JP2006169391A - Radiation-curable resin composition, optical waveguide using the same and method for manufacturing optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-curable resin composition which enables obtaining a high-definition pattern excellent in the shape in preparing an optical waveguide by the pattern-forming method using a fine lithography technique and has excellent storage stability, an optical waveguide using the resin composition, and a method for manufacturing an optical waveguide. <P>SOLUTION: The radiation-curable resin composition comprises a silicone polymer having a carbon-carbon unsaturated bond, a silicon-hydrogen bond, and an oxetanyl group in the molecule, a photoacid generator, and a dehydrating agent. The optical waveguide comprises a bottom clad layer, a core portion, and a top clad layer, and at least one of the bottom clad layer, core portion, and top clad layer is the above radiation-curable resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation curable resin composition, an optical waveguide using the same, and a method for manufacturing the optical waveguide.

  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 light loss, heat resistance, refractive index controllability, and ease of manufacture. 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 can be used for various physical properties such as thermo-optic effects, various forms forming properties such as film formation, and low-cost processes with low temperature and low vacuum. There is a feature in economic efficiency such as being possible, and 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 is produced by a selective polymerization method, a method combining reactive ion etching and photolithography, a direct exposure method, an injection molding method, a photo bleaching method, or 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. The direct exposure method and photo bleaching method require exposure through a mask, and the former requires subsequent development. In addition to using expensive equipment such as an exposure machine and a development device, a slightly complicated optical waveguide is produced. There was a problem that the process was 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 new 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 problems, the present invention makes it possible to obtain a high-definition and excellent-shaped pattern when producing an optical waveguide by a pattern formation method using a fine lithography technique such as nanoimprinting and storage. An object of the present invention is to provide a radiation curable resin composition excellent in stability, an optical waveguide using the resin composition, and a method for producing the optical waveguide.

  The present inventor can use a resin composition containing a silicon polymer having a carbon-carbon unsaturated bond, a silicon-hydrogen bond and an oxetanyl group in the molecule, a photoacid generator and a dehydrating agent, or in the molecule. -By using a silicon polymer having a carbon unsaturated bond, a silicon polymer having a silicon-hydrogen bond in the molecule and a silicon polymer having an oxetanyl group in the molecule, a photoacid generator and a dehydrating agent, It has been found that a high-definition and excellent pattern can be obtained when producing an optical waveguide by a pattern forming method such as nanoimprinting. Moreover, this resin composition is excellent in storage stability. The present invention has been completed based on this finding.

That is, the present invention
[1] The present invention relates to a radiation curable resin composition comprising a silicon polymer having a carbon-carbon unsaturated bond, a silicon-hydrogen bond and an oxetanyl group in a molecule, a photoacid generator and a dehydrating agent.
The present invention also provides [2] a silicon compound in which the silicon polymer is represented by the following general formula (I), a silicon compound represented by the following general formula (II), and a silicon represented by the following general formula (III) It is related with the radiation-curable resin composition as described in said [1] which is what hydrolyzed and co-condensed the compound.

[一般式(I)中、Ｒ^１は炭素‐炭素不飽和結合を有する基であり、ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。]

[In General Formula (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). ]

[一般式(II)中、ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。）

[In the general formula (II), X represents halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). )

[一般式(III)中、Ｙはオキセタニル基とケイ素を接続する基であって、−（ＣＲ^８Ｒ^９）_ｍ−あるいは−（ＣＲ^１０Ｒ^１１）_ｎ−Ｔ−（ＣＲ^１２Ｒ^１３）_ｐ−を表し、Ｔは−Ｏ−、−Ｃ（Ｏ）−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＳｉＲ^１４Ｒ^１５−を表す。Ｒ^３〜Ｒ^１５は同一、または異なり、水素原子、炭素数１〜１０の炭化水素基あるいはハロゲン化炭化水素基を表し、ｍ、ｎ、ｐは、それぞれ０〜６の整数を表す。ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。]
また、本発明は、［３］ 分子内に炭素-炭素不飽和結合を有するシリコンポリマ、分子内にケイ素‐水素結合を有するシリコンポリマ及び分子内にオキセタニル基を有するシリコンポリマ、光酸発生剤及び脱水剤を含有することを特徴とする放射線硬化性樹脂組成物に関する。
また、本発明は、［４］ 分子内に炭素-炭素不飽和結合を有するシリコンポリマが下記一般式（I）で表されるケイ素化合物を加水分解し、縮合させたものであり、分子内にケイ素‐水素結合を有するシリコンポリマが下記一般式（II）で表されるケイ素化合物を加水分解し、縮合させたものであり、分子内にオキセタニル基を有するシリコンポリマが下記一般式（III）で表されるケイ素化合物加水分解し、縮合させたものである上記［３］に記載の放射線硬化性樹脂組成物に関する。

