JP2008127212A - Surface-treated aluminum oxide particle - Google Patents
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Abstract
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本発明は、表面処理アルミニウム酸化物粒子に関し、詳しくは透明樹脂に添加する難燃剤として有用な表面処理アルミニウム酸化物粒子に関する。 The present invention relates to surface-treated aluminum oxide particles, and particularly relates to surface-treated aluminum oxide particles useful as a flame retardant added to a transparent resin.
水酸化アルミニウム粒子などのアルミニウム酸化物粒子は、熱可塑性樹脂中に分散させることにより難燃性を与える難燃剤として有用であり、特許文献１〔特開２００３−１７１１２０号公報〕には、水酸化アルミニウム粒子の表面にシランカップリング剤により表面処理を施した表面処理アルミニウム酸化物粒子が開示され、該粒子を透明樹脂中に分散させた透明樹脂組成物は、難燃性を示すことも開示されている。 Aluminum oxide particles such as aluminum hydroxide particles are useful as a flame retardant that imparts flame retardancy by being dispersed in a thermoplastic resin. Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-171120) discloses hydroxylation. Disclosed is a surface-treated aluminum oxide particle having a surface treated with a silane coupling agent on the surface of the aluminum particle, and it is also disclosed that the transparent resin composition in which the particle is dispersed in a transparent resin exhibits flame retardancy. ing.
かかるアルミニウム酸化物粒子としては、メタクリル樹脂、スチレン樹脂などのような透明樹脂に添加した場合に、高い難燃性と共に、高い透明性を示す透明樹脂組成物を与えうるものが求められている。 As such aluminum oxide particles, those which can give a transparent resin composition having high flame retardancy and high transparency when added to a transparent resin such as methacrylic resin or styrene resin are required.
そこで本発明者は、高い難燃性と共に高い透明性を示す透明樹脂組成物を与えうる表面処理アルミニウム酸化物粒子を開発するべく鋭意検討した結果、本発明に至った。 Therefore, the present inventors have intensively studied to develop surface-treated aluminum oxide particles capable of providing a transparent resin composition exhibiting high transparency with high flame retardancy, and as a result, have reached the present invention.
すなわち本発明は、アルミニウム酸化物粒子の表面に、式（Ｉ）
本発明の表面処理アルミニウム酸化物粒子を透明樹脂中に分散させた透明樹脂組成物は、高い難燃性と共に、高い透明性を示す。 The transparent resin composition in which the surface-treated aluminum oxide particles of the present invention are dispersed in a transparent resin exhibits high transparency as well as high flame retardancy.
本発明の表面処理アルミニウム酸化物粒子を構成するアルミニウム酸化物粒子としては、例えば結晶型がギブサイト型、バイヤライト型、ベーマイト型、擬ベーマイト型、ダイアスポア型などの水酸化アルミニウム（Ａｌ2Ｏ3・３Ｈ2Ｏ）、結晶型がα型、γ型、擬γ型、δ型、χ型、κ型、ρ型、θ型、η型などである酸化アルミニウム（Ａｌ2Ｏ3・ｎＨ2Ｏ、０≦ｎ＜３）などからなる酸化アルミニウム粒子が挙げられる。アルミニウム酸化物粒子は単一の結晶型からなる単一相であってもよいし、２以上の結晶型からなる混合相であってもよい。また、２種以上のアルミニウム酸化物粒子を組み合わせて用いてもよい。好ましいアルミニウム酸化物粒子は、加熱されることにより熱分解する際に吸熱作用を示す、ギブサイト型、バイヤライト型、ベーマイト型、擬ベーマイト型などの水酸化アルミニウム粒子である。 As the aluminum oxide particles constituting the surface-treated aluminum oxide particles of the present invention, for example, aluminum hydroxide (Al 2 O 3 .multidot. 3H 2 O), aluminum oxide (Al 2 O 3 .nH 2 O, crystal type α, γ, pseudo-γ, δ, χ, κ, ρ, θ, η, etc.) Examples thereof include aluminum oxide particles composed of 0 ≦ n <3) and the like. The aluminum oxide particles may be a single phase consisting of a single crystal type or a mixed phase consisting of two or more crystal types. Two or more kinds of aluminum oxide particles may be used in combination. Preferred aluminum oxide particles are gibbsite-type, bayerite-type, boehmite-type, pseudoboehmite-type aluminum hydroxide particles that exhibit an endothermic action when thermally decomposed by heating.
