JP2002080629A - Polyamide porous spherical particle and process for preparing it - Google Patents
Polyamide porous spherical particle and process for preparing itInfo
- Publication number
- JP2002080629A JP2002080629A JP2001016570A JP2001016570A JP2002080629A JP 2002080629 A JP2002080629 A JP 2002080629A JP 2001016570 A JP2001016570 A JP 2001016570A JP 2001016570 A JP2001016570 A JP 2001016570A JP 2002080629 A JP2002080629 A JP 2002080629A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- spherical particles
- solution
- porous
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特定の粒子径と細
孔径を有し、狭い粒子径分布をもち、比表面積の大きく
結晶化度の高いポリアミド多孔質球状粒子とその製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous polyamide spherical particle having a specific particle size and pore size, a narrow particle size distribution, a large specific surface area and a high degree of crystallinity, and a method for producing the same. is there.
【０００２】[0002]
【従来の技術】従来ポリアミドの粉末の製造方法として
は、化学的粉末化、機械的粉砕法、直接重合法とが知ら
れている。そのうち、化学的粉末化法は、ポリアミドの
溶媒と非溶媒を選択することによって、比較的均一な品
質の粉末ができることから、機能性を有するポリアミド
粒子には、最もこの方法が適していると考えられた。2. Description of the Related Art Conventionally, as a method for producing a polyamide powder, chemical pulverization, mechanical pulverization, and direct polymerization are known. Among them, the chemical pulverization method is considered to be most suitable for polyamide particles having functionality, because relatively uniform quality powder can be obtained by selecting a solvent and a non-solvent of the polyamide. Was done.
【０００３】例えば、Wei-Hsin Hou,Thomas B.Lloyd,J.
Applied Polymer Sci.,45,1783,(1992)には、ギ酸溶液
からポリアミド非溶媒の水から析出させて、粒径分布の
狭い粒子からなるポリアミド粒子の作製に関する技術が
開示されている。そこにはポリアミド種により、粒子の
表面の凹凸が異なることが観測されているが、それ以上
の詳しい粒子の構造に関しては述べられていない。For example, Wei-Hsin Hou, Thomas B. Lloyd, J.
Applied Polymer Sci., 45, 1783, (1992) discloses a technique for producing polyamide particles composed of particles having a narrow particle size distribution by precipitating from a formic acid solution from water of a polyamide non-solvent. It is observed that the surface irregularities of the particles differ depending on the type of polyamide, but no further detailed structure of the particles is described.
【０００４】また、特開昭５２−４３８６０号公報，特
開昭５２−１４６６８号公報，特開昭５２−１１０７６
５号公報には、ポリフェノールなどの吸着材に適した多
孔質ポリアミドの製法が開示されている。しかし、そこ
においては多孔質粒子というほかにそれ以上の知見の記
述はない。Further, Japanese Patent Application Laid-Open Nos. Sho 52-43860, Sho 52-14668, and Sho 52-11076
No. 5 discloses a method for producing a porous polyamide suitable for an adsorbent such as polyphenol. However, there is no further description of the findings other than the porous particles.
【０００５】ポリアミド粒子の製造については、この他
に、溶液から製造方法がいくつか開示されている。例え
ば、 特開平５−７０５９８号公報に、ナイロン１１ま
たは１２のメタクレゾール溶液を溶融状態で噴霧し、冷
却することによって、粒径２０μｍ以下の粉体とする化
粧品用ポリアミド粉体の製造方法が開示されている。[0005] Regarding the production of polyamide particles, several other production methods from solutions have been disclosed. For example, JP-A-5-70598 discloses a method for producing a cosmetic polyamide powder having a particle size of 20 μm or less by spraying a solution of nylon 11 or 12 in a molten state and cooling the solution. Have been.
【０００６】また、多孔質ポリマー粒子の製造方法とし
ては、特開平１−２７８５４１号公報に、曇点を有しう
るポリマー溶液を、一定の流速で一定の周期的な乱れを
加えながら、均一な大きさの液滴として、液体状態で開
口部から気相中に噴出させ、同符号の電荷を帯電させた
後、該液滴を曇点以下の温度にしてから、該液滴に自然
に濡れるほどの表面張力を有する該液滴の凝固液中に侵
入させ、凝固させることを特徴とする方法が開示されて
いる。この方法では、微小なポリマーくずが発生しない
で、多孔質な球状粒子を得ることができるが、やはり、
液滴を噴出させたり、電極での振動を加えたりして凝固
溶媒に侵入させるという煩雑な操作を必要としなければ
ならなかった。[0006] As a method for producing porous polymer particles, Japanese Patent Application Laid-Open No. 1-278541 discloses a method in which a polymer solution having a cloud point is uniformly mixed at a constant flow rate with a constant periodic disturbance. As a droplet of a size, the droplet is ejected into the gas phase from the opening in a liquid state and charged with the same sign, the droplet is cooled to a temperature equal to or lower than the cloud point, and then spontaneously wets the droplet. A method is disclosed in which the liquid droplets having a moderate surface tension are caused to penetrate into a coagulating liquid and solidified. In this method, porous spherical particles can be obtained without generating fine polymer scraps.
A complicated operation of injecting the droplet into the coagulating solvent by ejecting the droplet or applying vibration at the electrode had to be required.
【０００７】また、特開平３−２６７２９号公報には、
結晶性ポリマーが水素結合指数が異なる２種の溶媒、非
溶媒によって結晶化を起こさせ、乾燥して多孔質ポリマ
ー微小球を得る製造方法を開示されている。しかし、こ
の方法では、機械的せん断力を作用させる、もしくは超
音波分散力を作用させることにより粒子を微細化するこ
とを含んでいて、再現性がなかった。これは、機械的な
分散力に頼っていたため、粒子が凝集したり、粗大粒子
となってくることがあった。Further, Japanese Patent Application Laid-Open No. 3-26729 discloses that
A production method is disclosed in which a crystalline polymer is crystallized by two kinds of solvents and non-solvents having different hydrogen bond indices and dried to obtain porous polymer microspheres. However, this method does not have reproducibility since it involves making the particles finer by applying a mechanical shearing force or applying an ultrasonic dispersing force. Since this relies on mechanical dispersing force, the particles may aggregate or become coarse particles.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、均一
な粒子径のポリアミド多孔質球状粒子に関するもので、
特定の範囲の粒径、比較的粒子径分布、細孔径、比表面
積を持ち、該粒子は高結晶性である多孔質粒子であるこ
とを目的とする。An object of the present invention is to provide polyamide porous spherical particles having a uniform particle size.
It is intended to be a highly crystalline porous particle having a specific range of particle size, relatively particle size distribution, pore size, and specific surface area.
【０００９】[0009]
【課題を解決するための手段】本発明は、数平均粒子径
１〜３０μｍ、ＢＥＴ比表面積１００〜８００００ｍ ２
／ｋｇ、であるポリアミド多孔質球状粒子である。According to the present invention, a number average particle size is provided.
1-30 μm, BET specific surface area 100-80000 m 2
/ Kg, is a porous polyamide spherical particle.
【００１０】本発明の多孔質球状粒子は、平均細孔径が
０．０１〜０．２μｍであることが好ましい。[0010] The porous spherical particles of the present invention preferably have an average pore diameter of 0.01 to 0.2 µm.
【００１１】本発明の多孔質球状粒子は、多孔度指数
（ＲＩ）が５〜１００であることが好ましい。The porous spherical particles of the present invention preferably have a porosity index (RI) of 5 to 100.
【００１２】本発明の多孔質球状粒子は、結晶性で,Ｄ
ＳＣで測定された結晶化度が４０％より高いことが好ま
しい。The porous spherical particles of the present invention are crystalline,
Preferably, the crystallinity measured by SC is higher than 40%.