[In General Formula (III), Y is a group that connects an oxetanyl group and silicon, and-(CR ⁸ R ⁹ ) _m- or-(CR ¹⁰ R ¹¹ ) _n -T- (CR ¹² R ¹³ ) _p - represents, T is -O -, - C (O) -, - OC (O) -, - C (O) O -, - SiR 14 R 15 - represents a. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). ]
The present invention also provides [3] a silicon polymer having a carbon-carbon unsaturated bond in the molecule, a silicon polymer having a silicon-hydrogen bond in the molecule, a silicon polymer having an oxetanyl group in the molecule, a photoacid generator, and The present invention relates to a radiation curable resin composition containing a dehydrating agent.
The present invention also provides: [4] 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). A silicon polymer having a silicon-hydrogen bond is obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (II). A silicon polymer having an oxetanyl group in the molecule is represented by the following general formula (III). The present invention relates to the radiation curable resin composition according to the above [3], wherein the silicon compound is hydrolyzed and condensed.

[一般式(I)中、Ｒ^１は炭素‐炭素不飽和結合を有する基であり、ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。]

[In General Formula (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). ]

[一般式(II)中、ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。）

[In the general formula (II), X represents halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). )

[一般式(III)中、Ｙはオキセタニル基とケイ素を接続する基であって、−（ＣＲ^８Ｒ^９）_ｍ−あるいは−（ＣＲ^１０Ｒ^１１）_ｎ−Ｔ−（ＣＲ^１２Ｒ^１３）_ｐ−を表し、Ｔは−Ｏ−、−Ｃ（Ｏ）−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＳｉＲ^１４Ｒ^１５−を表す。Ｒ^３〜Ｒ^１５は同一、または異なり、水素原子、炭素数１〜１０の炭化水素基あるいはハロゲン化炭化水素基を表し、ｍ、ｎ、ｐは、それぞれ０〜６の整数を表す。ＸはハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。]
また、本発明は、［５］ 一般式（I）中のＲ^１がビニル基、スチリル基、（メタ）アクリロイル基、エチニル基、またはそれらの重水素置換体、あるいはハロゲン置換体から選ばれる少なくとも１種である上記［２］又は上記［４］に記載の放射線硬化性樹脂組成物に関する。
また、本発明は、［６］ 下部クラッド層、コア部分及び上部クラッド層とを含む光導波路において、前記下部クラッド層、コア部分あるいは上部クラッド層の少なくとも一つが、上記［１］ないし上記［５］のいずれかに記載の放射線硬化性組成物の硬化物であることを特徴とする光導波路に関する。
また、本発明は、［７］ 上記［１］ないし上記［５］のいずれかに記載の放射線硬化性樹脂組成物を基板上に塗布して塗布面を形成する工程と、該塗布面に対し、所定の形状で形成されたスタンパマスクを押圧し、露光、硬化することによりスタンピング成型する工程を含む光導波路の製造方法に関する。

[In General Formula (III), Y is a group that connects an oxetanyl group and silicon, and-(CR ⁸ R ⁹ ) _m- or-(CR ¹⁰ R ¹¹ ) _n -T- (CR ¹² R ¹³ ) _p - represents, T is -O -, - C (O) -, - OC (O) -, - C (O) O -, - SiR 14 R 15 - represents a. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). ]
Further, the present invention provides [5] wherein at least R ¹ in the general formula (I) is selected from a vinyl group, a styryl group, a (meth) acryloyl group, an ethynyl group, a deuterium substituent thereof, or a halogen substituent. It is related with the radiation curable resin composition as described in said [2] or said [4] which is 1 type.
The present invention also provides [6] an optical waveguide including a lower cladding layer, a core portion, and an upper cladding layer, wherein at least one of the lower cladding layer, the core portion, or the upper cladding layer is the above [1] to [5]. ] It is related with the optical waveguide characterized by being a hardened | cured material of the radiation curable composition in any one of.
The present invention also provides [7] a step of coating the radiation curable resin composition according to any one of [1] to [5] above on a substrate to form a coated surface; The present invention also relates to a method of manufacturing an optical waveguide including a step of stamping molding by pressing, exposing and curing a stamper mask formed in a predetermined shape.

