JP5288361B2 - Method for producing spherical polyamide particles - Google Patents
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本発明は粉体塗料、レーザー焼結用の焼結粉末やプラスチックマグネット用バインダーなどに使用される溶融
性を改善した球状ポリアミド粒子の製造方法及び溶融性を改善した球状ポリアミド粒子に関する。
The present invention relates to a method for producing spherical polyamide particles with improved meltability and spherical polyamide particles with improved meltability, which are used in powder coatings, sintered powders for laser sintering, binders for plastic magnets, and the like.
ポリアミド樹脂粉末は粉体塗料、レーザー焼結用の焼結粉末やプラスチックマグネット用バインダーなどに広く使用されているが、それらの用途に於ける品質向上や新規用途への展開により球状で粒径の比較的そろった品質の高いポリアミド樹脂粉体が求められるようになってきた。 Polyamide resin powders are widely used in powder coatings, sintered powders for laser sintering, binders for plastic magnets, etc., but their spherical and particle size has been improved by improving the quality of these applications and developing new applications. There has been a demand for polyamide resin powder having relatively high quality.
従来これらの用途に用いられるポリアミド樹脂粉末は溶媒の温度による溶解度の差を利用する化学粉砕方式で製造する方法（特許文献１〜３）や高速回転する円盤の上に溶融ポリアミド樹脂を滴下し、周囲に飛散させて微細な粉末を得る方法（特許文献４）等の方法により製造することが知られていたが、公知の方法で得られるものの多くは多孔質状であり球状にならない、あるいは粒度分布が広いという欠点があった。粉体塗料やレーザー焼結用の焼結粉末やプラスチックマグネット用バインダー分野等で使用するためには、球状で粒径の比較的そろった品質の高いポリアミド樹脂粉体が求められていた。 Conventionally, the polyamide resin powder used for these applications is a method of manufacturing by a chemical pulverization method using the difference in solubility depending on the temperature of the solvent (Patent Documents 1 to 3) or a molten polyamide resin is dropped on a high-speed rotating disk, It has been known to produce by a method such as a method of obtaining fine powder by scattering to the surroundings (Patent Document 4). However, most of the products obtained by a known method are porous and do not become spherical or have a particle size. There was a drawback of wide distribution. In order to be used in the fields of powder coatings, sintered powders for laser sintering, binders for plastic magnets, and the like, high quality polyamide resin powders having a spherical shape and a relatively uniform particle size have been demanded.
一方炭素数６〜１２のラクタム類の１種又は２種以上をパラフイン等の不活性溶媒中で、重合促進剤として三塩化リンを使用してアルカリ触媒重合を行って得られる球状のポリアミド粒子（特許文献５〜７）は球状で狭い粒度分布を有するが溶融性が悪いという欠点を有しているため用途が限定されていた。 On the other hand, spherical polyamide particles obtained by carrying out alkali-catalyzed polymerization using one or more of 6-12 carbon lactams in an inert solvent such as paraffin using phosphorus trichloride as a polymerization accelerator ( Patent Documents 5 to 7) are spherical and have a narrow particle size distribution, but have the disadvantage of poor meltability, so their applications are limited.
粉体塗料、レーザー焼結用の焼結粉末やプラスチックマグネット用バインダーに適する球状で狭い粒度分布を有し溶融性の良好なポリアミド粒子を得ることが本発明の課題である。 It is an object of the present invention to obtain spherical particles having a narrow particle size distribution suitable for powder coatings, sintered powders for laser sintering and binders for plastic magnets and having good meltability.
