JPH09157402A - Heat-shrinkable tube, its production and utilization thereof - Google Patents
Heat-shrinkable tube, its production and utilization thereofInfo
- Publication number
- JPH09157402A JPH09157402A JP25649996A JP25649996A JPH09157402A JP H09157402 A JPH09157402 A JP H09157402A JP 25649996 A JP25649996 A JP 25649996A JP 25649996 A JP25649996 A JP 25649996A JP H09157402 A JPH09157402 A JP H09157402A
- Authority
- JP
- Japan
- Prior art keywords
- tube
- heat
- polyphenylene sulfide
- shrinkable
- tube according
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 35
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 35
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 6
- 239000011147 inorganic material Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 description 16
- 239000010419 fine particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- -1 polyphenylene Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical class [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリフェニレンス
ルフィドより実質的に形成された熱収縮性チューブ、そ
の製造方法およびその利用に関する。さらに詳しくは、
本発明は熱収縮性を有し、制限収縮下における熱処理後
は極めて優れた耐熱性、耐燃焼性および耐薬品性を有
し、汎用電気絶縁材料や発熱体被覆材料等の利用価値を
有するポリフェニレンスルフィドよりなる熱収縮性チュ
ーブ、その製造方法およびその利用に関する。TECHNICAL FIELD The present invention relates to a heat-shrinkable tube substantially formed of polyphenylene sulfide, a method for producing the same, and use thereof. For more information,
INDUSTRIAL APPLICABILITY The present invention is polyphenylene having heat shrinkability, having extremely excellent heat resistance, combustion resistance and chemical resistance after heat treatment under limited shrinkage, and having utility value as a general-purpose electric insulating material or heating element coating material. TECHNICAL FIELD The present invention relates to a heat-shrinkable tube made of sulfide, a method for producing the same, and use thereof.
【０００２】[0002]
【従来の技術】コンデンサー用途等の汎用熱収縮性チュ
ーブ状電気絶縁材料としては、従来ポリ塩化ビニルチュ
ーブおよびポリエチレンテレフタレート（ＰＥＴ）チュ
ーブが知られている。しかし、これらの材料の耐熱性は
それぞれ１０５℃および１２０℃が限界である。一方、
最近環境対策として代替フロンの使用等により冷機用途
等において１３０℃以上の耐熱性を持つ汎用熱収縮性チ
ューブが望まれていた。さらに、汎用チューブ状耐熱材
料としてのＦ種（１５５℃以上連続使用可能）のものは
なく、該材料に対する業界からの要望が強かった。2. Description of the Related Art Polyvinyl chloride tubing and polyethylene terephthalate (PET) tubing are conventionally known as general-purpose heat-shrinkable tubular electrical insulating materials for use in capacitors and the like. However, the heat resistance of these materials is limited to 105 ° C and 120 ° C, respectively. on the other hand,
Recently, as an environmental measure, a general-purpose heat-shrinkable tube having heat resistance of 130 ° C. or higher has been desired in applications such as cooling machines by using alternative CFCs. Further, there is no general-purpose tubular heat-resistant material of type F (which can be continuously used at 155 ° C. or higher), and there has been a strong demand from the industry for the material.
【０００３】[0003]
【発明が解決しようとする課題】本発明の第１の目的
は、ポリフェニレンスルフィドより実質的になる熱収縮
性チューブを提供することにある。本発明の第２の目的
は、ポリフェニレンスルフィド樹脂が有している耐熱
性、耐燃焼性、電気特性、耐薬品性を生かすことができ
かつこれら特性を被覆材料あるいは保護材料として利用
することができる熱収縮性チューブを提供することにあ
る。本発明の第３の目的は、ポリフェニレンスルフィド
より実質的になる熱収縮性チューブの工業的に有利な製
造方法を提供することにある。本発明の他の目的は、前
記熱収縮性を利用して種々の製品を被覆あるいは保護し
た無機材料製品を提供することにある。SUMMARY OF THE INVENTION A first object of the present invention is to provide a heat-shrinkable tube which is substantially made of polyphenylene sulfide. The second object of the present invention is to utilize the heat resistance, combustion resistance, electrical characteristics and chemical resistance of the polyphenylene sulfide resin and to utilize these characteristics as a coating material or protective material. To provide a heat-shrinkable tube. A third object of the present invention is to provide an industrially advantageous method for producing a heat-shrinkable tube consisting essentially of polyphenylene sulfide. Another object of the present invention is to provide an inorganic material product in which various products are coated or protected by utilizing the heat shrinkability.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、前記本
発明の目的は、ポリフェニレンスルフィドより実質的に
形成される熱収縮性チューブによって達成される。ま
た、本発明によれば、本発明の他の目的は、ポリフェニ
レンスルフィドより実質的に形成される未延伸チューブ
を、８５〜１０５℃の温度で長さ方向に１.０５〜４.５
倍かつ長さ方向に対する直角方向（半径方向）に１.３
〜４.５倍延伸することを特徴とするポリフェニレンス
ルフィドより実質的に形成される熱収縮性チューブの製
造方法によって達成される。さらに、本発明によれば、
さらに他の目的は、ポリフェニレンスルフィドより実質
的に形成される熱収縮性チューブの熱収縮により表面が
被覆された無機材料製品が提供される。According to the present invention, the above-mentioned objects of the present invention are achieved by a heat-shrinkable tube formed substantially from polyphenylene sulfide. Further, according to the present invention, another object of the present invention is to provide an unstretched tube substantially formed of polyphenylene sulfide at a temperature of 85 to 105 ° C. in a longitudinal direction of 1.05 to 4.5.
