JP2021095486A - Thermally conductive composition and thermally conductive member - Google Patents
Thermally conductive composition and thermally conductive member Download PDFInfo
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- JP2021095486A JP2021095486A JP2019227166A JP2019227166A JP2021095486A JP 2021095486 A JP2021095486 A JP 2021095486A JP 2019227166 A JP2019227166 A JP 2019227166A JP 2019227166 A JP2019227166 A JP 2019227166A JP 2021095486 A JP2021095486 A JP 2021095486A
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- Prior art keywords
- cellulose
- thermally conductive
- weight
- heat
- meth
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、セルロース繊維と放熱性無機粒子を含む熱伝導性組成物と、これを用いた熱伝導性部材に関する。 The present invention relates to a heat conductive composition containing cellulose fibers and heat-dissipating inorganic particles, and a heat conductive member using the same.
近年、省エネルギーに代表されるエネルギーの効率的使用方法が注目されている一方で、電子部品の小型化、高密度化により発熱密度の増加が顕著となっており、各構成部材に使用される部品には熱伝導性の付与が求められている。 In recent years, while efficient methods of using energy represented by energy saving have been attracting attention, the increase in heat generation density has become remarkable due to the miniaturization and high density of electronic parts, and the parts used for each component. Is required to be imparted with thermal conductivity.
熱伝導性の付与を具現化するには、金属・金属酸化物・金属窒化物・合金といった、熱伝導性の高い放熱性無機粒子を用いることが多い。一般的に複雑な形状をした電気部品の部材を作製するには、上述した材料を何らかのマトリックス材料に混合した複合材として用いることが、費用対効果の面から望ましい。しかし、マトリックス材料に用いられることが多い合成樹脂の熱伝導率は放熱性無機粒子の１／１００程度以下であり、多量の放熱性無機粒子を混合する必要がある。一方、多量の放熱性無機粒子の添加は、成形性の劣化を招き、クラックやボイドの発生等、実用性を損なってしまうことがある。 In order to realize the impartation of thermal conductivity, heat-dissipating inorganic particles having high thermal conductivity, such as metals, metal oxides, metal nitrides, and alloys, are often used. Generally, in order to produce a member of an electric component having a complicated shape, it is desirable from the viewpoint of cost effectiveness to use the above-mentioned material as a composite material mixed with some matrix material. However, the thermal conductivity of the synthetic resin often used as a matrix material is about 1/100 or less of that of the heat-dissipating inorganic particles, and it is necessary to mix a large amount of the heat-dissipating inorganic particles. On the other hand, the addition of a large amount of heat-dissipating inorganic particles causes deterioration of moldability and may impair practicality such as generation of cracks and voids.
成形性の劣化を防ぐため、粒径の異なるフィラーを組み合わせて流動性を向上させる提案もなされている（例えば、特許文献１など参照）。しかしながら、硬化時のフィラー沈降による成型物のクラック発生を抑止するために詳細な粒径制御を実施する必要があるという問題点がある。 In order to prevent deterioration of moldability, it has been proposed to combine fillers having different particle diameters to improve fluidity (see, for example, Patent Document 1). However, there is a problem that it is necessary to carry out detailed particle size control in order to suppress the generation of cracks in the molded product due to the sedimentation of the filler during curing.
また、マトリックス材料としてセルロースナノファイバーを用いた放熱材も提案されている（例えば、特許文献２など参照）。 Further, a heat radiating material using cellulose nanofibers as a matrix material has also been proposed (see, for example, Patent Document 2).
ここで、セルロースについて説明すると、セルロースは再生可能資源として紙や機能性材料として様々な用途に利用されている。また、セルロース繊維として、セルロースをナノレベルに解繊したいわゆるナノセルロースが新しい機能をもった材料として注目されている。
ナノセルロースには化学酸化処理による１０ｎｍ以下の繊維径をもったセルロースナノファイバー（ＣＮＦ）（ＴＥＭＰＯ酸化ＣＮＦやリン酸化ＣＮＦと呼ばれ、シングルナノファイバーとも呼ばれる）、機械的・物理的な解繊による化学処理に比べて繊維径が大きなＣＮＦや、ミクロフィブリル、パルプを強酸等で処理して結晶性の高い部分を取り出したセルロースナノクリスタル（ＣＮＣ）、さらには微生物によって産生されたバクテリアセルロースなどが知られている。ナノセルロースは、カーボンファイバーやアラミド繊維に近い強度を持ち、鋼鉄の１／５の重量で、かつ５倍以上の強度である。
Here, when cellulose is described, cellulose is used as a renewable resource for various purposes such as paper and functional materials. Further, as a cellulose fiber, so-called nanocellulose, which is obtained by defibrating cellulose at the nano level, is attracting attention as a material having a new function.
Nanocellulose is made by chemical oxidation treatment of cellulose nanofibers (CNF) with a fiber diameter of 10 nm or less (called TEMPO oxide CNF or phosphorylated CNF, also called single nanofibers), and mechanical and physical defibration. CNF, which has a larger fiber diameter than chemical treatment, microfibrils, cellulose nanocrystals (CNC) obtained by treating pulp with strong acid, etc. to extract highly crystalline parts, and bacterial cellulose produced by microorganisms are known. Has been done. Nanocellulose has a strength close to that of carbon fiber and aramid fiber, is one-fifth the weight of steel, and is five times or more stronger.
特許文献２の技術は、セルロースナノファイバーが高い熱伝導率を有することに着目して、所定の化学修飾をしたセルロースナノファイバーをマトリックス材料として、熱伝導性無機粒子と複合化することにより、高い熱伝導率を有する放熱材を提案するものである。 Focusing on the fact that cellulose nanofibers have high thermal conductivity, the technique of Patent Document 2 is high by using cellulose nanofibers having a predetermined chemical modification as a matrix material and combining them with thermally conductive inorganic particles. It proposes a heat radiating material having thermal conductivity.
特許文献２の技術では、セルロースナノファイバーをマトリックス材料とするので、材料が固定的であり、幅広い分野への応用が困難である。
これに対し、本発明は、後述する通り、セルロース繊維をマトリックス材料とするのではなく、マトリックス材料にセルロース繊維を分散させるものである。
In the technique of Patent Document 2, since cellulose nanofibers are used as a matrix material, the material is fixed and it is difficult to apply it to a wide range of fields.
On the other hand, in the present invention, as will be described later, the cellulose fibers are not used as the matrix material, but the cellulose fibers are dispersed in the matrix material.
そこで、次に、マトリックス材料へのセルロース繊維の分散に関する従来技術についてみると、まず、マトリックス材料にセルロース繊維を分散させた複合材料としては、フィルム材料、ガスバリア材料、粘度調整剤、潤滑剤、植物育成剤、熱硬化樹脂、ＵＶや電子線などの放射線硬化樹脂、汎用樹脂との複合材料やゴムとの複合材料などとして広くその応用が期待されている。
そして、マトリックス材料へのセルロース繊維の分散、複合化には様々なアプローチがなされている。例えば、パルプと樹脂、さらには必要に応じて膨潤剤とを混合し、混練機を使って解繊する方法や、直径が１０ｎｍ未満のシングルナノサイズのＣＮＦ分散溶液を樹脂に混合して同様に混練機を使って解繊する方法などである。
Next, looking at the prior art regarding the dispersion of cellulose fibers in the matrix material, first, as the composite material in which the cellulose fibers are dispersed in the matrix material, a film material, a gas barrier material, a viscosity modifier, a lubricant, and a plant Its application is widely expected as a growth agent, a thermosetting resin, a radiation curable resin such as UV and electron beam, a composite material with a general-purpose resin, and a composite material with rubber.
Various approaches have been taken to disperse and composite cellulose fibers in matrix materials. For example, a method in which pulp and resin, and if necessary, a swelling agent are mixed and defibrated using a kneader, or a single nano-sized CNF dispersion solution having a diameter of less than 10 nm is mixed with resin in the same manner. This is a method of defibrating using a kneader.
ただし、これらの方法では、シングルナノレベルでの分散が困難で、狙った物性を得ることが難しいことが現状である。
その理由の一つは、セルロース繊維の多くはその表面に親水性官能基を持っているために水への親和性や分散性には優れるが、一般的に疎水性の高い樹脂への分散性は著しく悪いためである。特に、ＴＥＭＰＯ酸化法やリン酸処理法で作製されたＣＮＦはシングルナノレベルの繊維径であって有用であるが、表面にはカルボン酸塩基やリン酸塩基を持っているために疎水性樹脂への馴染みが極めて悪い。
However, with these methods, it is difficult to disperse at the single nano level, and it is difficult to obtain the desired physical properties.
One of the reasons is that many cellulose fibers have hydrophilic functional groups on their surfaces, so that they have excellent affinity and dispersibility in water, but generally dispersibility in highly hydrophobic resins. Is extremely bad. In particular, CNF produced by the TEMPO oxidation method or phosphoric acid treatment method is useful because it has a fiber diameter of a single nano level, but since it has a carboxylic acid base or a phosphoric acid base on its surface, it becomes a hydrophobic resin. Is extremely unfamiliar.
このようなセルロース繊維の分散性を改良するために、様々な技術検討がなされている。
その一つは、セルロース繊維の表面に存在する水酸基等を利用して化学反応によって疎水性官能基を導入する方法である。例えば、カプロラクトンのグラフト化（例えば、特許文献３など参照）や無水酢酸の付加反応によるアセチル化（例えば、特許文献４など参照）が知られている。
しかしながら、カプロラクトンのグラフトや無水酢酸等の付加反応によって疎水化する方法では、化学反応を伴うためにコストが著しく高くなること、また化学修飾によって導入された基の疎水性が十分ではなく分散できる樹脂が限られるという問題がある。
In order to improve the dispersibility of such cellulose fibers, various technical studies have been made.
One of them is a method of introducing a hydrophobic functional group by a chemical reaction using a hydroxyl group or the like existing on the surface of a cellulose fiber. For example, grafting of caprolactone (see, for example, Patent Document 3) and acetylation by addition reaction of acetic anhydride (see, for example, Patent Document 4) are known.