【００１３】本発明の多孔質球状粒子は、数平均粒子径
に対する体積平均粒子径の比（ＰＤＩ）が１〜１．５で
あることが好ましい。The porous spherical particles of the present invention preferably have a ratio of the volume average particle diameter to the number average particle diameter (PDI) of 1 to 1.5.
【００１４】また、本発明は、ポリアミドとその良溶媒
とからなる溶液（Ａ）と、ポリアミドの非溶媒（Ｂ）、
および水（Ｃ）を混合することにより、一時的に均一な
溶液を形成した後、ポリマーを析出して、球状粒子を得
ることを特徴とするポリアミド多孔質粒子の製造方法に
関するものである。Further, the present invention provides a solution (A) comprising a polyamide and a good solvent thereof, a non-solvent (B) of the polyamide,
The present invention relates to a method for producing porous polyamide particles, wherein a uniform solution is temporarily formed by mixing water and water (C) to precipitate a polymer to obtain spherical particles.
【００１５】また本発明は、ポリアミドの溶液（Ａ）の
溶媒が芳香族アルコールであることを特徴とするポリア
ミド多孔質球状粒子の製造方法に関する。The present invention also relates to a method for producing porous polyamide spherical particles, wherein the solvent of the polyamide solution (A) is an aromatic alcohol.
【００１６】本発明は、ポリアミドの溶液（Ａ）の溶媒
がギ酸であることを特徴とするポリアミド多孔質球状粒
子の製造方法に関する。The present invention relates to a method for producing porous polyamide spherical particles, wherein the solvent of the polyamide solution (A) is formic acid.
【００１７】本発明は、ポリアミドの芳香族アルコール
系溶液（Ａ）が、ポリアミド０．１〜３０重量％と芳香
族アルコール系溶媒９９．９〜７０重量％からなること
を特徴とするポリアミド多孔質粒子の製造方法に関す
る。The present invention is characterized in that the polyamide aromatic alcohol solution (A) comprises 0.1 to 30% by weight of a polyamide and 99.9 to 70% by weight of an aromatic alcohol solvent. The present invention relates to a method for producing particles.
【００１８】本発明は、ポリアミドの非溶媒（Ｂ）と水
（Ｃ）の合計重量割合が、ポリアミドの芳香族アルコー
ル系溶液（Ａ）の重量割合より大きいことを特徴とする
ポリアミド多孔質粒子の製造方法に関する。According to the present invention, there is provided a polyamide porous particle characterized in that the total weight ratio of the polyamide non-solvent (B) and water (C) is larger than the weight ratio of the polyamide aromatic alcohol solution (A). It relates to a manufacturing method.
【００１９】本発明は、水（Ｃ）の割合が、ポリアミド
の非溶媒（Ｂ）と水（Ｃ）の合計に対して、２〜９０重
量％であることを特徴とするポリアミド多孔質粒子の製
造方法に関する。According to the present invention, there is provided a polyamide porous particle characterized in that the proportion of water (C) is 2 to 90% by weight based on the sum of the non-solvent (B) and water (C) of the polyamide. It relates to a manufacturing method.
【００２０】本発明は、ポリアミドの非溶媒（Ｂ）が沸
点１００℃以下の脂肪族アルコールであることを特徴と
するポリアミド多孔質粒子の製造方法に関する。The present invention relates to a method for producing polyamide porous particles, wherein the non-solvent (B) of the polyamide is an aliphatic alcohol having a boiling point of 100 ° C. or lower.
【００２１】本発明は、ポリアミド溶液の温度が１０℃
より低い温度であることを特徴とするポリアミド多孔質
粒子の製造方法に関する。In the present invention, the temperature of the polyamide solution is 10 ° C.
The present invention relates to a method for producing polyamide porous particles, which is characterized by a lower temperature.
【００２２】[0022]
【発明の実施の形態】本発明は、特定の粒子径と細孔径
を有し、狭い粒子径分布をもち、比表面積の大きく結晶
化度の高いポリアミド多孔質球状粒子とその製造方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a porous polyamide spherical particle having a specific particle size and pore size, a narrow particle size distribution, a large specific surface area and a high degree of crystallinity, and a method for producing the same. is there.
【００２３】本発明に用いるポリアミドとしては、公知
の種々のものを挙げることができる。例えば、環状アミ
ドの開環重合、あるいはジカルボン酸とジアミンの重縮
合で得られる。モノマーとしては、ε−カプロラクタ
ム、ω−ラウロラクタム等の環状アミドを開環重合して
得られる結晶性ポリアミド、ε−アミノカプロン酸、ω
−アミノドデカン酸、ω−アミノウンデカン酸などのア
ミノ酸の重縮合、または蓚酸、アジピン酸、セバシン
酸、テレフタル酸、イソフタル酸、１，４−シクロヘキ
シルジカルボン酸などのジカルボン酸および誘導体とエ
チレンジアミン、ヘキサメチレンジアミン、１，４−シ
クロヘキシルジアミン、ｍ−キシリレンジアミン、ペン
タメチレンジアミン、デカメチレンジアミンなどのジア
ミンを重縮合して得られるものなどである。As the polyamide used in the present invention, various known polyamides can be mentioned. For example, it can be obtained by ring-opening polymerization of a cyclic amide or polycondensation of a dicarboxylic acid and a diamine. Examples of the monomer include a crystalline polyamide obtained by ring-opening polymerization of a cyclic amide such as ε-caprolactam and ω-laurolactam, ε-aminocaproic acid, ω
-Aminododecanoic acid, polycondensation of amino acids such as ω-aminoundecanoic acid, or dicarboxylic acids and derivatives such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid and ethylenediamine, hexamethylene Examples thereof include those obtained by polycondensing diamines such as diamine, 1,4-cyclohexyldiamine, m-xylylenediamine, pentamethylenediamine, and decamethylenediamine.
【００２４】本発明の結晶性ポリアミドは、単独重合体
及びこれらの共重合体からなる結晶性ポリアミドまたは
その誘導体である。具体的には、ポリアミド６、ポリア
ミド６６、ポリアミド１１，ポリアミド１２，ポリアミ
ド６１０、ポリアミド６６／６Ｔ（Ｔはテレフタル酸成
分を表す）などである。また上記ポリアミドの混合物で
あってもよい。特に好ましくは, ポリアミド６、ポリア
ミド６６が好ましい。The crystalline polyamide of the present invention is a crystalline polyamide comprising a homopolymer or a copolymer thereof or a derivative thereof. Specifically, examples thereof include polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, and polyamide 66 / 6T (T represents a terephthalic acid component). It may be a mixture of the above polyamides. Particularly preferably, polyamide 6 and polyamide 66 are preferred.
【００２５】本発明のポリアミドの分子量は、２，００
０〜１００，０００である。好ましくは５，０００〜４
０，０００である。The polyamide of the present invention has a molecular weight of 2,000
0 to 100,000. Preferably 5,000 to 4
It is 0000.
【００２６】本発明のポリアミド多孔質粒子は球状粒子
である。好ましくは多孔質粒子のうち少なくとも９０重
量％は球状粒子である。さらに好ましくは少なくとも９
８重量％球状粒子である。球状粒子が９０重量％より少
ないと、粉体材料としての流動性が劣るなど好ましくな
いことがある。The porous polyamide particles of the present invention are spherical particles. Preferably, at least 90% by weight of the porous particles are spherical particles. More preferably at least 9
8% by weight spherical particles. If the content of the spherical particles is less than 90% by weight, the fluidity of the powder material may be unfavorably low.