  According to the radiation curable resin composition of the present invention, a fine pattern can be formed by a simple method, and the formed pattern has excellent accuracy and shape, and in particular, an optical waveguide pattern excellent in heat resistance and light transmittance. be able to. In addition, according to the optical waveguide of the present invention and the manufacturing method thereof, a fine pattern excellent in pattern accuracy and shape can be formed easily and at low cost, and in combination with the excellent light transmittance, in the manufacture of the optical waveguide, An excellent effect can be exhibited. This resin composition is excellent in storage stability.

The radiation curable resin composition of the present invention comprises a silicon polymer having a carbon-carbon unsaturated bond, a silicon-hydrogen bond and an oxetanyl group in the molecule (hereinafter referred to as “silicon polymer A”).
There are various silicon polymers A. For example, those obtained by hydrolyzing and co-condensing silicon compounds of the following general formulas (I), (II) and (III) are preferable.

ここで、一般式（I）中、Ｒ^１は、炭素‐炭素不飽和結合を有する基であり、より具体的にはビニル基、スチリル基、（メタ）アクリロイル基、エチニル基、またはそれらの重水素置換体、あるいはハロゲン置換体から選ばれる少なくとも１種であることが好ましい。また、Ｘは、ハロゲンまたはＯＲ^２（Ｒ^２は炭素数１〜５のアルキル基を示す）である。一般式(III)中のＹは、オキセタニル基とケイ素を接続する基であって、−（ＣＲ^８Ｒ^９）_ｍ−あるいは−（ＣＲ^１０Ｒ^１１）_ｎ−Ｔ−（ＣＲ^１２Ｒ^１３）_ｐ−を表し、Ｔは−Ｏ−、−Ｃ（Ｏ）−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＳｉＲ^１４Ｒ^１５−を表す。Ｒ^３〜Ｒ^１５は同一、または異なり、水素原子、炭素数１〜１０の炭化水素基あるいはハロゲン化炭化水素基を表し、ｍ、ｎ、ｐは、それぞれ０〜６の整数を表す。

Here, in the general formula (I), R ¹ is a group having a carbon-carbon unsaturated bond, and more specifically, a vinyl group, a styryl group, a (meth) acryloyl group, an ethynyl group, or a combination thereof. It is preferably at least one selected from a hydrogen-substituted product or a halogen-substituted product. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). Y in the general formula (III) is a group connecting an oxetanyl group and silicon, and is — (CR ⁸ R ⁹ ) _m — or — (CR ¹⁰ R ¹¹ ) _n -T— (CR ¹² R ¹³ ) _p - represents, T is -O -, - C (O) -, - OC (O) -, - C (O) O -, - SiR 14 R 15 - represents a. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6.

  By the hydrolysis and cocondensation, a silsesquioxane compound containing a carbon-carbon unsaturated bond, a silicon-hydrogen bond and an oxetanyl group in the molecule is synthesized. In synthesizing 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), (II) and (III) during the hydrolysis and cocondensation is not particularly limited, but from the viewpoint of heat resistance and sensitivity to radiation. The silicon compound having a carbon-carbon unsaturated bond and the silicon compound having a silicon-hydrogen bond are preferably 10: 1 to 1:10 as molar equivalents, more preferably 7: 3 to 3: 7, The molar equivalent is preferably the same amount. Further, the total amount of these silicon compounds and the amount of the silicon compound containing an oxetanyl group are preferably 10: 7 to 10: 1 as a molar equivalent, and more preferably 10: 5 to 10: 2. Is preferred.

Examples of the solvent used in the condensation reaction of the silicon compounds represented by the above general formulas (I), (II) and (III) include aromatic solvents such as toluene and xylene and hydrophilic solvents such as ethanol and methanol. Alcohols such as 2-propanol, ketones such as acetone and methyl ethyl ketone, and ethers such as dioxane and tetrahydrofuran can be mixed and used.
In addition, in the hydrolysis / condensation reaction of the silicon compounds represented by the general formulas (I), (II) and (III), an inorganic acid such as hydrochloric acid or phosphoric acid or an organic acid such as oxalic acid is used as a catalyst. Can be used.

  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. Sufficient sensitivity is obtained when the weight average molecular weight is 800 or more, and sufficient mold transferability is obtained when the weight average molecular weight is 200,000 or less. 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 1,500 to 8,000. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.

