JP2024123721A - Siliceous mixture for forming a siliceous coating layer - Google Patents
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Abstract
Description
本発明は、粘度安定性に優れるシリカ質コーティング層形成用シリカ質混合液に関する。 The present invention relates to a siliceous mixture for forming a siliceous coating layer that has excellent viscosity stability.
シリカ質膜は、半導体や液晶などの電子デバイスの構成部材として、絶縁や保護などを目的として広く使用されている。 Siliceous films are widely used as components of electronic devices such as semiconductors and liquid crystal displays for purposes such as insulation and protection.
シリカ質膜の形成方法の一つとして、溶剤に溶解されたゾルゲル液やシリコン樹脂などを基材に塗布し、加熱するウェット法が知られている。シリコン樹脂の一種である水素化ポリシラザンや水素化ポリシロキサンなどは、加熱反応により高純度のシリカ質膜に転換できることが知られている（例えば、特許文献１、２参照）。 One method for forming a siliceous film is the wet method, in which a sol-gel liquid or silicone resin dissolved in a solvent is applied to a substrate and then heated. It is known that hydrogenated polysilazane and hydrogenated polysiloxane, which are types of silicone resin, can be converted into a high-purity siliceous film by a heat reaction (see, for example, Patent Documents 1 and 2).
また、形成されるシリカ質膜の耐熱性、気密封止性、耐久性、透明性確保などのため、シリカ質膜にシリカ微粒子を混合する手法が知られている（例えば、特許文献３、４、５参照）。 In addition, a method is known in which silica fine particles are mixed into the siliceous film to ensure the heat resistance, airtight sealing properties, durability, and transparency of the siliceous film that is formed (see, for example, Patent Documents 3, 4, and 5).
緻密性と均質性に優れるシリカ微粒子分散シリカ質膜をウェット法により得るための基本工程は次の通りである。
１．シリカ微粒子と、加熱するとシリカ質膜に転換するシリコン樹脂を均一混合する
２．混合液を基材に塗布し、加熱してシリコン樹脂をシリカ質へ転換する
The basic steps for obtaining a silica film containing dispersed silica particles, which is excellent in density and uniformity, by a wet method are as follows.
1. Mix silica particles and silicone resin that turns into a siliceous film when heated. 2. Apply the mixture to a substrate and heat it to turn the silicone resin into a siliceous film.
高密度のシリカ質膜を得るためには、できるだけ有機成分を含まないシリカ微粒子とシリコン樹脂を用いることが望ましい。例えば、水素化ポリシラザンや水素化ポリシロキサンなどは、Ｓｉに結合する側鎖が水素のみ（Ｓｉ－Ｈ結合、すなわちメチル基などの有機基を含まない）のシリコン樹脂であるため、加熱後の分解や収縮が少なく、高密度のシリカ質膜が得られる。 To obtain a high-density silica film, it is desirable to use silica particles and silicone resin that contain as few organic components as possible. For example, hydrogenated polysilazane and hydrogenated polysiloxane are silicone resins in which the side chains that bond to silicon contain only hydrogen (Si-H bonds, i.e., do not contain organic groups such as methyl groups), so there is little decomposition or shrinkage after heating, and a high-density silica film can be obtained.
しかし、Ｓｉ－Ｈ結合は、水やアルコールなどのＯＨ基と容易に反応して、重合・ゲル化を起こす。一方で、シリカ微粒子表面にはＯＨ基が残存する。そのため、シリカ微粒子と、Ｓｉ－Ｈ結合する側鎖が水素のみのシリコン樹脂と、を混合すると、混合液の粘度安定性が悪くなる。 However, Si-H bonds easily react with OH groups in water or alcohol, causing polymerization and gelation. On the other hand, OH groups remain on the surface of silica microparticles. Therefore, when silica microparticles are mixed with a silicone resin whose side chains that form Si-H bonds only contain hydrogen, the viscosity stability of the mixture becomes poor.
本発明の目的は、シリカ微粒子と、Ｓｉに結合する側鎖が水素のみのシリコン樹脂と、の混合液であって、粘度安定性に優れるシリカ質コーティング層形成用シリカ質混合液を提供することにある。 The object of the present invention is to provide a siliceous mixture for forming a siliceous coating layer, which is a mixture of silica fine particles and a silicone resin in which the side chains bonded to Si are only hydrogen, and has excellent viscosity stability.
本発明のシリカ質コーティング層形成用シリカ質混合液は、メチル基、エチル基、ビニル基、メタクリロキシ基またはアクリロキシ基を有する１種以上のシランカップリング剤で表面修飾した一次粒子径が１００ｎｍ以下のシリカ微粒子と、水素化ポリシロキサン、水素化ポリシラザンまたは水素化ポリシロキサザンと、を有機溶剤中で混合したものである。 The siliceous mixture for forming a siliceous coating layer of the present invention is a mixture of silica fine particles having a primary particle size of 100 nm or less and surface-modified with one or more silane coupling agents having a methyl group, an ethyl group, a vinyl group, a methacryloxy group, or an acryloxy group, and hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane in an organic solvent.
シランカップリング剤の量は、シリカ微粒子の量に対して０．１ｗｔ％以上３ｗｔ％以下としてもよい。 The amount of silane coupling agent may be 0.1 wt% or more and 3 wt% or less relative to the amount of silica fine particles.
