JP2006321843A - Organic-inorganic composite material structure and method for producing the same - Google Patents
Organic-inorganic composite material structure and method for producing the same Download PDFInfo
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本発明は、有機樹脂材料の諸特性を向上させるためにシリカ等の無機微粒子を均一分散させた有機無機複合体構造物とその製造方法に関するものであり、特に無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることができる有機無機複合体構造物及びその製造方法に関するものである。 The present invention relates to an organic-inorganic composite structure in which inorganic fine particles such as silica are uniformly dispersed in order to improve various properties of the organic resin material, and a method for producing the same, and in particular, the affinity between the inorganic fine particles and the organic resin material. The present invention relates to an organic-inorganic composite structure that can improve the above and obtain a dense composite structure and a method for producing the same.
近年、フェノール樹脂等の有機樹脂材料の性能を向上させるため、ゾル−ゲル法による有機無機ハイブリッド化が行われている。かかる複合材料は、高硬度・高耐火性の塗料として、或いは高強度の構造材料として、さらには耐フェード性の高い自動車用の摩擦材として、等の様々な用途がある。例えば、特許文献１に記載されたシリカ含有フェノール樹脂コーティング材及びその製造方法の発明においては、シリコンのアルコキシドに酸触媒を加えて加水分解し、それによってシリカヒドロゾルを生成させ、次いでフェノール樹脂を加え、シリカ微粒子をフェノール樹脂に分散含有させた高硬度・高耐火性を有するシリカ含有フェノール樹脂コーティング材が得られる。
しかしながら、上記特許文献１に記載された発明を始めとして、ゾル−ゲル法による複合材料の作製は溶融状態または溶媒・溶液中でシリカのゲル化過程を必要とするため、流動性を維持することが困難である。また、固化・溶媒除去時におけるクラックの発生等の問題もある。このため、成形材やバルク体としての利用が難しく、実際の使用では薄膜のフィルムやコーティング剤としての利用が殆どであった。 However, starting with the invention described in Patent Document 1, the production of composite materials by the sol-gel method requires a gelation process of silica in a molten state or in a solvent / solution, so that fluidity is maintained. Is difficult. There are also problems such as the occurrence of cracks during solidification and solvent removal. For this reason, the use as a molding material or a bulk body is difficult, and the use as a thin film or a coating agent was most in actual use.
そこで、本発明は、これを解決するため有機物とシリカの有機無機コンポジット体を予め作製し、これを微細化して樹脂中に添加することで流動性、クラック等の問題を解決し樹脂中にシリカの微細構造を取り入れることができる有機無機複合体構造物及びその製造方法を提供することを課題とするものである。 Therefore, in order to solve this problem, the present invention prepares an organic-inorganic composite of silica and silica in advance, and finely adds this to the resin to solve problems such as fluidity and cracks. It is an object of the present invention to provide an organic-inorganic composite structure capable of incorporating a fine structure of the above and a method for producing the same.
請求項１の発明にかかる有機無機複合体構造物は、第１の合成樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一に混合した後に固化させて得られる有機無機複合体を細かく粉砕して、第２の合成樹脂と均一に混合して固化させて得られるものである。 The organic-inorganic composite structure according to the invention of claim 1 is obtained by finely pulverizing an organic-inorganic composite obtained by adding a silica sol or titania sol to the first synthetic resin solution while stirring and mixing uniformly. Then, it is obtained by uniformly mixing and solidifying with the second synthetic resin.
請求項２の発明にかかる有機無機複合体構造物は、第１の熱硬化性樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一に混合した後に熱硬化させて得られる有機無機複合体を細かく粉砕して、第２の熱硬化性樹脂と均一に混合して熱硬化させ、アニーリングして得られるものである。 The organic-inorganic composite structure according to the invention of claim 2 is an organic-inorganic composite obtained by adding silica sol or titania sol to the first thermosetting resin solution while stirring and mixing uniformly, and then thermosetting. Is finely pulverized, uniformly mixed with the second thermosetting resin, thermally cured, and annealed.
請求項３の発明にかかる有機無機複合体構造物の製造方法は、第１の合成樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一な混合液を得る工程と、前記混合液を加熱して前記第１の合成樹脂を固化させて有機無機複合体を得る工程と、前記有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、第２の合成樹脂に前記複合体微細粉末を均一に混合して固化させる工程とを具備するものである。 According to a third aspect of the present invention, there is provided a method for producing an organic-inorganic composite structure comprising: adding a silica sol or titania sol to a first synthetic resin solution while stirring to obtain a uniform mixed solution; and heating the mixed solution. The first synthetic resin is solidified to obtain an organic-inorganic composite, the organic-inorganic composite is finely pulverized to obtain a fine composite powder, and the second synthetic resin is combined with the composite. And a step of uniformly mixing and solidifying the fine powder.
請求項４の発明にかかる有機無機複合体構造物の製造方法は、第１の熱硬化性樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一な混合液を得る工程と、前記混合液を加熱して前記第１の熱硬化性樹脂を熱硬化させて有機無機複合体を得る工程と、前記有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、第２の熱硬化性樹脂に前記複合体微細粉末を均一に混合して熱硬化させる工程と、より高温に加熱してアニーリングする工程とを具備するものである。 The method for producing an organic-inorganic composite structure according to the invention of claim 4 includes a step of adding a silica sol or titania sol to the first thermosetting resin solution while stirring to obtain a uniform mixed solution, and the mixed solution And heating the first thermosetting resin to obtain an organic-inorganic composite, finely pulverizing the organic-inorganic composite to obtain a composite fine powder, and second heat It comprises a step of uniformly mixing the composite fine powder in a curable resin and thermosetting, and a step of heating to a higher temperature and annealing.
請求項５の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、請求項２または請求項４の構成において、前記第１の熱硬化性樹脂と前記第２の熱硬化性樹脂とが同種の或いは架橋しうる熱硬化性樹脂であるものである。 An organic-inorganic composite structure or a method for producing an organic-inorganic composite structure according to the invention of claim 5 is the structure of claim 2 or claim 4, wherein the first thermosetting resin and the second heat are used. The curable resin is the same kind or a thermosetting resin that can be crosslinked.
請求項６の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、請求項１乃至請求項５のいずれか１つの構成において、前記シリカゾルまたはチタニアゾルの粒径が１ｎｍ〜１００ｎｍの範囲内であるものである。 The method for producing an organic-inorganic composite structure or an organic-inorganic composite structure according to the invention of claim 6 is the structure according to any one of claims 1 to 5, wherein the silica sol or titania sol has a particle size of 1 nm to It is within the range of 100 nm.
請求項７の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、請求項１乃至請求項６のいずれか１つの構成において、前記シリカゾルは水ガラスをイオン交換または酸中和して得られるものである。 According to a seventh aspect of the present invention, there is provided an organic-inorganic composite structure or a method for producing an organic-inorganic composite structure according to any one of the first to sixth aspects, wherein the silica sol is water-exchanged or acid-exchanged with water glass. It is obtained by neutralization.
請求項８の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、請求項２乃至請求項７のいずれか１つの構成において、前記第１の熱硬化性樹脂はレゾール型フェノール樹脂であり、前記第２の熱硬化性樹脂はノボラック型フェノール樹脂であるものである。 The organic-inorganic composite structure or the method for producing an organic-inorganic composite structure according to the invention of claim 8 is the structure according to any one of claims 2 to 7, wherein the first thermosetting resin is resole. And the second thermosetting resin is a novolac type phenolic resin.
