JP2006143835A - Radiation-curing resin composition, optical waveguide using the same and manufacturing method of the optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition capable of forming an optical waveguide pattern which is excellent in pattern precision and shape and is excellent in heat resistance and optical transparency, and a patten formation method whereby a fine pattern excellent in pattern precision and shape can be easily formed at a low cost. <P>SOLUTION: The radiation-curing resin composition contains (A) a silicon polymer having a carbon-carbon unsaturated bond and a silicon-hydrogen bond within a molecule and (B) a photoacid generator. The pattern formation method comprises a step wherein the resin composition is applied on a substrate to form an applied surface and a step wherein a stamper mask formed in a prescribed shape is pressed against the applied surface and subjected to radiation to perform stamping molding. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation curable resin composition containing a silicon polymer and a photoacid generator, an optical waveguide using the same, and a method for producing an optical path.

  Optical waveguides are attracting attention as optical transmission media because of demands for large capacity and high speed information processing in optical communication systems and computers. In general, optical waveguide materials are required to have conditions such as low optical loss, ease of manufacture, heat resistance, and refractive index controllability. As a low-loss optical waveguide, a quartz-based optical waveguide is mainly studied. However, there is a problem that a high temperature is required when the waveguide is manufactured, a special manufacturing apparatus is required, and manufacturing time is long. In contrast, polymer-based waveguide materials utilize various physical properties such as thermo-optic effects, various form-forming properties that can be formed into films relatively easily, and low-cost processes with low temperature and low vacuum. As shown in Non-Patent Document 1 and Patent Document 1, for example, various materials and manufacturing processes have been developed in recent years.

As shown in the above-mentioned literature, the polymer optical waveguide manufacturing method includes a selective polymerization method, a method combining reactive ion etching and photolithography, a direct exposure method, an injection molding method, a photo bleaching method, and the like. Can be mentioned.
The method using reactive ion etching can provide high processing accuracy, but has a problem in productivity and economy because it undergoes a vacuum process. In addition, the direct exposure method and the photo bleaching method require exposure through a mask, and the former method requires subsequent development. Use expensive equipment such as an exposure machine and a developing device. In addition, there is a problem that a slightly complicated optical waveguide manufacturing process is required.

  By the way, in recent years, for example, in the field of semiconductor microfabrication, a method called nanoimprinting as described in Non-Patent Document 2 is a method for realizing fine lithography exceeding the diffraction limit of light. Proposed as a technology. If such a pattern formation method is applied, it is considered that an optical waveguide can be manufactured by a simpler process. However, even if a conventional polymer waveguide material is directly applied to such a pattern forming method, a high-definition and excellent pattern cannot be obtained.

JP 2002-277664 A Toru Maruyama: IEICE Technical Report PS2002-17,19 (2002-5) S.Y. Chou et al .: J. Vac. Sci. Technol., B14, 4129 (1966)

  In view of the above-described problems, the present invention provides a resin composition capable of obtaining a high-definition and excellent-shaped pattern when manufacturing an optical waveguide by a pattern formation method using a fine lithography technique such as nanoimprinting. An object of the present invention is to provide a product, an optical waveguide using the resin composition, and a method for manufacturing the optical waveguide.

The present inventor uses (A) a radiation curable resin composition containing a silicon polymer having a carbon-carbon unsaturated bond and a silicon-hydrogen bond in the molecule and (B) a photoacid generator, or ( C) silicon polymer having a carbon-carbon unsaturated bond in the molecule, (D) a resin composition containing a silicon polymer having a silicon-hydrogen bond in the molecule, and (B) a radiation curable resin containing a photoacid generator It has been found that by using the composition, a high-definition and excellent pattern can be obtained when an optical waveguide is produced by a pattern forming method such as nanoimprinting. The present invention has been completed based on this finding.
That is, the present invention
(1) A radiation curable resin composition containing (A) a silicon polymer having a carbon-carbon unsaturated bond and a silicon-hydrogen bond in the molecule, and (B) a photoacid generator,
(2) (A) In the above (1), the silicon polymer is obtained by hydrolyzing and co-condensing a silicon compound represented by the following general formula (I) and a silicon compound represented by the following general formula (II). The radiation curable resin composition according to the description,
R ¹ -SiX ₃ (I)
(R ¹ is a group having a carbon-carbon unsaturated bond, and X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms).)
H-SiX ₃ (II)
(X is the same as above.)
(3) A radiation curable resin composition containing (C) a silicon polymer having a carbon-carbon unsaturated bond in the molecule, (D) a silicon polymer having a silicon-hydrogen bond in the molecule, and (B) a photoacid generator. object,
(4) (C) A silicon polymer having a carbon-carbon unsaturated bond in the molecule is obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (I). (D) In the molecule The radiation curable resin composition according to the above (3), wherein the silicon polymer having a silicon-hydrogen bond is obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (II):
R ¹ -SiX ₃ (I)
(R ¹ is a group having a carbon-carbon unsaturated bond, and X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms).)
H-SiX ₃ (II)
(X is the same as above.)
(5) R ¹ is selected from a vinyl group or a deuterium substitute thereof, a styryl group or a deuterium substitute or fluorine substitute thereof, a (meth) acryloyl group or a deuterium substitute thereof, an ethynyl group or a deuterium substitute thereof. The radiation curable resin composition according to the above (2) or (4), which is at least one kind
(6) In the optical waveguide including the lower cladding layer, the core portion, and the upper cladding layer, at least one of the lower cladding layer, the core portion, and the upper cladding layer is the radiation according to any one of (1) to (5) above. Optical waveguide which is hardened | cured material of curable resin composition, and the process of apply | coating (7) the radiation-curable resin composition in any one of said (1)-(5) on a board | substrate, and forming an application surface. And a method of manufacturing an optical waveguide including a molding step of pressing, exposing and curing a stamper mask formed in a predetermined shape against the coated surface,
Is to provide.

