JP2009068019A - Spherical silsesquioxane fine particle and surface modifier for polymer material - Google Patents
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本発明は、球状シルセスキオキサン微粒子及び高分子材料用表面改質剤に関する。高分子材料用表面改質剤、化粧品原料、コーティング材、診断薬用担体、塗料原料等として、球状シルセスキオキサン微粒子が広く利用されている。本発明は、粒子径の平均値が極めて小さく、また粒子径の分布が極めて狭い球状シルセスキオキサン微粒子及びかかる球状シルセスキオキサン微粒子から成る高分子材料用表面改質剤に関する。 The present invention relates to spherical silsesquioxane fine particles and a surface modifier for polymer materials. Spherical silsesquioxane fine particles are widely used as surface modifiers for polymer materials, cosmetic raw materials, coating materials, diagnostic agent carriers, paint raw materials, and the like. The present invention relates to spherical silsesquioxane fine particles having an extremely small average particle diameter and an extremely narrow particle size distribution, and a surface modifier for a polymer material comprising such spherical silsesquioxane fine particles.
従来、球状シルセスキオキサン微粒子は、１）アルカリ触媒存在下に、シラノール形成性ケイ素化合物を水と接触させ、加水分解反応及び縮合反応を同時に行なわせる方法（例えば特許文献１〜１４参照）、２）アルカリ触媒存在下に、シラノール形成性ケイ素化合物を水と接触させ、加水分解反応させてシラノール化合物とした後、該シラノール化合物を縮合反応させる方法（例えば特許文献１５参照）、３）無機酸触媒存在下に、シラノール形成性ケイ素化合物を水と接触させ、加水分解反応及び縮合反応を同時に行なわせる方法（例えば特許文献１６参照）、４）有機酸触媒存在下に、シラノール形成性ケイ素化合物を水と接触させ、加水分解反応させてシラノール化合物とした後、該シラノール化合物を縮合反応させる方法（例えば特許文献１７参照）等で得られている。 Conventionally, spherical silsesquioxane fine particles are: 1) a method in which a silanol-forming silicon compound is brought into contact with water in the presence of an alkali catalyst, and a hydrolysis reaction and a condensation reaction are simultaneously performed (for example, see Patent Documents 1 to 14); 2) A method in which a silanol-forming silicon compound is brought into contact with water in the presence of an alkali catalyst and hydrolyzed to form a silanol compound, followed by a condensation reaction of the silanol compound (see, for example, Patent Document 15), 3) inorganic acid A method in which a silanol-forming silicon compound is brought into contact with water in the presence of a catalyst, and a hydrolysis reaction and a condensation reaction are simultaneously performed (for example, see Patent Document 16). 4) A silanol-forming silicon compound is formed in the presence of an organic acid catalyst. A method of bringing the silanol compound into contact with water and hydrolyzing it to make a silanol compound, followed by condensation reaction of the silanol compound (for example, It has been obtained in Patent Document 17 reference) and the like.
ところが、これらの方法で得られる従来の球状シルセスキオキサン微粒子には、その粒子径の平均値が比較的に大きく、また粒子径の分布が比較的に広いという問題がある。具体的には、一般に得られる球状シルセスキオキサン微粒子の粒子径の平均値が１００ｎｍ以上であり、また粒子径の変動係数が３０％以上なのである。
本発明が解決しようとする課題は、粒子径の平均値が極めて小さく、また粒子径の分布が極めて狭い球状シルセスキオキサン微粒子及びかかる球状シルセスキオキサン微粒子から成る高分子材料用表面改質剤を提供する処にある。 The problems to be solved by the present invention include spherical silsesquioxane fine particles having an extremely small average particle diameter and an extremely narrow particle size distribution, and surface modification for polymer materials comprising such spherical silsesquioxane fine particles. It is in place to provide the agent.
しかして本発明者らは、前記の課題を解決するべく研究した結果、特定のシラノール形成性ケイ素化合物を、所定量の特定の酸触媒の存在下で、所定量の水と接触させ、所定の温度下で加水分解反応及び縮合反応を同時に行なわせることにより得られる球状シルセスキオキサン微粒子が正しく好適であることを見出した。 Thus, as a result of researches to solve the above problems, the present inventors contacted a specific silanol-forming silicon compound with a predetermined amount of water in the presence of a predetermined amount of a specific acid catalyst, It has been found that spherical silsesquioxane fine particles obtained by simultaneously performing a hydrolysis reaction and a condensation reaction at a temperature are suitable.
すなわち本発明は、下記の条件１〜５を同時に満足する条件下で、シラノール形成性ケイ素化合物を酸触媒存在下で水と接触させ、加水分解反応及び縮合反応を同時に行なわせることにより得られる粒子径の平均値が１０〜３０ｎｍ且つ粒子径の変動係数が１５％以下の球状シルセスキオキサン微粒子に係る。また本発明はかかる球状シルセスキオキサン微粒子から成る高分子材料用表面改質剤に係る。 That is, the present invention provides particles obtained by bringing a silanol-forming silicon compound into contact with water in the presence of an acid catalyst and simultaneously performing a hydrolysis reaction and a condensation reaction under the conditions that simultaneously satisfy the following conditions 1 to 5. The present invention relates to spherical silsesquioxane fine particles having an average diameter of 10 to 30 nm and a particle diameter variation coefficient of 15% or less. The present invention also relates to a surface modifier for polymer materials comprising such spherical silsesquioxane fine particles.