【００２７】本発明のポリアミド多孔質球状粒子は、数
粒子径１〜３０μｍ、ＢＥＴ比表面積１００〜８０００
０ｍ２／ｋｇであるポリアミド多孔質球状粒子である。
好ましくは数平均粒子径が１〜２５μｍである。数平均
粒子径が１μｍより小さいと取り扱い操作が悪くなる。
また数平均粒子径が３０μｍより大きいと触媒担持体な
どに用いるには不適当である。The porous polyamide spherical particles of the present invention have a number particle diameter of 1 to 30 μm and a BET specific surface area of 100 to 8000.
It is a polyamide porous spherical particle of 0 m 2 / kg.
Preferably, the number average particle size is 1 to 25 μm. When the number average particle diameter is smaller than 1 μm, handling operation becomes worse.
If the number average particle diameter is larger than 30 μm, it is not suitable for use as a catalyst carrier.
【００２８】本発明のポリアミド多孔質球状粒子のＢＥ
Ｔ比表面積は１００〜８００００ｍ ２／ｋｇである。好
ましくは、１０００〜６００００ｍ２／ｋｇ、さらに好
ましくは、３０００〜４００００ｍ２／ｋｇである。比
表面積が１００ｍ２／ｋｇより小さいと触媒などの担持
能力が低下するから好ましくない。また比表面積が８０
０００ｍ２／ｋｇであると取り扱いにくい。BE of porous polyamide spherical particles of the present invention
T specific surface area is 100 ~ 80000m 2/ Kg. Good
Preferably 1000 to 60000m2/ Kg, even better
Preferably, 3000-40000m2/ Kg. ratio
100m surface area2Less than / kg supports catalyst
It is not preferable because the ability is reduced. The specific surface area is 80
000m2/ Kg is difficult to handle.
【００２９】本発明の多孔質球状粒子の平均細孔径は、
０．０１〜０．２μｍであることが好ましい。さらに好
ましくは０．０２〜０．１μｍである。平均細孔径が
０．０１μｍより小さければ、触媒を担持しにくくな
る。平均細孔径が０．２μｍより大きければ、触媒の担
持力が低くなるから触媒の担持体としては上記範囲の平
均細孔径が好ましい。The average pore diameter of the porous spherical particles of the present invention is as follows:
Preferably it is 0.01 to 0.2 μm. More preferably, it is 0.02 to 0.1 μm. When the average pore diameter is smaller than 0.01 μm, it becomes difficult to support the catalyst. If the average pore diameter is larger than 0.2 μm, the catalyst carrying power will be low, so that the catalyst carrier preferably has an average pore diameter in the above range.
【００３０】本発明のポリアミド多孔質球状粒子の多孔
度指数（ＲＩ）は、５〜１００が好ましい。さらに好ま
しくは、多孔度指数が５〜７０である。ここで多孔度指
数（ＲＩ）とは、同じ直径の平滑な球状粒子の比表面積
に対し、多孔質の球状粒子の比表面積の比で表示したも
のと定義する。次式で表せる。多孔度指数が５より小さ
ければ、多孔質の程度が低すぎて触媒などの担持体とし
ての効果がすくない。多孔度が１００より大きければ形
状が不安定となるから、触媒担持体などには上記の範囲
が好ましい。The polyamide porous spherical particles of the present invention preferably have a porosity index (RI) of 5 to 100. More preferably, the porosity index is from 5 to 70. Here, the porosity index (RI) is defined as the ratio of the specific surface area of porous spherical particles to the specific surface area of smooth spherical particles having the same diameter. It can be expressed by the following equation. If the porosity index is less than 5, the degree of porosity is too low, and the effect as a carrier such as a catalyst is small. If the porosity is larger than 100, the shape becomes unstable. Therefore, the above range is preferable for the catalyst carrier and the like.
【００３１】[0031]
【数１】 ここで、ＲＩ；多孔度指数、Ｓ；多孔粒子の比表面積
[ｍ２/kg]、Ｓ０；同一粒子径の円滑な球状粒子の比表
面積[ｍ２/kg]である。Ｓ０は、次式に従って求めるこ
とができる。すなわち、観測された数平均球状粒子径ｄ
obs[m]、ポリアミドの密度ρ[ｋｇ／ｍ3]とすると、円
滑な球の比表面積Ｓ０は次式で表すことができる。(Equation 1) Here, RI: porosity index, S: specific surface area of porous particles
[m 2 / kg], S 0 ; Specific surface area [m 2 / kg] of smooth spherical particles having the same particle diameter. S 0 can be obtained according to the following equation. That is, the observed number average spherical particle diameter d
Assuming obs [m] and the density ρ [kg / m 3 ] of the polyamide, the specific surface area S 0 of the smooth sphere can be expressed by the following equation.
【数２】 ここでは、ポリアミド６ならびにポリアミド６６の密度
を結晶相１２３０ｋｇ／ｍ３、非晶相１１００ｋｇ／ｍ
３とした。(Equation 2) Here, the densities of the polyamide 6 and the polyamide 66 were determined to be 1230 kg / m 3 for the crystalline phase and 1100 kg / m 3 for the amorphous phase.
It was set to 3 .
【００３２】また本発明は、ポリアミドが結晶性である
ポリアミド多孔質球状粒子に関するものである。本発明
の多孔質ポリアミドは結晶性であって、融点が１１０〜
３２０℃である。好ましくは、１４０〜２８０℃であ
る。融点が１１０℃より低くなると、熱安定性が低くな
る。また融点が３２０℃より高くなると担持能力が低下
するから好ましくない。The present invention also relates to porous polyamide spherical particles in which the polyamide is crystalline. The porous polyamide of the present invention is crystalline and has a melting point of 110 to 110.
320 ° C. Preferably it is 140-280 degreeC. When the melting point is lower than 110 ° C., the thermal stability decreases. On the other hand, when the melting point is higher than 320 ° C., the carrying capacity is undesirably reduced.
【００３３】さらに、本発明は、ＤＳＣで測定された結
晶化度が４０％以上であるポリアミド多孔質球状粒子が
好ましい。ポリアミドの結晶化度は、Ｘ線解析より求め
る方法、ＤＳＣ測定法により求める方法、密度から求め
る方法があるが、ＤＳＣ測定法により求める方法が好適
がである。結晶化度が４０％以上であることが好まし
い。特に結晶化度が５０％より高いのが特に好ましい。
普通溶融物から結晶化させたポリアミドの結晶化度は高
いものでせいぜい３０％程度である。本発明のポリアミ
ドは結晶化度が４０％より高いことが好ましい。特に好
ましくは、結晶化度４５％より高いことが好ましい。結
晶化度が４０％より低いと、多孔質粒子が熱的に形状的
に不安定になるから好ましくない。In the present invention, porous polyamide spherical particles having a crystallinity of at least 40% as measured by DSC are preferred. The degree of crystallinity of the polyamide can be determined by X-ray analysis, determined by DSC measurement, or determined by density, but a method determined by DSC measurement is preferred. The crystallinity is preferably 40% or more. Particularly preferably, the degree of crystallinity is higher than 50%.
Usually, the crystallinity of polyamide crystallized from the melt is as high as about 30% at most. The polyamide of the present invention preferably has a crystallinity higher than 40%. Particularly preferably, the degree of crystallinity is higher than 45%. If the crystallinity is lower than 40%, the porous particles become thermally unstable in shape, which is not preferable.
