JP4564975B2 - Electric wires and cables with excellent water resistance - Google Patents
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- JP4564975B2 JP4564975B2 JP2007072631A JP2007072631A JP4564975B2 JP 4564975 B2 JP4564975 B2 JP 4564975B2 JP 2007072631 A JP2007072631 A JP 2007072631A JP 2007072631 A JP2007072631 A JP 2007072631A JP 4564975 B2 JP4564975 B2 JP 4564975B2
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Description
本発明は、非鉛の耐水性クロロプレンゴム組成物を用いた環境保全性の高い電線・ケーブルに関する。 The present invention relates to a high environmental integrity using a water-resistant chloroprene rubber composition of the non-lead wires and cables.
従来から、高い耐水性が要求される屋外配線用の電線・ケーブルなどのシース材料、あるいは空港の灯火設備回路用機器として配設される電気機器(例えばトランス)の防水被覆材料には、クロロプレンゴムに鉛化合物(例えば四酸化三鉛)を配合したクロロプレンゴム組成物が使用されている。 Conventionally, chloroprene rubber has been used as a sheath material for electric wires and cables for outdoor wiring that requires high water resistance, or as a waterproof coating material for electrical equipment (for example, transformers) installed as equipment for airport lighting equipment circuits. A chloroprene rubber composition in which a lead compound (for example, trilead tetraoxide) is blended is used.
しかし、近年の地球環境保全に対する意識の高まりとともに、環境負荷の大きい材料の使用を規制する動きが強まっており、上記鉛化合物は、その使用が制限されつつある。 However, with the recent increase in awareness of global environmental conservation, there is an increasing movement to regulate the use of materials with a large environmental load, and the use of the lead compounds is being restricted.
このため、鉛化合物を含まない、環境保全性に優れた耐水性クロロプレンゴム組成物が求められている。非鉛のクロロプレンゴム組成物としては、例えば、クロロプレンゴムに酸化マグネシウムや酸化亜鉛を配合した組成物(例えば、特許文献1参照)が知られている。 For this reason, the water-resistant chloroprene rubber composition excellent in environmental conservation which does not contain a lead compound is required. As a lead-free chloroprene rubber composition, for example, a composition in which chloroprene rubber is blended with magnesium oxide or zinc oxide (for example, see Patent Document 1) is known.
しかしながら、このような従来のクロロプレンゴム組成物は、耐水性に乏しく、上記用途には適用し難かった。
本発明の目的は、このような課題に対処するためになされたもので、鉛化合物を含まない、環境保全性に優れた、高い耐水性を有する耐水性クロロプレンゴム組成物を用いた電線・ケーブルを提供することにある。 An object of the present invention is to address such problems, and is an electric wire / cable that uses a water-resistant chloroprene rubber composition that does not contain a lead compound and has excellent environmental conservation and high water resistance. Is to provide.
本発明者らは、上記目的を達成するために鋭意検討した結果、(A)クロロプレンゴムに対して、(B)湿式法シリカと(C)合成ハイドロタルサイトとをそれぞれ特定量配合することで、鉛化合物を配合しなくても、耐水性に優れ、環境保全性の高い耐水性クロロプレンゴム組成物が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have blended (A) chloroprene rubber with specific amounts of (B) wet process silica and (C) synthetic hydrotalcite, respectively. The inventors have found that a water-resistant chloroprene rubber composition having excellent water resistance and high environmental conservation can be obtained without blending a lead compound, and has led to the present invention.
すなわち、本願発明は、非鉛の耐水性クロロプレンゴム組成物であって、(A)クロロプレンゴム100重量部に対して、(B)湿式法シリカ15〜30重量部と、(C)合成ハイドロタルサイト5〜20重量部とを含有する組成物からなる被覆を有することを特徴とする耐水性に優れた電線・ケーブルである。 That is, the present invention is a lead-free water-resistant chloroprene rubber composition comprising (B) 15-30 parts by weight of wet process silica and (C) synthetic hydrotal to 100 parts by weight of (A) chloroprene rubber. It is an electric wire / cable excellent in water resistance characterized by having a coating made of a composition containing 5 to 20 parts by weight of a site.