請求項１の発明にかかる有機無機複合体構造物は、第１の合成樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一に混合した後に固化させて得られる有機無機複合体を細かく粉砕して、第２の合成樹脂と均一に混合して固化させて得られる。 The organic-inorganic composite structure according to the invention of claim 1 is obtained by finely pulverizing an organic-inorganic composite obtained by adding a silica sol or titania sol to the first synthetic resin solution while stirring and mixing uniformly. Then, it is obtained by uniformly mixing with the second synthetic resin and solidifying.
ここで、第１の合成樹脂及び第２の合成樹脂としては、フェノール樹脂・エポキシ樹脂・ウレタン樹脂等の熱硬化性樹脂を始めとして、アクリル樹脂・ポリプロピレン樹脂・ポリスチレン樹脂・ナイロン等の熱可塑性樹脂、スチレン−ブタジエン−ラテックス（ＳＢＲ）ゴム等のエラストマー等の、種々の合成樹脂を用いることができる。 Here, as the first synthetic resin and the second synthetic resin, thermoplastic resins such as acrylic resin, polypropylene resin, polystyrene resin, and nylon, as well as thermosetting resins such as phenol resin, epoxy resin, and urethane resin are used. Various synthetic resins such as elastomers such as styrene-butadiene-latex (SBR) rubber can be used.
このように、本発明にかかる有機無機複合体構造物は、まず第１の合成樹脂とシリカゾルまたはチタニアゾルを均一に混合した後、一旦固化させて粉砕することによって、シリカゾルまたはチタニアゾルに第１の合成樹脂が密着して有機樹脂との親和性が向上した有機無機複合体粉末が得られる。これを第２の合成樹脂と均一に混合して固化させることによって、有機無機複合体粉末が第２の合成樹脂中に均一に分散した有機無機複合体構造物となる。したがって、単にシリカ等の微粉末を合成樹脂中に混合して固化させたものとは異なり、緻密な構造が得られるため強度が大幅に向上し、耐摩耗性等の諸特性も向上する。 As described above, the organic-inorganic composite structure according to the present invention is obtained by first uniformly mixing the first synthetic resin and the silica sol or titania sol, and then solidifying and grinding the first synthetic resin into the silica sol or titania sol. An organic-inorganic composite powder having an improved affinity with the organic resin due to the close contact of the resin is obtained. By uniformly mixing and solidifying this with the second synthetic resin, an organic-inorganic composite structure in which the organic-inorganic composite powder is uniformly dispersed in the second synthetic resin is obtained. Therefore, unlike the case where a fine powder such as silica is simply mixed in a synthetic resin and solidified, a dense structure is obtained, so that the strength is greatly improved and various properties such as wear resistance are improved.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. An organic-inorganic composite structure is obtained.
請求項２の発明にかかる有機無機複合体構造物は、第１の熱硬化性樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一に混合した後に熱硬化させて得られた有機無機複合体を細かく粉砕して、第２の熱硬化性樹脂と均一に混合して熱硬化させた後、より高温に加熱する等によってアニーリングして得られる。 The organic-inorganic composite structure according to the invention of claim 2 is an organic-inorganic composite obtained by adding silica sol or titania sol to the first thermosetting resin solution while stirring and mixing uniformly, and then thermosetting. After the body is finely pulverized, uniformly mixed with the second thermosetting resin and thermally cured, it is obtained by annealing, for example, by heating to a higher temperature.
ここで、第１の熱硬化性樹脂及び第２の熱硬化性樹脂としては、フェノール樹脂、エポキシ樹脂、ウレタン樹脂を始めとして、種々の熱硬化性樹脂を用いることができる。 Here, as the first thermosetting resin and the second thermosetting resin, various thermosetting resins such as a phenol resin, an epoxy resin, and a urethane resin can be used.
このように、本発明にかかる有機無機複合体構造物は、まず第１の熱硬化性樹脂とシリカゾルまたはチタニアゾルを均一に混合した後、一旦熱硬化させて粉砕することによって、シリカゾルまたはチタニアゾルに第１の熱硬化性樹脂が密着して有機樹脂との親和性が向上した有機無機複合体粉末が得られる。これを第２の熱硬化性樹脂と均一に混合して熱硬化させることによって、有機無機複合体粉末が第２の熱硬化性樹脂中に均一に分散した有機無機複合体構造物となる。したがって、単にシリカ等の微粉末を熱硬化性樹脂中に混合して熱硬化させたものとは異なり、緻密な構造が得られるため強度が大幅に向上し、耐摩耗性等の諸特性も向上する。 As described above, the organic-inorganic composite structure according to the present invention is obtained by first uniformly mixing the first thermosetting resin and the silica sol or titania sol, and then thermally curing and pulverizing the silica sol or titania sol. Thus, an organic-inorganic composite powder having an improved affinity with an organic resin can be obtained. By uniformly mixing this with the second thermosetting resin and thermosetting, an organic-inorganic composite structure in which the organic-inorganic composite powder is uniformly dispersed in the second thermosetting resin is obtained. Therefore, unlike those obtained by simply mixing silica and other fine powders in a thermosetting resin and thermosetting, a dense structure is obtained, so the strength is greatly improved and various properties such as wear resistance are also improved. To do.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. An organic-inorganic composite structure is obtained.
請求項３の発明にかかる有機無機複合体構造物の製造方法は、第１の合成樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一な混合液を得る工程と、混合液を加熱して第１の合成樹脂を固化させて有機無機複合体を得る工程と、有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、第２の合成樹脂に複合体微細粉末を均一に混合して固化させる工程とを具備する。 The method for producing an organic-inorganic composite structure according to the invention of claim 3 includes a step of adding a silica sol or titania sol to the first synthetic resin solution while stirring to obtain a uniform mixed solution, and heating the mixed solution. The first synthetic resin is solidified to obtain an organic-inorganic composite, the organic-inorganic composite is finely pulverized to obtain a fine composite powder, and the fine composite powder is uniformly applied to the second synthetic resin. And solidifying the mixture.
ここで、第１の合成樹脂及び第２の合成樹脂としては、フェノール樹脂・エポキシ樹脂・ウレタン樹脂等の熱硬化性樹脂を始めとして、アクリル樹脂・ポリプロピレン樹脂・ポリスチレン樹脂・ナイロン等の熱可塑性樹脂、スチレン−ブタジエン−ラテックス（ＳＢＲ）ゴム等のエラストマー等の、種々の合成樹脂を用いることができる。 Here, as the first synthetic resin and the second synthetic resin, thermoplastic resins such as acrylic resin, polypropylene resin, polystyrene resin, and nylon, as well as thermosetting resins such as phenol resin, epoxy resin, and urethane resin are used. Various synthetic resins such as elastomers such as styrene-butadiene-latex (SBR) rubber can be used.
このように、本発明にかかる有機無機複合体構造物の製造方法においては、まず第１の合成樹脂とシリカゾルまたはチタニアゾルを攪拌して均一に混合した後、一旦固化させて微細に粉砕することによって、シリカゾルまたはチタニアゾルに第１の合成樹脂が密着して有機樹脂との親和性が向上した複合体微細粉末が得られる。この複合体微細粉末を第２の合成樹脂と均一に混合して固化させることによって、有機無機複合体粉末が第２の合成樹脂中に均一に分散した有機無機複合体構造物となる。したがって、単にシリカ等の微粉末を合成樹脂中に混合して固化させる有機無機複合体構造物の製造方法とは異なり、緻密な構造が得られるため、強度が大幅に向上し、耐摩耗性等の諸特性も向上する。 Thus, in the method for producing an organic-inorganic composite structure according to the present invention, the first synthetic resin and the silica sol or titania sol are first stirred and mixed uniformly, and then solidified once and then finely pulverized. The first synthetic resin is in close contact with the silica sol or titania sol, and a composite fine powder having improved affinity with the organic resin is obtained. By uniformly mixing and solidifying the composite fine powder with the second synthetic resin, an organic-inorganic composite structure in which the organic-inorganic composite powder is uniformly dispersed in the second synthetic resin is obtained. Therefore, unlike a method of manufacturing an organic-inorganic composite structure in which a fine powder such as silica is simply mixed in a synthetic resin and solidified, a dense structure is obtained, so that the strength is greatly improved, wear resistance, etc. These characteristics are also improved.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物の製造方法となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. It becomes the manufacturing method of the organic-inorganic composite structure which can be performed.
