JP2008001750A - Silicone rubber composition, liquid silicone rubber composition, and braided tube - Google Patents

Silicone rubber composition, liquid silicone rubber composition, and braided tube Download PDF

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JP2008001750A
JP2008001750A JP2006170337A JP2006170337A JP2008001750A JP 2008001750 A JP2008001750 A JP 2008001750A JP 2006170337 A JP2006170337 A JP 2006170337A JP 2006170337 A JP2006170337 A JP 2006170337A JP 2008001750 A JP2008001750 A JP 2008001750A
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silicone rubber
rubber composition
braided
liquid silicone
tube
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JP4990565B2 (en
JP2008001750A5 (en
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Tatsuo Arakawa
辰雄 荒川
Tadao Suzuki
唯郎 鈴木
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Kurabe Industrial Co Ltd
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Kurabe Industrial Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone rubber composition and a liquid silicone rubber composition each having such high heat resistance as to be prevented from discoloration even under use in high-temperature circumstances, and to provide braided tubes using the silicone rubber composition and the liquid silicone rubber composition respectively. <P>SOLUTION: The silicone rubber composition is such that a silicone rubber is compounded with a titanium oxide-based yellow pigment. The liquid silicone rubber composition is such that a liquid silicone rubber is compounded with the titanium oxide-based yellow pigment. The braided tube is such as to be obtained by coating a textile yarn-braided sleeve with the silicone rubber composition. A second version of the braided tube is such as to be obtained by coating a textile yarn-braided sleeve with the liquid silicone rubber composition followed by curing the liquid silicone rubber composition. A third version of the braided tube is such as to be obtained by molding the silicone rubber composition into a tubular form as a rubber tube and then braiding textile yarns on the rubber tube to effect coating. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

本発明は、高温環境下での使用においても変色を抑制することが可能な優れた耐熱性を有したシリコーンゴム組成物及び液状シリコーンゴム組成物と、このシリコーンゴム組成物及び液状シリコーンゴム組成物を使用した編組チューブに関する。   The present invention relates to a silicone rubber composition and a liquid silicone rubber composition having excellent heat resistance capable of suppressing discoloration even when used in a high temperature environment, and the silicone rubber composition and liquid silicone rubber composition. Relates to a braided tube using

シリコーンゴムは、耐熱性、耐候性、柔軟性、絶縁性に優れており、各種電気絶縁材料や、ガスケット、パッキン等のシール材など、成形品として多種の用途で幅広く使用されている。また、このシリコーンゴムが液状の状態である液状シリコーンゴムは、シリコーンワニスとしても使用されており、ガラス繊維などを適度に収束するため、ガラス繊維などを編組したその外周に塗布されている。このような具体例として、例えば、編組チューブや編組電線などが挙げられる(例えば、特許文献1〜8参照。)。   Silicone rubber is excellent in heat resistance, weather resistance, flexibility and insulation, and is widely used in various applications as molded products such as various electrical insulation materials and sealing materials such as gaskets and packings. Further, the liquid silicone rubber in which the silicone rubber is in a liquid state is also used as a silicone varnish, and is applied to the outer periphery of the braided glass fiber in order to appropriately converge the glass fiber. As a specific example, for example, a braided tube, a braided electric wire, and the like can be given (for example, see Patent Documents 1 to 8).

特開平4−364928号公報Japanese Laid-Open Patent Publication No. 4-364828 特開平5−174652号公報Japanese Patent Laid-Open No. 5-174652 特開2005−2531号公報JP 2005-2531 A 特開2006−32028号公報JP 2006-32028 A 特開平2−106826号公報Japanese Patent Laid-Open No. 2-106826 特開平6−314524号公報JP-A-6-314524 特開平7−73736号公報JP-A-7-73736 特開2002−358847号公報JP 2002-358847 A

ところで、上記したような成型品や、編組チューブ、編組電線などを実使用に供する際には、他部材との識別や意匠性などの理由により着色する必要が生ずるが、この着色した色は、長期間の使用によっても変色せず、製造時の色を保っていることが望まれる。特にシリコーンゴムは、上記したように耐熱性に優れていることから、必然的に高温環境下で使用されることが多くなるので、着色に際してはこのような高温環境下でも変色が起こらないことが要求される。 By the way, when the molded product as described above, a braided tube, a braided electric wire and the like are used for actual use, it is necessary to color them for reasons such as identification with other members and design properties. It is desirable that the color at the time of manufacture is maintained without being discolored even after long-term use. In particular, since silicone rubber is excellent in heat resistance as described above, it is inevitably often used in a high temperature environment, so that coloration does not occur even under such a high temperature environment. Required.

