JP2010513739A - Method for producing cellulose multifilament having a low cross-sectional variation coefficient - Google Patents
Method for producing cellulose multifilament having a low cross-sectional variation coefficient Download PDFInfo
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- JP2010513739A JP2010513739A JP2009542633A JP2009542633A JP2010513739A JP 2010513739 A JP2010513739 A JP 2010513739A JP 2009542633 A JP2009542633 A JP 2009542633A JP 2009542633 A JP2009542633 A JP 2009542633A JP 2010513739 A JP2010513739 A JP 2010513739A
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920002678 cellulose Polymers 0.000 title description 3
- 239000001913 cellulose Substances 0.000 title description 3
- 230000015271 coagulation Effects 0.000 claims abstract description 43
- 238000005345 coagulation Methods 0.000 claims abstract description 43
- 229920000433 Lyocell Polymers 0.000 claims abstract description 41
- 230000005855 radiation Effects 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 16
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011550 stock solution Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 102000015081 Blood Coagulation Factors Human genes 0.000 claims abstract description 6
- 108010039209 Blood Coagulation Factors Proteins 0.000 claims abstract description 6
- 239000003114 blood coagulation factor Substances 0.000 claims abstract description 6
- 230000001112 coagulating effect Effects 0.000 claims abstract description 3
- 230000000704 physical effect Effects 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 abstract description 6
- 230000002285 radioactive effect Effects 0.000 abstract description 4
- 229920000875 Dissolving pulp Polymers 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 239000000835 fiber Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009661 fatigue test Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 125000001493 tyrosinyl group Chemical group [H]OC1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/02—Reinforcing materials; Prepregs
- D10B2505/022—Reinforcing materials; Prepregs for tyres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Tires In General (AREA)
Abstract
本発明は、断面が極めて均一なセルロース繊維に関し、より詳しくは、断面変動係数（Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ Ｖａｒｉａｔｉｏｎ ｏｆ ｓｅｃｔｉｏｎ ｄｉａｍｅｔｅｒ：ＣＶ（％））が低いセルロース繊維に関する。具体的に、Ｎ−メチルモルホリン−Ｎ−オキシド（以下、「ＮＭＭＯ」という）にセルロース粉末を溶解させて製造したマルチフィラメントを構成するモノフィラメントの断面変動係数が２．５以下となるセルロース繊維に関する。
本発明によれば、ｉ）セルロース粉末はＮＭＭＯ溶液に均一に分散、膨潤、および溶解して放射原液を製造するステップ、ｉｉ）放射原液を放射ノズルを介して空気層に放射するステップ、およびｉｉｉ）空気層に放射された放射原液を凝固浴で凝固させるステップを含むライオセルマルチフィラメント工法で製造されることが特徴である。特に、前記凝固浴で凝固させるステップにおいて、凝固係数＝ＴＤ’／ＴＣ、およびＴＤ’＝ＴＤ＋ＴＡ−９０で表示される凝固係数が０．８〜１．３の範囲に調節され、このとき、ＴＤは放射溶液の温度、ＴＡは空気層に付与される冷却空気の温度、ＴＣは凝固浴の温度をそれぞれ示すことを特徴とする。The present invention relates to a cellulose fiber having a very uniform cross section, and more particularly, to a cellulose fiber having a low coefficient of variation of section (CV (%)). Specifically, the present invention relates to a cellulose fiber in which a monofilament constituting a multifilament produced by dissolving cellulose powder in N-methylmorpholine-N-oxide (hereinafter referred to as “NMMO”) has a cross-sectional variation coefficient of 2.5 or less.
According to the present invention, i) the cellulose powder is uniformly dispersed, swelled and dissolved in the NMMO solution to produce a radiation stock solution, ii) the radiation stock solution is emitted to the air layer through a radiation nozzle, and iii. ) It is characterized in that it is manufactured by a lyocell multifilament method including a step of coagulating a radioactive stock solution radiated into the air layer in a coagulation bath. In particular, adjusting the in the step of solidifying in the coagulation bath, the coagulation factor = T D '/ T C, and T D' = coagulation factors represented by T D + T A -90 is in a range of 0.8 to 1.3 is, at this time, T D is characterized by indicating the temperature of the radiation solution, T a is the temperature of the cooling air applied to the air layer, T C is the temperature of the coagulation bath respectively.