  According to the resin composition of the present invention, a fine pattern can be formed by a simple method, and an optical waveguide excellent in accuracy and shape of the formed pattern, particularly excellent in heat resistance and light transmittance can be produced. The optical waveguide of the present invention is also excellent in birefringence, and is widely applied to optical waveguides, optical waveguide devices, optical integrated circuits, optical wiring boards, etc. widely used in optical communication, optical information processing or other optical fields. can do. Furthermore, according to the manufacturing method of the present invention, the high-performance optical waveguide can be manufactured easily and at low cost.

The radiation curable resin composition of the present invention contains a silicon polymer. Here, the silicon polymer is a polymer containing a silicon atom, and includes a substituted or unsubstituted polysiloxane and a polysilane in which carbon in the carbon-based organic polymer is replaced with a silicon atom. In the present invention, among these silicon polymers, those having a polysiloxane skeleton are preferred.
The radiation curable resin composition of the present invention comprises (A) a silicon polymer having a carbon-carbon unsaturated bond and a silicon-hydrogen bond in the molecule (hereinafter referred to as “silicon polymer A”).
Although there are various types of silicon polymer A, for example, those obtained by hydrolyzing and co-condensing the following general formula (I) and the following general formula (II) are preferable.
R ¹ -SiX ₃ (I)
H-SiX ₃ (II)
Here, R ¹ is a group having a carbon-carbon unsaturated bond. More specifically, R ¹ is a vinyl group or a deuterium substitute thereof, a styryl group or a deuterium substitute thereof or a fluorine substitute, or a (meth) acryloyl group. Or it is preferable that it is at least 1 sort (s) chosen from the deuterium substitution thing, an ethynyl group, or its deuterium substitution thing. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms).
By the hydrolysis / cocondensation, a silsesquioxane compound containing both a carbon-carbon unsaturated bond and a silicon-hydrogen bond in the molecule is synthesized. In synthesizing the silicon polymer A, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane or the like can be used as a terminal silanol sealant.

  The mixing ratio of the silicon compounds represented by the general formulas (I) and (II) in the hydrolysis / co-condensation is not particularly limited, but from the viewpoint of pattern formation efficiency, carbon-carbon unsaturation The number of bonds and the number of silicon-hydrogen bonds are preferably 10: 1 to 1:10 as molar equivalents, more preferably 7: 3 to 3: 7, and particularly preferably the molar equivalents are the same amount. .

As the solvent used in the condensation reaction of the silicon compounds represented by the above general formulas (I) and (II), various solvents can be used, for example, aromatic solvents such as toluene and xylene and hydrophilic solvents. For example, alcohols such as ethanol, methanol, and 2-propanol, ketones such as acetone and methyl ethyl ketone, and ethers such as dioxane and tetrahydrofuran can be mixed and used. These solvents can be used alone or in combination of two or more.
In addition, in the hydrolysis / condensation reaction of the silicon compounds represented by the general formulas (I) and (II), an inorganic acid such as hydrochloric acid or phosphoric acid or an organic acid such as oxalic acid may be used as a catalyst. it can.

  The weight average molecular weight (Mw) of the silicon polymer A synthesized as described above is preferably in the range of 800 to 200,000. When the weight average molecular weight is 800 or more, sufficient heating / curing property is obtained, and when the weight average molecular weight is 200,000 or less, sufficient mold transfer property is obtained. From the above viewpoint, the weight average molecular weight is preferably in the range of 1,000 to 10,000, and more preferably in the range of 3,000 to 8,000. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

  The resin composition for pattern formation of the present invention includes (C) a silicon polymer having a carbon-carbon unsaturated bond in the molecule (hereinafter referred to as “silicon polymer B”), and (D) a silicon-hydrogen bond in the molecule. Also included are those containing a silicon polymer having the following (hereinafter referred to as “silicon polymer C”). That is, a resin composition obtained by mixing silicon polymer B and silicon polymer C is also included in the resin composition for pattern formation of the present invention. In this case, the mixing ratio of the silicon polymer B and the silicon polymer C is not particularly limited as long as the effect of the present invention is achieved. However, the number of carbon-carbon unsaturated bonds and the number of silicon-hydrogen bonds are expressed as molar equivalents. The ratio is preferably 10: 1 to 1:10, more preferably 7: 3 to 3: 7, and particularly preferably the molar equivalent is the same amount from the viewpoint of pattern formation efficiency. Furthermore, a resin composition obtained by mixing silicon polymer A, silicon polymer B, and silicon polymer C is also included in the scope of the present invention.