窒素吸着法によるアルミニウム酸化物粒子のＢＥＴ比表面積は、透明性の点で、３０ｍ2／ｇ以上であり、通常はコストの点で６００ｍ2／ｇ以下である。 The BET specific surface area of the aluminum oxide particles by the nitrogen adsorption method is 30 m 2 / g or more in terms of transparency, and usually 600 m 2 / g or less in terms of cost.
アルミニウム酸化物粒子の粒子径は、入手の容易さの点で通常１ｎｍ以上であり、透明性の点で、通常１５０ｎｍ以下、好ましくは１００ｎｍ以下である。アルミニウム酸化物粒子の粒子径は、動的光散乱法による粒度分布曲線における５０質量％相当粒子径として測定される。 The particle diameter of the aluminum oxide particles is usually 1 nm or more in view of availability, and is usually 150 nm or less, preferably 100 nm or less in terms of transparency. The particle size of the aluminum oxide particles is measured as a particle size corresponding to 50% by mass in a particle size distribution curve by a dynamic light scattering method.
式（Ｉ）で示されるリン酸エステル化合物は、リン酸モノ−［２−（４−メトキシ−２，２，６，６−テトラメチル−ピペリジン−１−イルオキシ）−２−フェニル−エチル］エステル〔Phosphoric acid mono-[2-(4-methoxy-2,2,6,6-tetramethyl-piperidin-1-yloxy)-2-phenyl-ethyl] ester〕であり、非特許文献１〔Chemistry of Materials, Vol.15, p3-5, 2003〕および非特許文献２〔Macromolecules, Vol.7, p2203-2209, 2004〕に記載されている。 The phosphoric acid ester compound represented by the formula (I) is phosphoric acid mono- [2- (4-methoxy-2,2,6,6-tetramethyl-piperidin-1-yloxy) -2-phenyl-ethyl] ester [Phosphoric acid mono- [2- (4-methoxy-2,2,6,6-tetramethyl-piperidin-1-yloxy) -2-phenyl-ethyl] ester], Non-Patent Document 1 [Chemistry of Materials, Vol. 15, p3-5, 2003] and Non-Patent Document 2 [Macromolecules, Vol. 7, p2203-2209, 2004].
本発明の表面処理アルミニウム酸化物粒子は、例えばアルミニウム酸化物粒子の表面に、リン酸エステル化合物（Ｉ）を担持させたのち、スチレンを重合させる方法により製造することができる。 The surface-treated aluminum oxide particles of the present invention can be produced by, for example, a method of polymerizing styrene after supporting the phosphate ester compound (I) on the surface of the aluminum oxide particles.
アルミニウム酸化物粒子の表面に、リン酸エステル化合物（Ｉ）を担持させるには、例えばアルミニウム酸化物粒子をリン酸エステル化合物（Ｉ）と接触させればよい。リン酸エステル化合物（Ｉ）との接触は通常、テトラヒドロフランなどのようなリン酸エステル化合物（Ｉ）を溶解し得る有機溶媒中で行われ、例えばアルミニウム酸化物粒子、リン酸エステル化合物（Ｉ）および有機溶媒を混合することにより行われる。リン酸エステル化合物の使用量は、アルミニウム酸化物粒子に対して通常０．１質量倍〜１０質量倍であり、有機溶媒の使用量は、アルミニウム酸化物粒子に対して通常１０質量倍〜１０００質量倍である。 In order to carry the phosphate ester compound (I) on the surface of the aluminum oxide particles, for example, the aluminum oxide particles may be brought into contact with the phosphate ester compound (I). Contact with the phosphoric ester compound (I) is usually carried out in an organic solvent capable of dissolving the phosphoric ester compound (I) such as tetrahydrofuran, for example, aluminum oxide particles, phosphoric ester compound (I) and It is carried out by mixing organic solvents. The usage-amount of a phosphate ester compound is 0.1 mass times-10 mass times normally with respect to aluminum oxide particle, and the usage-amount of an organic solvent is 10 mass times-1000 mass normally with respect to aluminum oxide particle. Is double.
