JPS63315608A - Polyester fiber - Google Patents
Polyester fiberInfo
- Publication number
- JPS63315608A JPS63315608A JP14763287A JP14763287A JPS63315608A JP S63315608 A JPS63315608 A JP S63315608A JP 14763287 A JP14763287 A JP 14763287A JP 14763287 A JP14763287 A JP 14763287A JP S63315608 A JPS63315608 A JP S63315608A
- Authority
- JP
- Japan
- Prior art keywords
- tmf
- pref
- polyester
- polyethylene terephthalate
- strength
- 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
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 40
- 229920000728 polyester Polymers 0.000 title claims abstract description 34
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000012779 reinforcing material Substances 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000009987 spinning Methods 0.000 description 17
- 229920001971 elastomer Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DUILGEYLVHGSEE-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1CO1 DUILGEYLVHGSEE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高強度で耐久性に優れ、特にゴム補強用素材
として好適なポリエステル繊維に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester fiber that has high strength and excellent durability and is particularly suitable as a rubber reinforcing material.
（従来の技術）
ポリエチレンテレフタレート及びこれを主体とするポリ
エステルからなる繊維は、優れた力学的。(Prior Art) Fibers made of polyethylene terephthalate and polyester mainly composed of polyethylene terephthalate have excellent mechanical properties.
熱的特性を有し、タイヤコード、■ベルトコンベアベル
トホース等の産業資材用素材として広く使用されている
。特にゴム補強用素材としての用途が最も大きな割合を
占めており、高強度で耐久性に優れているとともに、熱
収縮率、モジュラス等とのバランスの取れたポリエステ
ル繊維が要望されている。It has thermal properties and is widely used as a material for industrial materials such as tire cords and belt conveyor belt hoses. In particular, polyester fibers are used most often as rubber reinforcing materials, and there is a demand for polyester fibers that have high strength and excellent durability, as well as a well-balanced thermal shrinkage rate and modulus.
従来、高強度のポリエステル繊維を得る方法として９例
えば特公昭４１−７８９２号公報に見られるように、高
重合度のポリマーを用い、低応力で紡糸して分子配向を
抑制し、得られた未延伸糸をできるだけ高倍率で延伸す
る方法が良く知られている。Conventionally, as a method for obtaining high-strength polyester fibers9, for example, as seen in Japanese Patent Publication No. 41-7892, a polymer with a high degree of polymerization is used and the molecular orientation is suppressed by spinning with low stress. A method of drawing drawn yarn at as high a magnification as possible is well known.
しかし、この方法では高強度の繊維は得られるものの、
非晶部が高配向化するため、熱収縮率が太き（、耐久性
が十分でない繊維しか得られない。However, although this method yields high-strength fibers,
Because the amorphous portion is highly oriented, only fibers with a high heat shrinkage rate (and insufficient durability) can be obtained.
これに対して、比較的高重合度のポリマーを用い、高応
力で紡糸し、低倍率で延伸することにより、非晶部の配
向度を低くシ、熱収縮率が小さく。On the other hand, by using a polymer with a relatively high degree of polymerization, spinning at high stress, and stretching at low magnification, the degree of orientation of the amorphous portion is low, and the heat shrinkage rate is low.
耐久性の良好な繊維を得る方法が提案されている（特開
昭５３−５８０３２号等）。しかしながら、この方法で
は、ゴム補強用素材として十分な高強度の繊維を得るこ
とは困難である。A method for obtaining fibers with good durability has been proposed (Japanese Patent Application Laid-Open No. 58032/1983, etc.). However, with this method, it is difficult to obtain fibers with sufficient strength as a rubber reinforcing material.
また、ポリエステル繊維をゴム補強用素材として使用す
る場合、撚糸工程及びディップ工程（接着剤を付与し、
熱処理する工程）を通す必要があり、原糸性能は優れて
いても、これらの工程を経たディップコードの性能にお
いて満足できないことも多かった。In addition, when using polyester fiber as a rubber reinforcing material, twisting process and dipping process (applying adhesive,
It is necessary to undergo a heat treatment step), and even though the yarn performance is excellent, the performance of the dip cord that has gone through these steps is often unsatisfactory.
（発明が解決しようとする問題点）
本発明は、高強度で耐久性に優れているとともに、熱収
縮率、モジュラス等とのバランスの取れたポリエステル
繊維であって、ディップコードにした後も優れた性能を
示すポリエステル繊維を提供しようとするものである。(Problems to be Solved by the Invention) The present invention is a polyester fiber that has high strength and excellent durability, and has a well-balanced thermal shrinkage rate, modulus, etc., and has excellent properties even after being made into a dip cord. The aim is to provide polyester fibers that exhibit superior performance.