However, the method of hydrophobizing by a graft of caprolactone or an addition reaction such as acetic anhydride involves a chemical reaction, which increases the cost significantly, and the hydrophobicity of the group introduced by the chemical modification is not sufficient and can be dispersed. There is a problem that is limited.
本発明は、放熱性無機粒子を沈降させることなく成型することができ、高い熱伝導性の付与が可能な熱伝導性組成物及びこれを用いた熱伝導性部材を提供することを目的としている。 An object of the present invention is to provide a heat conductive composition capable of molding heat-dissipating inorganic particles without sedimentation and imparting high heat conductivity, and a heat conductive member using the same. ..
本発明は、上記課題を解決するため、以下の構成を備える。
すなわち、本発明に係る熱伝導性組成物は、マトリックス材料中に、セルロース繊維と、セルロース誘導体にビニル系ポリマーがグラフトされた構造を備えるセルロース繊維分散用複合体と、放熱性無機粒子とを含有する。
また、本発明に係る熱伝導性部材は、上記本発明に係る熱伝導性組成物からなる。
The present invention has the following configurations in order to solve the above problems.
That is, the thermally conductive composition according to the present invention contains cellulose fibers, a cellulose fiber dispersion composite having a structure in which a vinyl polymer is grafted on a cellulose derivative, and heat-dissipating inorganic particles in a matrix material. To do.
Further, the heat conductive member according to the present invention is made of the above heat conductive composition according to the present invention.
本発明によれば、セルロース繊維分散用複合体を用いることにより、セルロース繊維を樹脂に十分に分散させることができ、セルロース繊維の分散によって放熱性無機粒子の沈降を防ぐことも可能となるため、放熱性無機粒子を沈降させることなく成型することができ、放熱性無機粒子のみをマトリックス材料に混合分散するよりも高い熱伝導率を付与することができる。 According to the present invention, by using the composite for dispersing cellulose fibers, the cellulose fibers can be sufficiently dispersed in the resin, and the dispersion of the cellulose fibers can prevent the heat-dissipating inorganic particles from settling. The heat-dissipating inorganic particles can be molded without sedimentation, and higher thermal conductivity can be imparted than when only the heat-dissipating inorganic particles are mixed and dispersed in the matrix material.
以下、本発明に係る熱伝導性組成物及びこれを用いた熱伝導性部材の好ましい実施形態について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。 Hereinafter, preferred embodiments of the thermally conductive composition according to the present invention and the thermally conductive member using the same will be described in detail, but the scope of the present invention is not limited to these explanations, and other than the following examples. As long as the gist of the present invention is not impaired, changes can be made as appropriate.
〔セルロース繊維分散用複合体〕
本発明で用いるセルロース繊維分散用複合体（以下、単に「複合体」ということがある）は、セルロース誘導体にビニル系ポリマーがグラフトされた構造を備える。
[Composite for dispersing cellulose fibers]
The cellulose fiber dispersion complex used in the present invention (hereinafter, may be simply referred to as “complex”) has a structure in which a vinyl-based polymer is grafted on a cellulose derivative.
＜セルロース誘導体＞
セルロース誘導体は、セルロースの水酸基の一部が置換されたものである。ただし、本発明において、後述のビニル系ポリマーがグラフトされたものについては、「複合体」と称して、「セルロース誘導体」とは用語上区別する。
<Cellulose derivative>
The cellulose derivative is one in which a part of the hydroxyl group of cellulose is substituted. However, in the present invention, those grafted with a vinyl-based polymer, which will be described later, are referred to as "complexes" and are distinguished from "cellulose derivatives" in terms of terms.
セルロース誘導体としては、従来公知のセルロース誘導体を用いることができ、具体的には、例えば、メチルセルロース、エチルセルロース、ブチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシブチルメチルセルロース、カルボキシメチルセルロース、酢酸セルロース、セルロースアセテートブチレート、セルロースアセテートプロピオネート、トリアセチルセルロース、ニトロセルロース、カチオン化セルロースなどが挙げられる。
なかでも有機溶剤への溶解度の高さやビニル系ポリマーのグラフトし易さ、入手性の観点からエチルセルロース、セルロースアセテートブチレート、トリアセチルセルロース、カチオン化セルロースが好ましい。
As the cellulose derivative, a conventionally known cellulose derivative can be used. Specifically, for example, methyl cellulose, ethyl cellulose, butyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, carboxymethyl cellulose, cellulose acetate, cellulose acetate. Butyrate, cellulose acetate propionate, triacetyl cellulose, nitro cellulose, cationized cellulose and the like can be mentioned.
Of these, ethyl cellulose, cellulose acetate butyrate, triacetyl cellulose, and cationized cellulose are preferable from the viewpoints of high solubility in organic solvents, ease of grafting of vinyl polymers, and availability.
これらの従来公知のセルロース誘導体には、通常、未修飾の水酸基が存在する。この水酸基を利用して、重合性不飽和基やチオール（メルカプト）基を導入することができる。このようにして重合性不飽和基やチオール基を導入することで、これらの官能基を基点として、後述するビニル系ポリマーのグラフトを容易に行うことができる。 These conventionally known cellulose derivatives usually have unmodified hydroxyl groups. This hydroxyl group can be used to introduce a polymerizable unsaturated group or a thiol (mercapto) group. By introducing a polymerizable unsaturated group or a thiol group in this way, it is possible to easily graft a vinyl-based polymer, which will be described later, using these functional groups as a base point.
上記重合性不飽和基やチオール基の導入は、例えば、上述した従来公知のセルロース誘導体に対して、昭和電工製カレンズＭＯＩやＡＯＩなどのイソシアネート系（メタ）アクリレート化合物を付加反応させる、無水（メタ）アクリル酸、無水マレイン酸などの無水物を付加反応させる、カルボジイミドなどの縮合剤を利用して（メタ）アクリル酸等を付加反応させる、（メタ）アクリル酸クロライド、チオール基をもった有機酸を反応させる等により、実施可能である。重合性不飽和二重結合又はチオール基をもった有機酸を例示すれば、（メタ）アクリル酸、マレイン酸、クロトン酸、ブテントリカルボン酸、４−エテニル安息香酸、３−メルカプトプロピオン酸等が挙げられる。
なお、本明細書において、「（メタ）アクリル酸」の表記は、メタアクリル酸とアクリル酸の双方を含む表記である。「（メタ）アクリレート」などの表記も同様である。
The introduction of the polymerizable unsaturated group or thiol group is carried out, for example, by adding an isocyanate-based (meth) acrylate compound such as Karenz MOI or AOI manufactured by Showa Denko to the above-mentioned conventionally known cellulose derivative. ) Addition reaction of anhydrides such as acrylic acid and maleic anhydride, addition reaction of (meth) acrylic acid using a condensing agent such as carbodiimide, (meth) acrylic acid chloride, organic acid having a thiol group It can be carried out by reacting with or the like. Examples of organic acids having a polymerizable unsaturated double bond or a thiol group include (meth) acrylic acid, maleic acid, crotonic acid, butentricarboxylic acid, 4-ethenylbenzoic acid, 3-mercaptopropionic acid and the like. Be done.
In addition, in this specification, the notation of "(meth) acrylic acid" is a notation including both methacrylic acid and acrylic acid. The same applies to notations such as "(meth) acrylate".
重合性不飽和基やチオール基の導入においては、公知技術同様に、各種の溶媒や触媒（有機金属材料、アミン等）を利用することができる。
また、導入される重合性不飽和基やチオール基の数は、セルロース誘導体１分子当たり平均で２０以下であることが望ましい。２０を超える数の導入ではグラフト重合時にゲル化する恐れがある。
上記の反応溶媒としては、酢酸エチル、酢酸プロピル、酢酸ブチル、テトラヒドロフラン、ジオキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、ピリジンなどの非プロトン性溶媒を、単独あるいは混合して使用することができる。
In the introduction of the polymerizable unsaturated group and the thiol group, various solvents and catalysts (organic metal materials, amines, etc.) can be used as in the known techniques.
Further, it is desirable that the number of polymerizable unsaturated groups and thiol groups introduced is 20 or less on average per molecule of the cellulose derivative. Introducing more than 20 may result in gelation during graft polymerization.
Examples of the above reaction solvent include aprotic solvents such as ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and pyridine. Can be used alone or in combination.
本発明において、セルロース誘導体は、カチオン基を有していてもよい。
セルロース誘導体がカチオン基を有することで、特に、ＴＥＭＰＯ酸化法やリン酸処理法で作製されたＣＮＦの分散性に優れた複合体となる。これらのＣＮＦは、その表面にカルボン酸塩基やリン酸塩基を持っているが、これらＣＮＦ表面の官能基と、セルロース誘導体のカチオン基との親和性により、ＣＮＦの分散が促進されるためである。
In the present invention, the cellulose derivative may have a cationic group.
Since the cellulose derivative has a cationic group, it becomes a complex having excellent dispersibility of CNF produced by the TEMPO oxidation method or the phosphoric acid treatment method. These CNFs have carboxylic acid bases and phosphate bases on their surfaces, and the affinity between the functional groups on the surface of these CNFs and the cation groups of the cellulose derivatives promotes the dispersion of CNFs. ..
カチオン基を有するセルロース誘導体としては、従来公知のカチオン化セルロースを用いても良いが、以下のようにして、カチオン基を有しないセルロース誘導体にカチオン基を導入することもできる。
すなわち、例えば、アミノ基を導入する方法として、塩化チオニル／アンモニアを反応させる方法、エポキシ基を導入した後にアンモニアや多価アミノ化合物を反応させる方法が知られている。さらには、アミノ基とカルボキシル基の双方を分子内にもった化合物を上記した縮合剤等を用いて反応させて導入する方法が実施できる。
上記の反応溶媒としては、酢酸エチル、酢酸プロピル、酢酸ブチル、テトラヒドロフラン、ジオキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、ピリジンなどの非プロトン性溶媒を、単独あるいは混合して使用することができる。
カチオン基は、セルロース誘導体１分子あたりに平均で１〜３０個の範囲が望ましい。
As the cellulose derivative having a cation group, conventionally known cationized cellulose may be used, but the cation group can also be introduced into the cellulose derivative having no cation group as follows.