  The radiation curable resin composition of the present invention comprises a silicon polymer having a carbon-carbon unsaturated bond in the molecule (hereinafter referred to as “silicon polymer B”), and a silicon polymer having a silicon-hydrogen bond in the molecule (hereinafter referred to as “silicon polymer B”). And a silicon polymer having an oxetanyl group in the molecule (hereinafter referred to as “silicon polymer D”). That is, a resin composition obtained by mixing silicon polymer B, silicon polymer C, and silicon polymer D is also included in the radiation curable resin composition of the present invention. In this case, the mixing ratio of silicon polymer B, silicon polymer C, and silicon polymer D is not particularly limited within the scope of the effects of the present invention. From the viewpoint of heat resistance and sensitivity to radiation, a carbon-carbon unsaturated bond is used. It is preferable that the silicon compound having a silicon compound and the silicon compound having a silicon-hydrogen bond are equivalent in molar equivalent, and the total amount of these silicon compounds and the amount of the silicon compound containing an oxetanyl group are 10 molar equivalents. : 7 to 10: 1 is preferable, and 10: 5 to 10: 2 is more preferable. Furthermore, a resin composition in which silicon polymer A, silicon polymer B, silicon polymer C, and silicon polymer D are mixed is also included in the scope of the present invention.

  The silicon polymer B includes various compounds, but those obtained by hydrolyzing and condensing a silicon compound represented by the following general formula (I) are preferable.

一般式(I)中のＲ^１及びＸは前述のものと同様である。この加水分解・縮合によって、分子内に炭素−炭素不飽和結合を含むシルセスキオキサン化合物が通常合成される。なお、シリコンポリマＢの合成時には、末端シラノールの封止剤として、ヘキサメチルジシロキサン、1,1,2,2-テトラメチルジシロキサンなどを用いることができる。

R ¹ and X in the general formula (I) 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 silicon polymer B, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, or the like can be used as a terminal silanol sealant.

  Although there are various compounds for silicon polymer C, a silicon compound represented by the following general formula (II) is preferably hydrolyzed and condensed.

一般式(II)中、Ｘは上記と同様である。この加水分解・縮合によって、分子内にケイ素−水素結合を含むシルセスキオキサン化合物が通常合成される。なお、シリコンポリマＣの合成時においても、末端シラノールの封止剤として、ヘキサメチルジシロキサン、1,1,2,2-テトラメチルジシロキサンなどを用いることができる。

In general formula (II), X is the same as described above. By this hydrolysis and condensation, a silsesquioxane compound containing a silicon-hydrogen bond in the molecule is usually synthesized. Even during the synthesis of silicon polymer C, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, or the like can be used as the terminal silanol sealant.

  Furthermore, although there are various compounds for silicon polymer D, it is preferable to hydrolyze and condense a silicon compound represented by the following general formula (III).

一般式(III)中、Ｙはオキセタニル基とケイ素を接続する基であって、−（ＣＲ^８Ｒ^９）_ｍ−あるいは−（ＣＲ^１０Ｒ^１１）_ｎ−Ｔ−（ＣＲ^１２Ｒ^１３）_ｐ−を表し、Ｔは−Ｏ−、−Ｃ（Ｏ）−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＳｉＲ^１４Ｒ^１５−を表す。Ｒ^３〜Ｒ^１５は同一、または異なり、水素原子、炭素数１〜１０の炭化水素基あるいはハロゲン化炭化水素基を表し、ｍ、ｎ、ｐは、それぞれ０〜６の整数を表す。また、Ｘは上記と同様である。この加水分解・縮合によって、分子内にオキセタニル基を含むシルセスキオキサン化合物が通常合成される。なお、シリコンポリマＤの合成時においても、末端シラノールの封止剤として、ヘキサメチルジシロキサン、1,1,2,2-テトラメチルジシロキサンなどを用いることができる。

In the general formula (III), Y is a group for connecting the oxetanyl group and silicon, and-(CR ⁸ R ⁹ ) _m- or-(CR ¹⁰ R ¹¹ ) _n -T- (CR ¹² R ¹³ ) _p- T represents —O—, —C (O) —, —OC (O) —, —C (O) O—, —SiR ¹⁴ R ¹⁵ —. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6. X is the same as described above. By this hydrolysis / condensation, a silsesquioxane compound containing an oxetanyl group in the molecule is usually synthesized. Even during the synthesis of the silicon polymer D, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, or the like can be used as a terminal silanol sealant.

The weight average molecular weight (Mw) of silicon polymer B, silicon polymer C and silicon polymer D is in the range of 800 to 200,000, and in the range of 1,000 to 10,000 for the same reason as silicon polymer A. In particular, it is preferably in the range of 1,500 to 8,000.
Further, as the solvent and catalyst in the hydrolysis / condensation of the silicon polymer B, the silicon polymer C, and the silicon polymer D, the same solvents and catalysts as those described for the silicon polymer A can be preferably used.