上記電線・ケーブルにおいて、前記組成物は、前記(A)クロロプレンゴム100重量部に対して、さらに、脂肪酸の亜鉛塩を0.5〜10重量部含有するものであってもよい。 The said electric wire and cable WHEREIN: The said composition may contain 0.5-10 weight part of zinc salts of a fatty acid further with respect to 100 weight part of said (A) chloroprene rubber | gum.
耐水性クロロプレンゴム組成物は、非鉛で環境保全性に優れ、高い耐水性を有する。
本発明の電線・ケーブルは、上記特性を有する組成物の被覆を備えているので、環境保全性が高く、かつ、耐水信頼性の向上を図ることができる。 Resistant aqueous chloroprene rubber composition is excellent in environmental resistance in lead-free, has a high water resistance.
Since the electric wire / cable of the present invention is provided with the coating of the composition having the above characteristics, the environmental conservation is high and the water resistance reliability can be improved .
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
[(A)成分]
(A)成分はベースとなる成分である。(A)成分のクロロプレンゴムは、特に限定されるものではなく、G型(硫黄変性)、W型(非硫黄変性)のいずれでもよい。例えば、昭和電工デュポン社製のネオプレンW、ネオプレンWX-J、ネオプレンWRT等、バイエル社製のバイプレン210、バイプレン110、バイプレン116、東ソー社製のスカイプレンB-30、スカイプレンB-31、スカイプレンR-10、スカイプレンTSR-48(以上、いずれも商品名)等が使用される。これらは1種単独または2種以上を混合して使用される。
[(A) component]
The component (A) is a base component. The chloroprene rubber as the component (A) is not particularly limited, and may be either G type (sulfur modified) or W type (non-sulfur modified). For example, Neoprene W, Neoprene WX-J, Neoprene WRT manufactured by Showa Denko DuPont, etc. Len R-10, Skyprene TSR-48 (all are trade names) are used. These are used individually by 1 type or in mixture of 2 or more types.
[(B)成分]
(B)成分の湿式法シリカは、後述する(C)成分と併用することで、優れた耐水性を組成物に付与することができる。
[Component (B)]
Component (B) wet process silica can impart excellent water resistance to the composition when used in combination with component (C) described below.
(B)成分は、二酸化ケイ素を主成分とする微粒子状の充填剤であり、通常、ケイ酸ナトリウム水溶液またはアルカリ土類金属ケイ酸塩を酸分解して製造される。 The component (B) is a fine particle filler mainly composed of silicon dioxide, and is usually produced by acid decomposition of an aqueous sodium silicate solution or an alkaline earth metal silicate.
(B)成分としては、公知のものを使用でき、例えば、カープレックス、トクシール、ニップシール、シルトン、ミズカシル、シリシア、ゼオシール(以上、いずれも商品名)などが挙げられる。 (B) A well-known thing can be used as a component, For example, a carplex, a toxeal, a nip seal, a sillton, Mizukasil, a silicia, a zeo seal (all are brand names) etc. are mentioned.
(B)成分の配合量は、(A)成分100重量部に対して10〜40重量部、好ましくは15〜30重量部である。配合量が10重量部未満であると、十分な耐水性が得られない。40重量部を超えると、組成物の粘度が上昇して加工性の低下を招き、さらには耐水性の効果はさほど変わらず、不経済である。 (B) The compounding quantity of a component is 10-40 weight part with respect to 100 weight part of (A) component, Preferably it is 15-30 weight part. If the blending amount is less than 10 parts by weight, sufficient water resistance cannot be obtained. If it exceeds 40 parts by weight, the viscosity of the composition will increase, resulting in a decrease in processability, and the water resistance effect will not change so much, which is uneconomical.
[(C)成分]
(C)成分の合成ハイドロタルサイトは、結晶性の多孔体であり、上記(B)成分と併用することで組成物に優れた耐水性を付与することができる。
[Component (C)]
The synthetic hydrotalcite of component (C) is a crystalline porous body, and can impart excellent water resistance to the composition when used in combination with component (B).
