JP5423129B2 - Rubber composition for hose and hose - Google Patents

Description

  The present invention relates to a rubber composition excellent in adhesiveness to a brass plating wire and particularly suitable for use as an inner tube rubber of a hydraulic hose, and a hose manufactured using the rubber composition.

  Hydraulic hoses are mainly used in construction machinery such as power shovels and bulldozers, and hydraulically operated machines such as hydraulic jacks, hydraulic punchers, hydraulic presses, hydraulic benders, and other industrial machines. It plays an important role in transmitting driving force.

  Therefore, this hydraulic hose is required to withstand high pressure and transmit the driving force (pressure) accurately and quickly, and has high oil resistance and low volume expansion due to pressure. Further, since the hydraulic oil becomes hot during the operation of the machine and is often used in a severe environment where vibration and bending are always applied, heat resistance and durability are also required.

  Due to its required characteristics, the hydraulic hose normally operates as shown in FIG. 1 with an inner rubber layer 2 made of rubber (hereinafter also referred to as “inner tube rubber”) filled with hydraulic oil from the inside. A reinforcing layer 3 for withstanding the pressure of oil and an outer rubber layer 4 (hereinafter also referred to as “outer rubber”) for preventing damage to the reinforcing layer 3 and the inner rubber layer 2 from the outside are sequentially laminated. Has a laminated structure. Moreover, providing the said reinforcement layer in multiple layers as needed is also generally performed.

  As the inner tube rubber, acrylonitrile butadiene rubber (NBR), which is generally excellent in oil resistance and heat resistance, is used, and a brass plating wire is generally used for the reinforcing layer 3. However, the NBR and the brass plating wire do not necessarily have sufficient adhesiveness, and may be peeled off at the interface due to bending, vibration or the like during use, which may cause early product damage.

  The sulfur-crosslinked polymer such as NBR and the brass plating wire are bonded together by forming a chemical bond between the polymer and copper in the brass plating via sulfur. At this time, in order to obtain good adhesion, it is important to keep a good balance between the crosslinking rate of rubber and the copper sulfide formation rate of brass plating. In order to improve the adhesion between the NBR and the brass-plated wire, it is effective to increase the amount of sulfur, but if the amount of sulfur increases, more crosslinks are formed in the rubber. The heat resistance may be insufficient. Therefore, it is difficult to achieve both good adhesion and heat resistance only by adjusting the amount of sulfur, and attempts have been made to add various adhesion aids to overcome this problem. It was.

  For example, in Japanese Patent Application Laid-Open No. 55-12138 (Patent Document 1) and Japanese Patent Application Laid-Open No. 56-162648 (Patent Document 2), an organic acid cobalt is added to a rubber composition to promote a copper sulfide formation reaction. Thus, attempts have been made to improve adhesiveness. However, when the above organic acid cobalt is blended, vulcanization delay occurs, so adjustment of the vulcanization time may be difficult, and there is a concern that the range of production conditions is narrow and difficult to handle at the production site. .

  JP-A-58-72436 (Patent Document 3) and JP-A-59-162648 (Patent Document 4) include a phenol resin and a maleic anhydride-modified polymer to improve the brass plating. A technique for improving adhesiveness by forming a hydrogen bond with a functional group is disclosed. However, in the method using the phenol resin, the rubber hardness may increase and fatigue may be reduced. In the method using the modified polymer, unvulcanized and vulcanized rubber may be used depending on the functional group of the modified polymer. The surface tackiness of the product may increase excessively, which may adversely affect workability and the appearance of the product.

  Furthermore, Japanese Patent Publication No. 7-68414 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2000-281836 (Patent Document 6) also propose a technique for improving adhesiveness by prescribing triazines.

  Thus, in the past, in order to firmly bond the NBR and the brass plating wire of the reinforcing layer, it has been necessary to blend the various adhesive aids described above. However, the cost increases due to the use of these adhesive aids. There are still concerns about such problems as causing adverse effects such as a decrease in workability due to an increase in viscosity, a decrease in fatigue due to an increase in hardness, and a decrease in vulcanization speed, and further improvement is desired.

