JPH07197311A - Magnetic fiber and its production - Google Patents
Magnetic fiber and its productionInfo
- Publication number
- JPH07197311A JPH07197311A JP5354648A JP35464893A JPH07197311A JP H07197311 A JPH07197311 A JP H07197311A JP 5354648 A JP5354648 A JP 5354648A JP 35464893 A JP35464893 A JP 35464893A JP H07197311 A JPH07197311 A JP H07197311A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic
- fiber
- particles
- magnetic particles
- organic polymer
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/143—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of wires
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、単繊維物性に優れ、紙
や不織布、織布、編織物等とするのに十分な加工性を有
し、且つ優れた磁気特性を発揮する磁性繊維およびその
製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a magnetic fiber which has excellent physical properties of monofilament, has sufficient processability to form paper, non-woven fabric, woven fabric, knitted fabric, etc. and exhibits excellent magnetic properties. The present invention relates to a manufacturing method thereof.
【０００２】[0002]
【従来の技術】これまで、磁性粒子を含有する繊維状有
機高分子としては、（１）高分子フィルム上に、磁性粒
子と高分子材料との混合物からなる磁性粒子含有層を形
成し、該複層フィルムを切断することにより得られる繊
維状の有機高分子（特開昭５９−４７７０８号公報）、
（２）フェライト粉末を含有する有機繊維を形成させ、
これを加熱、焼成することにより得られる複合フェライ
ト繊維（特開昭５９−１００７１８号公報）、（３）フ
ェライト粒子を含有するポリマー成分と導電性金属粒子
を含有するポリマー成分がサイドバイサイドに接合され
た電波吸収繊維（特開昭５９−１５１４９９）、（４）
磁性粒子を含有する熱可塑性ポリマーと繊維形成性ポリ
マ−からなる磁性複合繊維を用いた布帛（特開平５−２
２２６４７号公報）などが提案されている。2. Description of the Related Art Heretofore, as a fibrous organic polymer containing magnetic particles, (1) a magnetic particle-containing layer made of a mixture of magnetic particles and a polymer material is formed on a polymer film, A fibrous organic polymer obtained by cutting a multilayer film (JP-A-59-47708),
(2) Forming an organic fiber containing ferrite powder,
A composite ferrite fiber (Japanese Patent Laid-Open No. 59-100718) obtained by heating and firing this, (3) a polymer component containing ferrite particles and a polymer component containing conductive metal particles were joined side by side. Radio wave absorbing fiber (JP-A-59-151499), (4)
A fabric using a magnetic composite fiber composed of a thermoplastic polymer containing magnetic particles and a fiber-forming polymer (Japanese Patent Application Laid-Open No. 5-2
No. 22647) has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】これらの繊維状磁性有
機高分子は、磁性粒子を含有する層の繊維物性が極めて
貧弱なため、磁性粒子を含有しない繊維物性を補うため
の層との複合によって繊維全体としての物性を得ている
のである。即ち、未だ磁性粒子が分散した有機高分子層
自体で、紙や不織布、織布、編織物等として加工するの
に具備すべき繊維特性を備えた繊維状磁性有機高分子は
得られていないのが現状である。例えば、（１）、
（２）および（４）の場合、繊維自体の物性を補うた
め、（１）では繊維状に切断した高分子フィルムを支持
体とし、（２）では、有機繊維を加熱焼成することによ
り繊維強度を発現させている、また（４）では、繊維物
性を向上させるため芯鞘型とし、鞘の部分に繊維形成性
ポリマーをマトリックスとして用いている。このような
方法で繊維特性を発現させた場合、磁性粒子を含有する
部分の割合は、減少し、当然磁性繊維としての磁気特性
も低下する。Since these fibrous magnetic organic polymers have extremely poor fiber physical properties in the layer containing magnetic particles, they are combined with a layer for supplementing the fiber physical properties not containing magnetic particles. The physical properties of the fiber as a whole are obtained. That is, a fibrous magnetic organic polymer having the fiber characteristics required to be processed as a paper, a non-woven fabric, a woven fabric, a knitted fabric, etc. has not yet been obtained from the organic polymer layer itself in which magnetic particles are dispersed. Is the current situation. For example, (1),
In the cases of (2) and (4), in order to supplement the physical properties of the fiber itself, in (1) the polymer film cut into a fibrous state is used as a support, and in (2), the fiber strength is obtained by heating and firing the organic fiber. In (4), a core-sheath type is used to improve the physical properties of the fiber, and a fiber-forming polymer is used as a matrix in the sheath portion. When the fiber characteristics are expressed by such a method, the proportion of the portion containing the magnetic particles is decreased, and naturally the magnetic characteristics of the magnetic fiber are also decreased.
【０００４】また（３）の場合、本発明の実施例でも確
認されるとおり、磁性粒子の平均粒子径が３．０μｍと
大きいため、繊維を形成しているポリマー成分の不連続
性が大きく、良好な繊維特性を有する磁性繊維は得るこ
とは出来ない。さらに、サイドバイサイドであることに
より、フェライトの含有量が低く磁気特性も劣ったもの
となるといった欠点がある。Further, in the case of (3), as confirmed in the examples of the present invention, since the average particle diameter of the magnetic particles is as large as 3.0 μm, the discontinuity of the polymer component forming the fiber is large, Magnetic fibers with good fiber properties cannot be obtained. Further, the side-by-side has a drawback that the content of ferrite is low and the magnetic properties are inferior.
【０００５】本発明の目的は、磁性粒子が微粒であって
その含有量が高く、従って磁気特性に優れ、しかも紙や
不織布、織布、編織物等とするのに十分な繊維自体の特
性を有する磁性繊維を提供することにある。An object of the present invention is to provide magnetic particles which are fine particles and have a high content, and therefore have excellent magnetic properties, and which have sufficient properties of the fibers themselves to form paper, non-woven fabric, woven fabric, knitted fabric and the like. To provide a magnetic fiber having.
【０００６】[0006]
【課題を解決するための手段】本発明者は、磁性粒子を
均一に分散させた繊維状有機高分子について、鋭意研究
を続けてきた。その結果、微小粒子を繊維形成性の有機
高分子中に均一に分散させることにより、紙や不織布、
織布、編織物等とするために好適な柔軟性とそれらへの
加工に耐える繊維強度を有する磁性繊維を見出し本発明
を完成させるに到った。即ち、本発明は、磁性粒子が繊
維軸垂直断面において均一に分散し、かつ、単繊維強度
１ＭＰａ以上および単繊維伸度２％以上を有することを
特徴とする磁性繊維、及び球状の磁性粒子を、繊維形成
性の有機高分子または繊維形成性の有機高分子を含む溶
液中に分散させた後、紡糸することを特徴とする磁性繊
維の製造方法である。The inventor of the present invention has conducted extensive research on fibrous organic polymers in which magnetic particles are uniformly dispersed. As a result, by uniformly dispersing the fine particles in the fiber-forming organic polymer, paper or non-woven fabric,
The present invention has been completed by finding a magnetic fiber having suitable flexibility for forming a woven fabric, a knitted fabric and the like and a fiber strength capable of withstanding the processing thereof. That is, the present invention provides a magnetic fiber in which magnetic particles are uniformly dispersed in a cross section perpendicular to the fiber axis, and has a single fiber strength of 1 MPa or more and a single fiber elongation of 2% or more, and a spherical magnetic particle. The method for producing a magnetic fiber is characterized in that it is dispersed in a fiber-forming organic polymer or a solution containing a fiber-forming organic polymer and then spun.