【００３４】ポリアミドの結晶化度は、 Ｒ．Ｖｉｅｗ
ｅｇら、ｋｕｎｓｔｓｔｏｆｆｅIV ｐｏｌｙａｍｉｄ
ｅ、２１８頁、Ｃａｒｌ Ｈａｎｇｅｒ Ｖｅｒｌａ
ｇ、１９６６年の記載により、ポリアミド６、ポリアミ
ド６６の融解熱はそれぞれ４５ｃａｌ／ｇとして算出し
た。結晶化度は次の式から算出される。The crystallinity of polyamide is determined by View
eg et al., kunststoff IV polyamid
e, p. 218, Carl Hanger Verla
g, 1966, the heat of fusion of polyamide 6 and polyamide 66 were calculated as 45 cal / g, respectively. The crystallinity is calculated from the following equation.
【数３】 χ ；結晶化度（％） ΔＨobs；サンプルの融解熱 （ｃａｌ／ｇ） ΔＨｍ；ポリアミドの融解熱 （ｃａｌ／ｇ）(Equation 3) ；; crystallinity (%) ΔH obs ; heat of fusion of sample (cal / g) ΔH m ; heat of fusion of polyamide (cal / g)
【００３５】本発明のポリアミド多孔質粒子は、数平均
粒子径に対する体積平均粒子径の比が１〜１．５である
ポリアミド多孔質球状粒子に関する。本発明の多孔質ポ
リアミドの粒子径分布において、数平均粒子径（または
数基準平均粒子径）に対する体積平均粒子径（または体
積基準平均粒子径）の比が１〜１．５である。好ましく
は数平均粒子径と体積平均粒子径の比が１〜１．３であ
る。数平均粒子径に対する体積平均粒子径の比（粒度分
布指数ＰＤＩ）が１．５より大きいと粒子径分布が広く
なって、均一な粒子径の粒子が得られない。均一な粒子
径は、機能性粒子に適用する場合、予期した以上の物理
的化学的性質が発現することがあり好ましい。The polyamide porous particles of the present invention relate to polyamide spherical spherical particles having a volume average particle diameter to number average particle diameter ratio of 1 to 1.5. In the particle diameter distribution of the porous polyamide of the present invention, the ratio of the volume average particle diameter (or volume average particle diameter) to the number average particle diameter (or number average particle diameter) is 1 to 1.5. Preferably, the ratio of the number average particle diameter to the volume average particle diameter is from 1 to 1.3. If the ratio of the volume average particle size to the number average particle size (particle size distribution index PDI) is more than 1.5, the particle size distribution becomes wide, and particles having a uniform particle size cannot be obtained. When applied to functional particles, a uniform particle size is preferable because physical and chemical properties higher than expected may be exhibited.
【００３６】粒子径分布指数は次式で表される。 数平均粒子径 :The particle size distribution index is represented by the following equation. Number average particle size:
【数４】 体積平均粒子径:(Equation 4) Volume average particle size:
【数５】 粒子径分布指数：(Equation 5) Particle size distribution index:
【数６】 ここで、Ｘｉ；個々の粒子径、ｎは測定数である。(Equation 6) Here, Xi; individual particle diameter, n is the number of measurements.
【００３７】本発明の製造方法は、ポリアミドの溶液
に、ポリアミドに特定の非溶媒を混合して、均一な溶液
を形成させた後、析出させる方法である。The production method of the present invention is a method in which a specific non-solvent is mixed with a polyamide solution to form a uniform solution, followed by precipitation.
【００３８】本発明は、ポリアミドとのその良溶媒から
なる溶液（Ａ）に、ポリアミドの非溶媒（Ｂ）である脂
肪族アルコールと水（Ｃ）を添加して、一時的に均一な
溶液を形成させた後、その後、時間をおいて析出させ、
均一な粒径の多孔質ポリアミド球状粒子を得る製造方法
に関する。According to the present invention, an aliphatic alcohol which is a non-solvent (B) of polyamide and water (C) are added to a solution (A) comprising a polyamide and its good solvent to form a temporarily uniform solution. After being formed, then, after a while,
The present invention relates to a method for producing porous polyamide spherical particles having a uniform particle size.
【００３９】本発明における溶媒としては、芳香族アル
コール系溶液または蟻酸が好ましい。（Ａ）の溶媒とし
て、具体的には、０−クレゾール、ｍ−クレゾール、ｐ
−クレゾール、クロロフェノール等または蟻酸が好まし
い。これらは水（Ｃ）と少なくとも部分的に相溶するか
ら好ましい。As the solvent in the present invention, an aromatic alcohol solution or formic acid is preferred. As the solvent of (A), specifically, 0-cresol, m-cresol, p
-Cresol, chlorophenol or the like or formic acid is preferred. These are preferred because they are at least partially compatible with water (C).
【００４０】本発明のポリアミド溶液（Ａ）は、ポリア
ミドが０．１〜３０重量％、好ましくは、０．２〜２５
重量％、ポリアミドの溶媒が９９．９〜７０重量％、好
ましくは、９９．８〜７５重量％の範囲であることが好
ましい。ポリアミド溶液中でポリアミドの割合が３０重
量％を越えると、溶解しにくくなったり、均一な溶液に
ならないことがある。また、溶解しても溶液の粘度が高
くなり、扱いにくくなるので好ましくない。ポリアミド
の割合が０．１重量％より低くなると、ポリマー濃度が
低く、製品の生産性が低くなるので好ましくない。The polyamide solution (A) of the present invention contains 0.1 to 30% by weight of polyamide, preferably 0.2 to 25% by weight.
% By weight, and the solvent content of the polyamide is preferably 99.9 to 70% by weight, and more preferably 99.8 to 75% by weight. If the proportion of the polyamide in the polyamide solution exceeds 30% by weight, it may be difficult to dissolve or a uniform solution may not be obtained. Further, even if dissolved, the viscosity of the solution increases, which makes it difficult to handle, which is not preferable. When the proportion of the polyamide is lower than 0.1% by weight, the polymer concentration is low, and the productivity of the product is low.
【００４１】本発明のポリアミドの非溶媒（Ｂ）は、ポ
リアミドの溶液（Ａ）と、水（Ｃ）が少なくとも部分的
に相容するものが好ましい。また、水とは相容すること
が重要である。例えば、沸点１００℃以下の脂肪族アル
コール、ケトンなどが好ましい。具体的には、メタノー
ル、エタノール、プロパノール、アセトンまたはそれら
の混合物などが好ましい。The non-solvent (B) for the polyamide of the present invention is preferably one in which the solution (A) of the polyamide and the water (C) are at least partially compatible. It is important to be compatible with water. For example, aliphatic alcohols and ketones having a boiling point of 100 ° C. or less are preferable. Specifically, methanol, ethanol, propanol, acetone or a mixture thereof is preferred.
【００４２】本発明においては、ポリアミドの非溶媒
（Ｂ）と水（Ｃ）の合計重量割合が、ポリアミド溶液
（Ａ）の重量割合より多いことが好ましい。ポリアミド
の非溶媒（Ｂ）と水（Ｃ）の合計重量割合が、ポリアミ
ド溶液（Ａ）の重量割合より少ないと、ポリマーが十分
析出しないことがあるので好ましくない。また極端に多
すぎる時は、仕上げ工程の溶媒量が増えすぎて経済的で
ない。In the present invention, the total weight ratio of the polyamide non-solvent (B) and water (C) is preferably larger than the weight ratio of the polyamide solution (A). If the total weight ratio of the polyamide non-solvent (B) and water (C) is less than the weight ratio of the polyamide solution (A), the polymer may not be sufficiently precipitated, which is not preferable. On the other hand, when the amount is extremely large, the amount of the solvent in the finishing step is too large, which is not economical.
【００４３】本発明のポリアミドの非溶媒（Ｂ）と水
（Ｃ）の合計に対する水（Ｃ）の割合は、２〜９０重量
％、好ましくは、５〜８５重量％である。水の割合が２
重量％より少ない場合は、粒子にならない。９０重量％
より大きい場合は、水層が相分離するので好ましくな
い。The ratio of water (C) to the sum of the non-solvent (B) and water (C) of the polyamide of the present invention is 2 to 90% by weight, preferably 5 to 85% by weight. Water ratio is 2
If it is less than% by weight, it does not become particles. 90% by weight
If it is larger, the aqueous layer is phase separated, which is not preferable.