条件１：シラノール形成性ケイ素化合物が、メチルトリメトキシシランであること。 Condition 1: The silanol-forming silicon compound is methyltrimethoxysilane.
条件２：酸触媒が、ドデシルベンゼンスルホン酸であること。 Condition 2: The acid catalyst is dodecylbenzenesulfonic acid.
条件３：酸触媒の使用割合が、シラノール形成性ケイ素化合物１モル当たり０．００４〜０．０３モルであること。 Condition 3: The usage ratio of the acid catalyst is 0.004 to 0.03 mol per mol of the silanol-forming silicon compound.
条件４：シラノール形成性ケイ素化合物と水との使用割合が、シラノール形成性ケイ素化合物／水＝５／９５〜１６／８４（重量比）であること。 Condition 4: Use ratio of silanol-forming silicon compound and water is silanol-forming silicon compound / water = 5/95 to 16/84 (weight ratio).
条件５：加水分解反応及び縮合反応時の温度が、１５〜２５℃であること。 Condition 5: The temperature during the hydrolysis reaction and the condensation reaction is 15 to 25 ° C.
本発明に係る球状シルセスキオキサン微粒子は、後述する特定の条件１〜５を同時に満足する条件下で、シラノール形成性ケイ素化合物を酸触媒存在下で水と接触させ、加水分解反応及び縮合反応を同時に行なわせることにより得られるものである。 The spherical silsesquioxane fine particles according to the present invention are prepared by bringing a silanol-forming silicon compound into contact with water in the presence of an acid catalyst under the conditions simultaneously satisfying specific conditions 1 to 5 described later, and performing a hydrolysis reaction and a condensation reaction. Can be obtained simultaneously.
条件１は、シラノール形成性ケイ素化合物が、メチルトリメトキシシランであることである。メチルトリメトキシシランは、加水分解反応によって、１分子当たり３個のシラノール基を形成する。 Condition 1 is that the silanol-forming silicon compound is methyltrimethoxysilane. Methyltrimethoxysilane forms three silanol groups per molecule by a hydrolysis reaction.
条件２は、酸触媒が、ドデシルベンゼンスルホン酸であることである。 Condition 2 is that the acid catalyst is dodecylbenzenesulfonic acid.
条件３は、酸触媒の使用割合が、シラノール形成性ケイ素化合物１モル当たり、０．００４〜０．０３モルであることである。 Condition 3 is that the usage ratio of the acid catalyst is 0.004 to 0.03 mol per mol of the silanol-forming silicon compound.
条件４は、シラノール形成性ケイ素化合物と水との使用割合が、シラノール形成性ケイ素化合物／水＝５／９５〜１６／８４（重量比）、好ましくは７／９３〜１３／８７（重量比）であることである。ここで使用する水は脱イオン水が好ましい。 Condition 4 is that the use ratio of silanol-forming silicon compound and water is silanol-forming silicon compound / water = 5/95 to 16/84 (weight ratio), preferably 7/93 to 13/87 (weight ratio). It is to be. The water used here is preferably deionized water.
条件５は、加水分解反応及び縮合反応時の温度が、１５〜２５℃であることである。かかる温度の制御は、反応系の加熱や冷却の他に、シラノール形成性ケイ素化合物に対する酸触媒の使用割合、シラノール形成性ケイ素化合物と水との使用割合、シラノール形成性ケイ素化合物及び水の温度、反応装置等を適宜選択して行うことができる。 Condition 5 is that the temperature during the hydrolysis reaction and the condensation reaction is 15 to 25 ° C. Such temperature control includes, in addition to heating and cooling of the reaction system, the use ratio of the acid catalyst to the silanol-forming silicon compound, the use ratio of the silanol-forming silicon compound and water, the temperature of the silanol-forming silicon compound and water, A reaction apparatus or the like can be selected as appropriate.