着色される色に関して、黄色に着色をする場合に着目すると、従来のシリコーンゴムにおいては黄色の顔料として、一般的にカドミウム系顔料やアゾ系顔料が使用されている。しかしながら、カドミウム系顔料は毒性が強く、環境への影響という面からも使用することができなくなっている。また、アゾ系顔料をシリコーンゴムに配合した場合、シリコーンゴムが使用されるような高温環境下での長時間の使用では、変色してしまう可能性があるという問題があった。特に自動車等の部品に使用された際には、年数の経過に伴って部品の修理交換を行う場合があるが、そのときに変色をしていると、類似した部品との識別ができず、修理交換が非常に困難となってしまう可能性がある。   With regard to the color to be colored, when attention is paid to the case of coloring yellow, cadmium pigments and azo pigments are generally used as yellow pigments in conventional silicone rubber. However, cadmium pigments are highly toxic and can no longer be used from the viewpoint of environmental impact. Further, when an azo pigment is blended with silicone rubber, there is a problem that discoloration may occur when used for a long time in a high temperature environment where silicone rubber is used. Especially when used for parts such as automobiles, parts may be repaired and replaced over the years, but if it is discolored at that time, it cannot be distinguished from similar parts, Repairs and replacements can be very difficult.

本発明はこのような従来技術の問題点を解決するためになされたもので、その目的とするところは、高温環境下での使用においても変色を抑制することが可能な優れた耐熱性を有したシリコーンゴム組成物及び液状シリコーンゴム組成物と、このシリコーンゴム組成物及び液状シリコーンゴム組成物を使用した編組チューブを提供することにある。   The present invention has been made to solve such problems of the prior art, and its object is to have excellent heat resistance capable of suppressing discoloration even when used in a high temperature environment. Another object of the present invention is to provide a silicone rubber composition and a liquid silicone rubber composition, and a braided tube using the silicone rubber composition and the liquid silicone rubber composition.

上記目的を達成するべく、本発明の請求項1によるシリコーンゴム組成物は、シリコーンゴムに、酸化チタン系黄色顔料が配合されているものである。
また、請求項2による液状シリコーンゴム組成物は、液状シリコーンゴムに、酸化チタン系黄色顔料が配合されているものである。
また、請求項3による編組チューブは、繊維糸を編組してなる編組スリーブに、上記シリコーンゴム組成物を被覆してなるものである。
また、請求項4による編組チューブは、繊維糸を編組してなる編組スリーブに、上記液状シリコーンゴム組成物を塗布し、該液状シリコーンゴム組成物を硬化してなるものである。
また、請求項5による編組チューブは、上記シリコーンゴム組成物をチューブ状に成形してゴムチューブとし、該ゴムチューブ上に、繊維糸を編組することで被覆してなるものである。
In order to achieve the above object, the silicone rubber composition according to claim 1 of the present invention is one in which a titanium oxide yellow pigment is blended with a silicone rubber.
The liquid silicone rubber composition according to claim 2 is a liquid silicone rubber in which a titanium oxide yellow pigment is blended.
According to a third aspect of the present invention, there is provided a braided tube obtained by coating a braided sleeve formed by braiding fiber yarns with the silicone rubber composition.
A braided tube according to claim 4 is obtained by applying the liquid silicone rubber composition to a braided sleeve formed by braiding fiber yarns and curing the liquid silicone rubber composition.
A braided tube according to claim 5 is formed by forming the silicone rubber composition into a tube shape to form a rubber tube, and coating the rubber tube by braiding fiber yarns.