請求項４の発明にかかる有機無機複合体構造物の製造方法は、第１の熱硬化性樹脂の溶液にシリカゾルまたはチタニアゾルを攪拌しながら添加して均一な混合液を得る工程と、混合液を加熱して第１の熱硬化性樹脂を熱硬化させて有機無機複合体を得る工程と、有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、第２の熱硬化性樹脂に複合体微細粉末を均一に混合して熱硬化させる工程と、より高温に加熱してアニーリングする工程とを具備する。 According to a fourth aspect of the present invention, there is provided a method for producing an organic-inorganic composite structure comprising: adding a silica sol or titania sol to the first thermosetting resin solution while stirring to obtain a uniform mixed solution; A step of heating and thermosetting the first thermosetting resin to obtain an organic-inorganic composite; a step of finely pulverizing the organic-inorganic composite to obtain a composite fine powder; and a second thermosetting resin And a step of uniformly mixing and heat-curing the composite fine powder, and a step of heating to a higher temperature and annealing.
ここで、第１の熱硬化性樹脂及び第２の熱硬化性樹脂としては、フェノール樹脂、エポキシ樹脂、ウレタン樹脂を始めとして、種々の熱硬化性樹脂を用いることができる。 Here, as the first thermosetting resin and the second thermosetting resin, various thermosetting resins such as a phenol resin, an epoxy resin, and a urethane resin can be used.
このように、本発明にかかる有機無機複合体構造物の製造方法においては、まず第１の熱硬化性樹脂とシリカゾルまたはチタニアゾルを攪拌して均一に混合した後、一旦熱硬化させて微細に粉砕することによって、シリカゾルまたはチタニアゾルに第１の熱硬化性樹脂が密着して有機樹脂との親和性が向上した複合体微細粉末が得られる。この複合体微細粉末を第２の熱硬化性樹脂と均一に混合して熱硬化させることによって、有機無機複合体粉末が第２の熱硬化性樹脂中に均一に分散した有機無機複合体構造物となる。したがって、単にシリカ等の微粉末を熱硬化性樹脂中に混合して熱硬化させる有機無機複合体構造物の製造方法とは異なり、緻密な構造が得られるため、強度が大幅に向上し、耐摩耗性等の諸特性も向上する。 As described above, in the method for producing an organic-inorganic composite structure according to the present invention, the first thermosetting resin and the silica sol or titania sol are first stirred and mixed uniformly, and then thermally cured and finely pulverized. By doing so, the first thermosetting resin is brought into close contact with the silica sol or titania sol, and a composite fine powder having improved affinity with the organic resin is obtained. An organic-inorganic composite structure in which the organic-inorganic composite powder is uniformly dispersed in the second thermosetting resin by uniformly mixing the composite fine powder with the second thermosetting resin and thermosetting the mixture. It becomes. Therefore, unlike a method for producing an organic-inorganic composite structure in which a fine powder such as silica is simply mixed in a thermosetting resin and thermoset, a dense structure is obtained. Various characteristics such as wear are also improved.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物の製造方法となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. It becomes the manufacturing method of the organic-inorganic composite structure which can be performed.
請求項５の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、第１の熱硬化性樹脂と第２の熱硬化性樹脂とが同種の或いは架橋しうる熱硬化性樹脂である。ここで、同種の熱硬化性樹脂とは、フェノール樹脂同士、エポキシ樹脂同士、等を意味するものであり、具体的には第１の熱硬化性樹脂がレゾール型のフェノール樹脂で第２の熱硬化性樹脂がノボラック型のフェノール樹脂であるような場合を意味し、全く同一の熱硬化性樹脂の場合をも含むものである。また、架橋しうる熱硬化性樹脂とは、例えばフェノール樹脂とエポキシ樹脂のような場合である。 The method for producing an organic-inorganic composite structure or an organic-inorganic composite structure according to the invention of claim 5 is such that the first thermosetting resin and the second thermosetting resin are of the same type or can be crosslinked. Resin. Here, the same kind of thermosetting resin means phenol resins, epoxy resins, and the like. Specifically, the first thermosetting resin is a resol type phenol resin and the second heat resin. It means the case where the curable resin is a novolac type phenol resin, and includes the case of the exact same thermosetting resin. Moreover, the thermosetting resin which can be bridge | crosslinked is a case like a phenol resin and an epoxy resin, for example.
これによって、第１の熱硬化性樹脂が密着した複合体微細粉末と第２の熱硬化性樹脂との親和性がより高くなるため、より緻密な構造が得られ、強度が大幅に向上し、耐摩耗性等の諸特性も向上する。 Thereby, since the affinity between the composite fine powder to which the first thermosetting resin is in close contact and the second thermosetting resin becomes higher, a denser structure is obtained, and the strength is greatly improved. Various characteristics such as wear resistance are also improved.
このようにして、無機微粒子と有機樹脂材料の親和性をより向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物または有機無機複合体構造物の製造方法となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. An organic-inorganic composite structure or a method for producing an organic-inorganic composite structure can be obtained.
請求項６の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、シリカゾルまたはチタニアゾルの粒径が１ｎｍ〜１００ｎｍの範囲内、より好ましくは５ｎｍ〜５０ｎｍの範囲内である。 In the method for producing an organic-inorganic composite structure or an organic-inorganic composite structure according to the invention of claim 6, the silica sol or titania sol has a particle size in the range of 1 nm to 100 nm, more preferably in the range of 5 nm to 50 nm. .
本発明者らが鋭意実験研究を行った結果、シリカゾルまたはチタニアゾルの粒径が１ｎｍ〜１００ｎｍの範囲内、より好ましくは５ｎｍ〜５０ｎｍの範囲内である場合に、得られる有機無機複合体構造物の強度を始めとする諸特性が最も向上することを見出し、この知見に基づいて本発明を完成したものである。 As a result of the inventors' diligent experimental research, it was found that when the particle size of the silica sol or titania sol is in the range of 1 nm to 100 nm, more preferably in the range of 5 nm to 50 nm, the organic-inorganic composite structure obtained The inventors have found that various properties including strength are most improved, and have completed the present invention based on this finding.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物または有機無機複合体構造物の製造方法となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. An organic-inorganic composite structure or a method for producing an organic-inorganic composite structure can be obtained.
請求項７の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、シリカゾルが水ガラス（ケイ酸アルカリ塩水溶液）をイオン交換または酸中和して得られるものである。 The method for producing an organic-inorganic composite structure or an organic-inorganic composite structure according to the invention of claim 7 is obtained by subjecting silica sol to ion exchange or acid neutralization of water glass (alkali silicate aqueous solution). .
シリカゾルを得る方法としては、シリコンアルコキシドを加水分解する方法もあるが、シリコンアルコキシドは高価であるため、得られる有機無機複合体構造物のコストも高くなってしまう。そこで、シリコンアルコキシドに比較して遥かに安価な水ガラス（ケイ酸アルカリ塩水溶液）をイオン交換または酸中和して得られるシリカゾルを用いることによって、得られる有機無機複合体構造物のコストを低減することができる。 As a method for obtaining silica sol, there is a method in which silicon alkoxide is hydrolyzed. However, since silicon alkoxide is expensive, the cost of the resulting organic-inorganic composite structure is increased. Therefore, by using silica sol obtained by ion exchange or acid neutralization of water glass (alkali silicate aqueous solution), which is much cheaper than silicon alkoxide, the cost of the resulting organic-inorganic composite structure is reduced. can do.