  Another component of the radiation curable resin composition of the present invention is a photoacid generator, and a compound that generates an acidic active substance capable of photocrosslinking a silicon polymer when irradiated with radiation such as ultraviolet rays. Defined. Examples of the photoacid generator 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 diaryliodonium salt is preferably a compound represented by the following general formula (IV).

（一般式(IV)中、Ａｒはアリール基であり、Ｚ⁻はアニオンを表す。）。
一般式（IV）で示されるジアリールヨードニウム塩中のカチオンとしては、例えばジフェニルヨードニウム、４−メトキシフェニルフェニルヨードニウム、ビス（４−メトキシフェニル）ヨードニウムおよびビス（４−ｔ−ブチルフェニル）ヨードニウムなどが挙げられる。また、該アニオン（Ｚ⁻）は、例えばナフタレン−１−スルホナート、ナフタレン−２−スルホナート、２−ｔ−ブチルナフタレン−２−スルホナートなどのナフタレン誘導体、アントラセン−１−スルホナート、アントラセン−２−スルホナート、９−ニトロアントラセン−１−スルホナート、５，６−ジクロロアントラセン−３−スルホナート、９，１０−ジクロロアントラセン−２−スルホナート、９，１０−ジメトキシアントラセン−２−スルホナート、９，１０−ジエトキシアントラセン−２−スルホナート、ベンズ[a]アントラセン−４−スルホナートなどのアントラセン誘導体、フェナントレン−２−スルホナート、ピレンスルホナート、トリフェニレン−２−スルホナート、クリセン−２−スルホナート、アントラキノンスルホナートなどのその他の多環構造を有するアニオン、トリフルオロメタンスルホナート、ヘキサフルオロアンチモナート、テトラフルオロボレート、ヘキサフルオロホスフェート、ベンゼンスルホナートなどが挙げられ、これらの中では、アントラセン誘導体およびトリフルオロメタンスルホナートが好ましい。

(In the general formula (IV), Ar is an aryl group, and Z ⁻ represents an anion).
Examples of the cation in the diaryliodonium salt represented by the general formula (IV) include diphenyliodonium, 4-methoxyphenylphenyliodonium, bis (4-methoxyphenyl) iodonium, bis (4-t-butylphenyl) iodonium, and the like. It is done. The anion (Z ⁻ ) is, 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-sulfonate, 5,6-dichloroanthracene-3-sulfonate, 9,10-dichloroanthracene-2-sulfonate, 9,10-dimethoxyanthracene-2-sulfonate, 9,10-diethoxyanthracene- Anthracene derivatives such as 2-sulfonate, benz [a] anthracene-4-sulfonate, phenanthrene-2-sulfonate, pyrenesulfonate, triphenylene-2-sulfonate, chrysene-2-sulfonate, anthraquinones Other anions having other polycyclic structures such as phonate, trifluoromethanesulfonate, hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, benzenesulfonate, etc. Among these, anthracene derivatives and trifluoromethanesulfonate Is preferred.

  The triarylsulfonium salt has the general formula (V)

（一般式(V)中、ＡｒおよびＺは前記と同じ意味である）で示されるものである。
一般式(V)で示されるトリアリールスルホニウム塩中のカチオンとしては、例えばトリフェニルスルホニウム、メトキシフェニルジフェニルスルホニウム、ビス（メトキシフェニル）フェニルスルホニウム、トリス（メトキシフェニル）スルホニウム、４−メチルフェニルジフェニルスルホニウム、２，４，６−トリメチルフェニルジフェニルスルホニウム、４−ｔ−ブチルフェニルジフェニルスルホニウム、トリス（４−ｔ−ブチルフェニル）スルホニウムなどが挙げられる。また、アニオンの具体例は、前記ジアリールヨードニウム塩で例示したものと同様である。

(In the general formula (V), Ar and Z have the same meaning as described above).
Examples of the cation in the triarylsulfonium salt represented by the general formula (V) include triphenylsulfonium, methoxyphenyldiphenylsulfonium, bis (methoxyphenyl) phenylsulfonium, tris (methoxyphenyl) sulfonium, 4-methylphenyldiphenylsulfonium, Examples include 2,4,6-trimethylphenyldiphenylsulfonium, 4-t-butylphenyldiphenylsulfonium, and tris (4-t-butylphenyl) sulfonium. Specific examples of the anion are the same as those exemplified for the diaryl iodonium salt.