本発明によるシリコーンゴム組成物及び液状シリコーンゴム組成物は、シリコーンゴムに配合する黄色顔料として、酸化チタン系黄色顔料を使用することにより、高温環境下での使用においても変色を抑制することが可能な優れた耐熱性を得ることができる。
また、このようなシリコーンゴム組成物及び液状シリコーンゴム組成物によって得られた編組チューブは、高温環境下での使用においても変色を抑制することが可能な優れた耐熱性を得ることができる。そのため、例えば、電線束の収束具として自動車エンジンの近傍等の高温環境下に配置された場合にも、変色を抑制でき、他の電線束との識別を維持できる。
The silicone rubber composition and the liquid silicone rubber composition according to the present invention can suppress discoloration even in use in a high temperature environment by using a titanium oxide yellow pigment as a yellow pigment to be blended in the silicone rubber. Excellent heat resistance can be obtained.
Moreover, the braided tube obtained by such a silicone rubber composition and a liquid silicone rubber composition can obtain the outstanding heat resistance which can suppress discoloration also in the use in a high temperature environment. For this reason, for example, even when the wire bundle is disposed in a high-temperature environment such as in the vicinity of an automobile engine as a wire bundle converging tool, discoloration can be suppressed and identification with other wire bundles can be maintained.

以下、図面を参照して本発明の好ましい実施の形態を説明する。図1は、本発明の編組チューブの製造方法を実施するための装置の一例を示す説明図である。   Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view showing an example of an apparatus for carrying out the method for producing a braided tube of the present invention.

図1において、符号1は編組チューブ、符号2は編組スリーブ、符号3は製紐機、符号4は繊維糸、符号5はタンク、符号6は絞り、符号7は加熱炉、符号9はガイドプーリー、符号10は巻取り装置である。尚、繊維糸としては、無アルカリ性ガラス繊維糸を使用した。また、液状シリコーンゴムとしては、粘度が異なる2種類の液状シリコーンゴムを混合し、50Pa・sとしたものを使用した。このような液状シリコーンゴム100重量部に対し、酸化チタン系黄色顔料3重量部配合することで、本実施の形態による液状シリコーンゴム組成物とした。   In FIG. 1, reference numeral 1 is a braided tube, reference numeral 2 is a braided sleeve, reference numeral 3 is a stringing machine, reference numeral 4 is a fiber yarn, reference numeral 5 is a tank, reference numeral 6 is a throttle, reference numeral 7 is a heating furnace, reference numeral 9 is a guide pulley. Reference numeral 10 denotes a winding device. As the fiber yarn, an alkali-free glass fiber yarn was used. Further, as the liquid silicone rubber, a mixture of two types of liquid silicone rubbers having different viscosities to make 50 Pa · s was used. A liquid silicone rubber composition according to the present embodiment was prepared by blending 3 parts by weight of titanium oxide yellow pigment with 100 parts by weight of such liquid silicone rubber.

製造工程の流れを説明する。まず、無アルカリ性ガラス繊維糸4を編組密度13、編組厚さ0.25mmの条件で編組して内径5mmの編組スリーブ2とする。次いで、この編組スリーブ2を、上記液状シリコーンゴム組成物で満たされたタンク5内に連続的に導入して液状シリコーンゴム組成物を塗布する。このとき、過剰に付着した液状シリコーンゴム組成物は、絞り6によって除去され、液状シリコーンゴム組成物の肉厚が約0.5mmとなるように制御される。このようにして所定量の液状シリコーンゴム組成物を塗布した後、145〜165℃の温度に保持された長さ1.0mの加熱炉7内に連続的に導入して液状シリコーンゴム組成物を加熱硬化させた。このようにして液状シリコーンゴム組成物が塗布、加熱硬化された編組チューブ1は、ガイドプーリー9を経て、巻取装置10に巻き取られる。   The flow of the manufacturing process will be described. First, the alkali-free glass fiber yarn 4 is braided under the conditions of a braid density of 13 and a braid thickness of 0.25 mm to form a braided sleeve 2 having an inner diameter of 5 mm. Next, the braided sleeve 2 is continuously introduced into the tank 5 filled with the liquid silicone rubber composition to apply the liquid silicone rubber composition. At this time, the excessively adhered liquid silicone rubber composition is removed by the squeezing 6, and the thickness of the liquid silicone rubber composition is controlled to be about 0.5 mm. After applying a predetermined amount of the liquid silicone rubber composition in this way, the liquid silicone rubber composition is continuously introduced into a heating furnace 7 having a length of 1.0 m maintained at a temperature of 145 to 165 ° C. Heat-cured. The braided tube 1 to which the liquid silicone rubber composition has been applied and heat-cured in this manner is wound around the winding device 10 via the guide pulley 9.