シリカ微粒子の、水素化ポリシロキサン、水素化ポリシラザンまたは水素化ポリシロキサザンとの混合比率は、２ｗｔ％以上８０ｗｔ％以下としてもよい。 The mixing ratio of silica microparticles to hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane may be 2 wt% or more and 80 wt% or less.
有機溶剤は、水分含有量０．０３ｗｔ％以下である芳香族炭化水素類、飽和炭化水素類、エーテル類、エステル類またはケトン類から選ばれる単一または複数種類の溶媒から選択される化合物としてもよい。 The organic solvent may be a compound selected from a single or multiple types of solvents selected from aromatic hydrocarbons, saturated hydrocarbons, ethers, esters, or ketones, each having a water content of 0.03 wt% or less.
本発明によれば、シリカ微粒子と、Ｓｉに結合する側鎖が水素のみのシリコン樹脂と、の混合液であって、粘度安定性に優れるシリカ質コーティング層形成用シリカ質混合液を提供することができる。 According to the present invention, a siliceous mixture for forming a siliceous coating layer having excellent viscosity stability can be provided, which is a mixture of silica fine particles and a silicone resin in which the side chains bonded to Si are hydrogen only.
本発明のシリカ質コーティング層形成用シリカ質混合液は、表面修飾を行ったシリカ微粒子を有機溶剤に混合したものと、Ｓｉに結合する側鎖が水素のみのシリコン樹脂である水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンを有機溶剤に溶解したものと、を混合することにより得られる。 The siliceous mixture for forming a siliceous coating layer of the present invention is obtained by mixing surface-modified silica fine particles in an organic solvent with a solution of hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane, which is a silicon resin whose side chains bonded to silicon are hydrogen only, dissolved in an organic solvent.
シリカ微粒子は、一次粒子径が１００ｎｍ以下のものが好適である。 The silica microparticles preferably have a primary particle diameter of 100 nm or less.
シリカ微粒子の表面修飾は、メチル基、エチル基、ビニル基、メタクリロキシ基又はアクリロキシ基を有する１種以上のシランカップリング剤により行う。 The surface of the silica microparticles is modified with one or more silane coupling agents having a methyl group, an ethyl group, a vinyl group, a methacryloxy group, or an acryloxy group.
シリカ微粒子を表面修飾するシランカップリング剤の量は、シリカ微粒子の量に対して０．１ｗｔ％以上３ｗｔ％以下とするのが望ましく、０．２ｗｔ％以上２．５ｗｔ％以下とすることがより望ましい。０．１ｗｔ％未満であると、混合液調整後の粘度安定性が悪くなる。これは、樹脂の分子量上昇速度が速いためと考えられる。一方で、３ｗｔ％を超えると、形成されたシリカ質コーティング層に含有される有機成分量が増加してシリカ質コーティング層の密度が低下する。 The amount of silane coupling agent that modifies the surface of the silica microparticles is preferably 0.1 wt% to 3 wt% relative to the amount of silica microparticles, and more preferably 0.2 wt% to 2.5 wt%. If it is less than 0.1 wt%, the viscosity stability after the mixed solution is adjusted will be poor. This is thought to be because the molecular weight of the resin increases too quickly. On the other hand, if it exceeds 3 wt%, the amount of organic components contained in the formed siliceous coating layer will increase, decreasing the density of the siliceous coating layer.
有機溶剤は、水分含有量が０．０３ｗｔ％以下である、トルエン、キシレン、トリメチルベンゼン等の芳香族炭化水素類、ヘキサン、ヘキセン、オクタン等の飽和炭化水素類、ブチルエーテル、アミルエーテル、アニソール等のエーテル類、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類から選ばれる単一または複数種類の溶剤から選択される化合物が好適である。水分含有量が０．０３ｗｔ％を超えると、混合液調整後の粘度安定性が悪化する。これも、樹脂の分子量上昇速度が速いためと考えられる。そのため、用意した有機溶剤の水分含有量が０．０３ｗｔ％を超える場合、脱水処理で水分含有量を０．０３ｗｔ％以下とした上で混合に用いるとよい。 The organic solvent is preferably a compound selected from a single or multiple types of solvents selected from aromatic hydrocarbons such as toluene, xylene, and trimethylbenzene, saturated hydrocarbons such as hexane, hexene, and octane, ethers such as butyl ether, amyl ether, and anisole, esters such as ethyl acetate, propyl acetate, and butyl acetate, and ketones such as diethyl ketone, methyl isobutyl ketone, and cyclohexanone, all of which have a water content of 0.03 wt% or less. If the water content exceeds 0.03 wt%, the viscosity stability after the mixed liquid is adjusted deteriorates. This is also thought to be due to the rapid rate of increase in the molecular weight of the resin. Therefore, if the water content of the prepared organic solvent exceeds 0.03 wt%, it is recommended to use it for mixing after dehydrating the water content to 0.03 wt% or less.