Double and 1.3 in the direction perpendicular to the length direction (radial direction)
It is achieved by a method for producing a heat-shrinkable tube substantially formed from polyphenylene sulfide, which is characterized by stretching ~ 4.5 times. Furthermore, according to the present invention,
Still another object is to provide an inorganic material product whose surface is coated by heat shrinkage of a heat shrinkable tube formed substantially from polyphenylene sulfide.
【０００５】以下、本発明についてさらに詳細に説明す
る。本発明によって提供されるポリフェニレンスルフィ
ドより実質的になる熱収縮性チューブ（以下、これを単
に“熱収縮性ＰＰＳチューブ”と略称することがある）
は、熱処理、例えば１００℃の空気雰囲気下あるいは熱
水中において収縮し、長さ方向および／または長さ方向
に対する直角方向に長さあるいは円周が短くなる。The present invention will be described in more detail below. A heat-shrinkable tube consisting essentially of polyphenylene sulfide provided by the present invention (hereinafter, this may be simply referred to as "heat-shrinkable PPS tube").
Undergoes heat treatment, for example, contraction in an air atmosphere at 100 ° C. or in hot water, and the length or circumference is shortened in the length direction and / or the direction perpendicular to the length direction.
【０００６】本発明の熱収縮性ＰＰＳチューブは、長さ
方向および長さ方向に対する直角方向（“径方向”とい
う）の熱収縮率（％）が２０〜１００％、好ましくは２
５〜８０％の範囲である。さらに、本発明の熱収縮性Ｐ
ＰＳチューブは、長さ方向および径方向の合計収縮率
は、３０〜１５０％、好ましくは３５〜１００％、特に
好ましくは４０〜１００％である。ここで、熱収縮率は
後述するとおり、チューブを１００℃の熱水中３０秒間
保持した場合の元（収縮前）の長さに対する熱収縮した
長さの割合（％）を表すものとする。The heat-shrinkable PPS tube of the present invention has a heat shrinkage rate (%) of 20 to 100%, preferably 2 in the length direction and the direction perpendicular to the length direction (referred to as "radial direction").
It is in the range of 5 to 80%. Furthermore, the heat shrinkability P of the present invention
The PS tube has a total shrinkage ratio in the length direction and the radial direction of 30 to 150%, preferably 35 to 100%, and particularly preferably 40 to 100%. Here, as will be described later, the heat shrinkage ratio represents the ratio (%) of the heat-shrinkable length to the original length (before shrinkage) when the tube is held in hot water of 100 ° C. for 30 seconds.
【０００７】本発明の熱収縮性ＰＰＳチューブは、長さ
方向および径方向の収縮率の合計が前記範囲であること
が望ましいが、実際の用途においては径方向の収縮率が
長さ方向のそれよりも大きいものが適している。例えば
長さ方向の収縮率に対して径方向の収縮率は１.５倍以
上、望ましくは２倍〜５倍のものが適当である。具体的
には、長さ方向の収縮率は２〜３０％、好ましくは５〜
２０％であり、径方向の収縮率が２０〜１００％、好ま
しくは２５〜８０％、より好ましくは３０〜７０％のも
のが適当である。In the heat-shrinkable PPS tube of the present invention, it is desirable that the total of the shrinkage rates in the lengthwise direction and the radial direction is within the above range, but in actual use, the shrinkage rate in the radial direction is that in the lengthwise direction. A larger one is suitable. For example, the shrinkage ratio in the radial direction is 1.5 times or more, preferably 2 to 5 times the shrinkage ratio in the length direction. Specifically, the contraction rate in the length direction is 2 to 30%, preferably 5 to
It is 20% and the shrinkage in the radial direction is 20 to 100%, preferably 25 to 80%, more preferably 30 to 70%.
【０００８】熱収縮性ＰＰＳチューブの形状は、特に制
限を受けないが、製品の被覆や保護のためには、その製
品の大きさに適合するように調整して製造される。一般
には、厚み（膜厚）は１０〜３００μｍ、好ましくは１
５〜２５０μｍの範囲が望ましいが、この厚みは用途に
よりその最適範囲が決定される。特に２０〜２００μｍ
程度が最も望ましい。また、チューブの径方向の円周
（外周）は一般にその用途により決められるが、通常３
〜４００ｍｍ、好ましくは４〜３００ｍｍの範囲が望ま
しい。The shape of the heat-shrinkable PPS tube is not particularly limited, but for coating and protection of the product, it is adjusted and manufactured to fit the size of the product. Generally, the thickness (film thickness) is 10 to 300 μm, preferably 1
The range of 5 to 250 μm is desirable, but the optimum range of this thickness is determined by the application. 20 to 200 μm
The degree is the most desirable. Also, the circumference (outer circumference) of the tube in the radial direction is generally determined by its application, but is usually 3
The range of 400 mm, preferably 400 mm is desirable.