Japanese Patent Laid-Open No. 55-12138 JP-A-56-162648 JP 58-72436 A JP 59-162648 A Japanese Examined Patent Publication No. 7-68414 JP 2000-281836 A

  The present invention has been made in view of the above circumstances, and has excellent adhesion to a reinforcing material without using an adhesive aid, and can be suitably used as an inner tube rubber of a hydraulic hose, and the rubber composition It aims at providing the hose manufactured using the.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor optimized the blending ratio (mass ratio) of sulfur and zinc oxide (zinc white), the type and blending amount of the vulcanization accelerator, It has been found that a rubber composition that can be firmly bonded to a reinforcing material such as a brass-plated wire can be obtained without using a conventionally required adhesion assistant, and the present invention has been achieved.

That is, the present invention includes 80 parts by mass or more of acrylonitrile butadiene rubber (NBR) in 100 parts by mass of the rubber component, and 1.5 to 3 parts by mass of sulfur as a crosslinking agent with respect to 100 parts by mass of the rubber component. 1 to 5 parts by mass of a thiuram compound as a vulcanization accelerator, 0.5 to 10 parts by mass of zinc oxide (zinc flower), and a mixing ratio of sulfur and zinc flower (sulfur / zinc flower (mass ratio)) ) is, rubber composition for a hose, characterized in that 2.0 or more, and at least the inner tube rubber, the hose having a reinforcing layer consisting of brass-plated wire formed outside of the inner tube rubber A hose formed by forming the inner tube rubber with the rubber composition is provided.

  The rubber composition of the present invention comprises a brass-plated wire used as a reinforcing material for hydraulic hoses without reducing various properties such as oil resistance and handleability by selecting various compounding agents and optimizing their compounding amounts. It can be firmly bonded and can be suitably used as an inner tube rubber of a hydraulic hose. In this case, the inner tube rubber made of the rubber composition of the present invention and the brass-plated wire of the reinforcing layer are firmly bonded to each other, so that the hose has excellent durability so that neither of them peels off even in severe use. be able to. In addition, since it is not necessary to use an adhesion aid that leads to an increase in the cost of rubber, it can be made excellent in terms of cost. In addition, there is no fear of adverse effects on the physical properties of rubber other than adhesiveness such as vulcanization rate delay.

  The rubber composition of the present invention does not adversely affect the physical properties of rubber other than adhesiveness, has excellent adhesiveness to a brass plating wire used as a reinforcing material for a hydraulic hose, and the inner tube rubber of the hydraulic hose By using the rubber composition of the present invention for the inner tube rubber of a hydraulic hose, a hydraulic hose excellent in durability and cost performance can be provided.

It is a schematic perspective view which shows one Example of the hydraulic hose which concerns on this invention.

The rubber composition for a hose of the present invention uses a rubber component containing acrylonitrile butadiene rubber (NBR) in a predetermined ratio, sulfur as a crosslinking agent, thiuram compound as a vulcanization accelerator, and zinc oxide (zinc white). A predetermined amount is included, and the mixing ratio of sulfur and zinc white (sulfur / zinc white (mass ratio)) is set to 2.0 or more. In particular, the inner rubber layer 2 in the hydraulic hose 1 shown in FIG. It is suitably used as a rubber for forming.

  The rubber component includes NBR. In that case, the ratio of NBR in the rubber component is 80 parts by mass or more, preferably 90 parts by mass or more, and more preferably 100 parts by mass, out of 100 parts by mass of the rubber component. If the NBR ratio is less than the above range, the adhesiveness may be lowered.

  The NBR may be appropriately selected from known ones and is not particularly limited, but the amount of acrylonitrile (AN content) contained in the NBR is 28 to 41% by mass, particularly 35 to 41% by mass. A range is preferable. If the AN content exceeds 41% by mass, the low temperature characteristics and fatigue resistance may decrease and the hardness may increase, and if it is less than 28% by mass, the required oil resistance may not be achieved.