【０００７】さらに、本発明の磁性繊維の単繊維直径
は、１μｍから２００μｍの範囲にあることが好まし
く、また、用いられる磁性粒子はその一次粒子平均径
が、１．０μｍ以下であり、かつその含有量が１重量％
以上８５重量％以下であることが望ましい。また、磁性
繊維中での磁性粒子の分散に関しては、数２で定義され
る分散率が０．０１以上、１．０以下であることが望ま
しい。そして、繊維自体の保磁力は、０．００１Ｏｅ以
上であり、かつ最大磁束密度が１Ｇ以上が好適である。Further, the single fiber diameter of the magnetic fiber of the present invention is preferably in the range of 1 μm to 200 μm, and the magnetic particles used have an average primary particle diameter of 1.0 μm or less, and Content is 1% by weight
It is preferably not less than 85% by weight. Regarding the dispersion of the magnetic particles in the magnetic fiber, it is desirable that the dispersion rate defined by the equation 2 is 0.01 or more and 1.0 or less. The coercive force of the fiber itself is 0.001 Oe or more, and the maximum magnetic flux density is preferably 1 G or more.
【０００８】[0008]
【数２】 [Equation 2]
【０００９】また、本発明の磁性繊維の製造方法におい
ては、磁性粒子のカサ密度が、０．４ｇ／ｃｍ3 以上
１．３０ｇ／ｃｍ3 以下であるものが好適であり、そし
て、磁性粒子がスピネル型フェライトであるもののほう
が望ましい。本発明の磁性繊維は、紡糸を湿式紡糸方法
により行うことが好ましく、また、繊維形成性の有機高
分子が、アクリロニトリル系重合体を含むことが望まし
い。In the method for producing magnetic fibers of the present invention, it is preferable that the bulk density of the magnetic particles is 0.4 g / cm 3 or more and 1.30 g / cm 3 or less, and the magnetic particles are Spinel type ferrite is preferable. The magnetic fiber of the present invention is preferably spun by a wet spinning method, and the fiber-forming organic polymer preferably contains an acrylonitrile polymer.
【００１０】以下本発明を詳細に説明する。本発明の磁
性繊維は、単繊維強度１ＭＰａ以上および単繊維伸度２
％以上を有する。単繊維強度が１ＭＰａ未満および単繊
維伸度２％未満の場合、紙や不織布、織布、編織物等と
するのに十分な加工性は得られない。例えば、必要とさ
れる単繊維強度及び単繊維伸度が最も小さい紙用の磁性
繊維としてでも、紙製造の際の分散時の攪拌による磁性
繊維の破断、または、磁性繊維を含む紙自体の強度およ
び柔軟性不足といった問題が生じてくる。The present invention will be described in detail below. The magnetic fiber of the present invention has a single fiber strength of 1 MPa or more and a single fiber elongation of 2
% Or more. When the single fiber strength is less than 1 MPa and the single fiber elongation is less than 2%, sufficient workability cannot be obtained for producing paper, non-woven fabric, woven fabric, knitted fabric and the like. For example, even as a magnetic fiber for paper that has the smallest required single fiber strength and single fiber elongation, the magnetic fiber may be broken by stirring during dispersion during paper production, or the strength of the paper itself containing the magnetic fiber. And the problem of lack of flexibility arises.
【００１１】本発明の磁性繊維は、単繊維直径が、１μ
ｍから２００μｍの範囲にあることが好ましい。添加す
る磁性粒子の平均粒子径は、その繊維直径に応じて選択
できるが、単繊維直径が１μｍ未満の場合、磁性粒子の
平均粒子径に比べ繊維直径が小さくなりすぎるため、繊
維形成性有機高分子マトリックスの連続性が低下しす
ぎ、目的とする繊維物性を得ることは出来ない。また、
単繊維直径が２００μｍを越える場合は、繊維としての
柔軟性に欠けるため、加工あるいは製品に問題が生じる
ため好ましくない。The magnetic fiber of the present invention has a single fiber diameter of 1 μm.
It is preferably in the range of m to 200 μm. The average particle diameter of the magnetic particles to be added can be selected according to the fiber diameter thereof. However, when the single fiber diameter is less than 1 μm, the fiber diameter becomes too small as compared with the average particle diameter of the magnetic particles. The continuity of the molecular matrix is so low that the desired fiber physical properties cannot be obtained. Also,
When the single fiber diameter exceeds 200 μm, the flexibility as a fiber is lacking, which causes problems in processing or products, which is not preferable.
【００１２】本発明の磁性繊維は、分散させる磁性粒子
の一次粒子平均径が、１．０μｍ以下であり、かつその
含有量が１重量％以上８５重量％以下である場合が好ま
しい。磁性粒子の一次粒子平均径が、１．０μｍを越え
る場合繊維直径に対する相対的な粒子径が大きくなりす
ぎるため、繊維形成性有機高分子マトリックスの不連続
が生じ易くなり、特に粒子の凝集を伴った場合に顕著で
あり、目標とする繊維物性を得ることは出来ない。従っ
て、１．０μｍ以下の一次粒子平均径が好ましく、実用
性の点からは０．５μｍ以下の一次粒子平均径の磁性粒
子を用いることがさらに好ましい。磁性粒子の含有量
は、磁性材料としての磁気特性を発現させるため１重量
％以上が望ましいが、８５重量％を越えた場合、磁性粒
子の占有体積が大きくなりすぎるため、繊維形成性有機
高分子マトリックスの不連続が生じ目的とする繊維物性
を得ることが困難となる。The magnetic fibers of the present invention preferably have an average primary particle diameter of the magnetic particles to be dispersed of 1.0 μm or less and a content of 1% by weight or more and 85% by weight or less. When the average primary particle diameter of the magnetic particles exceeds 1.0 μm, the relative particle diameter relative to the fiber diameter becomes too large, so that discontinuity of the fiber-forming organic polymer matrix is likely to occur, especially with particle aggregation. In that case, the target fiber physical properties cannot be obtained. Therefore, the average primary particle diameter of 1.0 μm or less is preferable, and from the viewpoint of practicality, it is more preferable to use the magnetic particles having an average primary particle diameter of 0.5 μm or less. The content of the magnetic particles is preferably 1% by weight or more in order to develop the magnetic properties as a magnetic material, but when it exceeds 85% by weight, the volume occupied by the magnetic particles becomes too large, and thus the fiber-forming organic polymer is included. Discontinuity of the matrix occurs, making it difficult to obtain the desired fiber physical properties.
【００１３】磁性粒子の形状は、多角形、針状、球状、
立方体状、紡錘状、板状など形状に限定することなく使
用可能であるが、分散性および耐磨耗性の点から球状ま
たは紡錘状をしたもののほうが好ましい。なお、粒子径
の測定方法については、本発明の実施例の中で詳細に説
明する。The shape of the magnetic particles is polygonal, acicular, spherical,
It can be used without being limited to a cubic shape, a spindle shape, a plate shape, or the like, but a spherical shape or a spindle shape is preferable from the viewpoint of dispersibility and abrasion resistance. The method for measuring the particle size will be described in detail in the examples of the present invention.
