WO2019235073A1 - Rubber composition for hose, and hose - Google Patents

Rubber composition for hose, and hose Download PDF

Info

Publication number
WO2019235073A1
WO2019235073A1 PCT/JP2019/016178 JP2019016178W WO2019235073A1 WO 2019235073 A1 WO2019235073 A1 WO 2019235073A1 JP 2019016178 W JP2019016178 W JP 2019016178W WO 2019235073 A1 WO2019235073 A1 WO 2019235073A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber composition
hose
present
rubber
mass
Prior art date
Application number
PCT/JP2019/016178
Other languages
French (fr)
Japanese (ja)
Inventor
孝樹 杉原
Original Assignee
横浜ゴム株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Publication of WO2019235073A1 publication Critical patent/WO2019235073A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall

Definitions

  • the present invention relates to a rubber composition for a hose and a hose.
  • rubber hoses have been used as hydraulic pipes for construction machinery and the like and car air conditioner system hoses.
  • the rubber hose is fixed to the connecting portion by, for example, caulking with a metal fitting at the connecting portion.
  • the rubber hose is required to have good mountability with a metal fitting under a predetermined pressure.
  • the rubber used for the rubber hose is specifically required to have, for example, a high modulus (high hardness) and excellent compression set resistance.
  • the rubber used in rubber hoses has high modulus as described above and excellent compression set resistance, as well as excellent heat resistance. Desired.
  • Patent Document 1 discloses that, with respect to 100 parts by weight of an ethylene / ⁇ -olefin / nonconjugated polyene copolymer, X parts by weight of zinc oxide having a specific surface area of S (m 2 / g), and if necessary, A vulcanizable rubber composition containing Y parts by weight of polyethylene glycol and / or aliphatic ammonium added in such a manner that a specific formula relationship is established between S, X, and Y is described.
  • Patent Document 1 describes that the specific surface area of zinc oxide is preferably in the range of 1 to 30 m 2 / g.
  • an object of the present invention is to provide a rubber composition having a high modulus and excellent in compression set resistance and heat resistance. It is another object of the present invention to provide a hose that is excellent in fitting property and heat resistance.
  • the rubber composition contains a diene rubber, zinc oxide having a specific surface area within a predetermined range, and sulfur, and the zinc oxide and sulfur.
  • the inventors have found that a desired effect can be obtained when the content of is in a predetermined range, and have reached the present invention.
  • the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
  • the zinc oxide content is 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber
  • carbon black is contained, The rubber composition for a hose according to [1], wherein the content of the carbon black is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the rubber composition for hose according to [2], wherein the carbon black includes GPF grade carbon black and / or SRF grade carbon black.
  • the rubber composition for a hose of the present invention has a high modulus and is excellent in compression set resistance and heat resistance. Moreover, the hose of this invention is excellent in the mounting
  • FIG. 1 is a schematic perspective view showing an example of the hose of the present invention by cutting out each layer.
  • a numerical range expressed using “to” in the present specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • each component can be used alone or in combination of two or more of the substances corresponding to the component.
  • the content of the component means the total content of the two or more types of substances.
  • Each component described in this specification is not particularly limited with respect to its production method. For example, a conventionally well-known thing is mentioned. In the present specification, the fact that at least one of high modulus, compression set resistance and heat resistance is superior may be referred to as “the effect of the present invention is more excellent”.
  • the rubber composition for a hose of the present invention contains a diene rubber, zinc oxide having a specific surface area of 30 to 150 m 2 / g, and sulfur. Is a rubber composition for a hose having a content of 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber and a sulfur content of less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
  • the rubber composition of the present invention Since the rubber composition of the present invention has such a configuration, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed that it is as follows.
  • the amount of sulfur contained in the rubber composition of the present invention is set smaller than usual. It was considered that when the sulfur content is reduced, the resulting rubber may not have a high modulus and excellent compression set resistance.
  • the zinc oxide contained in the rubber composition of the present invention has a very high effect of activating sulfur because the specific surface area is in a predetermined range.
  • the content of sulfur contained in the rubber composition is at least as described above, and when the rubber composition contains a predetermined amount of zinc oxide, the modulus of the rubber obtained from the rubber composition and The inventor has found that compression set resistance and heat resistance can be balanced at a high level.
  • each component contained in the rubber composition of the present invention will be described in detail.
  • the diene rubber contained in the rubber composition of the present invention is not particularly limited as long as it is a polymer having a repeating unit of a compound having two double bonds per molecule.
  • the compound include conjugated diene compounds and non-conjugated diene compounds.
  • the diene rubber can include a polymer having a repeating unit of a non-conjugated diene compound.
  • the polymer may further have a repeating unit of a compound having an unsaturated bond other than the non-conjugated diene compound.
  • diene rubber examples include non-conjugated diene rubbers such as ethylene / ⁇ -olefin / diene copolymers.
  • ⁇ -olefin examples include propylene and butene.
  • Examples of the diene that can constitute the ethylene / ⁇ -olefin / diene copolymer include, for example, a non-conjugated diene compound.
  • Specific examples of the non-conjugated diene compound include dicyclopentadiene (DCPD); ethylidene norbornene such as 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene (HD).
  • the diene preferably contains at least ethylidene norbornene from the viewpoint that it is superior due to the effects of the present invention.
  • the diene rubber preferably contains an ethylene / propylene / diene copolymer (EPDM) from the viewpoints of excellent effects of the present invention and excellent ozone resistance.
  • EPDM ethylene / propylene / diene copolymer
  • the content of the constituent unit due to the diene is excellent due to the effects of the present invention, and from the viewpoint of excellent high crosslinking density and / or crosslinking speed, 2 to 12 mass of the diene rubber. % Is preferable, and 4 to 10% by mass is more preferable.
  • the reference of the content of the structural unit due to the diene can be the diene rubber itself having the structural unit due to the diene. Further, the reference of the content of the constituent unit by the diene may be the whole diene rubber.
  • the diene rubber may further contain a diene rubber other than the ethylene / ⁇ -olefin / diene copolymer.
  • the diene rubber that can be further contained is not particularly limited.
  • the content of the ethylene / ⁇ -olefin / diene copolymer can be 100% by mass or less based on the whole diene rubber.
  • the rubber composition of the present invention contains zinc oxide having a specific surface area of 30 to 150 m 2 / g.
  • the specific surface area of zinc oxide contained in the rubber composition of the present invention is 30 to 150 m 2 / g.
  • the effect of activating sulfur is high.
  • the modulus, compression set resistance and heat resistance can be balanced at a high level.
  • the specific surface area of the zinc oxide means a specific surface area by a BET (Brunauer-Emmett-Teller) method.
  • the specific surface area of the zinc oxide may be expressed as “BET specific surface area”.
  • the specific surface area of a certain zinc oxide is shown in a numerical range (for example, A to Bm 2 / g)
  • the sum of the lower limit (A) and the upper limit (B) of the numerical range is calculated as If the value [(A + B) / 2] divided by 2 satisfies the specific surface area “30 to 150 m 2 / g” of the zinc oxide in the present invention, the above-mentioned zinc oxide has the “specific surface area of 30 to 150 m 2 in the present invention. / G zinc oxide ”.
  • the specific surface area, more excellent effect of the present invention, from the viewpoint of excellent high crosslink density is preferably from 50 ⁇ 130m 2 / g, more preferably 60 ⁇ 100m 2 / g.
  • the method for producing the zinc oxide is not particularly limited. For example, a wet method is mentioned.
  • the content of the zinc oxide is 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber.
  • the content of the zinc oxide is preferably 4 to 12 parts by mass, preferably 6 to 11 parts by mass with respect to 100 parts by mass of the diene rubber, from the viewpoint that the effect of the present invention is excellent and the high crosslink density is excellent. Is more preferable.
  • the sulfur contained in the rubber composition of the present invention is not particularly limited.
  • the sulfur can function as, for example, a vulcanizing agent.
  • the form of sulfur is not particularly limited.
  • oil-treated ones and powdery ones can be mentioned.
  • the sulfur content is less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
  • the rubber composition of the present invention or the rubber obtained from the rubber composition of the present invention is excellent in heat resistance.
  • the sulfur content is preferably 0.1 parts by weight or more and less than 1.0 part by weight with respect to 100 parts by weight of the diene rubber from the viewpoint of being excellent due to the effect of the present invention, It is more preferable that it is 0.9 mass part.
  • the rubber composition of the present invention preferably satisfies the following formula (I) from the viewpoint that it is excellent by the effects of the present invention and is excellent in high crosslink density. 30 ⁇ [the specific surface area of the zinc oxide / the content of the sulfur] ⁇ 1,500 (I)
  • the “specific surface area of the zinc oxide” in the formula (I) means the specific surface area of the zinc oxide contained in the rubber composition of the present invention.
  • the “content of the sulfur” means the content of the sulfur with respect to 100 parts by mass of the diene rubber in the rubber composition of the present invention.
  • the lower limit in the above formula (I) is preferably 50 or more, more preferably 80 or more, and more preferably 90 or more from the viewpoint of being excellent due to the effects of the present invention and being excellent in high crosslink density.
  • the upper limit in the above formula (I) is preferably 500 or less, more preferably 300 or less, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in elongation at break.
  • the rubber composition of the present invention preferably satisfies the following formula (II) from the viewpoint that it is excellent by the effects of the present invention and is excellent in high crosslink density. 30 ⁇ [(the specific surface area of the zinc oxide ⁇ the content of the zinc oxide) / the content of the sulfur] ⁇ 30,000 (II)
  • the specific surface area of the zinc oxide and “the content of the sulfur” in the formula (II) are the same as those in the formula (I).
  • the “content of the zinc oxide” in the formula (II) means the content of zinc oxide having the predetermined specific surface area with respect to 100 parts by mass of the diene rubber in the rubber composition of the present invention.
  • the lower limit in the above formula (II) is preferably 400 or more, more preferably 800 or more, and still more preferably 900 or more, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in high crosslink density.
  • the upper limit in the above formula (II) is preferably 1,300 or less, and more preferably 1,100 or less, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in elongation at break.
  • the rubber composition of the present invention can further contain carbon black.
  • -Type of carbon black The type of carbon black is not particularly limited. Examples of the carbon black include soft carbon black such as FEF, GPF, SRF, FT, or MT grade carbon black from the viewpoint of superior heat resistance.
  • the carbon black preferably contains GPF grade carbon black and / or SRF grade carbon black from the viewpoint of superior heat resistance.
  • the iodine adsorption amount of the above carbon black is preferably 15 to 50 mg / g, more preferably 20 to 45 mg / g, from the viewpoint of excellent heat resistance and extrusion processability.
  • the iodine adsorption amount of carbon black can be measured according to JIS K6217-1: 2008.
  • the iodine adsorption amount of carbon black is shown in a numerical range (for example, A to Bm 2 / g), the sum of the lower limit value (A) and the upper limit value (B) of the numerical range.
  • the value [(A + B) / 2] divided by 2 should satisfy the above preferred range.
  • the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 20 ⁇ 10 3 to 45 ⁇ 10 3 m 2 / kg from the viewpoint of excellent heat resistance and extrusion processability. 25 ⁇ 10 3 to 40 ⁇ 10 3 m 2 / kg is more preferable.