  The aryldiazonium salt has the general formula (VI)

（一般式（VI）中、ＡｒおよびZは前記と同じ意味である）で示されるものである。
一般式（VI）で示されるアリールジアゾニウム塩中のカチオンとしては、特に限定されず、例えば、４-t-ブトキシベンゼンジアゾニウム、４-メトキシベンゼンジアゾニウム、４-モルホリノベンゼンジアゾニウム、４-ニトロベンゼンジアゾニウム、４-メチルベンゼンジアゾニウムなどが挙げられる。また、アニオンの具体例としては、前記ジアリールヨードニウム塩で例示したものと同様である。

(In the general formula (VI), Ar and Z have the same meaning as described above).
The cation in the aryldiazonium salt represented by the general formula (VI) is not particularly limited. For example, 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.

  The ratio of the acid generator used is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the silicon polymer. When there are too few acid generators, hardening by radiation irradiation may become inadequate. On the other hand, if the amount is too large, the light transmittance may be adversely affected.

  Another component of the radiation curable resin composition of the present invention is a dehydrating agent, and the type thereof is not particularly limited, but is selected from carboxylic acid esters, acetals, ketals, and carboxylic acid anhydrides. Preferably it is at least one compound.

  The carboxylic acid ester as the dehydrating agent is selected from carboxylic acid ortho ester and carboxylic acid silyl ester. Preferred carboxylic acid orthoesters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate and the like. Among these carboxylic acid orthoesters, ethyl orthoformate is particularly preferable from the viewpoint of exhibiting a more excellent dehydrating effect as a dehydrating agent and further improving storage stability. Furthermore, preferable carboxylic acid silyl esters include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and the like.

  Further, as acetals or ketals as a dehydrating agent, ketones or aldehydes such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetaldehyde, propionaldehyde, benzaldehyde and a monovalent alcohol reaction product, Examples include acetals and ketals such as dimethyl acetal, diethyl acetal, and dipropyl acetal, and acetals and ketals formed from a reaction product with a dihydric alcohol such as ethylene glycol.

  Preferred carboxylic acid anhydrides include formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, and the like. In particular, acetic anhydride, which is excellent in dehydration effect, is preferable from the above viewpoint.

  The use ratio of the dehydrating agent is not particularly limited, but may be usually 0.1 to 80 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 1 to 100 parts by weight with respect to 100 parts by weight of the silicon polymer. 10 parts by weight. If the added amount of the dehydrating agent is too small, the effect of improving the storage stability tends to be small, and conversely, even if the added amount of the dehydrating agent exceeds 80 parts by weight, the effect tends to be saturated.

  The radiation curable resin composition of the present invention may contain additives such as a surfactant and an adhesion aid in addition to the silicon polymers A, B, C and D, the photoacid generator and the dehydrating agent. . By adding a surfactant, the resulting composition can be easily applied, and the flatness of the resulting film is improved. Examples of the surfactant include BM-1000 (manufactured by BM Chemie), Megafax F142D, F172, F173 and F183 (manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC- 170C, Florard FC-430 and FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141 and S-145 (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.). The amount of the surfactant used is usually 5 parts by weight or less, preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the silicon polymer component.

  Moreover, the adhesiveness of the composition obtained improves by adding an adhesion assistant. The adhesion assistant is preferably a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. 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 amount of the adhesion aid used is usually 20 parts by weight or less, preferably 0.05 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the silicon polymer component. .

  The radiation curable resin composition of the present invention is used by dissolving the above-mentioned silicon polymer component, photoacid generator, dehydrating agent and other additives as required in an organic solvent.

  The organic solvent is not particularly limited as long as it does not react with the silicon polymer and the photoacid generator component and is soluble in each other, and preferably has a boiling point in the range of 50 to 200 ° C. under atmospheric pressure. It is an organic compound having a value, and each constituent component can be dissolved uniformly. Examples thereof include compounds selected from the group consisting of ether organic solvents, ketone organic solvents, ester organic solvents, aromatic hydrocarbon organic solvents, and alcohol organic solvents. Preferred organic solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl isobutyl ketone, methyl pentyl ketone, toluene, xylene and the like. The addition amount of the organic solvent is preferably in the range of 1 to 190 parts by weight with respect to 10 parts by weight of the total amount of the radiation curable resin composition. When the addition amount of the organic solvent is less than 1 part by mass, the uniformity of the radiation curable resin composition may be difficult, and when the addition amount exceeds 190 parts by mass, a sufficiently thick optical waveguide is formed. May be difficult to 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 used in the present invention will be described in detail below. The pattern forming method is an imprint method performed using the radiation curable 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, which is an original pattern of transfer, against a transfer material.
FIG. 1 shows a method of forming an optical waveguide core pattern by this method. First, a lower clad layer is formed on a substrate with a resin having a refractive index lower than that of the core resin, and the radiation curable resin composition of the present invention is laminated thereon as a core layer. A mold mask having a core shape to be formed here (core shape mask) is pressed, irradiated with radiation while applying pressure, heated and cured as necessary, the mold mask is separated, and a core pattern is formed. Finally, an embedded optical waveguide is obtained by forming an upper clad thereon 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-shaped mask) has a pattern in which the necessary irregularities of the core pattern are reversed. The mold mask can be used for stamping, and any material can be used as long as it transmits the radiation to be irradiated. However, as the inorganic material, sapphire, diamond, quartz, or the like is usually used. 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 and used as a mold mask. A pattern produced by stamping molding may be used as a mold mask.