ここで、このようにして得られた本実施の形態による編組チューブについて、加熱炉中に保持し、加熱前後の各試料の表面について、色測定を行った。加熱条件は、250℃の温度で6時間加熱、及び、300℃の温度で6時間加熱とした。測定には、色彩色差計(CR−200型:ミノルタ製)を用い、Yxy表色系モード(CIE-1931XYZ表色系)、及び、マンセル表色系(H・V・C)モードで計測した。また、上記液状シリコーンゴム組成物を150℃の温度で15分間加熱して作成したプレスシートについても、同様に加熱前後の各試料の表面について、色測定を行った。編組チューブに関する結果を表1、プレスシートに関する結果を表2に示す。   Here, the braided tube according to the present embodiment thus obtained was held in a heating furnace, and color measurement was performed on the surface of each sample before and after heating. The heating conditions were heating at 250 ° C. for 6 hours and heating at 300 ° C. for 6 hours. For the measurement, a color difference meter (CR-200 type: manufactured by Minolta) was used, and measurement was performed in the Yxy color system mode (CIE-1931XYZ color system) and the Munsell color system (H, V, C) mode. . Moreover, the color measurement was similarly performed about the surface of each sample before and behind heating about the press sheet produced by heating the said liquid silicone rubber composition for 15 minutes at the temperature of 150 degreeC. Table 1 shows the results for the braided tube, and Table 2 shows the results for the press sheet.

更に、比較の形態として、液状シリコーンゴム組成物として、液状シリコーンゴム100重量部に対し、アゾ系黄色顔料2重量部を配合したものについても、実施の形態と同様、編組チューブとプレスシートについて色測定を行った。 Further, as a comparative form, the liquid silicone rubber composition having 2 parts by weight of an azo-based yellow pigment blended with 100 parts by weight of the liquid silicone rubber is similar in color to the braided tube and the press sheet as in the embodiment. Measurements were made.

Figure 2008001750
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表1及び表2の結果より、本実施の形態と比べて、比較の形態はY値の低下が大きく、またx値、y値も大きく変化していた。これは、比較の形態の方が、明度が低くなって黒っぽく変色しているとともに、色度が無彩色に近くなっており、より変色の度合いが大きいことを示している。また、Yxy表色系のデータより、加熱前と加熱後の色差を求め、表1、表2に併せて示したが、これによっても、比較の形態の方が明らかに変色の度合いが大きいことが確認された。この結果は、マンセル表色系も同様で、比較の形態の方が、本実施の形態よりも色相・彩度・明度ともに変化が大きく、変色の度合いが大きいことを示している。   From the results shown in Tables 1 and 2, in the comparison form, the decrease in the Y value was large and the x value and the y value were also greatly changed compared to the present embodiment. This indicates that the comparative form has lower brightness and changes to blackish, and the chromaticity is closer to an achromatic color, indicating that the degree of change is greater. In addition, the color difference before and after heating was obtained from the data of the Yxy color system, and is shown together in Tables 1 and 2, but this also clearly shows that the degree of color change is clearly greater in the comparative form. Was confirmed. This result shows that the Munsell color system is the same, and that the comparison form has a larger change in hue, saturation, and brightness than the present embodiment, and the degree of color change is large.