  • the nitrogen adsorption specific surface area of carbon black can be measured according to JIS K6217-2: 2008.
  • the carbon black has a dibutyl phthalate (DBP) oil absorption of 55 to 100 ml / 100 g from the viewpoint of excellent heat resistance and extrusion processability.
  • DBP oil absorption of carbon black can be measured according to JIS K6217-4: 2008.
  • the content of carbon black is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint of excellent effects of the present invention and excellent reinforcement and heat resistance. It is preferably 50 to 100 parts by mass.
  • One preferred embodiment of the rubber composition of the present invention is that substantially no white filler is blended.
  • the white filler include silica, calcium carbonate, talc, clay, and mica.
  • substantially free of white filler means that the content of the white filler is 0 to 1.0% by mass with respect to the entire rubber composition of the present invention.
  • the rubber composition of the present invention can further contain an additive as necessary, as long as the effects of the present invention are not impaired.
  • additives include rubbers other than diene rubbers, resins, zinc oxides other than the above zinc oxide, vulcanization accelerators (for example, stearic acid), vulcanization retarders, processing aids such as softeners, Examples include vulcanization accelerators, anti-aging agents, and plasticizers.
  • the manufacturing method of the rubber composition of the present invention is not particularly limited. For example, it can be produced by mixing the above essential components and optional components that can be used as necessary under the conditions of 100 to 180 ° C.
  • the method for vulcanizing (crosslinking) the rubber composition of the present invention is not particularly limited.
  • the rubber composition of the present invention can be vulcanized (crosslinked) by press vulcanization, steam vulcanization, oven vulcanization (hot air vulcanization) or hot water vulcanization under conditions of 140 to 190 ° C., for example. .
  • the rubber composition of the present invention can be applied to, for example, a hose. It is preferable to apply the rubber composition of the present invention to the outermost layer of the hose.
  • the hose include a hydraulic operation hose and a car air conditioner system hose.
  • the hose of the present invention is a hose formed using the rubber composition for a hose of the present invention.
  • the hose of the present invention has a high modulus and is formed using the rubber composition for a hose of the present invention that is excellent in compression set resistance and heat resistance (the above high modulus, excellent compression set resistance) )) Excellent metal fitting and heat resistance. For this reason, the hose of this invention can be used in a higher temperature atmosphere, and can extend the product life of a hose than before.
  • the hose of the present invention is not particularly limited except that it is formed using the rubber composition of the present invention.
  • the rubber composition used for the hose of the present invention is not particularly limited as long as it is the rubber composition of the present invention.
  • hose of the present invention which member of the hose is formed of the rubber composition is not particularly limited. Especially, it is mentioned as one of the aspects with preferable that the hose of this invention has the outermost layer formed with the said rubber composition.
  • the outermost layer of the hose of the present invention can be formed from the rubber composition of the present invention.
  • the thickness of the outermost layer can be set to 0.2 to 4 mm, for example.
  • the hose of the present invention may further include at least one selected from the group consisting of a reinforcing member (reinforcing layer), an inner layer, and an intermediate rubber layer in addition to the outermost layer.
  • the reinforcing member may be a single layer or a plurality of layers. The same applies to the inner layer and the intermediate rubber layer.
  • the reinforcing member is not particularly limited. For example, a conventionally well-known thing is mentioned. Examples of the material of the reinforcing member include metals and fiber materials (polyamide, polyester, etc.). The reinforcing member may be surface-treated. Examples of the form of the reinforcing member include those braided into a spiral structure and / or a blade structure.
  • the rubber composition that can form the inner layer is not particularly limited. For example, you may form an inner layer with the rubber composition of this invention.
  • the thickness of the inner layer can be set to 0.2 to 4 mm, for example.
  • the rubber composition that can form the intermediate rubber layer is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • An intermediate rubber layer may be formed using the rubber composition of the present invention.
  • the intermediate rubber layer can be disposed, for example, between the outermost layer and the reinforcing member, between the inner layer and the reinforcing member, or between the reinforcing member and the reinforcing member.
  • the thickness of the intermediate rubber layer can be set to 0.2 to 0.7 mm, for example.
  • the hose of the present invention can have, for example, an inner layer, a reinforcing member, and an outermost layer in this order.
  • FIG. 1 is a schematic perspective view showing an example of the hose of the present invention by cutting out each layer.
  • the hose 1 has an inner layer 2, a reinforcing member 3 on the inner layer 2, and an outermost layer 4 on the reinforcing member 3.
  • the outermost layer 4 is formed of the rubber composition of the present invention.
  • the production method of the hose of the present invention is not particularly limited.
  • a rubber composition for forming an inner layer, a reinforcing member and a rubber composition for forming an outermost layer are laminated in this order on a mandrel to form a laminate, Cover the body with a nylon cloth, etc., and press laminate, steam vulcanization, oven vulcanization (hot air vulcanization) or hot water on the laminate covered with the above nylon cloth etc. under conditions of 140 to 190 ° C. and 30 to 180 minutes
  • the hose of the present invention can be produced by vulcanization and adhesion by vulcanization.
  • hose of the present invention examples include a hydraulic operation hose (hydraulic hose) and a car air conditioner system hose.
  • Each component of the following Table 1 was used in the composition (parts by mass) shown in the same table, and these were mixed with a stirrer to produce a composition. Specifically, first, the components shown in Table 1 below, excluding sulfur and the vulcanization accelerator, were mixed for 5 minutes with a Banbury mixer (3.4 liters) and released when the temperature reached 160 ° C. A master batch was obtained. Next, sulfur and a vulcanization accelerator were added to each masterbatch obtained as described above, and these were mixed with an open roll to obtain a rubber composition.
  • the modulus (high modulus) was evaluated as follows using a value measured at 100% modulus. In the present invention, when the 100% modulus (index) is 115% or more, it was evaluated as very high modulus. When the 100% modulus (index) was 110% or more and less than 115%, it was evaluated as slightly high modulus. When the 100% modulus (index) was 105% or more and less than 110%, it was evaluated that the modulus was slightly low. When the 100% modulus (index) was less than 105%, the modulus was evaluated as very low.
  • ⁇ ⁇ EB ⁇ EB (%) was calculated by applying the elongation value at break of the initial test piece and the test piece after heat aging formed from the same rubber composition to the following formula. The results are shown in Table 1.
  • ⁇ EB (%) [(EB of test piece after heat aging ⁇ EB of initial test piece) / EB of initial test piece] ⁇ 100
  • the mounting property of the metal with respect to a hose can be evaluated as follows.
  • the 100% modulus (index) was 115% or more and the compression set by the 96-hour compression test was 63% or less, it was evaluated that the wearability was very excellent.
  • the 100% modulus (index) is 110% or more and the compression set by the 96-hour compression test is 65% or less (except for the case where the wearability is very excellent), the wearability.
  • the wearability was rated as slightly better.
  • the 100% modulus (index) is less than 110%, or when the compression set by the 96-hour compression test exceeds 65% (except for the case where the wearability described later is very inferior)
  • the above attachment Evaluated as slightly inferior.
  • the 100% modulus (index) was less than 105% and the compression set by the 96-hour compression test exceeded 70%, the wearability was evaluated to be very poor.
  • Diene rubber 1 ethylene / propylene / diene copolymer.
  • EPDM 3092M manufactured by Mitsui Chemicals. Mooney viscosity 92.
  • the ethylene amount of the diene rubber 1 is 65% by mass, and the diene amount is 4.6% by mass.
  • the diene rubber 1 has a repeating unit of ethylidene norbornene as a diene.
  • Carbon black 1 SRF grade carbon black. N762, Asahi # 50 manufactured by Asahi Carbon Corporation. Iodine adsorption amount 20 ⁇ 5 mg / g, N 2 SA 29 ⁇ 10 3 m 2 / kg (representative value), DBP oil absorption 55 to 79 ml / 100 g (DBP oil absorption average value 67 ml / 100 g).
  • Carbon black 2 FEF grade carbon black. N550, Niteron # 10N, manufactured by Shin-Nikka Carbon Co., Ltd. Iodine adsorption amount 41 ⁇ 5 mg / g, N 2 SA 40 ⁇ 10 3 m 2 / kg (representative value), DBP oil absorption 121 ⁇ 6 ml / 100 g.
  • Comparison zinc oxide 1 3 types of zinc oxide, manufactured by Shodo Chemical Industries. BET specific surface area of 4 m 2 / g.
  • Zinc oxide 1 activated zinc white AZO, manufactured by Shodo Chemical Industry Co., Ltd. BET specific surface area of 60 to 90 m 2 / g. Highly active zinc oxide produced by a wet process. In the calculations of the formulas (I) and (II), the specific surface area of the zinc oxide 1 was 75 m 2 / g, which is the average of the above numerical range.
  • Comparative zinc oxide 2 META-Z102, manufactured by Inoue Lime Industry Co., Ltd. BET specific surface area of 12 m 2 / g.
  • Stearic acid “Stearic acid 50S” (Chiba Fatty Acid Co., Ltd.)
  • PVI (vulcanization retarder) N-cyclohexylthiophthalimide.
  • Product name retarder CTP manufactured by Toray Fine Chemical Co., Ltd., processing aid: softener.
  • Product name “SUNPAR 2280” (manufactured by Nippon Oil Corporation)
  • Vulcanization accelerator TT Tetramethylthiuram disulfide (thiuram type. Noxeller TT manufactured by Ouchi Shinsei Chemical Co., Ltd.)
  • Vulcanization accelerator DM Dibenzothiazyl disulfide (thiazole type. Sunseller DM, manufactured by Sanshin Chemical Industry Co., Ltd.)
  • Comparative Example 6 In Comparative Example 6 in which the specific surface area of zinc oxide was outside the predetermined range and the sulfur content was larger than the predetermined range, the modulus was low, and the heat resistance and compression set resistance were inferior. Comparative Example 7 having a sulfur content greater than the predetermined range was inferior in heat resistance and compression set resistance.
  • the rubber composition of the present invention has a high modulus and is excellent in compression set resistance and heat resistance.
  • Hose 2 Inner layer 3: Reinforcement member 4: Outermost layer

Abstract

The purpose of the present invention is to provide: a rubber composition which has a high modulus and is excellent in terms of compression set characteristics and heat resistance; and a hose which is excellent in terms of attachability with fittings and heat resistance. The present invention relates to: a rubber composition for hoses which comprises a diene-based rubber, zinc oxide having a specific surface area of 30-150 m2/g, and sulfur, wherein the content of the zinc oxide is 1-20 parts by mass per 100 parts by mass of the diene-based rubber and the content of the sulfur is less than 1 part by mass per 100 parts by mass of the diene-based rubber; and a hose formed using the rubber composition for hoses.

Description

ホース用ゴム組成物及びホースRubber composition for hose and hose
　本発明はホース用ゴム組成物及びホースに関する。 The present invention relates to a rubber composition for a hose and a hose.