（問題点を解決するための手段） 本発明の構成は１次のとおりである。(Means for solving problems) The configuration of the present invention is as follows.
ポリエチレンテレフタレート又はこれを主体とするポリ
エステルからなる繊維であって５次の（ａ）〜（ｆｌの
特性を同時に満足するポリエステル繊維。A polyester fiber which is made of polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate, and which simultaneously satisfies the characteristics of the fifth order (a) to (fl).
（ａｌ固有粘度 ： ０．９１以上（好ましくは１．
０以上）（ｂ）強 度 ：８．０ｇ／ｄ以上（好ま
しくは８．４ｇ／ｄ以上）
（Ｃ） Ｅ ｚ、 ｚｓ ： ４．５％以下（好
ましくは３．５％以下）
＋ｄ）△Ｈｍｆ ： １１．５ｃａｌ／ ｇ以上
（好ましくは１２．０ｃａｌ／ ｇ以上
（ｅ）Ｔｍｆ−ＴｍＦ ：２０℃以上（好ましくは２
２℃以上）
（ｆｌ非晶配向度ｆａ ： ０．７５以下ここで、Ｅ２
．２５は荷重２．２５ ｇ ／ ｄ時の伸度。(al intrinsic viscosity: 0.91 or more (preferably 1.
0 or more) (b) Strength: 8.0 g/d or more (preferably 8.4 g/d or more) (C) E z, zs: 4.5% or less (preferably 3.5% or less) +d)△ Hmf: 11.5 cal/g or more (preferably 12.0 cal/g or more (e) Tmf-TmF: 20°C or more (preferably 2
2°C or higher) (fl amorphous orientation degree fa: 0.75 or lower, where E2
．． 25 is the elongation at a load of 2.25 g/d.
ΔＨｍｆは示差走査熱量計（ＤＳＣ）における融解ピー
クの熱量。ΔHmf is the calorific value of the melting peak in differential scanning calorimeter (DSC).
Ｔｍｆは０．０５ ｇ ／ ｄの緊張状態で、 ＤＳＣ
で測定された融点。Tmf is 0.05 g/d under tension, DSC
Melting point measured at.
ＴｍＦは無緊張状態で、ＤＳＣで測定された融点。TmF is the melting point measured by DSC under stress-free conditions.
本発明におけるポリエステルは、ポリエチレンテレフタ
レート及びこれを主体とするポリエステルであり、各種
ジカルボン酸成分及びグリコール成分が１０モル％程度
まで共重合されていてもよい。The polyester in the present invention is polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate, and may be copolymerized with various dicarboxylic acid components and glycol components up to about 10 mol %.
そして、耐熱性を向上させるため、エポキシ化合物、カ
ーボネート化合物、カルボジイミド化合物。And epoxy compounds, carbonate compounds, and carbodiimide compounds to improve heat resistance.
イミノエーテル化合物等を反応させて末端カルボキシル
基量を低下させたものが好ましい。Preferably, the amount of terminal carboxyl groups is reduced by reacting with an iminoether compound or the like.
次に１本発明のポリエステル繊維の特性値について説明
する。Next, the characteristic values of the polyester fiber of the present invention will be explained.
まず９本発明のポリエステル繊維は、フェノールとテト
ラクロルエタンとの等重量混合溶媒を使用し、温度２０
℃で測定した固有粘度が０．９１以上の高分子量のもの
でなければならなず、特に固有粘度１．０以上のものが
好ましい。これは繊維が高強度を示すとともに、耐久性
向上に関与するタイ分子（ｔｉｅ ｍｏｌｅｃｕｌｅ）
の形成を増大させるために必要な要件である。First, the polyester fiber of the present invention is produced using a mixed solvent of equal weight of phenol and tetrachloroethane at a temperature of 20°C.
It must have a high molecular weight and have an intrinsic viscosity of 0.91 or more when measured at °C, and those with an intrinsic viscosity of 1.0 or more are particularly preferred. This is because the fiber exhibits high strength and also contains tie molecules that are involved in improving durability.
This is a necessary requirement to increase the formation of
強度は、ＪＩＳ Ｌ−１０１７の方法に準じて測定した
値。The strength is a value measured according to the method of JIS L-1017.