That is, for example, as a method for introducing an amino group, a method of reacting thionyl chloride / ammonia and a method of reacting ammonia or a polyvalent amino compound after introducing an epoxy group are known. Further, a method of introducing a compound having both an amino group and a carboxyl group in the molecule by reacting them with the above-mentioned condensing agent or the like can be carried out.
Examples of the above reaction solvent include aprotic solvents such as ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and pyridine. Can be used alone or in combination.
The average number of cation groups per molecule of the cellulose derivative is preferably in the range of 1 to 30.
＜ビニル系ポリマー＞
セルロース誘導体へのビニル系ポリマーのグラフトは、例えば、上述のようにして重合性不飽和基やチオール基が導入されたセルロース誘導体の存在下で、ビニル系モノマーをラジカル重合することにより行うことができる。重合性不飽和基やチオール基を基点としてビニル系ポリマーであるグラフト鎖が形成される。
<Vinyl polymer>
The graft of the vinyl-based polymer to the cellulose derivative can be carried out, for example, by radically polymerizing the vinyl-based monomer in the presence of the cellulose derivative into which the polymerizable unsaturated group or the thiol group has been introduced as described above. .. A graft chain, which is a vinyl-based polymer, is formed with a polymerizable unsaturated group or a thiol group as a base point.
上記において、ビニル系モノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレートなどのアルキル基炭素数１〜２０の（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、グリセリル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、繰り返しユニット数が１〜３０のメトキシポリエチレングリコール（メタ）アクリレート、繰り返しユニット数が１〜３０のメトキシポリプロピレングリコール（メタ）アクリレート、ブトキシジエチレングリコール（メタ）アクリレート、２−（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２−（メタ）アクリロイロキシエチルコハク酸、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチルメタアクリレート、２−（メタ）アクロイロキシエチルアシッドホスフェート、スチレン、スチレン誘導体、（メタ）アクリル酸、（メタ）アクリルアミド、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド、無水マレイン酸、（メタ）アクリロニトリル、Ｎ−ビニルピロリドン、シリコーン系（メタ）アクリレート（ＪＮＣ製、商品名サイラプレーン「ＦＭ−０７１１」、「ＦＭ−０７２１」、「ＦＭ−０７２５」等、信越化学社製：「Ｘ−２２−１７４ＤＸ」、「Ｘ−２２−２４２６」、「Ｘ−２２−２４７５」等））、フッ素置換基含有（メタ）アクリレート（ダイキン社製の種々のフッ素置換アルキル（メタ）アクリレートなど）などが挙げられる。 In the above, examples of the vinyl-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate, 2 -Alkyl group such as ethylhexyl (meth) acrylate (meth) acrylate with 1 to 20 carbon atoms, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glyceryl (meth) acrylate, dimethylaminoethyl (Meta) acrylate, diethylaminoethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, the number of repeating units is 1. ~ 30 methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate with 1 to 30 repeating units, butoxydiethylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (Meta) acryloyloxyethyl succinic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethylmethacrylate, 2- (meth) acryloxyethyl acid phosphate, styrene, styrene derivative, (meth) acrylic acid, ( Meta) acrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, maleic anhydride, (meth) acrylonitrile, N-vinylpyrrolidone, silicone-based (meth) acrylate (manufactured by JNC, trade name silaplane "FM-0711", "FM" -0721 "," FM-0725 ", etc., manufactured by Shin-Etsu Chemical Co., Ltd .:" X-22-174DX "," X-22-2426 "," X-22-2475 ", etc.)), containing fluorine substituent (meth) Examples thereof include acrylates (various fluorine-substituted alkyl (meth) acrylates manufactured by Daikin Co., Ltd.) and the like.
また、ゲル化によって溶剤へ不溶化しない程度の量で、エチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレートなどの多官能性（メタ）アクリレートやジビニルベンゼン等を利用することも可能である。また、これらの各モノマーは単独もしくは複数種を組み合わせて使用することができる。 It is also possible to use polyfunctional (meth) acrylates such as ethylene glycol di (meth) acrylate and hexanediol di (meth) acrylate, divinylbenzene, etc. in an amount that does not insolubilize in the solvent by gelation. .. In addition, each of these monomers can be used alone or in combination of two or more.
上記したビニル系モノマーの組み合わせによって生成するビニル系ポリマーの性質が変化し、特に有機溶剤や樹脂へのセルロース繊維の分散性能が変わる。一般論として分散させる対象となる樹脂前駆体や樹脂との親和性の指標としてＳｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ（ＳＰ）値が挙げられる。グラフトされたビニル系ポリマーと前記分散対象とのＳＰ値を近い値とするような設計が望ましいものとなる。特に実験値や計算値上のＳＰ値の差が１．０（（ｃａｌ／ｃｍ3）1/2）以内であることが望ましい。
また、ビニル系モノマーとして、２−ヒドロキシエチル（メタ）アクリレートなどの水酸基含有モノマーやポリアルキレンオキサイド系のモノマー成分、特に、繰り返しユニット数が１〜３０のメトキシポリエチレングリコール（メタ）アクリレート、繰り返しユニット数が１〜３０のメトキシポリプロピレングリコール（メタ）アクリレートを使用すると、セルロース繊維中に酸塩基等が存在した場合にも有効な相互作用の効果が期待できるため、共重合する一成分として使用することが望ましい。
The properties of the vinyl polymer produced by the combination of the vinyl-based monomers described above change, and in particular, the dispersion performance of the cellulose fibers in the organic solvent or resin changes. As a general theory, the Solubility Parameter (SP) value can be mentioned as an index of the affinity with the resin precursor or the resin to be dispersed. It is desirable to design the grafted vinyl polymer so that the SP value of the dispersion target is close to the SP value. In particular, it is desirable that the difference between the SP value on the experimental value and the calculated value is within 1.0 ((cal / cm 3 ) 1/2).
Further, as the vinyl-based monomer, a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate or a polyalkylene oxide-based monomer component, particularly, methoxypolyethylene glycol (meth) acrylate having 1 to 30 repeating units, and the number of repeating units. When a methoxypolypropylene glycol (meth) acrylate having a value of 1 to 30 is used, an effective interaction effect can be expected even when an acid base or the like is present in the cellulose fiber, so that it can be used as one component to be copolymerized. desirable.
さらには分散対象の材料（特に樹脂）との相互作用を持ったビニル系モノマーを選択することも望ましい。相互作用とはアルキル基等の疎水性相互作用、水酸基、アミン、カルボキシル基、アミド基等の水素結合、芳香族環によるπ−πなどの共役系スタックなどが挙げられ、このような官能基をもったものを使用することで実現できる。
さらにはまた、生成したビニル系ポリマー中に反応性基を導入し、分散対象の樹脂等との結合を形成させることも可能である。その一つの方法は、前記したグリシジル（メタ）アクリレートや３，４−エポキシシクロヘキシルメチル（メタ）アクリレートなどのエポキシ基をもったビニル系モノマーを共重合することである。他の方法としては、生成したビニル系ポリマー中の官能基、例えば水酸基やカルボキシル基等を利用して重合可能な（メタ）アクリレート基、ビニル基、アリル基等を化学反応で導入することである。このような反応性基の導入にはイソシアネート基含有（メタ）アクリレートであるカレンズＭＯ−ＩやＡＯ−Ｉ等（昭和電工製）、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレートなどを使用した付加反応で実現できる。
Furthermore, it is also desirable to select a vinyl-based monomer that has an interaction with the material to be dispersed (particularly resin). Examples of the interaction include hydrophobic interactions such as alkyl groups, hydrogen bonds such as hydroxyl groups, amines, carboxyl groups, and amide groups, and conjugated stacks such as π-π due to aromatic rings. It can be realized by using what you have.
Furthermore, it is also possible to introduce a reactive group into the produced vinyl-based polymer to form a bond with a resin or the like to be dispersed. One method is to copolymerize a vinyl-based monomer having an epoxy group such as the above-mentioned glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate. As another method, a functional group in the produced vinyl polymer, for example, a (meth) acrylate group, a vinyl group, an allyl group or the like which can be polymerized using a hydroxyl group or a carboxyl group is introduced by a chemical reaction. .. For the introduction of such a reactive group, isocyanate group-containing (meth) acrylates such as Karenz MO-I and AO-I (manufactured by Showa Denko), glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). This can be achieved by an addition reaction using acrylate or the like.
前記した重合性不飽和基またはチオール基を導入したセルロース誘導体とビニル系モノマーの重合にあたって、各々は重量比で１：９９〜９７：３の範囲内で配合されることが好ましい。この範囲外であるとセルロース繊維の分散剤としての効果が低くなる恐れがある。
なお、上記した重合において、ビニル系モノマーから形成されるビニル系ポリマーがすべてセルロース誘導体にグラフト（化学結合）される必要はない。ビニル系モノマーの単独重合によって生成するポリマーが含まれていてもよい。
In the polymerization of the above-mentioned polymerizable unsaturated group or thiol group-introduced cellulose derivative and vinyl-based monomer, it is preferable that each of them is blended in the range of 1:99 to 97: 3 in weight ratio. If it is out of this range, the effect of the cellulose fiber as a dispersant may be lowered.
In the above-mentioned polymerization, it is not necessary that all the vinyl-based polymers formed from the vinyl-based monomers are grafted (chemically bonded) to the cellulose derivative. A polymer produced by homopolymerization of a vinyl-based monomer may be contained.