　従来、建設機械等の油圧配管やカーエアコンシステムのホースには、ゴムホース（ゴム製のホース）が用いられている。
　上記ゴムホースは、接続部において例えば金具でかしめるなどすることによって、上記接続部に固定される。
　このため、上記ゴムホースには、所定の圧力下での金具との良好な装着性が求められる。これに伴い、上記ゴムホースに使用されるゴムは、具体的には例えば、高モジュラス（高硬度）であり、かつ、耐圧縮永久歪み性が優れる必要がある。
　また、ゴムホースは高温条件下で使用される場合があるため、ゴムホースに使用されるゴムは、上記のとおり高モジュラスであり耐圧縮永久歪み性に優れることの他に、耐熱性に優れることが同時に求められる。 Conventionally, rubber hoses (rubber hoses) have been used as hydraulic pipes for construction machinery and the like and car air conditioner system hoses.
The rubber hose is fixed to the connecting portion by, for example, caulking with a metal fitting at the connecting portion.
For this reason, the rubber hose is required to have good mountability with a metal fitting under a predetermined pressure. Along with this, the rubber used for the rubber hose is specifically required to have, for example, a high modulus (high hardness) and excellent compression set resistance.
In addition, since rubber hoses may be used under high temperature conditions, the rubber used in rubber hoses has high modulus as described above and excellent compression set resistance, as well as excellent heat resistance. Desired.
　一方、貯蔵安定性に優れた加硫可能なゴム組成物等の提供を目的として、エチレン・α－オレフィン・非共役ポリエン共重合体を含有する組成物が提案されている。
　例えば、特許文献１には、エチレン・α－オレフィン・非共役ポリエン共重合体１００重量部に対して、比表面積がＳ（ｍ2／ｇ）である酸化亜鉛をＸ重量部、および必要に応じて添加されるポリエチレングリコ－ルおよび／または脂肪族アンモニウムをＹ重量部含有しており、そのＳ、Ｘ、およびＹとの間に特定の式の関係が成り立つ加硫可能なゴム組成物が記載されている。
　また、特許文献１には、酸化亜鉛の比表面積は１～３０ｍ2／ｇの範囲が好ましいと記載されている。 On the other hand, for the purpose of providing a vulcanizable rubber composition having excellent storage stability, a composition containing an ethylene / α-olefin / non-conjugated polyene copolymer has been proposed.
For example, Patent Document 1 discloses that, with respect to 100 parts by weight of an ethylene / α-olefin / nonconjugated polyene copolymer, X parts by weight of zinc oxide having a specific surface area of S (m 2 / g), and if necessary, A vulcanizable rubber composition containing Y parts by weight of polyethylene glycol and / or aliphatic ammonium added in such a manner that a specific formula relationship is established between S, X, and Y is described. Has been.
Patent Document 1 describes that the specific surface area of zinc oxide is preferably in the range of 1 to 30 m 2 / g.
特開２００２－２５６１２号公報JP 2002-25612 A
　本発明者は特許文献１に記載されているような、エチレン・α－オレフィン・非共役ポリエン共重合体と酸化亜鉛と硫黄とを含有するゴム組成物から得られるゴムをホース用として評価したところ、上記ゴムにおいて、モジュラス、耐圧縮永久歪み性及び耐熱性のうちの少なくともいずれかが低い場合があることが明らかとなった（比較例１～６）。
　そこで、本発明は、高モジュラスであり、耐圧縮永久歪み性、耐熱性に優れるゴム組成物を提供することを目的とする。
　また、本発明は金具の装着性、耐熱性に優れるホースを提供することも目的とする。 The present inventor evaluated a rubber obtained from a rubber composition containing an ethylene / α-olefin / non-conjugated polyene copolymer, zinc oxide and sulfur as described in Patent Document 1 for a hose. It has been clarified that in the above rubber, at least one of modulus, compression set resistance and heat resistance may be low (Comparative Examples 1 to 6).
Accordingly, an object of the present invention is to provide a rubber composition having a high modulus and excellent in compression set resistance and heat resistance.
It is another object of the present invention to provide a hose that is excellent in fitting property and heat resistance.
　本発明者は、上記課題を解決すべく鋭意研究した結果、ゴム組成物が、ジエン系ゴムと、比表面積が所定の範囲である酸化亜鉛と、硫黄とを含有し、上記酸化亜鉛及び上記硫黄の含有量が所定の範囲であることによって所望の効果が得られることを見出し、本発明に至った。
　本発明は上記知見等に基づくものであり、具体的には以下の構成により上記課題を解決するものである。 As a result of intensive studies to solve the above problems, the present inventor has found that the rubber composition contains a diene rubber, zinc oxide having a specific surface area within a predetermined range, and sulfur, and the zinc oxide and sulfur. The inventors have found that a desired effect can be obtained when the content of is in a predetermined range, and have reached the present invention.
The present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
［１］　ジエン系ゴムと、比表面積が３０～１５０ｍ2／ｇである酸化亜鉛と、硫黄とを含有し、
　上記酸化亜鉛の含有量が、上記ジエン系ゴム１００質量部に対して、１～２０質量部であり、
　上記硫黄の含有量が、上記ジエン系ゴム１００質量部に対して、１質量部未満である、ホース用ゴム組成物。
［２］　更に、カーボンブラックを含有し、
　上記カーボンブラックの含有量が、上記ジエン系ゴム１００質量部に対して、３０～１３０質量部である、［１］に記載のホース用ゴム組成物。
［３］　上記カーボンブラックが、ＧＰＦ級カーボンブラック及び／又はＳＲＦ級カーボンブラックを含む、［２］に記載のホース用ゴム組成物。
［４］　上記ジエン系ゴムが、エチレン・プロピレン・ジエン共重合体を含む、［１］～［３］のいずれかに記載のホース用ゴム組成物。
［５］　下記式（Ｉ）を満たす、［１］～［４］のいずれかに記載のホース用ゴム組成物。
３０＜［上記酸化亜鉛の上記比表面積／上記硫黄の上記含有量］≦１，５００　　（Ｉ）
［６］　下記式（ＩＩ）を満たす、［１］～［５］のいずれかに記載のホース用ゴム組成物。
３０＜［（上記酸化亜鉛の上記比表面積×上記酸化亜鉛の上記含有量）／上記硫黄の上記含有量］≦３０，０００　　　（ＩＩ）
［７］　上記硫黄の含有量が、上記ジエン系ゴム１００質量部に対して、０．１質量部以上である、［１］～［６］のいずれかに記載のホース用ゴム組成物。
［８］　白色充填剤を実質的に配合しない、［１］～［７］のいずれかに記載のホース用ゴム組成物。
［９］　油圧作動用ホース又はカーエアコンシステム用ホースに使用される、［１］～［８］のいずれかに記載のホース用ゴム組成物。
［１０］　ホースの最外層に使用される、［１］～［９］のいずれかに記載のホース用ゴム組成物。
［１１］　［１］～［８］のいずれかに記載のホース用ゴム組成物を用いて形成されたホース。 [1] A diene rubber, zinc oxide having a specific surface area of 30 to 150 m 2 / g, and sulfur.
The zinc oxide content is 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber,
A rubber composition for a hose, wherein the sulfur content is less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
[2] Furthermore, carbon black is contained,
The rubber composition for a hose according to [1], wherein the content of the carbon black is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber.
[3] The rubber composition for hose according to [2], wherein the carbon black includes GPF grade carbon black and / or SRF grade carbon black.
[4] The rubber composition for a hose according to any one of [1] to [3], wherein the diene rubber contains an ethylene / propylene / diene copolymer.
[5] The rubber composition for a hose according to any one of [1] to [4], which satisfies the following formula (I).
30 <[the specific surface area of the zinc oxide / the content of the sulfur] ≦ 1,500 (I)
[6] The rubber composition for hoses according to any one of [1] to [5], which satisfies the following formula (II).
30 <[(the specific surface area of the zinc oxide × the content of the zinc oxide) / the content of the sulfur] ≦ 30,000 (II)
[7] The rubber composition for hoses according to any one of [1] to [6], wherein the sulfur content is 0.1 parts by mass or more with respect to 100 parts by mass of the diene rubber.
[8] The rubber composition for hoses according to any one of [1] to [7], which does not substantially contain a white filler.
[9] The rubber composition for a hose according to any one of [1] to [8], which is used for a hydraulic operation hose or a car air conditioner system hose.
[10] The rubber composition for a hose according to any one of [1] to [9], which is used for the outermost layer of the hose.
[11] A hose formed using the rubber composition for a hose according to any one of [1] to [8].
　本発明のホース用ゴム組成物は、高モジュラスであり、耐圧縮永久歪み性、耐熱性に優れる。
　また、本発明のホースは、金具の装着性、耐熱性に優れる。 The rubber composition for a hose of the present invention has a high modulus and is excellent in compression set resistance and heat resistance.
Moreover, the hose of this invention is excellent in the mounting | wearing property of a metal fitting, and heat resistance.
図１は、本発明のホースの一例について、各層を切り欠いて表した、模式的な斜視図である。FIG. 1 is a schematic perspective view showing an example of the hose of the present invention by cutting out each layer.
　本発明について以下詳細に説明する。
　なお、本明細書において、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、特に断りのない限り、各成分はその成分に該当する物質をそれぞれ単独でまたは２種以上を組み合わせて使用することができる。成分が２種以上の物質を含む場合、成分の含有量は、２種以上の物質の合計の含有量を意味する。
　本明細書に記載されている各成分はその製造方法について特に制限されない。例えば、従来公知のものが挙げられる。
　本明細書において、高モジュラス、耐圧縮永久歪み性及び耐熱性のうちの少なくとも１つがより優れることを、「本発明の効果がより優れる」ということがある。 The present invention will be described in detail below.
In the present specification, a numerical range expressed using “to” in the present specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, unless otherwise specified, each component can be used alone or in combination of two or more of the substances corresponding to the component. When a component contains two or more types of substances, the content of the component means the total content of the two or more types of substances.
Each component described in this specification is not particularly limited with respect to its production method. For example, a conventionally well-known thing is mentioned.
In the present specification, the fact that at least one of high modulus, compression set resistance and heat resistance is superior may be referred to as “the effect of the present invention is more excellent”.
［ホース用ゴム組成物］
　本発明のホース用ゴム組成物（本発明のゴム組成物）は、ジエン系ゴムと、比表面積が３０～１５０ｍ2／ｇである酸化亜鉛と、硫黄とを含有し、上記酸化亜鉛の含有量が上記ジエン系ゴム１００質量部に対して１～２０質量部であり、上記硫黄の含有量が上記ジエン系ゴム１００質量部に対して１質量部未満である、ホース用ゴム組成物である。 [Rubber composition for hose]
The rubber composition for a hose of the present invention (the rubber composition of the present invention) contains a diene rubber, zinc oxide having a specific surface area of 30 to 150 m 2 / g, and sulfur. Is a rubber composition for a hose having a content of 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber and a sulfur content of less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
　本発明のゴム組成物はこのような構成をとるため、所望の効果が得られるものと考えられる。その理由は明らかではないが、およそ以下のとおりと推測される。
　本発明において得られるゴムの耐熱性を向上させるため、本発明のゴム組成物に含有される硫黄の量は通常よりも少なく設定されている。
　上記硫黄の含有量を少なくすると、得られるゴムについて高いモジュラス及び優れた耐圧縮永久歪み性を確保できない場合があると考えられた。
　一方、本発明のゴム組成物に含有される酸化亜鉛は比表面積が所定の範囲であることによって、硫黄を活性化する効果が極めて高い。
　このため、ゴム組成物に含有される硫黄の含有量が上記のように少なくとも、ゴム組成物が所定の酸化亜鉛を特定量で含有することによって、上記ゴム組成物から得られるゴムの、モジュラス及び耐圧縮永久歪み性と耐熱性とを高いレベルでバランスさせることができることを本発明者は知見した。
　以下、本発明のゴム組成物に含有される各成分について詳述する。 Since the rubber composition of the present invention has such a configuration, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed that it is as follows.