このようにして、無機微粒子と有機樹脂材料の親和性を向上させて緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができるとともに、低コスト化できる有機無機複合体構造物または有機無機複合体構造物の製造方法となる。 In this way, by improving the affinity between the inorganic fine particles and the organic resin material to obtain a dense composite structure, the strength can be greatly improved, and various properties such as wear resistance can be improved. In addition, the organic-inorganic composite structure or the method for producing the organic-inorganic composite structure can be reduced in cost.
請求項８の発明にかかる有機無機複合体構造物または有機無機複合体構造物の製造方法は、第１の熱硬化性樹脂はレゾール型フェノール樹脂であり、第２の熱硬化性樹脂はノボラック型フェノール樹脂である。 In the method of manufacturing an organic-inorganic composite structure or an organic-inorganic composite structure according to the invention of claim 8, the first thermosetting resin is a resol type phenol resin, and the second thermosetting resin is a novolak type. It is a phenol resin.
レゾール型フェノール樹脂は通常メタノール溶液として市販されているため、シリカゾルまたはチタニアゾルと均一に混合するのが容易であり、ノボラック型フェノール樹脂は通常粉末状で市販されているため、粉砕して得られる複合体微細粉末と均一に混合するのが容易である。そして、第１の熱硬化性樹脂と第２の熱硬化性樹脂が同種のフェノール樹脂であるため、複合体微細粉末と第２の熱硬化性樹脂との親和性がより一層向上して、より緻密な有機無機複合体構造物を得ることができる。 Since resol type phenol resin is usually marketed as a methanol solution, it is easy to mix uniformly with silica sol or titania sol, and since novolac type phenol resin is usually marketed in powder form, it is a composite obtained by grinding. Easy to mix uniformly with fine body powder. Since the first thermosetting resin and the second thermosetting resin are the same type of phenol resin, the affinity between the composite fine powder and the second thermosetting resin is further improved. A dense organic-inorganic composite structure can be obtained.
このようにして、無機微粒子と有機樹脂材料の親和性をより一層向上させてより緻密な複合体構造を得ることによって、強度を大幅に向上させることができ、耐摩耗性等の諸特性も向上させることができる有機無機複合体構造物または有機無機複合体構造物の製造方法となる。 In this way, by further improving the affinity between the inorganic fine particles and the organic resin material to obtain a denser composite structure, the strength can be greatly improved, and various properties such as wear resistance are also improved. It becomes the manufacturing method of the organic inorganic composite structure or the organic inorganic composite structure which can be made to be made.
以下、本発明の実施の形態について、図１乃至図８を参照しつつ説明する。 Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 8.
図１は本発明の実施の形態にかかる有機無機複合体構造物の製造方法の概略を示すフローチャートである。図２は本発明の実施の形態にかかる有機無機複合体構造物の実施例１の曲げ強度を比較例１，比較例２，比較例５と比較して示した図である。図３は本発明の実施の形態にかかる有機無機複合体構造物の実施例１の摩擦摩耗試験における摩耗量を比較例１，比較例２，比較例５と比較して示した図である。図４は本発明の実施の形態にかかる有機無機複合体構造物の実施例１の摩擦摩耗試験におけるＰＶ値と摩擦係数との関係を比較例１，比較例２，比較例５と比較して示した図である。 FIG. 1 is a flowchart showing an outline of a method for producing an organic-inorganic composite structure according to an embodiment of the present invention. FIG. 2 is a diagram showing the bending strength of Example 1 of the organic-inorganic composite structure according to the embodiment of the present invention in comparison with Comparative Example 1, Comparative Example 2, and Comparative Example 5. FIG. 3 is a diagram showing the amount of wear in the friction wear test of Example 1 of the organic-inorganic composite structure according to the embodiment of the present invention in comparison with Comparative Example 1, Comparative Example 2, and Comparative Example 5. FIG. 4 shows the relationship between the PV value and the friction coefficient in the frictional wear test of Example 1 of the organic-inorganic composite structure according to the embodiment of the present invention compared with Comparative Example 1, Comparative Example 2, and Comparative Example 5. FIG.
図５は本発明の実施の形態にかかる有機無機複合体構造物の実施例２の曲げ強度を比較例２，比較例３，比較例４と比較して示した図である。図６は本発明の実施の形態にかかる有機無機複合体構造物の実施例２の摩擦摩耗試験におけるＰＶ値と摩擦係数との関係を比較例２，比較例３，比較例４と比較して示した図である。図７は本発明の実施の形態にかかる有機無機複合体構造物の実施例２の破断面の走査型電子顕微鏡（ＳＥＭ）写真を示す図である。図８は有機無機複合体構造物の比較例３の破断面の走査型電子顕微鏡（ＳＥＭ）写真を示す図である。 FIG. 5 is a diagram showing the bending strength of Example 2 of the organic-inorganic composite structure according to the embodiment of the present invention in comparison with Comparative Example 2, Comparative Example 3, and Comparative Example 4. FIG. 6 shows the relationship between the PV value and the friction coefficient in the friction and wear test of Example 2 of the organic-inorganic composite structure according to the embodiment of the present invention compared with Comparative Example 2, Comparative Example 3, and Comparative Example 4. FIG. FIG. 7: is a figure which shows the scanning electron microscope (SEM) photograph of the torn surface of Example 2 of the organic inorganic composite structure concerning embodiment of this invention. FIG. 8 is a view showing a scanning electron microscope (SEM) photograph of a fracture surface of Comparative Example 3 of the organic-inorganic composite structure.
まず、本発明の実施の形態にかかる有機無機複合体構造物の製造方法について、図１を参照して説明する。本実施の形態にかかる有機無機複合体構造物においては、第１の熱硬化性樹脂としてレゾール型のフェノール樹脂を、第２の熱硬化性樹脂としてノボラック型のフェノール樹脂を用いている。 First, the manufacturing method of the organic inorganic composite structure concerning embodiment of this invention is demonstrated with reference to FIG. In the organic-inorganic composite structure according to the present embodiment, a resol type phenol resin is used as the first thermosetting resin, and a novolac type phenol resin is used as the second thermosetting resin.
図１に示されるように、本実施の形態にかかる有機無機複合体構造物の製造方法は、まず樹脂・ゾル混合工程Ｓ１において、第１の熱硬化性樹脂としてのレゾール型のフェノール樹脂のメタノール溶液に、水ガラス（ケイ酸アルカリ塩水溶液）をイオン交換または酸中和して得られるシリカゾルを攪拌しながら添加して混合する。この混合液を、熱硬化工程Ｓ２において、加熱して硬化させ、有機無機複合体固形物を得る。次に、この有機無機複合体固形物を、複合体粉砕工程Ｓ３において、回転式粉砕機で微細粉末に粉砕する。 As shown in FIG. 1, in the method for producing an organic-inorganic composite structure according to the present embodiment, first, in a resin / sol mixing step S1, methanol of a resol type phenol resin as a first thermosetting resin is used. A silica sol obtained by ion exchange or acid neutralization of water glass (alkali silicate aqueous solution) is added to the solution while stirring and mixed. In the thermosetting step S2, this mixed liquid is heated and cured to obtain an organic-inorganic composite solid. Next, this organic-inorganic composite solid material is pulverized into a fine powder by a rotary pulverizer in the composite pulverization step S3.
