Example 1 In the general formula (Formula 1), R ¹ = R ² = R ³ = R ⁴ = H, n =
Bis (4-vinylthiophenyl) sulfide 1 which is 0
20 parts by weight of 1,3-butylene glycol dimethacrylate, 17 parts by weight of glycidyl methacrylate, 2 parts by weight of benzyl dimethyl ketal as a curing agent, and γ-
Mix 2 parts by weight of aminopropyltrimethoxysilane,
An ultraviolet curable resin composition (1) having a refractive index of 1.65 was prepared by filtering with a filter having a pore size of 0.1 μm.
The refractive index is a wavelength of 633 nm by the prism coupler method.
It was measured at. The ultraviolet curable resin composition (1) prepared in this example was applied onto a silicon substrate by spin coating to form 20
The layers were laminated to a thickness of μm and irradiated with ultraviolet rays having a light intensity of 10 mW / cm ² for 10 minutes to be cured. Next, in the general formula (Formula 1),
R ¹ = R ² = R ³ = R ⁴ = H, bis (4-
100 parts by weight of vinylthiophenyl) sulfide, 1,
20 parts by weight of 3-butylene glycol dimethacrylate,
Add 10 parts by weight of glycidyl methacrylate and 2 parts by weight of benzyl dimethyl ketal as a curing agent to give a refractive index of 1.6.
The ultraviolet curable resin composition (2) of 6 was prepared, and this resin was laminated by a spin coating method to a thickness of 10 μm. A resist pattern having a width of 8 μm was formed thereon by a photo process, reactive reactive ion etching in oxygen gas was performed, and then the resist was removed to form a core portion of the optical waveguide. Further, the ultraviolet curable resin composition (1) prepared in this example was laminated by a spin coating method to a thickness of 20 μm, and irradiated with ultraviolet rays having a light amount of 10 mW / cm ² for 10 minutes to be cured. The optical loss of the optical waveguide manufactured in this example was 0.50 dB / cm when examined with a semiconductor laser having a wavelength of 1300 nm.

Example 2 In the general formula (Formula 1), R ¹ = R ² = R ³ = R ⁴ = H, n =
Bis (4-vinylthiophenyl) sulfide 1 which is 0
00 parts by weight, 28 parts by weight of glycidyl methacrylate,
2 parts by weight of benzoyl peroxide as a curing agent and 2 parts by weight of γ-mercaptopropyltrimethoxysilane were blended,
A thermosetting resin composition (3) having a refractive index of 1.68 was prepared by filtering with a filter having a pore size of 0.1 μm. The refractive index was measured at a wavelength of 633 nm by the prism coupler method. The thermosetting resin composition (3) prepared in this example was laminated on a silicon substrate to a thickness of 20 μm by a spin coating method, and heat-cured at 100 ° C. for 2 hours. Next, in the general formula (Formula 1), R ¹ = R ² = R ³ = R ⁴ = H, n = 0
Bis (4-vinylthiophenyl) sulfide 10 which is
13 parts by weight of glycidyl methacrylate and 2 parts by weight of benzoyl peroxide as a curing agent were mixed with 0 parts by weight to prepare a thermosetting resin composition (4) having a refractive index of 1.69, and this resin was spin-coated by a spin coating method. Laminated to a thickness of 10 μm. A resist pattern having a width of 8 μm was formed thereon by a photo process, reactive reactive ion etching in oxygen gas was performed, and then the resist was removed to form a core portion of the optical waveguide. Furthermore, the thermosetting resin composition (3) prepared in this example was laminated by a spin coating method to a thickness of 10 μm, and heat-cured at 100 ° C. for 2 hours. When the optical loss of the optical waveguide manufactured in this example was examined with a semiconductor laser having a wavelength of 1300 nm, it was 0.45 dB.
/ Cm.