In order to improve the heat resistance of the rubber obtained in the present invention, the amount of sulfur contained in the rubber composition of the present invention is set smaller than usual.
It was considered that when the sulfur content is reduced, the resulting rubber may not have a high modulus and excellent compression set resistance.
On the other hand, the zinc oxide contained in the rubber composition of the present invention has a very high effect of activating sulfur because the specific surface area is in a predetermined range.
For this reason, the content of sulfur contained in the rubber composition is at least as described above, and when the rubber composition contains a predetermined amount of zinc oxide, the modulus of the rubber obtained from the rubber composition and The inventor has found that compression set resistance and heat resistance can be balanced at a high level.
Hereinafter, each component contained in the rubber composition of the present invention will be described in detail.
＜ジエン系ゴム＞
　本発明のゴム組成物に含有されるジエン系ゴムは、１分子当たり二重結合を２つ有する化合物による繰り返し単位を有するポリマーであれば特に制限されない。
　上記化合物としては、共役ジエン系化合物、非共役ジエン系化合物が挙げられる。
　上記ジエン系ゴムは、非共役ジエン系化合物による繰り返し単位を有するポリマーを含むことができる。
　上記ポリマーは、更に、非共役ジエン系化合物以外の、不飽和結合を有する化合物による繰り返し単位を有してもよい。 <Diene rubber>
The diene rubber contained in the rubber composition of the present invention is not particularly limited as long as it is a polymer having a repeating unit of a compound having two double bonds per molecule.
Examples of the compound include conjugated diene compounds and non-conjugated diene compounds.
The diene rubber can include a polymer having a repeating unit of a non-conjugated diene compound.
The polymer may further have a repeating unit of a compound having an unsaturated bond other than the non-conjugated diene compound.
　上記ジエン系ゴムとしては、例えば、エチレン・α－オレフィン・ジエン共重合体のような非共役ジエン系ゴムが挙げられる。
　上記エチレン・α－オレフィン・ジエン共重合体を構成し得るα－オレフィンとしては、例えば、プロピレン、ブテン等が挙げられる。 Examples of the diene rubber include non-conjugated diene rubbers such as ethylene / α-olefin / diene copolymers.
Examples of the α-olefin that can constitute the ethylene / α-olefin / diene copolymer include propylene and butene.
　上記エチレン・α－オレフィン・ジエン共重合体を構成し得るジエンとしては、例えば、例えば非共役ジエン化合物が挙げられる。
　上記非共役ジエン化合物としては具体的には例えばジシクロペンタジエン（ＤＣＰＤ）；５－エチリデン－２－ノルボルネン（ＥＮＢ）のようなエチリデンノルボルネン；１，４－ヘキサジエン（ＨＤ）が挙げられる。
　上記ジエンは、本発明の効果により優れるという観点から、エチリデンノルボルネンを少なくとも含むことが好ましい。 Examples of the diene that can constitute the ethylene / α-olefin / diene copolymer include, for example, a non-conjugated diene compound.
Specific examples of the non-conjugated diene compound include dicyclopentadiene (DCPD); ethylidene norbornene such as 5-ethylidene-2-norbornene (ENB); 1,4-hexadiene (HD).
The diene preferably contains at least ethylidene norbornene from the viewpoint that it is superior due to the effects of the present invention.
　上記ジエン系ゴムは、本発明の効果により優れ、耐オゾン性に優れるという観点から、エチレン・プロピレン・ジエン共重合体（ＥＰＤＭ）を含むことが好ましい。 The diene rubber preferably contains an ethylene / propylene / diene copolymer (EPDM) from the viewpoints of excellent effects of the present invention and excellent ozone resistance.
　上記ジエン系ゴムにおいて、上記ジエン（例えばエチリデンノルボルネン）による構成単位の含有量は、本発明の効果により優れ、高架橋密度及び／又は架橋速度に優れるという観点から、上記ジエン系ゴムの２～１２質量％が好ましく、４～１０質量％がより好ましい。
　なお、本発明において、上記ジエン（例えばエチリデンノルボルネン）による構成単位の含有量の基準は、上記ジエンによる構成単位を有する上記ジエン系ゴム自体とできる。また、上記ジエンによる構成単位の含有量の基準は、上記ジエン系ゴム全体であってもよい。 In the diene rubber, the content of the constituent unit due to the diene (eg, ethylidene norbornene) is excellent due to the effects of the present invention, and from the viewpoint of excellent high crosslinking density and / or crosslinking speed, 2 to 12 mass of the diene rubber. % Is preferable, and 4 to 10% by mass is more preferable.
In the present invention, the reference of the content of the structural unit due to the diene (for example, ethylidene norbornene) can be the diene rubber itself having the structural unit due to the diene. Further, the reference of the content of the constituent unit by the diene may be the whole diene rubber.
　上記ジエン系ゴムがエチレン・α－オレフィン・ジエン共重合体を含む場合、上記ジエン系ゴムは上記エチレン・α－オレフィン・ジエン共重合体以外のジエン系ゴムを更に含むことができる。上記の、更に含むことができるジエン系ゴムは特に制限されない。 When the diene rubber contains an ethylene / α-olefin / diene copolymer, the diene rubber may further contain a diene rubber other than the ethylene / α-olefin / diene copolymer. The diene rubber that can be further contained is not particularly limited.
　上記ジエン系ゴムがエチレン・α－オレフィン・ジエン共重合体を含む場合、上記エチレン・α－オレフィン・ジエン共重合体の含有量は、上記ジエン系ゴム全体に対して、１００質量％以下とできる。 When the diene rubber contains an ethylene / α-olefin / diene copolymer, the content of the ethylene / α-olefin / diene copolymer can be 100% by mass or less based on the whole diene rubber. .
＜＜酸化亜鉛＞＞
　本発明のゴム組成物は、比表面積が３０～１５０ｍ2／ｇである酸化亜鉛を含有する。 << Zinc oxide >>
The rubber composition of the present invention contains zinc oxide having a specific surface area of 30 to 150 m 2 / g.
＜比表面積＞
　本発明のゴム組成物に含有される酸化亜鉛の比表面積は、３０～１５０ｍ2／ｇである。
　本発明のゴム組成物において、上記酸化亜鉛の比表面積が所定の範囲であることによって、硫黄を活性化する効果が高く、本発明のゴム組成物又は本発明のゴム組成物から得られるゴムにおいて、モジュラス及び耐圧縮永久歪み性と耐熱性とを高いレベルでバランスさせることができると考えられる。 <Specific surface area>
The specific surface area of zinc oxide contained in the rubber composition of the present invention is 30 to 150 m 2 / g.
In the rubber composition of the present invention, when the specific surface area of the zinc oxide is within a predetermined range, the effect of activating sulfur is high. In the rubber composition of the present invention or the rubber obtained from the rubber composition of the present invention, It is considered that the modulus, compression set resistance and heat resistance can be balanced at a high level.
　本発明において、上記酸化亜鉛の比表面積は、ＢＥＴ（Ｂｒｕｎａｕｅｒ－Ｅｍｍｅｔｔ－Ｔｅｌｌｅｒ）法による比表面積を意味する。なお、上記酸化亜鉛の比表面積を「ＢＥＴ法比表面積」と表す場合がある。 In the present invention, the specific surface area of the zinc oxide means a specific surface area by a BET (Brunauer-Emmett-Teller) method. The specific surface area of the zinc oxide may be expressed as “BET specific surface area”.
　なお、本発明において、ある酸化亜鉛の比表面積が数値範囲（例えばＡ～Ｂｍ2／ｇ）で示されている場合、上記数値範囲の下限値（Ａ）と上限値（Ｂ）との合計を２で割った値［（Ａ＋Ｂ）／２］が本発明における酸化亜鉛の比表面積「３０～１５０ｍ2／ｇ」を満たせば、上記ある酸化亜鉛は、本発明における「比表面積が３０～１５０ｍ2／ｇである酸化亜鉛」に該当するものとする。 In the present invention, when the specific surface area of a certain zinc oxide is shown in a numerical range (for example, A to Bm 2 / g), the sum of the lower limit (A) and the upper limit (B) of the numerical range is calculated as If the value [(A + B) / 2] divided by 2 satisfies the specific surface area “30 to 150 m 2 / g” of the zinc oxide in the present invention, the above-mentioned zinc oxide has the “specific surface area of 30 to 150 m 2 in the present invention. / G zinc oxide ”.
　上記比表面積は、本発明の効果により優れ、高架橋密度に優れるという観点から、５０～１３０ｍ2／ｇであることが好ましく、６０～１００ｍ2／ｇがより好ましい。 The specific surface area, more excellent effect of the present invention, from the viewpoint of excellent high crosslink density is preferably from 50 ~ 130m 2 / g, more preferably 60 ~ 100m 2 / g.
　上記酸化亜鉛の製造方法は特に制限されない。例えば、湿式法が挙げられる。 The method for producing the zinc oxide is not particularly limited. For example, a wet method is mentioned.
＜酸化亜鉛の含有量＞
　本発明において、上記酸化亜鉛の含有量は、上記ジエン系ゴム１００質量部に対して、１～２０質量部である。
　上記酸化亜鉛の含有量は、本発明の効果により優れ、高架橋密度に優れるという観点から、上記ジエン系ゴム１００質量部に対して、４～１２質量部であることが好ましく、６～１１質量部がより好ましい。 <Zinc oxide content>
In the present invention, the content of the zinc oxide is 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber.
The content of the zinc oxide is preferably 4 to 12 parts by mass, preferably 6 to 11 parts by mass with respect to 100 parts by mass of the diene rubber, from the viewpoint that the effect of the present invention is excellent and the high crosslink density is excellent. Is more preferable.
＜＜硫黄＞＞
　本発明のゴム組成物に含有される硫黄は特に制限されない。
　本発明のゴム組成物において、上記硫黄は例えば加硫剤として機能できる。 << Sulfur >>
The sulfur contained in the rubber composition of the present invention is not particularly limited.
In the rubber composition of the present invention, the sulfur can function as, for example, a vulcanizing agent.
　上記硫黄の形態は特に制限されない。例えば、油処理されたもの、粉末状のものが挙げられる。 The form of sulfur is not particularly limited. For example, oil-treated ones and powdery ones can be mentioned.
＜硫黄の含有量＞
　本発明において、上記硫黄の含有量は、上記ジエン系ゴム１００質量部に対して、１質量部未満である。
　硫黄の含有量が所定の範囲であることによって、本発明のゴム組成物又は本発明のゴム組成物から得られるゴムは耐熱性に優れる。
　上記硫黄の含有量は、本発明の効果により優れるという観点から、上記ジエン系ゴム１００質量部に対して、０．１質量部以上１．０質量部未満であることが好ましく、０．５～０．９質量部であることがより好ましい。 <Sulfur content>
In the present invention, the sulfur content is less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
When the sulfur content is within a predetermined range, the rubber composition of the present invention or the rubber obtained from the rubber composition of the present invention is excellent in heat resistance.