すなわち、荷重−伸長試験における切断時の荷重を、測
定前の実測繊度で除した値であり、８．０ｇ／ｄ以上、
好ましくは８．４ｇ／ｄ以上であることが必要である。In other words, it is the value obtained by dividing the load at the time of cutting in the load-elongation test by the actual fineness before measurement, which is 8.0 g / d or more,
Preferably, it needs to be 8.4 g/d or more.
またｌ Ｅ２．２５は１強度測定時の荷重−伸長曲線に
おいて、荷重２．２５ ｇ ／ ｄの時点での伸度を示
し。In addition, lE2.25 indicates the elongation at a load of 2.25 g/d in the load-elongation curve during 1 strength measurement.
コンピュータ処理により求められ、４．５％以下。Determined by computer processing, 4.5% or less.
好ましくは３．５％以下であることが必要である。It is preferably 3.5% or less.
この値が小さいことは、中間モジュラスが高いことを意
味し、ディップ処理工程におけるディップ伸び現象を小
さくシ、高強力、高ヤング率を発現させるのに必須の要
件である。A small value means a high intermediate modulus, which is an essential requirement for minimizing the dip elongation phenomenon in the dip treatment process and achieving high strength and Young's modulus.
ΔＨｍｆは、パーキンエルマー社製示差走査熱量計ＤＳ
Ｃ−２Ｃ型を使用し、試料（原糸）重量３ｍｇｒ 昇温
速度２０℃／分１窒素雰囲気下で測定したもので。ΔHmf is a PerkinElmer differential scanning calorimeter DS
Measurements were made using C-2C type under a nitrogen atmosphere at a sample (original yarn) weight of 3 mgr and a heating rate of 20°C/min.
１１．５ｃａｌ／ ｇ以上、好ましくは１２．０ｃａｌ
／ ｇ以上であることが必要である。この値は、繊維の
結晶化の程度に依存し、結晶部を主とした繊維の微細構
造の完成度を示すものであって、この値が大きいことは
繊維が高強力、高モジュラス及び高耐久性を有すること
を示すものである。11.5 cal/g or more, preferably 12.0 cal
/ g or more. This value depends on the degree of crystallization of the fiber and indicates the completeness of the fiber's microstructure, which is mainly composed of crystalline parts. A large value indicates that the fiber has high strength, high modulus, and high durability. This indicates that the person has a sexual nature.
繊維の融点（Ｔｍｆ及びＴ ｍＦ）は、原糸のモノフィ
ラメント３ｍｇを、長さ１０ｍｍ、幅３１醜、厚さ０．
５１の銅板に、０．０５ｇ／ｄの荷重下又は無荷重下で
。The melting points (Tmf and TmF) of the fibers are as follows: 3 mg of raw monofilament is 10 mm long, 31 mm wide, and 0.0 mm thick.
51 copper plate under a load of 0.05 g/d or under no load.
５１１幅に巻き付け、試料の先端を結び、余剰の銅板を
切り落とした後、ΔＨｍｆの測定と同一条件で測定した
値である。なお、 ＤＳＣのレファレンス側のセルには
同形状の銅板を挿入しておく。This is a value measured under the same conditions as the measurement of ΔHmf after winding the sample to a width of 511 mm, tying the tip of the sample, and cutting off the excess copper plate. Note that a copper plate of the same shape is inserted into the reference side cell of the DSC.
ＴｍＦは通常の融点であるが、Ｔｍｆはタイ分子に起因
するスーパーヒーティング性を示す値であり。TmF is a normal melting point, but Tmf is a value indicating superheating property due to tie molecules.
本発明の繊維はＴｍｆ−ＴｍＦ （＝ΔＴ）の値が２０
℃以上、好ましくは２２°Ｃ以上であることを特徴とす
るものである。ΔＴの値はタイ分子形成量の重要な指標
をなすものであり、この値が大きい繊維はタイ分子が繊
維の結晶部と非晶部との連結を強固にすることから１特
に結晶と非晶との境界で起こる破断現象の防止に有効に
寄与し、結果として高強力、高耐久性を示すことになる
。The fiber of the present invention has a Tmf-TmF (=ΔT) value of 20
℃ or higher, preferably 22°C or higher. The value of ΔT is an important indicator of the amount of tie molecules formed, and fibers with a large value have a strong connection between the crystalline and amorphous parts of the fiber. This effectively contributes to the prevention of the rupture phenomenon that occurs at the boundary with the steel, and as a result, it exhibits high strength and high durability.