  A portion other than the above NBR in the rubber component can be blended with known natural or synthetic rubber. Specifically, butadiene rubber, styrene / butadiene rubber, ethylene / propylene / diene rubber, isoprene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, isobutylene / isoprene rubber, acrylonitrile / butadiene rubber, silicone rubber, acrylic rubber, epoxidized natural rubber , Synthetic rubbers such as acrylate butadiene rubbers and the like, and those in which the molecular chain ends of these synthetic rubbers or natural rubbers are modified. One or more of these may be appropriately selected and used. . When the above rubber is blended, it is preferably 20 parts by mass or less, particularly 10 parts by mass or less, out of 100 parts by mass of the rubber component.

  In the present invention, sulfur is used as a crosslinking agent. The blending amount is preferably 1.5 to 3 parts by mass, particularly 1.5 to 2.5 parts by mass, and more preferably 1.5 to 2 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount exceeds 3 parts by mass, good adhesiveness can be obtained, but the heat resistance may decrease, and if it is less than 1.5 parts by mass, the adhesiveness may decrease. There is.

  A thiuram compound is used as the vulcanization accelerator. Specifically, a known vulcanization accelerator such as tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD) or the like is preferably used. It is possible to select one or two or more from these as appropriate. Moreover, a commercial item can be used for said vulcanization accelerator, for example, Nouchira TT (TMTD), Noxeller TS (TMTM), Noxeller TET (TETD), and Noxeller TBT made by Ouchi Shinsei Chemical Industry Co., Ltd. (TBTD) or the like can be used. The blending amount of the vulcanization accelerator is preferably 1 to 5 parts by mass, particularly 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the rubber component. If the amount exceeds 5 parts by mass, the rubber hardness will increase, the elongation at break will decrease, and the vulcanization accelerator residue may bleed out after vulcanization. Vulcanization rate cannot be obtained, and productivity may be adversely affected.

  In addition, in the range which does not deviate from the object of the present invention, thiazole compounds other than the thiuram compounds (2-mercaptobenzothiazole: MBT, dibenzothiazoyl disulfide: MBTS, etc.), guanidines (di-o-tolylguanidine: DOTG, 1,3-diphenylguanidine: DPG, etc., sulfenamide type (N-dichloro-2-benzothiazoylsulfenamide: CBS, N-tert-butyl-2-benzothiazolylsulfenamide: BBS, etc. ) Vulcanization accelerators can also be blended. When blending a vulcanization accelerator other than these thiuram compounds, the blending amount is 2 parts by mass or less with respect to 100 parts by mass of the rubber component, and the total amount with the thiuram compound is 5 parts by mass or less. It is preferable to do so.

  Zinc oxide (zinc white) is used as a vulcanization accelerating aid, and its blending amount is 0.5 to 10 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component. It is preferable that When the amount exceeds 10 parts by mass, the adhesiveness may be lowered. When the amount is less than 0.5 parts by mass, the vulcanization rate may be significantly reduced.

  Furthermore, in the present invention, the blending ratio of sulfur and zinc white (sulfur / zinc white (mass ratio)) is preferably 0.4 or more, particularly 2.0 or more. The upper limit is not particularly limited, but is preferably 6.0 or less, particularly 3.0 or less. When the said mixture ratio deviates from the said range, there exists a possibility of causing the fall of adhesiveness.

  Further, in the present invention, the above rubber component, as long as it does not impair the effects of the present invention, if necessary, other crosslinking agents (vulcanizing agents), vulcanization accelerators and vulcanization acceleration assistants, Carbon used, anti-aging agent, plasticizer, petroleum resin, vulcanization retarder, waxes, antioxidant, filler, foaming agent, oil, lubricant, tackifier, UV absorber, dispersant, phase Additives such as a solubilizer and a homogenizer can be appropriately blended.

  Known carbon can be used, and is not particularly limited. Examples thereof include carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, MT, In the present invention, SRF can be preferably used. Moreover, these carbon blacks may be used individually by 1 type, and may use 2 or more types together. The compounding amount of the carbon black is preferably 50 to 150 parts by mass, particularly 80 to 120 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount exceeds 150 parts by mass, the viscosity of the unvulcanized rubber may increase too much, which may reduce kneading, rolling, and extrusion workability. If the blending amount is less than 50 parts by mass, the strength necessary for a hydraulic hose is increased. May not be obtained.