The sulfur content is preferably 0.1 parts by weight or more and less than 1.0 part by weight with respect to 100 parts by weight of the diene rubber from the viewpoint of being excellent due to the effect of the present invention, It is more preferable that it is 0.9 mass part.
・式（Ｉ）
　本発明のゴム組成物は、本発明の効果により優れ、高架橋密度に優れるという観点から、下記式（Ｉ）を満たすことが好ましい。
３０＜［上記酸化亜鉛の上記比表面積／上記硫黄の上記含有量］≦１，５００　　（Ｉ） ・ Formula (I)
The rubber composition of the present invention preferably satisfies the following formula (I) from the viewpoint that it is excellent by the effects of the present invention and is excellent in high crosslink density.
30 <[the specific surface area of the zinc oxide / the content of the sulfur] ≦ 1,500 (I)
　上記式（Ｉ）における「上記酸化亜鉛の上記比表面積」は、本発明のゴム組成物に含有される上記酸化亜鉛が有する上記比表面積を意味する。
　「上記硫黄の上記含有量」は、本発明のゴム組成物における、上記ジエン系ゴム１００質量部に対する上記硫黄の含有量を意味する。 The “specific surface area of the zinc oxide” in the formula (I) means the specific surface area of the zinc oxide contained in the rubber composition of the present invention.
The “content of the sulfur” means the content of the sulfur with respect to 100 parts by mass of the diene rubber in the rubber composition of the present invention.
　なお、本発明において、ある酸化亜鉛の比表面積が数値範囲（Ａ～Ｂｍ2／ｇ）で示されている場合、上記数値範囲の下限値（Ａ）と上限値（Ｂ）との合計を２で割った値［（Ａ＋Ｂ）／２］を式（Ｉ）の「酸化亜鉛の比表面積」に代入するものとする。式（ＩＩ）についても同様である。 In the present invention, when the specific surface area of a certain zinc oxide is indicated by a numerical range (A to Bm 2 / g), the sum of the lower limit (A) and the upper limit (B) of the numerical range is 2 The value [(A + B) / 2] divided by is substituted for “specific surface area of zinc oxide” in formula (I). The same applies to formula (II).
　上記式（Ｉ）における下限は、本発明の効果により優れ、高架橋密度に優れるという観点から、５０以上が好ましく、８０以上が好ましく、９０以上がより好ましい。
　上記式（Ｉ）における上限は、本発明の効果により優れ、破断伸びに優れるという観点から、５００以下が好ましく、３００以下がより好ましい。 The lower limit in the above formula (I) is preferably 50 or more, more preferably 80 or more, and more preferably 90 or more from the viewpoint of being excellent due to the effects of the present invention and being excellent in high crosslink density.
The upper limit in the above formula (I) is preferably 500 or less, more preferably 300 or less, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in elongation at break.
・式（ＩＩ）
　本発明のゴム組成物は、本発明の効果により優れ、高架橋密度に優れるという観点から、下記式（ＩＩ）を満たすことが好ましい。
３０＜［（上記酸化亜鉛の上記比表面積×上記酸化亜鉛の上記含有量）／上記硫黄の上記含有量］≦３０，０００　　　（ＩＩ） Formula (II)
The rubber composition of the present invention preferably satisfies the following formula (II) from the viewpoint that it is excellent by the effects of the present invention and is excellent in high crosslink density.
30 <[(the specific surface area of the zinc oxide × the content of the zinc oxide) / the content of the sulfur] ≦ 30,000 (II)
　上記式（ＩＩ）における「上記酸化亜鉛の上記比表面積」、「上記硫黄の上記含有量」は、上記式（Ｉ）と同様である。
　上記式（ＩＩ）における「上記酸化亜鉛の上記含有量」は、本発明のゴム組成物における、上記ジエン系ゴム１００質量部に対する、上記所定の比表面積を有する酸化亜鉛の含有量を意味する。 “The specific surface area of the zinc oxide” and “the content of the sulfur” in the formula (II) are the same as those in the formula (I).
The “content of the zinc oxide” in the formula (II) means the content of zinc oxide having the predetermined specific surface area with respect to 100 parts by mass of the diene rubber in the rubber composition of the present invention.
　上記式（ＩＩ）における下限は、本発明の効果により優れ、高架橋密度に優れるという観点から、４００以上が好ましく、８００以上がより好ましく、９００以上が更に好ましい。
　上記式（ＩＩ）における上限は、本発明の効果により優れ、破断伸びに優れるという観点から、１，３００以下が好ましく、１，１００以下がより好ましい。 The lower limit in the above formula (II) is preferably 400 or more, more preferably 800 or more, and still more preferably 900 or more, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in high crosslink density.
The upper limit in the above formula (II) is preferably 1,300 or less, and more preferably 1,100 or less, from the viewpoint that it is excellent due to the effects of the present invention and is excellent in elongation at break.
（カーボンブラック）
　本発明のゴム組成物は、更に、カーボンブラックを含有することができる。
・カーボンブラックの種類
　上記カーボンブラックの種類は特に制限されない。
　カーボンブラックの種類としては、耐熱性により優れるという観点から、例えば、ＦＥＦ、ＧＰＦ、ＳＲＦ、ＦＴ又はＭＴ級カーボンブラックのようなソフトカーボンブラックが挙げられる。
　上記カーボンブラックは、耐熱性により優れるという観点から、ＧＰＦ級カーボンブラック及び／又はＳＲＦ級カーボンブラックを含むことが好ましい。 (Carbon black)
The rubber composition of the present invention can further contain carbon black.
-Type of carbon black The type of carbon black is not particularly limited.
Examples of the carbon black include soft carbon black such as FEF, GPF, SRF, FT, or MT grade carbon black from the viewpoint of superior heat resistance.
The carbon black preferably contains GPF grade carbon black and / or SRF grade carbon black from the viewpoint of superior heat resistance.
・よう素吸着量
　上記カーボンブラックのよう素吸着量は、耐熱性と押し出し加工性に優れるという観点から、１５～５０ｍｇ／ｇであることが好ましく、２０～４５ｍｇ／ｇであることがより好ましい。
　カーボンブラックのよう素吸着量は、ＪＩＳ　Ｋ６２１７－１：２００８に準じて測定できる。 -Iodine adsorption amount The iodine adsorption amount of the above carbon black is preferably 15 to 50 mg / g, more preferably 20 to 45 mg / g, from the viewpoint of excellent heat resistance and extrusion processability.
The iodine adsorption amount of carbon black can be measured according to JIS K6217-1: 2008.
　なお、本発明において、カーボンブラックのよう素吸着量が数値範囲（例えばＡ～Ｂｍ2／ｇ）で示されている場合、上記数値範囲の下限値（Ａ）と上限値（Ｂ）との合計を２で割った値［（Ａ＋Ｂ）／２］が上記好適範囲を満たせばよい。カーボンブラックの窒素吸着比表面積、ＤＢＰ吸油量についても同様である。 In the present invention, when the iodine adsorption amount of carbon black is shown in a numerical range (for example, A to Bm 2 / g), the sum of the lower limit value (A) and the upper limit value (B) of the numerical range. The value [(A + B) / 2] divided by 2 should satisfy the above preferred range. The same applies to the nitrogen adsorption specific surface area and DBP oil absorption of carbon black.
・窒素吸着比表面積
　上記カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ）は、耐熱性と押し出し加工性に優れるという観点から、２０×１０3～４５×１０3ｍ2／ｋｇであることが好ましく、２５×１０3～４０×１０3ｍ2／ｋｇであることがより好ましい。
　カーボンブラックの窒素吸着比表面積は、ＪＩＳ　Ｋ６２１７－２：２００８に準じて測定できる。 Nitrogen adsorption specific surface area The nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably 20 × 10 3 to 45 × 10 3 m 2 / kg from the viewpoint of excellent heat resistance and extrusion processability. 25 × 10 3 to 40 × 10 3 m 2 / kg is more preferable.
The nitrogen adsorption specific surface area of carbon black can be measured according to JIS K6217-2: 2008.
・ＤＢＰ吸油量
　上記カーボンブラックのジブチルフタレート（ＤＢＰ）吸油量は、耐熱性と押し出し加工性に優れるという観点から、５５～１００ｍｌ／１００ｇであることが好ましい。
　カーボンブラックのＤＢＰ吸油量は、ＪＩＳ　Ｋ６２１７－４：２００８に準じて、測定できる。 DBP oil absorption The carbon black has a dibutyl phthalate (DBP) oil absorption of 55 to 100 ml / 100 g from the viewpoint of excellent heat resistance and extrusion processability.
The DBP oil absorption of carbon black can be measured according to JIS K6217-4: 2008.
・カーボンブラックの含有量
　上記カーボンブラックの含有量は、本発明の効果により優れ、補強性と耐熱性に優れるという観点から、上記ジエン系ゴム１００質量部に対して、３０～１３０質量部であることが好ましく、５０～１００質量部がより好ましい。 -Content of carbon black The content of carbon black is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber from the viewpoint of excellent effects of the present invention and excellent reinforcement and heat resistance. It is preferably 50 to 100 parts by mass.
　本発明のゴム組成物は、白色充填剤を実質的に配合しないことが好ましい態様の１つとして挙げられる。
　上記白色充填剤としては、シリカ、炭酸カルシウム、タルク、クレー又はマイカが挙げられる。
　本発明において、白色充填剤を実質的に含有しないとは、上記白色充填剤の含有量が、本発明のゴム組成物全体に対して０～１．０質量％であることを意味する。 One preferred embodiment of the rubber composition of the present invention is that substantially no white filler is blended.
Examples of the white filler include silica, calcium carbonate, talc, clay, and mica.
In the present invention, “substantially free of white filler” means that the content of the white filler is 0 to 1.0% by mass with respect to the entire rubber composition of the present invention.
（添加剤）
　本発明のゴム組成物は、必要に応じて、本発明の効果を損なわない範囲で、更に添加剤を含有することができる。
　添加剤としては、例えば、ジエン系ゴム以外のゴム、樹脂、上記酸化亜鉛以外の酸化亜鉛、加硫促進助剤（例えば、ステアリン酸）、加硫遅延剤、軟化剤のような加工助剤、加硫促進剤、老化防止剤、可塑剤などが挙げられる。 (Additive)
The rubber composition of the present invention can further contain an additive as necessary, as long as the effects of the present invention are not impaired.
Examples of additives include rubbers other than diene rubbers, resins, zinc oxides other than the above zinc oxide, vulcanization accelerators (for example, stearic acid), vulcanization retarders, processing aids such as softeners, Examples include vulcanization accelerators, anti-aging agents, and plasticizers.
（ゴム組成物の製造方法）
　本発明のゴム組成物はその製造方法について特に制限されない。例えば、上記必須成分と、必要に応じて使用することができる任意成分とを１００～１８０℃の条件下で混合することによって製造することができる。 (Method for producing rubber composition)
The manufacturing method of the rubber composition of the present invention is not particularly limited. For example, it can be produced by mixing the above essential components and optional components that can be used as necessary under the conditions of 100 to 180 ° C.