セルロース誘導体にグラフトして形成するビニル系ポリマーの分子量は、重量平均分子量で１０００〜５０万の範囲から選択されることが好ましい。前記重量平均分子量が１０００未満であると分散剤としての効果が低下する恐れがあり、また、前記重量平均分子量が５０万を超えると粘度が高くなりすぎる傾向がある。
なお、セルロース誘導体、このセルロース誘導体にグラフトされるビニル系ポリマー、及びそれらの複合体の各重量平均分子量は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）による標準ポリスチレン換算値である。
The molecular weight of the vinyl polymer formed by grafting on the cellulose derivative is preferably selected from the range of 10 to 500,000 in terms of weight average molecular weight. If the weight average molecular weight is less than 1000, the effect as a dispersant may be lowered, and if the weight average molecular weight exceeds 500,000, the viscosity tends to be too high.
The weight average molecular weight of the cellulose derivative, the vinyl polymer grafted on the cellulose derivative, and the composite thereof is a standard polystyrene conversion value by gel permeation chromatography (GPC).
さらに形成されるセルロース誘導体とビニル系ポリマーとの複合体（セルロース繊維分散用複合体）の分子量は、重量平均分子量で５０００〜８０万の範囲が好ましい。この重量平均分子量は、セルロース誘導体へ結合されたビニル系ポリマーと、結合体や結合されていないビニル系ポリマー（単独重合体）を含むものとする。
なお、ＧＰＣ法によって測定される上記複合体の分子量は、セルロース誘導体固有の溶液特性が原因と思われるが、単純にセルロース誘導体とビニル系ポリマーとの総和とはならない場合がある。詳細は不明であるがセルロース誘導体にビニル系ポリマーが結合することによって、高分子鎖の広がり等やセルロース誘導体間の相互作用が変化する可能性がある。したがって、あくまでもＧＰＣ法での測定分子量となる。
Further, the molecular weight of the composite of the cellulose derivative and the vinyl polymer (complex for dispersing the cellulose fibers) to be formed is preferably in the range of 5,000 to 800,000 in terms of weight average molecular weight. This weight average molecular weight is assumed to include a vinyl-based polymer bonded to a cellulose derivative and a bonded or non-bonded vinyl-based polymer (homopolymer).
The molecular weight of the complex measured by the GPC method is considered to be due to the solution characteristics peculiar to the cellulose derivative, but it may not be simply the sum of the cellulose derivative and the vinyl polymer. Although the details are unknown, the binding of the vinyl polymer to the cellulose derivative may change the spread of the polymer chain and the interaction between the cellulose derivatives. Therefore, it is the molecular weight measured by the GPC method.
重合に使用可能な有機溶剤としては、例えば、酢酸エチル、酢酸ブチル、テトラヒドロフラン、ジオキサン、アセトン、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、エチルアルコール、イソプロピルアルコール、ブチルアルコール、ベンジルアルコール、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、エチルラクテート、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート（ブチルカルビトールアセテート）、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールブチルメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールジメチルエーテル、プロピレングリコールジアセテート、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールジブチルエーテル、トリプロピレングリコールジメチルエーテル、ジヒドロターピネオールアセテート、ターピネオール、ジヒドロターピネオール、ジヒドロターピネオールアセテートなどの１種か混合物が好適である。 Examples of organic solvents that can be used for polymerization include ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, ethyl alcohol, isopropyl alcohol, butyl alcohol, benzyl alcohol, dimethylformamide, and dimethyl. Acetamide, N-methylpyrrolidone, ethyllactate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl carbitol acetate), diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether , Propropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, dihydro One or a mixture of tarpineol acetate, tarpineol, dihydro tarpineol, dihydro tarpineol acetate and the like is suitable.
重合開始剤としては、例えば、過酸化物系やアゾ系の各種タイプのラジカル重合開始剤を使用することができる。また、重合時の濃度、開始剤濃度等は公知の技術の範囲内で実施可能である。 As the polymerization initiator, for example, various types of peroxide-based and azo-based radical polymerization initiators can be used. Further, the concentration at the time of polymerization, the concentration of the initiator and the like can be carried out within the range of known techniques.
セルロース誘導体にビニル系モノマーを重合した後、必要に応じて貧溶媒による沈殿精製を実施することも従前のポリマー精製と同様に可能である。未反応モノマー、副生成物やビニル系ポリマーの単独重合体等を除去することができる。 After polymerizing a vinyl-based monomer on a cellulose derivative, it is also possible to carry out precipitation purification with a poor solvent if necessary, as in the case of conventional polymer purification. Unreacted monomers, by-products, homopolymers of vinyl-based polymers, etc. can be removed.
〔熱伝導性組成物及びこれを用いた熱伝導性部材〕
次に、本発明の熱伝導性組成物及びこれを用いた熱伝導性部材について説明をする。
本発明の熱伝導性組成物（以下、単に「組成物」という場合がある。）は、上で詳述した複合体と、セルロース繊維と放熱性無機粒子を含むものである。
以下、マトリックス材料として樹脂前駆体を含む第１の構成と、マトリックス材料として樹脂を含む第２の構成を、本発明に係る熱伝導性組成物の好適例として例示する。
[Thermal conductive composition and the thermally conductive member using the same]
Next, the heat conductive composition of the present invention and the heat conductive member using the same will be described.
The thermally conductive composition of the present invention (hereinafter, may be simply referred to as “composition”) contains the composite described in detail above, cellulose fibers, and heat-dissipating inorganic particles.
Hereinafter, a first configuration containing a resin precursor as a matrix material and a second configuration containing a resin as a matrix material will be exemplified as preferred examples of the thermally conductive composition according to the present invention.
＜第１の構成：樹脂前駆体分散組成物とその製造方法＞
本発明の組成物の第１の構成は、前記複合体と、セルロース繊維と、放熱性無機粒子と、樹脂前駆体を含む組成物である。
<First composition: resin precursor dispersion composition and method for producing the same>
The first composition of the composition of the present invention is a composition containing the composite, cellulose fibers, heat-dissipating inorganic particles, and a resin precursor.
ナノセルロースなどのセルロース繊維と前記複合体を所定濃度で混合し、さらに有機溶剤と樹脂前駆体を加えて、均一な分散溶液とすることができる。
水媒体中にセルロース繊維が分散した形態はＣＮＦやＣＮＣの市販品として入手可能であるが、例えば、これを原料として用いて水と有機溶剤を樹脂前駆体へと置換することによって、セルロース繊維が樹脂前駆体に分散した組成物を製造することができ、さらに放熱性無機粒子を混合分散することで樹脂前駆体分散組成物となる。
Cellulose fibers such as nanocellulose and the complex can be mixed at a predetermined concentration, and an organic solvent and a resin precursor can be further added to obtain a uniform dispersion solution.
A form in which cellulose fibers are dispersed in an aqueous medium is available as a commercially available product of CNF or CNC. For example, by using this as a raw material and substituting water and an organic solvent with a resin precursor, the cellulose fibers can be obtained. A composition dispersed in a resin precursor can be produced, and further, the heat-dissipating inorganic particles are mixed and dispersed to obtain a resin precursor-dispersed composition.
市販品やサンプルとして入手可能なセルロース繊維としては、王子ホールディングス製のスラリー状ＣＮＦ（リン酸化処理品、名称：アウロ・ヴィスコ）、パウダー状ＣＮＦ、日本製紙製のＴＥＭＰＯ酸化法ＣＮＦ、中越パルプ製のＮａｎｏｆｏｒｅｓｔ−Ｓ、大王製紙製の水分散ＣＮＦ（名称：ＥＬＬＥＸ−Ｓ）、第一工業製薬製のＴＥＭＰＯ酸化法による水分散型ＣＮＦ（名称：レオクリスタ）などの繊維径が４ｎｍから５００ｎｍのものが挙げられる。 Cellulose fibers available on the market and as samples include slurry CNF (phosphorylated product, name: Auro Visco) manufactured by Oji Holdings, powder CNF, TEMPO oxidation method CNF manufactured by Nippon Paper Industries, and Chuetsu Pulp. Nanoforest-S, water-dispersed CNF (name: ELLEX-S) manufactured by Daio Paper, and water-dispersed CNF (name: Leocrysta) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. by the TEMPO oxidation method, etc., have fiber diameters of 4 nm to 500 nm. Be done.
ここで、樹脂前駆体とは、重合反応等によって高分子材料を形成するものであり、（メタ）アクリレート系化合物、ビニル系化合物、アリル系化合物、酸無水物、アミン系化合物、イソシアネート系化合物、エポキシ化合物や反応性シリコーン化合物等が使用可能である。これらの中でも、特に、反応性と汎用性の高さから、（メタ）アクリレート系化合物、ビニル化合物やエポキシ化合物や反応性シリコーン化合物が好ましく使用される。 Here, the resin precursor forms a polymer material by a polymerization reaction or the like, and is a (meth) acrylate compound, a vinyl compound, an allyl compound, an acid anhydride, an amine compound, an isocyanate compound, or the like. Epoxy compounds, reactive silicone compounds and the like can be used. Among these, (meth) acrylate compounds, vinyl compounds, epoxy compounds and reactive silicone compounds are particularly preferably used because of their high reactivity and versatility.
（メタ）アクリレート系化合物としては、単官能（メタ）アクリレート化合物として炭素数１〜３０のアルキル系、メトキシエチレンオキサイド系、ビスフェノールＡ骨格系、芳香族系の（メタ）アクリレート化合物などが、二官能（メタ）アクリレート化合物としてエチレングリコール系、プロピレングリコール系、ビスフェノールＡ骨格系、フルオレン骨格系、トリシクロデカン骨格系等のジ（メタ）アクリレート化合物などが、それ以上の多官能（メタ）アクリレート化合物としてグリセリン骨格系（メタ）アクリレート化合物、（モノ−、ジ−、トリ−）トリメチロールプロパン骨格系、イソシアヌレート骨格系多官能（メタ）アクリレート化合物、（モノ−、ジ−、トリ−）ペンタエリスリトール骨格系多官能（メタ）アクリレート化合物などの多官能（メタ）アクリレート化合物などが挙げられる。 As the (meth) acrylate compound, as a monofunctional (meth) acrylate compound, an alkyl compound having 1 to 30 carbon atoms, a methoxyethylene oxide compound, a bisphenol A skeleton compound, an aromatic (meth) acrylate compound and the like are bifunctional. Di (meth) acrylate compounds such as ethylene glycol, propylene glycol, bisphenol A skeleton, fluorene skeleton, and tricyclodecane skeleton as (meth) acrylate compounds are more polyfunctional (meth) acrylate compounds. Glycerin skeleton (meth) acrylate compound, (mono-, di-, tri-) trimethylolpropane skeleton, isocyanurate skeleton polyfunctional (meth) acrylate compound, (mono-, di-, tri-) pentaerythritol skeleton Examples thereof include polyfunctional (meth) acrylate compounds such as system polyfunctional (meth) acrylate compounds.