  As the anti-aging agent, known ones can be used, and are not particularly limited, but one or more of phenol-based anti-aging agent, imidazole-based anti-aging agent, amine-based anti-aging agent and the like are used. Can be used. The blending amount of the anti-aging agent is preferably 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component.

  As the plasticizer, known ones can be used and are not particularly limited. Specifically, process oils such as aromatic oil, naphthenic oil, paraffin oil, palm oil, castor oil, etc. Vegetable oils, synthetic oils such as alkylbenzene oil, and ester plasticizers such as DOA (dioctyl adipate). These can be used alone or in combination of two or more. The compounding amount of the plasticizer is preferably 5 to 15 parts by mass with respect to 100 parts by mass of the rubber component.

  As the petroleum resin, known aromatic hydrocarbon resins, aliphatic hydrocarbon resins and the like can be used. These petroleum resins may be used alone or in combination of two or more. In addition, it is preferable that the compounding quantity of the said petroleum resin shall be 1-5 mass parts with respect to 100 mass parts of said rubber components.

  A known vulcanization retarder can be used and is not particularly limited, and examples thereof include N-cyclohexylthiophthalimide (SantogardPVI: manufactured by Monsato). The amount of the vulcanization retarder is preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the rubber component.

  When obtaining the rubber composition of the present invention, there is no particular limitation on the blending method of each of the above components, and all the component raw materials may be blended and kneaded at once, and each component may be divided into two or three stages. You may mix | blend and knead | mix. In the kneading, a kneader such as a roll, an internal mixer, a Banbury rotor or the like can be used.

  The vulcanization conditions for curing the rubber composition are not particularly limited, but vulcanization conditions for 10 to 90 minutes can be generally employed at 140 to 180 ° C.

  When manufacturing a rubber hose having a reinforcing layer using the rubber composition of the present invention, a normal method can be adopted. For example, when manufacturing a hydraulic hose 1 as shown in FIG. It can be produced by the method shown below.

  First, the rubber composition of the present invention is extrusion-molded on the outer side of a core (mandrel) having the same diameter as the inner diameter of the hose to cover the mandrel, thereby forming an inner rubber layer (inner tube rubber) 2 (inner Tube extrusion process). Next, a predetermined number of brass-plated wires are knitted outside the inner rubber layer 2 formed in the inner tube extrusion step, and a reinforcing layer 3 is laminated (knitting step). The rubber composition to be formed is extruded to form an outer rubber layer (outer rubber) 4 (outer extrusion process). Furthermore, the outer surface of the outer rubber layer 4 formed in the jacket extrusion step is coated with a resin (resin mold coating step), and vulcanized under normal conditions (vulcanization step). After vulcanization, the above-mentioned coating resin is peeled off (resin mold peeling step), and the mandrel is removed (mandrel extraction step), whereby a hydraulic hose 1 having a reinforcing layer 3 between the inner tube rubber 2 and the outer jacket rubber 4 It becomes. The hydraulic hose 1 thus obtained is excellent in durability that the inner tube rubber 2 and the brass plating wire of the reinforcing layer 3 are firmly bonded to each other so that they do not peel off even in severe use. It will be. In addition, since it is not necessary to use an adhesion aid that leads to an increase in the cost of rubber, it can be made excellent in terms of cost. In addition, there is no fear of adverse effects on the physical properties of rubber other than adhesiveness such as vulcanization rate delay.

  The structure of the hydraulic hose 1 may be a three-layer structure in which the inner tube rubber 2, the reinforcing layer 3 and the outer cover rubber 4 are sequentially laminated from the inside as described above. Although not shown in the drawing, the reinforcing layer may be a two-layered structure, and a five-layer structure in which an intermediate layer (intermediate rubber) is arranged between the two reinforcing layers. May be set as appropriate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