次いで、上記のようにして得られた実施の形態による編組チューブと、比較の形態による編組チューブについて、絶縁破壊電圧の試験を行った。試験方法は、以下に示す4条件にて行った。絶縁破壊電圧の試験結果を表3に示す。
(1)常態 長さ約100mmの試料を採り、内径に密接するまっすぐな金属棒をこれに差し入れて内側電極とし、外側の中央部50mm巾に金属箔を密接して巻き付けて外側電極とする。常温の室内において、試料に波高率が1.34〜1.48の間にあるような商用周波数の電圧を加え、零から毎秒約500Vの割合で均一に上昇させて加え、絶縁破壊電圧を測定する。
(2)折り曲げ後 長さ約150mmの試料に、内側に密接する柔軟性物質(シリコーンゴム電線)を差し込み、公称内径の20倍の直径をもった丸棒に沿って、静かに巻き付ける。その後、試料から柔軟性物質を取り除き、試料に金属箔を密着させて巻き付けて外側電極とし、常態の試験と同様の方法で絶縁破壊電圧を測定する。
(3)吸湿後 内容量500ccの広口栓瓶に、適当な長さの試料と約5ccの水を入れたガラス製小容器とを共に入れて密封し、20±15℃にて24時間保持した後、取り出し、表面の水分を拭きとって直ちに、常態の試験と同様の方法で絶縁破壊電圧を測定する。
(4)高温 長さ約100mmの試料を250℃±5℃に保った恒温槽中で6時間加熱する。その後、取り出して常温に冷却し、常態の試験と同様の方法で絶縁破壊電圧を測定する。
Next, a dielectric breakdown voltage test was performed on the braided tube according to the embodiment obtained as described above and the braided tube according to the comparative example. The test method was performed under the following four conditions. Table 3 shows the breakdown voltage test results.
(1) Normal state A sample having a length of about 100 mm is taken, and a straight metal rod in close contact with the inner diameter is inserted into the inner electrode, and a metal foil is closely wound around the outer central portion 50 mm wide to form the outer electrode. In a room temperature room, a commercial frequency voltage with a crest factor between 1.34 and 1.48 is applied to the sample, and the voltage is uniformly increased from zero at a rate of about 500 V per second, and the breakdown voltage is measured. To do.
(2) After bending Insert a flexible material (silicone rubber electric wire) in close contact with a sample having a length of about 150 mm, and gently wrap the sample along a round bar having a diameter 20 times the nominal inner diameter. Thereafter, the flexible material is removed from the sample, and a metal foil is tightly wound around the sample to form an outer electrode, and the dielectric breakdown voltage is measured by the same method as in the normal test.
(3) After moisture absorption In a 500 cc wide-mouth stopper bottle, a sample of an appropriate length and a small glass container containing about 5 cc of water are put together and sealed, and kept at 20 ± 15 ° C. for 24 hours. Then, the dielectric breakdown voltage is measured by the same method as in the normal test immediately after taking out and wiping off the moisture on the surface.
(4) High temperature A sample having a length of about 100 mm is heated for 6 hours in a thermostatic chamber maintained at 250 ° C. ± 5 ° C. Then, it takes out, cools to normal temperature, and measures a dielectric breakdown voltage by the method similar to a normal test.

更に、UL Subject224 VW−1に準拠して、燃焼性の試験を行った。燃焼性の試験の結果を表3に併せて示す。   Further, a flammability test was performed in accordance with UL Subject224 VW-1. The results of the flammability test are also shown in Table 3.

Figure 2008001750
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表3の結果より、酸化チタン系黄色顔料を配合した実施の形態による編組チューブは、アゾ系の黄色顔料を使用した比較の形態による編組チューブに対して、8〜20%の絶縁破壊電圧の向上が見られた。この効果は、特に吸湿後において顕著であった。絶縁破壊電圧の向上が見られた理由として詳しい検証はなされていないが、無極性のシリコーンゴム中に、微細ボイド等を起因として電荷が蓄積し、これを基点として絶縁破壊が生じていたものが、酸化チタン系黄色顔料を配合することによって蓄積された電荷が漏洩し、絶縁破壊を起こし難くなったものと推測される。   From the results of Table 3, the braided tube according to the embodiment containing the titanium oxide-based yellow pigment has an improved breakdown voltage of 8 to 20% as compared with the braided tube according to the comparative embodiment using the azo-based yellow pigment. It was observed. This effect was particularly remarkable after moisture absorption. Although detailed verification has not been made as a reason why the breakdown voltage has been improved, charges accumulated in non-polar silicone rubber due to fine voids, etc., causing dielectric breakdown based on this. It is presumed that the accumulated charges leaked by blending the titanium oxide yellow pigment, and it was difficult for dielectric breakdown to occur.

また、燃焼性の試験については、実施の形態、比較の形態ともに合格となっており、優れた難燃性を有していることが確認された。   Moreover, about the test of combustibility, both embodiment and the comparison form passed, and it was confirmed that it has the outstanding flame retardance.

本発明は上記の実施の形態に限定されるものではない、以下に他の形態について説明する。   The present invention is not limited to the above embodiment, and other embodiments will be described below.