表面修飾を行ったシリカ微粒子の、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンとの混合比率は、２ｗｔ％以上８０ｗｔ％以下（すなわち、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンの混合比率として２０ｗｔ％以上９８ｗｔ％以下）とするのが望ましい。さらに、５ｗｔ％以上７２ｗｔ％以下とすることがより望ましい。シリカ微粒子の混合比率が２ｗｔ％未満の場合、混合液を基板に塗布し加熱するとクラックが生じやすくなる。これは、内部応力によると考えられる。また、シリカ微粒子の混合比率が８０ｗｔ％を超える場合、加熱後の膜密度が低くなる。これは、シリカ微粒子間を空隙なく埋めるマトリックスとして働くシリコン樹脂の量が不十分なためと考えられる。 The mixing ratio of the surface-modified silica particles to hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane is preferably 2 wt% or more and 80 wt% or less (i.e., the mixing ratio of hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane is 20 wt% or more and 98 wt% or less). It is more preferable to set it to 5 wt% or more and 72 wt% or less. If the mixing ratio of silica particles is less than 2 wt%, cracks are likely to occur when the mixed liquid is applied to a substrate and heated. This is thought to be due to internal stress. Also, if the mixing ratio of silica particles exceeds 80 wt%, the film density after heating is low. This is thought to be due to an insufficient amount of silicone resin that acts as a matrix to fill the spaces between the silica particles without leaving any gaps.
以上のように調整したシリカ質コーティング層形成用シリカ質混合液によれば、シリカ微粒子と、Ｓｉに結合する側鎖が水素のみのシリコン樹脂と、の混合液であって、粘度安定性に優れるシリカ質コーティング層形成用シリカ質混合液を提供することができる。 The siliceous mixed liquid for forming a siliceous coating layer prepared as described above is a mixture of silica fine particles and a silicone resin in which the side chains bonded to Si are only hydrogen, and it is possible to provide a siliceous mixed liquid for forming a siliceous coating layer that has excellent viscosity stability.
＜各実施例の構成要素の説明＞
実施例の説明に先立ち、各実施例の構成要素となる、シリカ微粒子の表面修飾方法、ポリマー（水素化ポリシロキサン、水素化ポリシラザン及び水素化ポリシロキサザン）の合成方法、シリカ微粒子とシリコン樹脂との混合方法、及び実施結果の評価方法について説明する。
<Description of components of each embodiment>
Prior to describing the examples, the components of each example, namely, a method for surface modification of silica fine particles, a method for synthesizing polymers (hydrogenated polysiloxane, hydrogenated polysilazane, and hydrogenated polysiloxazane), a method for mixing silica fine particles with silicone resin, and a method for evaluating the results will be described.
・シリカ微粒子の表面修飾方法（Ａ１）
撹拌機、加熱装置を備えた容量１Ｌのガラス製反応器に、シリカ微粒子の材料としてコロイダルシリカ（日産化学工業社製スノーテックスＯＳ：平均粒径１０ｎｍ、固形分濃度２０％）を室温下で３００ｇを撹拌しながら注入し、更にイソプロパノール２００ｇを注入した。これに、シランカップリング剤である３－メタクリロキシプロピルトリメトキシシラン（信越化学工業社製ＫＢＭ－５０３）３ｇを注入し、４０℃に加熱して６０時間保持した。
シリカ微粒子の粒径は、製膜後の断面電子顕微鏡（ＳＥＭ）観察にて３ｎｍ～２５ｎｍの範囲であることを確認した。
室温まで放冷した後、３５％塩酸（本田薬品社製）２０ｇを注入してシリカ微粒子を沈殿させ、これをガラスフィルター（Ｐ１６グレード）で濾過し、続いて、濾過残渣を純水でよく洗浄した。更にこれを１００℃の真空乾燥機で十分に乾燥させた。
Surface modification method for silica fine particles (A1)
Into a 1 L glass reactor equipped with a stirrer and a heater, 300 g of colloidal silica (Nissan Chemical Industries, Ltd., Snowtex OS: average particle size 10 nm, solid content concentration 20%) was poured as a silica fine particle material at room temperature while stirring, and 200 g of isopropanol was further poured in. To this, 3 g of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-503) as a silane coupling agent was poured, and the mixture was heated to 40° C. and maintained for 60 hours.
The particle size of the silica fine particles was confirmed to be in the range of 3 nm to 25 nm by cross-sectional observation with a scanning electron microscope (SEM) after the film formation.
After cooling to room temperature, 20 g of 35% hydrochloric acid (Honda Pharmaceutical Co., Ltd.) was poured in to precipitate silica fine particles, which were then filtered through a glass filter (P16 grade), and the filtration residue was thoroughly washed with pure water and then thoroughly dried in a vacuum dryer at 100°C.
・表面修飾量の算出
表面修飾方法（Ａ１）により得られた、表面修飾後のシリカ微粒子１０ｇを、モレキュラーシーブ４Ａで乾燥させたメチルエチルケトン（水分量０．０２％）４０ｇと混合し、超音波分散した。これにＣＤＣｌ３を加えて、１Ｈ－ＮＭＲ（４００ＭＨｚ）を測定した。ケミカルシフト１．０６ｐｐｍ（メチルエチルケトンのエチル基－ＣＨ２ＣＨ３）とケミカルシフト５．５ｐｐｍ及び６．１ｐｐｍ（３－メタクリロキシプロピルトリメトキシシランのアクリル基の＝ＣＨ２）に帰属されるピーク積分値より、シリカ微粒子に対する表面修飾量を計算した結果、２．５ｗｔ％であった。
Calculation of the amount of surface modification 10 g of surface-modified silica fine particles obtained by the surface modification method (A1) was mixed with 40 g of methyl ethyl ketone (water content 0.02%) dried with molecular sieve 4A, and ultrasonically dispersed. CDCl 3 was added to this, and 1 H-NMR (400 MHz) was measured. The amount of surface modification relative to the silica fine particles was calculated from the peak integral values attributable to a chemical shift of 1.06 ppm (ethyl group of methyl ethyl ketone -CH 2 CH 3 ) and chemical shifts of 5.5 ppm and 6.1 ppm (acrylic group of 3-methacryloxypropyltrimethoxysilane =CH 2 ), resulting in a value of 2.5 wt %.