本発明者は鋭意研究した結果、球状ポリアミド粒子を水媒体中で形状を保持したまま加水分解を行い、溶融性を改善できることを見出し本発明を完成した。すなわち本発明は球状ポリアミド粒子を、水媒体中で形状を保持したまま加水分解することを特徴とする溶融性を改善した球状ポリアミド粒子の製造方法、ならびにその製造方法で得られた球状ポリアミド粒子に関するものである。好ましくは球状ポリアミド粒子が炭素数６〜１２のラクタム類の１種又は２種以上をパラフイン中で、重合促進剤として三塩化リンを使用してアルカリ触媒重合を行って得られる球状ポリアミド粒子である。水媒体中に加水分解触媒を加えることが好ましく、触媒としては炭素数１〜４の有機酸、硫酸、塩酸、硝酸及び燐酸から選ばれる酸があげられる。さらに炭素数１〜４の低級アルコールから選ばれたアルコール及び／または界面活性剤を添加し目的の球状ポリアミド粒子を製造することができる。 As a result of diligent research, the present inventors have found that spherical polyamide particles can be hydrolyzed while maintaining the shape in an aqueous medium to improve the meltability, thereby completing the present invention. That is, the present invention relates to a method for producing spherical polyamide particles having improved meltability, characterized by hydrolyzing spherical polyamide particles while maintaining their shape in an aqueous medium, and spherical polyamide particles obtained by the production method. Is. Preferably, the spherical polyamide particles are spherical polyamide particles obtained by alkali-catalyzed polymerization using phosphorus trichloride as a polymerization accelerator in one or more kinds of lactams having 6 to 12 carbon atoms in paraffin. . A hydrolysis catalyst is preferably added to the aqueous medium, and examples of the catalyst include acids selected from organic acids having 1 to 4 carbon atoms, sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Furthermore, the target spherical polyamide particles can be produced by adding an alcohol and / or a surfactant selected from lower alcohols having 1 to 4 carbon atoms.
本発明の方法で製造された球状ポリアミド粒子は粉体塗料、レーザー焼結用の焼結粉末やプラスチックマグネット用バインダーなどの使用に適するものである。 The spherical polyamide particles produced by the method of the present invention are suitable for use in powder paints, sintered powders for laser sintering, binders for plastic magnets, and the like.
本発明の溶融性を改善した球状ポリアミド粒子の製造方法について以下に詳細に述べる。均質な球状で、狭い粒度分布幅を有するが溶融性が悪い球状ポリアミド粒子の製法は公知であり、特許文献５〜７に示される方法で製造することができる。例えば、ラウロラクタム及び／または炭素数６〜８のラクタム類の１種又は２種以上をパラフイン中で、重合促進剤として三塩化リンを使用してアルカリ触媒重合を行って得られる事が知られている。本発明に用いる球状ポリアミド粒子の粒径は特に限定されないが３μｍ以上２００μｍ以下が好ましい。
本発明の溶融性を改善した球状ポリアミド粒子は上記の溶融性が悪い球状ポリアミド粒子を水媒体中で形状を保持したまま加水分解して製造することができる。また水媒体中には加水分解を触媒する物質、及び／または、ポリアミド粒子と水の親和性を増すため低級アルコールや界面活性剤を含有させることが好ましい。
水の量は球状ポリアミド粒子１部に対して水１〜２０部が用いられるが特に水２〜１０部が好ましい。水の量が多いと容積効率が悪くなり、分離に手間がかかり、また水の量が少ないと攪拌が困難となる。
加水分解触媒としてはポリアミド粒子を加水分解させるものであれば特に限定されないが例えば加水分解酵素、有機酸及び無機酸等があげられる。有機酸としては蟻酸、酢酸、プロピオン酸等の炭素数１〜４の有機酸が好ましく、無機酸としては硫酸、塩酸、硝酸、燐酸が好ましく、これらの酸の１種又は２種以上を用いることができる。反応活性や経済性から硫酸、塩酸及び硝酸が特に好ましい。それらの酸の添加量は特に限定されないがポリアミドの１基本モルの０．１〜１０倍当量、好ましくは０．３〜５．０倍当量を使用することが好ましい。
球状ポリアミド粒子と水の親和性を増すためにメチルアルコール、エチルアルコール、イソプロピルアルコール、ブチルアルコール等の炭素数１〜４の低級アルコール及び／または界面活性剤を添加することができる。界面活性剤としてはアニオン性界面活性剤、非イオン性界面活性剤やカチオン性界面活性剤が使用できるが、酸に対する安定性や濡れ性改善の性能等から非イオン性界面活性剤が好ましい。非イオン性界面活性剤は特に限定されるものではないが、例えばポリオキシエチレンアルキルフェノール、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルケニルエーテルなどが上げられる。これらの非イオン性界面活性剤は一種を単独で用いても二種以上を併用しても良い。
低級アルコールや界面活性剤の添加量は限定されないが、添加量が少ないと球状ポリアミド粒子の水媒体中への分散が悪くなり、多すぎると反応時の泡立ちが多くなったり経済性が悪くなるため好ましくない。好ましくは低級アルコールの添加量は球状ポリアミド粒子の濡れ性が改善する量、すなわち水媒体１００部に対して５〜２０部であり、界面活性剤の添加量は水媒体１００部に対して０．０５〜５部である。
加水分解の反応温度は処理後の球状ポリアミド粒子の融点以下で行うことができるが、反応操作や反応制御の容易さから８０〜１５０℃が好ましい。反応温度が８０℃より低いと処理時間が長くかかり、反応温度が１５０℃より高いと高加圧下の反応となるため反応が煩雑となったり、加水分解反応の制御が難しくなり加水分解反応が進みすぎて球状ポリアミド粒子の物性が悪くなったりするため好ましくない。
球状ポリアミド粒子の溶融性は触媒の種類や量、処理温度及び処理時間によって容易にコントロールが可能であり目的の性能に合わせてそれらを設定することができる。