かくして接触させた後、固液分離することにより、固形分として、表面にリン酸エステル化合物（Ｉ）が担持されたアルミニウム酸化物粒子を得ることができる。得られた粒子は、エタノールなどのようなアルコール溶媒で洗浄してもよい。 Thus, after making it contact, the aluminum oxide particle by which phosphate ester compound (I) was carry | supported on the surface as solid content can be obtained by carrying out solid-liquid separation. The obtained particles may be washed with an alcohol solvent such as ethanol.
このようにしてアルミニウム酸化物粒子の表面にリン酸エステル化合物を担持させたのち、スチレンを重合させる。スチレンを重合させるには、例えばリン酸エステル化合物（Ｉ）を担持したのちのアルミニウム酸化物粒子の存在下に、スチレンを重合温度に加熱すればよく、具体的には、例えばリン酸エステル化合物（Ｉ）を担持したのちのアルミニウム酸化物粒子をスチレン中に分散させた後、重合温度に加熱すればよい。スチレンの使用量は、アルミニウム酸化物粒子に対して過剰量、例えば３質量倍〜１０００質量倍である。重合温度は通常０℃〜１６０℃であり、重合時間は通常０．５時間〜２０時間である。 In this way, after the phosphate compound is supported on the surface of the aluminum oxide particles, styrene is polymerized. In order to polymerize styrene, for example, styrene may be heated to the polymerization temperature in the presence of aluminum oxide particles after supporting phosphate compound (I). Specifically, for example, phosphate compound ( The aluminum oxide particles after supporting I) may be dispersed in styrene and then heated to the polymerization temperature. The usage-amount of styrene is an excess amount with respect to aluminum oxide particle, for example, 3 mass times-1000 mass times. The polymerization temperature is usually from 0 ° C to 160 ° C, and the polymerization time is usually from 0.5 hours to 20 hours.
重合温度に加熱されることにより、アルミニウム酸化物粒子の表面に担持されたリン酸エステル化合物（Ｉ）を重合開始剤としてスチレンの重合が開始され、スチレンが表面にグラフト重合されて、目的の表面処理アルミニウム酸化物粒子を得ることができる。 By heating to the polymerization temperature, polymerization of styrene is initiated using the phosphate ester compound (I) supported on the surface of the aluminum oxide particles as a polymerization initiator, and styrene is graft-polymerized on the surface. Treated aluminum oxide particles can be obtained.
得られた表面処理アルミニウム酸化物粒子は、固液分離により、重合後の重合混合物から容易に取り出すことができる。取り出された表面処理アルミニウム酸化物粒子には、アルミニウム酸化物粒子の表面にグラフト重合されていないポリスチレンが付着していることがあるが、かかるポリスチレンは、例えばクロロホルムなどのようなポリスチレンを溶解しうる有機溶媒により洗浄すればよい。 The obtained surface-treated aluminum oxide particles can be easily taken out from the polymerization mixture after polymerization by solid-liquid separation. The surface-treated aluminum oxide particles taken out may have ungrafted polystyrene attached to the surface of the aluminum oxide particles. Such polystyrene can dissolve polystyrene such as chloroform. What is necessary is just to wash | clean with an organic solvent.