【０００９】本発明のチューブを形成するポリフェニレ
ンスルフィドは、通常フィルム基板またはその他の化成
品の成形用樹脂として使用されているものであればよ
い。好ましく使用されるポリフェニレンスルフィドは、
全繰り返し単位の少なくとも８０モル％、好ましくは少
なくとも９０モル％がパラフェニレンスルフィド、The polyphenylene sulfide forming the tube of the present invention may be any one that is usually used as a molding resin for film substrates or other chemical products. The polyphenylene sulfide preferably used is
At least 80 mol% and preferably at least 90 mol% of all repeating units are paraphenylene sulfides,
【００１０】[0010]
【化３】 Embedded image
【００１１】単位から構成されるものである。It is composed of units.
【００１２】本発明の目的の１つである耐熱性や電気特
性を有する被覆用チューブの形成という範囲を損なわな
い限り、他の単位を２０モル％以下、好ましくは１０モ
ル％以下共重合していてもよい。また、共重合によって
成形性や他の性質を改良することもできる。共重合しう
る他の単位としては、例えば下記単位を挙げることがで
きる。Other units are copolymerized in an amount of 20 mol% or less, preferably 10 mol% or less, as long as the range of forming a coating tube having heat resistance and electrical properties, which is one of the objects of the present invention, is not impaired. May be. It is also possible to improve moldability and other properties by copolymerization. Examples of other units that can be copolymerized include the following units.
【００１３】[0013]
【化４】 Embedded image
【００１４】本発明において、使用するポリフェニレン
スルフィドは、実質的に直鎖状のポリマー構造を有する
ものが好ましい。しかし、熱収縮性や得られた被覆材料
としての特性に支障がない限り、１０モル％以下、好ま
しくは５モル％以下、特に１モル％以下の単位は架橋構
造を有していてもよい。一部架橋構造を付与することに
より、粘度の調整を行なうこともできる。The polyphenylene sulfide used in the present invention preferably has a substantially linear polymer structure. However, 10 mol% or less, preferably 5 mol% or less, and particularly 1 mol% or less of units may have a crosslinked structure as long as the heat shrinkability and the properties of the obtained coating material are not affected. The viscosity can be adjusted by imparting a partially crosslinked structure.
【００１５】本発明のチューブは、前記ポリフェニレン
スルフィドより形成されるが、特性および加工性の改良
のために他の耐熱性のポリマーを全体の３０重量％以
下、好ましくは２０重量％以下ブレンドすることができ
る。特に好ましくは１０重量％以下をブレンドすること
ができる。ポリフェニレンスルフィドにブレンドするこ
とができるポリマーとしては、ポリスルホン、ポリオレ
フィン、ポリフェニレンエーテル、ポリエーテルイミ
ド、ポリエーテルケトン、ポリエステル、フッ素樹脂、
ポリアリレート等が挙げられる。これらの他のポリマー
をブレンドすることは、チューブの引裂強度の改良のた
めにしばしば有効である。The tube of the present invention is formed from the above polyphenylene sulfide, but in order to improve the characteristics and processability, other heat resistant polymers should be blended in an amount of 30% by weight or less, preferably 20% by weight or less based on the whole amount. You can Particularly preferably, 10% by weight or less can be blended. Examples of the polymer that can be blended with polyphenylene sulfide include polysulfone, polyolefin, polyphenylene ether, polyetherimide, polyether ketone, polyester, fluororesin,
Examples include polyarylate. Blending these other polymers is often effective for improving the tear strength of the tube.
【００１６】また、必要に応じて安定剤、着色剤、酸化
防止剤、紫外線吸収剤、消泡剤等の添加剤を含有するも
のであってもよい。さらに、チューブの滑り性を向上さ
せるために、有機滑剤、無機の滑剤等の微粒子を含有せ
しめるが、滑り性を付与する微粒子としては、カオリ
ン、クレー、炭酸カルシウム、酸化ケイ素、テレフタル
酸カルシウム、酸化アルミニウム、酸化チタン、リン酸
カルシウム、フッ化リチウム等の公知の不活性外部粒子
の他に、ポリフェニレンスルフィドの溶融押出に際し
て、不溶性の高融点有機化合物、架橋ポリマーが適して
いる。Further, it may contain additives such as a stabilizer, a colorant, an antioxidant, an ultraviolet absorber and an antifoaming agent, if necessary. Further, in order to improve the slidability of the tube, fine particles such as an organic lubricant and an inorganic lubricant are contained, and the fine particles imparting the slidability include kaolin, clay, calcium carbonate, silicon oxide, calcium terephthalate, and oxide. In addition to known inert external particles such as aluminum, titanium oxide, calcium phosphate, and lithium fluoride, insoluble high melting point organic compounds and crosslinked polymers are suitable for melt extrusion of polyphenylene sulfide.