続いて、この微細粉末を第２の熱硬化性樹脂としてのノボラック型のフェノール樹脂（粉末）と均一に混合する。そして、この混合粉末を加熱加圧成形工程Ｓ５において、加熱加圧成形機によって加熱加圧して成形体として、アニーリング工程Ｓ６において、より高い温度で加熱してアフターキュアすることによって、本実施の形態にかかる有機無機複合体構造物が得られる。本実施の形態においては、配合を変えて、実施例１及び実施例２の有機無機複合体構造物を製造した。 Subsequently, the fine powder is uniformly mixed with a novolac-type phenol resin (powder) as the second thermosetting resin. Then, this mixed powder is heated and pressed by a heating and pressing molding machine in a heating and pressing molding step S5 to form a molded body, which is then heated and cured at a higher temperature in the annealing step S6. The organic-inorganic composite structure according to the above is obtained. In the present embodiment, the organic-inorganic composite structures of Example 1 and Example 2 were manufactured by changing the composition.
本実施の形態にかかる実施例１の有機無機複合体構造物は、フェノール樹脂（住友ベークライト（株）ＰＲ５４５６２、レゾール型、メタノール溶剤、固形分５０％）４０重量部に対してメタノール６０重量部を加え、均一になるように調整した溶液に、シリカゾルを固形分として２重量部になるように攪拌しながら添加した。この溶液を室温で３０分間保持してシリカをゲル化させた後、１５０℃で硬化させた。こうして得られた複合体を透過型電子顕微鏡（ＴＥＭ）で観察したところ、５ｎｍ〜５０ｎｍのシリカ粒子が樹枝状に連鎖して分散している状態が観察された。 The organic-inorganic composite structure of Example 1 according to the present embodiment is obtained by adding 60 parts by weight of methanol to 40 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd. PR54562, resol type, methanol solvent, solid content 50%). In addition, the silica sol was added to the solution adjusted to be uniform so that the solid content was 2 parts by weight with stirring. This solution was kept at room temperature for 30 minutes to gel the silica and then cured at 150 ° C. When the thus obtained composite was observed with a transmission electron microscope (TEM), it was observed that silica particles of 5 nm to 50 nm were dispersed in a dendritic manner.
この複合体を回転式粉砕機で粉砕し、フェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）を８０重量部に対して、複合体粉砕物を２０重量部加え、さらにヘキサミン９．９重量部を加えて混合した後に、１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて実施例１の有機無機複合体構造物が得られた。 This composite was pulverized with a rotary pulverizer, and 20 parts by weight of the composite pulverized product was added to 80 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content 100%). after further added and mixed hexamine 9.9 parts by weight, pressure curing at 160 ° C. (degassing before molding pressure 400 kgf / cm 2, degassing number 3 times, venting after molding pressure 500 kgf / cm 2, pressing time 15 minutes), and then after-curing at 160 ° C. for 1 hour, 180 ° C. for 1 hour, and 200 ° C. for 1 hour, an organic-inorganic composite structure of Example 1 was obtained.
本実施の形態にかかる実施例２の有機無機複合体構造物は、フェノール樹脂（住友ベークライト（株）ＰＲ５４５６２、レゾール型、メタノール溶剤、固形分５０％）６０重量部に対してメタノール９０重量部を加え、均一になるように調整した溶液に、シリカゾルを固形分として７０重量部になるように攪拌しながら添加した。この溶液を室温で３０分間保持してシリカをゲル化させた後、１５０℃で硬化させた。 The organic-inorganic composite structure of Example 2 according to the present embodiment is obtained by adding 90 parts by weight of methanol to 60 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd. PR54562, resol type, methanol solvent, solid content 50%). In addition, the silica sol was added to the solution adjusted to be uniform while stirring so that the solid content was 70 parts by weight. This solution was kept at room temperature for 30 minutes to gel the silica and then cured at 150 ° C.
こうして得られた複合体を回転式粉砕機で粉砕し、フェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）を８０重量部に対して、複合体粉砕物を２０重量部加えてシリカ分として１４重量部になるようにし、さらにヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて実施例２の有機無機複合体構造物が得られた。 The composite thus obtained was pulverized by a rotary pulverizer, and 80 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content: 100%) and 20% by weight of the composite pulverized product. In addition, 14 parts by weight of silica is added, and 9.9 parts by weight of hexamine is further added and mixed, followed by pressure curing at 160 ° C. (molding pressure before degassing 400 kgf / cm 2 , degassing 3 times, After degassing, a molding pressure of 500 kgf / cm 2 , a pressurization time of 15 minutes), and then after-curing at 160 ° C. for 1 hour, 180 ° C. for 1 hour, and 200 ° C. for 1 hour are used. Things were obtained.
一方、比較例１としては、フェノール樹脂（住友ベークライト（株）ＰＲ５４５６２、レゾール型、メタノール溶剤、固形分５０％）を１５０℃で熱硬化させ、この硬化物を回転式粉砕機で粉砕し、フェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）を８０重量部に対して、粉砕物を２０重量部加えて、さらにヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて比較例１の有機複合体構造物とした。 On the other hand, as Comparative Example 1, a phenol resin (Sumitomo Bakelite Co., Ltd. PR54562, resol type, methanol solvent, solid content 50%) was thermally cured at 150 ° C., and the cured product was pulverized with a rotary pulverizer. After adding 80 parts by weight of resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content: 100%), 20 parts by weight of the pulverized product and 9.9 parts by weight of hexamine are added and mixed. ° C. in pressure curing (degassed before molding pressure 400 kgf / cm 2, degassing number 3 times, venting after molding pressure 500 kgf / cm 2, pressing time 15 min) was one hour thereafter 160 ° C., at 180 ° C. After curing for 1 hour at 200 ° C. for 1 hour, an organic composite structure of Comparative Example 1 was obtained.
また、比較例２としては、フェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）を８０重量部に対して、ヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて比較例２の有機構造物とした。 Further, as Comparative Example 2, phenolic resin (Sumitomo Bakelite Co., Ltd., Novolak type, powder, 100% solid content) was added to 9.9 parts by weight of hexamine with respect to 80 parts by weight, and then mixed at 160 ° C. in pressure curing (degassed before molding pressure 400 kgf / cm 2, degassing number 3 times, venting after molding pressure 500 kgf / cm 2, pressing time 15 min) was one hour thereafter 160 ° C., 1 at 180 ° C. After curing at 200 ° C. for 1 hour, the organic structure of Comparative Example 2 was obtained.
また、比較例３としては、微細シリカ粒子（信越化学工業（株）ＫＭＰ５９０、疎水性）をフェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）８６重量部に対して１４重量部加え、さらにヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて比較例３の有機無機複合体構造物とした。 Moreover, as Comparative Example 3, fine silica particles (Shin-Etsu Chemical Co., Ltd. KMP590, hydrophobic) were added to 86 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content 100%). 14 parts by weight, and further 9.9 parts by weight of hexamine were added and mixed, followed by pressure curing at 160 ° C. (molding pressure before degassing 400 kgf / cm 2 , degassing three times, molding pressure after degassing 500 kgf / cm 2 And then after-curing at 160 ° C. for 1 hour, at 180 ° C. for 1 hour, and at 200 ° C. for 1 hour to obtain an organic-inorganic composite structure of Comparative Example 3.