(C)成分としては、公知のものを使用でき、例えば、化学式Mg4Al2(OH)12CO3・3H2O、Mg4.5Al2(OH)13CO3・3.5H2O、Mg6Al2(OH)16CO3・4H2O、Al2O3・xH2O、2.5MgO・Al2O3・xH2O(xは0<x≦0.33を満足する数である。)で表されるようなものが挙げられる。これらは1種単独または2種以上を混合して使用される。
The component (C), can be used known ones, for example, the formula Mg 4 Al 2 (OH) 12 CO 3 · 3H 2 O, Mg 4.5 Al 2 (OH) 13
(C)成分の配合量は、(A)成分100重量部に対して3〜30重量部、好ましくは5〜20重量部の範囲である。配合量が3重量部未満であると、十分な耐水性の効果が得られない。一方、30重量部を越えると、組成物の粘度が上昇して加工性の低下を招き、耐水性の効果はさほど変わらず、不経済である。 (C) The compounding quantity of a component is 3-30 weight part with respect to 100 weight part of (A) component, Preferably it is the range of 5-20 weight part. If the blending amount is less than 3 parts by weight, sufficient water resistance effect cannot be obtained. On the other hand, when the amount exceeds 30 parts by weight, the viscosity of the composition increases to cause a decrease in workability, and the water resistance effect is not so changed, which is uneconomical.
[その他任意成分]
本発明の耐水性クロロプレンゴム組成物には、上記(A)〜(C)の各成分を基本成分とし、これらに必要に応じて、任意成分として加工助剤を配合してもよい。
[Other optional ingredients]
In the water-resistant chloroprene rubber composition of the present invention, each of the above components (A) to (C) may be a basic component, and a processing aid may be blended as an optional component to these components as necessary.
加工助剤は、組成物に良好な加工性を付与する成分であり、例えば脂肪酸の金属塩が好ましい。脂肪酸は、飽和、不飽和のいずれあってもよい。 The processing aid is a component that imparts good processability to the composition, and for example, a metal salt of a fatty acid is preferable. The fatty acid may be either saturated or unsaturated.
脂肪酸の金属塩としては、例えば、オクタン酸、デカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、イコサン酸、オレイン酸、リノール酸、リノレン酸、ステアリン酸、及び一部分岐構造を有するイソステアリン酸などの飽和もしくは不飽和脂肪酸の亜鉛塩、カルシウム塩、マグネシウム塩などの金属塩が挙げられ、なかでも、脂肪酸を構成する炭素数が8〜22の亜鉛塩が好ましい。これらを1種単独または2種以上を混合して用いることができる。 Examples of fatty acid metal salts include saturated acids such as octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, icosanoic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, and isostearic acid having a partially branched structure. Or metal salts, such as a zinc salt of unsaturated fatty acid, a calcium salt, and a magnesium salt, are mentioned, Especially, the C2-C22 zinc salt which comprises a fatty acid is preferable. These can be used individually by 1 type or in mixture of 2 or more types.
脂肪酸の金属塩の配合量は、(A)成分100重量部に対して0.5〜10重量部、好ましくは1〜5重量部である。配合量が0.5重量部未満では、十分な加工性が得られない。一方、10重量部を越えると、加工性に関する効果はさほど変わらず、不経済である。 The compounding amount of the fatty acid metal salt is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight per 100 parts by weight of component (A). If the blending amount is less than 0.5 parts by weight, sufficient processability cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the effect on workability does not change so much, which is uneconomical.