本発明の表面処理アルミニウム酸化物粒子は、難燃剤として有用であり、これを透明樹脂中に分散させた透明樹脂組成物は、高い難燃性を示すと共に、高い透明性をも示す。 The surface-treated aluminum oxide particles of the present invention are useful as a flame retardant, and a transparent resin composition in which the surface-treated aluminum oxide particles are dispersed in a transparent resin exhibits high flame retardancy and high transparency.
透明樹脂としては、例えばポリスチレンが挙げられる。 Examples of the transparent resin include polystyrene.
透明樹脂組成物における表面処理アルミニウム酸化物粒子の含有量は、透明樹脂に対して０．００１質量部〜１質量部である。 Content of the surface treatment aluminum oxide particle in a transparent resin composition is 0.001 mass part-1 mass part with respect to transparent resin.
透明樹脂組成物は、例えば透明樹脂が熱可塑性樹脂である場合には、透明樹脂および表面処理アルミニウム酸化物粒子を溶融混練すればよい。また、透明樹脂を溶解しうる揮発性の溶媒に透明樹脂を溶解させると共に表面処理アルミニウム酸化物粒子を分散させ、次いで溶媒を揮発させてもよい。 For example, when the transparent resin is a thermoplastic resin, the transparent resin composition may be obtained by melt-kneading the transparent resin and the surface-treated aluminum oxide particles. Alternatively, the transparent resin may be dissolved in a volatile solvent capable of dissolving the transparent resin, the surface-treated aluminum oxide particles may be dispersed, and then the solvent may be volatilized.
透明樹脂組成物の成形は通常の方法、例えば押出成形法、射出成形法、プレス成形法、流延キャスト法などの方法により行うことができる。 The transparent resin composition can be molded by an ordinary method such as an extrusion molding method, an injection molding method, a press molding method, or a cast casting method.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、各実施例における評価方法は以下のとおりである。
（１）透明性
実施例で得たフィルムについて、紫外可視分光光度計〔日立製作所社製、「Ｕ−３３１０」〕を用いて、波長７００ｎｍにおける光線透過率を求めた。
（２）熱分解開始温度
実施例で得たフィルムについて、熱重量分析装置〔リガク社製「ＴＧ−８１２０」〕を用いて、窒素ガス雰囲気下に昇温速度１０℃／分にて５０℃から８００℃まで昇温した際に、急激な質量減少が開始する温度を熱分解開始温度として求めた。
（３）ＢＥＴ比表面積
比表面積測定装置〔マウンテック社製「Macsorb Model-1201」〕を用いて窒素ガス吸着法により求めた。
（４）５０質量％相当粒子径
粒度分析計〔日機装社製「Nanotrac Model UPA-EX150」を用いて動的光散乱法により粒度分布曲線を求め、その５０質量％相当粒子径を求めた。
（５）表面処理アルミニウム酸化物粒子の表面にグラフト重合されたポリスチレンの分子量
表面処理アルミニウム酸化物粒子の表面に付着しているグラフト重合されていないポリスチレンをテトラヒドロフランに溶解させ、ゲルパーミエーションクロマトグラフ（ＧＰＣ）法により、このポリスチレンの重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を求めた。ＧＰＣ法では、ゲルパーミエーションクロマトグラフ（ＧＰＣ）カラム〔昭和電工社製「ＧＰＣＫＦ−８０４」〕を装着したＧＰＣ装置〔東ソー社製「ＨＬＣ−８１２０ＧＰＣ」〕を用い、溶離液としてテトラヒドロフランを用いた。
In addition, the evaluation method in each Example is as follows.
(1) Transparency About the film obtained in the Example, the light transmittance at a wavelength of 700 nm was determined using an ultraviolet-visible spectrophotometer [manufactured by Hitachi, Ltd., “U-3310”].