本発明に係る球状シルセスキオキサン微粒子は、以上説明したような特定の条件１〜５を同時に満足する条件下で、シラノール形成性ケイ素化合物を酸触媒の存在下で水と接触させ、加水分解反応及び縮合反応を同時に行なわせることにより得られるものである。より具体的には例えば、前記した特定の条件１〜５を同時に満足することを前提として、１）反応容器に水及び酸触媒を仕込んだ後、攪拌しつつシラノール形成性ケイ素化合物を滴下し、反応系の温度を制御しながら加水分解反応及び縮合反応を同時に行なわせる方法、２）反応容器に水を仕込んでおき、攪拌しつつ酸触媒及びこれとは別のシラノール形成性ケイ素化合物を同時に滴下して、反応系の温度を制御しながら加水分解反応及び縮合反応を同時に行なわせる方法等が挙げられる。かかる方法により、球状シルセスキオキサン微粒子はその半透明の水性懸濁液として得られるので、これをアルカリで中和した水性懸濁液とし、更に乾燥して、例えばスプレードライヤーにより１００〜２５０℃で加熱乾燥して、所望通りの球状シルセスキオキサン微粒子を得る。 The spherical silsesquioxane fine particles according to the present invention are hydrolyzed by bringing a silanol-forming silicon compound into contact with water in the presence of an acid catalyst under the conditions satisfying the specific conditions 1 to 5 as described above. It is obtained by carrying out the reaction and the condensation reaction simultaneously. More specifically, for example, on the assumption that the specific conditions 1 to 5 described above are satisfied at the same time, 1) after adding water and an acid catalyst to the reaction vessel, the silanol-forming silicon compound is dropped while stirring, A method in which the hydrolysis reaction and the condensation reaction are simultaneously performed while controlling the temperature of the reaction system. 2) Water is charged in a reaction vessel, and an acid catalyst and a silanol-forming silicon compound different from this are dropped simultaneously while stirring. For example, a method in which a hydrolysis reaction and a condensation reaction are simultaneously performed while controlling the temperature of the reaction system. By this method, since the spherical silsesquioxane fine particles are obtained as a translucent aqueous suspension, this is made into an aqueous suspension neutralized with an alkali, and further dried, for example, 100 to 250 ° C. with a spray dryer. And dried by heating to obtain spherical silsesquioxane fine particles as desired.
かくして得られる本発明に係る球状シルセスキオキサン微粒子は、粒子径の平均値が１０〜３０ｎｍで且つ粒子径の変動係数が１５％以下のものとなる。 The spherical silsesquioxane fine particles according to the present invention thus obtained have an average particle diameter of 10 to 30 nm and a particle diameter variation coefficient of 15% or less.
本発明に係る高分子材料用表面改質剤は、前記した本発明に係る球状シルセスキオキサン微粒子から成るものである。前記した本発明に係る球状シルセスキオキサン微粒子は、高分子材料用表面改質剤、化粧品原料、コーティング材、診断薬用担体、塗料原料等として広く利用できる。なかでも、前記した本発明に係る球状シルセスキオキサン微粒子は、粒子径の平均値が極めて小さく、また粒子径の分布が極めて狭いため、従来の球状シルセスキオキサン微粒子と比べて、フィルムやシート等の高分子材料成形品表面への高速塗工性に優れ、かかる高分子材料成形品表面に平滑性、密着防止性及び離型性等の表面特性を安定して付与することができるので、高分子材料用表面改質剤として、特に滑剤として有用である。 The surface modifier for a polymer material according to the present invention comprises the spherical silsesquioxane fine particles according to the present invention described above. The spherical silsesquioxane fine particles according to the present invention described above can be widely used as a surface modifier for polymer materials, cosmetic raw materials, coating materials, diagnostic carriers, coating raw materials, and the like. Especially, since the above-mentioned spherical silsesquioxane fine particles according to the present invention have an extremely small average particle diameter and a very narrow particle size distribution, the film or film is smaller than the conventional spherical silsesquioxane fine particles. Because it is excellent in high-speed coating properties on the surface of polymer material molded products such as sheets, it can stably impart surface properties such as smoothness, adhesion prevention and release properties to the surface of such polymer material molded products. It is useful as a surface modifier for polymer materials, particularly as a lubricant.
本発明に係る高分子材料用表面改質剤を適用する高分子材料としては、ポリエステル、ナイロン、ポリエチレン、ポリプロピレン、ポリカプロラクトン、アクリル樹脂、スチレン系樹脂、ポリカーボネート等の合成高分子から成形された合成高分子フィルムやシート、同様の合成高分子から成形されたフィラメントヤーンやステープルファイバー等の合成繊維が挙げられる。 The polymer material to which the surface modifier for the polymer material according to the present invention is applied is a synthetic material molded from a synthetic polymer such as polyester, nylon, polyethylene, polypropylene, polycaprolactone, acrylic resin, styrenic resin, and polycarbonate. Examples include polymer films and sheets, and synthetic fibers such as filament yarns and staple fibers formed from similar synthetic polymers.
本発明に係る高分子材料用表面改質剤を合成高分子フィルムの滑剤として適用する方法としては、高分子材料用表面改質剤の水性懸濁液を調製し、又は本発明の製造方法によって得られる前記の水性懸濁液をそのまま使用して、これをローラータッチ法、スプレー法、スピンコート法等の公知の方法によって合成高分子フィルムの表面に塗布する方法が挙げられる。塗布する工程としては、合成高分子フィルムの製造工程において、これらの溶融押出し直後における延伸配向前の工程、一軸延伸配向後における二軸延伸配向前の工程等が挙げられる。これらの工程で塗布する場合に通常は、高分子材料用表面改質剤を、合成高分子フィルム１ｍ２当たり、０．０１〜０．２ｇとなるように塗布する。 As a method of applying the surface modifier for a polymer material according to the present invention as a lubricant for a synthetic polymer film, an aqueous suspension of the surface modifier for a polymer material is prepared, or by the production method of the present invention. Examples thereof include a method in which the obtained aqueous suspension is used as it is and applied to the surface of the synthetic polymer film by a known method such as a roller touch method, a spray method, a spin coating method or the like. Examples of the coating step include a step before stretch orientation immediately after melt extrusion in the synthetic polymer film production step, a step before biaxial stretch orientation after uniaxial stretch orientation, and the like. When apply | coating at these processes, the surface modifier for polymeric materials is normally apply | coated so that it may become 0.01-0.2g per 1 m < 2 > of synthetic polymer films.