The radiation dose during molding is preferably 5 to 500 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.

  For pattern formation, heat treatment is preferably performed simultaneously with irradiation of radiation or after irradiation of radiation to promote curing of the radiation curable 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 70 to 200 ° C, and particularly preferably in the range of 80 to 150 ° C. Moreover, it is possible to heat and harden by raising the temperature stepwise. The heating time is preferably 0.01 to 0.5 hours.

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 to suppress deterioration of the material or to remove bubbles in the material, or the pattern can be formed in a vacuum.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, 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), 3-ethyl-3 (triethoxysilylpropoxymethyl) oxetane (9.0 g, 28 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 wt%, 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 silsesquioxane compound (hereinafter referred to as silicon polymer 1) as a colorless transparent viscous liquid. Got.
The weight average molecular weight (Mw) of this compound was found to be 4,500 and the dispersity (Mw / Mn) was 2.9 by GPC analysis. Here, Mn represents the number average molecular weight.
This silicon polymer was confirmed to have a vinyl group, silicon-hydrogen bond and oxetanyl group as carbon-carbon unsaturated bonds in the molecule by NMR spectrum and infrared absorption spectrum.

(Synthesis Example 2)
Vinyltrimethoxysilane and 1,1,2,2-tetramethyldisiloxane were reacted under the same conditions as in Synthesis Example 1 to obtain a colorless and transparent viscous liquid silicon polymer (hereinafter referred to as silicon polymer 2). . The weight average molecular weight (Mw) of this compound was found to be 7,000 and the dispersity (Mw / Mn) was 3.0 by GPC analysis. When confirmed by NMR spectrum and infrared absorption spectrum in the same manner as in Synthesis Example 1, it was a silicon polymer (polysilsesquioxane) having a carbon-carbon unsaturated bond due to a vinyl group in the molecule.

(Synthesis Example 3)
Triethoxysilane and 1,1,2,2-tetramethyldisiloxane were reacted under the same conditions as in Synthesis Example 1 to obtain a colorless and transparent viscous liquid silicon polymer (hereinafter referred to as silicon polymer 3). The weight average molecular weight (Mw) of this compound was found to be 3,050 and the dispersity (Mw / Mn) was 1.7 by GPC analysis. When confirmed with an NMR spectrum and an infrared absorption spectrum as in Synthesis Example 1, it was a silicon polymer (polysilsesquioxane) having a silicon-hydrogen bond in the molecule.

Example 1
To 1100 parts by weight of silicon polymer, 1.0 part by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator and 3.0 parts by weight of ethyl orthoformate as a dehydrating agent are dissolved in 100 parts by weight of propylene glycol monomethyl ether. A radiation curable resin composition was prepared. This radiation curable resin composition was applied onto a silicon substrate to form a thin film having a thickness of about 10 μm. A quartz mold mask having a 5 μm / 5 μm line / space core shape unevenness is pressed onto the surface of this thin film, pressed at 3 MPa, and irradiated with 20 mJ / cm ² of ultraviolet light at 50 ° C. at 50 ° C. Heated and cured for 2 seconds. After cooling, when the mold mask was removed, a 5 μm / 5 μm space / line pattern 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 birefringence of this heat-cured film showed a small value of 0.0002. 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% weight loss temperature) measured with TG-DTA (manufactured by Seiko Denshi) was 450 ° C., indicating high thermal stability. Thus, the radiation curable resin composition containing silicon polymer 1 is excellent in transparency and heat resistance, does not require a development process, is cured at a low temperature, and can be formed in a short time due to high sensitivity. It was found that the pattern can be formed by a simple manufacturing process and is useful as an optical waveguide material. Moreover, it was confirmed that the performance of the radiation curable resin composition of the present invention does not change at least at least 1 month at room temperature and at least 3 months at refrigerated (−5 ° C.) storage. On the other hand, when no dehydrating agent was contained, an increase in viscosity was observed after storage at room temperature for 1 month.