As the silicon polymer B, there are various compounds, but those obtained by hydrolyzing and condensing the silicon compound represented by the general formula (I) are preferable. R ¹ and X are the same as those described above.
By this hydrolysis and condensation, a silsesquioxane compound containing a carbon-carbon unsaturated bond in the molecule is usually synthesized. In synthesizing the silicon polymer B, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, or the like can be used as a terminal silanol sealant.

Next, there are various compounds with respect to the silicon polymer C, but the silicon compound represented by the general formula (II) is preferably hydrolyzed and condensed. X is the same as above.
By this hydrolysis and condensation, a silsesquioxane compound containing a silicon-hydrogen bond in the molecule is usually synthesized. It should be noted that hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, and the like can also be used as the terminal silanol sealant during the synthesis of the silicon polymer C.

  The weight average molecular weights (Mw) of the silicon polymer B and the silicon polymer C are in the range of 800 to 200,000, more preferably in the range of 1,000 to 10,000, particularly 3 for the same reason as the silicon polymer A. It is preferably within the range of 8,000 to 8,000. Further, as the solvent and the catalyst in the hydrolysis / condensation of the silicon polymer B and the silicon polymer C, the same solvents and catalysts as those described for the silicon polymer A can be suitably used.

Next, the photoacid generator (B) in the radiation curable resin composition of the present invention can be used to crosslink the silicon polymers as the components (A), (C) and (D) by light irradiation. Refers to a compound that produces an acidic active substance.
Specific examples include onium compounds such as diaryl iodonium salts, triaryl sulfonium salts, aryl diazonium salts, imide sulfonate derivatives, tosylate compounds, carbonate compounds of benzyl derivatives, and halides of triazine derivatives.

The diaryl iodonium salt has the following general formula (III)
_{^{Ar 2 I + Y - ··· (}} III)
[Wherein Ar represents an aryl group and Y ⁻ represents an anionic group]. The cation in the diaryliodonium salt represented by the general formula (III) is not particularly limited, and examples thereof include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-methoxyphenyl) iodonium, and bis (4-t-butylphenyl). ) Iodonium and the like. Further, the anion Y ⁻ is not particularly limited, and for example, naphthalene derivatives such as naphthalene-1-sulfonate, naphthalene-2-sulfonate, 2-t-butylnaphthalene-2-sulfonate, anthracene-1-sulfonate, anthracene-2- Sulfonate, 9-nitroanthracene-1-sulphonate, 5,6-dichloroanthracene-3-sulphonate, 9,10-dichloroanthracene-2-sulphonate, 9,10-dimethoxyanthracene-2-sulphonate, 9,10-diethoxy Anthracene derivatives such as anthracene-2-sulfonate, benz [a] anthracene-4-sulfonate, phenanthrene-2-sulfonate, pyrenesulfonate, triphenylene-2-sulfonate, chrysene-2-sulfonate, anthra Examples include anions having other polycyclic structures such as nonsulfonates, trifluoromethanesulfonate, hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, benzenesulfonate, etc. Among these, anthracene derivatives and trifluoromethane Sulfonate is preferred.

Next, the triarylsulfonium salt has the general formula (IV)
_{^{Ar 3 S + Y - ··· (}} IV)
[Wherein Ar and Y are as defined above]. The cation in the triarylsulfonium salt represented by the general formula (IV) is not particularly limited. For example, triphenylsulfonium, methoxyphenyldiphenylsulfonium, bis (methoxyphenyl) phenylsulfonium, tris (methoxyphenyl) sulfonium, 4- Examples thereof include methylphenyldiphenylsulfonium, 2,4,6-trimethylphenyldiphenylsulfonium, 4-t-butylphenyldiphenylsulfonium, tris (4-t-butylphenyl) sulfonium, and the like. Specific examples of the anion are the same as those exemplified for the diaryl iodonium salt.

The aryldiazonium salt has the general formula (V)
_{^{ArN 2 + Y - ··· (V}} )
[Wherein Ar and Y are as defined above]. The cation in the aryldiazonium salt represented by the general formula (V) is not particularly limited, and examples thereof include 4-t-butoxybenzenediazonium, 4-methoxybenzenediazonium, 4-morpholinobenzenediazonium, 4-nitrobenzenediazonium, 4 -Methylbenzenediazonium and the like. Specific examples of the anion are the same as those exemplified for the diaryl iodonium salt.