Description
本発明は、断面が極めて均一なセルロース繊維に関し、より詳しくは、断面変動係数（Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ Ｖａｒｉａｔｉｏｎ ｏｆ ｓｅｃｔｉｏｎ ｄｉａｍｅｔｅｒ：ＣＶ（％））が低いセルロース繊維に関する。具体的に、Ｎ−メチルモルホリン−Ｎ−オキシド（以下、「ＮＭＭＯ」という）にセルロース粉末を溶解させて製造したマルチフィラメントを構成するモノフィラメントの断面変動係数が２．５以下となるセルロース繊維に関する。 The present invention relates to a cellulose fiber having a very uniform cross section, and more particularly, to a cellulose fiber having a low coefficient of variation of section (CV (%)). Specifically, the present invention relates to a cellulose fiber in which a monofilament constituting a multifilament produced by dissolving cellulose powder in N-methylmorpholine-N-oxide (hereinafter referred to as “NMMO”) has a cross-sectional variation coefficient of 2.5 or less.
ライオセル繊維は、ＮＭＭＯにセルロースを溶解させた放射原液から製造された繊維であり、優れた吸湿性、乾燥強度、湿潤強度、およびモジュラスを有する。また、製造工程過程において有害物質が発生せず、ビスコースレーヨンとは違って親環境的な繊維として認識されている。このようなライオセル繊維は、レーヨンを代替してタイヤコードとして用いることができるが、タイヤコード素材として高強力を発現するためには、マルチフィラメントを構成するモノフィラメントの断面直径の均一性が必須となる。このような均一性は、モノフィラメントの断面変動係数で表示することができる。 The lyocell fiber is a fiber manufactured from a radioactive stock solution in which cellulose is dissolved in NMMO, and has excellent hygroscopicity, dry strength, wet strength, and modulus. Also, no harmful substances are generated during the manufacturing process, and it is recognized as an environmentally friendly fiber unlike viscose rayon. Such lyocell fiber can be used as a tire cord in place of rayon, but in order to develop high strength as a tire cord material, the uniformity of the cross-sectional diameter of monofilaments constituting the multifilament is essential. . Such uniformity can be expressed by the cross-sectional variation coefficient of the monofilament.
ライオセル繊維の製造方法と関連した先行技術を詳察すれば、特許文献１には、断面変動率が６．５％以上となるライオセル繊維について開示されている。しかしながら、特許文献１に開示された発明は、断面変動率を高めることを目的とする。さらに実施形態で開示されているように、強度が０．７〜５．０ｇ／ｄの値を有しているため、産業用繊維、特にタイヤコード用繊維には適さない。 If the prior art relevant to the manufacturing method of a lyocell fiber is examined in detail, Patent Document 1 discloses a lyocell fiber having a cross-sectional variation rate of 6.5% or more. However, the invention disclosed in Patent Document 1 aims to increase the cross-sectional variation rate. Further, as disclosed in the embodiment, since the strength has a value of 0.7 to 5.0 g / d, it is not suitable for industrial fibers, particularly tire cord fibers.
他の先行技術である特許文献２の発明は、繊維の長手方向による断面変動率が６〜１７ＣＶ％となり、繊維間の断面変動率が１０〜２２ＣＶ％となるライオセル繊維について開示している。しかしながら、提示された断面変動率値は、繊維の長手方向および繊維間に対するすべての値がタイヤコード用ライオセル繊維として用いるには適さない。 The invention of Patent Document 2, which is another prior art, discloses a lyocell fiber in which the cross-sectional variation rate in the longitudinal direction of the fiber is 6 to 17 CV% and the cross-sectional variation rate between the fibers is 10 to 22 CV%. However, the proposed cross-sectional variation values are not suitable for use as tire cord lyocell fibers in that all values for the longitudinal direction of the fibers and between the fibers are used.
本発明は、このような公知のライオセル繊維の断面変動率を改善するために、工程内の空気層における温度と凝固浴の温度を調節して、タイヤコード用マルチフィラメントを構成するモノフィラメントの断面変動係数を２．５以下に改善する方法を提案する。 In order to improve the cross-sectional variation rate of such a known lyocell fiber, the present invention adjusts the temperature in the air layer and the temperature of the coagulation bath in the process to change the cross-sectional variation of the monofilament constituting the multifilament for tire cord. A method for improving the coefficient to 2.5 or less is proposed.
本発明は、空気層における冷却空気の温度と凝固浴の温度を調節し、タイヤコード用マルチフィラメントを構成するモノフィラメントの断面変動係数を２．５以下に調節して、高強力のタイヤコード用ディップコードとして用いることができるライオセル繊維を提供することを目的とする。 The present invention adjusts the temperature of the cooling air in the air layer and the temperature of the coagulation bath, adjusts the cross-sectional variation coefficient of the monofilament constituting the multifilament for tire cords to 2.5 or less, and provides a high-strength tire cord dip. An object is to provide a lyocell fiber that can be used as a cord.