本発明によると、粒子径が極めて小さく、また粒子径の分布が極めて狭い球状シルセスキオキサン微粒子を提供できるという効果がある。 According to the present invention, there is an effect that it is possible to provide spherical silsesquioxane fine particles having a very small particle size and a very narrow particle size distribution.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例、参考例及び比較例において、部は重量部を、また％は重量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples, Reference Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight”.
試験区分１（球状シルセスキオキサン微粒子の製造と評価）
・実施例１
反応容器に水６７２ｇ及びドデシルベンゼンスルホン酸６ｇ（０．０１８モル）を仕込み、攪拌しながら、メチルトリメトキシシラン９０ｇ（０．６６モル）を１０分間かけて滴下し、加水分解反応及び縮合反応を同時に行なわせた。滴下中は、発熱による反応系の温度上昇を２０〜２５℃に制御するため、適宜冷却した。メチルトリメトキシシランの滴下終了後、更に反応系の温度を２０〜２５℃に制御しながら、攪拌を続けて、メチルトリメトキシシラン滴下開始から２４時間後に、５％水酸化ナトリウム水溶液１４．７ｇを投入して触媒を中和し、加水分解反応及び縮合反応を終了させて、水性懸濁液を得た。この水性懸濁液をスプレードライヤーで乾燥処理して、白色粉体４２ｇを得た。この白色粉体を元素分析、ＮＭＲ分析、ＩＣＰ発光分光分析により分析したところ、ケイ素含有量４１％、炭素含有量１８％の球状シルセスキオキサン微粒子であり、走査型電子顕微鏡による任意の１００個の球状シルセスキオキサン微粒子の測定結果から、粒子径の平均値２１ｎｍ、粒子径の変動係数１２％の球状シルセスキオキサン微粒子であった。これを球状シルセスキオキサン微粒子（Ｐ−１）とした。
Test category 1 (Production and evaluation of spherical silsesquioxane fine particles)
Example 1
Into the reaction vessel, 672 g of water and 6 g (0.018 mol) of dodecylbenzenesulfonic acid were charged, and 90 g (0.66 mol) of methyltrimethoxysilane was added dropwise over 10 minutes with stirring to conduct hydrolysis reaction and condensation reaction. I made it happen simultaneously. During dripping, in order to control the temperature rise of the reaction system due to heat generation to 20 to 25 ° C., cooling was appropriately performed. After completion of the dropwise addition of methyltrimethoxysilane, stirring was continued while controlling the temperature of the reaction system at 20 to 25 ° C., and 14.7 g of 5% aqueous sodium hydroxide solution was added 24 hours after the start of dropwise addition of methyltrimethoxysilane. The catalyst was added to neutralize the catalyst, the hydrolysis reaction and the condensation reaction were terminated, and an aqueous suspension was obtained. This aqueous suspension was dried with a spray dryer to obtain 42 g of white powder. This white powder was analyzed by elemental analysis, NMR analysis, and ICP emission spectroscopic analysis. As a result, spherical silsesquioxane fine particles having a silicon content of 41% and a carbon content of 18% were obtained. From the measurement results of the spherical silsesquioxane fine particles, the spherical silsesquioxane fine particles having an average particle diameter of 21 nm and a coefficient of variation of the particle diameter of 12%. This was designated as spherical silsesquioxane fine particles (P-1).
・実施例又は参考例２〜７及び比較例１〜８
実施例１の球状シルセスキオキサン微粒子（Ｐ−１）と同様にして、実施例又は参考例２〜７の球状シルセスキオキサン微粒子（Ｐ−２）〜（Ｐ−７）及び比較例１〜８の球状シルセスキオキサン微粒子（Ｒ−１）〜（Ｒ−８）を得た。これらの内容を表１にまとめて示した。
Examples or Reference Examples 2 to 7 and Comparative Examples 1 to 8
In the same manner as the spherical silsesquioxane fine particles (P-1) of Example 1, the spherical silsesquioxane fine particles (P-2) to (P-7) of Examples or Reference Examples 2 to 7 and Comparative Example 1 were used. ˜8 spherical silsesquioxane fine particles (R-1) to (R-8) were obtained. These contents are summarized in Table 1.