【００１４】本発明の磁性繊維は、数２で定義される分
散率が０．０１以上、１．０以下であるほうが好まし
い。この式に於ける完全分散した１次磁性粒子とは、隣
あった粒子がお互いに接しない１次粒子の状態で分散し
た粒子であり、凝集磁性粒子とは、磁性繊維断面におい
て隣あった粒子が、１次元的あるいは２次元的および３
次元的に接した状態にあるものを言い、この凝集磁性粒
子の粒子数とは、この凝集体を１つの粒子とみなした場
合の粒子の数を言う。また、凝集磁性粒子中の個々の１
次磁性粒子とは、凝集した磁性粒子の塊の中の１つ１つ
の１次粒子の粒子数である。この分散率が、０．０１未
満である場合繊維形成性有機高分子マトリックスの不連
続性が大きくなり、目的とする繊維物性を発現すること
がしにくくなる。また、完全分散の場合、即ち凝集磁性
粒子が観測されない場合分散率は、１．０となり、繊維
物性を維持して磁気特性を発現するのに最も望ましい。The magnetic fiber of the present invention preferably has a dispersion rate defined by the equation 2 of 0.01 or more and 1.0 or less. The completely dispersed primary magnetic particles in this formula are particles in which adjacent particles are dispersed in the state of primary particles that do not contact each other, and agglomerated magnetic particles are particles that are adjacent in a magnetic fiber cross section. But one-dimensional or two-dimensional and three
The number of particles of the agglomerated magnetic particles refers to the number of particles when the agglomerates are regarded as one particle. In addition, the individual 1 in the aggregated magnetic particles
The secondary magnetic particles are the number of particles of each primary particle in the aggregate of aggregated magnetic particles. When this dispersion ratio is less than 0.01, the discontinuity of the fiber-forming organic polymer matrix becomes large, and it becomes difficult to exhibit the desired fiber physical properties. In the case of complete dispersion, that is, when agglomerated magnetic particles are not observed, the dispersion rate is 1.0, which is most desirable for maintaining the fiber physical properties and developing the magnetic properties.
【００１５】本発明の磁性繊維は、保持力が０．００１
Ｏｅ以上であり、かつ最大磁束密度が１Ｇ以上であるほ
うが好ましい。磁性繊維に要求される磁気特性は、その
用途により異なり、用途に応じて適切な磁気特性を設定
すればよいが、保持力が０．００１Ｏｅ未満であり、か
つ最大磁束密度が１Ｇ未満である場合、磁気特性を要求
される磁性繊維としては能力が不十分である。The magnetic fiber of the present invention has a holding force of 0.001.
It is preferable that it is Oe or more and the maximum magnetic flux density is 1 G or more. The magnetic properties required for magnetic fibers differ depending on the application, and appropriate magnetic properties may be set according to the application. When the coercive force is less than 0.001 Oe and the maximum magnetic flux density is less than 1G. However, the ability as a magnetic fiber that requires magnetic properties is insufficient.
【００１６】本発明の磁性繊維を製造するためには、球
状の磁性粒子を繊維形成性の有機高分子、または繊維形
成性の有機高分子を含む溶液中に分散させた後、紡糸す
ることが必要である。磁性粒子を均一に分散させること
は難しく、一般に速い撹拌速度で、長時間分散させる必
要がある。この原因は、一般の非磁性粒子に比べ、磁性
を有するが故に粒子同士が磁力により凝集しやすくなっ
ているためである。また、この磁気凝集力は粒子同士の
接触が一次元および２次元的な場合、即ち多角形、針
状、立方体状、板状の場合顕著である。しかし、球状の
磁性粒子の場合、粒子同士が点接触となるため、この磁
気による凝集力が低下し、分散性が向上する。なお、こ
こでいう球状とは一次磁性粒子径の短径／長径の比で定
義する真球度が０．８以上のものを言う。In order to produce the magnetic fiber of the present invention, spherical magnetic particles may be dispersed in a fiber-forming organic polymer or a solution containing the fiber-forming organic polymer and then spun. is necessary. It is difficult to uniformly disperse the magnetic particles, and it is generally necessary to disperse the magnetic particles at a high stirring speed for a long time. The reason for this is that particles are more likely to aggregate due to magnetic force because they have magnetism, as compared with general non-magnetic particles. Further, this magnetic cohesive force is remarkable when the particles are in one-dimensional or two-dimensional contact, that is, in the case of polygon, needle, cube, or plate. However, in the case of spherical magnetic particles, the particles are in point contact with each other, so that the cohesive force due to this magnetism is reduced and the dispersibility is improved. The term "spherical" as used herein means that the sphericity defined by the ratio of the minor axis / major axis of the primary magnetic particle diameter is 0.8 or more.
【００１７】本発明の磁性繊維の製造においては、磁性
粒子のカサ密度が、０．４ｇ／ｃｍ3 以上１．３０ｇ／
ｃｍ3 以下であることが好ましい。磁気特性を向上させ
るためには、できるだけ磁性粒子の充填密度を上げる必
要がある。従って、磁性粒子のカサ密度が０．４ｇ／ｃ
ｍ3 未満の場合、目的の磁気特性を得るために必要な磁
性粒子量が多くなりすぎるため、繊維物性の低下が起こ
り、好ましくない。また、１．３０ｇ／ｃｍ3 を越える
ものは、磁性粒子の比重が重くなりすぎるため、分散性
が悪くなるといった欠点がある。In the production of the magnetic fiber of the present invention, the bulk density of the magnetic particles is 0.4 g / cm 3 or more and 1.30 g /
It is preferably not more than cm 3 . In order to improve the magnetic properties, it is necessary to increase the packing density of magnetic particles as much as possible. Therefore, the bulk density of the magnetic particles is 0.4 g / c
If it is less than m 3, the amount of magnetic particles required to obtain the desired magnetic properties becomes too large, and the physical properties of the fiber deteriorate, which is not preferable. On the other hand, if it exceeds 1.30 g / cm 3 , the specific gravity of the magnetic particles becomes too heavy, resulting in poor dispersibility.
【００１８】分散させる磁性粒子自体の一次粒子平均径
は、１．０μｍ以下が好ましく、実用性の点からは０．
５μｍ以下の一次粒子平均径の磁性粒子を用いることが
さらに好ましい。１．０μｍを越える場合繊維直径に対
する相対的な粒子径が大きくなりすぎるため、繊維形成
性有機高分子マトリックスの不連続が生じ易くなり、特
に粒子の凝集を伴った場合に顕著であり、良好な加工性
能を有する磁性繊維は得ることが困難となる。The average primary particle diameter of the magnetic particles to be dispersed is preferably 1.0 μm or less.
It is more preferable to use magnetic particles having an average primary particle diameter of 5 μm or less. If it exceeds 1.0 μm, the relative particle diameter relative to the fiber diameter becomes too large, so that discontinuity of the fiber-forming organic polymer matrix is likely to occur, which is particularly remarkable when particles are aggregated, which is excellent. It is difficult to obtain a magnetic fiber having processing performance.
【００１９】本発明の磁性繊維に使用可能な磁性粒子と
しては、鉄、コバルト、ニッケル、などを主成分とする
金属粒子およびそれらを成分とする合金粒子、マグネタ
イト、バリウムフェライトなどの酸化鉄を主成分とする
複合金属酸化物粒子、サマリウム、イットリウムなどの
希土類元素とコバルト、ニッケルなどの３ｄ遷移元素と
の金属間化合物粒子やネオジウム・鉄・ホウ素、プラセ
オジウム・鉄・ホウ素などの希土類元素と鉄、ホウ素か
らなる金属間化合物粒子などの強磁性およびフェリ磁性
を有するものがあげられる。この中でも特に実用性の点
から、大きい自発磁化と高いキューリー点を示す、スピ
ネル型フェライトであることが好ましい。また、磁性成
分には熱安定剤、紫外線吸収剤、流動改質剤、着色剤、
顔料などの添加剤の混合も可能である。The magnetic particles usable in the magnetic fiber of the present invention are mainly metal particles containing iron, cobalt, nickel and the like as main components, alloy particles containing them as a component, and iron oxide such as magnetite and barium ferrite. Composite metal oxide particles as components, intermetallic compound particles of rare earth elements such as samarium and yttrium and 3d transition elements such as cobalt and nickel, and rare earth elements such as neodymium / iron / boron and praseodymium / iron / boron and iron, Examples thereof include particles having ferromagnetism and ferrimagnetism, such as particles of an intermetallic compound made of boron. Among these, from the viewpoint of practicality, a spinel type ferrite showing a large spontaneous magnetization and a high Curie point is preferable. Further, the magnetic component includes a heat stabilizer, an ultraviolet absorber, a flow modifier, a colorant,
It is also possible to mix additives such as pigments.