本発明に係るライオセル繊維は、凝固係数の制御によってタイヤコード用ディップコードとしての使用に適した物性を有することができる。ライオセル繊維の断面変動係数は、タイヤコードの耐疲労度を決定する重要な因子の１つとなる。本発明によって、断面変動係数は、凝固係数の調節によって必要な範囲に制限することができる。これにより、本発明は、タイヤコード用ディップコードとして適切に用いることができるライオセルマルチフィラメントを製造することができるという利点を有する。 The lyocell fiber according to the present invention can have physical properties suitable for use as a dip cord for tire cords by controlling the coagulation coefficient. The cross-sectional variation coefficient of the lyocell fiber is one of important factors that determine the fatigue resistance of the tire cord. According to the present invention, the cross-sectional variation coefficient can be limited to a necessary range by adjusting the solidification coefficient. Thereby, this invention has the advantage that the lyocell multifilament which can be used appropriately as a dip cord for tire cords can be manufactured.
ライオセル繊維の製造工程そのものは公知されているが、それぞれの工程条件に応じて互いに異なる物性を有したライオセル繊維が製造されるようになる。特に、放射ノズルにおける放射圧力、オリフィスの直径およびオリフィスの個数、放射速度、空気層での冷却空気の温度および風速、凝固浴の温度および濃度、巻取り速度などは、ライオセル繊維の物性を決定する重要な媒介変数となる。本発明に係るライオセル繊維は、工程過程において工程条件が制御されて製造され、これにしたがってタイヤコードに適した物性を有するようになる。 The manufacturing process of lyocell fiber itself is known, but lyocell fiber having different physical properties is manufactured according to each process condition. In particular, the radiation pressure at the radiation nozzle, the diameter of the orifice and the number of orifices, the radiation speed, the temperature and wind speed of the cooling air in the air layer, the temperature and concentration of the coagulation bath, the winding speed, etc. determine the physical properties of the lyocell fiber. It becomes an important parameter. The lyocell fiber according to the present invention is produced by controlling the process conditions in the process, and has physical properties suitable for the tire cord according to this.
製造されたライオセル繊維の物性は、提示された因子またはその他の因子によって独立的に影響を受けるのではなく、全体的に互いに関連性を持ちながら影響を受けるようになる。本発明は、このような因子が関連性を有するように制御されることを特徴とする。
製造されたライオセル繊維の均一性に影響を及ぼす要因は、空気層で冷却される条件と凝固する条件とに分けることができる。したがって、条件因子は、空気層での冷却空気の温度と凝固浴の温度の関数である凝固係数で表現することができ、凝固係数は下記のような式で表示される。
The physical properties of the manufactured lyocell fibers are not influenced independently by the presented factors or other factors, but are influenced by being totally related to each other. The present invention is characterized in that such factors are controlled to be related.
Factors affecting the uniformity of the manufactured lyocell fibers can be divided into conditions for cooling in the air layer and conditions for solidification. Therefore, the condition factor can be expressed by a solidification coefficient that is a function of the temperature of the cooling air in the air layer and the temperature of the solidification bath, and the solidification coefficient is expressed by the following equation.
凝固係数＝ＴＤ’／ＴＣ＝０．８〜１．３
（ＴＤ’＝ＴＤ＋ＴＡ−９０）
前記した式において、ＴＤは放射溶液の温度、ＴＡは空気層に付与される冷却空気の温度、ＴＣは凝固浴の温度をそれぞれ示す。
Coagulation factor = T D '/ T C = 0.8~1.3
(T D '= T D + T A -90)
In the above-mentioned formulas, T D indicates the temperature of the radiation solution, T A is the temperature of the cooling air applied to the air layer, T C is the temperature of the coagulation bath respectively.
本発明に係るライオセル繊維の製造過程において、凝固係数は０．８〜１．３となるように調節される。このような凝固係数の調節によって冷却された放射溶液の温度と凝固浴の温度が類似した範囲に調節され、さらに凝固浴に入った放射溶液に含まれたＮＭＭＯが凝固浴内部に最大限ゆっくりと拡散する。そして、このような緩和した拡散速度によって、モノフィラメントの均一性が向上するようになる。このような緩和した拡散速度のために凝固係数は０．８〜１．３範囲に調節され、これによって断面変動率が低いライオセル繊維が製造される過程を下記で説明する。 In the production process of the lyocell fiber according to the present invention, the coagulation coefficient is adjusted to be 0.8 to 1.3. By adjusting the coagulation coefficient, the temperature of the cooled radiation solution and the temperature of the coagulation bath are adjusted to a similar range, and the NMMO contained in the radiation solution that has entered the coagulation bath slowly and slowly enters the coagulation bath. Spread. And, the uniformity of the monofilament is improved by such a relaxed diffusion rate. The solidification coefficient is adjusted in the range of 0.8 to 1.3 due to such a relaxed diffusion rate, and the process of producing a lyocell fiber having a low cross-sectional variation rate will be described below.