【００４４】本発明における溶液の添加順序は、溶液の
均一性が保たれれば、特に制限はないが、ポリアミド非
溶媒（Ｂ）と水（Ｃ）を混合した後、ポリアミド溶液
（Ａ）を加えるのが好ましい。また、（Ａ）に、（Ｂ）
を添加し、次に（Ｃ）を加えてもよい。または、（Ａ）
に（Ｃ）を混合した後で（Ｂ）を加えてもよい。The order of addition of the solution in the present invention is not particularly limited as long as the uniformity of the solution is maintained. After mixing the polyamide non-solvent (B) and water (C), the polyamide solution (A) is added. It is preferred to add. (A), (B)
And then (C). Or (A)
(B) may be added after mixing (C).
【００４５】本発明においては、ポリアミドの溶液
（Ａ）と非溶媒（Ｂ）と水（Ｃ）の３者が肉眼で観察し
て均一相容系になることが重要であり、（Ａ），
（Ｂ），（Ｃ）のそれぞれの割合は、均一溶液となる溶
媒組成を選ぶ必要がある。これにより、均一な溶液を形
成させて、時間的な経過を経て、相分離を利用して、均
一な粒子径の多孔質粒子を析出させるものである。In the present invention, it is important that the polyamide solution (A), the non-solvent (B) and the water (C) are observed with the naked eye to form a homogeneous compatible system.
For each ratio of (B) and (C), it is necessary to select a solvent composition that results in a uniform solution. Thus, a uniform solution is formed, and after a lapse of time, porous particles having a uniform particle diameter are deposited by utilizing phase separation.
【００４６】均一な溶液を形成する時間は、たとえば、
０．１秒〜２４０分程度の時間である。好ましくは１秒
〜１２０分間が適当である。一時的にも、均一な溶液を
形成することが重要である。必要ならば、適当な撹拌を
加えるほうが好ましい。The time for forming a uniform solution is, for example,
The time is about 0.1 second to 240 minutes. Preferably, 1 second to 120 minutes is appropriate. It is important to form a homogeneous solution, even temporarily. If necessary, it is preferable to add appropriate stirring.
【００４７】本発明において、均一な溶液になるまでの
溶液において均一になるまでの撹拌方法は、混合溶液が
迅速に均一になるような方法がよい。思いがけなく、撹
拌の方法に依存して得られる多孔性球状粒子の大きさが
変わることが見られる。例えば、マグネチックスターラ
ーのような回転式撹拌機の場合、粒径が５〜１５μｍの
多孔質球状粒子が生成する。In the present invention, the stirring method until the solution becomes uniform until the solution becomes uniform is preferably such that the mixed solution quickly becomes uniform. Unexpectedly, it can be seen that the size of the resulting porous spherical particles varies depending on the method of stirring. For example, in the case of a rotary stirrer such as a magnetic stirrer, porous spherical particles having a particle size of 5 to 15 μm are generated.
【００４８】また、本発明において、均一な溶液を形成
するまでの間に、位置の変換が比較的よい撹拌の場合、
さらに大きな粒径が生成する。例えばＶブレンダー、手
振動、バイブレータなどの振動式撹拌の場合１５〜２５
μｍの多孔質粒子が生成する。その機構についてはよく
わかっていないが、器壁に結晶核が一時的に生成して
も、また再溶解し、溶媒が均一になるところまで核が発
生しないから、核が少なくなり、その結果、大粒子に成
長すると思われる。Further, in the present invention, in the case where stirring is performed with a relatively good change of position before forming a uniform solution,
Larger particle sizes are produced. For example, in the case of a vibratory stirring such as a V blender, a hand vibration, a vibrator, etc.
μm porous particles are produced. Although the mechanism is not well understood, even if crystal nuclei are temporarily generated on the vessel wall, they are re-dissolved and nuclei are not generated until the solvent becomes uniform, so the number of nuclei decreases, and as a result, It seems to grow into large particles.
【００４９】この撹拌方法の異なるものでも、均一な粒
径分布は均一であって、ＰＤＩは１〜１．５である。
溶液が均一になるまでの期間の撹拌方法の違いで多孔質
球状粒子の大きさに依存するものであって、肉眼で見
て、析出が始まった以降は撹拌の方法には依存しない。Even with the different stirring methods, the uniform particle size distribution is uniform, and the PDI is 1 to 1.5.
The difference in the stirring method during the period until the solution becomes uniform depends on the size of the porous spherical particles, and does not depend on the stirring method after precipitation has started with the naked eye.
【００５０】本発明において、均一な溶液を形成したな
らば、撹拌の必要はなく、ポリアミド粒子が析出し始め
る時以降は、静置しておくことが好ましい。撹拌しても
よいがポリアミド粒子の形状、大きさには影響がないと
思われる。In the present invention, if a uniform solution is formed, stirring is not necessary, and it is preferable that the polyamide particles are allowed to stand still after the precipitation starts. Although stirring may be performed, it seems that the shape and size of the polyamide particles are not affected.
【００５１】前記の均一な溶液からポリマー粒子を析出
させる温度は、５〜６０℃が好ましい。温度によって
は、溶液が均一になる組成範囲が広くなることがある。
温度が５０℃より低いと、均一になる領域が狭くなる溶
媒組成の範囲が場合がある。温度が６０℃より高いと、
溶媒の蒸気圧が高くなり好ましくない。The temperature at which the polymer particles are precipitated from the uniform solution is preferably 5 to 60 ° C. Depending on the temperature, the composition range in which the solution is uniform may be widened.
If the temperature is lower than 50 ° C., the range of the solvent composition in which the region to be homogenized becomes narrow may be limited. If the temperature is higher than 60 ° C,
The vapor pressure of the solvent is undesirably high.
【００５２】本発明において、ポリアミド溶液の混合物
が５〜１０℃であることが特に好ましい。この温度で
は、粒子径が２〜１０μｍの多孔質球形粒子ができる。
この現象は低温のため核生成が早くなり、その結果核の
数が多くなり、小さな粒子になると思われる。In the present invention, it is particularly preferable that the mixture of the polyamide solution is at 5 to 10 ° C. At this temperature, porous spherical particles having a particle size of 2 to 10 μm are formed.
This phenomenon is thought to result in faster nucleation due to the lower temperature, resulting in more nuclei and smaller particles.
【００５３】析出したポリアミド粒子は、溶液から遠心
分離、濾過、デカンテイションなどの通常の方法で単離
することができる。例えば、縣濁した溶液を、メタノー
ルで希釈して、遠心分離に掛けてもよい。数回メタノー
ルで洗浄して遠心分離に掛けてもよい。次に熱風乾燥、
真空乾燥に供してもよい。The precipitated polyamide particles can be isolated from the solution by a usual method such as centrifugation, filtration, decantation and the like. For example, the suspended solution may be diluted with methanol and centrifuged. It may be washed several times with methanol and centrifuged. Then hot air drying,
It may be subjected to vacuum drying.
【００５４】このようにして製造されたポリマー粒子
は、均一な粒径の多孔質球状ポリアミド粒子となる。ポ
リアミド粒子の粒子径は、１〜３０μｍ、好ましくは１
〜２５μｍで、かさ密度は、０．１〜０．４g/cm3であ
る。また、ＢＥＴ比表面積は１０００〜８００００m2/
ｋg、好ましくは１０００〜６００００m2/ｋg、さらに
好ましくは３０００〜４００００m2/ｋgである。粒子径
が１μｍより小さすぎると、粉体として取り扱いにくく
なる。３０μｍより大きすぎると、触媒担持体やトナー
担持体としての効果が劣る。The polymer particles produced in this manner become porous spherical polyamide particles having a uniform particle size. The particle size of the polyamide particles is 1 to 30 μm, preferably 1 to 30 μm.