また、比較例４としては、微細シリカ粒子（信越化学工業（株）Ｘ−２４−９１６３Ａ、親水性）をフェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）８６重量部に対して１４重量部加え、さらにヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて比較例４の有機無機複合体構造物とした。 Moreover, as Comparative Example 4, fine silica particles (Shin-Etsu Chemical Co., Ltd. X-24-9163A, hydrophilic) were added to phenol resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content 100%) 86 weight. 14 parts by weight with respect to the parts, and further 9.9 parts by weight of hexamine and mixed, followed by pressure curing at 160 ° C. (molding pressure before degassing 400 kgf / cm 2 , number of degassing three times, molding pressure after degassing 500 kgf / cm 2 , pressurization time 15 minutes), and then after-curing at 160 ° C. for 1 hour, 180 ° C. for 1 hour, and 200 ° C. for 1 hour to obtain an organic-inorganic composite structure of Comparative Example 4.
さらに、比較例５としては、フェノール樹脂（住友ベークライト（株）、ノボラック型、粉末状、固形分１００％）８０重量部をメタノール３２０重量部に溶解させて、これにコロイダルシリカ（日産化学工業（株）スノーテックスＯ、ＳｉＯ2 ２０％）を８重量部添加後、室温で４８時間、さらに６０℃で５時間減圧乾燥して溶媒を除去したものを粉砕し、ヘキサミン９．９重量部を加えて混合した後に１６０℃で加圧硬化（ガス抜き前成形圧力４００ｋｇｆ／ｃｍ2 、ガス抜き回数３回、ガス抜き後成形圧力５００ｋｇｆ／ｃｍ2 、加圧時間１５分間）させ、その後１６０℃で１時間、１８０℃で１時間、２００℃で１時間、アフターキュアさせて比較例５の有機無機複合体構造物とした。 Furthermore, as Comparative Example 5, 80 parts by weight of phenol resin (Sumitomo Bakelite Co., Ltd., novolak type, powder, solid content 100%) was dissolved in 320 parts by weight of methanol, and colloidal silica (Nissan Chemical Industries ( After adding 8 parts by weight of Snowtex O, SiO 2 20%), the solvent was removed by drying under reduced pressure at room temperature for 48 hours and further at 60 ° C. for 5 hours, and 9.9 parts by weight of hexamine was added. after mixing Te to pressure curing at 160 ° C. (degassing before molding pressure 400 kgf / cm 2, degassing number 3 times, venting after molding pressure 500 kgf / cm 2, pressing time 15 min) was, 1 thereafter 160 ° C. After curing at 180 ° C. for 1 hour and 200 ° C. for 1 hour, an organic-inorganic composite structure of Comparative Example 5 was obtained.
以上のようにして製造した本実施の形態にかかる実施例１及び実施例２の有機無機複合体構造物、並びに比較例１〜比較例５の各構造物の諸特性を測定した。その結果を、表１に示す。 Various characteristics of the organic-inorganic composite structures of Example 1 and Example 2 and the structures of Comparative Examples 1 to 5 according to the present embodiment manufactured as described above were measured. The results are shown in Table 1.
まず、表１に示されるように、３点曲げ強度を測定した。３点曲げ強度の供試体の寸法は、幅１０ｍｍ×長さ８０ｍｍ×厚さ２．５ｍｍであり、支点間距離５０ｍｍで行った。その結果は、実施例１の有機無機複合体構造物が１３７．５ＭＰａであり、実施例２の有機無機複合体構造物が１３１．６ＭＰａであったのに対して、比較例１は１０５．５ＭＰａ、比較例２は１１３．８ＭＰａ、比較例３は８９．０ＭＰａ、比較例４は７３．９ＭＰａ、比較例５は１０３．８ＭＰａであり、実施例１及び実施例２の有機無機複合体構造物に比較して、比較例１〜比較例５の各構造物はいずれも低強度であった。 First, as shown in Table 1, the three-point bending strength was measured. The dimensions of the three-point bending strength specimen were 10 mm wide × 80 mm long × 2.5 mm thick, and the distance between the fulcrums was 50 mm. As a result, the organic-inorganic composite structure of Example 1 was 137.5 MPa and the organic-inorganic composite structure of Example 2 was 131.6 MPa, whereas Comparative Example 1 was 105.5 MPa. Comparative Example 2 is 113.8 MPa, Comparative Example 3 is 89.0 MPa, Comparative Example 4 is 73.9 MPa, Comparative Example 5 is 103.8 MPa, and the organic-inorganic composite structures of Examples 1 and 2 are In comparison, each structure of Comparative Examples 1 to 5 had low strength.
また、鈴木式摩擦摩耗試験によって、ＰＶ値（摩擦圧力Ｐに摩擦速度Ｖを乗じたもの。単位ｋｇ・ｍ／ｃｍ2 ）＝７００のときの１時間当りの摩耗量を測定したところ、表１に示されるように、有機化合物のみの構造物である比較例１が２７．７ｍｇ、比較例２が２５．９ｍｇといずれも摩耗量が多いのに対して、本実施の形態にかかる実施例１の有機無機複合体構造物が１．８ｍｇであり、実施例２の有機無機複合体構造物が２．３ｍｇといずれも非常に少なくなっており、ナノメートルレベルのシリカ微粒子が均一分散したことによって、耐摩耗性が向上していることが分かる。なお、比較例においても、有機無機複合体構造物である比較例３は２．２ｍｇ、比較例４は２．５ｍｇ、比較例５は２．５ｍｇと、いずれも摩耗量は少なかった。 In addition, when the PV value (the friction pressure P multiplied by the friction velocity V. Unit kg · m / cm 2 ) = 700 was measured by Suzuki-type friction wear test, the amount of wear per hour was measured. As shown in FIG. 2, the comparative example 1 which is a structure composed of only an organic compound has a large wear amount of 27.7 mg and the comparative example 2 has 25.9 mg. The organic-inorganic composite structure was 1.8 mg, and the organic-inorganic composite structure of Example 2 was 2.3 mg, both of which were very small, and the nanometer-level silica fine particles were uniformly dispersed. It can be seen that the wear resistance is improved. In Comparative Examples, Comparative Example 3 which is an organic-inorganic composite structure was 2.2 mg, Comparative Example 4 was 2.5 mg, and Comparative Example 5 was 2.5 mg.
さらに、摩擦係数を測定したところ、ＰＶ値＝４００の場合の摩擦係数が、有機化合物のみの構造物である比較例１が０．４１、比較例２が０．５６と大きい値であるのに対して、本実施の形態にかかる実施例１の有機無機複合体構造物が０．１２であり、実施例２の有機無機複合体構造物が０．０５と小さくなっており、ナノメートルレベルのシリカ微粒子が均一分散したことによって、滑りが良くなっていることが分かる。なお、比較例においても、有機無機複合体構造物である比較例３は０．０９、比較例４は０．０９、比較例５は０．１７と、いずれも小さい値であった。 Furthermore, when the friction coefficient was measured, the friction coefficient in the case of PV value = 400 was as large as 0.41 in Comparative Example 1, which is a structure of only an organic compound, and 0.56 in Comparative Example 2. On the other hand, the organic-inorganic composite structure of Example 1 according to the present embodiment is 0.12, and the organic-inorganic composite structure of Example 2 is as small as 0.05. It can be seen that the sliding is improved by the uniform dispersion of the silica fine particles. Also in the comparative example, Comparative Example 3 which is an organic-inorganic composite structure was 0.09, Comparative Example 4 was 0.09, and Comparative Example 5 was 0.17, both of which were small values.