(2) Thermal decomposition starting temperature About the film obtained in the example, from a thermogravimetric analyzer (“TG-8120” manufactured by Rigaku Corporation) at a temperature rising rate of 10 ° C./min in a nitrogen gas atmosphere. When the temperature was raised to 800 ° C., the temperature at which sudden mass reduction started was determined as the thermal decomposition start temperature.
(3) BET specific surface area It was determined by a nitrogen gas adsorption method using a specific surface area measuring device ["Macsorb Model-1201" manufactured by Mountec Co., Ltd.].
(4) 50 mass% equivalent particle size particle size analyzer [Nikkiso's “Nanotrac Model UPA-EX150” was used to determine the particle size distribution curve by the dynamic light scattering method, and the 50 mass% equivalent particle size was obtained.
(5) Molecular weight of polystyrene graft-polymerized on the surface of the surface-treated aluminum oxide particles The ungrafted polystyrene adhering to the surface of the surface-treated aluminum oxide particles is dissolved in tetrahydrofuran, and a gel permeation chromatograph ( The weight average molecular weight (Mw) and number average molecular weight (Mn) of this polystyrene were determined by the GPC method. In the GPC method, a GPC apparatus (“HLC-8120GPC” manufactured by Tosoh Corporation) equipped with a gel permeation chromatograph (GPC) column [“GPCKF-804” manufactured by Showa Denko KK] was used, and tetrahydrofuran was used as an eluent.
参考例１〔リン酸エステル化合物の製造〕
〔４−メトキシ−２，２，６，６−テトラメチルピペリジニル−１−オキシルの製造〕
４−ヒドロキシ−２，２，６，６−テトラメチルピペリジニル−１−オキシル１０ｇをジメチルホルムアミド２００ｍＬに溶解させたのち、水素化ナトリウム２．７９ｇを加え、撹拌した。水素ガスの発生が確認できなくなったのち、ヨウ化メチル５．４３ｍＬ（１２．４ｇ）を加え、さらに６時間撹拌した。その後、ジエチルエーテルを加え、その後、希塩酸〔ＨＣｌ濃度１モル／Ｌ〕で洗浄し、さらに純水で洗浄した後、無水硫酸マグネシウムを加えて乾燥し、減圧濃縮した。濃縮後の残渣を、ヘキサンおよび酢酸エチルを等容量比で混合した混合溶媒を展開溶媒としたシリカゲルカラムクロマトグラフ処理に付して精製し、収率４５．５％で４−メトキシ−２，２，６，６−テトラメチルピペリジニル−１−オキシルを得た。
Reference Example 1 [Production of phosphate ester compound]
[Production of 4-methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl]
After 10 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl was dissolved in 200 mL of dimethylformamide, 2.79 g of sodium hydride was added and stirred. After generation of hydrogen gas could not be confirmed, methyl iodide (5.43 mL, 12.4 g) was added, and the mixture was further stirred for 6 hours. Then, diethyl ether was added, then washed with dilute hydrochloric acid [HCl concentration 1 mol / L], further washed with pure water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue after concentration was purified by silica gel column chromatography using a mixed solvent in which hexane and ethyl acetate were mixed at an equal volume ratio as a developing solvent, and 4-methoxy-2,2 was obtained in a yield of 45.5%. , 6,6-tetramethylpiperidinyl-1-oxyl was obtained.