・シリカ微粒子の表面修飾方法（Ａ２）
表面修飾方法（Ａ１）のうち、シリカ微粒子の材料としてコロイダルシリカ（日産化学工業社製スノーテックスＯＬ：平均粒径５０ｎｍ、固形分濃度２０％）を使用した以外は、表面修飾方法（Ａ１）と同様の方法で生成物を得た。表面修飾量の算出も同様の方法で行い、計算結果は１．６ｗｔ％であった。
シリカ微粒子の粒径は、製膜後の断面電子顕微鏡（ＳＥＭ）観察にて２５ｎｍから９５ｎｍの範囲であることを確認した。
Surface modification method for silica fine particles (A2)
A product was obtained in the same manner as in surface modification method (A1), except that colloidal silica (Snowtex OL, manufactured by Nissan Chemical Industries, Ltd.: average particle size 50 nm, solid content concentration 20%) was used as the material for the silica fine particles. The amount of surface modification was also calculated in the same manner, and the calculated result was 1.6 wt%.
The particle size of the silica fine particles was confirmed to be in the range of 25 nm to 95 nm by cross-sectional observation with a scanning electron microscope (SEM) after the film formation.
・シリカ微粒子の表面修飾方法（Ａ３）
表面修飾方法（Ａ１）のうち、シランカップリング剤としてビニルトリメトキシシラン（信越化学工業社製ＫＢＭ－１００３）を使用した以外は、表面修飾方法（Ａ１）と同様の方法で生成物を得た。表面修飾量の算出は、シランカップリング剤の帰属をケミカルシフト５．８から６．１ｐｐｍ（ビニルトリメトキシシランのビニル基の－ＣＨ＝ＣＨ２）とした以外は、表面修飾方法（Ａ１）と同様の方法で行い、計算結果は０．７ｗｔ％であった。
Surface modification method for silica fine particles (A3)
A product was obtained in the same manner as in the surface modification method (A1), except that vinyltrimethoxysilane (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. The amount of surface modification was calculated in the same manner as in the surface modification method (A1), except that the silane coupling agent was assigned to a chemical shift of 5.8 to 6.1 ppm (-CH=CH2 of the vinyl group of vinyltrimethoxysilane), and the calculated result was 0.7 wt%.
・シリカ微粒子の表面修飾方法（Ａ４）
表面修飾方法（Ａ１）のうち、シランカップリング剤としてメチルトリメトキシシラン（東京化成工業社製Ｍ０６６０）を使用した以外は、表面修飾方法（Ａ１）と同様の方法で生成物を得た。表面修飾量の算出は、シランカップリング剤の帰属をケミカルシフト０．１ｐｐｍ（メチルトリメトキシシランのメチル基のプロトン）とした以外は、表面修飾方法（Ａ１）と同様の方法で行い、計算結果は０．２ｗｔ％であった。
Surface modification method for silica fine particles (A4)
A product was obtained in the same manner as in the surface modification method (A1), except that methyltrimethoxysilane (M0660 manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the silane coupling agent in the surface modification method (A1). The amount of surface modification was calculated in the same manner as in the surface modification method (A1), except that the silane coupling agent was assigned a chemical shift of 0.1 ppm (the proton of the methyl group of methyltrimethoxysilane), and the calculated result was 0.2 wt%.
・シリカ微粒子の表面修飾方法（Ｂ１）
表面修飾方法（Ａ１）のうち、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業社製ＫＢＭ－５０３）の注入量を１２ｇとした以外は、表面修飾方法（Ａ１）と同様の方法で生成物を得た。表面修飾量の算出も、表面修飾方法（Ａ１）と同様の方法で行い、計算結果は３．８ｗｔ％であった。
Surface modification method for silica fine particles (B1)
A product was obtained in the same manner as in surface modification method (A1), except that the amount of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) injected was changed to 12 g. The amount of surface modification was also calculated in the same manner as in surface modification method (A1), and the calculated result was 3.8 wt %.
・シリカ微粒子の表面修飾方法（Ｂ２）
表面修飾方法（Ａ１）のうち、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業社製ＫＢＭ－５０３）の注入量を０．５ｇとした以外は、表面修飾方法（Ａ１）と同様の方法で生成物を得た。表面修飾量の算出も、表面修飾方法（Ａ１）と同様の方法で行い、計算結果は０．０５ｗｔ％であった。
Surface modification method for silica fine particles (B2)
A product was obtained in the same manner as in surface modification method (A1), except that the amount of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) injected was changed to 0.5 g. The amount of surface modification was also calculated in the same manner as in surface modification method (A1), and the calculated result was 0.05 wt %.