・実施例８
反応容器に水５８８ｇを仕込み、攪拌しながら、メチルトリメトキシシラン９０ｇ（０．６６モル）と、ドデシルベンゼンスルホン酸６ｇ（０．０１８モル）を溶解した水溶液９０ｇとを、１０分間かけて同時に滴下した。滴下中は、発熱による反応系の温度上昇を２０〜２５℃に制御するため、適宜冷却した。メチルトリメトキシシラン及びドデシルベンゼンスルホン酸水溶液の滴下終了後、更に反応系の温度を２０〜２５℃に制御しながら、攪拌を続けて、これらの滴下開始から２４時間後に、５％水酸化ナトリウム水溶液１４．７ｇを投入して触媒を中和し、加水分解反応及び縮合反応を終了させて、水性懸濁液を得た。この水性懸濁液をスプレードライヤーで乾燥処理して、白色粉体４２ｇを得た。この白色粉体について実施例１と同様に分析し、測定したところ、粒子径の平均値２２ｎｍ、粒子径の変動係数１２％の球状シルセスキオキサン微粒子であった。これを球状シルセスキオキサン微粒子（Ｐ−８）とした。
Example 8
While charging 588 g of water in a reaction vessel and stirring, 90 g (0.66 mol) of methyltrimethoxysilane and 90 g of an aqueous solution in which 6 g (0.018 mol) of dodecylbenzenesulfonic acid is dissolved are dropped simultaneously over 10 minutes. did. During dripping, in order to control the temperature rise of the reaction system due to heat generation to 20 to 25 ° C., cooling was appropriately performed. After completion of the dropwise addition of the aqueous solution of methyltrimethoxysilane and dodecylbenzenesulfonic acid, stirring was continued while controlling the temperature of the reaction system at 20 to 25 ° C., and 24% after the start of the dropwise addition, 5% aqueous sodium hydroxide solution 14.7 g was added to neutralize the catalyst, the hydrolysis reaction and the condensation reaction were terminated, and an aqueous suspension was obtained. This aqueous suspension was dried with a spray dryer to obtain 42 g of white powder. The white powder was analyzed and measured in the same manner as in Example 1. As a result, spherical silsesquioxane fine particles having an average particle diameter of 22 nm and a particle diameter variation coefficient of 12% were obtained. This was designated as spherical silsesquioxane fine particles (P-8).
・参考例９〜１１
実施例８の球状シルセスキオキサン微粒子（Ｐ−８）と同様にして、参考例９〜１１の球状シルセスキオキサン微粒子（Ｐ−９）〜（Ｐ−１１）を得た。これらの内容を表１にまとめて示した。
Reference examples 9-11
In the same manner as the spherical silsesquioxane fine particles (P-8) of Example 8, spherical silsesquioxane fine particles (P-9) to (P-11) of Reference Examples 9 to 11 were obtained. These contents are summarized in Table 1.
比較例９
反応容器にｐＨ１２．５の水酸化ナトリウム水溶液８００ｇを入れ、撹拌しつつ、昇温した。液温が５０℃に到達したところで、メチルトリメトキシシラン６７ｇ（０．４９モル）を５分間かけて滴下した。滴下中は、発熱による反応系の温度上昇を５０〜５５℃に制御するため、適宜冷却した。滴下終了後、さらに２分間撹拌した後、撹拌を止め、静置下に５０〜５５℃で１時間熟成した。その後、５０％酢酸水溶液８ｇを添加して触媒を中和し、濾過した。濾別したケークを取出し、１５０℃で２時間乾燥して白色粉末２８ｇを得た。この白色粉末を実施例１と同様にして測定したところ、粒子径の平均値５００ｎｍ、粒子径の変動係数１５％の球状シルセスキオキサン微粒子であった。これを球状シルセスキオキサン微粒子（Ｒ−９）とした。
Comparative Example 9
A reaction vessel was charged with 800 g of an aqueous sodium hydroxide solution having a pH of 12.5, and the temperature was raised while stirring. When the liquid temperature reached 50 ° C., 67 g (0.49 mol) of methyltrimethoxysilane was added dropwise over 5 minutes. During dripping, in order to control the temperature rise of the reaction system due to heat generation to 50 to 55 ° C., cooling was appropriately performed. After completion of the dropwise addition, the mixture was further stirred for 2 minutes, then the stirring was stopped, and the mixture was aged at 50 to 55 ° C. for 1 hour while standing still. Thereafter, 8 g of 50% aqueous acetic acid solution was added to neutralize the catalyst, followed by filtration. The cake separated by filtration was taken out and dried at 150 ° C. for 2 hours to obtain 28 g of white powder. When this white powder was measured in the same manner as in Example 1, it was spherical silsesquioxane fine particles having an average particle diameter of 500 nm and a particle diameter variation coefficient of 15%. This was designated as spherical silsesquioxane fine particles (R-9).
比較例１０
反応容器に水２１６ｇ及び酢酸０．０４ｇを仕込み、撹拌しつつメチルトリメトキシシラン２７２ｇ（２．０モル）を加えた。加水分解反応が進行し、１０分間で液温が６０℃に上昇した。４時間撹拌を続けた後、濾過して透明なシラノール溶液を得た。別の反応容器に水２０００ｇ及び２８％アンモニア水溶液５０ｇを仕込み、２５℃に調温した。これを撹拌しながら、前記のシラノール溶液４８８ｇを１０分間かけて滴下した。滴下終了後、１６時間撹拌を続けた。反応系を遠心分離処理して沈降物を取り出し、１５０℃で２時間乾燥して白色粉末１３１ｇを得た。この白色粉末を実施例１と同様にして測定したところ、粒子径の平均値１３０ｎｍ、粒子径の変動係数３０％の球状シルセスキオキサン微粒子であった。これを球状シルセスキオキサン微粒子（Ｒ−１０）とした。
Comparative Example 10
A reaction vessel was charged with 216 g of water and 0.04 g of acetic acid, and 272 g (2.0 mol) of methyltrimethoxysilane was added with stirring. The hydrolysis reaction proceeded, and the liquid temperature rose to 60 ° C. in 10 minutes. Stirring was continued for 4 hours, followed by filtration to obtain a transparent silanol solution. In another reaction vessel, 2000 g of water and 50 g of 28% aqueous ammonia solution were charged, and the temperature was adjusted to 25 ° C. While stirring this, 488 g of the silanol solution was added dropwise over 10 minutes. After completion of dropping, stirring was continued for 16 hours. The reaction system was centrifuged and the precipitate was taken out and dried at 150 ° C. for 2 hours to obtain 131 g of a white powder. When this white powder was measured in the same manner as in Example 1, it was spherical silsesquioxane fine particles having an average particle diameter of 130 nm and a particle diameter variation coefficient of 30%. This was designated as spherical silsesquioxane fine particles (R-10).