[Examples 1 to 23, Reference Examples 1 to 7 , Comparative Examples 1 to 27]
A rubber composition having the composition shown in Table 1 was used as a basic composition, and kneaded according to a conventional method using the composition shown in the following tables, and a rectangular unvulcanized rubber sheet having a width of 120 mm, a length of 120 mm, and a thickness of 2 mm was obtained. It produced and evaluated the adhesiveness with a brass plating wire with the following method.
"Evaluation method"
・ Adhesiveness (wire peeling test)
Three sets of five brass plating wires with a diameter of 0.3 mm and a length of 100 mm arranged in one set were arranged on the surface of the prepared unvulcanized rubber sheet, and both ends thereof were fixed with tape. Next, in this state, the unvulcanized rubber sheet was vulcanized at 150 ° C. for 60 minutes, and then the wire was peeled off from the rubber sheet, and the surface state of the peeled wire was visually observed. The evaluation of adhesiveness is performed by calculating the ratio of the wire with rubber attached to the surface to the total number of wires bonded to the unvulcanized rubber sheet. did.

  First, Table 1 shows the basic composition of the rubber composition of the present invention.

ＮＢＲ：ＪＳＲ（株）製「ＪＳＲ Ｎ２３０Ｓ」（ＡＮ含量３５質量％）
カーボンブラック：ＳＲＦ級カーボンブラック、旭カーボン（株）製「旭＃５０」
老化防止剤：大内新興化学工業（株）製「ノクラック２２４」
石油樹脂：炭素数４〜５の炭化水素留分重合物、東燃化学（株）製「ＥＳＣＯＲＥＺ１１０２」
可塑剤：ＤＯＡ（ジオクチルアジペート）、新日本理化（株）製「サンソサイザーＤＯＡ」
硫黄：鶴見化学工業（株）製「サルファックス５」
加硫促進剤１：ＴＭＴＭ、大内新興化学工業（株）製「ノクセラーＴＳ」
加硫促進剤２：ＭＢＴＳ、大内新興化学工業（株）製「ノクセラーＤＭ」
亜鉛華：東邦亜鉛（株）製「銀嶺ＳＲ」
加硫遅延剤：Ｍｏｎｓａｔｏ社製「ＳａｎｔｏｇａｒｄＰＶＩ」

NBR: “JSR N230S” manufactured by JSR Corporation (AN content 35% by mass)
Carbon black: SRF grade carbon black, "Asahi # 50" manufactured by Asahi Carbon Co., Ltd.
Anti-aging agent: “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Petroleum resin: hydrocarbon fraction polymer having 4 to 5 carbon atoms, “ESCOREZ1102” manufactured by Tonen Chemical Co., Ltd.
Plasticizer: DOA (dioctyl adipate), “Sanso Sizer DOA” manufactured by Shin Nippon Rika Co., Ltd.
Sulfur: “Sulfax 5” manufactured by Tsurumi Chemical Co., Ltd.
Vulcanization accelerator 1: TMTM, “Noxeller TS” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator 2: MBTS, “Noxeller DM” manufactured by Ouchi Shinsei Chemical Co., Ltd.
Zinc Hana: “Ginza SR” manufactured by Toho Zinc Co., Ltd.
Vulcanization retarder: “SantogardPVI” manufactured by Monsato

  In this invention, the adhesiveness with respect to the brass plating wire in each compounding was examined by changing the kind and compounding quantity of each component based on the basic compounding of the said Table 1.

  First, Table 2 shows the results of studying the case where a rubber component other than NBR is used in combination with another rubber and the blending ratio of NBR is changed.

ＳＢＲ：ＪＳＲ（株）製「ＪＳＲ １５００」
ＥＰＤＭ：ＪＳＲ（株）製「ＪＳＲ ＥＰ３３」
（基）：基本配合
※上記表２中の実施例及び比較例は、表１の基本配合に対して表中で示したＮＢＲ以外のゴム種を選択配合したものであり、ゴム成分以外の他の配合成分は表１と同一である。

SBR: “JSR 1500” manufactured by JSR Corporation
EPDM: “JSR EP33” manufactured by JSR Corporation
(Base): Basic blending * The examples and comparative examples in Table 2 above are prepared by selectively blending rubber types other than NBR shown in the table with respect to the basic blending in Table 1, and other than rubber components. The blending components are the same as in Table 1.

  From the results of Table 2 above, it was confirmed that, in the rubber composition of the present invention, excellent adhesiveness to the brass-plated wire can be obtained by setting the blending ratio of NBR in the rubber component within the range of the present invention.