（ゴム組成物の加硫（架橋））
　本発明のゴム組成物を加硫（架橋）する方法は特に制限されない。本発明のゴム組成物を、例えば、１４０～１９０℃の条件下において、プレス加硫、蒸気加硫、オーブン加硫（熱気加硫）または温水加硫して加硫（架橋）することができる。 (Vulcanization of rubber composition (crosslinking))
The method for vulcanizing (crosslinking) the rubber composition of the present invention is not particularly limited. The rubber composition of the present invention can be vulcanized (crosslinked) by press vulcanization, steam vulcanization, oven vulcanization (hot air vulcanization) or hot water vulcanization under conditions of 140 to 190 ° C., for example. .
　本発明のゴム組成物は、例えば、ホースに適用することができる。本発明のゴム組成物をホースの最外層に適用することが好ましい。
　上記ホースとしては、例えば、油圧作動用ホース、カーエアコンシステム用ホースが挙げられる。 The rubber composition of the present invention can be applied to, for example, a hose. It is preferable to apply the rubber composition of the present invention to the outermost layer of the hose.
Examples of the hose include a hydraulic operation hose and a car air conditioner system hose.
［ホース］
　本発明のホースは、本発明のホース用ゴム組成物を用いて形成されたホースである。
　本発明のホースは、高モジュラスであり、耐圧縮永久歪み性、耐熱性に優れる本発明のホース用ゴム組成物を用いて形成されるので、（上記の高モジュラス、優れた耐圧縮永久歪み性により）金具の装着性に優れ、耐熱性に優れる。
　このため、本発明のホースは、より高い温度雰囲気下で使用でき、且つホースの製品寿命を従来よりも延ばす事ができる。 [hose]
The hose of the present invention is a hose formed using the rubber composition for a hose of the present invention.
The hose of the present invention has a high modulus and is formed using the rubber composition for a hose of the present invention that is excellent in compression set resistance and heat resistance (the above high modulus, excellent compression set resistance) )) Excellent metal fitting and heat resistance.
For this reason, the hose of this invention can be used in a higher temperature atmosphere, and can extend the product life of a hose than before.
　本発明のホースは、本発明のゴム組成物を用いて形成されること以外は特に制限されない。
　本発明のホースに使用されるゴム組成物は本発明のゴム組成物であれば特に制限されない。 The hose of the present invention is not particularly limited except that it is formed using the rubber composition of the present invention.
The rubber composition used for the hose of the present invention is not particularly limited as long as it is the rubber composition of the present invention.
　本発明のホースにおいて、上記ホースのいずれの部材を上記ゴム組成物で形成するかは特に制限されない。
　なかでも、本発明のホースは、上記ゴム組成物で形成された最外層を有することが好ましい態様の１つとして挙げられる。 In the hose of the present invention, which member of the hose is formed of the rubber composition is not particularly limited.
Especially, it is mentioned as one of the aspects with preferable that the hose of this invention has the outermost layer formed with the said rubber composition.
（最外層）
　本発明のホースの最外層を本発明のゴム組成物で形成することができる。
　最外層の厚みは例えば０．２～４ｍｍとすることができる。 (Outermost layer)
The outermost layer of the hose of the present invention can be formed from the rubber composition of the present invention.
The thickness of the outermost layer can be set to 0.2 to 4 mm, for example.
　本発明のホースは上記最外層以外に、更に、補強部材（補強層）、内層及び中間ゴム層からなる群から選ばれる少なくとも１種を有することができる。補強部材は１層又は複数の層であってもよい。内層及び中間ゴム層も同様である。 The hose of the present invention may further include at least one selected from the group consisting of a reinforcing member (reinforcing layer), an inner layer, and an intermediate rubber layer in addition to the outermost layer. The reinforcing member may be a single layer or a plurality of layers. The same applies to the inner layer and the intermediate rubber layer.
（補強部材）
　補強部材は特に限定されない。例えば、従来公知のものが挙げられる。
　補強部材の材質としては、例えば、金属、繊維材料（ポリアミド、ポリエステル等）が挙げられる。補強部材は表面処理されたものであってもよい。
　補強部材の形態としては、例えば、スパイラル構造及び／又はブレード構造に編組されたものが挙げられる。 (Reinforcing member)
The reinforcing member is not particularly limited. For example, a conventionally well-known thing is mentioned.
Examples of the material of the reinforcing member include metals and fiber materials (polyamide, polyester, etc.). The reinforcing member may be surface-treated.
Examples of the form of the reinforcing member include those braided into a spiral structure and / or a blade structure.
（内層）
　内層を形成しうるゴム組成物は特に制限されない。例えば、本発明のゴム組成物で内層を形成してもよい。
　内層の厚みは例えば０．２～４ｍｍとすることができる。 (Inner layer)
The rubber composition that can form the inner layer is not particularly limited. For example, you may form an inner layer with the rubber composition of this invention.
The thickness of the inner layer can be set to 0.2 to 4 mm, for example.
（中間ゴム層）
　中間ゴム層を形成しうるゴム組成物は特に制限されない。例えば、従来公知のものが挙げられる。中間ゴム層を本発明のゴム組成物を用いて形成してもよい。
　中間ゴム層は、例えば、最外層と補強部材との間、内層と補強部材との間、又は、補強部材と補強部材との間に配置することができる。
　中間ゴム層の厚みは例えば０．２～０．７ｍｍとすることができる。 (Intermediate rubber layer)
The rubber composition that can form the intermediate rubber layer is not particularly limited. For example, a conventionally well-known thing is mentioned. An intermediate rubber layer may be formed using the rubber composition of the present invention.
The intermediate rubber layer can be disposed, for example, between the outermost layer and the reinforcing member, between the inner layer and the reinforcing member, or between the reinforcing member and the reinforcing member.
The thickness of the intermediate rubber layer can be set to 0.2 to 0.7 mm, for example.
　本発明のホースは、例えば、内層、補強部材及び最外層をこの順番で有することができる。 The hose of the present invention can have, for example, an inner layer, a reinforcing member, and an outermost layer in this order.
　本発明のホースの例について添付の図面を参照して説明する。本発明は添付の図面に制限されない。
　図１は、本発明のホースの一例について、各層を切り欠いて表した、模式的な斜視図である。
　図１において、ホース１は、内層２を有し、内層２の上に補強部材３を有し、補強部材３の上に最外層４を有する。
　最外層４を本発明のゴム組成物で形成することが好ましい態様の１つとして挙げられる。 An example of the hose of the present invention will be described with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a schematic perspective view showing an example of the hose of the present invention by cutting out each layer.
In FIG. 1, the hose 1 has an inner layer 2, a reinforcing member 3 on the inner layer 2, and an outermost layer 4 on the reinforcing member 3.
One preferred embodiment is that the outermost layer 4 is formed of the rubber composition of the present invention.
　本発明のホースはその製造方法について特に制限されない。例えば、マンドレル上に、内層を形成するためのゴム組成物、補強部材および最外層を形成するためのゴム組成物（例えば本発明のゴム組成物）をこの順に積層させて積層体とし、上記積層体をナイロン布などで覆い、上記ナイロン布などで覆われた積層体を１４０～１９０℃、３０～１８０分の条件で、プレス加硫、蒸気加硫、オーブン加硫（熱気加硫）または温水加硫することにより加硫接着させて本発明のホースを製造することができる。 The production method of the hose of the present invention is not particularly limited. For example, a rubber composition for forming an inner layer, a reinforcing member and a rubber composition for forming an outermost layer (for example, the rubber composition of the present invention) are laminated in this order on a mandrel to form a laminate, Cover the body with a nylon cloth, etc., and press laminate, steam vulcanization, oven vulcanization (hot air vulcanization) or hot water on the laminate covered with the above nylon cloth etc. under conditions of 140 to 190 ° C. and 30 to 180 minutes The hose of the present invention can be produced by vulcanization and adhesion by vulcanization.
　本発明のホースの具体的な用途としては、例えば、油圧作動用ホース（油圧ホース）、カーエアコンシステム用ホースが挙げられる。 Specific examples of the use of the hose of the present invention include a hydraulic operation hose (hydraulic hose) and a car air conditioner system hose.
　以下に実施例を示して本発明を具体的に説明する。ただし本発明はこれらに限定されない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
＜ゴム組成物の製造＞
　下記第１表の各成分を同表に示す組成（質量部）で用いて、これらを撹拌機で混合し、組成物を製造した。
　具体的には、まず、下記第１表に示す成分のうち硫黄及び加硫促進剤を除く成分をバンバリーミキサー（３．４リットル）で５分間混合し、１６０℃に達したときに放出し、マスターバッチを得た。
　次に、上記のとおり得られた各マスターバッチに硫黄と加硫促進剤とを加え、これらをオープンロールで混合し、ゴム組成物を得た。 <Manufacture of rubber composition>
Each component of the following Table 1 was used in the composition (parts by mass) shown in the same table, and these were mixed with a stirrer to produce a composition.
Specifically, first, the components shown in Table 1 below, excluding sulfur and the vulcanization accelerator, were mixed for 5 minutes with a Banbury mixer (3.4 liters) and released when the temperature reached 160 ° C. A master batch was obtained.
Next, sulfur and a vulcanization accelerator were added to each masterbatch obtained as described above, and these were mixed with an open roll to obtain a rubber composition.
（加硫シート（加硫直後）の作製）
　上記のとおり得られた各ゴム組成物を１５３℃のプレス成型機を用い、面圧３．０ＭＰａの圧力下で４５分間加硫して、２ｍｍ厚の加硫シート（加硫直後）を作製した。 (Preparation of vulcanized sheet (immediately after vulcanization))
Each rubber composition obtained as described above was vulcanized for 45 minutes under a surface pressure of 3.0 MPa using a press molding machine at 153 ° C. to prepare a vulcanized sheet having a thickness of 2 mm (immediately after vulcanization). .
＜＜評価＞＞
　本発明において、初期試験片の引張物性、耐熱性及び耐圧縮永久歪み性を以下のとおり評価した。結果を第１表に示す。
＜引張物性（モジュラス等）＞
　後述のとおり、初期試験片の引張物性（１００％モジュラス、引張強さ及び破断時伸び）を測定した。各実施例、比較例の各引張物性の結果を比較例１の結果を１００％とする指数（％）で表す。上記各引張物性の指数を第１表に示す。 << Evaluation >>
In the present invention, the tensile physical properties, heat resistance and compression set resistance of the initial test piece were evaluated as follows. The results are shown in Table 1.
<Tensile properties (modulus, etc.)>
As described later, the tensile properties (100% modulus, tensile strength and elongation at break) of the initial test piece were measured. The result of each tensile physical property of each Example and Comparative Example is expressed as an index (%) with the result of Comparative Example 1 being 100%. Table 1 shows the indices of the above-mentioned tensile properties.
・引張試験に用いる初期試験片の作製
　上記のとおり作製された各加硫シートからＪＩＳ３号ダンベル状の試験片を打ち抜き、初期試験片を得た。 -Preparation of initial test piece used for tensile test A JIS No. 3 dumbbell-shaped test piece was punched out from each vulcanized sheet prepared as described above to obtain an initial test piece.