繊維糸としては、例えば、ガラス繊維、アルミナ繊維、シリカ繊維、アルミナ−シリカ繊維、カーボン繊維等の無機繊維、ポリエステル繊維、全芳香族ポリエステル繊維、芳香族ポリアミド繊維、ポリフェニレンサルファイド繊維、ナイロン繊維等の有機繊維、銅線、銅合金線、ステンレス線等の金属細線などが挙げられ特に限定されない。これらは使用条件等を考慮して適宜選択すれば良い。勿論、単独で編組しても良いし、複数種を併用して編組しても良い。 Examples of the fiber yarn include inorganic fibers such as glass fiber, alumina fiber, silica fiber, alumina-silica fiber, and carbon fiber, polyester fiber, wholly aromatic polyester fiber, aromatic polyamide fiber, polyphenylene sulfide fiber, and nylon fiber. Examples thereof include fine metal wires such as organic fibers, copper wires, copper alloy wires, and stainless steel wires, and are not particularly limited. These may be appropriately selected in consideration of usage conditions and the like. Of course, you may braid independently and may braid combining multiple types.

酸化チタン系黄色顔料は、公知の物を使用すれば良く、例えば、TiO−NiO−Sb三成分系のもの、TiO−Cr−Sb三成分系のもの、TiO−BaO−NiO三成分系のもの、これらに少量の各種金属酸化物を含ませたものなどが知られている。酸化チタン系黄色顔料の配合量は、目的とする色相に応じて適宜設定すれば良く、例えば、液状シリコーンゴム100重量部に対し、0.5〜20.0重量部配合することが考えられる。 As the titanium oxide yellow pigment, a known material may be used, for example, a TiO 2 —NiO—Sb 2 O 3 ternary system, a TiO 2 —Cr 2 O 3 —Sb 2 O 3 ternary system, or the like. TiO 2 —BaO—NiO ternary system and those containing a small amount of various metal oxides are known. What is necessary is just to set the compounding quantity of a titanium oxide type yellow pigment suitably according to the target hue, for example, it is possible to mix | blend 0.5-20.0 weight part with respect to 100 weight part of liquid silicone rubbers.

また、編組チューブにおいては、シリコーンワニスの粘度や塗布工程の条件等を設定することよって、図2に示すような、編組のみからなる層1a、編組にシリコーンワニスが含浸した層1b、シリコーンワニスのみからなる層1c、の各層の厚さを制御することができる。各層の厚さは、目的とする特性や使用形態等を考慮して適宜設定すれば良いが、シリコーンワニスのみからなる層1cの厚さが全体の厚さの1/7〜2/9となるようにすれば、良好な外観を保持しつつ、編組チューブの端面においてホツレが発生し難くなるため好ましい。   Further, in the braided tube, by setting the viscosity of the silicone varnish, the conditions of the coating process, etc., as shown in FIG. 2, the layer 1a consisting of only the braid, the layer 1b in which the braid is impregnated with the silicone varnish, only the silicone varnish The thickness of each layer of the layer 1c made of can be controlled. The thickness of each layer may be appropriately set in consideration of the intended characteristics and usage, but the thickness of the layer 1c made of only the silicone varnish is 1/7 to 2/9 of the total thickness. In this case, it is preferable that the end face of the braided tube is hardly generated while maintaining a good appearance.

製造工程について、上記の実施の形態では、編組工程とシリコーンワニス塗布工程が同時となった工程により、編組チューブを作成したが、この製造工程に限定されることはない。例えば、編組スリーブを一度巻取り装置で巻取り、その後改めて液状シリコーンゴム組成物で満たされたタンクに導入して、液状シリコーンゴム組成物を塗布するというように、これらの工程を別工程としても構わない。   Regarding the manufacturing process, in the above embodiment, the braided tube is created by the process in which the braiding process and the silicone varnish application process are performed simultaneously, but the manufacturing process is not limited to this. For example, the braided sleeve is wound once with a winding device, and then introduced into a tank filled with the liquid silicone rubber composition, and the liquid silicone rubber composition is applied. I do not care.

上記の実施の形態は、編組スリーブに液状シリコーンゴム組成物を塗布する形態であったが、編組チューブとしての使用のみでなく、例えば、特開2006−32028号公報に開示されたような編組電線への応用も考えられる。編組電線の具体的な態様としては、導体上に絶縁被覆が施された電線に、繊維糸を編組して編組被覆を施し、次いでこの編組被覆に液状シリコーンゴム組成物を塗布した後、加熱硬化させ、電線と編組被覆をと接着一体化したものなどが挙げられる。   In the above embodiment, the liquid silicone rubber composition is applied to the braided sleeve. However, the embodiment is not limited to use as a braided tube. For example, a braided electric wire as disclosed in JP-A-2006-32028 is used. Application to is also conceivable. As a specific embodiment of the braided electric wire, an electric wire having an insulation coating on a conductor is braided by knitting fiber yarns, and then a liquid silicone rubber composition is applied to the braided coating, followed by heat curing. And an electric wire and a braided coating are bonded and integrated.