・水素化ポリシラザンの合成方法
撹拌機、冷却装置を備えた容量２ＬのＳＵＳ３１６製反応器を乾燥窒素により十分に乾燥させた後、乾燥ピリジン１５００ｇを入れて、撹拌しながら０℃に冷却した。これに、ジクロロシラン１２０ｇを１時間かけて加え、ピリジンとジクロロシラン錯体を形成した。引き続き温度を０℃に維持しつつ、撹拌しながら乾燥アンモニア１２０ｇを５時間かけて注入した。反応終了後、乾燥窒素雰囲気下でスラリー状生成物を濾過精度１００μｍのＳＵＳ３１６製フィルターで濾別して、濾液１１００ｇを得た。これをロータリーエバポレーターで減圧留去すると、粘性樹脂状生成物３０ｇが得られた。得られた生成物の数平均分子量をＧＰＣにより測定したところ、標準ポリスチレン換算で１２００であった。これをＦＴＩＲスペクトル測定した結果、波数３３５０ｃｍ－１、１１７５ｃｍ－１のＮＨに基づく吸収、及び２１７０ｃｍ－１の、１０００～８００ｃｍ－１のＳｉＨに基づく吸収が確認された。
- Synthesis method of hydrogenated polysilazane After thoroughly drying a 2L SUS316 reactor equipped with a stirrer and a cooling device with dry nitrogen, 1500g of dry pyridine was added and cooled to 0°C while stirring. 120g of dichlorosilane was added to the reactor over 1 hour to form a pyridine-dichlorosilane complex. While maintaining the temperature at 0°C, 120g of dry ammonia was added over 5 hours while stirring. After the reaction was completed, the slurry product was filtered with a SUS316 filter with a filtration accuracy of 100 μm under a dry nitrogen atmosphere to obtain 1100g of filtrate. This was distilled under reduced pressure with a rotary evaporator to obtain 30g of a viscous resinous product. The number average molecular weight of the product obtained was measured by GPC and found to be 1200 in terms of standard polystyrene. The FTIR spectrum of this product confirmed absorptions at wave numbers of 3350 cm -1 and 1175 cm -1 due to NH, and absorptions at 2170 cm -1 and 1000 to 800 cm -1 due to SiH.
・水素化ポリシロキサザンの合成方法
撹拌機、冷却装置を備えた容量２ＬのＳＵＳ３１６製反応器を乾燥窒素により十分に乾燥させた後、乾燥ピリジン１５００ｇを入れて、撹拌しながら０℃に冷却した。これに、ジクロロシラン１２０ｇを１時間かけて加え、ピリジンとジクロロシラン錯体を形成した。引き続き温度を０℃に維持しつつ、撹拌しながら純水５．５ｇと乾燥ピリジン２００ｇの混合液を１時間かけて注入し、更にこれに引き続き、乾燥アンモニア８０ｇを４時間かけて注入した。反応終了後、乾燥窒素雰囲気下でスラリー状生成物を濾過精度１００μｍのＳＵＳ３１６製フィルターで濾別して、濾液１２００ｇを得た。これをロータリーエバポレーターで減圧留去すると、粘性樹脂状生成物２７ｇが得られた。得られた生成物の数平均分子量をＧＰＣにより測定したところ、標準ポリスチレン換算で１１００であった。これをＦＴＩＲスペクトル測定した結果、波数３３５０ｃｍ－１、１１７５ｃｍ－１のＮＨに基づく吸収、２１７０ｃｍ－１の、１０００～８００ｃｍ－１のＳｉＨに基づく吸収、及び１０８０ｃｍ－１のＳｉＯに基づく吸収が確認された。
- Synthesis method of hydrogenated polysiloxazane A 2L SUS316 reactor equipped with a stirrer and a cooling device was thoroughly dried with dry nitrogen, and then 1500g of dry pyridine was added and cooled to 0°C while stirring. 120g of dichlorosilane was added to the reactor over 1 hour to form a pyridine-dichlorosilane complex. While maintaining the temperature at 0°C, a mixture of 5.5g of pure water and 200g of dry pyridine was poured over 1 hour while stirring, and then 80g of dry ammonia was poured over 4 hours. After the reaction was completed, the slurry product was filtered under a dry nitrogen atmosphere with a SUS316 filter with a filtration accuracy of 100 μm to obtain 1200g of filtrate. This was distilled under reduced pressure with a rotary evaporator to obtain 27g of a viscous resin-like product. The number average molecular weight of the obtained product was measured by GPC and found to be 1100 in terms of standard polystyrene. The FTIR spectrum of this product confirmed absorptions due to NH at wave numbers of 3350 cm -1 and 1175 cm -1 , absorptions due to SiH at 2170 cm -1 and 1000 to 800 cm -1 , and absorption due to SiO at 1080 cm -1 .