・引張試験
　上記のとおり得られた各初期試験片を用いて、ＪＩＳ　Ｋ６２５１：２０１０に準じて、２３℃±２℃、引張速度５００ｍｍ／分の条件下で引張試験を行い、１００％モジュラス（Ｍ１００％）、引張強さ（ＴＢ）［ＭＰａ］及び破断時伸び（ＥＢ）［％］を測定した。 Tensile test Using each of the initial test pieces obtained as described above, a tensile test was performed in accordance with JIS K6251: 2010 under the conditions of 23 ° C. ± 2 ° C. and a tensile speed of 500 mm / min, and 100% modulus (M100 %), Tensile strength (TB) [MPa] and elongation at break (EB) [%].
・引張物性（初期）の評価基準
・・モジュラス（高モジュラス）（初期）
　なお、本発明において、モジュラス（高モジュラス）は、１００％モジュラスで測定された値を用いて、以下のように評価された。
　本発明において、１００％モジュラス（指数）が１１５％以上である場合、非常に高モジュラスであると評価した。
　１００％モジュラス（指数）が１１０％以上１１５％未満である場合、やや高モジュラスであると評価した。
　１００％モジュラス（指数）が１０５％以上１１０％未満である場合、モジュラスがやや低いと評価した。
　１００％モジュラス（指数）が１０５％未満である場合、モジュラスが非常に低いと評価した。 -Evaluation criteria for tensile properties (initial)-Modulus (high modulus) (initial)
In the present invention, the modulus (high modulus) was evaluated as follows using a value measured at 100% modulus.
In the present invention, when the 100% modulus (index) is 115% or more, it was evaluated as very high modulus.
When the 100% modulus (index) was 110% or more and less than 115%, it was evaluated as slightly high modulus.
When the 100% modulus (index) was 105% or more and less than 110%, it was evaluated that the modulus was slightly low.
When the 100% modulus (index) was less than 105%, the modulus was evaluated as very low.
・・引張強さ（ＴＢ）（初期）の評価基準
　本発明において、引張強さ（指数）が１００％を超える場合、引張強さに非常に優れると評価した。
　引張強さ（指数）が９７％以上１００％以下である場合、引張強さにやや優れると評価した。
　引張強さ（指数）が９７％未満である場合、引張強さが低いと評価した。 .. Evaluation Criteria for Tensile Strength (TB) (Initial) In the present invention, when the tensile strength (index) exceeds 100%, it was evaluated that the tensile strength is very excellent.
When the tensile strength (index) was 97% or more and 100% or less, it was evaluated that the tensile strength was slightly superior.
When the tensile strength (index) was less than 97%, it was evaluated that the tensile strength was low.
・・破断時伸び（ＥＢ）（初期）の評価基準
　本発明において、破断時伸び（指数）が８０％以上である場合、破断時伸びに優れると評価した。
　破断時伸び（指数）が８０％未満である場合、破断時伸びが低いと評価した。 .. Evaluation criteria for elongation at break (EB) (initial) In the present invention, when the elongation at break (index) was 80% or more, it was evaluated that the elongation at break was excellent.
When the elongation at break (index) was less than 80%, the elongation at break was evaluated as low.
＜耐熱性＞
・加熱老化後試験片の作製
　上記のとおり、各加硫シートからＪＩＳ３号ダンベル状の試験片を打ち抜き、得られた初期試験片を１３０℃の条件下に１６８時間置く加熱老化試験を行い、加熱老化後試験片を得た。 <Heat resistance>
・ Preparation of test pieces after heat aging As described above, a JIS No. 3 dumbbell-shaped test piece was punched from each vulcanized sheet, and the resulting initial test piece was subjected to a heat aging test for 168 hours at 130 ° C. A specimen was obtained after aging.
・引張試験
　上記のとおり得られた各加熱老化後試験片を用いて、上記＜引張物性＞と同様に引張試験を行い、各加熱老化後試験片の破断時伸び（ＥＢ）［％］を測定した。 ・ Tensile test Using each test specimen after heat aging obtained as described above, a tensile test was performed in the same manner as the above <Tensile physical properties>, and the elongation at break (EB) [%] of each test specimen after heat aging was measured. did.
・ΔＥＢ
　同一のゴム組成物から形成された、初期試験片及び加熱老化後試験片の上記破断時伸びの値を下記式に当てはめて、ΔＥＢ（％）を算出した。結果を第１表に示す。
ΔＥＢ（％）＝［（加熱老化後試験片のＥＢ－初期試験片のＥＢ）／初期試験片のＥＢ］×１００ ・ ΔEB
ΔEB (%) was calculated by applying the elongation value at break of the initial test piece and the test piece after heat aging formed from the same rubber composition to the following formula. The results are shown in Table 1.
ΔEB (%) = [(EB of test piece after heat aging−EB of initial test piece) / EB of initial test piece] × 100
・・ΔＥＢの評価基準
　上記ΔＥＢ（％）の絶対値が０に近いほど耐熱性に優れる。
　本発明において、上記ΔＥＢの絶対値が３９％以下である場合、耐熱性に非常に優れると評価した。
　上記ΔＥＢの絶対値が３９％を超え４５％以下である場合、耐熱性にやや優れると評価した。
　上記ΔＥＢの絶対値が４５％を超え５０％以下である場合、耐熱性にやや劣ると評価した。
　上記ΔＥＢの絶対値が５０％を超える場合、耐熱性に非常に劣ると評価した。 -Evaluation criteria of ΔEB The closer the absolute value of ΔEB (%) is to 0, the better the heat resistance.
In the present invention, when the absolute value of ΔEB was 39% or less, it was evaluated that the heat resistance was very excellent.
When the absolute value of ΔEB was more than 39% and 45% or less, it was evaluated that the heat resistance was slightly superior.
When the absolute value of the ΔEB was more than 45% and 50% or less, it was evaluated that the heat resistance was slightly inferior.
When the absolute value of ΔEB exceeded 50%, it was evaluated that the heat resistance was very poor.
＜耐圧縮永久歪み性＞
・圧縮永久歪み評価用のサンプルの作製
　厚さがＪＩＳ　Ｋ６２６２：２０１３に準拠する大形試験片サイズになるように未加硫サンプルを作成し、１５３℃で４５分間熱プレスし、圧縮永久歪み評価用のサンプル（直径２９ｍｍ×厚さ１２．５ｍｍ）を作製した。 <Compression set resistance>
・ Preparation of samples for compression set evaluation Uncured samples were prepared so that the thickness would be the size of a large test piece conforming to JIS K6262: 2013, and hot pressed at 153 ° C. for 45 minutes to evaluate compression set Sample (diameter 29 mm × thickness 12.5 mm) was prepared.
・圧縮永久歪みの測定
　ＪＩＳ　Ｋ６２６２：２０１３に準じて、上記のとおり得られたサンプルを専用治具で圧縮し（圧縮率４０％）、１３０℃の条件下に、２４時間又は９６時間置く圧縮試験を行い、上記圧縮試験後の圧縮永久歪みを測定した。結果を第１表に示す。
　一般的に圧縮永久歪みの値が小さいほど耐圧縮永久歪み性に優れる。
　本発明において、耐圧縮永久歪み性を、上記９６時間圧縮試験による圧縮永久歪みで評価した。 ・ Measurement of compression set According to JIS K6262: 2013, the sample obtained as described above was compressed with a dedicated jig (compression rate 40%) and placed under conditions of 130 ° C. for 24 hours or 96 hours. The compression set after the compression test was measured. The results are shown in Table 1.
Generally, the smaller the compression set value, the better the compression set resistance.
In the present invention, compression set resistance was evaluated by compression set by the 96-hour compression test.
・・圧縮永久歪み（％）の評価基準
　本発明において、上記９６時間圧縮試験による圧縮永久歪みが６３％以下である場合、耐圧縮永久歪み性に非常に優れると評価した。
　上記９６時間圧縮試験による圧縮永久歪みが６３％を超え６５％以下である場合、耐圧縮永久歪み性にやや優れると評価した。
　上記９６時間圧縮試験による圧縮永久歪みが６５％を超え７０％以下である場合、耐圧縮永久歪み性にやや劣ると評価した。
　上記９６時間圧縮試験による圧縮永久歪みが７０％を超える場合、耐圧縮永久歪み性に非常に劣ると評価した。 .. Evaluation Criteria for Compression Set (%) In the present invention, when the compression set by the 96-hour compression test is 63% or less, it was evaluated that the compression set resistance was very excellent.
When the compression set by the 96-hour compression test was more than 63% and 65% or less, it was evaluated that the compression set resistance was slightly superior.
When the compression set by the 96-hour compression test was more than 65% and 70% or less, it was evaluated that the compression set resistance was slightly inferior.
When the compression set by the 96-hour compression test exceeded 70%, it was evaluated that the compression set resistance was very poor.
（金属の装着性）
　なお、本発明において、ホースに対する金属の装着性を以下のように評価できる。
　本発明において、１００％モジュラス（指数）が１１５％以上であり、かつ、上記９６時間圧縮試験による圧縮永久歪みが６３％以下である場合、上記装着性が非常に優れると評価した。
　１００％モジュラス（指数）が１１０％以上であり、かつ、上記９６時間圧縮試験による圧縮永久歪みが６５％以下である場合（ただし、上記装着性に非常に優れる場合を除く。）、上記装着性がやや優れると評価した。
　１００％モジュラス（指数）が１１０％未満である場合、又は、上記９６時間圧縮試験による圧縮永久歪みが６５％を超える場合（ただし、後述する装着性に非常に劣る場合を除く。）、上記装着性がやや劣ると評価した。
　１００％モジュラス（指数）が１０５％未満であり、かつ、上記９６時間圧縮試験による圧縮永久歪みが７０％を超える場合、上記装着性が非常に劣ると評価した。 (Metal wearability)
In addition, in this invention, the mounting property of the metal with respect to a hose can be evaluated as follows.
In the present invention, when the 100% modulus (index) was 115% or more and the compression set by the 96-hour compression test was 63% or less, it was evaluated that the wearability was very excellent.
When the 100% modulus (index) is 110% or more and the compression set by the 96-hour compression test is 65% or less (except for the case where the wearability is very excellent), the wearability. Was rated as slightly better.
When the 100% modulus (index) is less than 110%, or when the compression set by the 96-hour compression test exceeds 65% (except for the case where the wearability described later is very inferior), the above attachment. Evaluated as slightly inferior.
When the 100% modulus (index) was less than 105% and the compression set by the 96-hour compression test exceeded 70%, the wearability was evaluated to be very poor.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　第１表に示した各成分の詳細は以下のとおりである。
・ジエン系ゴム１：エチレン・プロピレン・ジエン共重合体。ＥＰＤＭ　３０９２Ｍ、三井化学社製。ムーニー粘度９２。ジエン系ゴム１のエチレン量は６５質量％であり、ジエン量は４．６質量％である。ジエン系ゴム１はジエンとしてのエチリデンノルボルネンによる繰り返し単位を有する。 Details of each component shown in Table 1 are as follows.
Diene rubber 1: ethylene / propylene / diene copolymer. EPDM 3092M, manufactured by Mitsui Chemicals. Mooney viscosity 92. The ethylene amount of the diene rubber 1 is 65% by mass, and the diene amount is 4.6% by mass. The diene rubber 1 has a repeating unit of ethylidene norbornene as a diene.