The method for producing spherical polyamide particles with improved meltability according to the present invention will be described in detail below. A method for producing spherical polyamide particles having a uniform spherical shape and a narrow particle size distribution width but poor meltability is known, and can be produced by the methods described in Patent Documents 5 to 7. For example, it is known that one or two or more kinds of laurolactam and / or lactams having 6 to 8 carbon atoms can be obtained by carrying out alkali-catalyzed polymerization using phosphorus trichloride as a polymerization accelerator in paraffin. ing. The particle size of the spherical polyamide particles used in the present invention is not particularly limited, but is preferably 3 μm or more and 200 μm or less.
The spherical polyamide particles with improved meltability according to the present invention can be produced by hydrolyzing the above-mentioned spherical polyamide particles with poor meltability while maintaining the shape in an aqueous medium. The aqueous medium preferably contains a substance that catalyzes hydrolysis and / or a lower alcohol or a surfactant in order to increase the affinity of the polyamide particles and water.
The amount of water is 1 to 20 parts of water with respect to 1 part of the spherical polyamide particles, but 2 to 10 parts of water is particularly preferable. When the amount of water is large, the volumetric efficiency is deteriorated, and it takes time and effort to separate. When the amount of water is small, stirring becomes difficult.
The hydrolysis catalyst is not particularly limited as long as it can hydrolyze the polyamide particles, and examples thereof include hydrolase, organic acid and inorganic acid. The organic acid is preferably an organic acid having 1 to 4 carbon atoms such as formic acid, acetic acid and propionic acid, and the inorganic acid is preferably sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, and one or more of these acids should be used. Can do. In view of reaction activity and economy, sulfuric acid, hydrochloric acid and nitric acid are particularly preferable. The addition amount of these acids is not particularly limited, but it is preferable to use 0.1 to 10 times equivalent, preferably 0.3 to 5.0 times equivalent of one basic mole of polyamide.
In order to increase the affinity of the spherical polyamide particles and water, a lower alcohol having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol and / or a surfactant can be added. As the surfactant, an anionic surfactant, a nonionic surfactant or a cationic surfactant can be used, but a nonionic surfactant is preferred from the standpoint of acid stability and performance of improving wettability. The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene alkylphenol, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether and the like. These nonionic surfactants may be used alone or in combination of two or more.
The amount of the lower alcohol or surfactant added is not limited, but if the amount added is small, the dispersion of the spherical polyamide particles in the aqueous medium will be poor, and if it is too large, foaming during the reaction will increase and the economy will be poor. It is not preferable. Preferably, the addition amount of the lower alcohol is an amount that improves the wettability of the spherical polyamide particles, that is, 5 to 20 parts with respect to 100 parts of the aqueous medium, and the addition amount of the surfactant is 0.00 with respect to 100 parts of the aqueous medium. 05 to 5 parts.