ビニル化合物としては、ジビニルベンゼン、スチレン、スチレン誘導体、ビニルナフタレン、アクリロニトリルなどが挙げられる。 Examples of the vinyl compound include divinylbenzene, styrene, styrene derivatives, vinylnaphthalene, acrylonitrile and the like.
エポキシ化合物としては、ビスフェノールＡ系、ビスフェノールＦ系、ビスフェノールＳ、ノボラックフェノール系、レゾールフェノール系、ナフタレン系、ビフェニル系、およびこれらの水添化合物、イソシアヌレート系、ポリブタジエン系などの骨格をもったグリシジルエーテル系、グリシジルアミド系、グリシジルエステル系、脂環式エポキシ系などの多官能エポキシ化合物や反応性希釈剤である単官能等のエポキシ化合物が挙げられる。 Epoxy compounds include bisphenol A-based, bisphenol F-based, bisphenol S, novolak phenol-based, resolphenol-based, naphthalene-based, biphenyl-based, and glycidyl having a skeleton such as these hydrogenated compounds, isocyanurate-based, and polybutadiene-based. Examples thereof include polyfunctional epoxy compounds such as ether type, glycidylamide type, glycidyl ester type and alicyclic epoxy type, and monofunctional epoxy compounds which are reactive diluents.
反応性シリコーン化合物としては、例えば信越化学工業製の種々のＲＴＶシリコーンゴムやＬＩＭ（Liquid Injection Molding）用シリコーンが使用可能である。これに限定されず２液系等の縮合系、付加系、UV硬化系の種々のＲＴＶシリコーンゴムやＬＩＭ用シリコーン材料を使用することができる。 As the reactive silicone compound, for example, various RTV silicone rubbers manufactured by Shin-Etsu Chemical Co., Ltd. and silicones for LIM (Liquid Injection Molding) can be used. Not limited to this, various RTV silicone rubbers such as two-component condensation type, addition type, and UV curable type, and silicone materials for LIM can be used.
放熱性無機粒子としては、アルミナ（酸化アルミニウム）、窒化ホウ素、窒化ケイ素、シリカ（酸化ケイ素）、水酸化アルミニウム、硫酸バリウム、窒化アルミニウム等が挙げられる。また、黒鉛、金、銀、ニッケル、銅等の導電性を有する放熱性無機粒子であってもよい。放熱性無機粒子は、１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
特に、黒鉛、窒化ホウ素、アルミナ、窒化アルミニウム及びシリカからなる群より選択される少なくとも１種を含むことが好ましい。
Examples of the heat-dissipating inorganic particles include alumina (aluminum oxide), boron nitride, silicon nitride, silica (silicon oxide), aluminum hydroxide, barium sulfate, and aluminum nitride. Further, it may be heat-dissipating inorganic particles having conductivity such as graphite, gold, silver, nickel and copper. One type of heat-dissipating inorganic particles may be used alone, or two or more types may be used in combination.
In particular, it is preferable to contain at least one selected from the group consisting of graphite, boron nitride, alumina, aluminum nitride and silica.
放熱性無機粒子の平均粒子径を測定する方法としてはレーザー回折散乱法、遠心沈降法、コールター法や画像解析法等がある。本発明においては、平均粒子径として特に限定するわけではないが、レーザー回折散乱法で測定した値として例えば、０．１〜１０００μｍが好ましく、０．５〜５００μｍがより好ましい。
以下、放熱性無機粒子の平均粒子径の値について記載するときは、レーザー回折散乱法で測定した値を記載している。
As a method for measuring the average particle size of the heat-dissipating inorganic particles, there are a laser diffraction / scattering method, a centrifugal sedimentation method, a Coulter method, an image analysis method and the like. In the present invention, the average particle size is not particularly limited, but the value measured by the laser diffraction / scattering method is, for example, preferably 0.1 to 1000 μm, more preferably 0.5 to 500 μm.
Hereinafter, when describing the value of the average particle size of the heat-dissipating inorganic particles, the value measured by the laser diffraction / scattering method is described.
上記した中でも、熱伝導率とコストの観点から、アルミナ（酸化アルミニウム）及び窒化アルミニウムからなる群より選択される少なくとも１種を含むことがより好ましい。 Among the above, it is more preferable to contain at least one selected from the group consisting of alumina (aluminum oxide) and aluminum nitride from the viewpoint of thermal conductivity and cost.
アルミナ（酸化アルミニウム）は、化学的にも安定で、絶縁性にも優れており好ましい。特に、球状の酸化アルミニウムを用いることで高充填した際の粘度上昇を和らげることができる。酸化アルミニウム粒子の市販品としては、ＤＡＷ−０５（電気化学工業（株）製、平均粒子径５μｍ）、ＤＡＷ−０７（電気化学工業（株）製、平均粒子径８μｍ）、ＤＡＷ−４５（電気化学工業（株）製、平均粒子径４５μｍ）等が挙げられる。 Alumina (aluminum oxide) is preferable because it is chemically stable and has excellent insulating properties. In particular, by using spherical aluminum oxide, it is possible to mitigate the increase in viscosity at the time of high filling. Commercially available products of aluminum oxide particles include DAW-05 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 5 μm), DAW-07 (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 8 μm), DAW-45 (electricity). (Made by Chemical Industry Co., Ltd., average particle size 45 μm) and the like.
窒化アルミニウムは高い絶縁性能を保有し、熱伝導率が酸化アルミニウムの約１０倍と高い。配合することで非常に高い熱伝導率を得ることが可能である。窒化アルミニウム粒子の市販品としてはＴＦＺ−Ａ０２Ｐ（東洋アルミニウム（株）製、平均粒子径１．５μｍ）、ＴＦＺ−Ａ１０Ｐ（東洋アルミニウム（株）製、平均粒子径１０μｍ）、ＴＦＺ−Ａ１５Ｐ（東洋アルミニウム（株）製、平均粒子径１５μｍ）が挙げられる。 Aluminum nitride has high insulation performance, and its thermal conductivity is about 10 times higher than that of aluminum oxide. It is possible to obtain a very high thermal conductivity by blending. Commercially available products of aluminum nitride particles include TFZ-A02P (manufactured by Toyo Aluminum Co., Ltd., average particle size 1.5 μm), TFZ-A10P (manufactured by Toyo Aluminum Co., Ltd., average particle size 10 μm), and TFZ-A15P (Toyo Aluminum Co., Ltd.). (Manufactured by Co., Ltd., average particle size 15 μm).
樹脂前駆体への分散の方法の一例としては、水分散系セルロース繊維、前記複合体および前記有機溶剤と樹脂前駆体を混合し、その後、水と有機溶剤を加熱や減圧によって留去した後に放熱性無機粒子を混合する方法が例示できる。 As an example of the method of dispersion in the resin precursor, water-dispersed cellulose fibers, the composite, and the organic solvent and the resin precursor are mixed, and then water and the organic solvent are distilled off by heating or reducing pressure, and then heat is dissipated. A method of mixing the sex-inorganic particles can be exemplified.
セルロース繊維と複合体との配合は各重量比で１：０．０１〜１：１０の範囲が好ましい。特に好ましい範囲は１：０．０５〜１：２の範囲である。この範囲を超えると分散性や特性が悪化する可能性がある。
また、樹脂前駆体は（セルロース繊維＋複合体）の重量に対して、５倍重量〜２００倍重量の範囲となることが好ましく、放熱性無機粒子は樹脂前駆体の重量に対して０．５倍重量〜２０倍重量の範囲となることが好ましい。この範囲を超えると熱伝導性付与の効果が不十分となる恐れや、高粘度により分散性が低下する恐れがある。
また、（メタ）アクリレート系化合物を用いる場合は、保存安定性を向上させる目的でハイドロキノン類などの重合禁止剤を添加することも従来技術同様に実施可能である。
The composition of the cellulose fibers and the complex is preferably in the range of 1: 0.01 to 1:10 in each weight ratio. A particularly preferable range is the range of 1: 0.05 to 1: 2. If this range is exceeded, the dispersibility and characteristics may deteriorate.
Further, the resin precursor preferably has a weight in the range of 5 times to 200 times the weight of the (cellulose fiber + composite), and the heat-dissipating inorganic particles are 0.5 times the weight of the resin precursor. It is preferably in the range of double weight to 20 times weight. If it exceeds this range, the effect of imparting thermal conductivity may be insufficient, or the dispersibility may decrease due to high viscosity.
When a (meth) acrylate compound is used, it is possible to add a polymerization inhibitor such as hydroquinone for the purpose of improving storage stability, as in the prior art.
第１の構成の組成物を用いることにより、種々の熱伝導性部材を得ることができる。すなわち、第１の構成の組成物は、例えば、ＵＶ硬化材料、熱硬化材料、接着剤、配合材、各種部品の原料等として広く応用することができる。 By using the composition of the first constitution, various heat conductive members can be obtained. That is, the composition having the first constitution can be widely applied as, for example, a UV curing material, a thermosetting material, an adhesive, a compounding material, a raw material for various parts, and the like.
＜第２の構成：樹脂分散組成物とその製造方法＞
本発明の組成物の第２の構成は、前記複合体と、セルロース繊維、樹脂と放熱性無機粒子を含む組成物である。
<Second composition: resin dispersion composition and its manufacturing method>
The second composition of the composition of the present invention is a composition containing the composite, cellulose fibers, a resin and heat-dissipating inorganic particles.