Examples of the imide sulfonate derivative include trifluoromethanesulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethane sulfonate, and phthalimide trifluoromethane sulfonate.
Examples of the tosylate compound include benzyl derivatives such as benzyl tosylate, nitrobenzyl tosylate, and dinitrobenzyl tosylate.
Furthermore, examples of the carbonate compound of the benzyl derivative include benzyl carbonate derivatives such as benzyl carbonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate.
Examples of the halide of the triazine derivative include trichloromethyltriazine derivatives such as 2,4,6- (trichloromethyl) -s-triazine.

  (B) The usage-amount of a photo-acid generator should be the range of 0.5-20 mass parts normally with respect to 100 mass parts of silicon polymers which are (A), (C) and (D) component. preferable. Curing by radiation irradiation is sufficiently obtained when the amount is 0.5 parts by mass or more, and good light transmittance is obtained when the amount is 20 parts by mass or less. From the above viewpoint, the use ratio of the (B) photoacid generator is preferably 1 to 15 parts by mass, particularly preferably 1 to 10 parts by mass.

The composition of the present invention may contain additives such as a surfactant and an adhesion assistant in addition to the components (A) to (D). The addition of the surfactant makes it easy to apply the resulting composition and improves the smoothness of the film, and the addition of an adhesion assistant can improve the adhesion to the substrate.
The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant and a silicone-based surfactant. Specifically, for example, BM-1000 (manufactured by BM Chemie), Megafax F142D, F172, F173, and F183 (Dainippon Ink Chemical Co., Ltd.), Florard FC-135, FC-170C, Fluorad FC-430 and FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, S-113, S-131, S-141 and S-145 (manufactured by Asahi Glass Co., Ltd.), Fluorosurfactants such as SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.), alkylglyceryl ether-modified silicone, poly Oxyethylene-methylpolysiloxane copolymer, dimethicone polyol, alkyl dimethicone polio Silicone surfactants such as silicone and cross-linked alkyl polyether-modified silicones can be used.
The use ratio of the surfactant is usually preferably 5 parts by mass or less, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the silicon polymer as the components (A), (C) and (D). It is.

  Further, the adhesion aid is not particularly limited. For example, a titanate coupling agent, a silane compound having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, a vinyl group, an amino group, or a mercapto group ( Functional silane coupling agents). Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycid. Examples thereof include xylpropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The use ratio of the adhesion assistant is usually preferably 20 parts by mass or less, more preferably 0.05 parts per 100 parts by mass of the silicon polymer as the components (A), (C) and (D). -10 parts by mass, particularly preferably 0.5-10 parts by mass.

The composition of the present invention comprises the above-mentioned (A), (C) and (D) component silicon polymer, (B) component photoacid generator, and other additives added as necessary. Usually dissolved in an organic solvent and mixed uniformly.
The organic solvent used here is not particularly limited as long as it does not react with (A), (C) and (D) component silicon polymer and (B) the photoacid generator and dissolves them. However, an organic compound having a boiling point under atmospheric pressure in the range of 50 to 200 ° C. is preferable because of easy handling. Specific examples include ether organic solvents, ketone organic solvents, ester organic solvents, aromatic hydrocarbon organic solvents, alcohol organic solvents, and the like. These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
Specific examples of particularly preferable organic solvents among the organic solvents exemplified above include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl pentyl ketone, toluene, xylene and the like.
Moreover, it is preferable that the addition amount of an organic solvent shall be the range of 10-1900 mass parts with respect to 100 mass parts of whole quantity of a radiation curable resin composition. When the addition amount of the organic solvent is 10 parts by mass or more, the uniformity of the radiation curable resin composition can be obtained, and when the addition amount is 1900 parts by mass or less, a sufficiently thick optical waveguide is formed. Can do.
The resin composition of the present invention is usually filtered before use. Examples of the filtering means include use of a fluororesin filter having a pore diameter of 1.0 to 0.2 μm.

Next, the pattern forming method of the present invention will be described in detail below. The pattern formation method of the present invention is an imprint method performed using the resin composition of the present invention. Here, imprinting is a kind of stamping molding method, in which a pattern is formed by pressing a mold to be a transfer original pattern against a transfer material.
FIG. 1 shows a method of forming an optical waveguide pattern as an example of pattern formation by this method. First, the lower clad layer 2 is formed on the substrate 1, and the resin composition of the present invention is laminated thereon as the core layer 3. A mold mask (core shape mask 4) having a core shape to be formed here is pressed, irradiated with radiation, heated and cured while applying pressure, and then cooled as necessary to separate the mold mask, A core pattern is formed. Finally, an embedded optical waveguide is obtained by forming the upper clad 6 on this with a resin having a refractive index lower than that of the resin on which the optical waveguide core pattern is formed.