【００１７】チューブ中に含有される微粒子の平均粒径
は、０.０１〜１０μｍ、好ましくは０.１〜１０μｍで
あり、特に好ましくは４〜１０μｍである。ここで平均
粒径とは、レーザー回析法（例えば島津製作所製 ＳＡ
ＤＬ−１１００）を用いて測定した重量分の累積重量分
布が５０％になるときの粒径を平均粒径とした。The average particle size of the fine particles contained in the tube is 0.01 to 10 μm, preferably 0.1 to 10 μm, and particularly preferably 4 to 10 μm. Here, the average particle size means a laser diffraction method (for example, SA manufactured by Shimadzu Corporation).
The particle size at which the cumulative weight distribution measured by using DL-1100) becomes 50% was taken as the average particle size.
【００１８】その粒径分布としては、粒径４〜３０μｍ
の範囲の大粒径粒子を通常含有する。分布は好ましくは
４〜２５μｍである。４μｍより小さい粒子のみを含有
する場合は、チューブの開口性等に顕著な効果を現さな
い。また、３０μｍより大きい粒子を含有する場合は、
特に厚みの薄いチューブの場合欠陥を生じ、強度低下を
招くおそれがある。この大粒径粒子の含有量として、全
粒子１００重量％中２〜８０重量％が好ましく、より好
ましくは１０〜７０重量％、最も好ましくは２０〜６０
重量％である。The particle size distribution is such that the particle size is 4 to 30 μm.
It usually contains large-sized particles in the range of. The distribution is preferably 4-25 μm. When only particles smaller than 4 μm are contained, no remarkable effect is exerted on the tube opening property and the like. When it contains particles larger than 30 μm,
Especially in the case of a thin tube, defects may occur and the strength may be reduced. The content of the large-sized particles is preferably 2 to 80% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight based on 100% by weight of all particles.
% By weight.
【００１９】微粒子の含有効果は、特に延伸による微粒
子の突起が起こりにくい低延伸倍率のチューブに著し
い。また、これらのチューブは、未延伸チューブに内圧
をかけ膨張させ延伸管で径を規制するため、延伸管と接
触する外部表面は微粒子の突起が小さくなり印刷性が良
好となる。それに対し延伸管と接触しないチューブ内面
は、微粒子の突起が発現しやすく、そのため開口性も向
上する。微粒子の含有量は、樹脂（ＰＰＳ）１００重量
部に対し、０.０５〜４重量部であり、好ましくは０.０
２〜２.５重量部である。The effect of containing fine particles is remarkable especially in a tube having a low draw ratio in which protrusion of fine particles due to stretching hardly occurs. In addition, since these tubes are expanded by applying internal pressure to the unstretched tubes and controlling the diameter by the stretched tubes, the projections of fine particles are reduced on the outer surface in contact with the stretched tubes, and the printability is improved. On the other hand, protrusions of fine particles are likely to appear on the inner surface of the tube that does not come into contact with the stretched tube, and thus the opening property is also improved. The content of fine particles is 0.05 to 4 parts by weight, preferably 0.0 to 100 parts by weight of the resin (PPS).
It is 2 to 2.5 parts by weight.
【００２０】前記したポリフェニレンスルフィドは、溶
融押出装置により融点以上の温度に加熱溶融され、リン
グダイから連続的に押し出した後、強制的に冷却され未
延伸チューブに成型される。強制冷却の手段としては、
低温の水に浸漬する方法、冷却風による方法等を用いる
ことができる。The above-mentioned polyphenylene sulfide is heated and melted to a temperature equal to or higher than the melting point by a melt extrusion device, continuously extruded from a ring die, then forcibly cooled and molded into an unstretched tube. As means of forced cooling,
A method of immersing in low temperature water, a method of using cooling air, or the like can be used.
【００２１】このようにして得られた未延伸チューブ
は、チューブ内側より圧縮気体で加圧し、二軸延伸す
る。延伸法は特に限定されるものではないが、例えば未
延伸チューブの一方の端から圧縮気体による圧力を管の
内側に加えつつ一定速度で送り出し、次いで温水または
赤外線ヒーター等により予熱し、径方向の延伸倍率を規
制する延伸温度に加熱した延伸管の中に入れ二軸延伸を
行う。延伸管の適当な位置で延伸される様に温度条件等
を設定する。延伸後冷却し、一対のニップロールにより
挟んで延伸圧力を保持しながら延伸チューブとして引き
取り巻取られる。延伸は、長さ方向または径方向のいず
れの順序でもよいが、同時に行なうのが好ましい。The unstretched tube thus obtained is biaxially stretched by pressurizing it with a compressed gas from the inside of the tube. Although the stretching method is not particularly limited, for example, pressure is applied from one end of an unstretched tube by a compressed gas to the inside of the tube while being sent at a constant speed, and then preheated with hot water or an infrared heater, and the like. Biaxial stretching is performed by placing the film in a stretching tube heated to a stretching temperature that regulates the stretching ratio. Temperature conditions and the like are set so that stretching is performed at an appropriate position in the stretching tube. After stretching, it is cooled, and is taken up and wound up as a stretching tube while holding the stretching pressure while being sandwiched between a pair of nip rolls. Stretching may be performed in either the longitudinal direction or the radial direction, but is preferably performed simultaneously.