樹脂としては、各種アクリル系樹脂、ポリスチレン、アクリロニトリル−スチレン樹脂、アクリロニトリル−ブタジエン−スチレン樹脂、各種ポリカーボネート、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ニトリルゴム、ブタジエンゴム、ポリ（スチレン−ブタジエン）、ポリイソプレン、エチレン−プロピレン−ジエンゴム、各種ポリエステル、各種ポリウレタン、各種ナイロン樹脂（ポリアミド）、ポリアセタール、ポリビニルブチラールなどのポリビニルアセタール、エチルセルロースやセルロースアセテートブチレートや酢酸セルロースなどのセルロース系樹脂、ポリフェニレンオキサイド、ポリフェニレンスルフィド、フェノール樹脂、シリコーン系樹脂、フッ素系樹脂などが挙げられる。 Resins include various acrylic resins, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, various polycarbonates, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, nitrile rubber, butadiene rubber, and poly (styrene-butadiene). , Polyisoprene, ethylene-propylene-diene rubber, various polyesters, various polyurethanes, various nylon resins (polyamides), polyvinyl acetals such as polyacetal and polyvinyl butyral, cellulose resins such as ethyl cellulose, cellulose acetate butyrate and cellulose acetate, polyphenylene oxide, Examples thereof include polyphenylene sulfide, phenol resin, silicone resin, and fluorine resin.
第２の構成に係る組成物を製造する方法としては、複数の方法が例示できる。
例えば、前記した複合体とセルロース繊維（及び必要に応じて水や有機溶剤）を混合し、これに前記した樹脂と放熱性無機粒子を混合した上、必要に応じて加熱しながらニーダーや連続式二軸混練機等を用いて機械的に混練する方法が挙げられる。
また、その他の方法として、前記複合体とセルロース繊維と有機溶剤からなる分散液を減圧下で脱水した後、前記した樹脂のなかで有機溶剤への溶解性のあるものを選択の上、それを溶解させた溶液に放熱性無機粒子を混合分散し、セルロース繊維と放熱性無機粒子が均一に分散した溶液を調製後に有機溶剤を除去する方法も挙げられる。
これらの方法は使用する樹脂の種類によって使い分けることが好ましい。
As a method for producing the composition according to the second constitution, a plurality of methods can be exemplified.
For example, the above-mentioned composite is mixed with cellulose fibers (and water or an organic solvent if necessary), the above-mentioned resin and heat-dissipating inorganic particles are mixed thereto, and then a kneader or a continuous type is used while heating as necessary. A method of mechanically kneading using a twin-screw kneader or the like can be mentioned.
As another method, after dehydrating the dispersion liquid consisting of the complex, the cellulose fibers and the organic solvent under reduced pressure, a resin having solubility in the organic solvent is selected from the above-mentioned resins, and the solution is used. Another method is to mix and disperse the heat-dissipating inorganic particles in the dissolved solution to prepare a solution in which the cellulose fibers and the heat-dissipating inorganic particles are uniformly dispersed, and then remove the organic solvent.
It is preferable to use these methods properly depending on the type of resin used.
セルロース繊維と複合体との配合は、第１の構成と同様に、各重量比で１：０．０１〜１：１０の範囲が好ましい。この範囲を超えると分散性や特性が悪化する可能性がある。
また、樹脂は（セルロース繊維＋複合体）の重量に対して、５倍重量〜１００倍重量の範囲となることが好ましく、放熱性無機粒子は樹脂の重量に対して０．５倍重量〜２０倍重量の範囲となることが好ましい。
The composition of the cellulose fibers and the complex is preferably in the range of 1: 0.01 to 1:10 in each weight ratio, as in the first configuration. If this range is exceeded, the dispersibility and characteristics may deteriorate.
Further, the resin preferably has a weight in the range of 5 times to 100 times the weight of the (cellulose fiber + composite), and the heat-dissipating inorganic particles have a weight of 0.5 times to 20 times the weight of the resin. It is preferably in the range of double weight.
セルロース繊維や放熱性無機粒子については、第１の構成についての説明と同様である。 The cellulose fibers and the heat-dissipating inorganic particles are the same as those described in the first configuration.
第２の構成の組成物を用いることにより、種々の熱伝導性部材を得ることができる。すなわち、第２の構成の組成物は、例えば、加熱成型や機械加工等によって形成された構造体として各種の部品等に応用することができる。さらに、塗布や溶融成型によって形成されたフィルム形状などとして応用することもできる。 By using the composition of the second constitution, various heat conductive members can be obtained. That is, the composition having the second constitution can be applied to various parts and the like as a structure formed by, for example, heat molding or machining. Further, it can be applied as a film shape formed by coating or melt molding.
熱伝導性部材としては、本発明の熱伝導性組成物のみを成型、フィルム化、繊維化したもの、さらには樹脂フィルムや金属（板、フィルム）の上に塗布して積層した構成、炭素繊維、ガラス繊維、高分子繊維と複合化した構成など、各種のものが実現可能である。また熱伝導性部材には保護層、接着層や離型層を設けていても良い。
本熱伝導性部材は、放熱部材や放熱と電磁波シールド機能を併せ持った部材、放熱と高周波ノイズ抑制効果を併せ持った部材などとして使用可能な有用なものである。
As the heat conductive member, only the heat conductive composition of the present invention is molded, formed into a film, and fiberized, and further, a structure obtained by coating and laminating on a resin film or a metal (plate, film), carbon fiber. , Glass fiber, composite structure with polymer fiber, etc. can be realized. Further, the heat conductive member may be provided with a protective layer, an adhesive layer or a mold release layer.
This heat conductive member is useful as a heat radiating member, a member having both heat radiating and electromagnetic wave shielding functions, a member having both heat radiating and high frequency noise suppressing effect, and the like.
＜本発明の組成物における任意成分＞
上記した本発明の組成物には、前記した複合体、セルロース繊維、放熱性無機粒子、樹脂前駆体や樹脂の他にも様々な材料を配合しても構わない。
これらを例示すれば、有機溶剤、界面活性剤、可塑剤、粘度調整剤、消泡剤、レベリング剤、ＵＶ吸収剤や酸化防止剤などの安定剤、カーボンブラック、色素、ポリマー粒子、金属粒子、エポキシ硬化剤、硬化促進触媒、重合開始剤などである。これらの材料は、組成物の全体重量に対して、例えば、０．００１重量％〜９０重量％の範囲内で配合することができる。
<Arbitrary component in the composition of the present invention>
In addition to the above-mentioned composite, cellulose fiber, heat-dissipating inorganic particles, resin precursor and resin, various materials may be blended in the above-mentioned composition of the present invention.
Examples include organic solvents, surfactants, plasticizers, viscosity modifiers, defoamers, leveling agents, stabilizers such as UV absorbers and antioxidants, carbon blacks, dyes, polymer particles, metal particles, etc. Epoxy curing agents, curing acceleration catalysts, polymerization initiators, etc. These materials can be blended in the range of, for example, 0.001% by weight to 90% by weight based on the total weight of the composition.
以下、本発明に係る熱伝導性組成物及びこれを用いた熱伝導性部材について、実施例及び比較例を示す。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, examples and comparative examples of the heat conductive composition according to the present invention and the heat conductive member using the same will be shown. However, the present invention is not limited to these examples.
〔反応性セルロース誘導体の合成〕
＜合成例Ａ＞
エチルセルロース（ダウケミカル社製の「エトセルＳＴＤ−４」、数平均分子量：１．３７万）１００重量部、酢酸エチル４００重量部を反応容器に加えて混合し、エチルセルロースを酢酸エチルに均一溶解させた溶液を調製した。
上記溶液に、縮合剤としてジイソプロピルカルボジイミド２．８２重量部、反応促進剤としてジメチルアミノピリジン０．０５重量部、及びメタクリル酸１．９２重量部を添加、混合した。引き続き、４０℃で２４時間撹拌して反応を実施し、エチルセルロースにメタクリレート基を導入した。
反応の進行状態は酸価測定によって確認でき、上記４０℃での２４時間の撹拌によって反応は完了していた。得られたサンプルを採取し、乾燥させて、1Ｈ−ＮＭＲ分析を実施した結果、仕込んだメタクリル酸と同モル量のメタクリレート基がエチルセルロースに導入されていることがわかった。また、導入されたメタクリレート基は、エチルセルロース鎖１本あたり平均で３個であった。
[Synthesis of reactive cellulose derivative]
<Synthesis example A>
100 parts by weight of ethyl cellulose (“Etocell STD-4” manufactured by Dow Chemical Co., Ltd., number average molecular weight: 137,000) and 400 parts by weight of ethyl acetate were added to the reaction vessel and mixed to uniformly dissolve ethyl cellulose in ethyl acetate. The solution was prepared.
To the above solution, 2.82 parts by weight of diisopropylcarbodiimide as a condensing agent, 0.05 parts by weight of dimethylaminopyridine as a reaction accelerator, and 1.92 parts by weight of methacrylic acid were added and mixed. Subsequently, the reaction was carried out with stirring at 40 ° C. for 24 hours to introduce a methacrylate group into ethyl cellulose.
The progress of the reaction could be confirmed by measuring the acid value, and the reaction was completed by stirring at 40 ° C. for 24 hours. The obtained sample was collected, dried, and subjected to 1 H-NMR analysis. As a result, it was found that the same molar amount of methacrylate groups as the charged methacrylic acid was introduced into ethyl cellulose. In addition, the number of methacrylate groups introduced was 3 on average per ethyl cellulose chain.