The reaction temperature for the hydrolysis can be carried out below the melting point of the spherical polyamide particles after the treatment, but is preferably 80 to 150 ° C. from the viewpoint of easy reaction operation and reaction control. If the reaction temperature is lower than 80 ° C, it takes a long time. If the reaction temperature is higher than 150 ° C, the reaction becomes highly pressurized and the reaction becomes complicated and the hydrolysis reaction becomes difficult to control. This is not preferable because the physical properties of the spherical polyamide particles deteriorate.
The meltability of the spherical polyamide particles can be easily controlled by the type and amount of the catalyst, the processing temperature and the processing time, and can be set according to the target performance.
加水分解処理後はろ過、中和、洗浄等の通常の分離精製操作を行うことにより溶媒中の球状ポリアミド粒子を単離することができる。また必要に応じて過酸化水素等で脱色することができる。 After the hydrolysis treatment, the spherical polyamide particles in the solvent can be isolated by performing ordinary separation and purification operations such as filtration, neutralization, and washing. Moreover, it can decolorize with hydrogen peroxide etc. as needed.
上記の方法によって得られた球状ポリアミド粒子は要求特性に応じて耐熱剤、紫外線吸収剤、耐候剤、帯電防止剤、滑剤、着色剤、安定剤、分散剤などを添加しても良く、また他の粉末状樹脂と混合して用いることもできる。 The spherical polyamide particles obtained by the above method may be added with a heat-resistant agent, an ultraviolet absorber, a weathering agent, an antistatic agent, a lubricant, a colorant, a stabilizer, a dispersant, etc. according to the required properties. It can also be used by mixing with a powdered resin.
本発明の方法により球形で比較的粒子径の分布幅が狭く、融点幅も狭く、溶融性の良い球状ポリアミド粒子が製造される。一般的にこの方法で製造された球状ポリアミド粒子は粉体塗料、レーザー焼結用の焼結粉末やプラスチックマグネット用バインダー等での使用に適するものである。
（実施例）
According to the method of the present invention, spherical polyamide particles having a spherical shape and a relatively narrow particle diameter distribution width, a narrow melting point width, and a good melting property are produced. In general, the spherical polyamide particles produced by this method are suitable for use in powder coatings, sintered powders for laser sintering, binders for plastic magnets, and the like.
(Example)
次に本発明の実施例及び比較例をあげて説明するが、本発明はこれらに限定されるものではない。 Next, although an example and a comparative example of the present invention are given and explained, the present invention is not limited to these.
下記実施例で用いた評価方法を以下にまとめて示す。なお、％は重量％を示す。
［評価方法］
融点測定方法
微量融点融点測定器ＭＰ−Ｓ３型（株式会社柳本製作所製））を使用して測定した。カバーグラスの上に
少量のポリアミド粒子をのせ、昇温し、結晶が融け始めてから全体が均一透明になるまでのところを融
点とした。
粒子径及び粒度分布
粒子径及び粒度分布の測定にはレーザー回折式粒度分布測定装置ＳＡＬＤ−２０００（株式会社島津製作所製）を用いて行った。
（比較例１）
The evaluation methods used in the following examples are summarized below. In addition,% shows weight%.
[Evaluation method]
Melting point measurement method
Measurement was performed using a micro melting point melting point measuring device MP-S3 type (manufactured by Yanagimoto Seisakusho Co., Ltd.) A small amount of polyamide particles were placed on the cover glass, the temperature was raised, and the point from when the crystals began to melt until the whole became uniformly transparent was taken as the melting point.
Particle size and particle size distribution Measurement of particle size and particle size distribution was performed using a laser diffraction particle size distribution analyzer SALD-2000 (manufactured by Shimadzu Corporation).
(Comparative Example 1)
特許文献６の実施例１に記載の方法に準じて平均粒子径８μｍの球状ポリアミド粒子を製造した。
なお、９０％以上の粒子が粒子径６．８μｍ〜１０．３μｍの範囲に入り、その粒度分布は極めてシャープであった。
（比較例２）
According to the method described in Example 1 of Patent Document 6, spherical polyamide particles having an average particle diameter of 8 μm were produced.