Example 3 In the general formula (Formula 1), R ¹ = R ² = R ³ = R ⁴ = H, n =
Bis (4-vinylthiophenyl) sulfide 1 which is 0
80 parts by weight of 1,3-butylene glycol dimethacrylate, 70 parts by weight of glycidyl methacrylate, 2 parts by weight of benzyl dimethyl ketal as a curing agent, and γ-
Mix 2 parts by weight of aminopropyltrimethoxysilane,
An ultraviolet curable resin composition (5) having a refractive index of 1.61 was prepared by filtering with a filter having a pore size of 0.5 μm.
The ultraviolet curable resin composition (5) prepared in this example was laminated on a silicon substrate by a spin coating method to a thickness of 10 μm and irradiated with ultraviolet rays having a light intensity of 10 mW / cm ² for 10 minutes to be cured. A clad layer was formed. Next, the following formula (Formula 4):

[0035]

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[Wherein R is the following formula (Formula 5):

[0037]

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A non-linear material (having a refractive index of 1.62 and a 10% chloroform solution) represented by the following formula is applied and dried (at a temperature of 90 ° C.) to form a core layer (thickness: 5 μm). The core ridge is formed by the RIE method by the photo process as in the second embodiment (core width 5 μm, height 5).
μm). Further, the ultraviolet curable resin composition (5) used for the lower clad was applied thereon to prepare a buried type nonlinear waveguide having a 5 μm square cross section. Wavelength 1.3 μm
The optical loss was measured with a semiconductor laser of 1 dB / c
It was confirmed that the single mode operation was performed at about m. Also,
When a 1.3 μm Nd: YAG laser beam was introduced,
Self-phase modulation, which is a third-order nonlinear phenomenon, can also be confirmed, and the nonlinear refractive index n ₂ converted from it is 5 × 10 to 12 cm.
It was about ² / W.

[0039]

As described above, since the present invention uses a core material or a clad material that does not use a solvent, the problem due to the solvent is solved and the waveguide forming process is simplified. Further, since the planarization is easy, it is possible to realize an optical waveguide capable of multilayer optical wiring.

[Brief description of drawings]

FIG. 1 is a process drawing showing an example of a method for manufacturing an optical waveguide of the present invention.

[Explanation of symbols]

A: substrate, B: lower clad, C: core layer, D: resist, E: mask, F: side and upper clads

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Masahito Nakano 1 346, Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Sumitomo Seika Co., Ltd. (72) Inventor, Katsumasa Yamamoto 1-346, Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture In Sumitomo Seika Co., Ltd. (72) Inventor Michio Suzuki 1 at 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Sumitomo Seika Co., Ltd.

Claims (5)

[Claims] 1. A liquid ultraviolet curable resin composition or thermosetting resin composition in which a core portion or a clad portion of an optical waveguide can be controlled in a range of a refractive index of 1.52 to 1.74 and can be applied without a solvent. An optical waveguide characterized by being formed from a material. 2. An ultraviolet curable resin composition or a thermosetting resin composition has the following formulas (A) to (C): (A) The following general formula (Formula 1): (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different,
A vinyl sulfide compound represented by hydrogen, halogen, or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 0 to 10, (B) the following general formula (Formula 2): (In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different,
A methacrylic acid derivative represented by hydrogen, halogen, or an alkyl group having 1 to 6 carbon atoms), (C) a methacrylic acid derivative represented by the above general formula (Formula 2), and the following general formula (Formula 2) 3): Vinyl compound containing at least one sulfur selected from the group consisting of a prepolymer obtained by addition reaction with a thiol represented by the formula (wherein, m represents an integer of 1 to 4) 2. The optical waveguide according to claim 1, wherein the optical waveguide is composed of 100 parts by weight and 500 parts by weight or less of a vinyl compound containing no sulfur. 3. The optical waveguide according to claim 2, wherein R ¹ , R ² , R ³ and R ⁴ of the vinyl sulfide compound represented by the general formula (Formula 1) are hydrogen. 4. The optical waveguide according to claim 2, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ of the methacrylic acid derivative represented by the general formula (Formula 2) are hydrogen. 5. The prepolymer has a mercapto group of a thiol represented by the general formula (Formula 3) in a functional group equivalent ratio of 0 with respect to a methacryloyl group of a methacrylic acid derivative represented by the general formula (Formula 2). 3. The optical waveguide according to claim 2, which is obtained by an addition reaction in the range of 0.05 to 1.0.