〜25 μm, the bulk density is 0.1-0.4 g / cm 3 . The BET specific surface area is 1000 to 80000 m 2 /
kg, preferably 1000 to 60000 m 2 / kg, more preferably 3000 to 40000 m 2 / kg. If the particle size is smaller than 1 μm, it becomes difficult to handle as a powder. If it is too large, the effect as a catalyst carrier or toner carrier will be poor.
【００５５】このようにして製造されたポリマー粒子
は、均一な粒径の多孔質ポリアミド粒子となる。かさ密
度は、０．１〜０．４g/cm3、好ましくは０．２〜０．
３g/cm3である。また、粒子径分布（ＰＤＩ）は１．０
〜１．５で、多孔度指数（ＲＩ）は５〜７０の多孔質で
ある。The polymer particles produced in this manner become porous polyamide particles having a uniform particle size. The bulk density is 0.1 to 0.4 g / cm 3 , preferably 0.2 to 0.
3 g / cm 3 . The particle size distribution (PDI) is 1.0
At １．５1.5, the porosity index (RI) is 5-70 porosity.
【００５６】このようにして製造されたポリマー粒子
は、また、ポリアミドの結晶化度は、ＤＳＣ測定より４
０％以上であり、平均細孔径は０．０１〜０．２μｍで
ある。The polymer particles thus produced showed a polyamide crystallinity of 4 as measured by DSC.
0% or more, and the average pore diameter is 0.01 to 0.2 μm.
【００５７】本発明の多孔質球状粒子は触媒担持体、粉
体塗料、電子写真のトナーの他エレクトロニクス用、医
療用、食品工業分野用の機能性粒子として供給できる。The porous spherical particles of the present invention can be supplied as functional particles for use in electronics, medical and food industries, in addition to catalyst carriers, powder coatings, and toners for electrophotography.
【００５８】[0058]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらの実施例に限定されるものではな
い。また、粒子径、比表面積、平均細孔径、結晶化度な
どの測定は次のように行った。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The measurement of the particle diameter, the specific surface area, the average pore diameter, the crystallinity, etc. was performed as follows.
【００５９】（平均粒子径、粒度分布指数）走査型電子
顕微鏡で観察して、粒子形状と大きさとを観察した。球
形粒子は粒径を読みとった。ダンベル状粒子は粒子の投
影面積から相当円の直径を読みとった。いずれも１００
個の数平均粒子径と体積平均粒子径、粒度分布指数（Ｐ
ＤＩ）はを前出の式を用いて算出した。(Average Particle Diameter, Particle Size Distribution Index) Observation with a scanning electron microscope was conducted to observe the particle shape and size. For spherical particles, the particle size was read. For the dumbbell-shaped particles, the diameter of the equivalent circle was read from the projected area of the particles. All are 100
Number average particle diameter, volume average particle diameter, particle size distribution index (P
DI) was calculated using the above equation.
【００６０】（細孔径分布）水銀ポロシメーターで測定
した。測定範囲は０．００３４〜４００μｍで測定し
た。平均細孔径を求めた。(Pore Size Distribution) Measured with a mercury porosimeter. The measurement range was 0.0034 to 400 μm. The average pore size was determined.
【００６１】（比表面積・多孔度指数）ポリアミド粒子
の比表面積は、窒素吸着によるＢＥＴ法で３点測定でお
こなった。この値から、前に述べた式に従って多孔度指
数を求めた。(Specific surface area / porosity index) The specific surface area of the polyamide particles was measured at three points by the BET method using nitrogen adsorption. From this value, the porosity index was determined according to the previously described equation.
【００６２】（結晶化度）ポリアミドの結晶化度は、Ｄ
ＳＣ（示差走査熱量計）で測定した。前に述べた方法で
行った。(Crystallinity) The crystallinity of polyamide is D
It measured with SC (differential scanning calorimeter). Performed in the manner previously described.
【００６３】実施例１ ポリアミド６（分子量１３，０００）を、濃度１．０重
量％ｍ−クレゾール溶液１０．５重量％とし、メタノー
ル７８．９重量％と水１０．５重量％を混合し、ポリア
ミド溶液に、マグネチックスターラーで撹拌しながら添
加した。１分攪拌後、溶液は均一になった。温度は室温
で行った。撹拌を止め、静置して３０分後に、ポリマー
が析出してきた。さらに２４時間静置して、析出終了さ
せた。その後遠心分離でポリマーを単離した。Example 1 Polyamide 6 (molecular weight: 13,000) was adjusted to a concentration of 1.0% by weight of m-cresol solution at 10.5% by weight, and 78.9% by weight of methanol and 10.5% by weight of water were mixed. It was added to the polyamide solution while stirring with a magnetic stirrer. After stirring for 1 minute, the solution became homogeneous. The temperature was performed at room temperature. The stirring was stopped, and the polymer was deposited 30 minutes after standing still. The precipitation was completed by leaving still for 24 hours. Thereafter, the polymer was isolated by centrifugation.
【００６４】得られた粒子を走査型電子顕微鏡で観察し
たところ、数平均粒子径９．２１μｍ、体積平均粒子径
９．７６μｍの比較的均一な球形粒子であった。ＰＤＩ
は１．０６であった。比表面積９８００ｍ２／ｋｇであ
り、多孔度指数ＲＩは１７．２であった。ポリマー粒子
のかさ密度は、０．２２g/cm3、結晶化度は５８％であ
った。結果をまとめて表２に示す。When the obtained particles were observed with a scanning electron microscope, they were relatively uniform spherical particles having a number average particle diameter of 9.21 μm and a volume average particle diameter of 9.76 μm. PDI
Was 1.06. The specific surface area was 9,800 m 2 / kg, and the porosity index RI was 17.2. The bulk density of the polymer particles was 0.22 g / cm 3 , and the crystallinity was 58%. Table 2 summarizes the results.
【００６５】実施例２ 実施例１のポリアミド１．０重量％ｍ−クレゾール溶液
を１５．０重量％とし、メタノール７５．０重量％と水
１０．０重量％をスターラーで混合した以外は、実施例
１と同様にした。１分攪拌後、溶液は均一になった。静
置し４０分後に、ポリマーが析出してきた。２４時間静
置して、析出終了させた。その後遠心分離でポリマーを
単離した。結果を表２に示す。Example 2 The procedure of Example 1 was repeated except that the polyamide 1.0% by weight m-cresol solution was 15.0% by weight, and 75.0% by weight of methanol and 10.0% by weight of water were mixed with a stirrer. Same as Example 1. After stirring for 1 minute, the solution became homogeneous. After 40 minutes of standing, the polymer had precipitated. This was left standing for 24 hours to complete the precipitation. Thereafter, the polymer was isolated by centrifugation. Table 2 shows the results.
【００６６】実施例３ 実施例１と同じポリアミド濃度５．０重量％のｍ−クレ
ゾール溶液１４．３重量％とし、メタノール７１．４重
量％と水１４．３重量％をマグネチックスターラーで撹
拌混合した以外は、実施例１と同様にした。１分攪拌
後、溶液は均一になった。撹拌下２分後に、ポリマーが
析出してきた。２４時間静置して、析出終了させた。そ
の後遠心分離でポリマーを単離した。結果を表２に示
す。電子顕微鏡写真を図１に示す。Example 3 The same m-cresol solution as in Example 1 having a polyamide concentration of 5.0% by weight was prepared as 14.3% by weight, and 71.4% by weight of methanol and 14.3% by weight of water were stirred and mixed with a magnetic stirrer. Except having performed, it carried out similarly to Example 1. After stirring for 1 minute, the solution became homogeneous. After 2 minutes with stirring, a polymer had precipitated. This was left standing for 24 hours to complete the precipitation. Thereafter, the polymer was isolated by centrifugation. Table 2 shows the results. An electron micrograph is shown in FIG.