〔ベンゾイル化および加水分解〕
上記で得た４−メトキシ−２，２，６，６−テトラメチルピペリジニル−１−オキシル３．８２ｇを窒素ガス気流下にスチレン３００ｍＬ（２７１ｇ）に溶解させ、過酸化ベンゾイル６．６７ｇを加え、９６℃に加熱し、同温度で４５分間保持して反応させた。反応後の反応混合物を、クロロホルムおよび酢酸エチルを等容量比で混合した混合溶媒を展開溶媒としたシリカゲルカラムクロマトグラフ処理に付して精製した。精製後の精製物をエタノール２０ｍＬに溶解させ、水酸化ナトリウム水溶液〔濃度２モル／Ｌ〕１０ｍＬを滴下して加え、８０℃に昇温し、同温度で６時間反応させた。反応後の反応混合物からエタノールを減圧留去し、得られた残渣に純水を加え、酢酸エチルで抽出処理し、得られた抽出液を無水硫酸マグネシウムで乾燥処理した後、溶媒留去し、残渣をカラムクロマトグラフ処理して、式（Ｉ−１）
3.82 g of 4-methoxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl obtained above was dissolved in 300 mL (271 g) of styrene under a nitrogen gas stream, and 6.67 g of benzoyl peroxide was dissolved. In addition, the mixture was heated to 96 ° C. and kept at the same temperature for 45 minutes for reaction. The reaction mixture after the reaction was purified by silica gel column chromatography using a mixed solvent in which chloroform and ethyl acetate were mixed at an equal volume ratio as a developing solvent. The purified product after purification was dissolved in 20 mL of ethanol, 10 mL of an aqueous sodium hydroxide solution (concentration 2 mol / L) was added dropwise, the temperature was raised to 80 ° C., and the mixture was reacted at the same temperature for 6 hours. Ethanol was distilled off under reduced pressure from the reaction mixture after the reaction, pure water was added to the obtained residue, extraction treatment was performed with ethyl acetate, and the resulting extract was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue is subjected to column chromatography to give the formula (I-1)
〔リン酸エステル化合物の製造〕
上記で得た式（Ｉ−１）で示される化合物１０．５ｇとトリエチルアミン０．９１ｍＬ（０．６６ｇ）を予め乾燥処理したテトラヒドロフラン４０ｍＬに溶解させて、式（Ｉ−１）で示される化合物の溶液を得た。オキシ塩化リン０．３ｍＬ（０．５１ｇ）を予め乾燥処理したテトラヒドロフラン２０ｍＬに溶解させた溶液に、上記で得た式（Ｉ−１）で示される化合物の溶液に、１５分掛けて滴下して加えた。その後、室温（概ね２５℃）にて２時間撹拌したのち、析出したトリエチルアミン塩酸塩を濾別し、得られた濾液に、イオン交換水を加え、その後、テトラヒドロフランを減圧留去した。減圧留去後をクロロホルムで抽出処理し、得られた抽出液を硫酸ナトリウムにより乾燥した。乾燥後、クロロホルムを減圧留去し、残渣を、クロロホルムおよびメタノールを等容量比で混合した混合溶媒を展開溶媒としたシリカゲルカラムクロマトグラフ処理に付して精製し、クロロホルムに溶解させたのち未溶解分を濾別し、クロロホルムを溶媒留去して、式（Ｉ）で示されるリン酸エステル化合物を得た。
[Production of phosphate ester compound]
10.5 g of the compound represented by the formula (I-1) obtained above and 0.91 mL (0.66 g) of triethylamine were dissolved in 40 mL of previously dried tetrahydrofuran, and the compound of the formula (I-1) was dissolved. A solution was obtained. To a solution of 0.3 mL (0.51 g) of phosphorus oxychloride dissolved in 20 mL of previously dried tetrahydrofuran was added dropwise over 15 minutes to the solution of the compound represented by formula (I-1) obtained above. added. Then, after stirring at room temperature (approximately 25 ° C.) for 2 hours, the precipitated triethylamine hydrochloride was filtered off, ion-exchanged water was added to the obtained filtrate, and then tetrahydrofuran was distilled off under reduced pressure. After evaporation under reduced pressure, the mixture was extracted with chloroform, and the resulting extract was dried over sodium sulfate. After drying, chloroform was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using a mixed solvent of chloroform and methanol mixed at an equal volume ratio as a developing solvent, dissolved in chloroform, and then undissolved. The fraction was separated by filtration, and chloroform was distilled off to obtain a phosphate ester compound represented by the formula (I).