【００２２】長さ方向の延伸倍率は、未延伸チューブの
送り速度と延伸後のニップロール速度との比で決めら
れ、径方向の延伸倍率は未延伸外径と延伸チューブ外径
の比で決められる。これ以外の延伸加圧方法として、未
延伸チューブ送り出し側と延伸チューブ引き取り側双方
をニップロールに挟み封入した圧縮気体の内圧を維持す
る方法も採用できる。The stretching ratio in the length direction is determined by the ratio of the feed rate of the unstretched tube to the nip roll speed after stretching, and the stretching ratio in the radial direction is determined by the ratio of the unstretched outer diameter and the stretched tube outer diameter. . As another stretching pressurizing method, a method in which both the unstretched tube delivery side and the stretched tube take-up side are sandwiched between nip rolls to maintain the internal pressure of the compressed gas sealed therein can be employed.
【００２３】延伸条件は、使用するポリマーの性質およ
び目的のチューブの熱収縮性により異なるが、通常延伸
温度は８５〜１０５℃、好ましくはガラス転位点以上１
００℃以下であり、延伸倍率は長さ方向１.０５〜４.５
倍、好ましくは１.０５〜３.０倍、径方向１.３〜４.５
倍、好ましくは１.３〜３.５倍の範囲である。また、面
延伸倍率で１.５〜１５倍の範囲が有利である。The stretching conditions vary depending on the properties of the polymer used and the heat shrinkability of the target tube, but the stretching temperature is usually 85 to 105 ° C., preferably 1 or higher than the glass transition point.
The stretching ratio is 1.05 to 4.5 in the longitudinal direction.
Double, preferably 1.05-3.0 times, radial 1.3-4.5
It is in the range of 1.2 times, preferably 1.3 to 3.5 times. Further, the area stretching ratio of 1.5 to 15 times is advantageous.
【００２４】前記条件で延伸されたチューブは、例えば
１００℃の温水に３０秒間浸漬するテスト条件下で径方
向に通常２０％以上の収縮率を有し、例えばコンデンサ
ーを中に入れ加熱収縮せしめる絶縁被覆、電線を中に通
して加熱収縮せしめる絶縁用とし、あるいはラッピング
の目的に有効に使用できる。The tube stretched under the above conditions usually has a shrinkage ratio of 20% or more in the radial direction under a test condition of being immersed in hot water of 100 ° C. for 30 seconds, and for example, an insulating material which can be heat-shrinked by inserting a capacitor therein. It can be effectively used for insulation such that a coating or electric wire is passed through it to cause heat shrinkage, or for the purpose of wrapping.
【００２５】また、該倍率範囲で延伸されたチューブを
緊張下、または制限収縮下にて２００℃以上、該フィル
ムの融点以下の温度範囲で熱固定することにより、さら
に熱に対し極めて優れた性能を持ち、目的によっては初
めより緊張下で熱固定したチューブでの使用もできる。Further, the tube stretched in the above range of magnification is heat-set in a temperature range of not lower than 200 ° C. and not higher than the melting point of the film under tension or limited shrinkage, so that a further excellent performance against heat can be obtained. Depending on the purpose, it can also be used in a tube that has been heat-fixed under tension from the beginning.
【００２６】かくして本発明によれば、前記熱収縮性チ
ューブを使用して各種無機材料製品の表面を被覆した製
品も提供される。表面の被覆の対象となる製品として
は、ポリフェニレンスルフィドの特性（例えば絶縁性、
耐熱性）を利用しうるものであればよく、例えば金属材
料製品およびガラス製品が挙げられる。具体的には、金
属材料製品としては、コンデンサー、電線（丸線、角
線）、鋼管または電気機器が例示され、この電気機器と
してはモーターコイルエンド、トランス、口出線を含
み、また小型モーターの全体を被覆することもできる。
また、ガラス製品としては、例えば電球、蛍光灯が示さ
れ、殊にファクシミリやイメージスキャナーの蛍光灯被
覆チューブとしても利用可能である。Thus, according to the present invention, there is also provided a product obtained by coating the surface of various inorganic material products using the heat-shrinkable tube. As a product to be coated on the surface, the properties of polyphenylene sulfide (for example, insulating property,
Heat resistance), and examples thereof include metal material products and glass products. Specifically, examples of the metal material product include a condenser, an electric wire (round wire, square wire), a steel pipe, or an electric device. The electric device includes a motor coil end, a transformer, a lead wire, and a small motor. Can be coated entirely.