  Table 3 shows the results of studies on the use of NBR with different AN (acrylonitrile) contents.

Ｎｉｐｏｌ ＤＮ３０６：日本ゼオン（株）製
ＮＡＮＣＡＲ１０３２：南帝化学工業社製
ＪＳＲ Ｎ２３０ＳＶ：ＪＳＲ（株）製
ＪＳＲ Ｎ２１５ＳＬ：ＪＳＲ（株）製
ＪＳＲ Ｎ２３０Ｓ：ＪＳＲ（株）製
ＪＳＲ Ｎ２２０Ｓ：ＪＳＲ（株）製
（基）：基本配合
※上記表３中の実施例は、表１の基本配合に対してＡＮ含量の異なるＮＢＲを選択配合したものであり、ＮＢＲ以外の他の配合成分は表１と同一である。

Nipol DN306: Nippon Zeon Co., Ltd. NANCAR 1032: Nansei Chemical Industry Co., Ltd. JSR N230SV: JSR Co., Ltd. JSR N215SL: JSR Co., Ltd. JSR N230S: JSR Co., Ltd. JSR N220S: JSR Co., Ltd. ( Group): Basic formulation * The examples in Table 3 above are prepared by selectively blending NBRs having different AN contents with respect to the basic formulations in Table 1, and the other components other than NBR are the same as those in Table 1. .

  From the results of Table 3 above, it was confirmed that by using NBR whose AN content falls within the scope of the present invention, excellent adhesion to a brass-plated wire can be obtained.

  Next, Tables 4 to 8 show the results of examining the blends in which sulfur / zinc white (mass ratio) was changed from the basic blends in Table 1 above.

※上記表４中の実施例及び比較例は、表１の基本配合に対して硫黄及び亜鉛華の配合量を変えたものであり、硫黄及び亜鉛華以外の配合成分は表１と同一である。

* The examples and comparative examples in Table 4 above are obtained by changing the blending amounts of sulfur and zinc white with respect to the basic blends in Table 1. The blending components other than sulfur and zinc white are the same as in Table 1. .

（基）：基本配合
※上記表５中の実施例、参考例及び比較例は、表１の基本配合に対して硫黄及び亜鉛華の配合量を変えたものであり、硫黄及び亜鉛華以外の配合成分は表１と同一である。

(Base): Basic formulation * The examples , reference examples and comparative examples in Table 5 above are obtained by changing the blending amounts of sulfur and zinc white with respect to the basic formulation of Table 1, except for sulfur and zinc white. The blending components are the same as in Table 1.

※上記表６中の参考例及び比較例は、表１の基本配合に対して硫黄及び亜鉛華の配合量を変えたものであり、硫黄及び亜鉛華以外の配合成分は表１と同一である。

* The reference examples and comparative examples in Table 6 above are obtained by changing the blending amounts of sulfur and zinc white with respect to the basic blends in Table 1. The blending components other than sulfur and zinc white are the same as in Table 1. .

※上記表７中の参考例及び比較例は、表１の基本配合に対して硫黄及び亜鉛華の配合量を変えたものであり、硫黄及び亜鉛華以外の配合成分は表１と同一である。

* The reference examples and comparative examples in Table 7 above are obtained by changing the blending amounts of sulfur and zinc white with respect to the basic blends in Table 1. The blending components other than sulfur and zinc white are the same as in Table 1. .

※上記表８中の実施例、参考例及び比較例は、表１の基本配合に対して硫黄及び亜鉛華の配合量を変えたものであり、硫黄及び亜鉛華以外の配合成分は表１と同一である。

* The examples , reference examples and comparative examples in Table 8 above are obtained by changing the blending amounts of sulfur and zinc white with respect to the basic blends in Table 1. Are the same.

  From the results of Tables 4 to 8 above, it is confirmed that the blending amount of sulfur and zinc white, and sulfur / zinc white (mass ratio) are within the scope of the present invention, thereby having excellent adhesion to a brass plating wire. It was done.

  Tables 9 and 10 show the results of examining the blends obtained by changing the types and blending amounts of the vulcanization accelerators from the basic blends in Table 1 above.