また、鈴木式摩擦摩耗試験において、摩擦によって試料が炭化してしまうＰＶ値を示すＰＶ限界は、表１に示されるように、本実施の形態にかかる実施例１の有機無機複合体構造物が４９００であり、実施例２の有機無機複合体構造物が３７００といずれも大きな値を示したのに対して、比較例１は１９００、比較例２は１９００、比較例３は１９００、比較例４は２５００と、いずれも小さい値であった。なお、本実施の形態にかかる実施例１，実施例２に準じた製造方法を採った比較例５は、ＰＶ限界＝４９００と大きい値であった。 Moreover, in the Suzuki type frictional wear test, the PV limit indicating the PV value at which the sample is carbonized due to friction is as shown in Table 1. As shown in Table 1, the organic-inorganic composite structure of Example 1 according to this embodiment is The organic-inorganic composite structure of Example 2 showed a large value of 3700, whereas Comparative Example 1 was 1900, Comparative Example 2 was 1900, Comparative Example 3 was 1900, and Comparative Example 4 Was 2500, both of which were small values. In addition, the comparative example 5 which employ | adopted the manufacturing method according to Example 1 and Example 2 concerning this Embodiment was a large value with PV limit = 4900.
次に、シリカ添加量が少なめの本実施の形態にかかる実施例１の有機無機複合体構造物と、有機化合物のみの構造物である比較例１，比較例２、及びコロイダルシリカを添加した有機無機複合体構造物である比較例５とを比較して、図２乃至図４を参照して、さらに詳しく説明する。 Next, the organic-inorganic composite structure of Example 1 according to the present embodiment with a small amount of silica added, Comparative Example 1 and Comparative Example 2 that are structures of only an organic compound, and organic to which colloidal silica was added Comparison will be made in more detail with reference to FIGS. 2 to 4 in comparison with Comparative Example 5 which is an inorganic composite structure.
図２に示されるように、３点曲げ強度は、実施例１の有機無機複合体構造物が１３７．５ＭＰａと突出して大きく、比較例１は１０５．５ＭＰａ、比較例２は１１３．８ＭＰａ、比較例５は１０３．８ＭＰａといずれも小さい。これは、実施例１の有機無機複合体構造物がレゾール型のフェノール樹脂にシリカゾルを混合して硬化させ、この有機無機複合体を一度粉砕してからノボラック型のフェノール樹脂に混合して加熱加圧して成形体とすることによって、シリカ微粒子を含む複合体とノボラック型のフェノール樹脂との相溶性が向上して、緻密な有機無機複合体構造物が形成されたためと考えられる。 As shown in FIG. 2, the three-point bending strength of the organic-inorganic composite structure of Example 1 is as large as 137.5 MPa, with Comparative Example 1 being 105.5 MPa and Comparative Example 2 being 113.8 MPa. Example 5 is as small as 103.8 MPa. This is because the organic-inorganic composite structure of Example 1 is mixed with a resole-type phenol resin and cured with silica sol, and this organic-inorganic composite is pulverized once and then mixed with a novolac-type phenol resin and heated. It is considered that by forming the compact by pressing, the compatibility between the composite containing silica fine particles and the novolac-type phenol resin was improved, and a dense organic-inorganic composite structure was formed.
次に、図３に示されるように、鈴木式摩擦摩耗試験によるＰＶ値＝７００のときの１時間当りの摩耗量については、有機化合物のみの構造物である比較例１が２７．７ｍｇ、比較例２が２５．９ｍｇといずれも摩耗量が多いのに対して、本実施の形態にかかる実施例１の有機無機複合体構造物が１．８ｍｇであり、比較例５は２．５ｍｇと、いずれも摩耗量は少なかった。これによって、構造が緻密でなくてもシリカ微粒子を含む複合体とすることによって、耐摩耗性が向上することが分かる。 Next, as shown in FIG. 3, the amount of wear per hour when the PV value by the Suzuki friction wear test is 700 is 27.7 mg in Comparative Example 1 which is a structure containing only an organic compound. While Example 2 has 25.9 mg and a large amount of wear, the organic-inorganic composite structure of Example 1 according to the present embodiment is 1.8 mg, and Comparative Example 5 has 2.5 mg. In all cases, the amount of wear was small. Thus, it can be seen that wear resistance is improved by forming a composite containing silica fine particles even if the structure is not dense.
さらに、図４に示されるように、鈴木式摩擦摩耗試験によるＰＶ値と摩擦係数μとの関係については、本実施の形態にかかる実施例１の有機無機複合体構造物と比較例５がＰＶ値＝４００からＰＶ限界のＰＶ値＝４９００まで一貫して摩擦係数μが小さいのに対して、比較例１，比較例２はＰＶ限界のＰＶ値＝１９００まで摩擦係数μが大きい。これは、実施例１と比較例５がシリカ微粒子を含む複合体であることによって、滑りが良くなったためと考えられる。 Furthermore, as shown in FIG. 4, regarding the relationship between the PV value and the friction coefficient μ in the Suzuki friction and wear test, the organic-inorganic composite structure of Example 1 and Comparative Example 5 according to this embodiment are PV. The friction coefficient μ is consistently small from the value = 400 to the PV limit PV value = 4900, while the comparative examples 1 and 2 have a large friction coefficient μ up to the PV limit PV value = 1900. This is thought to be due to the fact that Example 1 and Comparative Example 5 were composites containing silica fine particles, resulting in improved slip.
次に、シリカ添加量が多めの本実施の形態にかかる実施例２の有機無機複合体構造物と、有機化合物のみの構造物である比較例２、及び微細シリカ粒子を混合した有機無機複合体構造物である比較例３，比較例４とを比較して、図５乃至図８を参照して、さらに詳しく説明する。 Next, the organic-inorganic composite obtained by mixing the organic-inorganic composite structure of Example 2 according to the present embodiment with a large amount of silica added, Comparative Example 2 which is a structure containing only an organic compound, and fine silica particles A comparison between Comparative Example 3 and Comparative Example 4 which are structures will be described in more detail with reference to FIGS.
図５に示されるように、３点曲げ強度は、実施例２の有機無機複合体構造物が１３１．６ＭＰａと突出して大きく、比較例２は１１３．８ＭＰａ、比較例３は８９．０ＭＰａ、比較例４は７３．９ＭＰａといずれも小さい。これは、実施例２の有機無機複合体構造物がレゾール型のフェノール樹脂にシリカゾルを混合して硬化させ、この有機無機複合体を一度粉砕してからノボラック型のフェノール樹脂に混合して加熱加圧して成形体とすることによって、シリカ微粒子を含む複合体とノボラック型のフェノール樹脂との相溶性が向上して、緻密な有機無機複合体構造物が形成されたためと考えられる。 As shown in FIG. 5, the three-point bending strength of the organic-inorganic composite structure of Example 2 is as large as 131.6 MPa, Comparative Example 2 is 113.8 MPa, and Comparative Example 3 is 89.0 MPa. Example 4 is as small as 73.9 MPa. This is because the organic-inorganic composite structure of Example 2 was mixed with silica sol in a resol-type phenol resin and cured, and this organic-inorganic composite was pulverized once and then mixed with a novolac-type phenol resin and heated. It is considered that by forming the compact by pressing, the compatibility between the composite containing silica fine particles and the novolac-type phenol resin was improved, and a dense organic-inorganic composite structure was formed.
この点について、図７及び図８の走査型電子顕微鏡（ＳＥＭ）写真を参照して説明する。図７に示される実施例２にかかる有機無機複合体構造物の破断面の５０００倍のＳＥＭ写真においては、構造が極めて緻密であり、シリカ粒子も写真では判別することができず、ナノメートルレベルの微細粒子として混合されていることが分かる。これに対して、図８に示される比較例３にかかる有機無機複合体構造物の破断面の５０００倍のＳＥＭ写真においては、シリカ粒子が数ミクロンレベルで混在していることがはっきりと示されており、基材であるノボラック型フェノール樹脂との親和性も良くないことが分かる。 This point will be described with reference to scanning electron microscope (SEM) photographs of FIGS. In the SEM photograph of 5000 times the fracture surface of the organic-inorganic composite structure according to Example 2 shown in FIG. 7, the structure is extremely dense, and the silica particles cannot be distinguished from the photograph. It can be seen that the fine particles are mixed. In contrast, the SEM photograph of 5000 times the fracture surface of the organic-inorganic composite structure according to Comparative Example 3 shown in FIG. 8 clearly shows that silica particles are mixed at a level of several microns. It can be seen that the affinity with the novolac type phenolic resin as the base material is not good.