・表面修飾を行ったシリカ微粒子と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンと、の混合方法（Ｍ１）
混合に用いる有機溶剤、一例としてメチルイソブチルケトンに、２５０℃で乾燥させたモレキュラーシーブ４Ａを室温下で投入し、７２時間放置して脱水処理を行った。脱水処理後の有機溶剤の水分量が０．０３ｗｔ％（３００ｐｐｍ）以下であることをカールフィッシャー水分計により確認した後、当該有機溶剤を、撹拌機を備え、乾燥窒素により十分に乾燥させたＳＵＳ３１６製容器に注入した。以上の操作は、窒素ボックス内で実施した。当該有機溶剤が注入された容器に、表面修飾を行ったシリカ微粒子を濃度２０ｗｔ％になるように室温下で注入して混合し、十分に撹拌する。
また別途、同様の方法で乾燥した有機溶剤を別のＳＵＳ３１６製容器に注入し、窒素ボックス内で、当該有機溶剤が注入された容器に、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンを濃度２０ｗｔ％になるように室温下で注入し混合して溶解させ、十分に撹拌する。
続いて、表面修飾を行ったシリカ微粒子を混合した有機溶剤と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンが溶解された有機溶剤を、乾燥窒素で十分に乾燥させた新たなＳＵＳ３１６製容器に、室温下で撹拌しながら注入する。なお、表面修飾を行ったシリカ微粒子を混合した有機溶剤と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンが溶解された有機溶剤の混合比率は、条件によって調節する。
- Method of mixing surface-modified silica fine particles with hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane (M1)
Molecular sieve 4A dried at 250°C was added to the organic solvent used for mixing, for example, methyl isobutyl ketone, at room temperature, and left for 72 hours to perform dehydration treatment. After confirming with a Karl Fischer moisture meter that the moisture content of the organic solvent after dehydration was 0.03 wt% (300 ppm) or less, the organic solvent was poured into a SUS316 container equipped with a stirrer and thoroughly dried with dry nitrogen. The above operations were carried out in a nitrogen box. The surface-modified silica fine particles were poured into the container into which the organic solvent was poured at room temperature to a concentration of 20 wt%, mixed, and thoroughly stirred.
Separately, the organic solvent dried in the same manner is poured into another SUS316 container, and within the nitrogen box, hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane is poured into the container into which the organic solvent has been poured at room temperature to a concentration of 20 wt %, mixed and dissolved, and thoroughly stirred.
Next, the organic solvent containing the surface-modified silica fine particles and the organic solvent containing hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane are poured into a new SUS316 container that has been thoroughly dried with dry nitrogen, while stirring at room temperature. The mixing ratio of the organic solvent containing the surface-modified silica fine particles and the organic solvent containing hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane is adjusted depending on the conditions.
・表面修飾を行ったシリカ微粒子と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンと、の混合方法（Ｍ２）
混合に用いる有機溶剤の脱水処理を行わない以外は、混合方法（Ｍ１）と同様の方法で混合した。なお、一例として脱水処理を行わなかったメチルイソブチルケトンの水分量は、カールフィッシャー水分計にて０．０５ｗｔ％以上であった。
- Method of mixing surface-modified silica fine particles with hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane (M2)
The organic solvent used in the mixing was mixed in the same manner as in the mixing method (M1), except that the organic solvent used in the mixing was not dehydrated. As an example, the water content of methyl isobutyl ketone, which was not dehydrated, was 0.05 wt % or more when measured with a Karl Fischer moisture meter.
・表面修飾を行ったシリカ微粒子と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンのそれぞれと、を混合した各混合液の保存安定性評価方法
各混合液を注射器で３ｃｃ分取し、アドバンテック社ディスポフィルター（２５ｍｍ径、濾過精度１μｍ）を用いて濾過する。そして、濾過後の混合液の粘度を、振動式粘度計（セコニック社製ＶＭ－１０Ａ）を用いて測定した。
また別途、各混合液を窒素雰囲気中、室温で１時間放置した上で、注射器で３ｃｃ分取し、アドバンテック社ディスポフィルター（２５ｍｍ径、濾過精度１μｍ）を用いて濾過する。そして、濾過後の混合液の粘度を、振動式粘度計（セコニック社製ＶＭ－１０Ａ）を用いて測定した。
- Evaluation method for storage stability of each mixture obtained by mixing surface-modified silica fine particles with hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane: 3 cc of each mixture was taken with a syringe and filtered using a disposable filter (25 mm diameter, filtration accuracy 1 μm) manufactured by Advantech Co., Ltd. The viscosity of the mixture after filtration was measured using a vibration viscometer (VM-10A manufactured by Sekonic Co., Ltd.).
Separately, each mixture was left to stand at room temperature for 1 hour in a nitrogen atmosphere, and then 3 cc of each mixture was taken with a syringe and filtered using a disposable filter (25 mm diameter, filtration accuracy 1 μm) made by Advantech Co., Ltd. The viscosity of the mixture after filtration was measured using a vibration viscometer (VM-10A made by Sekonic Corporation).
・表面修飾を行ったシリカ微粒子と、水素化ポリシロキサン、水素化ポリシラザン又は水素化ポリシロキサザンのそれぞれと、を混合した各混合液を用いて形成した薄膜の評価方法
各混合液を注射器で３ｃｃ分取し、アドバンテック社ディスポフィルター（２５ｍｍ径、濾過精度１μｍ）を用いて濾過する。そして、濾過後の混合液を８インチシリコンウェハーにメイン回転数８００～１５００ｒｐｍの範囲でスピンコートした。続いて、塗布したシリコンウェハーを１２０℃のホットプレートにより大気雰囲気中で２分間加熱して溶剤を飛散させ、更に、５００℃のオーブンにより大気雰囲気中で９０分間加熱してシリカ質膜に転換させる。オーブンを室温まで放冷した後、目視及び１００倍の光学顕微鏡でクラックの有無を観察し、更にエリプソメーター（大塚電子社製ＦＥ－５０００）を用いて膜厚を測定した（８ポイントの平均値）。また、このシリカ膜付きシリコンウェハーと混合液を塗布する前のシリコンウェハーの重量差と、塗布面積とから、シリカ質膜の密度を算出した。
- Method for evaluating thin films formed using each mixed solution obtained by mixing surface-modified silica particles with hydrogenated polysiloxane, hydrogenated polysilazane, or hydrogenated polysiloxazane. 3 cc of each mixed solution was taken with a syringe and filtered using an Advantech disposable filter (25 mm diameter, filtration accuracy 1 μm). The filtered mixed solution was then spin-coated onto an 8-inch silicon wafer at a main rotation speed of 800 to 1500 rpm. The coated silicon wafer was then heated in an air atmosphere on a hot plate at 120°C for 2 minutes to evaporate the solvent, and further heated in an oven at 500°C for 90 minutes in an air atmosphere to convert it into a siliceous film. After cooling the oven to room temperature, the presence or absence of cracks was observed visually and with a 100x optical microscope, and the film thickness was measured using an ellipsometer (FE-5000 manufactured by Otsuka Electronics Co., Ltd.) (average value of 8 points). The density of the siliceous film was calculated from the weight difference between the silicon wafer with the silica film and the silicon wafer before the mixture was applied, and the applied area.