As shown in FIG. 1, the mold mask (core shape mask 4) has a pattern in which the necessary irregularities of the core pattern are reversed. The mold can be used for stamping, and any material can be used as long as it transmits the radiation to be irradiated. Usually, sapphire, diamond, quartz or the like is used as the inorganic material. In the case of an organic material, polyimide resin, polyamideimide resin, polyamide resin, polyester resin, polycarbonate resin, epoxy resin, fluororesin, polysulfone resin, silicone resin, or the like can be used.
For the production of the mold mask, processing methods such as ordinary photolithography, electron beam lithography, X-ray lithography and the like are used. Further, irregularities may be produced by ablation processing using a laser beam or the like and used as a mold mask. Further, a pattern produced by stamping molding may be used as a mold mask.

The radiation dose during molding is preferably 10 to 5000 mJ / cm ² . Visible light, ultraviolet rays, infrared rays, X-rays and the like can be used as the type of radiation to be irradiated, but ultraviolet rays are particularly preferable.
Moreover, it is preferable to carry out a heat treatment at the time of molding simultaneously with or after radiation irradiation to promote curing of the radiation curable resin composition, and the heating temperature is preferably 50 to 350 ° C. When it is 50 ° C. or higher, the curing reaction is sufficient, and when it is 350 ° C. or lower, there is no deterioration. From the above viewpoint, it is more preferably in the range of 80 to 200 ° C, and particularly preferably in the range of 90 to 150 ° C. The heating time is preferably 0.01 to 1 hour.

In order to improve the release after stamping, a release agent may be applied on the mold pattern or the transfer substrate.
Furthermore, an inert gas such as nitrogen, helium, or argon can be used as necessary, for example, by suppressing deterioration of the material or removing bubbles in the material, or the pattern can be formed in a vacuum.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Synthesis example 1
In a 200 mL separable flask, vinyltriethoxysilane (13.3 g, 70 mmol), triethoxysilane (11.5 g, 70 mmol), 1,1,2,2-tetramethyldisiloxane (0.67 g, 5 mmol), 2-propanol ( 30 g) and toluene (60 g) were charged. Under stirring at room temperature (25 ° C.), 8.3 g of hydrochloric acid (1.3%, HCl: 3 mmol, water: 450 mmol) was added over 5 minutes. After stirring and standing at room temperature overnight, the reaction solvent and the like were distilled off under reduced pressure in a water bath at 70 to 80 ° C. to obtain a colorless and transparent viscous liquid. This is dissolved in toluene, washed with water, acid is removed, dried over anhydrous sodium sulfate, and then the solvent is distilled off to form a colorless viscous liquid. As a carbon-carbon unsaturated bond, a vinyl group and silicon- A silicon polymer (silsesquioxane compound (hereinafter referred to as “VH-SQ”)) having a hydrogen bond in the molecule was obtained (yield: 9.8 g, yield: 98%).
GPC analysis of this compound revealed that the weight average molecular weight (Mw) was 5,500 and the molecular weight distribution (Mw / Mn) was 2.9. Here, Mn represents the number average molecular weight.
In the NMR spectrum of VH-SQ, the absorption derived from silicon-hydrogen bonded to the silsesquioxane skeleton at 4.2 to 4.5 ppm shows the methyl derived from 1,1,2,2-tetramethyldisiloxane at 0.2 to 0.3 ppm. Absorption based on vinyl groups was observed at 5.8-6.3 ppm. From the intensity of each NMR signal, it was found that the composition was as per the charge ratio.
In addition, as a result of measuring the infrared absorption spectrum, the absorption derived from the silicon-hydrogen bond bonded to the silsesquioxane skeleton is in the vicinity of 2250 cm ^{−1 in} the dimethylsilyl group originating from 1,1,2,2-tetramethyldisiloxane. Absorption due to silicon-hydrogen bonds was observed in the vicinity of 2140 cm ⁻¹ . Absorption due to the carbon-carbon double bond and carbon-hydrogen bond of the vinyl group was observed at 1600, 1410, and 970 cm ⁻¹ , and absorption due to the silicon-oxygen-silicon bond was observed near 1130 cm ⁻¹ . From these results, it was confirmed that this VH-SQ polymer had a carbon-carbon double bond and a silicon-hydrogen bond in the molecule.

Synthesis Examples 2 to 11
The silicon polymer according to the present invention was synthesized under the same conditions as in Synthesis Example 1 using the reagents shown in Table 1. About these silicon polymers, when it confirmed by the NMR spectrum and the infrared absorption spectrum similarly to the synthesis example 1, all the silicon polymers synthesize | combined by the synthesis examples 2-9 are a carbon-carbon unsaturated bond and silicon- in the molecule | numerator. It was a silicon polymer (polysilsesquioxanes) having hydrogen bonds. The silicon polymer synthesized by Synthesis Example 10 is a silicon polymer having a silicon-hydrogen bond in the molecule, and the silicon polymer synthesized by Synthesis Example 11 is a silicon polymer having a carbon-carbon unsaturated bond in the molecule. It was confirmed that. The molecular weight and molecular weight distribution of the silicon polymer obtained in each synthesis example are also shown in Table 1.