ライオセル繊維の製造のための原料として、重合度が８００〜１２００であり、α−セルロース含有量が９３％以上となるソフトウッドパルプが粉砕機を用いて平均直径が５００μｍである粉末形態に粉砕される。そして、水の含有量が１０〜２０ｗｔ％となるＮＭＭＯ溶液が準備される。さらに、準備されたパルプ粉末とＮＭＭＯ溶液は、圧縮機に同時に注入される。この後、９０〜１１０℃の温度に維持された圧縮機で、セルロース粉末はＮＭＭＯ溶液に均一に分散、膨潤、および溶解した後、９０〜１１０℃の放射ラインを介して放射ノズルに移送されながら放射原液となる。そして、放射原液は、放射ノズルを介して放射されながらフィラメント糸となる。 As a raw material for the production of lyocell fiber, soft wood pulp having a polymerization degree of 800 to 1200 and an α-cellulose content of 93% or more is pulverized into a powder form having an average diameter of 500 μm using a pulverizer. The And the NMMO solution from which content of water will be 10-20 wt% is prepared. Further, the prepared pulp powder and NMMO solution are simultaneously injected into the compressor. Thereafter, the cellulose powder is uniformly dispersed, swelled and dissolved in the NMMO solution by a compressor maintained at a temperature of 90 to 110 ° C., and then transferred to the radiation nozzle through the radiation line of 90 to 110 ° C. It becomes a radioactive stock solution. The radiation stock solution becomes a filament yarn while being radiated through the radiation nozzle.
本発明に係るライオセル繊維の製造過程において、放射ノズルの直径は８０〜１３０ｍｍとすることができる。放射ノズルの直径が決定されれば、オリフィスの個数およびオリフィスの直径に対する長さ比が決定されるようになる。オリフィスの個数は８００〜１２００個、オリフィスの直径は８００〜２０００μｍ、オリフィスの長さは直径に対する長さ比が２〜５となるようにそれぞれ選択される。放射原液は空気層に放射される。空気層で放射原液を延伸させるために、冷却および固化が行われる。このために低い温度の空気が付与されるようになり、空気の温度は０℃〜２５℃に調節されるようになる。 In the manufacturing process of the lyocell fiber according to the present invention, the diameter of the radiation nozzle may be 80 to 130 mm. Once the diameter of the radiation nozzle is determined, the number of orifices and the ratio of the length to the diameter of the orifice are determined. The number of orifices is 800 to 1200, the diameter of the orifice is 800 to 2000 μm, and the length of the orifice is selected so that the length ratio to the diameter is 2 to 5. The radioactive stock solution is radiated to the air layer. Cooling and solidification are performed to stretch the radiation stock solution in the air layer. For this reason, low temperature air is applied, and the temperature of the air is adjusted to 0 ° C to 25 ° C.
空気層で冷却および固化された原液は、凝固浴において一定の濃度および温度の凝固溶液内で凝固しながらフィラメント糸となる。本発明に係るライオセル繊維は、このような凝固過程において凝固係数が予め決定された値を有するように制御され、これによって必要な物性を有することができるようになる。
条件因子は、空気層で冷却空気の温度と凝固浴の温度の関数である凝固係数で表現することができ、凝固係数は下記のような式で表示される。
The stock solution cooled and solidified in the air layer becomes a filament yarn while coagulating in a coagulation solution having a constant concentration and temperature in a coagulation bath. The lyocell fiber according to the present invention is controlled so that the coagulation coefficient has a predetermined value in such a coagulation process, and thereby has necessary physical properties.
The condition factor can be expressed by a solidification coefficient which is a function of the temperature of the cooling air and the temperature of the solidification bath in the air layer, and the solidification coefficient is expressed by the following equation.