参考例２〔水酸化アルミニウム粒子の製造〕
アルミニウムアルコキシドを加水分解して得た擬ベーマイト型水酸化アルミニウム粒子〔ＢＥＴ比表面積２９０ｍ2／ｇ〕２００ｇを希硝酸〔濃度１モル／Ｌ〕１８００ｍＬに加え、超音波を照射して分散させた後、８５℃に加熱し、同温度を２時間保持した。その後、遠心分離処理により粗粒子を除去し、高圧ホモジナイザーにより粉砕処理して、５０質量％相当粒子径３７ｎｍのベーマイト型水酸化アルミニウム粒子が分散された分散液を得た。この分散液の固形分濃度は３．６質量％であり、水素イオン濃度はｐＨ３．５であった。
Reference Example 2 [Production of aluminum hydroxide particles]
After adding 200 g of pseudo boehmite type aluminum hydroxide particles [BET specific surface area 290 m 2 / g] obtained by hydrolysis of aluminum alkoxide to 1800 mL of dilute nitric acid [concentration 1 mol / L], and then irradiating with ultrasonic waves, The mixture was heated to 85 ° C. and kept at the same temperature for 2 hours. Thereafter, coarse particles were removed by a centrifugal separation treatment and pulverized by a high-pressure homogenizer to obtain a dispersion liquid in which boehmite-type aluminum hydroxide particles having a particle diameter corresponding to 50% by mass of 37 nm were dispersed. The solid content concentration of this dispersion was 3.6% by mass, and the hydrogen ion concentration was pH 3.5.
上記で得た分散液にテトラヒドロフランを加えてベーマイト型水酸化アルミニウム粒子を凝集させ、遠心分離処理により固形分として凝集物を得、その後、減圧乾燥した。 Tetrahydrofuran was added to the dispersion obtained above to agglomerate boehmite-type aluminum hydroxide particles, and agglomerates were obtained as a solid content by centrifugation, and then dried under reduced pressure.
実施例１
〔リン酸エステル化合物の担持〕
参考例１で得たリン酸エステル化合物（Ｉ）２０ｍｇおよび参考例２で減圧乾燥した後のベーマイト型水酸化アルミニウム粒子２０ｍｇをテトラヒドロフラン４０ｍＬに加え、室温（約２５℃）にて撹拌した。その後、超音波を照射し、遠心分離処理により固形分を得た。得られた固形分をエタノールと混合した後、デカンテーションにより固形分を得る洗浄操作を繰り返して洗浄し、遠心分離処理によりエタノールを除去した後、減圧乾燥して、ベーマイト型水酸化アルミニウム粒子の表面にリン酸エステル化合物（Ｉ）を担持させた。
Example 1
[Support of phosphate ester compound]
20 mg of the phosphoric ester compound (I) obtained in Reference Example 1 and 20 mg of boehmite type aluminum hydroxide particles after drying under reduced pressure in Reference Example 2 were added to 40 mL of tetrahydrofuran and stirred at room temperature (about 25 ° C.). Thereafter, ultrasonic waves were applied to obtain a solid content by centrifugation. After the obtained solid content is mixed with ethanol, the washing operation for obtaining the solid content by decantation is repeated and washed, the ethanol is removed by centrifugation, and then dried under reduced pressure to obtain the surface of the boehmite type aluminum hydroxide particles. The phosphoric acid ester compound (I) was supported on.