・比較例１１
反応容器にｐＨ４．０の塩酸水溶液５００ｇ及びメチルトリメトキシシラン１００ｇ（０．７４モル）を仕込み、５時間撹拌して、加水分解反応及び縮合反応を同時に行なわせ、シルセスキオキサンの硬化物を得た。この硬化物をアトマイザーで粉砕し、白色粉体４４ｇを得た。この白色粉末を実施例１と同様にして測定したところ、粒子径の平均値５０００ｎｍ、粒子径の変動係数７５％のシルセスキオキサン微粒子であった。これをシルセスキオキサン微粒子（Ｒ−１１）とした。
Comparative Example 11
A reaction vessel was charged with 500 g of a hydrochloric acid aqueous solution of pH 4.0 and 100 g (0.74 mol) of methyltrimethoxysilane, and stirred for 5 hours to simultaneously perform a hydrolysis reaction and a condensation reaction, and a cured product of silsesquioxane was obtained. Obtained. This cured product was pulverized with an atomizer to obtain 44 g of a white powder. The white powder was measured in the same manner as in Example 1 and found to be silsesquioxane fine particles having an average particle diameter of 5000 nm and a particle diameter variation coefficient of 75%. This was designated as silsesquioxane fine particles (R-11).
・比較例１２
反応容器に水２１６ｇ及び酢酸０．０４ｇを仕込み、撹拌しつつメチルトリメトキシシラン２７２ｇ（２．０モル）を加えた。加水分解反応が進行し、１０分間で液温が６０℃に上昇した。４時間撹拌を続けた後、濾過して透明なシラノール溶液を得た。別の反応容器に水４７５ｇ及びドデシルベンゼンスルホン酸５０ｇ（０．１５モル）を仕込み、液温を８０〜８５℃に加熱調温した。これを撹拌しながら、先のシラノール溶液３００ｇを２時間かけて滴下した。滴下終了後、１５分間撹拌を続けた後、冷却し、炭酸ナトリウム水溶液でｐＨ７となるよう中和して、水性懸濁液を得た。この水性懸濁液を遠心分離処理して沈降物を取り出し、１５０℃で２時間乾燥して、白色粉末７５ｇを得た。この白色粉末を実施例１と同様にして測定したところ、粒子径の平均値８５ｎｍ、粒子径の変動係数５５％の球状シルセスキオキサン微粒子であった。これを球状シルセスキオキサン微粒子（Ｒ−１２）とした。
Comparative Example 12
A reaction vessel was charged with 216 g of water and 0.04 g of acetic acid, and 272 g (2.0 mol) of methyltrimethoxysilane was added with stirring. The hydrolysis reaction proceeded, and the liquid temperature rose to 60 ° C. in 10 minutes. Stirring was continued for 4 hours, followed by filtration to obtain a transparent silanol solution. In a separate reaction vessel, 475 g of water and 50 g (0.15 mol) of dodecylbenzenesulfonic acid were charged, and the temperature of the liquid was adjusted to 80 to 85 ° C. While stirring this, 300 g of the previous silanol solution was dropped over 2 hours. After completion of the dropwise addition, stirring was continued for 15 minutes, followed by cooling and neutralization with an aqueous sodium carbonate solution to pH 7 to obtain an aqueous suspension. The aqueous suspension was centrifuged to remove the precipitate, and dried at 150 ° C. for 2 hours to obtain 75 g of white powder. When this white powder was measured in the same manner as in Example 1, it was spherical silsesquioxane fine particles having an average particle diameter of 85 nm and a particle diameter variation coefficient of 55%. This was designated as spherical silsesquioxane fine particles (R-12).