* 1 VH-SQ: vinyl-hydrogen-silsesquioxane * 2 St-H-SQ: styryl-hydrogen-silsesquioxane * 3 V-St-H-SQ: vinyl-styryl-hydrogen-sil Sesquioxane * 4 Ph-H-SQ: Phenyl-hydrogen-silsesquioxane * 5 V-Ph-H-SQ: Vinyl-phenyl-hydrogen-silsesquioxane * 6 VFH-SQ: Vinyl-fluoro -Hydrogen-silsesquioxane * 7 Acry-H-SQ: 3-acryloxypropyl-hydrogen-silsesquioxane * 8 H-SQ: hydrogen-silsesquioxane * 9 VF-SQ: vinyl- Fluoro-silsesquioxane * 10 TRIES: Triethoxysilane * 11 V-TRIES: Vinyltriethoxysilane * 12 V-TRIMS: Vinyltrimethoxysilane * 13 St-TRIMS: Styryltrimethoxysilane * 14 Ph-TRIMS: Phenyltrimethoxysilane * 15 F-TRIES: Fluorotriethoxysilane * 16 Acry-TRIMS: 3-acryloxypropyltrimethoxysilane * 17 TMDSO: 1,1,2,2-tetramethyldisiloxane

Example 1
Radiation curable by uniformly mixing 1.0 part by weight of triphenylsulfonium trifluoromethanesulfonate and 100 parts by weight of propylene glycol monomethyl ether as photoacid generators with 100 parts by weight of VH-SQ produced in Synthesis Example 1. A resin composition was prepared. The composition was applied on a silicon substrate to form a thin film having a thickness of about 100 μm. A quartz mold mask with a 50 μm / 50 μm line / space irregular shape imitating the core shape is pressed onto the surface of this thin film, pressed at 3 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. And cured for 0.05 hour. When the mold mask was removed after cooling, a space / line pattern of 50 μm / 50 μm in which the unevenness of the mask was reversed was formed. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. The refractive index (1300 nm) of this heat-cured film was 1.4572 in the TE mode and 1.4570 in the TM mode, and the birefringence was as small as 0.0002. The TE mode (Transvers Electric mode) is a wave whose electric field vector is perpendicular to the light propagation axis (direction), and the TM mode (Transvers Magnetic mode) is a magnetic field vector perpendicular to the light propagation axis (direction). Say waves.
The optical waveguide loss was 0.1 dB / cm at 1300 nm, and it was found that the optical loss was extremely small. Furthermore, the decomposition temperature (5% mass reduction temperature) measured by TG-DTA (manufactured by Seiko Denshi) was 488 ° C., and the mass loss rate at 800 ° C. was 9.8%, indicating a very high thermal stability. As described above, the radiation curable resin composition containing the VH-SQ polymer is excellent in transparency and heat resistance, does not require a development process, can be formed in a short time, and can be formed by a simple manufacturing process. It has been found that it is useful as an optical waveguide material.

Example 2
The radiation curable resin composition prepared in Example 1 was applied on a silicon substrate to form a thin film having a thickness of about 10 μm. A mold mask having a 5 μm / 5 μm line / space concavo-convex shape imitating the core shape is pressed onto the surface of the thin film, pressed at 5 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. Heated and cured for 05 hours. After cooling, when the mold mask was removed, a space / line pattern of 5 μm / 5 μm in which the unevenness of the mask was reversed was formed. As in Example 1, the shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed.

Example 3
A radiation curable resin composition was prepared in the same manner as described in Example 1, except that VH-SQ produced in Synthesis Example 2 was used instead of VH-SQ produced in Synthesis Example 1. . A space / line pattern was formed using the composition in the same manner as in Example 2. As in Example 2, the shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed.

Example 4
To 100 parts by mass of V-St-H-SQ of Synthesis Example 4, 1.0 part by mass of triphenylsulfonium trifluoromethanesulfonate and 100 parts by mass of propylene glycol monomethyl ether as a photoacid generator were mixed uniformly to produce radiation. A curable resin composition was prepared. The composition was applied on a silicon substrate to form a thin film having a thickness of about 100 μm. A quartz mold mask with a 50 μm / 50 μm line / space irregular shape imitating the core shape is pressed onto the surface of this thin film, pressed at 3 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. And cured for 0.05 hour. When the mold mask was removed after cooling, a space / line pattern of 50 μm / 50 μm in which the unevenness of the mask was reversed was formed. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. The refractive index (1300 nm) of this heat-cured film was 1.5291 in the TE mode and 1.5290 in the TM mode, and the birefringence was as small as 0.0001. The optical waveguide loss was 0.15 dB / cm at 1300 nm, and it was found that the optical loss was extremely small. Furthermore, the decomposition temperature (5% mass reduction temperature) measured with TG-DTA (manufactured by Seiko Denshi) was 490 ° C., and the mass loss rate at 800 ° C. was 30%, indicating extremely high thermal stability. As described above, the resin composition containing V-St-H-SQ is excellent in transparency and heat resistance, can be patterned by a simple production process, and is found to be useful as an optical waveguide material. It was.