【００２０】本発明に用いられる有機高分子としては、
繊維形成性を有する限り特に限定は無く例えば、ポリエ
ステル、ポリアクリロニトリル、ポリアマイド、ポリオ
レフィン、ポリエ−テル、ポリビニル系ポリマ−等が挙
げられ、特に磁性粒子の表面が疎水化処理が施されてい
ない場合、粒子自体の親水性が強いため、紡糸の際に水
性溶剤を用いて得られるポリマー、例えば、ポリアクリ
ロニトリル、ポリビニルアルコールが好ましく用いられ
る。また、磁性粒子の表面が疎水化処理が施されている
場合、ポリオレフィン、ポリエステル、ポリエーテル、
ポリビニル系ポリマーが好ましい。The organic polymer used in the present invention includes
There is no particular limitation as long as it has a fiber-forming property, for example, polyester, polyacrylonitrile, polyamide, polyolefin, polyether, polyvinyl polymer and the like, particularly when the surface of the magnetic particles is not subjected to a hydrophobic treatment, Since the particles themselves have strong hydrophilicity, polymers obtained by using an aqueous solvent during spinning, such as polyacrylonitrile and polyvinyl alcohol, are preferably used. Further, when the surface of the magnetic particles is subjected to a hydrophobic treatment, polyolefin, polyester, polyether,
Polyvinyl-based polymers are preferred.
【００２１】また、その紡糸方法に関しては、溶融紡
糸、湿式紡糸あるいは乾式紡糸等のいずれの方式でも可
能であり、有機高分子の性状から判断し、適宜選択でき
る。本発明に用いた球状磁性粒子を用いる場合には、磁
性粒子が湿式法で得られることから、その表面は親水性
を有しているため、水系の溶媒、あるいは、水との相溶
性の良い有機溶媒、例えばジメチルホルムアミド、ジメ
チルスルフォキシド、ジメチルアセトアミド、Ｎーメチ
ルピロリドンなどを用い湿式紡糸する方法が望ましく、
また磁性粒子表面との親和性の高いアクリロニトリル系
重合体を含む有機高分子が好ましい。Regarding the spinning method, any method such as melt spinning, wet spinning or dry spinning can be used, and it can be appropriately selected by judging from the properties of the organic polymer. When the spherical magnetic particles used in the present invention are used, since the magnetic particles are obtained by a wet method, the surface thereof has hydrophilicity, and therefore has good compatibility with an aqueous solvent or water. A wet spinning method using an organic solvent such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone is preferable,
Further, an organic polymer containing an acrylonitrile-based polymer having a high affinity with the surface of the magnetic particles is preferable.
【００２２】[0022]
【作用】本発明は、磁性粒子を均一に分散させることに
より、これまでになかった磁性繊維を開発することがで
きた。分散性を向上させた機構としては、１つめは、磁
性粒子を球状とすることにより粒子間を点接触とし、磁
気凝集力を防ぐ、２つめは、磁性粒子の表面に保護層を
形成し、紡糸溶液中での安定性が増すこと、３つめとし
ては、ポリアクリロニトリルといった親水性の高いポリ
マー系を用いることによりポリマーと磁性粒子とのの親
和性が向上したことなどが考えられる。The present invention has made it possible to develop an unprecedented magnetic fiber by uniformly dispersing magnetic particles. As a mechanism for improving the dispersibility, the first is to make the magnetic particles spherical so as to make point contact between the particles and prevent magnetic cohesive force. The second is to form a protective layer on the surface of the magnetic particles, It is considered that the stability in the spinning solution is increased, and the third is that the affinity between the polymer and the magnetic particles is improved by using a highly hydrophilic polymer system such as polyacrylonitrile.
【００２３】[0023]
【実施例】以下、実施例によって本発明を具体的に説明
するが、本発明の要旨はこれによって限定されるもので
はない。まず各種の評価事項の測定方法を説明する。EXAMPLES The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited thereto. First, a method of measuring various evaluation items will be described.
【００２４】磁性繊維に含まれる磁性粒子の１次粒子の
粒子径は、繊維軸垂直断面を走査型電子顕微鏡、および
または透過型電子顕微鏡で測定を行った。球状粒子の場
合は、その粒子直径を粒子径とし、針状のものは、針の
長さ方向における長さの半分を粒子径とし、それ以外の
粒子形状のものは、観測された粒子の外接円の直径を粒
子径とし、一次粒子平均径は、粒子１００個を測定し、
その数平均粒子径を計算により算出する。なお、凝集磁
性粒子においても、それを構成する一次粒子について測
定を行う。The particle size of the primary particles of the magnetic particles contained in the magnetic fiber was measured by a scanning electron microscope and / or a transmission electron microscope in a cross section perpendicular to the fiber axis. In the case of spherical particles, the particle diameter is the particle diameter, needle-shaped ones have a particle diameter of half the length in the length direction of the needle, and other particle-shaped ones are the circumscribed particles of the observed particles. The diameter of the circle is taken as the particle diameter, and the average primary particle diameter is obtained by measuring 100 particles,
The number average particle diameter is calculated. Even in the case of agglomerated magnetic particles, the primary particles forming the particles are also measured.
【００２５】分散率の測定は、磁性繊維の繊維軸垂直断
面を透過型電子顕微鏡で測定、あるいはＸ線マイクロア
ナライザーを用いて、磁性粒子を構成する金属元素の面
分析を行い、１次磁性粒子として分散しているものか、
凝集しているものかを判定し、磁性繊維の直径が１０μ
ｍ以上の場合１０平方マイクロメートルあたりの、また
磁性繊維の直径が１０μｍ未満の場合繊維軸垂直全断面
の１次磁性粒子と凝集磁性粒子の個数を測定し、「磁性
繊維繊維軸垂直断面の単位面積における完全分散した１
次磁性粒子および凝集磁性粒子の粒子数」とした。ま
た、同じ１０平方マイクロメートルあるいは繊維全断面
の中における凝集磁性粒子については、各々の凝集磁性
粒子を構成する１次粒子の個数を測定し分散した１次粒
子の個数とあわせて、「磁性繊維断面の単位面積におけ
る完全分散した１次磁性粒子、および凝集磁性粒子中の
個々の１次磁性粒子の粒子数」とし、数２に基づいて分
散率を計算した。The dispersion rate is measured by measuring the cross section of the magnetic fiber perpendicular to the fiber axis with a transmission electron microscope or by using an X-ray microanalyzer to perform a surface analysis of the metal elements constituting the magnetic particles to obtain the primary magnetic particles. Is dispersed as
Determine if they are aggregated and the diameter of the magnetic fiber is 10μ
In the case of m or more, the number of primary magnetic particles and agglomerated magnetic particles per 10 square micrometer in the case where the diameter of the magnetic fiber is less than 10 μm and the total cross section perpendicular to the fiber axis is measured. Fully dispersed 1 in area
The number of secondary magnetic particles and agglomerated magnetic particles ”. For agglomerated magnetic particles in the same 10 square micrometers or the entire fiber cross section, the number of primary particles constituting each agglomerated magnetic particle was measured and combined with the number of dispersed primary particles to obtain "magnetic fiber". The number of particles of the individual primary magnetic particles in the completely dispersed primary magnetic particles and the agglomerated magnetic particles in the unit area of the cross section was defined as “the number of individual primary magnetic particles”, and the dispersion rate was calculated based on Equation 2.
【００２６】カサ密度は、ＪＩＳ Ｋ ５１０１に記載
の方法により測定した。The bulk density was measured by the method described in JIS K 5101.