凝固係数＝ＴＤ’／ＴＣ、ＴＤ’＝ＴＤ＋ＴＡ−９０
前記した式において、ＴＤは放射溶液の温度、ＴＡは空気層に付与される冷却空気の温度、ＴＣは凝固浴の温度をそれぞれ示す。本発明に係る製造方法において、凝固係数は０．８〜１．３とすることができる。
Coagulation factor = T D '/ T C, T D' = T D + T A -90
In the above-mentioned formulas, T D indicates the temperature of the radiation solution, T A is the temperature of the cooling air applied to the air layer, T C is the temperature of the coagulation bath respectively. In the production method according to the present invention, the coagulation coefficient can be set to 0.8 to 1.3.
凝固係数の調節のために、凝固浴の濃度は、ＮＭＭＯの濃度が５〜２０ｗｔ％となるように調節される。凝固係数が０．８〜１．３である場合、放射原液の温度と凝固浴の温度がほぼ類似し、放射原液に存在するＮＭＭＯが凝固浴に拡散する速度が最大限低くなり、これによって均一な凝固が誘導されるようになる。したがって、マルチフィラメントを構成するモノフィラメントの断面が極めて均一になり、高強力を発現することができる。 In order to adjust the coagulation coefficient, the concentration of the coagulation bath is adjusted so that the concentration of NMMO is 5 to 20 wt%. When the coagulation coefficient is 0.8 to 1.3, the temperature of the radiation stock solution and the temperature of the coagulation bath are almost similar, and the rate at which NMMO present in the radiation stock solution diffuses into the coagulation bath is maximized, which makes it uniform. Coagulation is induced. Therefore, the cross section of the monofilament constituting the multifilament becomes extremely uniform, and high strength can be expressed.
上記で説明した方法によって製造されたライオセル繊維は、生コードを経てディップコードとして製造される。生コードは、２本のライオセル繊維に適当な数の下撚および
上撚を加えて製造される。適切には、下撚の数／上撚の数は３００／３００ＴＰＭ〜５００／５００ＴＰＭとすることができるが、上撚および下撚の数を必ずしも同じにする必要はない。下撚および上撚を加えて製造された生コードは、ディッピング液に浸漬される。この後、生コードに樹脂層が付着されれば、タイヤ用ディップコードとなる。
The lyocell fiber manufactured by the method described above is manufactured as a dip cord through a raw cord. The raw cord is manufactured by adding an appropriate number of twists and twists to the two lyocell fibers. Suitably, the number of lower twists / number of upper twists can be 300/300 TPM to 500/500 TPM, but the number of upper twists and lower twists need not necessarily be the same. The raw cord produced by adding the lower twist and the upper twist is immersed in a dipping solution. Thereafter, if a resin layer is attached to the raw cord, the tire dip cord is obtained.
本発明に係るタイヤコード用ライオセル繊維は、全体繊度が８００〜３３００デニール（ｄｅｎｉｅｒ）となり、それぞれのフィラメントの繊度は０．５〜２．０デニール（ｄｅｎｉｅｒ）となる。本発明によって凝固係数を０．８〜１．３に調節して製造されたライオセル繊維の物性は、下記のとおりである。
１）マルチフィラメントの強度 ６．４〜８．３ｇ／ｄ
２）切断伸度 ５．７〜７．１％
３）モノフィラメントの断面変動係数 ２．５％以下
The tyrosyl fiber for tire cords according to the present invention has an overall fineness of 800 to 3300 denier, and each filament has a fineness of 0.5 to 2.0 denier. The physical properties of lyocell fibers produced by adjusting the coagulation coefficient to 0.8 to 1.3 according to the present invention are as follows.
1) Strength of multifilament 6.4 to 8.3 g / d
2) Cutting elongation 5.7-7.1%
3) Coefficient of variation of cross section of monofilament 2.5% or less
本発明に係るライオセル繊維によって製造されたディップコードの物性は、下記のとおりである。
１）強度 ４〜６ｇ／ｄ
２）切断伸度 ５〜１０％
３）耐疲労度 ７０〜１００％
The physical properties of the dip cord produced by the lyocell fiber according to the present invention are as follows.
1) Strength 4-6 g / d
2) Cutting elongation 5-10%
3) Fatigue resistance 70-100%
以下、具体的な実施例および比較例を提示して本発明の構成および効果をより詳細に説明するが、これらの実施例は本発明をより明確に理解させるためのものに過ぎず、本発明の範囲を限定するものではない。 Hereinafter, the configuration and effects of the present invention will be described in more detail by presenting specific examples and comparative examples. However, these examples are only for the purpose of more clearly understanding the present invention, and the present invention. It does not limit the range.
実施例および比較例において、ライオセルマルチフィラメントの物性は、下記のような方法によって評価した。 In Examples and Comparative Examples, the physical properties of lyocell multifilaments were evaluated by the following methods.