Further, as the glass product, for example, a light bulb and a fluorescent lamp are shown, and particularly, it can be used as a fluorescent lamp-covered tube for a facsimile or an image scanner.
【００２７】[0027]
【発明の効果】本発明のポリフェニレンスルフィドより
実質的になる熱収縮性チューブは、Ｆ種（１５５℃以上
連続使用可能）の耐熱性と優れた難燃性（ＵＬ規格２２
４でＶＷ−１）、耐薬品性、電気特性を持ち、またガラ
ス転移点以上の温度で容易に収縮するため、耐熱被覆用
として極めて有用な新規なチューブである。INDUSTRIAL APPLICABILITY The heat-shrinkable tube substantially made of the polyphenylene sulfide of the present invention has heat resistance of type F (can be continuously used at 155 ° C. or higher) and excellent flame retardancy (UL standard 22).
4 has VW-1), chemical resistance, and electrical characteristics, and easily shrinks at a temperature above the glass transition point, so that it is an extremely useful novel tube for heat-resistant coating.
【００２８】従って、従来の汎用熱収縮性チューブでは
耐熱性の不足するコンデンサー被覆絶縁用、平角線、渡
り線等の被覆、ターミナルの保護ラッピング、折り畳ん
だ形でテーピングとして、また発熱体の絶縁被覆として
最適である。さらに、性能として驚くべきことに、熱収
縮被覆後、半田づけ等の工程で再加熱（例えば１６０
℃、３分）されても耐熱性が高いことにより変形等が発
生しないため利用価値は非常に高い。Therefore, the conventional general-purpose heat-shrinkable tube has insufficient heat resistance for insulation of capacitors, insulation of flat wires, crossovers, etc., protective wrapping of terminals, taping in a folded form, and insulation coating of heating elements. As is the best. In addition, surprisingly as a performance, after heat shrink coating, reheating (eg 160
Even if it is kept at 3 ° C for 3 minutes), its high heat resistance does not cause deformation or the like, so its utility value is extremely high.
【００２９】特性の評価法 本発明における各特性は、以下の方法によって測定され
た。（１）熱収縮率 １００℃の温水に３０秒間浸漬し、前後の長さおよび径
を測定することにより収縮率を算出した。（２）高温耐熱 熱固定したチューブはそのままで、熱収縮チューブはチ
ューブ内径より２ｍｍ小さい鉄製円筒を入れ、１８０
℃、２０秒加熱収縮後、２００℃で１００時間処理し変
形および外観の変化をみた。外観は、目視にて表面の割
れ、しわやめくれの発生を観察して判断した。Evaluation Method of Properties Each property in the present invention was measured by the following methods. (1) Heat shrinkage rate The heat shrinkage rate was calculated by immersing in hot water at 100 ° C. for 30 seconds and measuring the length and diameter before and after. (2) The heat-shrinkable tube is fixed as it is, and the heat-shrinkable tube is inserted into an iron cylinder 2 mm smaller than the inner diameter of the tube.
After heat shrinkage at 20 ° C. for 20 seconds, it was treated at 200 ° C. for 100 hours to see deformation and change in appearance. The appearance was judged by visually observing the occurrence of surface cracks, wrinkles and swelling.
【００３０】（３）再加熱後変形 半田工程等での耐熱性を評価するため、熱収縮性チュー
ブ内径より２ｍｍ小さく、長さは５ｍｍ小さいコンデン
サーを入れ、１８０℃、２０秒加熱収縮後、１６０℃、
３分再加熱し、フクレ等の外観変化を評価した。（４）耐熱焼性 チューブの難燃性評価に使用されるＵＬ２２４ Optiona
l VW-1 Flame Testによった。（５）引裂強度 エレメンドルフ引裂試験（ＪＩＳ Ｋ７１２８ Ｂ 法
準拠）によった。 (3) In order to evaluate the heat resistance in the deformed soldering process after reheating , a condenser that is smaller than the inner diameter of the heat-shrinkable tube by 2 mm and a length of 5 mm is inserted, and after heating and shrinking at 180 ° C. for 20 seconds, 160 ℃,
It was reheated for 3 minutes and the appearance change such as blister was evaluated. (4) UL224 Optiona used for flame retardancy evaluation of heat resistant tubing
l According to VW-1 Flame Test. (5) Tear strength It was based on the Elemendorf tear test (based on JIS K7128 B method).
【００３１】[0031]
【実施例】以下、本発明を実施例によりさらに詳しく説
明する。 実施例１ 呉羽化学工業（株）製ポリフェニレンスルフィドＰＦ３
５０Ａ１００重量部に対し、平均粒径４.８μｍの（全
不活性外部粒子１００重量％中、４〜２５μｍの大粒径
粒子を５７.８重量％含有する）カオリンを０.２重量部
添加した材料を乾燥後３１０℃で溶融し、リングダイを
通じて押出し、水に浸漬、冷却固化し未延伸チューブを
得た。。The present invention will be described in more detail with reference to the following examples. Example 1 Polyphenylene sulfide PF3 manufactured by Kureha Chemical Industry Co., Ltd.