表１において、
＊１：シラノール形成性ケイ素化合物１モルに対する酸触媒のモル数
Ａ−１：メチルトリメトキシシラン
Ａ−２：プロピルトリメトキシシラン
Ａ−３：フェニルトリメトキシシラン
Ｂ−１：ドデシルベンゼンスルホン酸
Ｂ−２：ジノニルベンゼンスルホン酸
Ｂ−３：酸性硫酸ドデシル
Ｂ−４：リン酸モノデシル＝二水素
ＢＲ−１：硫酸
ＢＲ−２：トリメチルラウリルアンモニウムクロライド
ＢＲ−３：水酸化ナトリウム
In Table 1,
* 1: Number of moles of acid catalyst per mole of silanol-forming silicon compound A-1: Methyltrimethoxysilane A-2: Propyltrimethoxysilane A-3: Phenyltrimethoxysilane B-1: Dodecylbenzenesulfonic acid B- 2: dinonylbenzenesulfonic acid B-3: acidic dodecyl sulfate B-4: monodecyl phosphate = dihydrogen BR-1: sulfuric acid BR-2: trimethyllauryl ammonium chloride BR-3: sodium hydroxide
試験区分２（高分子材料用表面改質剤としての評価）
・平滑性の評価
２５℃のオルソクロロフェノール中で測定した極限粘度が０．６２の、無機質フィラーを全く含まないポリエチレンテレフタレートを、エクストルーダーで口金から押し出し、これを４０℃に冷却したドラム上で静電印加を行ないながら厚さ１５２μｍの押し出しフィルムとし、続いて９３℃に加熱した金属ロール上で長手方向へ３．６倍に延伸して、一軸延伸フィルムとした。次にこの一軸延伸フィルムがテンターに至る直前の位置で、該一軸延伸フィルムの片面上に、試験区分１で合成した球状シルセスキオキサン微粒子の０．１％水性懸濁液を３本のロールからなるコーターヘッドから均一塗布した。この際の球状シルセスキオキサン微粒子の塗工量は上記一軸延伸フィルム１ｍ2当り２．３ｇとした（この塗布量は、下記の二軸延伸フィルムでは１ｍ2当り０．０１２９ｇに相当する）。最後に片面塗工した一軸延伸フィルムをテンター内に導き、１０１℃で横方向へ３．５倍に延伸し、更に２２５℃で６．３秒間熱固定して、二軸延伸フィルムとした（片面塗工後のフィルムが加熱を受けた時間は合計で１１秒間である）。この二軸延伸フィルムを２３℃×６５％ＲＨの雰囲気にて調湿し、同条件下で、梨地表面のステンレス板に対する動摩擦係数を摩擦係数測定機（東洋精機社製のＴＲ型、荷重２００ｇ、速度３００ｍｍ／分）で測定し、下記の基準で評価した。結果を表２にまとめて示した。
◎：動摩擦係数が０．３未満、優れている。
○：動摩擦係数が０．３以上０．５未満、良好である。
△：動摩擦係数が０．５以上０．７未満、やや劣る。
×：動摩擦係数が０．７以上、劣る。
Test category 2 (Evaluation as surface modifier for polymer materials)
・ Evaluation of smoothness Polyethylene terephthalate having an intrinsic viscosity of 0.62 measured in orthochlorophenol at 25 ° C. and containing no inorganic filler is extruded from a die with an extruder, and this is cooled on a drum cooled to 40 ° C. An extruded film having a thickness of 152 μm was formed while applying static electricity, and then stretched 3.6 times in the longitudinal direction on a metal roll heated to 93 ° C. to obtain a uniaxially stretched film. Next, at a position just before the uniaxially stretched film reaches the tenter, three rolls of 0.1% aqueous suspension of spherical silsesquioxane fine particles synthesized in Test Section 1 are formed on one side of the uniaxially stretched film. The coater head was uniformly coated. The coating amount of the spherical silsesquioxane fine particles at this time was 2.3 g per 1 m 2 of the uniaxially stretched film (this coating amount corresponds to 0.0129 g per 1 m 2 for the following biaxially stretched film). Finally, the uniaxially stretched film coated on one side was introduced into a tenter, stretched 3.5 times in the transverse direction at 101 ° C., and further heat-set at 225 ° C. for 6.3 seconds to obtain a biaxially stretched film (single side The total time for which the coated film was heated was 11 seconds). The biaxially stretched film was conditioned in an atmosphere of 23 ° C. × 65% RH, and under the same conditions, the coefficient of dynamic friction with respect to the stainless steel plate on the satin surface was determined by a friction coefficient measuring machine (TR type manufactured by Toyo Seiki Co., Ltd., load 200 g, At a speed of 300 mm / min) and evaluated according to the following criteria. The results are summarized in Table 2.
A: The coefficient of dynamic friction is less than 0.3, which is excellent.
○: The coefficient of dynamic friction is 0.3 or more and less than 0.5, which is good.
(Triangle | delta): A dynamic friction coefficient is 0.5 or more and less than 0.7, and is somewhat inferior.
X: The dynamic friction coefficient is inferior by 0.7 or more.
・高速塗工性の評価
前記の一軸延伸フィルム上に、球状シルセスキオキサン微粒子の０．１％水性懸濁液を、スピンコーターによるスピンコート法により、回転速度４０００ｒｐｍで高速塗工した。一軸延伸フィルムの高速塗工面を走査型電子顕微鏡で観察し、球状シルセスキオキサン微粒子の水性懸濁液の高速塗工性を下記の基準で評価した。結果を表２にまとめて示した。
評価基準
◎：均一な塗工膜である。
○：ほぼ均一な塗工膜である。
△：塗工抜けが幾分あるが、全体としてはほぼ均一な塗工膜である。
×：塗工抜けが多く、不均一な塗工膜である。
Evaluation of high-speed coating property A 0.1% aqueous suspension of spherical silsesquioxane fine particles was applied onto the uniaxially stretched film at a rotational speed of 4000 rpm by a spin coating method using a spin coater. The high-speed coating surface of the uniaxially stretched film was observed with a scanning electron microscope, and the high-speed coating property of the aqueous suspension of spherical silsesquioxane fine particles was evaluated according to the following criteria. The results are summarized in Table 2.