本発明においては、上記のような液状シリコーンゴム組成物としての使用のみでなく、固形のシリコーンゴムに酸化チタン系黄色顔料を配合し、それによって得られたシリコーンゴム組成物を一般的な各種成型品とすることもできる。この際の酸化チタン系黄色顔料の配合料は、目的とする色相や使用環境等に応じて適宜設定すれば良いが、シリコーンゴム100重量部に対して、酸化チタン系黄色顔料は、0.5〜20.0重量部配合することが考えられる。このようなシリコーンゴム組成物によれば、例えば、導体の外周に、本発明のシリコーンゴム組成物を押出成形等により被覆し、絶縁電線とすることもできる。このような形態においては、押出成形等による被覆後にシリコーンゴムの加硫工程を設けることも考えられる。また、このようなシリコーンゴム組成物それ単体を用い、押出成形や射出成形などにより、グロメット、パッキンをはじめとした一般的な各種成型品とすることもできる。   In the present invention, not only as a liquid silicone rubber composition as described above, but also by blending a solid silicone rubber with a titanium oxide yellow pigment, the resulting silicone rubber composition is formed into various general moldings. It can also be a product. In this case, the titanium oxide yellow pigment compounding agent may be appropriately set according to the target hue, use environment, etc., but the titanium oxide yellow pigment is 0.5 parts per 100 parts by weight of the silicone rubber. It is conceivable to add ˜20.0 parts by weight. According to such a silicone rubber composition, for example, the insulated rubber wire can be formed by coating the outer circumference of the conductor with the silicone rubber composition of the present invention by extrusion molding or the like. In such a form, a silicone rubber vulcanization step may be provided after coating by extrusion molding or the like. In addition, such a silicone rubber composition itself can be used to form general various molded articles such as grommets and packings by extrusion molding or injection molding.

参考ではあるが、本発明の知見より、以下のような発明の展開を行うことができる。   For reference, the following inventions can be developed based on the knowledge of the present invention.

上記実施の形態では、液状シリコーンゴムに酸化チタン系黄色顔料を配合したが、例えば、アルキッドワニスやアクリルワニスに酸化チタン系黄色顔料を配合し、それによって得られたアルキッドワニスやアクリルワニスを編組スリーブに塗布して編組チューブとすることもできる。この際の酸化チタン系黄色顔料の配合料は、目的とする色相や使用環境等に応じて適宜設定すれば良いが、アルキッドワニスもしくはアクリルワニス100重量部に対して、酸化チタン系黄色顔料0.5〜20.0重量部を配合することが考えられる。   In the above embodiment, the titanium oxide yellow pigment is blended with the liquid silicone rubber. For example, the titanium oxide yellow pigment is blended with the alkyd varnish or acrylic varnish, and the alkyd varnish or acrylic varnish obtained thereby is braided sleeve. A braided tube can also be applied by coating. The compounding agent for the titanium oxide yellow pigment at this time may be appropriately set according to the target hue, the use environment, etc., but the titanium oxide yellow pigment is added in an amount of 0.1% to 100 parts by weight of the alkyd varnish or acrylic varnish. It is possible to mix | blend 5-20.0 weight part.

本発明においては、シリコーンゴムに酸化チタン系黄色顔料を配合したが、他の耐熱性ゴム材料、例えば、フッ素ゴムに酸化チタン系黄色顔料を配合することも考えられる。フッ素ゴムも、シリコーンゴムと同様、高温化で使用されることが多い材料であるが、酸化チタン系黄色顔料を使用することで、そのような状況においても、変色を防止することができる。   In the present invention, the titanium oxide yellow pigment is blended with the silicone rubber, but it is also conceivable to blend the titanium oxide yellow pigment with another heat resistant rubber material, for example, fluorine rubber. Fluorine rubber is also a material often used at high temperatures, like silicone rubber, but discoloration can be prevented even in such a situation by using a titanium oxide yellow pigment.