〔スチレンのグラフト重合〕
上記でリン酸エステル化合物（Ｉ）を担持させた後のベーマイト型水酸化アルミニウム粒子３ｍｇおよびスチレン２３０ｇを混合し、超音波を照射したのち、脱気処理し、密封した状態で１２５℃に加熱し、同温度を保持して重合させた。その後、冷却し、クロロホルムにより洗浄して、グラフト重合されていないポリスチレンを除去し、遠心分離処理により固形分を得、得られた固形分を減圧乾燥して、表面処理アルミニウム酸化物粒子を得た。この表面処理アルミニウム酸化物粒子の表面にグラフト重合されたポリスチレンの数平均分子量（Ｍｎ）は１４５００であり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は１．３２であった。
[Styrene Graft Polymerization]
After mixing 3 mg of boehmite type aluminum hydroxide particles and 230 g of styrene after supporting the phosphate ester compound (I) as described above, the mixture was irradiated with ultrasonic waves, degassed, and heated to 125 ° C. in a sealed state. The polymerization was carried out while maintaining the same temperature. Then, it was cooled and washed with chloroform to remove polystyrene that was not graft-polymerized, solid content was obtained by centrifugation, and the obtained solid content was dried under reduced pressure to obtain surface-treated aluminum oxide particles. . The number average molecular weight (Mn) of polystyrene graft-polymerized on the surface of the surface-treated aluminum oxide particles is 14500, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1. .32.
〔ポリスチレン組成物の製造〕
クロロホルム１００質量部に対して、ポリスチレン〔数平均分子量２３００００、Ｍｗ／Ｍｎ１．９６〕４質量部を加えて溶解させ、次いで上記で得た表面処理アルミニウム酸化物粒子０．２１７６質量部を加えて撹拌して、分散液を得た。この分散液を硝子シャーレに注ぎ入れ、大気中でクロロホルムを揮発させたのち、１１４℃（３８７Ｋ）で２４時間加熱して、厚み６０μｍ〜８０μｍのキャストフィルムを得た。このキャストフィルムは、ポリスチレン１００質量部あたり５．４４質量部の表面処理水酸化アルミニウム粒子を含んでいる。
[Production of polystyrene composition]
To 100 parts by mass of chloroform, 4 parts by mass of polystyrene [number average molecular weight 230000, Mw / Mn 1.96] is added and dissolved, and then 0.2176 parts by mass of the surface-treated aluminum oxide particles obtained above are added and stirred. A dispersion was obtained. The dispersion was poured into a glass petri dish and chloroform was volatilized in the air, and then heated at 114 ° C. (387 K) for 24 hours to obtain a cast film having a thickness of 60 μm to 80 μm. This cast film contains 5.44 parts by mass of surface-treated aluminum hydroxide particles per 100 parts by mass of polystyrene.
このキャストフィルムの光線透過率は８４％であり、熱分解開始温度は６７９℃、熱分解終了温度は７２４℃であった。 The cast film had a light transmittance of 84%, a thermal decomposition start temperature of 679 ° C., and a thermal decomposition end temperature of 724 ° C.
比較例１
実施例１で得た表面処理アルミニウム酸化物粒子に代えて、参考例２で得たベーマイト型水酸化アルミニウム粒子０．２０４質量部を用いた以外は実施例１と同様に操作して、厚み６０μｍ〜８０μｍのキャストフィルムを得た。このキャストフィルムは、ポリスチレン１００質量部あたり５．１質量部のベーマイト型水酸化アルミニウム粒子を含んでいる。
Comparative Example 1
A thickness of 60 μm was obtained in the same manner as in Example 1 except that 0.204 parts by mass of boehmite type aluminum hydroxide particles obtained in Reference Example 2 were used instead of the surface-treated aluminum oxide particles obtained in Example 1. A cast film of ˜80 μm was obtained. This cast film contains 5.1 parts by mass of boehmite type aluminum hydroxide particles per 100 parts by mass of polystyrene.
このキャストフィルムの光線透過率は６８％であり、熱分解開始温度は６６６℃、熱分解終了温度は７０２℃であった。 The cast film had a light transmittance of 68%, a thermal decomposition start temperature of 666 ° C., and a thermal decomposition end temperature of 702 ° C.
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| WO2021115810A1 (en) | 2019-12-13 | 2021-06-17 | Henkel Ag & Co. Kgaa | Thermally conductive polyurethane adhesive composition |
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