【００６７】粒子径分布を図３〜４に示す。粒子径分布
は単分散に近いものであった（ＰＤＩ １．０６）。ポ
リマー粒子のかさ密度は、０．２２g/cm3、比表面積９
８００ｍ２／ｋｇであり、多孔質粒子であった。多孔度
指数（ＲＩ）は１６．０であった。平均細孔径は０．０
４μｍであった。結晶化度は５６％の高結晶化度であっ
た。The particle size distribution is shown in FIGS. The particle size distribution was close to monodisperse (PDI 1.06). The bulk density of the polymer particles is 0.22 g / cm 3 and the specific surface area is 9
800 m 2 / kg, and the particles were porous. The porosity index (RI) was 16.0. The average pore size is 0.0
It was 4 μm. The crystallinity was as high as 56%.
【００６８】実施例４ 実施例１と同じポリアミド濃度２．０重量％の温度５０
℃のｍ−クレゾール溶液、１４．３重量％とし、メタノ
ール７１．４重量％と水１４．３重量％をマグネチック
スターラーで混合した以外は、実施例１と同様にした。
スターラーで１分攪拌後、溶液は均一になった。撹拌下
２分後に、ポリマーが析出してきた。１０時間静置し
て、析出終了させた。その後遠心分離でポリマーを単離
した。結果を表２に示す。Example 4 The same temperature as in Example 1 with a polyamide concentration of 2.0% by weight and a temperature of 50
The procedure of Example 1 was repeated except that the m-cresol solution at 14.degree. C. was 14.3% by weight, and 71.4% by weight of methanol and 14.3% by weight of water were mixed with a magnetic stirrer.
After stirring for 1 minute with a stirrer, the solution became homogeneous. After 2 minutes with stirring, a polymer had precipitated. This was left standing for 10 hours to complete the precipitation. Thereafter, the polymer was isolated by centrifugation. Table 2 shows the results.
【００６９】実施例５ ポリアミド６６（分子量１１，０００）を、濃度１．０
重量％、ｍ−クレゾール溶液２９．４重量％とし、メタ
ノール４１．２重量％と水２９．４重量％を混合し、ポ
リアミド溶液にスターラーで撹拌しながら添加した。１
０秒間撹拌後溶液は均一になった。その後ポリマーが析
出してきた。２４時間静置して析出を完了させた。その
後、遠心分離でポリマーを単離した。走査型電子顕微鏡
で観察したところ、数平均径３．７０μｍ、体積平均径
４．２０μｍ、ＰＤＩ１．１４の比較的狭い球状粒子で
あった。比表面積１２、１００ｍ２／ｋｇ、ＲＩは８．
８であった。結晶化度は５９％であった。Example 5 Polyamide 66 (molecular weight: 11,000) was prepared at a concentration of 1.0
% By weight, 29.4% by weight of an m-cresol solution, 41.2% by weight of methanol and 29.4% by weight of water were mixed, and added to the polyamide solution while stirring with a stirrer. 1
After stirring for 0 seconds, the solution became homogeneous. Thereafter, the polymer was precipitated. The precipitation was completed by standing for 24 hours. Thereafter, the polymer was isolated by centrifugation. Observation with a scanning electron microscope revealed that the particles were relatively narrow spherical particles having a number average diameter of 3.70 μm, a volume average diameter of 4.20 μm, and PDI of 1.14. Specific surface area: 12, 100 m 2 / kg, RI: 8.
It was 8. The crystallinity was 59%.
【００７０】比較例１ 実施例１と同じポリアミド６を、濃度１．０重量％ｍ−
クレゾール溶液３０重量％とし、メタノール７０重量％
と、水を添加しなかった。マグネチックスターラーで撹
拌した。直ちにポリマーが析出してきた。２時間静置し
て、析出終了させた。その後遠心分離でポリマーを単離
した。走査型電子顕微鏡で観察したところ、粒子状では
なく、フィルム状であった。Comparative Example 1 The same polyamide 6 as in Example 1 was used at a concentration of 1.0% by weight m-
Cresol solution 30% by weight, methanol 70% by weight
And no water was added. The mixture was stirred with a magnetic stirrer. The polymer immediately precipitated. The precipitation was completed by allowing to stand for 2 hours. Thereafter, the polymer was isolated by centrifugation. Observation with a scanning electron microscope revealed that the film was not a particle but a film.
【００７１】比較例２ 実施例１と同じポリアミド６を、濃度１．０重量％ｍ−
クレゾール溶液５０重量％とし、水５０重量％とし、マ
グネチックスターラーで撹拌した。メタノールを添加し
なかった。溶液は相分離して混じり合わずポリマーは析
出しなかった。Comparative Example 2 The same polyamide 6 as in Example 1 was used at a concentration of 1.0% by weight m-
The cresol solution was made 50% by weight, water was made 50% by weight, and the mixture was stirred with a magnetic stirrer. No methanol was added. The solution was phase separated and did not mix, and no polymer precipitated.
【００７２】比較例３ 溶液の組成を、ポリアミドの溶液をｍ−クレゾール溶液
６０．０重量％とし、メタノール２０．０重量％と水２
０．０重量％とした。ポリマーは析出しなかった。Comparative Example 3 The composition of the solution was such that the polyamide solution was 60.0% by weight of m-cresol solution, 20.0% by weight of methanol and 2% by weight of water.
0.0% by weight. No polymer precipitated.
【００７３】比較例４ 溶液の組成を濃度１．０重量％ポリアミドのｍ−クレゾ
ール溶液２２．０重量％とし、メタノール５５．６重量
％と水２２．２重量％とした。２分間撹拌し、２０分後
に析出した。２４時間静置してポリマーを析出終了させ
た。その後遠心分離でポリマーを単離した。走査型電子
顕微鏡で観察したところ、鼓状（ダンベル状）粒子を呈
していて、完全な球状粒子ではなかった。Comparative Example 4 The composition of the solution was 1.0% by weight of a polyamide m-cresol solution of 22.0% by weight, 55.6% by weight of methanol and 22.2% by weight of water. The mixture was stirred for 2 minutes and precipitated after 20 minutes. The polymer was left standing for 24 hours to complete the precipitation. Thereafter, the polymer was isolated by centrifugation. Observation with a scanning electron microscope revealed that the particles were drum-shaped (dumbbell-shaped) and not perfectly spherical.
【００７４】実施例６ ポリアミド溶液の溶媒をｍ−クレゾールからギ酸に変え
たほかは、実施例３と同じようにしてポリアミド粒子を
製造した。結果を表２に示す。Example 6 Polyamide particles were produced in the same manner as in Example 3, except that the solvent in the polyamide solution was changed from m-cresol to formic acid. Table 2 shows the results.
【００７５】実施例７ ポリアミド溶液の温度、非溶媒の温度、水の温度を５℃
に保持したほかは、実施例３と同様にしてポリアミド粒
子を製造した。比較的小さな多孔球状粒子が得られた。
結果を表２に示す。Example 7 The temperature of the polyamide solution, the temperature of the non-solvent, and the temperature of water were 5 ° C.
The polyamide particles were produced in the same manner as in Example 3 except that the particles were kept as described above. Relatively small porous spherical particles were obtained.