以上のように本発明によれば、高温環境下での使用においても変色を抑制することが可能な優れた耐熱性を有したシリコーンゴム組成物及び液状シリコーンゴム組成物と、このシリコーンゴム組成物及び液状シリコーンゴム組成物を使用した編組チューブを提供することができる。また、編組電線への応用も可能である。また、その他にも、本発明によるシリコーンゴム組成物は、グロメット、パッキンをはじめとした一般的な各種成型品に応用することができる。 As described above, according to the present invention, a silicone rubber composition and a liquid silicone rubber composition having excellent heat resistance capable of suppressing discoloration even when used under a high temperature environment, and the silicone rubber composition And a braided tube using the liquid silicone rubber composition. Moreover, the application to a braided electric wire is also possible. In addition, the silicone rubber composition according to the present invention can be applied to various general molded products such as grommets and packings.

本発明の編組チューブの製造方法を実施するための装置の一例を示す説明図である。It is explanatory drawing which shows an example of the apparatus for enforcing the manufacturing method of the braided tube of this invention. 本発明による編組チューブを示す、一部拡大断面図である。It is a partially expanded sectional view which shows the braided tube by this invention.

符号の説明Explanation of symbols

1 編組チューブ
2 編組スリーブ
3 製紐機
4 繊維糸
5 タンク
6 絞り
7 加熱炉
9 ガイドプーリー
10 巻取り装置
DESCRIPTION OF SYMBOLS 1 Braided tube 2 Braided sleeve 3 String making machine 4 Fiber yarn 5 Tank 6 Drawing 7 Heating furnace 9 Guide pulley 10 Winding device

Claims (5)

シリコーンゴムに、酸化チタン系黄色顔料が配合されているシリコーンゴム組成物。 A silicone rubber composition in which a titanium oxide yellow pigment is blended with silicone rubber. 液状シリコーンゴムに、酸化チタン系黄色顔料が配合されている液状シリコーンゴム組成物。 A liquid silicone rubber composition in which a titanium oxide yellow pigment is blended with a liquid silicone rubber. 繊維糸を編組してなる編組スリーブに、請求項1記載のシリコーンゴム組成物を被覆してなる編組チューブ。 A braided tube formed by coating the silicone rubber composition according to claim 1 on a braided sleeve formed by braiding fiber yarns. 繊維糸を編組してなる編組スリーブに、請求項2記載の液状シリコーンゴム組成物を塗布し、該液状シリコーンゴム組成物を硬化してなる編組チューブ。 A braided tube formed by applying the liquid silicone rubber composition according to claim 2 to a braided sleeve formed by braiding fiber yarns and curing the liquid silicone rubber composition. 請求項1記載のシリコーンゴム組成物をチューブ状に成形してゴムチューブとし、該ゴムチューブ上に、繊維糸を編組することで被覆してなる編組チューブ。
A braided tube formed by forming the silicone rubber composition according to claim 1 into a tube shape to form a rubber tube, and coating the rubber tube by braiding fiber yarns.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012164688A (en) * 2011-02-03 2012-08-30 Nok Corp Grommet for electromagnetic wave shield

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57139141A (en) * 1981-02-24 1982-08-27 Toshiba Silicone Co Ltd Flame-retardant silicone rubber composition
JPH05125283A (en) * 1991-11-01 1993-05-21 Toshiba Silicone Co Ltd Flame-retardant silicone rubber composition for covering electric wire
JP2000513700A (en) * 1997-06-06 2000-10-17 ロディア シミ Compounds based on titanium, cerium and alkali or alkaline earths, their preparation and their use as pigments for coloring
WO2006062057A1 (en) * 2004-12-06 2006-06-15 Sigmax Ltd. Heat-resistant sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57139141A (en) * 1981-02-24 1982-08-27 Toshiba Silicone Co Ltd Flame-retardant silicone rubber composition
JPH05125283A (en) * 1991-11-01 1993-05-21 Toshiba Silicone Co Ltd Flame-retardant silicone rubber composition for covering electric wire
JP2000513700A (en) * 1997-06-06 2000-10-17 ロディア シミ Compounds based on titanium, cerium and alkali or alkaline earths, their preparation and their use as pigments for coloring
WO2006062057A1 (en) * 2004-12-06 2006-06-15 Sigmax Ltd. Heat-resistant sheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012164688A (en) * 2011-02-03 2012-08-30 Nok Corp Grommet for electromagnetic wave shield

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