【００２７】実施例１ 重量増が２．０重量％となるようにＮーβ（アミノエチ
ル）ーγーアミノプロピルトリメトキシシランで表面処
理を行った一次粒子平均径０．５μｍのＭｎ−Ｚｎ系球
状フェライト粒子（真球度０．９８）１０重量部と固有
粘度０．７５のポリエチレンテレフタレート９０重量部
を混合し、紡糸温度２８０℃で直径０．２０ｍｍのオリ
フィスから紡出し、冷却、オイリングしながら８００ｍ
／ｍｉｎの速度で巻き取り、更に９０℃で延伸倍率２．
５に延伸し、１５０℃で緊張熱処理し、繊維直径１００
μｍの磁性繊維を得た。この磁性繊維を評価したとこ
ろ、単繊維強度２３ＭＰａ、単繊維伸度１７％、分散率
は、０．０１、保磁力は、０．００２Ｏｅ、最大磁束密
度は、１５Ｇであり、加工に十分耐えるだけの繊維物性
を有していた。Example 1 Mn-Zn having an average primary particle diameter of 0.5 μm was surface-treated with N-β (aminoethyl) -γ-aminopropyltrimethoxysilane so that the weight increase was 2.0% by weight. 10 parts by weight of spherical spherical ferrite particles (sphericity 0.98) and 90 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.75 are mixed, spun at a spinning temperature of 280 ° C. from an orifice having a diameter of 0.20 mm, cooled, and oiled. 800m
1. Winding at a speed of / min, and draw ratio at 90 ° C. 2.
Stretched to 5 and subjected to tension heat treatment at 150 ° C, fiber diameter 100
A magnetic fiber of μm was obtained. When this magnetic fiber was evaluated, the single fiber strength was 23 MPa, the single fiber elongation was 17%, the dispersion rate was 0.01, the coercive force was 0.002 Oe, and the maximum magnetic flux density was 15 G, which was sufficient to withstand processing. It had the following fiber physical properties.
【００２８】実施例２ 一次粒子平均径０．３μｍの立方状磁性粒子２５０重量
部をアクリロニトリル２５００重量部に加え分散させ、
これに４０％水酸化カリウム溶液１３重量部を加え５０
℃で１８時間シアノエチル化反応を行った。得られた粒
子は、脱溶剤、洗浄後乾燥し、シアノエチル化磁性粒子
を得た。Example 2 250 parts by weight of cubic magnetic particles having an average primary particle diameter of 0.3 μm were added to 2500 parts by weight of acrylonitrile and dispersed.
Add 13 parts by weight of 40% potassium hydroxide solution to this and add 50
A cyanoethylation reaction was performed at 18 ° C. for 18 hours. The obtained particles were desolvated, washed and dried to obtain cyanoethylated magnetic particles.
【００２９】得られた磁性粒子１０重量部と重量平均分
子量８９０００のアクリロニトリル／アクリル酸メチル
共重合体９０重量部をチオシアン酸ナトリウムの５５％
水溶液５００重量部に７３℃で溶解および撹拌分散する
ことにより紡糸原液を得た。該紡糸原液を孔径０．３６
ｍｍ、孔数１００の紡糸ノズルを用いてー２℃、１５％
のチオシアン酸ナトリウム水溶液中に紡出した後、水
洗、延伸（総延伸倍率１２倍）、乾燥緻密化、捲縮処
理、緩和熱処理及び油剤処理を施して単繊維直径８０μ
ｍの磁性繊維を得た。この磁性繊維を評価したところ、
単繊維強度４３ＭＰａ、単繊維伸度１８％、分散率は、
０．０８、保磁力は、０．１５Ｏｅ、最大磁束密度は、
５．４Ｇであった。なお、紡糸及び磁性繊維の加工性を
評価するためのスワッチの作成の際には、ノズル詰ま
り、糸切れ等のトラブルは発生せず、作業性は良好であ
った。10 parts by weight of the obtained magnetic particles and 90 parts by weight of an acrylonitrile / methyl acrylate copolymer having a weight average molecular weight of 89000 were added to 55% of sodium thiocyanate.
A spinning stock solution was obtained by dissolving in 500 parts by weight of an aqueous solution at 73 ° C. and stirring and dispersing. The spinning solution has a pore size of 0.36
mm, using a spinning nozzle with 100 holes at -2 ° C, 15%
After being spun into an aqueous solution of sodium thiocyanate, washed with water, drawn (total draw ratio: 12 times), dried and densified, crimped, relaxed and heat treated with an oil agent to obtain a single fiber diameter of 80 μm.
m magnetic fiber was obtained. When this magnetic fiber was evaluated,
The single fiber strength is 43 MPa, the single fiber elongation is 18%, and the dispersion rate is
0.08, coercive force 0.15 Oe, maximum magnetic flux density
It was 5.4G. No problems such as nozzle clogging and yarn breakage occurred during the production of the swatch for evaluating the processability of the spinning and magnetic fibers, and the workability was good.
【００３０】実施例３ー１ １リットルの水に硫酸第一鉄１９８．６ｇを溶解し、こ
の水溶液を８０℃とした。これに空気を吹き込み、撹拌
しながら水酸化ナトリウム水溶液を用いこの液のｐＨを
７に調整することによりスピネル型球状磁性粒子を得
た。得られた磁性粒子のカサ密度は、０．７ｇ／ｃｍ3
であり、また一次粒子平均径は０．１８μｍ、真球度は
０．９９であった。Example 3-1 198.6 g of ferrous sulfate was dissolved in 1 liter of water, and this aqueous solution was heated to 80 ° C. Air was blown into this, and the pH of this solution was adjusted to 7 with an aqueous sodium hydroxide solution while stirring to obtain spinel type spherical magnetic particles. The bulk density of the obtained magnetic particles is 0.7 g / cm 3.
The average primary particle diameter was 0.18 μm, and the sphericity was 0.99.
【００３１】重量平均分子量８９０００のアクリロニト
リル／アクリル酸メチル共重合体９５重量部をチオシア
ン酸ナトリウムの５５％水溶液５００重量部に７３℃で
溶解し、得られた磁性粒子５重量部を添加、さらに５時
間撹拌を行いこの磁性粒子を分散することにより紡糸原
液を得た。95 parts by weight of an acrylonitrile / methyl acrylate copolymer having a weight average molecular weight of 89000 was dissolved in 500 parts by weight of a 55% aqueous solution of sodium thiocyanate at 73 ° C., and 5 parts by weight of the obtained magnetic particles were added. A spinning stock solution was obtained by stirring for a period of time and dispersing the magnetic particles.
【００３２】該紡糸原液を孔径０．０４ｍｍ、孔数１０
０の紡糸ノズルを用いてー２℃、１５％のチオシアン酸
ナトリウム水溶液中に紡出した後、水洗、延伸（総延伸
倍率１２倍）、乾燥緻密化、捲縮処理、緩和熱処理及び
油剤処理を施して単繊維直径９μｍの磁性繊維を得た。
この磁性繊維を評価したところ、単繊維強度８２ＭＰ
ａ、単繊維伸度２３％、分散率は、０．８９、保磁力
は、０．０８Ｏｅ、最大磁束密度は、２３０Ｇであっ
た。なお、紡糸及び磁性繊維の加工性を評価するための
スワッチの作成の際には、ノズル詰まり、糸切れ等のト
ラブルは発生せず、作業性は良好であった。The spinning solution was prepared with a pore size of 0.04 mm and a pore number of 10
After spinning into a 15% sodium thiocyanate aqueous solution at −2 ° C. using a spinning nozzle No. 0, washing with water, stretching (total stretching ratio: 12 times), dry densification, crimping treatment, relaxation heat treatment and oil treatment This was applied to obtain a magnetic fiber having a single fiber diameter of 9 μm.