また、図６に示されるように、鈴木式摩擦摩耗試験によるＰＶ値と摩擦係数μとの関係については、本実施の形態にかかる実施例２及び微細シリカ粒子を混合した有機無機複合体構造物である比較例３，比較例４が、ＰＶ値＝４００から各ＰＶ限界まで一貫して摩擦係数μが小さいのに対して、比較例２はＰＶ限界のＰＶ値＝１９００まで摩擦係数μが大きい。これは、実施例２，比較例３，比較例４がシリカ微粒子を含む複合体であることによって、滑りが良くなったためと考えられる。 Further, as shown in FIG. 6, regarding the relationship between the PV value and the friction coefficient μ in the Suzuki friction and wear test, an organic-inorganic composite structure in which Example 2 according to the present embodiment and fine silica particles are mixed is used. In Comparative Example 3 and Comparative Example 4, the friction coefficient μ is consistently small from the PV value = 400 to each PV limit, whereas in Comparative Example 2, the friction coefficient μ is large up to the PV value of the PV limit = 1900. . This is considered to be due to the fact that Example 2, Comparative Example 3, and Comparative Example 4 were composites containing silica fine particles, and slipping was improved.
このようにして、本実施の形態にかかる有機無機複合体構造物及びその製造方法においては、ナノメートルレベルの微細なシリカ粒子が均一にノボラック型フェノール樹脂中に分散して、曲げ強度・耐摩耗性・摩擦係数・ＰＶ限界の各種物性が向上して、優れた特性を有する有機無機複合体構造物を得ることができる。 Thus, in the organic-inorganic composite structure and the manufacturing method thereof according to the present embodiment, fine silica particles of nanometer level are uniformly dispersed in the novolac-type phenol resin, and bending strength / wear resistance Various properties such as property, friction coefficient, and PV limit are improved, and an organic-inorganic composite structure having excellent characteristics can be obtained.
本実施の形態においては、有機無機複合体構造物を得るための合成樹脂として熱硬化性樹脂としてのフェノール樹脂を用いているが、アクリル樹脂・ポリプロピレン樹脂・ポリスチレン樹脂・ナイロン等の熱可塑性樹脂、スチレン−ブタジエン−ラテックス（ＳＢＲ）ゴム等のエラストマー等の、種々の合成樹脂を用いることができる。 In the present embodiment, a phenol resin as a thermosetting resin is used as a synthetic resin for obtaining an organic-inorganic composite structure, but a thermoplastic resin such as an acrylic resin, a polypropylene resin, a polystyrene resin, and nylon, Various synthetic resins such as elastomers such as styrene-butadiene-latex (SBR) rubber can be used.
また、本実施の形態においては、有機無機複合体構造物を得るための熱硬化性樹脂としてフェノール樹脂を用いているが、エポキシ樹脂、ウレタン樹脂を始めとして、その他の熱硬化性樹脂を用いることもできる。 In this embodiment, a phenol resin is used as a thermosetting resin for obtaining an organic-inorganic composite structure, but other thermosetting resins such as an epoxy resin and a urethane resin are used. You can also.
さらに、本実施の形態においては、有機無機複合体構造物を得るための無機材料として水ガラスを原料としたシリカゾルを用いているが、シリコンアルコキシドを原料としたシリカゾルを用いても良いし、シリカゾルの代わりにチタニアゾルを用いることもできる。 Further, in the present embodiment, silica sol using water glass as a raw material is used as an inorganic material for obtaining an organic-inorganic composite structure, but silica sol using silicon alkoxide as a raw material may be used. It is also possible to use titania sol instead of.
本発明を実施するに際しては、有機無機複合体構造物のその他の部分の構成、組成、材質、大きさ、形状、数量、製造方法等についても、また有機無機複合体構造物の製造方法のその他の工程についても、本実施の形態に限定されるものではない。 In practicing the present invention, the structure, composition, material, size, shape, quantity, manufacturing method, etc. of other parts of the organic-inorganic composite structure, and other methods for manufacturing the organic-inorganic composite structure This process is not limited to the present embodiment.
本発明にかかる有機無機複合体構造物は、上述の如く、高強度で耐摩耗性が高く、摩擦係数が小さいという優れた特性を有しているため、自動車におけるブレーキパッドやクラッチディスクといった摩擦材や、高硬度・高耐火性を有するシリカ含有フェノール樹脂コーティング材、さらには摺動材、接着剤、等に応用することができる。 As described above, the organic-inorganic composite structure according to the present invention has excellent properties such as high strength, high wear resistance, and a low friction coefficient. Therefore, the friction material such as a brake pad and a clutch disk in an automobile is used. It can also be applied to silica-containing phenolic resin coating materials having high hardness and high fire resistance, as well as sliding materials and adhesives.
Claims (8)
前記混合液を加熱して前記第１の合成樹脂を固化させて有機無機複合体を得る工程と、
前記有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、
第２の合成樹脂に前記複合体微細粉末を均一に混合して固化させる工程と
を具備することを特徴とする有機無機複合体構造物の製造方法。 Adding a silica sol or titania sol to the first synthetic resin solution with stirring to obtain a uniform mixed solution;
Heating the mixed liquid to solidify the first synthetic resin to obtain an organic-inorganic composite;
Finely pulverizing the organic-inorganic composite to obtain a composite fine powder;
And a step of uniformly mixing and solidifying the composite fine powder in a second synthetic resin.
前記混合液を加熱して前記第１の熱硬化性樹脂を熱硬化させて有機無機複合体を得る工程と、
前記有機無機複合体を微細に粉砕して複合体微細粉末を得る工程と、
第２の熱硬化性樹脂に前記複合体微細粉末を均一に混合して熱硬化させる工程と、
より高温に加熱してアニーリングする工程と
を具備することを特徴とする有機無機複合体構造物の製造方法。 Adding a silica sol or titania sol to the first thermosetting resin solution while stirring to obtain a uniform mixed solution;
Heating the mixed liquid to thermoset the first thermosetting resin to obtain an organic-inorganic composite;
Finely pulverizing the organic-inorganic composite to obtain a composite fine powder;
A step of uniformly mixing and heat-curing the composite fine powder in a second thermosetting resin;
And a step of annealing at a higher temperature to produce an organic-inorganic composite structure.
8. The first thermosetting resin is a resol type phenol resin, and the second thermosetting resin is a novolac type phenol resin. Organic-inorganic composite structure or method for producing organic-inorganic composite structure.
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| CN102277004A (en) * | 2011-07-12 | 2011-12-14 | 泉州兴源塑料有限公司 | Strengthening and toughening master batch used for vinyl polymer and method for preparing same |
| CN111393794A (en) * | 2019-12-20 | 2020-07-10 | 浙江工业大学 | Preparation method of anti-pollution high-toughness melamine material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102277004A (en) * | 2011-07-12 | 2011-12-14 | 泉州兴源塑料有限公司 | Strengthening and toughening master batch used for vinyl polymer and method for preparing same |
| CN102277004B (en) * | 2011-07-12 | 2013-04-24 | 泉州兴源塑料有限公司 | Strengthening and toughening master batch used for vinyl polymer and method for preparing same |
| CN111393794A (en) * | 2019-12-20 | 2020-07-10 | 浙江工业大学 | Preparation method of anti-pollution high-toughness melamine material |
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