Evaluation criteria A: Uniform coating film.
○: Almost uniform coating film.
Δ: Although there is some coating omission, the coating film is almost uniform as a whole.
X: There are many coating omissions and it is a non-uniform coating film.
・剥離性（密着防止性又は離型性）の評価
前記の一軸延伸フィルム上に、球状シルセスキオキサン微粒子の０．１％水性懸濁液を、スピンコーターによるスピンコート法により、回転速度４０００ｒｐｍで高速塗工した。一軸延伸フィルムの高速塗工面に粘着テープを貼り合わせ、２０mm幅に切り出し、一軸延伸フィルムの高速塗工面と粘着テープとの間の１８０度剥離力をテンシロンにより測定して、下記の基準で評価した。結果を表２にまとめて示した。
◎：剥離力が１０ｇ／２０mm未満、優れている。
○：剥離力が１０ｇ／２０mm以上５０ｇ／２０mm未満、良好である。
△：剥離力が５０ｇ／２０mm以上７０ｇ／２０mm未満、やや劣る。
×：剥離力が７０ｇ／２０mm以上、劣る。
-Evaluation of peelability (adhesion prevention or releasability) A 0.1% aqueous suspension of spherical silsesquioxane fine particles on the uniaxially stretched film was rotated at 4000 rpm by a spin coater using a spin coater. High speed coating. Adhesive tape was bonded to the high-speed coated surface of the uniaxially stretched film, cut into a width of 20 mm, 180 degree peel force between the high-speed coated surface of the uniaxially stretched film and the adhesive tape was measured with Tensilon, and evaluated according to the following criteria. . The results are summarized in Table 2.
A: Excellent peel strength of less than 10 g / 20 mm.
○: The peel force is 10 g / 20 mm or more and less than 50 g / 20 mm, which is good.
Δ: Peeling force is 50 g / 20 mm or more and less than 70 g / 20 mm or slightly inferior.
X: The peeling force is inferior by 70 g / 20 mm or more.
表２において、
Ｐ−１〜Ｐ−１１及びＲ−１〜Ｒ−１２：試験区分１で合成した球状シルセスキオキサン微粒子
In Table 2,
P-1 to P-11 and R-1 to R-12: spherical silsesquioxane fine particles synthesized in test category 1
Claims (4)
条件１：シラノール形成性ケイ素化合物が、メチルトリメトキシシランであること。
条件２：酸触媒が、ドデシルベンゼンスルホン酸であること。
条件３：酸触媒の使用割合が、シラノール形成性ケイ素化合物１モル当たり０．００４〜０．０３モルであること。
条件４：シラノール形成性ケイ素化合物と水との使用割合が、シラノール形成性ケイ素化合物／水＝５／９５〜１６／８４（重量比）であること。
条件５：加水分解反応及び縮合反応時の温度が、１５〜２５℃であること。 The average particle diameter obtained by bringing the silanol-forming silicon compound into contact with water in the presence of an acid catalyst and simultaneously performing a hydrolysis reaction and a condensation reaction under the conditions that simultaneously satisfy the following conditions 1 to 5: Spherical silsesquioxane fine particles having a particle size variation coefficient of 15% or less of 10 to 30 nm.
Condition 1: The silanol-forming silicon compound is methyltrimethoxysilane.
Condition 2: The acid catalyst is dodecylbenzenesulfonic acid.
Condition 3: The usage ratio of the acid catalyst is 0.004 to 0.03 mol per mol of the silanol-forming silicon compound.
Condition 4: The use ratio of the silanol-forming silicon compound and water is silanol-forming silicon compound / water = 5/95 to 16/84 (weight ratio).
Condition 5: The temperature during the hydrolysis reaction and the condensation reaction is 15 to 25 ° C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018149475A1 (en) * | 2017-02-14 | 2018-08-23 | Wacker Chemie Ag | Method for producing spherical polysilsesquioxane particles |
| WO2019079194A3 (en) * | 2017-10-16 | 2019-05-23 | Polyone Corporation | Inherently flame retardant compound to diffuse visible light from fixtures containing light emitting diodes and panels made therefrom |
| US11535737B2 (en) | 2017-02-09 | 2022-12-27 | Geon Performance Solutions, Llc | Thermally conductive polyvinyl halide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11535737B2 (en) | 2017-02-09 | 2022-12-27 | Geon Performance Solutions, Llc | Thermally conductive polyvinyl halide |
| WO2018149475A1 (en) * | 2017-02-14 | 2018-08-23 | Wacker Chemie Ag | Method for producing spherical polysilsesquioxane particles |
| US11028228B2 (en) | 2017-02-14 | 2021-06-08 | Wacker Chemie Ag | Process for producing sperhical polysilsesquioxane particles |
| WO2019079194A3 (en) * | 2017-10-16 | 2019-05-23 | Polyone Corporation | Inherently flame retardant compound to diffuse visible light from fixtures containing light emitting diodes and panels made therefrom |
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