When this magnetic fiber was evaluated, the single fiber strength was 82MP.
a, single fiber elongation 23%, dispersion rate 0.89, coercive force 0.08 Oe, and maximum magnetic flux density 230G. During the production of the swatch for evaluating the processability of the spinning and magnetic fibers, nozzle clogging, yarn breakage, and other troubles did not occur, and workability was good.
【００３３】実施例３ー２ 磁性粒子を３６０重量部を用いさらに、孔径０．１２ｍ
ｍのノズルを用いた以外は、実施例３ー１と同じ方法で
直径５０μｍの磁性繊維を得た。この磁性繊維を評価し
たところ、単繊維強度２７０ＭＰａ、単繊維伸度３２
％、分散率は０．８５、保磁力は１．５Ｏｅ、最大磁束
密度は、３．２ｋＧであった。なお、紡糸及びスワッチ
の作成の際には、ノズル詰まり、糸切れ等のトラブルは
発生せず、作業性は良好であった。Example 3-2 360 parts by weight of magnetic particles were used, and the pore size was 0.12 m.
A magnetic fiber having a diameter of 50 μm was obtained in the same manner as in Example 3-1, except that the m nozzle was used. When this magnetic fiber was evaluated, the single fiber strength was 270 MPa and the single fiber elongation was 32.
%, The dispersion rate was 0.85, the coercive force was 1.5 Oe, and the maximum magnetic flux density was 3.2 kG. No problems such as nozzle clogging and yarn breakage occurred during spinning and swatch production, and workability was good.
【００３４】実施例３ー３ 磁性粒子を４０重量部を用いさらに、孔径０．４２ｍｍ
のノズルを用いた以外は、実施例３ー１と同じ方法で直
径１８０μｍの磁性繊維を得た。この磁性繊維を評価し
たところ、単繊維強度２６ＭＰａ、単繊維伸度４％、分
散率は０．８１、保磁力は０．６２Ｏｅ、最大磁束密度
は、１．２ＫＧであった。なお、紡糸及びスワッチの作
成の際には、ノズル詰まり、糸切れ等のトラブルは発生
せず、作業性は良好であった。Example 3-3 40 parts by weight of magnetic particles were used, and the pore diameter was 0.42 mm.
A magnetic fiber having a diameter of 180 μm was obtained in the same manner as in Example 3-1 except that the nozzle of No. 1 was used. When this magnetic fiber was evaluated, the single fiber strength was 26 MPa, the single fiber elongation was 4%, the dispersion rate was 0.81, the coercive force was 0.62 Oe, and the maximum magnetic flux density was 1.2 KG. No problems such as nozzle clogging and yarn breakage occurred during spinning and swatch production, and workability was good.
【００３５】実施例３ー４ 孔径０．０２ｍｍのノズルを用いた以外は、実施例３ー
１と同じ方法で磁性繊維を得ようとしたが、紡出の際糸
切れが発生し、連続した糸は、得られなかった。断片的
に得られた繊維状物の直径は、０．７μｍであった。Example 3-4 A magnetic fiber was tried to be obtained by the same method as in Example 3-1 except that a nozzle having a hole diameter of 0.02 mm was used. However, yarn breakage occurred during spinning, and the fiber was continuous. No thread was obtained. The diameter of the fibrous material obtained in pieces was 0.7 μm.
【００３６】実施例３ー５ 孔径０．７０ｍｍのノズルを用いた以外は、実施例３ー
３と同じ方法で単繊維直径２３０μｍの磁性繊維を得
た。この磁性繊維を評価したところ、単繊維強度２ＭＰ
ａ、単繊維伸度１．５％であった。磁性繊維の加工性を
評価するためのスワッチの作成を行ったところ、単繊維
強度および単繊維伸度伸度が弱すぎるため糸切れが発生
し、加工することが出来なかった。Example 3-5 A magnetic fiber having a single fiber diameter of 230 μm was obtained in the same manner as in Example 3-3 except that a nozzle having a hole diameter of 0.70 mm was used. When this magnetic fiber was evaluated, the single fiber strength was 2MP.
a, Single fiber elongation was 1.5%. When a swatch was prepared to evaluate the processability of the magnetic fiber, the single fiber strength and the single fiber elongation were too weak, and a yarn breakage occurred, which made it impossible to process.
【００３７】実施例４ー１ 一次粒子平均径０．８μｍの磁性粒子を用いた以外は、
実施例３ー１と同じ方法で磁性繊維を試作した。紡出の
際、わずかに糸切れが発生したが、繊維状のものが連続
して得られた。この磁性繊維を評価したところ、単繊維
直径は９．０μｍ、単繊維強度７ＭＰａ、単繊維伸度
３．２％であり、加工するために必要な最低の繊維物性
は備えていた。また、分散率は０．０５、保磁力は０．
２１Ｏｅ、最大磁束密度は、３１０Ｇであった。Example 4-1 Except that magnetic particles having an average primary particle diameter of 0.8 μm were used,
A magnetic fiber was experimentally manufactured by the same method as in Example 3-1. Although a slight yarn breakage occurred during spinning, a fibrous material was continuously obtained. When this magnetic fiber was evaluated, the diameter of the single fiber was 9.0 μm, the strength of the single fiber was 7 MPa, the elongation of the single fiber was 3.2%, and the minimum fiber physical properties required for processing were provided. The dispersion rate is 0.05 and the coercive force is 0.1.
21 Oe, the maximum magnetic flux density was 310G.
【００３８】実施例４ー２ 一次粒子平均径２．０μｍの磁性粒子を用いた以外は、
実施例３ー１と同じ方法で紡出を試みたが、ノズル詰ま
りが起こり繊維状物は得られなかった。。Example 4-2 Except that magnetic particles having an average primary particle diameter of 2.0 μm were used.
An attempt was made to carry out spinning in the same manner as in Example 3-1, but nozzle clogging occurred and no fibrous material was obtained. .
【００３９】実施例５ー１ ８００重量部の磁性粒子を用いた以外は、実施例３ー２
と同じ方法で紡出を試みたが、ノズル詰まりが起こり繊
維状物は得られなかった。Example 5-1 Example 3-1 except that 800 parts by weight of magnetic particles were used.
An attempt was made to carry out spinning in the same manner as, but nozzle clogging occurred and no fibrous material was obtained.
【００４０】実施例５ー２ ０．５重量部の磁性粒子と重量平均分子量８９０００の
アクリロニトリル／アクリル酸メチル共重合体９０重量
部を用いたこと以外は、実施例３ー２と同様な方法で紡
糸を行った。得られた繊維の単繊維強度は１２６ＭＰａ
また、単繊維伸度は、３２％と望ましい繊維物性を有し
ていたが、保持力は、測定限界以下（０．００００１Ｏ
ｅ以下）であり、最大磁束密度は、０．０００３Ｇであ
り、磁性繊維として実用的なものではなかった。Example 5-2 The same procedure as in Example 3-2 except that 0.5 parts by weight of magnetic particles and 90 parts by weight of an acrylonitrile / methyl acrylate copolymer having a weight average molecular weight of 89000 were used. Spinning was performed. The single fiber strength of the obtained fiber is 126 MPa.
Further, the single fiber elongation had a desirable fiber physical property of 32%, but the holding power was less than the measurement limit (0.00001O).
e or less), and the maximum magnetic flux density was 0.0003 G, which was not practical as a magnetic fiber.
【００４１】実施例６ 磁性粒子の分散時間を１０分間としたこと以外は、実施
例３ー２と同様な方法で紡糸を試みたが、ノズル詰まり
および糸切れが発生し、連続して繊維を得ることはでき
なかった。また、この際得られた短い繊維状物を分析し
たところ、分散率は、０．００４であった。Example 6 Spinning was tried in the same manner as in Example 3-2, except that the dispersion time of the magnetic particles was 10 minutes, but nozzle clogging and yarn breakage occurred, and fibers were continuously formed. I couldn't get it. Further, when the short fibrous material obtained at this time was analyzed, the dispersity was 0.004.