ＴＴ：ＴＭＴＤ、大内新興化学工業（株）製「ノクセラーＴＴ」
ＴＢＴ：ＴＢＴＤ、大内新興化学工業（株）製「ノクセラーＴＢＴ」
ＴＳ：ＴＭＴＭ、大内新興化学工業（株）製「ノクセラーＴＳ」
※上記表９中の実施例は、表１の基本配合の加硫促進剤１，２に変えて、表中に示した加硫促進剤を選択配合したものであり、これら加硫促進剤以外の他の配合成分は表１と同一である。

TT: TMTD, “Noxeller TT” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
TBT: TBTD, “Noxeller TBT” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
TS: TMTM, “Noxeller TS” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* The examples in Table 9 above are obtained by selectively blending the vulcanization accelerators shown in the table in place of the vulcanization accelerators 1 and 2 of the basic composition in Table 1. Other than these vulcanization accelerators The other ingredients are the same as in Table 1.

Ｍ：ＭＢＴ、大内新興化学工業（株）製「ノクセラーＭ」（チアゾール系加硫促進剤）
ＤＭ：ＭＢＴＳ、大内新興化学工業（株）製「ノクセラーＤＭ」（チアゾール系加硫促進剤）
ＤＴ：ＤＯＴＧ、大内新興化学工業（株）製「ノクセラーＤＴ」（グアニジン系加硫促進剤）
Ｄ：ＤＰＧ、大内新興化学工業（株）製「ノクセラーＤ」（グアニジン系加硫促進剤）
ＣＺ：ＣＢＳ、大内新興化学工業（株）製「ノクセラーＣＺ」（スルフェンアミド系加硫促進剤）
ＮＳ：ＢＢＳ、大内新興化学工業（株）製「ノクセラーＮＳ−Ｆ」（スルフェンアミド系加硫促進剤）
※上記表１０中の比較例は、表１の基本配合の加硫促進剤１，２に変えて、表中に示した加硫促進剤を選択配合したものであり、これら加硫促進剤以外の他の配合成分は表１と同一である。

M: MBT, “Noxeller M” (Thiazole vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
DM: MBTS, “Noxeller DM” (thiazole vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
DT: DOTG, “Noxeller DT” (guanidine-based vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Co., Ltd.
D: DPG, “Noxeller D” (guanidine-based vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
CZ: CBS, “Noxeller CZ” (sulfenamide vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
NS: BBS, “Noxeller NS-F” (sulfenamide vulcanization accelerator) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* The comparative examples in Table 10 above are prepared by selectively blending the vulcanization accelerators shown in the table in place of the vulcanization accelerators 1 and 2 of the basic composition in Table 1, except for these vulcanization accelerators. The other ingredients are the same as in Table 1.

  From the results of Table 9 and Table 10 above, it was confirmed that by using a thiuram compound as a vulcanization accelerator, excellent adhesion to a brass-plated wire was obtained.

1 Hydraulic hose 2 Internal rubber layer (inner pipe rubber)
3 Reinforcing layer 4 Outer rubber layer (outer rubber)

Claims (4)

Among 100 parts by mass of the rubber component, 80 parts by mass or more of acrylonitrile butadiene rubber (NBR) is included,
For 100 parts by mass of the rubber component,
1.5 to 3 parts by mass of sulfur as a crosslinking agent,
1 to 5 parts by mass of a thiuram compound as a vulcanization accelerator,
Containing 0.5 to 10 parts by mass of zinc oxide (zinc flower),
And the rubber | gum composition for hoses characterized by the compounding ratio (sulfur / zinc white (mass ratio)) of the said sulfur and zinc white being 2.0 or more.   The rubber composition for a hose according to claim 1, wherein the rubber composition is a rubber hose having a reinforcing layer made of a brass-plated wire and forming a rubber layer that directly adheres to the brass-plated wire of the reinforcing layer.   A hose comprising at least an inner tube rubber and a reinforcing layer made of a brass-plated wire formed on the outer side of the inner tube rubber, wherein the inner tube rubber is formed of the rubber composition according to claim 1.   The hose according to claim 3, which is a hydraulic hose filled with hydraulic oil of a hydraulic drive device.

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