In addition, 90% or more of the particles were in the range of 6.8 μm to 10.3 μm in particle size, and the particle size distribution was extremely sharp.
(Comparative Example 2)
温度計、滴下ロート、撹拌機、窒素ガス流入口をセットした１０００ｍｌの四つ口フラスコにイソパラフィン（ペガゾールＡＳ−１００、エクソンモービル化学有限会社製）４０８ｇ、ラウロラクタム１０６ｇ、カプロラクタム６．８ｇ、金属カリウム２．５ｇ、ステアリン酸３．５ｇを添加し、窒素気流下に５００ｒｐｍで撹拌しながら１７５℃まで加温し、そこに三塩化リン１．７ｇを添加した。次に種として比較例１で製造した平均粒子径８μｍのポリアミド微粒子を３３．４％含有するスラリー２９．０ｇを添加し、撹拌を４５分間続けた。反応液は冷却後、ろ過し、固液分離を行なうことにより、ポリアミドケーキを得た。本ポリアミドケーキにイソプロピルアルコール２００ｇを加え、３０分撹拌後ろ過しポリアミドケーキを得た。さらに、本操作を３回繰り返し、得られたポリアミドケーキを１０ｍｍＨｇ減圧下、８０℃で８時間乾燥し、球状ポリアミド粒子を得た。なお、本製造における最終収率は７４％であった。また、得られた球状ポリアミド粒子の平均粒子径を測定した結果、１９μｍであった。なお９０％以上の粒子が粒子径１９μｍ〜３４μｍの範囲に入り、その粒度分布は極めてシャープであった。
（比較例３）
Isoparaffin (Pegazol AS-100, manufactured by ExxonMobil Chemical Co., Ltd.) 408 g, Laurolactam 106 g, Caprolactam 6.8 g, Metallic potassium 2.5 g and 3.5 g of stearic acid were added and heated to 175 ° C. with stirring at 500 rpm under a nitrogen stream, and 1.7 g of phosphorus trichloride was added thereto. Next, 29.0 g of a slurry containing 33.4% of polyamide fine particles having an average particle diameter of 8 μm produced in Comparative Example 1 was added as a seed, and stirring was continued for 45 minutes. The reaction solution was cooled, filtered, and solid-liquid separation was performed to obtain a polyamide cake. To this polyamide cake, 200 g of isopropyl alcohol was added, stirred for 30 minutes and then filtered to obtain a polyamide cake. Furthermore, this operation was repeated three times, and the obtained polyamide cake was dried at 80 ° C. under reduced pressure of 10 mmHg for 8 hours to obtain spherical polyamide particles. The final yield in this production was 74%. Moreover, it was 19 micrometers as a result of measuring the average particle diameter of the obtained spherical polyamide particle. In addition, 90% or more of the particles were in the range of 19 μm to 34 μm in particle size, and the particle size distribution was extremely sharp.
(Comparative Example 3)
イソパラフィン（前述）４０８ｇ、ラウロラクタム １０５．６ｇ、カプロラクタム ６．８ｇ、金属カリウム２．５ｇ、ステアリン酸３．５ｇ、三塩化リン１．７ｇ、種として比較例２で製造した平均粒子径１９μｍのポリアミド微粒子を３３．４％含有するスラリー３１．４ｇを使用して比較例２と同様に重合反応を行った。
得られた球状ポリアミド粒子の最終収率は８５％であった。また、得られた球状ポリアミド粒子の平均粒子径を測定した結果、４４μｍであった。なお９０％以上の粒子が粒子径４２μｍ〜７７μｍの範囲に入り、その粒度分布は極めてシャープであった。
408 g of isoparaffin (previously described), 105.6 g of laurolactam, 6.8 g of caprolactam, 2.5 g of potassium metal, 3.5 g of stearic acid, 1.7 g of phosphorus trichloride, a polyamide having an average particle diameter of 19 μm produced as a seed in Comparative Example 2 A polymerization reaction was carried out in the same manner as in Comparative Example 2 using 31.4 g of a slurry containing 33.4% of fine particles.