（イ）強度（ｇ／ｄ）および切断伸度（％）
マルチフィラメントを１０７℃で２時間乾燥した後に、インストロン社の低速伸張型引張試験機で測定した。測定は、マルチフィラメントに８０ｔｐｍ（８０回ｔｗｉｓｔ／ｍ）の撚りを付加した後、試料長２５０ｍｍ、引張速度３００ｍ／ｍｉｎの条件下で行われた。
(A) Strength (g / d) and elongation at break (%)
The multifilament was dried at 107 ° C. for 2 hours, and then measured with an Instron low-speed extension type tensile tester. The measurement was performed under the conditions of a sample length of 250 mm and a tensile speed of 300 m / min after adding 80 tpm (80 twists / m) to the multifilament.
（ロ）断面変動係数ＣＶ（％）
顕微鏡を用いてマルチフィラメントのモノフィラメントそれぞれの面積を求めて断面変動係数（Ｃｏｅｆｆｉｃｉｅｎｔ ｏｆ Ｖａｒｉａｔｉｏｎ）を計算した。この値は変量が分散する程度を示すものであり、標準偏差を平均値で割った値を意味する。
凝固係数に応じて製造された多様なライオセル繊維の物性を表１で提示した。
(B) Section variation coefficient CV (%)
The area of each multifilament monofilament was determined using a microscope, and the coefficient of variation of the cross-section (Coefficient of Variation) was calculated. This value indicates the degree to which the variable is dispersed, and means a value obtained by dividing the standard deviation by the average value.
The physical properties of various lyocell fibers produced according to the coagulation coefficient are presented in Table 1.
（ハ）耐疲労度（％）
タイヤコードの疲労試験に通常的に用いられるＧｏｏｄｒｉｃｈ Ｄｉｓｃ Ｆａｔｉｇｕｅ Ｔｅｓｔｅｒを用いて疲労試験を行った後、残余強力を測定して耐疲労度を比較した。疲労試験は、１２０℃、２５００ＲＰＭ、圧縮１０％および１８％の条件下で行われ、疲労試験後、テトラクロロエチレン液に２４時間浸漬してゴムを膨潤させた後、ゴムとコードを分離して残余強力を測定した。残余強力の測定は、１０７℃で２時間乾燥させた後、通常の引張強度試験機を用いて（イ）の方法によって測定した。
(C) Fatigue resistance (%)
After conducting a fatigue test using a Goodrich Disc Fatigue Tester, which is usually used for a tire cord fatigue test, the residual strength was measured and the fatigue resistance was compared. The fatigue test is performed under the conditions of 120 ° C., 2500 RPM, compression 10% and 18%. After the fatigue test, the rubber is swollen by immersion in a tetrachloroethylene solution for 24 hours, and then the rubber and the cord are separated to obtain a residual strength. Was measured. The residual strength was measured by the method (a) using a normal tensile strength tester after drying at 107 ° C. for 2 hours.
（実施例）
実施例１
重合度（ＤＰｗ）が１，２００（α−セルロース含有量；９７％）であるパルプ粉末と共にＮＭＭＯ．１Ｈ２０、没食子酸プロピル（ｐｒｏｐｙｌ ｇａｌｌａｔｅ）０．０１ｗｔ％を用いて濃度１１．５％のセルロース溶液を製造した。直径が１００ｍｍであり、オリフィス数がそれぞれ１０００である放射ノズルを用い、オリフィス直径は１５０μｍを用いた。このとき、オリフィス直径と長さの比（Ｌ／Ｄ）はすべて４であるノズルを用いた。放射ノズル（ｈｅａｄ ｔｅｍｐ．；１００℃）から吐出された溶液は、空気層（ａｉｒ ｇａｐ）距離５０ｍｍを通過する時点に温度５℃の冷却空気を５ｍ／ｓｅｃの風速で付与し、最終フィラメント繊度が１，０００デニールとなるように吐出量と放射速度を調節して放射した。このとき、凝固液の温度は１５℃とし、凝固係数が１となるようにした。凝固浴の濃度は水８０％、ＮＭＭＯ２０％に調整し、この後に水洗および乾燥過程を経て巻き取ってフィラメント原糸を得た。得られたフィラメントの物性を表１に示した。
(Example)
Example 1
Along with pulp powder having a polymerization degree (DPw) of 1,200 (α-cellulose content: 97%), NMMO. A 11.5% cellulose solution was prepared using 1H 2 0, 0.01% by weight of propyl gallate. A radiation nozzle having a diameter of 100 mm and 1000 orifices was used, and an orifice diameter of 150 μm was used. At this time, a nozzle having an orifice diameter / length ratio (L / D) of 4 was used. The solution discharged from the radiation nozzle (head temp .; 100 ° C.) is applied with cooling air at a temperature of 5 ° C. at a wind speed of 5 m / sec when passing through an air gap distance of 50 mm, and the final filament fineness is Radiation was performed by adjusting the discharge amount and the radiation speed so as to be 1,000 denier. At this time, the temperature of the coagulation liquid was set to 15 ° C. so that the coagulation coefficient was 1. The concentration of the coagulation bath was adjusted to 80% water and 20% NMMO, and then wound through water washing and drying processes to obtain a filament yarn. Table 1 shows the physical properties of the filaments obtained.