To 100 parts by weight of 50A, 0.2 parts by weight of kaolin having an average particle size of 4.8 μm (containing 57.8% by weight of large particle size particles of 4 to 25 μm in 100% by weight of all inert outer particles) was added. The material was dried, melted at 310 ° C., extruded through a ring die, immersed in water, cooled and solidified to obtain an unstretched tube. .
【００３２】この未延伸チューブの外径、厚みは表１に
示した。この未延伸チューブを１００℃の温水、内径１
６ｍｍφの延伸管を使用し、２.０ｋｇ／ｃｍ2の圧空に
よりチューブに内圧をかけ表１に示す条件にて延伸後水
にて冷却し、５０μの延伸熱収縮性チューブを得た。得
られた熱収縮性チューブの形状および特性を表１に示し
た。The outer diameter and thickness of this unstretched tube are shown in Table 1. This unstretched tube is heated to 100 ° C with 1
Using a 6 mmφ stretched tube, an internal pressure was applied to the tube by compressed air of 2.0 kg / cm 2 , and the tube was stretched under the conditions shown in Table 1 and then cooled with water to obtain a 50 μ stretched heat-shrinkable tube. Table 1 shows the shape and characteristics of the obtained heat-shrinkable tube.
【００３３】実施例２および３ 表１に示す条件以外は実施例１と同一条件にて延伸チュ
ーブをつくった。その特性を表１に示すが、耐熱性に優
れ、再加熱での変形もなく加工適性に優れている。Examples 2 and 3 Stretched tubes were prepared under the same conditions as in Example 1 except for the conditions shown in Table 1. The characteristics are shown in Table 1, and it has excellent heat resistance, no deformation by reheating, and excellent workability.
【００３４】実施例４ 表１に示す条件以外は実施例１と同一条件にて延伸チュ
ーブを得、その後延伸条件と同一緊張下で（２０ｋｇ／
ｃｍ2加圧、長さ方向は延伸後の同一長さ維持）２５０
℃、６０秒間熱固定した。得られたフィルムは、熱収縮
率の低い安定した特性を示した。Example 4 A stretched tube was obtained under the same conditions as in Example 1 except for the conditions shown in Table 1, and then under the same tension as the stretching conditions (20 kg /
cm 2 pressurization, length direction maintains the same length after stretching) 250
It was heat-set at 60 ° C. for 60 seconds. The obtained film showed stable properties with low heat shrinkage.
【００３５】実施例５および６ ポリフェニレンスルフィド原料をそれぞれ大日本インキ
化学工業株式会社製ＰＸ００１０および東洋紡績株式会
社製 ＬＤ−１０Ｐを使用する以外は実施例１と同一条
件にて延伸チューブをつくった。その特性を第１表に示
す。汎用のポリエチレンテレフタレートチューブでは、
高温耐熱で完全な変形が認められ、再加熱後変形もフク
レが発生し、半田加工等の加工適性上の問題があるが、
表１に示す通りいずれも優れた特性を示す。Examples 5 and 6 Stretched tubes were prepared under the same conditions as in Example 1 except that PX0010 manufactured by Dainippon Ink and Chemicals, Inc. and LD-10P manufactured by Toyobo Co., Ltd. were used as polyphenylene sulfide raw materials, respectively. The characteristics are shown in Table 1. In general-purpose polyethylene terephthalate tube,
Complete deformation is recognized due to high temperature heat resistance, blistering occurs even after deformation after reheating, and there is a problem in workability such as soldering,
As shown in Table 1, all show excellent characteristics.
【００３６】実施例７ 呉羽化学工業（株）製ポリフェニレンスルフィド樹脂Ｒ
３２００ ８０重量％とテイジンアモコ製ポリスルホン
樹脂Ｐ１７００ ２０重量％をチップブレンドした原料
を使用する以外は実施例３と同一条件にて延伸チューブ
をつくった。半径方向の引裂強度の改善効果が認められ
た。Example 7 Polyphenylene sulfide resin R manufactured by Kureha Chemical Industry Co., Ltd.
A stretched tube was produced under the same conditions as in Example 3 except that a raw material obtained by chip-blending 80% by weight of 3200 and 20% by weight of polysulfone resin P1700 manufactured by Teijin Amoco was used. The effect of improving the tear strength in the radial direction was recognized.
【００３７】[0037]
【表１】 [Table 1]
Claims (10)
形成された熱収縮性チューブ。1. A heat-shrinkable tube substantially formed from polyphenylene sulfide.
（％）が２０〜１００％の値を有する請求項１記載のチ
ューブ。2. The tube according to claim 1, wherein the heat shrinkage percentage (%) in the direction perpendicular to the length direction has a value of 20 to 100%.