The final yield of the obtained spherical polyamide particles was 85%. Moreover, it was 44 micrometers as a result of measuring the average particle diameter of the obtained spherical polyamide particle. In addition, 90% or more of the particles were in the range of 42 μm to 77 μm in particle size, and the particle size distribution was extremely sharp.
比較例３で得られた平均粒径４４μｍの球状ポリアミド粒子 ０．２５ｇ及びイソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液２．５ｇを封管中に入れ１２５℃〜１３０℃で８時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥し、目的の球状ポリアミド粒子を得た。 0.25 g of spherical polyamide particles having an average particle size of 44 μm obtained in Comparative Example 3 and 2.5 g of 1N sulfuric acid aqueous solution containing 10% of isopropyl alcohol were placed in a sealed tube and subjected to a hydrolysis reaction at 125 ° C. to 130 ° C. for 8 hours. went. Thereafter, the spherical polyamide particles were separated by filtration, neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles.
イソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液の代わりにイソプロピルアルコールを１０％含有する１Ｎ塩酸水溶液を用いる以外は実施例１と同様に反応を行い目的の球状ポリアミド粒子を得た。 Reaction was carried out in the same manner as in Example 1 except that a 1N hydrochloric acid aqueous solution containing 10% isopropyl alcohol was used instead of a 1N sulfuric acid aqueous solution containing 10% isopropyl alcohol to obtain the desired spherical polyamide particles.
イソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液の代わりにイソプロピルアルコールを１０％含有する０．５Ｎ塩酸水溶液を用いる以外は実施例１と同様に反応を行い目的の球状ポリアミド粒子を得た。 The reaction was carried out in the same manner as in Example 1 except that a 0.5N hydrochloric acid aqueous solution containing 10% isopropyl alcohol was used instead of a 1N sulfuric acid aqueous solution containing 10% isopropyl alcohol to obtain the desired spherical polyamide particles.
イソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液の代わりにイソプロピルアルコールを１０％含有する１Ｎ燐酸水溶液を用いる以外は実施例１と同様に反応を行い目的の球状ポリアミド粒子を得た。 Reaction was carried out in the same manner as in Example 1 except that a 1N phosphoric acid aqueous solution containing 10% isopropyl alcohol was used instead of a 1N sulfuric acid aqueous solution containing 10% isopropyl alcohol to obtain the desired spherical polyamide particles.
イソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液の代わりにイソプロピルアルコールを１０％含有する１Ｎ酢酸水溶液を用いる以外は実施例１と同様に反応を行い目的の球状ポリアミド粒子を得た。 Reaction was carried out in the same manner as in Example 1 except that a 1N aqueous acetic acid solution containing 10% isopropyl alcohol was used instead of a 1N aqueous sulfuric acid solution containing 10% isopropyl alcohol to obtain the desired spherical polyamide particles.
実施例１〜５によって得られた加水分解処理後の球状ポリアミド粒子の融点、平均粒子径及びその形状を比較例３と比較し表１に示した。表１に示すように加水分解処理を行ったものは平均粒子径及びその形状は変化がなかったが融点が低下し、その幅も狭くなり溶融性が改善した。 Table 1 shows the melting point, average particle diameter, and shape of the spherical polyamide particles obtained by hydrolysis in Examples 1 to 5 in comparison with Comparative Example 3. As shown in Table 1, in the case where the hydrolysis treatment was performed, the average particle diameter and the shape thereof were not changed, but the melting point was lowered, the width was narrowed, and the meltability was improved.
比較例３で得られた平均粒径４４μｍの球状ポリアミド粒子１０ｇ及びイソプロピルアルコール１０％含有する１Ｎ硫酸水溶液１００ｇを温度計、撹拌機をセットした３００ｍｌの四つ口フラスコに入れ、８９℃〜９２℃で２４時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥し目的の球状ポリアミド粒子を得た。得られた球状ポリアミド粒子は平均粒子径およびその形状に変化がなかったが融点は１６８〜１７４℃と低下し、その幅も狭くなり溶融性が改善した。 10 g of spherical polyamide particles having an average particle size of 44 μm obtained in Comparative Example 3 and 100 g of 1N sulfuric acid aqueous solution containing 10% of isopropyl alcohol were put into a 300 ml four-necked flask equipped with a thermometer and a stirrer, and 89 ° C. to 92 ° C. The hydrolysis reaction was carried out for 24 hours. Thereafter, the spherical polyamide particles were separated by filtration, neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles. The obtained spherical polyamide particles had no change in average particle diameter and shape, but the melting point was lowered to 168 to 174 ° C., the width was narrowed, and the meltability was improved.