さらに、その他の任意成分として、可塑剤、軟化剤、酸化防止剤、紫外線吸収剤、熱老化防止剤、加硫促進剤、滑剤、着色剤、安定剤などの添加剤を本発明の効果を阻害しない範囲で、必要に応じて配合することができる。例えば、可塑剤としては、ステアリン酸、オレイン酸などの脂肪酸およびこれらの金属塩などが挙げられる。また、軟化剤としては、鉱物油、ワックス、パラフィン類などが挙げられる。さらに、上述したクロロプレンゴムとともに、本発明の効果を阻害しない範囲で天然ゴムを配合することもできる。天然ゴムは、特に制限されるものではなく、RSSグレード、SMRグレードのいずれであってもよい。 In addition, additives such as plasticizers, softeners, antioxidants, UV absorbers, heat aging inhibitors, vulcanization accelerators, lubricants, colorants, stabilizers, and the like as other optional components inhibit the effects of the present invention. In the range not to be, it can mix | blend as needed. For example, examples of the plasticizer include fatty acids such as stearic acid and oleic acid, and metal salts thereof. Examples of the softener include mineral oil, wax, paraffins and the like. Furthermore, a natural rubber can also be mix | blended with the chloroprene rubber mentioned above in the range which does not inhibit the effect of this invention. Natural rubber is not particularly limited, and may be either RSS grade or SMR grade.
本発明の耐水性クロロプレンゴム組成物の製造方法としては、(A)〜(C)成分の基本成分と上記任意成分をバンバリーミキサ、タンブラー、加圧ニーダ、混練押出機、ミキシングローラなどの周知の混練機を用いて均一に混練する方法が挙げられる。 As a method for producing the water-resistant chloroprene rubber composition of the present invention, the basic components (A) to (C) and the optional components described above are well known, such as Banbury mixers, tumblers, pressure kneaders, kneading extruders, mixing rollers, and the like. The method of uniformly kneading using a kneader is mentioned.
このようにして得られた耐水性クロロプレンゴム組成物を、導体外周に直接もしくは他の被覆を介して押出被覆するか、あるいはテープ状に成形したものを巻き付けて、100〜200℃で0.5〜120分間加熱して加硫硬化することにより、本発明の電線・ケーブルが製造される。 The water-resistant chloroprene rubber composition thus obtained is extrusion-coated directly on the outer periphery of the conductor or through another coating, or is wound into a tape-shaped one and is wound at 100 to 200 ° C. to 0.5 The wire / cable of the present invention is produced by heating for 120 minutes to cure and cure.
加硫硬化した後の、本組成物の硬化物は、70℃の温水に20日間浸漬したときの単位表面積当たりの吸水量が7mg/cm2以下の耐水性能を有する。一般に、耐水性の要求性能(規格値)が10mg/cm2以下であることから、極めて優れた耐水性を有している。 The cured product of the present composition after vulcanization and curing has a water resistance of 7 mg / cm 2 or less when absorbed in warm water at 70 ° C. for 20 days. Generally, since the required performance (standard value) of water resistance is 10 mg / cm 2 or less, it has extremely excellent water resistance.
なお、本発明の組成物は、電線・ケーブル以外に、耐水性が要求される各種電気機器にも適用することができる。特に、高い耐水性が要求される空港灯火設備回路用機器(例えばトランス)に適用した場合に、顕著な効果があらわれる。 The composition of the present invention can also be applied to various electric devices that require water resistance in addition to electric wires and cables. In particular, when applied to an airport lighting equipment circuit device (for example, a transformer) requiring high water resistance, a remarkable effect appears.
図1に、本発明に係る電線・ケーブルの一例を示す。 FIG. 1 shows an example of an electric wire / cable according to the present invention.