Example 5
To 100 parts by mass of V-Ph-H-SQ in Synthesis Example 6, 1.0 parts by mass of triphenylsulfonium trifluoromethanesulfonate and 100 parts by mass of propylene glycol monomethyl ether as a photoacid generator were uniformly mixed to produce radiation. A curable resin composition was prepared. The composition was applied on a silicon substrate to form a thin film having a thickness of about 10 μm. A mold mask having a 5 μm / 5 μm line / space concavo-convex shape imitating the core shape is pressed onto the surface of the thin film, pressed at 5 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. Heated and cured for 05 hours. After cooling, when the mold mask was removed, a space / line pattern of 5 μm / 5 μm in which the unevenness of the mask was reversed was formed. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. The refractive index (1300 nm) of this heat-cured film was 1.4926 in the TE mode and 1.4924 in the TM mode, and the birefringence was as small as 0.0002. The optical waveguide loss was 0.15 dB / cm at 1300 nm, and it was found that the optical loss was extremely small. Furthermore, the decomposition temperature (5% mass reduction temperature) measured by TG-DTA (manufactured by Seiko Denshi) was 490 ° C., and the mass loss rate at 800 ° C. was 28%, indicating extremely high thermal stability. As described above, the radiation curable resin composition containing the V-Ph-H-SQ polymer is excellent in transparency and heat resistance, can be patterned by a simple production process, and is useful as an optical waveguide material. I found out.

Example 6
To 100 parts by mass of VFH-SQ in Synthesis Example 7, 1.0 part by mass of triphenylsulfonium trifluoromethanesulfonate and 100 parts by mass of propylene glycol monomethyl ether as a photoacid generator are uniformly mixed to form a radiation curable resin composition. Using the product, a pattern was formed in the same manner as in Example 2. A space / line pattern of 5 μm / 5 μm was formed, and the shape of the transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that a good pattern was formed with a straight edge portion. The refractive index (1300 nm) of this heat-cured film was 1.44461 in the TE mode and 1.4460 in the TM mode, and the birefringence was as extremely small as 0.0001. The optical waveguide loss was 0.1 dB / cm at 1300 nm, and it was found that the optical loss was extremely small. Thus, it was found that the radiation curable resin composition containing the VFH-SQ polymer is excellent in transparency, can be patterned by a simple manufacturing process, and is useful as an optical waveguide material.

Example 7
A space / line pattern was formed in the same manner as in Example 6 except that VFH-SQ produced in Synthesis Example 8 was used instead of VFH-SQ in Synthesis Example 7. As in Example 6, the shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed.

Example 8
To 100 parts by mass of Acry-H-SQ in Synthesis Example 9, 1.0 part by mass of triphenylsulfonium trifluoromethanesulfonate and 100 parts by mass of propylene glycol monomethyl ether as a photoacid generator are uniformly mixed, and radiation curable. A pattern was formed in the same manner as in Example 1 using the resin composition. A space / line pattern of 50 μm / 50 μm was formed, and the shape of the transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that a good pattern was formed with a straight edge portion. As described above, the radiation-curable resin composition containing the Acry-H-SQ polymer can be patterned by a simple production process as in Example 1, and is found to be useful as an optical waveguide material. It was.

Example 9
100 parts by mass of H-SQ of Synthesis Example 10 and VF-SQ of Synthesis Example 11 mixed in equimolar amounts, 1.0 parts by mass of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator, propylene glycol acetate 100 parts by mass of monomethyl ether were uniformly mixed, and a pattern was formed in the same manner as in Example 1 using the radiation curable resin composition. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. In this way, a VF-SQ polymer having a vinyl group as a carbon-carbon unsaturated bond group and an H-SQ polymer having a silicon-hydrogen bond are mixed, and a radiation curable resin composition is combined with a photoacid generator. Even when configured, it was shown that a pattern can be formed in the same manner as a silicon polymer having these carbon-carbon unsaturated bond groups and silicon-hydrogen bond groups in a single molecule.