以上の構成要素を前提に、８つの実施例及び５つの比較例について、それぞれの構成及び実施結果を以下に示す。なお、図１は以下に示す内容を一覧表にまとめたものである。網掛け部分は、実施例１との実施条件の相違を示しており、太枠は問題のある実施結果を示している。 Based on the above components, the configurations and implementation results of eight examples and five comparative examples are shown below. Note that Figure 1 is a table summarizing the contents shown below. The shaded areas indicate differences in implementation conditions from Example 1, and the bold frames indicate problematic implementation results.
＜実施例１＞
以下の条件にて混合液の調整を行った。
・シリカ微粒子の表面修飾方法：Ａ１
・ポリマー：水素化ポリシラザン
・表面修飾後のシリカ微粒子とポリマーとの混合方法：Ｍ１
・混合に用いる有機溶剤：メチルイソブチルケトン
・表面修飾後のシリカ微粒子とポリマーとの混合比率：３０対７０（重量基準）
Example 1
The mixture was prepared under the following conditions.
Surface modification method for silica fine particles: A1
Polymer: Hydrogenated polysilazane Method of mixing surface-modified silica particles and polymer: M1
Organic solvent used for mixing: methyl isobutyl ketone Mixing ratio of surface-modified silica particles to polymer: 30:70 (by weight)
評価結果
・混合液の保存安定性：濾過直後粘度１．４ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.4 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.3 g/ cm3
＜実施例２＞
ポリマーを水素化ポリシロキサザンとした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 2
A mixed solution was prepared under the same conditions as in Example 1, except that the polymer was hydrogenated polysiloxazane.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．２ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.2 g/ cm3
＜実施例３＞
シリカ微粒子の表面修飾方法をＡ２とした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 3
The mixed solution was prepared under the same conditions as in Example 1, except that the surface modification method of the silica fine particles was changed to A2.
評価結果
・混合液の保存安定性：濾過直後粘度１．４ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.4 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.3 g/ cm3
＜実施例４＞
シリカ微粒子の表面修飾方法をＡ３とした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 4
The mixed solution was prepared under the same conditions as in Example 1, except that the surface modification method of the silica fine particles was changed to A3.
評価結果
・混合液の保存安定性：濾過直後粘度１．４ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.4 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.3 g/ cm3
＜実施例５＞
シリカ微粒子の表面修飾方法をＡ４とした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 5
The mixed solution was prepared under the same conditions as in Example 1, except that the surface modification method of the silica fine particles was changed to A4.
評価結果
・混合液の保存安定性：濾過直後粘度１．４ｃＰ、１時間放置後粘度１．５ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.4 cP, Viscosity after standing for 1 hour: 1.5 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.3 g/ cm3
＜実施例６＞
表面修飾後のシリカ微粒子とポリマーとの混合比率を５対９５とした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 6
A mixed solution was prepared under the same conditions as in Example 1, except that the mixing ratio of the surface-modified silica fine particles to the polymer was 5:95.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．２ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.2 g/ cm3
＜実施例７＞
表面修飾後のシリカ微粒子とポリマーとの混合比率を７２対２８とした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 7
The mixture was prepared under the same conditions as in Example 1, except that the mixing ratio of the surface-modified silica fine particles to the polymer was 72:28.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．４ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.4 g/ cm3
＜実施例８＞
混合に用いる有機溶剤をメチルエチルケトンとした以外は、実施例１と同じ条件にて混合液の調整を行った。
Example 8
A mixed solution was prepared under the same conditions as in Example 1, except that the organic solvent used for mixing was methyl ethyl ketone.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film: 2.3 g/ cm3
＜比較例１＞
シリカ微粒子の表面修飾方法をＢ１とした以外は、実施例１と同じ条件にて混合液の調整を行った。
<Comparative Example 1>
The mixed solution was prepared under the same conditions as in Example 1, except that the surface modification method for the silica fine particles was changed to B1.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．３ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度１．９ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.3 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film was 1.9 g/ cm3
＜比較例２＞
シリカ微粒子の表面修飾方法をＢ２とした以外は、実施例１と同じ条件にて混合液の調整を行った。
<Comparative Example 2>
The mixed solution was prepared under the same conditions as in Example 1, except that the surface modification method of the silica fine particles was changed to B2.