電線・ケーブルは、銅やアルミなどからなる導体1上にポリエチレンや架橋ポリエチレン、EPゴムなどの絶縁層2を被覆した絶縁線心3を複数本(図面の例では3本)撚り合わせてケーブルコア4を形成するとともに、このケーブルコア4上に耐水シース5を設けた構造となっている。耐水シース5は、前述した耐水性クロロプレンゴム組成物の押出しにより形成されている。
For electric wires and cables, a cable core is formed by twisting a plurality of insulated wire cores 3 (three in the example of the drawing) in which an insulating
よって、電線・ケーブルは、耐水シース5が優れた耐水性をもつ非鉛のクロロプレンゴム組成物で形成されているので、高い信頼性を有している。このため、電線・ケーブルは、屋外で使用され雨水に曝されるような、高い耐水性が要求される用途に好適である。
Therefore, since the electric wire / cable is formed of the lead-free chloroprene rubber composition having excellent water resistance, the water-
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
実施例1
クロロプレンゴム(昭和電工デュポン社製、商品名ネオプレンGS)100重量部と、湿式法シリカ(日本シリカ工業社製、商品名ニップシールVN−3)20重量部と、合成ハイドロタルサイト(協和化学工業社製、商品名DHT−4A)16重量部とを加圧ニーダを用いて均一に混練してクロロプレンゴム組成物を得た。
Example 1
100 parts by weight of chloroprene rubber (manufactured by Showa Denko DuPont, trade name Neoprene GS), 20 parts by weight of wet-process silica (trade name: Nipsil VN-3, manufactured by Nippon Silica Kogyo Co., Ltd.), and synthetic hydrotalcite (Kyowa Chemical Industry Co., Ltd.) A chloroprene rubber composition was obtained by uniformly kneading 16 parts by weight of a product, trade name DHT-4A) using a pressure kneader.
次いで、5.5mm2の銅導体上に1mm厚のEPゴム絶縁層を設けた絶縁線心を3本撚り合わせつつ、その外周に上記組成物を押出被覆して約1.5mm厚のシースを形成し、外径約16mmのケーブルを製造した。 Next, while twisting three insulation cores each having a 1 mm thick EP rubber insulating layer on a 5.5 mm 2 copper conductor, the above composition was extrusion coated on the outer periphery to form a sheath having a thickness of about 1.5 mm. A cable having an outer diameter of about 16 mm was produced.
実施例2〜6、比較例1〜8
配合成分および配合量を表1に示すように変えた以外は、実施例1と同様にしてクロロプレンゴム組成物を得、さらに、得られた組成物を用いて実施例1と同様にしてケーブルを製造した。
Examples 2-6, Comparative Examples 1-8
A chloroprene rubber composition was obtained in the same manner as in Example 1 except that the blending components and blending amounts were changed as shown in Table 1, and a cable was obtained in the same manner as in Example 1 using the obtained composition. Manufactured.
上記各実施例および各比較例で得られたクロロプレンゴム組成物について、下記に示す方法で各種特性を評価した。なお、実施例4において使用した脂肪酸金属塩は、ラインケミー社製の商品名アクチプラストPPである。比較例5で使用した鉛は、関東化学社製の商品名酸化鉛(IV)、鉛(II)である。比較例6で使用した酸化マグネシウムは、協和化学工業社製の商品名キョーワマグ150あり、酸化亜鉛は、堺化学工業社製の商品名酸化亜鉛1種である。 About the chloroprene rubber composition obtained by each said Example and each comparative example, various characteristics were evaluated by the method shown below. In addition, the fatty acid metal salt used in Example 4 is the trade name Actyplast PP manufactured by Rhein Chemie. Lead used in Comparative Example 5 is trade names of lead (IV) oxide and lead (II) manufactured by Kanto Chemical Co., Inc. Magnesium oxide used in Comparative Example 6 is Kyowa Mag 150 manufactured by Kyowa Chemical Industry Co., Ltd., and zinc oxide is one type of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.
[耐水性]
クロロプレンゴム組成物をミキシングロールでシート状に成形し、シート化されたものをプレス機にて圧力20MPa、160℃、30分間の条件下で加熱加圧成型して30mm×30mm×2mmの試験片を作成した。この試験片を70℃の温水中に20日間浸漬した後の質量増加(試料片の単位表面積あたりの吸水量(mg/cm2))で評価した。
[water resistant]
A chloroprene rubber composition was formed into a sheet with a mixing roll, and the sheet was heated and pressure-molded under a pressure of 20 MPa, 160 ° C. for 30 minutes using a press machine, and a 30 mm × 30 mm × 2 mm test piece It was created. The test piece was evaluated by mass increase (water absorption per unit surface area (mg / cm 2 )) after being immersed in warm water at 70 ° C. for 20 days.