(Example 2)
To 100 parts by weight of silicon polymer 2 and silicon polymer 3 equimolarly mixed with oxetanylsilsesquioxane (OX-SQ, manufactured by Toagosei Co., Ltd.) at a ratio of 1/5 mole to this, A radiation curable resin composition in which 1.0 part by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator and 3.0 parts by weight of ethyl orthoformate as a dehydrating agent are dissolved in 100 parts by weight of propylene glycol monomethyl ether is used. In the same manner as in Example 1, a core pattern 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 silicon polymer 2 having a vinyl group as a carbon-carbon unsaturated bond group, a silicon polymer 3 having a silicon-hydrogen bond, and oxetanylsilsesquioxane, which is a silicon polymer having an oxetanyl group, are mixed to form a photoacid. Even when a radiation curable resin composition is formed in combination with a generator, a pattern can be formed in the same manner as a compound having these carbon-carbon unsaturated bond group, silicon-hydrogen bond group and oxetanyl group in a single molecule. It was shown that. Similar to the silicon polymer 1 of Example 1, this radiation curable resin composition is also excellent in transparency and heat resistance, can be formed by a simple manufacturing process, and is useful as an optical waveguide material. I understood that. Moreover, it was confirmed that the performance of the radiation curable resin composition of the present invention does not change at least at least 1 month at room temperature and at least 3 months at refrigerated (−5 ° C.) storage.

Explanatory drawing of the process of forming an optical waveguide pattern by applying this invention.

Explanation of symbols

1: Mold mask (for core)
2: Core 3: Lower clad 4: Substrate 5: Upper clad

Claims (7)

A radiation curable resin composition comprising a silicon polymer having a carbon-carbon unsaturated bond, a silicon-hydrogen bond and an oxetanyl group in the molecule, a photoacid generator and a dehydrating agent. The silicon polymer hydrolyzes and co-condenses a silicon compound represented by the following general formula (I), a silicon compound represented by the following general formula (II) and a silicon compound represented by the following general formula (III). The radiation curable resin composition according to claim 1, wherein

[In General Formula (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). ]

[In the general formula (II), X represents halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). )

[In General Formula (III), Y is a group that connects an oxetanyl group and silicon, and-(CR ⁸ R ⁹ ) _m- or-(CR ¹⁰ R ¹¹ ) _n -T- (CR ¹² R ¹³ ) _p - represents, T is -O -, - C (O) -, - OC (O) -, - C (O) O -, - SiR 14 R 15 - represents a. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). ] It contains a silicon polymer having a carbon-carbon unsaturated bond in the molecule, a silicon polymer having a silicon-hydrogen bond in the molecule, and a silicon polymer having an oxetanyl group in the molecule, a photoacid generator and a dehydrating agent. A radiation curable resin composition. 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), and a silicon polymer having a silicon-hydrogen bond in the molecule is The silicon compound represented by the following general formula (II) is hydrolyzed and condensed, and the silicon polymer having an oxetanyl group in the molecule hydrolyzes the silicon compound represented by the following general formula (III), The radiation curable resin composition according to claim 3, which is condensed.

[In General Formula (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). ]

[In the general formula (II), X represents halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). )

[In General Formula (III), Y is a group that connects an oxetanyl group and silicon, and-(CR ⁸ R ⁹ ) _m- or-(CR ¹⁰ R ¹¹ ) _n -T- (CR ¹² R ¹³ ) _p - represents, T is -O -, - C (O) -, - OC (O) -, - C (O) O -, - SiR 14 R 15 - represents a. R ^{3 to} R ¹⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and m, n and p each represents an integer of 0 to 6. X is halogen or OR ² (R ² represents an alkyl group having 1 to 5 carbon atoms). ] The R ¹ in the general formula (I) is at least one selected from a vinyl group, a styryl group, a (meth) acryloyl group, an ethynyl group, a deuterium substituent thereof, or a halogen substituent. Item 5. A radiation curable resin composition according to Item 4. 6. An optical waveguide including a lower cladding layer, a core portion, and an upper cladding layer, wherein at least one of the lower cladding layer, the core portion, or the upper cladding layer is radiation curable according to any one of claims 1 to 5. An optical waveguide, which is a cured product of the composition. A process for forming a coated surface by applying the radiation curable resin composition according to any one of claims 1 to 5 on a substrate, and a stamper mask formed in a predetermined shape on the coated surface. An optical waveguide manufacturing method including a step of stamping molding by pressing, exposing, and curing.

Images