【００４２】実施例７ 実施例３ー１の磁性粒子の作成において、水酸化ナトリ
ウムによりｐＨを１３．２に調整することにより一次粒
子平均径０．２μｍの立方状磁性粒子を得た。この磁性
粒子を用い、実施例３ー２と同じ方法で紡出を試みた
が、ノズル詰まりが起き繊維状物は得られなかった。Example 7 In the preparation of magnetic particles of Example 3-1, the pH was adjusted to 13.2 with sodium hydroxide to obtain cubic magnetic particles having an average primary particle diameter of 0.2 μm. Using these magnetic particles, an attempt was made to carry out spinning in the same manner as in Example 3-2, but nozzle clogging occurred and no fibrous material was obtained.
【００４３】実施例８ー１ カサ密度０．３ｇ／ｃｍ3 の磁性粒子を用いた以外は、
実施例３ー１と同じ処方で磁性繊維を作成した。この磁
性繊維を評価したところ、単繊維強度１５ＭＰａ、単繊
維伸度３．２％であり、加工するために必要な最低の繊
維物性は備えていたが、保磁力は測定感度以下、最大磁
束密度は、０．０４Ｇであり実用に共しうる磁気特性は
備えていなかった。Example 8-1 Except that magnetic particles having a bulk density of 0.3 g / cm 3 were used,
Magnetic fibers were prepared with the same formulation as in Example 3-1. When this magnetic fiber was evaluated, the single fiber strength was 15 MPa, the single fiber elongation was 3.2%, and it had the minimum fiber physical properties necessary for processing, but the coercive force was less than the measurement sensitivity and the maximum magnetic flux density. Is 0.04 G, which means that it has no magnetic characteristics suitable for practical use.
【００４４】実施例８ー２ カサ密度１．４ｇ／ｃｍ3 の磁性粒子を用いた以外は、
実施例３ー１と同じ処方で紡糸のための溶液を作成しよ
うとしたが、粒子の沈降が生じ分散が非常に困難であっ
た。そして、この溶液を用いて紡出を試みたが、ノズル
詰まるが起き繊維は得ることができなかった。Example 8-2 Except that magnetic particles having a bulk density of 1.4 g / cm 3 were used.
An attempt was made to prepare a solution for spinning with the same formulation as in Example 3-1, but sedimentation of particles occurred and dispersion was extremely difficult. Then, an attempt was made to spin using this solution, but nozzle clogging occurred and fibers could not be obtained.
【００４５】実施例９ 実施例３ー１の磁性粒子の作成において、空気を通気す
る際の温度を６５℃とし、一次粒子平均径０．３μｍの
ゲータイト磁性粒子を得た。この磁性粒子を用い、実施
例３ー２と同じ方法で磁性繊維を得た。この磁性繊維を
評価したところ、単繊維強度６０ＭＰａ、単繊維伸度１
２％であり、加工するために必要な最低の繊維物性は備
えていたが、保磁力は測定感度以下、最大磁束密度は、
０．０００５Ｇであり実用に共しうる磁気特性は備えて
いなかった。Example 9 Goethite magnetic particles having an average primary particle diameter of 0.3 μm were obtained at a temperature of 65 ° C. when aerated with air in the preparation of the magnetic particles of Example 3-1. Using these magnetic particles, magnetic fibers were obtained in the same manner as in Example 3-2. When this magnetic fiber was evaluated, the single fiber strength was 60 MPa and the single fiber elongation was 1.
2%, which had the minimum fiber physical properties necessary for processing, but the coercive force was less than the measurement sensitivity, and the maximum magnetic flux density was
The magnetic property was 0.0005 G, which was not suitable for practical use.
【００４６】実施例１０ 実施例３ー１で得られた磁性粒子３０重量部と分子量５
００００の低密度ポリエチレン７０重量部を混ぜ、紡糸
温度１８０℃で直径０．２５ｍｍのオリフィスから紡出
を試みたが、ノズル詰まりが起き、繊維は得られなかっ
た。Example 10 30 parts by weight of the magnetic particles obtained in Example 3-1 and a molecular weight of 5
70 parts by weight of 0000 low-density polyethylene was mixed and an attempt was made to spin from an orifice having a diameter of 0.25 mm at a spinning temperature of 180 ° C. However, nozzle clogging occurred and no fiber was obtained.
【００４７】[0047]
【発明の効果】本発明の磁性繊維は、加工性に優れ、
紙、不織布および織布とすることが可能であるため様々
な用途に使用することが可能であり、特に限定はされな
いが、例えば、環境分野では、エンジンオイルフィルタ
ー、排水フィルター、防塵マスク、防塵フィルター。バ
イオ関係では、磁気ネットおよび土壌改良剤。電気・電
子分野では、電波吸収体、電磁遮断体、磁気ファスナー
および磁性導電繊維。医療・ヘルスケア分野では、磁気
バンド、磁気ベッド、健康肌着、健康保持具および磁化
水の製造。情報・記録分野では、磁気表示体、電磁応答
マーカー、ワイヤーメモリー、圧力センサー、力学量検
出素子、電磁センサーおよび電磁ブラシ。その他、制振
材料、磁場硬化コンクリート用繊維、ブレーキシュー、
スポーツ用品および複合材などの分野への応用が可能で
ある。The magnetic fiber of the present invention has excellent workability,
Since it can be made into paper, non-woven fabric, and woven fabric, it can be used in various applications, and is not particularly limited.For example, in the environmental field, engine oil filters, drainage filters, dust masks, dust filters, etc. . In biotechnology, magnetic nets and soil conditioners. In the electric and electronic fields, electromagnetic wave absorbers, electromagnetic shields, magnetic fasteners and magnetic conductive fibers. In the medical / healthcare field, we manufacture magnetic bands, magnetic beds, health underwear, health care equipment, and magnetized water. In the information / recording field, magnetic display, electromagnetic response marker, wire memory, pressure sensor, mechanical quantity detection element, electromagnetic sensor and electromagnetic brush. Others, damping materials, magnetic field hardening concrete fibers, brake shoes,
It can be applied to fields such as sports equipment and composite materials.
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Claims (10)
分散し、かつ、単繊維強度１ＭＰａ以上および単繊維伸
度２％以上を有することを特徴とする磁性繊維。1. A magnetic fiber, wherein magnetic particles are uniformly dispersed in a cross section perpendicular to the fiber axis, and have a single fiber strength of 1 MPa or more and a single fiber elongation of 2% or more.
範囲にあることを特徴とする請求項１記載の磁性繊維。2. The magnetic fiber according to claim 1, wherein the single fiber diameter is in the range of 1 μm to 200 μm.
０μｍ以下であり、かつその含有量が１重量％以上８５
重量％以下であることを特徴とする請求項１または請求
項２記載の磁性繊維。3. The magnetic particles have an average primary particle diameter of 1.
0 μm or less and the content is 1% by weight or more and 85
The magnetic fiber according to claim 1 or 2, wherein the content is less than or equal to wt%.
１．０以下であることを特徴とする請求項１から３のい
ずれかに記載の磁性繊維。 【数１】 4. The magnetic fiber according to any one of claims 1 to 3, wherein the dispersion rate defined by the equation 1 is 0.01 or more and 1.0 or less. [Equation 1]
つ最大磁束密度が１Ｇ以上であることを特徴とする請求
項１から４のいずれかに記載の磁性繊維。5. The magnetic fiber according to claim 1, which has a coercive force of 0.001 Oe or more and a maximum magnetic flux density of 1 G or more.