Table 2 shows the results.
【００７６】実施例８ 均一な溶液が形成されるまでの期間、撹拌方法を、Ｖブ
レンダーによる方法に換えたほかは実施例３と同様にし
てポリアミド粒子を製造した。比較的大きな多孔質球状
粒子が得られた。電子顕微鏡写真を図２に示す。結果を
表２に示す。Example 8 Polyamide particles were produced in the same manner as in Example 3 except that the stirring method was changed to a method using a V blender until a uniform solution was formed. Relatively large porous spherical particles were obtained. An electron micrograph is shown in FIG. Table 2 shows the results.
【００７７】[0077]
【表１】 [Table 1]
【００７８】[0078]
【表２】 [Table 2]
【００７９】[0079]
【発明の効果】本発明のポリアミド多孔質球状粒子は、
同じ粒径の球状粒子よりも表面積が大きく、特定の平均
細孔径、粒子径分布、多孔度を有している。また、内部
構造は高結晶化度のポリアミドから成り立っており、熱
的安定性にも優れており、各種触媒の担持体、電子写真
のトナー、表示機器などの電子材料、クロマトグラフィ
ー、吸着材など食品工業、医療分野などの機能性粒子と
して供給できる。The porous polyamide spherical particles of the present invention are:
It has a larger surface area than spherical particles of the same particle size, and has a specific average pore size, particle size distribution, and porosity. In addition, the internal structure is made of polyamide with high crystallinity, and has excellent thermal stability. Carriers for various catalysts, toner for electrophotography, electronic materials such as display devices, chromatography, adsorbents, etc. It can be supplied as functional particles in the food industry, medical field, etc.
【図面の簡単な説明】[Brief description of the drawings]
【図１】図１は、本発明の実施例３で得られたポリアミ
ド多孔質粒子の粒子形状を示す図面に代える電子顕微鏡
写真である。FIG. 1 is an electron microscope photograph instead of a drawing showing the particle shape of the polyamide porous particles obtained in Example 3 of the present invention.
【図２】図２は、本発明の実施例８で得られたポリアミ
ド多孔質粒子の粒子形状を示す図面に代える電子顕微鏡
写真である。FIG. 2 is an electron micrograph instead of a drawing showing the particle shape of the polyamide porous particles obtained in Example 8 of the present invention.
【図３】図３は、本発明の実施例３で得られたポリアミ
ド多孔質粒子の数粒子径分布を示す図である。FIG. 3 is a diagram showing a number particle size distribution of polyamide porous particles obtained in Example 3 of the present invention.
【図４】図４は、本発明の実施例３で得られたポリアミ
ド多孔質粒子の体積粒子径分布を示す図である。FIG. 4 is a diagram showing a volume particle size distribution of polyamide porous particles obtained in Example 3 of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅野 之彦 千葉県市原市五井南海岸８番の１ 宇部興 産株式会社高分子研究所内 Ｆターム(参考） 4F074 AA71 AC16 AD04 AD09 CB31 CB33 CB34 CB44 CB45 DA03 DA24 DA59 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yukihiko Asano 8-1 Goi-minamikaigan, Ichihara-shi, Chiba F-term in the Polymer Research Laboratory Ube Industries, Ltd. 4F074 AA71 AC16 AD04 AD09 CB31 CB33 CB34 CB44 CB45 DA03 DA24 DA59
Claims (15)
積１００〜８００００ｍ ２／ｋｇであるポリアミド多孔
質球状粒子。1. A BET specific surface having a number average particle size of 1 to 30 μm.
100-100,000m 2/ Kg of porous polyamide
Spherical particles.
請求項１記載の多孔質球状粒子。2. The porous spherical particles according to claim 1, having an average pore diameter of 0.01 to 0.2 μm.
２記載のポリアミド多孔質球状粒子。3. A porosity index of from 5 to 100.
2. Polyamide porous spherical particles according to 2.
である請求項１〜３記載のポリアミド多孔質球状粒子。4. The polyamide spherical spherical particles according to claim 1, wherein the degree of crystallinity measured by DSC is 40% or more.
が１〜１．５である請求項１〜４記載のポリアミド多孔
質球状粒子。5. The polyamide porous spherical particles according to claim 1, wherein the ratio of the volume average particle diameter to the number average particle diameter is 1 to 1.5.
１〜５記載のポリアミド多孔質球状粒子。6. The polyamide spherical spherical particles according to claim 1, wherein the number average particle diameter is 1 to 15 μm.
項１〜５記載のポリアミド多孔質球状粒子。7. The polyamide porous spherical particles according to claim 1, wherein the number average particle diameter is 15 to 25 μm.
（Ａ）と、ポリアミドの非溶媒（Ｂ）、および水（Ｃ）
を混合することにより、一時的に均一な溶液を形成した
後、ポリマーを析出して、球状粒子を得ることを特徴と
するポリアミド多孔質球状粒子の製造方法。8. A solution (A) comprising a polyamide and a solvent thereof, a non-solvent (B) of the polyamide, and water (C).
The method for producing porous spherical spherical particles of polyamide, characterized in that, after mixing, a uniform solution is temporarily formed, and then the polymer is precipitated to obtain spherical particles.
ルコールである請求項８記載のポリアミド多孔質球状粒
子の製造方法。9. The method for producing porous polyamide spherical particles according to claim 8, wherein the solvent of the polyamide solution (A) is an aromatic alcohol.
ある請求項８記載のポリアミド多孔質球状粒子の製造方
法。10. The process for producing porous polyamide spherical particles according to claim 8, wherein the solvent of the polyamide solution (A) is formic acid.
０．１〜３０重量％と溶媒９９．９〜７０重量％からな
る請求項８および９記載のポリアミド多孔質球状粒子の
製造方法。11. The method for producing porous polyamide spherical particles according to claim 8, wherein the polyamide solution (A) comprises 0.1 to 30% by weight of a polyamide and 99.9 to 70% by weight of a solvent.
合計重量割合が、ポリアミド溶液（Ａ）の重量割合より
大きいことを特徴とする請求項８〜９記載のポリアミド
多孔質球状粒子の製造方法。12. The polyamide porous spherical particles according to claim 8, wherein the total weight ratio of the polyamide non-solvent (B) and water (C) is larger than the weight ratio of the polyamide solution (A). Manufacturing method.
（Ｂ）と水（Ｃ）の合計に対して、２〜９０重量％であ
る請求項８、９、１１および１２記載のポリアミド多孔
質球状粒子の製造方法。13. The polyamide according to claim 8, wherein the proportion of water (C) is 2 to 90% by weight based on the total of the non-solvent (B) and water (C) of the polyamide. A method for producing porous spherical particles.
℃以下の脂肪族アルコールである請求項８〜１３記載の
ポリアミド多孔質球状粒子の製造方法。14. A polyamide non-solvent (B) having a boiling point of 100
The method for producing porous polyamide spherical particles according to any one of claims 8 to 13, wherein the aliphatic alcohol is an aliphatic alcohol having a temperature of not higher than 0C.
温度である請求項８記載のポリアミド多孔質球状粒子の
製造方法。15. The method for producing porous polyamide spherical particles according to claim 8, wherein the temperature of the polyamide solution is lower than 10 ° C.
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| WO2006112028A1 (en) * | 2005-04-15 | 2006-10-26 | Ube Industries, Ltd. | Method for purifying porous polyamide fine powder |
| JP2006348281A (en) * | 2005-05-17 | 2006-12-28 | Ube Ind Ltd | Spherical polyamide porous powder and polyamide porous particle |
| WO2007037211A1 (en) * | 2005-09-27 | 2007-04-05 | Ube Industries, Ltd. | Polyamide porous spherical particle |
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