また、非晶配向度ｆａは、複屈折Δｎ、結晶結晶化度Ｘ
高結晶有複屈折Δｎ ｃ（＝０．２２０） 、非晶の固
有複屈折Δｎａ（＝０．２７５）及び結晶配列関数ｆｃ
から次式で求められる。In addition, the amorphous orientation fa is the birefringence Δn, the crystallinity X
Highly crystalline birefringence Δn c (=0.220), amorphous intrinsic birefringence Δna (=0.275) and crystal orientation function fc
It can be obtained from the following formula.
ここで、Δｎは１通常の偏光顕微鏡を使用するベレンク
コンペンセーター法で求められ、ｆｃは。Here, Δn is determined by the Berenck compensator method using a normal polarizing microscope, and fc is.
広角Ｘ線回折で測定された平均配向角、すなわち回折パ
ターンの平均角度中について解析して得られる平均配向
角θを用い２次式で求められる。It is determined by a quadratic equation using the average orientation angle measured by wide-angle X-ray diffraction, that is, the average orientation angle θ obtained by analyzing the average angle of the diffraction pattern.
ｆｃ ＝ １／ ２ （ａｃｏｓ２θ−１）Ｘは、リグ
ロインと四塩化炭素とからなる密度勾配管法で、２５℃
で測定された試料の密度ρ、結晶密度ρｃ（＝ １．４
５５ｇ／ ｃｎり及び非晶密度ρａ（＝１．３３５ｇ／
ｃｒＡから次式で求められる。fc = 1/2 (acos2θ-1)X is a density gradient tube method consisting of ligroin and carbon tetrachloride at 25°C.
The density ρ of the sample measured at ρ, the crystal density ρc (= 1.4
55g/cn and amorphous density ρa (=1.335g/
It is determined from crA using the following formula.
ｆａは、ポリエステル繊維をゴム補強材とじて用いたと
き１繰り返される伸長圧縮疲労に対する耐久性に関与す
るもので１本発明のポリエステル繊維は、ｆａが０．７
５以下でなければならない。fa is involved in the durability against elongation and compression fatigue that is repeated once when polyester fibers are used as a rubber reinforcing material.The polyester fiber of the present invention has an fa of 0.7.
Must be 5 or less.
なお５本発明のポリエステル繊維のｆｃは、特に限定さ
れるものではないが、 ０．９４程度の値を示す。また
、Ｘの値は、 ０．４０〜０．４５程度である。Note that the fc of the polyester fiber of the present invention is not particularly limited, but exhibits a value of about 0.94. Moreover, the value of X is about 0.40 to 0.45.
上記の各特性を同時に満足する本発明のポリエステル繊
維は、高強度で耐久性に優れているとともに、熱収縮率
、モジュラス等とのバランスの取れたポリエステル繊維
であって、ディップコードにした後も優れた性能を示す
ポリエステル繊維である。The polyester fiber of the present invention, which satisfies each of the above characteristics at the same time, is a polyester fiber that has high strength and excellent durability, and has a well-balanced thermal shrinkage rate, modulus, etc., and even after being made into a dip cord. It is a polyester fiber that exhibits excellent performance.
次に５本発明のポリエステル繊維の製造法について説明
する。Next, the method for manufacturing polyester fiber of the present invention will be explained.
まず１重縮合装置からの高粘度の溶融ポリエステルを直
接紡糸機に導くか１あるいは一旦チツブ化した高粘度の
ポリエステルをエクストルーダー等により溶融して紡糸
機に導き、常法により紡出し、７００〜５０００ｍ／ｍ
ｉｎ程度の速度で引き取る。この際３通常、紡糸時の粘
度低下を見込んで、目的とする繊維の固有粘度よりも若
干高い粘度のポリエステルを使用する。First, the high viscosity molten polyester from the single polycondensation device is directly introduced into the spinning machine, or the high viscosity polyester that has been made into a single layer is melted using an extruder, etc. and introduced into the spinning machine, and then spun using a conventional method. 5000m/m
Pick it up at a speed of about 100 mph. In this case, 3 usually a polyester with a viscosity slightly higher than the intrinsic viscosity of the target fiber is used in anticipation of a decrease in viscosity during spinning.