比較例３で得られた平均粒径４４μｍの球状ポリアミド粒子４５ｇ及びナロアクティＨＮ９５（ポリオキシエチレンアルキルエーテル型非イオン性界面活性剤、三洋化成株式会社製）を０．２６％含有する１Ｎ硫酸水溶液１００ｇを９５℃〜９８℃で２１時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥し目的の球状ポリアミド粒子を得た。 45 g of spherical polyamide particles having an average particle diameter of 44 μm obtained in Comparative Example 3 and 100 g of 1N sulfuric acid aqueous solution containing 0.26% of Naroacti HN95 (polyoxyethylene alkyl ether type nonionic surfactant, manufactured by Sanyo Chemical Co., Ltd.) Was subjected to a hydrolysis reaction at 95 ° C to 98 ° C for 21 hours. Thereafter, the spherical polyamide particles were separated by filtration, neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles.
ナロアクティＨＮ９５（前述）を０．２６％含有する１Ｎ硫酸水溶液の代わりにナロアクティＨＮ９５（前述）を０．２６％含有する２Ｎ硫酸水溶液用い、処理時間を４時間とした以外は実施例７と同様に反応を行い目的の球状ポリアミド粒子を得た。 The same procedure as in Example 7 except that instead of the 1N sulfuric acid aqueous solution containing 0.26% Naloacti HN95 (previously described), a 2N sulfuric acid aqueous solution containing 0.26% Naroacti HN95 (previously described) was used and the treatment time was changed to 4 hours. Reaction was performed to obtain the desired spherical polyamide particles.
ナロアクティＨＮ９５（前述）を０．２６％含有する１Ｎ硫酸水溶液の代わりにナロアクティＨＮ９５（前述）を０．２６％含有する２Ｎ塩酸水溶液用い、処理時間を４時間とした以外は実施例７と同様に反応を行い目的の球状ポリアミド粒子を得た。 The same procedure as in Example 7 except that instead of the 1N sulfuric acid aqueous solution containing 0.26% Naloacti HN95 (previously described), a 2N hydrochloric acid aqueous solution containing 0.26% Naroacti HN95 (previously described) was used and the treatment time was changed to 4 hours. Reaction was performed to obtain the desired spherical polyamide particles.
実施例７〜９によって得られた加水分解処理後の球状ポリアミド粒子の融点、平均粒子径及びその形状を比較例３と比較し表２に示した。表２に示すように加水分解処理を行ったものは平均粒子径及びその形状は変化がなかったが融点が低下し、その幅も狭くなり溶融性が改善した。 The melting point, average particle diameter and shape of the spherical polyamide particles after hydrolysis obtained in Examples 7 to 9 are shown in Table 2 in comparison with Comparative Example 3. As shown in Table 2, the average particle diameter and the shape of the product subjected to the hydrolysis treatment were not changed, but the melting point was lowered, the width was narrowed, and the meltability was improved.
比較例３で得られた平均粒径４４μｍの球状ポリアミド粒子１０ｇ及び２Ｎ塩酸水溶液１００ｇを温度計、撹拌機をセットした３００ｍｌの四つ口フラスコに入れ、９５℃〜９８℃で４時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥することにより目的とする球状ポリアミド粒子を得た。得られた加水分解処理後の球状ポリアミド粒子の融点、平均粒子径及びその形状を比較例３と比較し表３に示した。表３に示すように加水分解処理を行ったものは平均粒子径及びその形状は変化がなかったが融点が低下し、その幅も狭くなり溶融性が改善した。 10 g of spherical polyamide particles having an average particle size of 44 μm obtained in Comparative Example 3 and 100 g of 2N hydrochloric acid aqueous solution are put into a 300 ml four-necked flask equipped with a thermometer and a stirrer, and hydrolyzed at 95 to 98 ° C. for 4 hours. Went. Thereafter, filtration was performed to separate the spherical polyamide particles, and neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles. The melting point, average particle diameter and shape of the obtained spherical polyamide particles after the hydrolysis treatment are shown in Table 3 in comparison with Comparative Example 3. As shown in Table 3, the average particle diameter and the shape of the product subjected to the hydrolysis treatment were not changed, but the melting point was lowered, the width was narrowed, and the meltability was improved.