[加工性]
クロロプレンゴム組成物を20mm押出機でテープ状に押出す際の加工性を評価した。
[Machinability]
The processability when the chloroprene rubber composition was extruded into a tape shape with a 20 mm extruder was evaluated.
[引張強さ]
上記と同様にして試験片を作成し、JIS K 6251に準拠して引張強さを測定した。
これらの結果を表1に示す。
Test pieces were prepared in the same manner as described above, and the tensile strength was measured according to JIS K 6251.
These results are shown in Table 1.
表1から明らかなように、(A)クロロプレンゴム100重量部に対して、(B)湿式シリカを10〜40重量部配合し、(C)合成ハイドロタルサイトを3〜30重量部配合した実施例1〜6は、非鉛であり環境保全性に優れるとともに、鉛化合物(鉛)を使用しなくても耐水性が5〜6mg/cm2であり、耐水性の要求性能(規格値)が10mg/cm2以下であることから、極めて優れた耐水性を発揮している。 As is apparent from Table 1, (A) 10 to 40 parts by weight of wet silica is blended with 100 parts by weight of chloroprene rubber, and (C) 3 to 30 parts by weight of synthetic hydrotalcite is blended. Examples 1 to 6 are lead-free and excellent in environmental conservation, and water resistance is 5 to 6 mg / cm 2 without using a lead compound (lead), and the required performance (standard value) of water resistance is Since it is 10 mg / cm 2 or less, extremely excellent water resistance is exhibited.
特に、脂肪酸金属塩をさらに配合した実施例4は、高い耐水性とともに、優れた加工性を有する。 In particular, Example 4 further blended with a fatty acid metal salt has excellent processability as well as high water resistance.
1…導体、2…絶縁層、3…絶縁線心、4…ケーブルコア、5…シース。 DESCRIPTION OF SYMBOLS 1 ... Conductor, 2 ... Insulating layer, 3 ... Insulated wire core, 4 ... Cable core, 5 ... Sheath.
Claims (2)
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Application Number | Priority Date | Filing Date | Title |
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JP2007072631A JP4564975B2 (en) | 2007-03-20 | 2007-03-20 | Electric wires and cables with excellent water resistance |
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JP2012233146A (en) * | 2011-04-18 | 2012-11-29 | Katsuta Kako Kk | New anti-aging agent and rubber composition obtained by blending the same |
JP5734777B2 (en) * | 2011-07-19 | 2015-06-17 | 株式会社フジクラ | Cable manufacturing method |
JP2014009333A (en) * | 2012-07-02 | 2014-01-20 | Yokohama Rubber Co Ltd:The | Rubber composition, and vulcanization rubber product and hose using the same |
JP5761154B2 (en) * | 2012-10-22 | 2015-08-12 | 日立金属株式会社 | Chloroprene rubber composition, insulated wire and cable using the same |
JP2015115090A (en) * | 2013-12-06 | 2015-06-22 | 昭和電線ケーブルシステム株式会社 | Electric wire and cable |
JP2016084449A (en) * | 2014-10-29 | 2016-05-19 | 住友電気工業株式会社 | Abrasion resistant chlorine-based polymer composition and chlorine-based polymer coated cable |
JP7432820B2 (en) | 2020-03-16 | 2024-02-19 | 東ソー株式会社 | Laminate and its manufacturing method |
WO2021234762A1 (en) * | 2020-05-18 | 2021-11-25 | 三菱電機株式会社 | Handrail and method for manufacturing same |
WO2022113896A1 (en) * | 2020-11-26 | 2022-06-02 | デンカ株式会社 | Rubber composition, vulcanized object obtained from said rubber composition, and vulcanized molded object obtained from said rubber composition |
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JPH01268736A (en) * | 1988-04-20 | 1989-10-26 | Toyoda Gosei Co Ltd | Rubber compound |
JPH03268942A (en) * | 1990-03-19 | 1991-11-29 | Tosoh Corp | Composite body |
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JP2003161390A (en) * | 2001-11-27 | 2003-06-06 | Toyo Tire & Rubber Co Ltd | Flexible tube |
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