紡糸に際しては、冷却を均一にし、糸条の均斉度を高め
るため、糸条のフィラメント数、単糸デニール、紡糸口
金の吐出孔の孔径及び配列、紡糸温度、加熱フードの長
さ、冷却ゾーンの長さ、冷却風の温度、速度、吹きつけ
方法（円周吹きつけ又は横吹きつけ）等を、ポリエステ
ルの固有粘度や紡糸速度との関連において、最適な組み
合わせとすることが必要である。During spinning, in order to uniformly cool the yarn and improve the uniformity of the yarn, the number of filaments in the yarn, the single yarn denier, the diameter and arrangement of the spinneret discharge holes, the spinning temperature, the length of the heating hood, and the size of the cooling zone are controlled. It is necessary to optimally combine the length, cooling air temperature, speed, blowing method (circumferential blowing or horizontal blowing), etc. in relation to the intrinsic viscosity of the polyester and the spinning speed.
本発明のポリエステル繊維を得るには、高応力紡糸法を
採用することが必要で、紡出糸の応力が０゜０５〜１．
０ｇ／ｄとなるようにすることが望ましい。紡出糸のの
応力を高める方法としては、紡糸速度（引取速度）を太
き（する方法や紡出糸の冷却を速める方法等が採用され
る。そして、未延伸糸の複屈折が１５ Ｘ １０−３以
上、好ましくは２５Ｘ１０−’〜７０ Ｘ １０− ’
となるようにする。In order to obtain the polyester fiber of the present invention, it is necessary to employ a high stress spinning method, and the stress of the spun yarn is 0°05 to 1.0°.
It is desirable to set it to 0 g/d. As a method for increasing the stress of the spun yarn, methods such as increasing the spinning speed (take-up speed) or speeding up the cooling of the spun yarn are adopted. 10-3 or more, preferably 25X10-' to 70X10-'
Make it so that
次いで、この未延伸糸を加熱ローラ、加熱プレート、ス
チームジェット等により加熱しながら。Next, this undrawn yarn is heated using a heating roller, a heating plate, a steam jet, etc.
１段又は多段で延伸する。延伸は、紡糸に連続して行う
スピンドロー法でも、一旦未延伸糸を巻き取った後延伸
する二工程法のいずれの方法によってもよい。延伸倍率
は、紡糸時の紡糸応力と延伸温度及び時間の組み合わせ
により最適な条件が選ばれる。Stretch in one stage or in multiple stages. Stretching may be carried out by either a spin-draw method performed continuously after spinning, or a two-step method in which the undrawn yarn is once wound up and then stretched. The optimum stretching ratio is selected depending on the combination of spinning stress during spinning, stretching temperature and time.
（実施例） 次に１本発明を実施例により具体的に説明する。(Example) Next, one embodiment of the present invention will be specifically explained using examples.
実施例
第１表に示した固有粘度のポリエチレンテレフタレート
チップにＮ−グリシジルフタルイミドを第１表に示した
量で添加し／エクストルーダー型溶融紡糸機に供給し、
紡糸温度３００〜３１０℃（この範囲で最適温度に設定
）で、直径０ 、６ ｘｘの吐出孔を２５２個有する紡
糸口金を用いて紡出し、雰囲気温度周方向から吹きつけ
て冷却し、オイリングローラで紡糸油剤を付与した後１
８５℃に加熱された引取ローラで、 ２０００ｍ ／
ｍ ｉ ｎの速度で引き取り、第１表に示す複屈折の未
延伸糸を得た。 （この際の紡糸応力は、 ０．０８〜
０．２０ｇ／ｄの範囲であった。）なお、未延伸糸の複
屈折は、引取ローラを非加熱にして、これに未延伸糸を
巻きつけて試料を採取して測定したものである。Example N-glycidyl phthalimide was added in the amount shown in Table 1 to polyethylene terephthalate chips having an intrinsic viscosity shown in Table 1, and the chips were fed to an extruder type melt spinning machine.
Spinning is performed at a spinning temperature of 300 to 310°C (set to the optimum temperature within this range) using a spinneret having 252 discharge holes with diameters of 0 and 6 xx, cooled by blowing from the circumferential direction at the ambient temperature, and After applying the spinning oil in 1
2000m/2000m with a take-off roller heated to 85℃
The yarn was taken off at a speed of min to obtain an undrawn yarn with birefringence shown in Table 1. (The spinning stress at this time is 0.08~
It was in the range of 0.20 g/d. ) The birefringence of the undrawn yarn was measured by taking a sample by winding the undrawn yarn around the take-up roller without heating it.