評価結果
・混合液の保存安定性：濾過直後粘度１．４ｃＰ、１時間放置後粘度１．８ｃＰ
・混合液で形成した薄膜の評価：クラック有り、シリカ質膜の密度２．３ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.4 cP, Viscosity after standing for 1 hour: 1.8 cP
Evaluation of the thin film formed from the mixed solution: Cracks were present, and the density of the siliceous film was 2.3 g/cm 3
＜比較例３＞
表面修飾後のシリカ微粒子とポリマーとの混合比率を１．５対９８．５とした以外は、実施例１と同じ条件にて混合液の調整を行った。
<Comparative Example 3>
The mixture was prepared under the same conditions as in Example 1, except that the mixing ratio of the surface-modified silica fine particles to the polymer was 1.5:98.5.
評価結果
・混合液の保存安定性：濾過直後粘度１．３ｃＰ、１時間放置後粘度１．４ｃＰ
・混合液で形成した薄膜の評価：クラック多数、シリカ質膜の密度は評価不能
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.3 cP, Viscosity after standing for 1 hour: 1.4 cP
Evaluation of thin film formed from mixed liquid: Many cracks, density of silica film cannot be evaluated
＜比較例４＞
表面修飾後のシリカ微粒子とポリマーとの混合比率を８５対１５とした以外は、実施例１と同じ条件にて混合液の調整を行った。
<Comparative Example 4>
The mixture was prepared under the same conditions as in Example 1, except that the mixing ratio of the surface-modified silica fine particles to the polymer was 85:15.
評価結果
・混合液の保存安定性：濾過直後粘度１．５ｃＰ、１時間放置後粘度１．５ｃＰ
・混合液で形成した薄膜の評価：クラック無し、シリカ質膜の密度１．８ｇ／ｃｍ３
Evaluation results Storage stability of the mixed liquid: Viscosity immediately after filtration: 1.5 cP, Viscosity after standing for 1 hour: 1.5 cP
Evaluation of the thin film formed from the mixed solution: No cracks, density of the siliceous film was 1.8 g/ cm3
＜比較例５＞
表面修飾後のシリカ微粒子とポリマーとの混合方法をＭ２とした以外は、実施例１と同じ条件にて混合液の調整を行った。
<Comparative Example 5>
A mixed solution was prepared under the same conditions as in Example 1, except that the method of mixing the surface-modified silica fine particles and the polymer was changed to M2.
評価結果
・混合液の保存安定性：フィルター詰まりによる濾過不能のため評価不能
・混合液で形成した薄膜の評価：濾液が得られなかったため評価不能
Evaluation results ・Storage stability of the mixed solution: Unable to evaluate due to filter clogging. ・Evaluation of the thin film formed by the mixed solution: Unable to evaluate due to no filtrate obtained.
本発明は上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。すなわち、本発明において表現されている技術的思想の範囲内で適宜変更が可能であり、その様な変更や改良を加えた形態も本発明の技術的範囲に含む。
The present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiment is an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. In other words, appropriate modifications are possible within the scope of the technical idea expressed in the present invention, and forms with such modifications and improvements are also included in the technical scope of the present invention.
Claims (4)
A siliceous mixture for forming a siliceous coating layer according to claim 2 or 3, wherein the organic solvent is a compound selected from a single or multiple types of solvents selected from aromatic hydrocarbons, saturated hydrocarbons, ethers, esters or ketones, each having a water content of 0.03 wt% or less.
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| JPH1192664A (en) * | 1997-09-24 | 1999-04-06 | Dow Corning Asia Kk | Silicone-based coating material for forming transparent hydrophilic coating film and formation of hydrophilic coating film |
| JP2005298740A (en) * | 2004-04-14 | 2005-10-27 | Admatechs Co Ltd | Surface-treated particle of metal oxide, and resin composition |
| JP2009040991A (en) * | 2007-03-28 | 2009-02-26 | Hitachi Chem Co Ltd | Coating liquid composition, heat-resistant coating film and method for forming the film |
| JP2016175790A (en) * | 2015-03-19 | 2016-10-06 | セイコーインスツル株式会社 | Method for producing silica-based particle dispersion |
| JP2019182893A (en) * | 2018-04-02 | 2019-10-24 | 大塚 啓太郎 | Siliceous coating composition, light transmitting member and forming method of siliceous coating layer |
| WO2020230823A1 (en) * | 2019-05-14 | 2020-11-19 | 日産化学株式会社 | Ketone solvent dispersion silica sol and resin composition |
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2023
- 2023-03-01 JP JP2023031355A patent/JP2024123721A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1192664A (en) * | 1997-09-24 | 1999-04-06 | Dow Corning Asia Kk | Silicone-based coating material for forming transparent hydrophilic coating film and formation of hydrophilic coating film |
| JP2005298740A (en) * | 2004-04-14 | 2005-10-27 | Admatechs Co Ltd | Surface-treated particle of metal oxide, and resin composition |
| JP2009040991A (en) * | 2007-03-28 | 2009-02-26 | Hitachi Chem Co Ltd | Coating liquid composition, heat-resistant coating film and method for forming the film |
| JP2016175790A (en) * | 2015-03-19 | 2016-10-06 | セイコーインスツル株式会社 | Method for producing silica-based particle dispersion |
| JP2019182893A (en) * | 2018-04-02 | 2019-10-24 | 大塚 啓太郎 | Siliceous coating composition, light transmitting member and forming method of siliceous coating layer |
| WO2020230823A1 (en) * | 2019-05-14 | 2020-11-19 | 日産化学株式会社 | Ketone solvent dispersion silica sol and resin composition |
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