分子または繊維形成性の有機高分子を含む溶液中に分散
させた後、紡糸することを特徴とする磁性繊維の製造方
法。6. A method for producing a magnetic fiber, wherein spherical magnetic particles are dispersed in a fiber-forming organic polymer or a solution containing a fiber-forming organic polymer and then spun.
3 以上１．３０ｇ／ｃｍ3 以下であることを特徴とする
請求項６記載の磁性繊維の製造方法。7. The bulk density of the magnetic particles is 0.4 g / cm.
The method for producing magnetic fibers according to claim 6, wherein the amount is 3 or more and 1.30 g / cm 3 or less.
ことを特徴とする、請求項６または請求項７記載の磁性
繊維の製造方法。8. The method for producing a magnetic fiber according to claim 6, wherein the magnetic particles are spinel type ferrite.
徴とする、請求項７または８記載の磁性繊維の製造方
法。9. The method for producing a magnetic fiber according to claim 7, wherein the spinning is performed by a wet spinning method.
ニトリル系重合体を含むことを特徴とする、請求項６か
ら９のいずれかに記載の磁性繊維の製造方法。10. The method for producing a magnetic fiber according to claim 6, wherein the fiber-forming organic polymer contains an acrylonitrile polymer.
Priority Applications (1)
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|---|---|---|---|
| JP35464893A JP3362493B2 (en) | 1993-12-28 | 1993-12-28 | Magnetic fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35464893A JP3362493B2 (en) | 1993-12-28 | 1993-12-28 | Magnetic fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07197311A true JPH07197311A (en) | 1995-08-01 |
| JP3362493B2 JP3362493B2 (en) | 2003-01-07 |
Family
ID=18438971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35464893A Expired - Fee Related JP3362493B2 (en) | 1993-12-28 | 1993-12-28 | Magnetic fiber and method for producing the same |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215779A (en) * | 1994-01-27 | 1995-08-15 | Japan Exlan Co Ltd | Cyanoethylated ceramic particles, ceramic-containing fiber using same and its production |
| WO1999062082A1 (en) * | 1998-05-28 | 1999-12-02 | Commissariat A L'energie Atomique | Inductive textile and use of such a textile in inductive devices |
| WO2001025514A1 (en) * | 1999-10-04 | 2001-04-12 | Insung Powdertech Co., Ltd. | Fibre and fabrics with magnetic material |
| KR20020077747A (en) * | 2001-04-02 | 2002-10-14 | 인성파우더 테크(주) | Synthetic Fiber with Magnetic Material |
| US6866437B2 (en) | 2000-03-03 | 2005-03-15 | L'oreal | Device having a magnetic applicator and/or wiper member |
| US20130252497A1 (en) * | 2011-11-14 | 2013-09-26 | Faserinstitut Bremen E.V. | Thermoplastic fibre, hybrid yarn, fibre perform and method for producing fibre performs for fibre composite components, in particular high performance fibre composite component, using the same, fibre composite component and method for producing fibre composite components, in particular high performance fibre composite components |
| WO2014014038A1 (en) * | 2012-07-17 | 2014-01-23 | ユニプラス滋賀株式会社 | Magnetic monofilament, magnetic brush, and production method for said magnetic monofilament and said magnetic brush |
| CN103726192A (en) * | 2013-12-26 | 2014-04-16 | 江苏华超纺织实业有限公司 | Magnetic silk fabric |
| WO2018175134A1 (en) * | 2017-03-23 | 2018-09-27 | Boston Materials Llc | Fiber-reinforced composites, methods therefor, and articles comprising the same |
| JP2022521221A (en) * | 2020-01-10 | 2022-04-06 | 華南理工大学 | Magnetic fiber material and its manufacturing method and use |
| CN115044994A (en) * | 2022-06-29 | 2022-09-13 | 华中科技大学 | Power generation composite fiber, preparation method and application thereof |
| US11479656B2 (en) | 2019-07-10 | 2022-10-25 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| CN117211011A (en) * | 2023-11-09 | 2023-12-12 | 山东华业无纺布有限公司 | Mattress material containing magnetic fibers and preparation method thereof |
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- 1993-12-28 JP JP35464893A patent/JP3362493B2/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07215779A (en) * | 1994-01-27 | 1995-08-15 | Japan Exlan Co Ltd | Cyanoethylated ceramic particles, ceramic-containing fiber using same and its production |
| WO1999062082A1 (en) * | 1998-05-28 | 1999-12-02 | Commissariat A L'energie Atomique | Inductive textile and use of such a textile in inductive devices |
| FR2779266A1 (en) * | 1998-05-28 | 1999-12-03 | Commissariat Energie Atomique | INDUCTIVE TEXTILE AND USE OF SUCH A TEXTILE IN INDUCTIVE DEVICES |
| WO2001025514A1 (en) * | 1999-10-04 | 2001-04-12 | Insung Powdertech Co., Ltd. | Fibre and fabrics with magnetic material |
| US6866437B2 (en) | 2000-03-03 | 2005-03-15 | L'oreal | Device having a magnetic applicator and/or wiper member |
| US7168874B2 (en) | 2000-03-03 | 2007-01-30 | L'oreal S.A. | Device having a magnetic applicator and/or wiper member |
| KR20020077747A (en) * | 2001-04-02 | 2002-10-14 | 인성파우더 테크(주) | Synthetic Fiber with Magnetic Material |
| US20130252497A1 (en) * | 2011-11-14 | 2013-09-26 | Faserinstitut Bremen E.V. | Thermoplastic fibre, hybrid yarn, fibre perform and method for producing fibre performs for fibre composite components, in particular high performance fibre composite component, using the same, fibre composite component and method for producing fibre composite components, in particular high performance fibre composite components |
| JPWO2014014038A1 (en) * | 2012-07-17 | 2016-07-07 | ユニプラス滋賀株式会社 | Magnetic monofilament, magnetic brush, and manufacturing method thereof |
| WO2014014038A1 (en) * | 2012-07-17 | 2014-01-23 | ユニプラス滋賀株式会社 | Magnetic monofilament, magnetic brush, and production method for said magnetic monofilament and said magnetic brush |
| CN103726192A (en) * | 2013-12-26 | 2014-04-16 | 江苏华超纺织实业有限公司 | Magnetic silk fabric |
| WO2018175134A1 (en) * | 2017-03-23 | 2018-09-27 | Boston Materials Llc | Fiber-reinforced composites, methods therefor, and articles comprising the same |
| US11840028B2 (en) | 2018-12-10 | 2023-12-12 | Boston Materials, Inc. | Systems and methods for carbon fiber alignment and fiber-reinforced composites |
| US11479656B2 (en) | 2019-07-10 | 2022-10-25 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| US11767415B2 (en) | 2019-07-10 | 2023-09-26 | Boston Materials, Inc. | Systems and methods for forming short-fiber films, composites comprising thermosets, and other composites |
| US11820880B2 (en) | 2019-07-10 | 2023-11-21 | Boston Materials, Inc. | Compositions and methods for carbon fiber-metal and other composites |
| JP2022521221A (en) * | 2020-01-10 | 2022-04-06 | 華南理工大学 | Magnetic fiber material and its manufacturing method and use |
| CN115044994A (en) * | 2022-06-29 | 2022-09-13 | 华中科技大学 | Power generation composite fiber, preparation method and application thereof |
| CN117211011A (en) * | 2023-11-09 | 2023-12-12 | 山东华业无纺布有限公司 | Mattress material containing magnetic fibers and preparation method thereof |
| CN117211011B (en) * | 2023-11-09 | 2024-02-06 | 山东华业无纺布有限公司 | Mattress material containing magnetic fibers and preparation method thereof |
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