向に対する直角方向の熱収縮率（％）の合計収縮率が３
０〜１５０％の値を有する請求項１記載のチューブ。3. The total shrinkage ratio of the heat shrinkage ratio (%) in the length direction and the heat shrinkage ratio (%) in the direction perpendicular to the length direction is 3.
The tube according to claim 1, having a value of 0 to 150%.
位の８０モル％以上が下記式 【化１】 で表される単位である請求項１記載のチューブ。4. The polyphenylene sulfide has the following formula in which 80 mol% or more of repeating units are represented by the following formula: The tube according to claim 1, which is a unit represented by:
０μｍの範囲である請求項１記載のチューブ。5. The film forming the tube has a thickness of 10 to 30.
The tube according to claim 1, which is in the range of 0 μm.
が、３〜４００ｍｍの範囲である請求項１記載のチュー
ブ。6. The tube according to claim 1, wherein the length of the circumference in the direction perpendicular to the length direction is in the range of 3 to 400 mm.
表面が被覆された無機材料製品。7. An inorganic material product whose surface is coated by heat shrinkage of the tube according to claim 1.
の被覆のための使用。8. Use of a tube according to claim 1 for coating an inorganic material product.
形成される未延伸チューブを、８５〜１０５℃の温度で
長さ方向に１.０５〜４.５倍かつ長さ方向に対する直角
方向（半径方向）に１.３〜４.５倍延伸することを特徴
とするポリフェニレンスルフィドより実質的になる熱収
縮性チューブの製造方法。9. An unstretched tube substantially formed of polyphenylene sulfide is 1.05-4.5 times in the length direction at a temperature of 85 to 105 ° C. and in a direction (radial direction) perpendicular to the length direction. A method for producing a heat-shrinkable tube which is substantially made of polyphenylene sulfide, characterized in that it is stretched 1.3 to 4.5 times.
単位の８０モル％以上が下記式 【化２】 で表される単位である請求項９記載のチューブの製造方
法。10. Polyphenylene sulfide has the following formula in which 80 mol% or more of repeating units are represented by the following formula: The method for producing a tube according to claim 9, which is a unit represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25649996A JPH09157402A (en) | 1995-10-06 | 1996-09-27 | Heat-shrinkable tube, its production and utilization thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-259865 | 1995-10-06 | ||
| JP25986595 | 1995-10-06 | ||
| JP25649996A JPH09157402A (en) | 1995-10-06 | 1996-09-27 | Heat-shrinkable tube, its production and utilization thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09157402A true JPH09157402A (en) | 1997-06-17 |
Family
ID=26542750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25649996A Pending JPH09157402A (en) | 1995-10-06 | 1996-09-27 | Heat-shrinkable tube, its production and utilization thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09157402A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008114731A1 (en) * | 2007-03-15 | 2008-09-25 | Mitsubishi Plastics, Inc. | Resin composition used for heat shrinkable member, heat shrinkable tube composed of the resin composition, and member covered with the tube |
| WO2010027084A1 (en) * | 2008-09-08 | 2010-03-11 | 三菱樹脂株式会社 | Polyphenylene sulfide-based heat-shrinkable tube and member covered with said tube |
| JP2011116010A (en) * | 2009-12-02 | 2011-06-16 | Mitsubishi Plastics Inc | Polyphenylene sulfide-based heat shrinkable tube and member coated therewith |
-
1996
- 1996-09-27 JP JP25649996A patent/JPH09157402A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008114731A1 (en) * | 2007-03-15 | 2008-09-25 | Mitsubishi Plastics, Inc. | Resin composition used for heat shrinkable member, heat shrinkable tube composed of the resin composition, and member covered with the tube |
| EP2123718A1 (en) * | 2007-03-15 | 2009-11-25 | Mitsubishi Plastics, Inc. | Resin composition used for heat shrinkable member, heat shrinkable tube composed of the resin composition, and member covered with the tube |
| JP5225976B2 (en) * | 2007-03-15 | 2013-07-03 | 三菱樹脂株式会社 | Resin composition used for heat-shrinkable member, heat-shrinkable tube comprising the resin composition, and member coated with the tube |
| EP2123718A4 (en) * | 2007-03-15 | 2013-07-17 | Mitsubishi Plastics Inc | Resin composition used for heat shrinkable member, heat shrinkable tube composed of the resin composition, and member covered with the tube |
| WO2010027084A1 (en) * | 2008-09-08 | 2010-03-11 | 三菱樹脂株式会社 | Polyphenylene sulfide-based heat-shrinkable tube and member covered with said tube |
| US8361575B2 (en) | 2008-09-08 | 2013-01-29 | Mitsubishi Plastics, Inc. | Polyphenylene sulfide-based heat-shrinkable tube and component covered with the tube |
| JP2011116010A (en) * | 2009-12-02 | 2011-06-16 | Mitsubishi Plastics Inc | Polyphenylene sulfide-based heat shrinkable tube and member coated therewith |
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