＜合成例Ｂ＞
エチルセルロース（ダウケミカル社製の「エトセルＳＴＤ−４」、数平均分子量：１．３７万）１００重量部、酢酸エチル４００重量部を反応容器に加えて混合し、エチルセルロースを酢酸エチルに均一溶解させた溶液を調製した。
上記溶液に、縮合剤としてジイソプロピルカルボジイミド４．５９重量部、反応促進剤としてジメチルアミノピリジン０．０９重量部、及びメタクリル酸３．１３重量部を添加、混合した。引き続き、４０℃で２４時間撹拌して反応を実施し、エチルセルロースにメタクリレート基を導入した。
反応の進行状態は酸価測定によって確認でき、上記４０℃での２４時間の撹拌によって反応は完了していた。得られたサンプルを採取し、乾燥させて、1Ｈ−ＮＭＲ分析を実施した結果、仕込んだメタクリル酸と同モル量のメタクリレート基がエチルセルロースに導入されていることがわかった。また、導入されたメタクリレート基は、エチルセルロース鎖１本あたり平均で５個であった。
<Synthesis example B>
100 parts by weight of ethyl cellulose (“Etocell STD-4” manufactured by Dow Chemical Co., Ltd., number average molecular weight: 137,000) and 400 parts by weight of ethyl acetate were added to the reaction vessel and mixed to uniformly dissolve ethyl cellulose in ethyl acetate. The solution was prepared.
To the above solution, 4.59 parts by weight of diisopropylcarbodiimide as a condensing agent, 0.09 parts by weight of dimethylaminopyridine as a reaction accelerator, and 3.13 parts by weight of methacrylic acid were added and mixed. Subsequently, the reaction was carried out with stirring at 40 ° C. for 24 hours to introduce a methacrylate group into ethyl cellulose.
The progress of the reaction could be confirmed by measuring the acid value, and the reaction was completed by stirring at 40 ° C. for 24 hours. The obtained sample was collected, dried, and subjected to 1 H-NMR analysis. As a result, it was found that the same molar amount of methacrylate groups as the charged methacrylic acid was introduced into ethyl cellulose. In addition, the number of methacrylate groups introduced was 5 on average per ethyl cellulose chain.
〔複合体の合成〕
＜合成例１＞
合成例Ａで得られたセルロース誘導体１５重量部、酢酸エチル１７０重量部（セルロース誘導体とビニル系モノマーの合計量に対して、反応後のポリマー成分が１５〜３０重量％となるように濃度を酢酸エチルにて調整）を反応容器へ加え混合し、セルロース誘導体を溶解した。そこへブチルメタクリレート１５重量部、重合開始剤としてアゾイソブチロニトリル（ＡＩＢＮ）０．６重量部を加え、反応容器内を窒素ガスで十分にした後、８０℃で８時間重合反応を実施した。
[Composite synthesis]
<Synthesis example 1>
15 parts by weight of the cellulose derivative obtained in Synthesis Example A and 170 parts by weight of ethyl acetate (accumulation is adjusted so that the polymer component after the reaction is 15 to 30% by weight based on the total amount of the cellulose derivative and the vinyl-based monomer. (Adjusted with ethyl) was added to the reaction vessel and mixed to dissolve the cellulose derivative. 15 parts by weight of butyl methacrylate and 0.6 parts by weight of azobisisobutyronitrile (AIBN) as a polymerization initiator were added thereto, and the inside of the reaction vessel was sufficiently filled with nitrogen gas, and then the polymerization reaction was carried out at 80 ° C. for 8 hours. ..
＜合成例２〜６＞
用いたセルロース誘導体、ビニル系モノマー組成、セルロース誘導体とビニル系モノマーの比率を表１に示す条件とした以外は合成例１と同様な条件で複合体の合成を行った。
<Synthesis Examples 2-6>
The composite was synthesized under the same conditions as in Synthesis Example 1 except that the cellulose derivative, the vinyl-based monomer composition, and the ratio of the cellulose derivative to the vinyl-based monomer used were set as the conditions shown in Table 1.
表１に記載のビニル系モノマーの詳細は、それぞれ、以下のとおりである。
ＢＭＡ：ブチルメタクリレート
ＬＭＡ：ラウリルメタクリレート
ＦＭ−０７１１：シリコーン系メタクリレート（ＪＮＣ製、商品名サイラプレーン（登録商標）「ＦＭ−０７１１」）
ＧＭＡ：グリシジルメタクリレート
The details of the vinyl-based monomers shown in Table 1 are as follows.
BMA: Butyl methacrylate LMA: Lauryl methacrylate FM-0711: Silicone methacrylate (manufactured by JNC, trade name Silaplane (registered trademark) "FM-0711")
GMA: Glycidyl Methacrylate
また、表１には、得られた複合体の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）も示したが、これらの値は、以下の条件で測定したものである。
ＧＰＣ装置：東ソー社製「ＨＬＣ−８３２０ＧＰＣ」、
カラム：ＴＳＫｇｅｌ ＧＭＨＸＬ、
測定温度（設定温度）：４０℃、
移動相：テトラヒドロフラン
Table 1 also shows the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained complex, and these values were measured under the following conditions.
GPC device: "HLC-8320GPC" manufactured by Tosoh Corporation,
Column: TSKgel GMHXL,
Measurement temperature (set temperature): 40 ° C,
Mobile phase: tetrahydrofuran
＜比較合成例１＞
比較評価のためにセルロース誘導体を含まない単独のビニル系ポリマーを合成した。
具体的には、ブチルメタクリレート３０重量部、酢酸エチル７０重量部、重合開始剤としてアゾイソブチロニトリル（ＡＩＢＮ）０．６重量部を加え、反応容器内を窒素ガスで十分にした後、８０℃で８時間重合反応を実施した。重量平均分子量が２０万のポリブチルメタクリレートを得た。
<Comparative synthesis example 1>
For comparative evaluation, a single vinyl polymer containing no cellulose derivative was synthesized.
Specifically, 30 parts by weight of butyl methacrylate, 70 parts by weight of ethyl acetate, and 0.6 parts by weight of azoisobutyronitrile (AIBN) as a polymerization initiator are added, and the inside of the reaction vessel is sufficiently filled with nitrogen gas, and then 80. The polymerization reaction was carried out at ° C. for 8 hours. Polybutyl methacrylate having a weight average molecular weight of 200,000 was obtained.
〔樹脂前駆体分散組成物の実施例〕
＜実施例１Ａ＞
ガラス製フラスコ容器にＴＥＭＰＯ酸化法ＣＮＦ（ＣＮＦ固形分量２重量％水分散液：第一工業製薬製）を５０重量部（ＣＮＦ固形分１重量部）、合成例４で得られた複合体（セルロース誘導体−ビニル系ポリマー複合体）を固形分として１重量部（酢酸エチル溶液として添加）、ＹＤ−８１２５（ビスフェノールＡ型エポキシ樹脂）を５０重量部投入し、高速攪拌機を用いて３０分間撹拌・混合を行った。その後、ロータリーエバポレータを用いて減圧下で脱水を行い、ＹＤ−８１２５に対して２重量％の濃度にてＣＮＦを分散した液体を得た。その後、放熱性無機粒子としてトーヤルナイト（登録商標）ＴＦＺ−Ａ１５Ｐ（窒化アルミニウム、東洋アルミニウム（株）製、平均粒子径１５μｍ）を１２１重量部投入しロール分散機にて混合分散を実施して樹脂前駆体分散組成物を作製した。
[Examples of Resin Precursor Dispersion Composition]
<Example 1A>
50 parts by weight (1 part by weight of CNF solid content) of TEMPO oxidation method CNF (CNF solid content 2% by weight aqueous dispersion: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a glass flask container, and the composite (cellulose) obtained in Synthesis Example 4. 1 part by weight (added as an ethyl acetate solution) as a solid content (derivative-vinyl polymer composite) and 50 parts by weight of YD-8125 (bisphenol A type epoxy resin) are added, and the mixture is stirred and mixed for 30 minutes using a high-speed stirrer. Was done. Then, dehydration was carried out under reduced pressure using a rotary evaporator to obtain a liquid in which CNF was dispersed at a concentration of 2% by weight with respect to YD-8125. After that, 121 parts by weight of Toyalnite (registered trademark) TFZ-A15P (aluminum nitride, manufactured by Toyo Aluminum Co., Ltd., average particle diameter 15 μm) was added as heat-dissipating inorganic particles, and mixed and dispersed by a roll disperser to carry out resin. A precursor dispersion composition was prepared.
なお、表２に記載の各原料の詳細は以下のとおりである。
ＣＮＦ１：第一工業製薬製のセルロースナノファイバー（レオクリスタ／２重量％水分散液）
ＣＮＦ２：中越パルプ製のＮａｎｏｆｏｒｅｓｔ−Ｓ（１０重量％水分散液）
ＹＤ−８１２５：ビスフェノールＡタイプ２官能エポキシ（日鉄ケミカル＆マテリアル製）
ＫＥ−１９３５−Ａ：ＬＩＭ用シリコーンゴム（信越化学工業製）
なお、複合体は、有効成分１０重量％酢酸エチル溶液として用いた。
The details of each raw material shown in Table 2 are as follows.
CNF1: Cellulose nanofiber manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (Leocrysta / 2 wt% aqueous dispersion)
CNF2: Nanoforcest-S (10 wt% aqueous dispersion) made by Chuetsu Pulp
YD-8125: Bisphenol A type bifunctional epoxy (manufactured by Nittetsu Chemical & Materials)
KE-1955-A: Silicone rubber for LIM (manufactured by Shin-Etsu Chemical Co., Ltd.)
The complex was used as a 10 wt% ethyl acetate solution of the active ingredient.
＜実施例２Ａ〜７Ａ＞
実施例１Ａと同様の操作で複合体を種々に変更して、ＣＮＦを種々樹脂前駆体に分散した組成物を作製した。なお、実施例７ＡにおいてはＣＮＦとして非ＴＥＭＰＯ酸化の中越パルプ製のＮａｎｏｆｏｒｅｓｔ−Ｓを使用した。
<Examples 2A to 7A>
The complex was variously changed by the same operation as in Example 1A to prepare a composition in which CNF was dispersed in various resin precursors. In Example 7A, Nanoforest-S made of non-TEMPO-oxidized Chuetsu Pulp was used as CNF.
＜比較例１Ａ〜２Ａ＞
ＣＮＦを含まない状態で樹脂前駆体に放熱性無機粒子を混合分散した。
＜比較例３Ａ＞
比較合成例１で作製したセルロース誘導体を含まないビニル系ポリマーのみを使用し、水分散ＣＮＦ中のＣＮＦ量に対してポリマー固形分が１００重量％となる量を添加し、実施例１Ａと同様の方法でＹＤ−８１２５への分散を実施した。
<Comparative Examples 1A to 2A>
The heat-dissipating inorganic particles were mixed and dispersed in the resin precursor without containing CNF.