実施例２および３
実施例１と同じ製造方法によってライオセルマルチフィラメントを製造した。ただし、空気層で冷却空気の温度を１０℃および１５℃にそれぞれ調節して付与し、凝固係数が１となるように凝固浴の温度を２０℃および２５℃にそれぞれ調節した。得られたフィラメントの物性を表１に示した。
Examples 2 and 3
A lyocell multifilament was produced by the same production method as in Example 1. However, the temperature of the cooling air in the air layer was adjusted to 10 ° C. and 15 ° C., respectively, and the temperature of the coagulation bath was adjusted to 20 ° C. and 25 ° C. so that the coagulation coefficient was 1. Table 1 shows the physical properties of the filaments obtained.
実施例４〜６
実施例１と同じ製造方法によってライオセルマルチフィラメントを製造した。ただし、最終フィラメント繊度が１，５００デニールとなるように吐出量と放射速度を調節して放射した。このとき、凝固液の温度は、凝固係数が１となるようにした。得られたフィラメントの物性を表１に示した。
Examples 4-6
A lyocell multifilament was produced by the same production method as in Example 1. However, the discharge amount and the radiation speed were adjusted so that the final filament fineness was 1,500 denier. At this time, the temperature of the coagulation liquid was set so that the coagulation coefficient was 1. Table 1 shows the physical properties of the filaments obtained.
（比較例）
比較例１および２
実施例１と同じ製造方法を介してライオセルマルチフィラメントを製造した。ただし、凝固係数を０．７５と１．３３となるように、凝固浴の温度を２０℃および１５℃にそれぞれ調節した。得られたフィラメントの物性を表２に示した。
(Comparative example)
Comparative Examples 1 and 2
A lyocell multifilament was produced through the same production method as in Example 1. However, the temperature of the coagulation bath was adjusted to 20 ° C. and 15 ° C., respectively, so that the coagulation coefficients were 0.75 and 1.33. Table 2 shows the physical properties of the filaments obtained.
比較例３および４
実施例３および４と同じ製造方法によってライオセルマルチフィラメントを製造した。ただし、凝固係数が２．５および２．０となるようにし、凝固浴の温度を１０℃および１５℃にそれぞれ調節して放射した。得られたフィラメントの物性を表２に示した。
Comparative Examples 3 and 4
A lyocell multifilament was produced by the same production method as in Examples 3 and 4. However, the coagulation coefficient was set to 2.5 and 2.0, and the temperature of the coagulation bath was adjusted to 10 ° C. and 15 ° C., respectively. Table 2 shows the physical properties of the filaments obtained.
表１を参照すれば、凝固係数が１に調節される場合、断面変動率が減少するということが分かる。これに比べて、凝固係数が１から逸脱する場合、表２に示したように断面変動係数がそれぞれ２．７、２．９となり、モノフィラメント面積の不均一性が増加した。このとき、マルチフィラメントの強度低下はもちろん、断面変動係数が増加してモノフィラメントの均一性が低下したことが分かる。実施例１〜６は、凝固係数を１に調節して得られたライオセルマルチフィラメントの断面変動率を提示したものである。実際に凝固係数が０．８〜１に調節されれば、断面変動率が２．５以下となるライオセルマルチフィラメントが得られることが分かる。 Referring to Table 1, it can be seen that when the solidification coefficient is adjusted to 1, the cross-sectional variation rate decreases. In contrast, when the solidification coefficient deviates from 1, the cross-sectional variation coefficients were 2.7 and 2.9, respectively, as shown in Table 2, and the monofilament area non-uniformity increased. At this time, not only the strength of the multifilament is decreased, but also the cross-sectional variation coefficient is increased, and the uniformity of the monofilament is decreased. Examples 1 to 6 present the cross-sectional variation rates of lyocell multifilaments obtained by adjusting the coagulation coefficient to 1. It can be seen that if the solidification coefficient is actually adjusted to 0.8 to 1, a lyocell multifilament having a cross-sectional variation rate of 2.5 or less can be obtained.