そして、未延伸糸を巻き取ることなく、前記加熱引取ロ
ーラと非加熱の第１ネルソンローラとの間で延伸倍率１
．４５で第１段延伸し５次いで第１ネルソンローラと２
４０℃に加熱された第２不ルソンローラとの間で、４０
０℃のスチームジェット装置を通して１第２段延伸し、
第２ネルソンローラと１００℃に加熱された弛緩ローラ
との間で、第１表に示す弛緩率で弛緩しながら巻き取っ
た。なお、第２段延伸倍率は、弛緩率を考慮して第１表
に示した全延伸倍率となる倍率とした。Then, without winding up the undrawn yarn, the drawing ratio is 1 between the heated take-off roller and the unheated first Nelson roller.
．． First stage stretching with 45, then first nelson roller and 2
40°C between the second Furson roller heated to 40°C.
1 second stage stretching through a steam jet device at 0°C;
The film was wound up between a second Nelson roller and a relaxation roller heated to 100° C. while being relaxed at the relaxation rate shown in Table 1. Note that the second stage stretching ratio was set to the total stretching ratio shown in Table 1 in consideration of the relaxation rate.
得られた１０００ｄ／２５２ ｆの延伸糸（原糸）の物
性を第１表に示す。Table 1 shows the physical properties of the obtained 1000 d/252 f drawn yarn (original yarn).
なお、延伸糸の弛緩率を変えることによって生じるデニ
ール変化は１吐出量を調整することにより調整した。得
られた延伸糸の末端カルボキシル基量は、すべて９．５
〜１０．８ ｇ ｅ ｑ ／１０’ ｇポリマーの範囲
であった。Note that the denier change caused by changing the relaxation rate of the drawn yarn was adjusted by adjusting the discharge amount. The terminal carboxyl group content of the drawn yarns obtained was all 9.5.
~10.8 g eq /10'g polymer.
また、この原糸に１ リング撚糸機によりＺ方向に４９
回／１０ｃ＋ｏの下撚をかけ１次いで２本を合糸しなか
らＳ方向に４９回／１０印の上撚をかけて生コードを製
造し１次いで、リッッラー社製シングルディソビングマ
シンを使用してディップ処理し、ディップコードとした
。In addition, this yarn is twisted by 49 in the Z direction using a 1-ring twisting machine.
After twisting 10 times/10 c+o, first, then doubling the two strands, then twisting 49 times/10 marks in the S direction to produce a raw cord, and then using a single dissolving machine made by Riller. It was then subjected to dip treatment and made into a dip cord.
なお、ディップ処理の条件及びディップコードの性能の
評価法は１次のとおりである。Note that the conditions for dipping treatment and the method for evaluating the performance of the dip code are as follows.
ディップ几 の条
■ディップ液
レゾルシンーホルマリンーゼンタンクラテソクス液（レ
ゾルシンとホルムアルデヒドとのモル比１：１．２の反
応物１重量部に対して、固形分として４．３重量部のラ
テックスを混合した濃度２０重量％の液で、Ｎａ０Ｉ−
１でｐＨ９，５に調整したもの）８３重量部とバルカボ
ンドＥ １７重量部とからなる混合液。Dip solution ■ Dip liquid Resorcinol-Formalin-Zentan Crateox solution (4.3 parts by weight of latex as a solid content for 1 part by weight of the reactant with a molar ratio of resorcin and formaldehyde of 1:1.2) The mixed solution with a concentration of 20% by weight is Na0I-
A mixed solution consisting of 83 parts by weight of Vulkabond E (adjusted to pH 9.5 in Example 1) and 17 parts by weight of VALKABOND E.
ここで、ゼンタソクラテックスは、ゼネラルタイヤ社の
商品名で、ブタジェン−スチレン−ビニルビリジン系ラ
テックスでり、バルカボンドＥは。Here, Zentasocratex is a trade name of General Tire Co., Ltd., and is a butadiene-styrene-vinylpyridine-based latex, and Vulkabond E is a product name of General Tire Company.
バルナックス社の商品名で、２，６−ビス（２’、４’
−ジヒドロキシフェニル−４−クロロフェノールの固形
分濃度２０重量％のアンモニア水溶液である。It is a product name of Barnax Co., Ltd., and is a 2,6-bis (2', 4'
This is an ammonia aqueous solution of -dihydroxyphenyl-4-chlorophenol with a solid content concentration of 20% by weight.