<Comparative Example 3A>
Only the vinyl-based polymer prepared in Comparative Synthesis Example 1 containing no cellulose derivative was used, and an amount such that the polymer solid content was 100% by weight based on the amount of CNF in the water-dispersed CNF was added, and the same as in Example 1A. Dispersion to YD-8125 was carried out by the method.
比較例１Ａ〜３Ａを作製した後、密閉したガラス瓶に入れて４０℃恒温槽にて７日間放置したところ、表面に樹脂が染み出しており、底部分にはフィラーによるハードケーキが形成されていたが、実施例１Ａ〜７Ａに対して同様の処理を行っても変化は無く、フィラーの沈降が抑えられていた。 After producing Comparative Examples 1A to 3A, when they were placed in a closed glass bottle and left in a constant temperature bath at 40 ° C. for 7 days, the resin exuded on the surface and a hard cake made of a filler was formed on the bottom portion. However, there was no change even when the same treatment was performed on Examples 1A to 7A, and the sedimentation of the filler was suppressed.
〔樹脂前駆体分散組成物の硬化体作製〕
樹脂前駆体にＹＤ−８１２５を使用した場合は硬化触媒として１−ベンジル−２−メチルイミダゾールを組成物１００重量部に対して２重量部配合し、１００℃×２時間＋１５０℃×５時間加熱して硬化した。
一方、樹脂前駆体にＫＥ−１９３５−Ａを使用した場合は硬化剤としてＫＥ−１９３５−Ｂを組成物１００重量部に対して１７重量部配合し、１２０℃×１時間＋１５０℃×１時間加熱して硬化した。
[Preparation of cured product of resin precursor dispersion composition]
When YD-8125 was used as the resin precursor, 2 parts by weight of 1-benzyl-2-methylimidazole was added to 100 parts by weight of the composition as a curing catalyst, and the mixture was heated at 100 ° C. × 2 hours + 150 ° C. × 5 hours. Hardened.
On the other hand, when KE-1955-A was used as the resin precursor, 17 parts by weight of KE-1955-B was added to 100 parts by weight of the composition and heated at 120 ° C. × 1 hour + 150 ° C. × 1 hour. And cured.
〔樹脂前駆体分散組成物の硬化体評価〕
（株）アイフェイズ製 ａｉ−Ｐｈａｓｅ Ｍｏｂｉｌｅ Ｍ３ ｔｙｐｅ１を用いて熱伝導率を測定した。
結果を表２に記載するが、ＣＮＦと複合体を配合することにより非配合品と比較して熱伝導率の向上が見られた。
[Evaluation of cured product of resin precursor dispersion composition]
The thermal conductivity was measured using an ai-Phase Mobile M3 type 1 manufactured by iPhase Co., Ltd.
The results are shown in Table 2. The combination of CNF and the complex showed an improvement in thermal conductivity as compared with the non-blended product.
〔樹脂分散組成物の実施例〕
＜実施例１Ｂ＞
ガラス製容器にＴＥＭＰＯ酸化法ＣＮＦ（ＣＮＦ固形分量２重量％水分散液：第一工業製薬製）を５０重量部（ＣＮＦ固形分１重量部）、合成例２で得られた複合体（セルロース誘導体−ビニル系ポリマー複合体）を固形分として１重量部（酢酸エチル溶液として添加）、ＥＰ６５（ＥＰＤＭゴム）の１０％トルエン溶液を５００重量部投入し、高速攪拌機を用いて３０分間撹拌・混合を行った。その後、ロータリーエバポレータを用いて減圧下で脱水と溶剤置換を行い、ＥＰ６５に対して２重量％の濃度にてＣＮＦを分散したトルエン溶液を得た。その後、放熱性無機粒子としてトーヤルナイトＴＦＺ−Ａ１５Ｐ（窒化アルミニウム）を２０８重量部投入し混合分散を実施した。その後、離型処理ポリエチレンテレフタレートフィルム上にワイヤバーでコーティング、乾燥させて、厚み約１００μｍの熱伝導性フィルムを作製した。樹脂前駆体分散組成物の場合と同様に熱伝導率を測定した。ＣＮＦを配合したフィルムでは１１Ｗ／ｍ・Ｋであったが、配合していないフィルムでは９Ｗ／ｍ・Ｋであり、向上が見られた。
[Examples of Resin Dispersion Composition]
<Example 1B>
50 parts by weight (1 part by weight of CNF solid content) of TEMPO oxidation method CNF (CNF solid content 2% by weight aqueous dispersion: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a glass container, and the complex (cellulose derivative) obtained in Synthesis Example 2. 1 part by weight (added as an ethyl acetate solution) as a solid content (vinyl-based polymer composite) and 500 parts by weight of a 10% toluene solution of EP65 (EPDM rubber) were added, and the mixture was stirred and mixed for 30 minutes using a high-speed stirrer. went. Then, dehydration and solvent substitution were carried out under reduced pressure using a rotary evaporator to obtain a toluene solution in which CNF was dispersed at a concentration of 2% by weight with respect to EP65. Then, 208 parts by weight of Toyalnite TFZ-A15P (aluminum nitride) was added as heat-dissipating inorganic particles to carry out mixing and dispersion. Then, the release-treated polyethylene terephthalate film was coated with a wire bar and dried to prepare a heat conductive film having a thickness of about 100 μm. The thermal conductivity was measured in the same manner as in the case of the resin precursor dispersion composition. The film containing CNF was 11 W / m · K, but the film not containing CNF was 9 W / m · K, showing an improvement.
＜実施例２Ｂ＞
ガラス製容器にＴＥＭＰＯ酸化法ＣＮＦ（ＣＮＦ固形分量２重量％水分散液：第一工業製薬製）を５０重量部（ＣＮＦ固形分１重量部）、合成例２で得られた複合体（セルロース誘導体−ビニル系ポリマー複合体）を固形分として１重量部（酢酸エチル溶液として添加）、ポリメタクリル酸メチル（ＰＭＭＡ）樹脂（自社製造の重量平均分子量Ｍｗ＝５５万）５０重量部、トルエン４５０重量部投入し、高速攪拌機を用いて３０分間撹拌・混合を行った。その後、ロータリーエバポレータを用いて減圧下で脱水と溶剤置換を行った後、放熱性無機粒子としてトーヤルナイトＴＦＺ−Ａ１５Ｐ（窒化アルミニウム）を２０８重量部投入し混合分散を実施した。その後、離型処理ポリエチレンテレフタレートフィルム上にワイヤバーでコーティング、乾燥させて、厚み約１００μｍの熱伝導性フィルムを作製した。樹脂前駆体分散組成物の場合と同様に熱伝導率を測定した。ＣＮＦを配合したフィルムでは１０Ｗ／ｍ・Ｋであったが、配合していないフィルムでは８．５Ｗ／ｍ・Ｋであり、向上が見られた。
<Example 2B>
50 parts by weight (1 part by weight of CNF solid content) of TEMPO oxidation method CNF (CNF solid content 2% by weight aqueous dispersion: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a glass container, and the complex (cellulose derivative) obtained in Synthesis Example 2. -Vinyl polymer composite) as solid content 1 part by weight (added as ethyl acetate solution), polymethyl methacrylate (PMMA) resin (weight average molecular weight Mw = 550,000 manufactured in-house) 50 parts by weight, toluene 450 parts by weight The mixture was charged and stirred and mixed for 30 minutes using a high-speed stirrer. Then, after dehydration and solvent substitution under reduced pressure using a rotary evaporator, 208 parts by weight of Toyalnite TFZ-A15P (aluminum nitride) was added as heat-dissipating inorganic particles to carry out mixing and dispersion. Then, the release-treated polyethylene terephthalate film was coated with a wire bar and dried to prepare a heat conductive film having a thickness of about 100 μm. The thermal conductivity was measured in the same manner as in the case of the resin precursor dispersion composition. The film containing CNF was 10 W / m · K, but the film not containing CNF was 8.5 W / m · K, showing an improvement.
実施例１Ｂ，２Ｂで作製した無機粒子分散液を２３℃恒温室で７日間保存したが、フィラーの沈降は確認できなかった。ＣＮＦを配合していない分散液について同様に２３℃恒温室で７日間保存した場合にはフィラーの沈降が見られたため、ＣＮＦの分散によって、フィラーの沈降が抑制できていることが分かった。 The inorganic particle dispersions prepared in Examples 1B and 2B were stored in a constant temperature room at 23 ° C. for 7 days, but no sedimentation of the filler could be confirmed. Similarly, when the dispersion liquid containing no CNF was stored in a constant temperature room at 23 ° C. for 7 days, sedimentation of the filler was observed. Therefore, it was found that the dispersion of CNF suppressed the sedimentation of the filler.
〔熱伝導性部材への適応例〕
実施例１Ｂで作製した熱伝導性フィルムに粘着層として日東電工製のＰＥＴ基材両面テープＮｏ．５６０５を用いて電解銅箔と積層することで電磁波シールド機能を併せ持った部材を作製することが出来る。また、同様に実施例２Ｂで作製した熱伝導性フィルムの上にＵＶ硬化型のハードコート剤を５μｍの厚みでコーティングすることにより表面に保護層を有する熱伝導性フィルムとすることが可能である。
[Example of application to thermally conductive members]
Nitto Denko's PET base material double-sided tape No. 2 as an adhesive layer on the heat conductive film produced in Example 1B. A member having an electromagnetic wave shielding function can be manufactured by laminating with an electrolytic copper foil using 5605. Similarly, by coating the heat conductive film produced in Example 2B with a UV curable hard coating agent to a thickness of 5 μm, it is possible to obtain a heat conductive film having a protective layer on the surface. ..
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| CN110093012A (en) * | 2019-04-30 | 2019-08-06 | 重庆大学 | A kind of high-thermal-conductivity epoxy resin composite material and preparation method |
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