比較例１で得られた平均粒径８μｍの球状ポリアミド粒子０．２５ｇ及びイソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液２．５ｇを封管中に入れ、１２５℃〜１３０℃で８時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥して目的とする球状ポリアミド粒子を得た。得られた加水分解処理後の球状ポリアミド粒子の融点、平均粒子径及びその形状を比較例１と比較し表４に示した。表４に示すように加水分解処理を行ったものは平均粒子径及びその形状は変化がなかったが融点が低下し、その幅も狭くなり溶融性が改善した。 0.25 g of spherical polyamide particles having an average particle diameter of 8 μm obtained in Comparative Example 1 and 2.5 g of 1N sulfuric acid aqueous solution containing 10% of isopropyl alcohol were placed in a sealed tube and hydrolyzed at 125 ° C. to 130 ° C. for 8 hours. Went. Thereafter, the spherical polyamide particles were separated by filtration, neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles. The melting point, average particle diameter and shape of the obtained spherical polyamide particles after the hydrolysis treatment are shown in Table 4 in comparison with Comparative Example 1. As shown in Table 4, the average particle diameter and the shape of the product subjected to the hydrolysis treatment were not changed, but the melting point was lowered, the width was narrowed, and the meltability was improved.
比較例２で得られた平均粒径１９μｍの球状ポリアミド粒子０．２５ｇ及びイソプロピルアルコールを１０％含有する１Ｎ硫酸水溶液２．５ｇを封管中に入れ、１２５℃〜１３０℃で８時間加水分解反応を行った。その後ろ過して球状ポリアミド粒子を分離し、炭酸ナトリウム水溶液で中和、水洗及びイソプロピルアルコール洗浄後乾燥して目的とする球状ポリアミド粒子を得た。得られた加水分解処理後の球状ポリアミド粒子の融点、平均粒子径及びその形状を比較例２と比較し表５に示した。表５に示すように加水分解処理を行ったものは平均粒子径及びその形状は変化がなかったが融点が低下し、その幅も狭くなり溶融性が改善した。 0.25 g of spherical polyamide particles having an average particle diameter of 19 μm obtained in Comparative Example 2 and 2.5 g of 1N sulfuric acid aqueous solution containing 10% of isopropyl alcohol were placed in a sealed tube and hydrolyzed at 125 ° C. to 130 ° C. for 8 hours. Went. Thereafter, the spherical polyamide particles were separated by filtration, neutralized with an aqueous sodium carbonate solution, washed with water and isopropyl alcohol, and then dried to obtain the desired spherical polyamide particles. The melting point, average particle diameter, and shape of the obtained spherical polyamide particles after the hydrolysis treatment are shown in Table 5 in comparison with Comparative Example 2. As shown in Table 5, the average particle diameter and the shape of those subjected to the hydrolysis treatment were not changed, but the melting point was lowered, the width was narrowed, and the meltability was improved.
本発明による溶融性を改善した球状ポリアミド粒子は球状で粒度分布が狭く良好な溶融性を有し、粉体塗料やレーザー焼結用の焼結粉末やプラスチックマグネット用バインダー分野等に用いることができる。 The spherical polyamide particles with improved meltability according to the present invention are spherical and have a good meltability with a narrow particle size distribution, and can be used in powder coatings, sintered powders for laser sintering, binder fields for plastic magnets, etc. .
Claims (4)
The method for producing spherical polyamide particles according to any one of claims 1 to 3, wherein an alcohol and / or a surfactant selected from lower alcohols having 1 to 4 carbon atoms are added to the aqueous medium.
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