■ディップ処理の乾燥、熱処理条件
乾燥ゾーン ８０℃×３０秒
キユアリングゾーン ２４０℃×８０秒×２回ディップ
張力 ０．５ｋｇ／コード（４、５ｋｇ中間伸度
４．０％に設定）ディップコードの 箭
■引張特性
ＪＩＳ Ｌ １０１７法に準じて測定した。ただし、熱
収縮率は、１８０℃×３０分の条件で測定した。■Drying and heat treatment conditions for dip treatment Drying zone: 80℃ x 30 seconds Curing zone: 240℃ x 80 seconds x 2 times Dip tension: 0.5kg/cord (4, 5kg intermediate elongation set at 4.0%) Dip cord - Tensile properties Measured according to JIS L 1017 method. However, the heat shrinkage rate was measured under the conditions of 180°C x 30 minutes.
■疲労性
ＪＩＳ Ｌ １０１７． グツドイヤー法マロリーチュ
ーブテスト法に準じて、チューブテスターの角度６０度
及び９０度１回転速度３５Ｑｒｐｍ、 ３０分反転下に
測定した。■Fatigue JIS L 1017. According to the Goodyear method and Mallory tube test method, the measurement was carried out using a tube tester at angles of 60 degrees and 90 degrees, at a rotational speed of 35 Qrpm, and with inversion for 30 minutes.
角度が６０度のときは、３時間疲労させた後、ゴムから
注意深くコードを取り出し、引張強力を測定して１強力
保持率を求めた。When the angle was 60 degrees, after 3 hours of fatigue, the cord was carefully removed from the rubber, the tensile strength was measured, and the 1 strength retention rate was determined.
また、角度が９０度のときは、疲労によりチューブが破
裂するまでの時間（分）を測定した。Further, when the angle was 90 degrees, the time (minutes) until the tube burst due to fatigue was measured.
ディップコードの性能を第１表に示す。The performance of the dip cord is shown in Table 1.
第１表の結果から分かるように１本発明で規定する各特
性を同時に満足するポリエステル繊維は。As can be seen from the results in Table 1, there is one polyester fiber that simultaneously satisfies each of the characteristics specified in the present invention.
ゴム補強用素材としての性能を直接表すディップコード
性能において１強度、熱収縮率、モジュラスと耐疲労性
で代表される耐久性等とのトークルハランスに優れた。In terms of dip cord performance, which directly indicates the performance as a rubber reinforcing material, it has excellent torque resistance in terms of strength, heat shrinkage rate, modulus, and durability represented by fatigue resistance.
ゴム補強用素材として好ましいものであり、特に１１ｍ
５〜８のものは著しく性能の優れたものである。It is preferable as a material for rubber reinforcement, especially 11m
Those with scores 5 to 8 have extremely excellent performance.
第１表
本コード取り出し不可能
庄 ＋１ｌＮ−グリＺ尋フ外イ：Ｆｍｔ量の単位は重量
％である。Table 1: Main code cannot be removed.
ｔ２Ｈｂｌ〜８力慣施例で、１ｍ９〜１１は比較例、
１ｍ１２は市販の高強力タイプポリエステル繊維の列を
示す参考例である。t2Hbl~8 force conventional example, 1m9~11 is a comparative example,
1 m12 is a reference example showing a row of commercially available high-strength type polyester fibers.
（発明の効果）
本発明によれば、高強度で耐久性に優れているとともに
、熱収縮率、モジュラス等とのバランスの取れたポリエ
ステル繊維であって、ディップコードにした後も優れた
性能を示すゴム補強用素材として好適なポリエステル繊
維が提供される。(Effects of the Invention) According to the present invention, the polyester fiber has high strength and excellent durability, and has a well-balanced thermal shrinkage rate, modulus, etc., and has excellent performance even after being made into a dip cord. Polyester fibers suitable as rubber reinforcing materials are provided.