Claims (6)
前記凝固浴で凝固させるステップは、凝固係数＝ＴＤ’／ＴＣ、およびＴＤ’＝ＴＤ＋ＴＡ−９０で表示される凝固係数が０．８〜１．３の範囲に調節され、前記において、ＴＤは放射溶液の温度、ＴＡは空気層に付与される冷却空気の温度、ＴＣは凝固浴の温度をそれぞれ示すことを特徴とするライオセルマルチフィラメントの製造方法。 Cellulose powder is uniformly dispersed, swelled, and dissolved in an NMMO solution to produce a radiation stock solution; the radiation stock solution is emitted to the air layer through a radiation nozzle; and the radiation stock solution emitted to the air layer is coagulated. A method for producing a lyocell multifilament comprising a step of coagulating in a bath, comprising:
It said step of solidifying in the coagulation bath, the coagulation factor = T D '/ T C, and T D' = T D + T clotting factor represented by A -90 is adjusted to a range of 0.8 to 1.3, in the, T D is the temperature of the radiation solution, T a is the temperature of the cooling air applied to the air layer, T C is the manufacturing method of the lyocell multifilament, characterized in that indicating the temperature of the coagulation bath respectively.
全体繊度 ８００〜３３００デニール；
それぞれのフィラメントの繊度 ０．５〜２．０デニール（ｄｅｎｉｅｒ）；
強度 ６．４〜８．３ｇ／ｄ、
切断伸度 ５．７〜７．１％、
モノフィラメントの断面変動係数 ２．５％以下。 A rio-cell multifilament for tire dip cord, which is manufactured by the method of claim 1 and has the following physical properties:
Total fineness 800-3300 denier;
Fineness of each filament 0.5-2.0 denier;
Strength 6.4-8.3 g / d,
Cutting elongation 5.7-7.1%,
Monofilament cross-sectional variation coefficient 2.5% or less.
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| KR1020060136132A KR100824980B1 (en) | 2006-12-28 | 2006-12-28 | Cellulose multi-filament with lower coefficient of variation of section diameter |
| PCT/KR2007/006410 WO2008082092A1 (en) | 2006-12-28 | 2007-12-10 | Process for producing cellulose multi-filament with lower coefficient of variation of section diameter |
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| EP (1) | EP2097562B1 (en) |
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- 2006-12-28 KR KR1020060136132A patent/KR100824980B1/en active IP Right Grant
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2007
- 2007-12-10 EP EP07851381A patent/EP2097562B1/en active Active
- 2007-12-10 US US12/521,362 patent/US20110003148A1/en not_active Abandoned
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10510333A (en) * | 1994-12-12 | 1998-10-06 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Solvent spun cellulose filament |
| JPH10505886A (en) * | 1995-01-10 | 1998-06-09 | コートールズ ファイバース（ホールディングス）リミティド | Manufacture of extruded articles |
| JP3852631B2 (en) * | 1997-05-29 | 2006-12-06 | 東洋紡績株式会社 | Regenerated cellulose fiber and method for producing the same |
| JP2003266510A (en) * | 2002-03-18 | 2003-09-24 | Toyobo Co Ltd | Method for manufacturing cellulose molded body |
| JP2004211277A (en) * | 2002-12-26 | 2004-07-29 | Hyosung Corp | Lyocell multifilament for tire cord and method of producing the same |
| JP2006188806A (en) * | 2004-12-30 | 2006-07-20 | Hyosung Corp | Method for producing cellulose fiber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016507412A (en) * | 2013-01-29 | 2016-03-10 | コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Reinforcing layer for articles made of elastomeric material, preferably for pneumatic vehicle tires, and pneumatic vehicle tires |
| JP2017528616A (en) * | 2014-09-30 | 2017-09-28 | コーロン インダストリーズ インク | Lyocell crimp fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4593676B2 (en) | 2010-12-08 |
| CN101578401B (en) | 2012-02-01 |
| KR100824980B1 (en) | 2008-04-28 |
| EP2097562A4 (en) | 2010-08-25 |
| CN101578401A (en) | 2009-11-11 |
| US20110003148A1 (en) | 2011-01-06 |
| EP2097562A1 (en) | 2009-09-09 |
| WO2008082092A1 (en) | 2008-07-10 |
| EP2097562B1 (en) | 2012-11-28 |
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