Example 10
100 parts by mass of St-H-SQ in Synthesis Example 3 are mixed uniformly with 1.0 part by mass of triphenylsulfonium trifluoromethanesulfonate and 100 parts by mass of propylene glycol monomethyl ether as a photoacid generator, and are radiation curable. A resin composition was obtained. The composition was applied on a silicon substrate to form a thin film having a thickness of about 10 μm. A mold mask having a 5 μm / 5 μm line / space concavo-convex shape imitating the core shape is pressed onto the surface of the thin film, pressed at 5 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. Heated and cured for 05 hours. After cooling, when the mold mask was removed, a space / line pattern of 5 μm / 5 μm in which the unevenness of the mask was reversed was formed. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. The refractive index (1300 nm) of this heat-cured film was 1.5405 in the TE mode and 1.5391 in the TM mode, and the birefringence was as small as 0.0014.
The optical waveguide loss was 0.15 dB / cm at 1300 nm, and it was found that the optical loss was extremely small. Furthermore, the decomposition temperature (5% mass reduction temperature) measured with TG-DTA (manufactured by Seiko Denshi) was 499 ° C., indicating extremely high thermal stability. Thus, the radiation curable resin composition containing the St—H—SQ polymer can be patterned by a simple production process, as in Example 1, and is useful as an optical waveguide material. I understood.

Example 11
100 parts by mass of Ph-H-SQ of Synthesis Example 5 and VF-SQ of Synthesis Example 11 mixed in equimolar amounts, 1.0 parts by mass of triphenylsulfonium trifluoromethanesulfonate as acetic acid generator, acetic acid 100 parts by mass of propylene glycol monomethyl ether was uniformly mixed to obtain a radiation curable resin composition. The composition was applied on a silicon substrate to form a thin film having a thickness of about 10 μm. A mold mask having a 5 μm / 5 μm line / space concavo-convex shape imitating the core shape is pressed onto the surface of the thin film, pressed at 5 MPa, and irradiated with 300 mJ / cm ² of ultraviolet light at 120 ° C. Heated and cured for 05 hours. After cooling, when the mold mask was removed, a space / line pattern of 5 μm / 5 μm in which the unevenness of the mask was reversed was formed. The shape of the core transfer pattern was rectangular by observation with a scanning electron microscope, and it was found that the edge portion was linear and a good pattern was formed. Thus, a radiation-curable resin composition is prepared by mixing a VF-SQ polymer having a vinyl group as a carbon-carbon unsaturated bond group and a Ph-H-SQ polymer having a silicon-hydrogen bond and combining with a photoacid generator. It was shown that even when the product was constituted, it was possible to form a pattern in the same manner as a silicon polymer having these carbon-carbon unsaturated bond groups and silicon-hydrogen bond groups in a single molecule.

  According to the resin composition of the present invention, a fine pattern can be formed by a simple method, and an optical waveguide pattern excellent in accuracy and shape of the formed pattern, particularly excellent in heat resistance and light transmittance can be formed. . Further, according to the pattern forming method of the present invention, a fine pattern excellent in pattern accuracy and shape can be formed easily and at low cost, and an excellent effect can be exhibited particularly in the manufacture of an optical waveguide.

It is a schematic diagram which shows the process of forming an optical waveguide pattern.

Explanation of symbols

1. Substrate 2. Lower cladding 3. Core layer 4. 4. Core shape mask Core 6. Upper cladding

Claims (7)

  (A) A radiation curable resin composition containing a silicon polymer having a carbon-carbon unsaturated bond and a silicon-hydrogen bond in the molecule, and (B) a photoacid generator. The radiation curing according to claim 1, wherein (A) the silicon polymer is obtained by hydrolyzing and cocondensing a silicon compound represented by the following general formula (I) and a silicon compound represented by the following general formula (II). Resin composition.
R ¹ -SiX ₃ (I)
(R ¹ is a group having a carbon-carbon unsaturated bond, and X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms).)
H-SiX ₃ (II)
(X is the same as above.)   A radiation curable resin composition comprising (C) a silicon polymer having a carbon-carbon unsaturated bond in the molecule, (D) a silicon polymer having a silicon-hydrogen bond in the molecule, and (B) a photoacid generator. (C) A silicon polymer having a carbon-carbon unsaturated bond in the molecule is obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (I). (D) Silicon-hydrogen in the molecule The radiation curable resin composition according to claim 3, wherein the silicon polymer having a bond is obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (II).
R ¹ -SiX ₃ (I)
(R ¹ is a group having a carbon-carbon unsaturated bond, and X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms).)
H-SiX ₃ (II)
(X is the same as above.) R ¹ is at least one selected from a vinyl group or a deuterium substitute thereof, a styryl group or a deuterium substitute or fluorine substitute thereof, a (meth) acryloyl group or a deuterium substitute thereof, an ethynyl group or a deuterium substitute thereof. The radiation curable resin composition according to claim 2, which is a seed.   In the optical waveguide including the lower cladding layer, the core portion, and the upper cladding layer, at least one of the lower cladding layer, the core portion, and the upper cladding layer is formed of the radiation curable resin composition according to any one of claims 1 to 5. An optical waveguide that is a cured product. A step of applying a radiation curable resin composition according to any one of claims 1 to 5 on a substrate to form an application surface, and pressing a stamper mask formed in a predetermined shape against the application surface The manufacturing method of the optical waveguide including the formation process which exposes and hardens | cures.

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