Claims (1)
るポリエステルからなる繊維であって、次の（ａ）〜（
ｆ）の特性を同時に満足するポリエステル繊維。 （ａ）固有粘度：０．９１以上 （ｂ）強度：８．０ｇ／ｄ以上 （ｃ）Ｅ＿２＿．＿２＿５：４．５％以下 （ｄ）△Ｈｍｆ：１１．５ｃａｌ／ｇ以上 （ｅ）Ｔｍｆ−ＴｍＦ：２０℃以上 （ｆ）非晶配向度ｆａ：０．７５以下 ここで、Ｅ＿２＿．＿２＿５は荷重２．２５ｇ／ｄ時の
伸度、△Ｈｍｆは示差走査熱量計（ＤＳＣ）における融
解ピークの熱量、 Ｔｍｆは０．０５ｇ／ｄの緊張状態で、ＤＳＣで測定さ
れた融点、 ＴｍＦは無緊張状態で、ＤＳＣで測定された融点。(1) A fiber made of polyethylene terephthalate or a polyester mainly composed of polyethylene terephthalate, which has the following properties (a) to (
A polyester fiber that simultaneously satisfies the characteristics f). (a) Intrinsic viscosity: 0.91 or more (b) Strength: 8.0 g/d or more (c) E_2_. _2_5: 4.5% or less (d) ΔHmf: 11.5 cal/g or more (e) Tmf-TmF: 20°C or more (f) Amorphous orientation fa: 0.75 or less, where E_2_. _2_5 is the elongation at a load of 2.25 g/d, ΔHmf is the heat value of the melting peak in a differential scanning calorimeter (DSC), Tmf is the melting point measured by DSC under tension of 0.05 g/d, TmF is Melting point measured by DSC under tension.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14763287A JPS63315608A (en) | 1987-06-12 | 1987-06-12 | Polyester fiber |
| EP88305370A EP0295147B1 (en) | 1987-06-12 | 1988-06-13 | High strength polyester yarn |
| DE19883883301 DE3883301T2 (en) | 1987-06-12 | 1988-06-13 | Polyester yarn with high strength. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14763287A JPS63315608A (en) | 1987-06-12 | 1987-06-12 | Polyester fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63315608A true JPS63315608A (en) | 1988-12-23 |
Family
ID=15434720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14763287A Pending JPS63315608A (en) | 1987-06-12 | 1987-06-12 | Polyester fiber |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0295147B1 (en) |
| JP (1) | JPS63315608A (en) |
| DE (1) | DE3883301T2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2569720B2 (en) * | 1988-05-09 | 1997-01-08 | 東レ株式会社 | Industrial polyester fiber, method for producing the same, and processing cord for tire cord |
| US5067538A (en) * | 1988-10-28 | 1991-11-26 | Allied-Signal Inc. | Dimensionally stable polyester yarn for highly dimensionally stable treated cords and composite materials such as tires made therefrom |
| DE69031949T2 (en) * | 1989-08-04 | 1998-08-06 | Kao Corp | POLYESTER FIBER |
| ID846B (en) * | 1991-12-13 | 1996-08-01 | Kolon Inc | FIBER YARN, POLYESTER TIRE THREAD AND HOW TO PRODUCE IT |
| JP6539329B2 (en) * | 2017-11-15 | 2019-07-03 | 旭化成株式会社 | Ultra-high molecular weight polyethylene fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116414A (en) * | 1982-12-24 | 1984-07-05 | Unitika Ltd | Polyester yarn for reinforcing rubber |
| JPS6088120A (en) * | 1983-10-20 | 1985-05-17 | Asahi Chem Ind Co Ltd | Polyester yarn |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966867A (en) * | 1968-08-31 | 1976-06-29 | Akzona Incorporated | Manufacture of unique polyethylene terephthalate fiber |
| US4070432A (en) * | 1975-02-13 | 1978-01-24 | Allied Chemical Corporation | Production of low shrink polyester fiber |
| JPS57154410A (en) * | 1981-03-13 | 1982-09-24 | Toray Ind Inc | Polyethylene terephthalate fiber and its production |
| US4690866A (en) * | 1984-07-09 | 1987-09-01 | Teijin Limited | Polyester fiber |
-
1987
- 1987-06-12 JP JP14763287A patent/JPS63315608A/en active Pending
-
1988
- 1988-06-13 DE DE19883883301 patent/DE3883301T2/en not_active Revoked
- 1988-06-13 EP EP88305370A patent/EP0295147B1/en not_active Revoked
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59116414A (en) * | 1982-12-24 | 1984-07-05 | Unitika Ltd | Polyester yarn for reinforcing rubber |
| JPS6088120A (en) * | 1983-10-20 | 1985-05-17 | Asahi Chem Ind Co Ltd | Polyester yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0295147B1 (en) | 1993-08-18 |
| DE3883301T2 (en) | 1993-12-09 |
| DE3883301D1 (en) | 1993-09-23 |
| EP0295147A2 (en) | 1988-12-14 |
| EP0295147A3 (en) | 1989-10-11 |
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