・カーボンブラック１：ＳＲＦ級カーボンブラック。Ｎ７６２、旭♯５０旭カーボン社製。よう素吸着量２０±５ｍｇ／ｇ、Ｎ2ＳＡ２９×１０3ｍ2／ｋｇ（代表値）、ＤＢＰ吸油量５５～７９ｍｌ／１００ｇ（ＤＢＰ吸油量平均値６７ｍｌ／１００ｇ）。
・カーボンブラック２：ＦＥＦ級カーボンブラック。Ｎ５５０、ニテロン♯１０Ｎ、新日化カーボン社製。よう素吸着量４１±５ｍｇ／ｇ、Ｎ2ＳＡ４０×１０3ｍ2／ｋｇ（代表値）、ＤＢＰ吸油量１２１±６ｍｌ／１００ｇ。 Carbon black 1: SRF grade carbon black. N762, Asahi # 50 manufactured by Asahi Carbon Corporation. Iodine adsorption amount 20 ± 5 mg / g, N 2 SA 29 × 10 3 m 2 / kg (representative value), DBP oil absorption 55 to 79 ml / 100 g (DBP oil absorption average value 67 ml / 100 g).
Carbon black 2: FEF grade carbon black. N550, Niteron # 10N, manufactured by Shin-Nikka Carbon Co., Ltd. Iodine adsorption amount 41 ± 5 mg / g, N 2 SA 40 × 10 3 m 2 / kg (representative value), DBP oil absorption 121 ± 6 ml / 100 g.
・比較酸化亜鉛１：酸化亜鉛３種、正同化学工業社製。ＢＥＴ法比表面積４ｍ2／ｇ。 ・ Comparison zinc oxide 1: 3 types of zinc oxide, manufactured by Shodo Chemical Industries. BET specific surface area of 4 m 2 / g.
・酸化亜鉛１：活性亜鉛華ＡＺＯ、正同化学工業社製。ＢＥＴ法比表面積６０～９０ｍ2／ｇ。湿式法で製造された高活性の酸化亜鉛。
　なお、式（Ｉ）、式（ＩＩ）の計算において、酸化亜鉛１の比表面積を、上記数値範囲の平均である７５ｍ2／ｇとした。 Zinc oxide 1: activated zinc white AZO, manufactured by Shodo Chemical Industry Co., Ltd. BET specific surface area of 60 to 90 m 2 / g. Highly active zinc oxide produced by a wet process.
In the calculations of the formulas (I) and (II), the specific surface area of the zinc oxide 1 was 75 m 2 / g, which is the average of the above numerical range.
・比較酸化亜鉛２：ＭＥＴＡ－Ｚ１０２、井上石灰工業社製。ＢＥＴ法比表面積１２ｍ2／ｇ。 Comparative zinc oxide 2: META-Z102, manufactured by Inoue Lime Industry Co., Ltd. BET specific surface area of 12 m 2 / g.
・ステアリン酸：「ステアリン酸５０Ｓ」（千葉脂肪酸社製）
・ＰＶＩ（加硫遅延剤）：Ｎ－シクロヘキシルチオフタルイミド。商品名リターダーＣＴＰ、東レファインケミカル社製
・加工助剤：軟化剤。商品名「ＳＵＮＰＡＲ　２２８０」（日本サン石油社製）
・加硫促進剤　ＴＴ：テトラメチルチウラムジスルフィド（チウラム系。大内新興化学工業社製ノクセラーＴＴ）
・加硫促進剤　ＤＭ：ジベンゾチアジルジスルフィド（チアゾール系。サンセラーＤＭ、三新化学工業社製） ・ Stearic acid: “Stearic acid 50S” (Chiba Fatty Acid Co., Ltd.)
PVI (vulcanization retarder): N-cyclohexylthiophthalimide. Product name retarder CTP, manufactured by Toray Fine Chemical Co., Ltd., processing aid: softener. Product name “SUNPAR 2280” (manufactured by Nippon Oil Corporation)
・ Vulcanization accelerator TT: Tetramethylthiuram disulfide (thiuram type. Noxeller TT manufactured by Ouchi Shinsei Chemical Co., Ltd.)
・ Vulcanization accelerator DM: Dibenzothiazyl disulfide (thiazole type. Sunseller DM, manufactured by Sanshin Chemical Industry Co., Ltd.)
・硫黄：油処理硫黄、細井化学工業社製。上記油処理硫黄は硫黄を９５質量％含む。なお、第１表の「硫黄」欄に示す硫黄の含有量は、硫黄正味の量である。 ・ Sulfur: Oil-treated sulfur, manufactured by Hosoi Chemical Co., Ltd. The oil-treated sulfur contains 95% by mass of sulfur. In addition, the sulfur content shown in the “sulfur” column of Table 1 is the net amount of sulfur.
　第１表に示す結果から明らかなように、酸化亜鉛の比表面積が所定の範囲を外れる比較例１、２は、モジュラスが低く、耐熱性、耐圧縮永久歪み性が劣った。
　酸化亜鉛の比表面積が所定の範囲を外れ、硫黄の含有量が所定の範囲より多い比較例３は、モジュラスが低く、耐熱性及び耐圧縮永久歪み性が劣った。
　酸化亜鉛の比表面積が所定の範囲を外れ、硫黄の含有量が比較例３より更に多い比較例４は、耐熱性、耐圧縮永久歪み性が劣った。
　酸化亜鉛の比表面積が所定の範囲を外れる比較例５は、モジュラスが低く、耐熱性、耐圧縮永久歪み性が劣った。
　酸化亜鉛の比表面積が所定の範囲を外れ、硫黄の含有量が所定の範囲より多い比較例６は、モジュラスが低く、耐熱性、耐圧縮永久歪み性が劣った。
　硫黄の含有量が所定の範囲より多い比較例７は、耐熱性、耐圧縮永久歪み性が劣った。 As is apparent from the results shown in Table 1, Comparative Examples 1 and 2 in which the specific surface area of zinc oxide deviates from the predetermined range had a low modulus and inferior heat resistance and compression set resistance.
In Comparative Example 3 in which the specific surface area of zinc oxide was outside the predetermined range and the sulfur content was larger than the predetermined range, the modulus was low, and the heat resistance and compression set resistance were inferior.
Comparative Example 4 in which the specific surface area of zinc oxide was outside the predetermined range and the sulfur content was higher than that in Comparative Example 3 was inferior in heat resistance and compression set resistance.
In Comparative Example 5 in which the specific surface area of zinc oxide is outside the predetermined range, the modulus was low, and the heat resistance and compression set resistance were inferior.
In Comparative Example 6 in which the specific surface area of zinc oxide was outside the predetermined range and the sulfur content was larger than the predetermined range, the modulus was low, and the heat resistance and compression set resistance were inferior.
Comparative Example 7 having a sulfur content greater than the predetermined range was inferior in heat resistance and compression set resistance.
　これに対して、本発明のゴム組成物は、高モジュラスであり、耐圧縮永久歪み性、耐熱性に優れた。 On the other hand, the rubber composition of the present invention has a high modulus and is excellent in compression set resistance and heat resistance.
　１：ホース
　２：内層
　３：補強部材
　４：最外層 1: Hose 2: Inner layer 3: Reinforcement member 4: Outermost layer

Claims (11)

  1. 　ジエン系ゴムと、比表面積が３０～１５０ｍ2／ｇである酸化亜鉛と、硫黄とを含有し、
    　前記酸化亜鉛の含有量が、前記ジエン系ゴム１００質量部に対して、１～２０質量部であり、
    　前記硫黄の含有量が、前記ジエン系ゴム１００質量部に対して、１質量部未満である、ホース用ゴム組成物。     Containing a diene rubber, zinc oxide having a specific surface area of 30 to 150 m 2 / g, and sulfur,
    The zinc oxide content is 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber,
    A rubber composition for hoses, wherein the sulfur content is less than 1 part by mass with respect to 100 parts by mass of the diene rubber.
  2. 　更に、カーボンブラックを含有し、
    　前記カーボンブラックの含有量が、前記ジエン系ゴム１００質量部に対して、３０～１３０質量部である、請求項１に記載のホース用ゴム組成物。     In addition, containing carbon black,
    The rubber composition for a hose according to claim 1, wherein a content of the carbon black is 30 to 130 parts by mass with respect to 100 parts by mass of the diene rubber.
  3. 　前記カーボンブラックが、ＧＰＦ級カーボンブラック及び／又はＳＲＦ級カーボンブラックを含む、請求項２に記載のホース用ゴム組成物。 The rubber composition for a hose according to claim 2, wherein the carbon black contains GPF grade carbon black and / or SRF grade carbon black.
  4. 　前記ジエン系ゴムが、エチレン・プロピレン・ジエン共重合体を含む、請求項１～３のいずれか１項に記載のホース用ゴム組成物。 The rubber composition for a hose according to any one of claims 1 to 3, wherein the diene rubber contains an ethylene / propylene / diene copolymer.
  5. 　下記式（Ｉ）を満たす、請求項１～４のいずれか１項に記載のホース用ゴム組成物。
    ３０＜［前記酸化亜鉛の前記比表面積／前記硫黄の前記含有量］≦１，５００　　（Ｉ）     The rubber composition for a hose according to any one of claims 1 to 4, which satisfies the following formula (I):
    30 <[the specific surface area of the zinc oxide / the content of the sulfur] ≦ 1,500 (I)
  6. 　下記式（ＩＩ）を満たす、請求項１～５のいずれか１項に記載のホース用ゴム組成物。
    ３０＜［（前記酸化亜鉛の前記比表面積×前記酸化亜鉛の前記含有量）／前記硫黄の前記含有量］≦３０，０００　　　（ＩＩ）     The rubber composition for a hose according to any one of claims 1 to 5, which satisfies the following formula (II):
    30 <[(the specific surface area of the zinc oxide × the content of the zinc oxide) / the content of the sulfur] ≦ 30,000 (II)
  7. 　前記硫黄の含有量が、前記ジエン系ゴム１００質量部に対して、０．１質量部以上である、請求項１～６のいずれか1項に記載のホース用ゴム組成物。 The rubber composition for a hose according to any one of claims 1 to 6, wherein the sulfur content is 0.1 parts by mass or more with respect to 100 parts by mass of the diene rubber.
  8. 　白色充填剤を実質的に配合しない、請求項１～７のいずれか１項に記載のホース用ゴム組成物。 The rubber composition for hoses according to any one of claims 1 to 7, which does not substantially contain a white filler.
  9. 　油圧作動用ホース又はカーエアコンシステム用ホースに使用される、請求項１～８のいずれか１項に記載のホース用ゴム組成物。 9. The rubber composition for a hose according to any one of claims 1 to 8, which is used for a hydraulic operation hose or a car air conditioner system hose.
  10. 　ホースの最外層に使用される、請求項１～９のいずれか１項に記載のホース用ゴム組成物。 The rubber composition for a hose according to any one of claims 1 to 9, which is used for an outermost layer of the hose.
  11. 　請求項１～８のいずれか１項に記載のホース用ゴム組成物を用いて形成されたホース。 A hose formed using the rubber composition for a hose according to any one of claims 1 to 8.
PCT/JP2019/016178 2018-06-06 2019-04-15 Rubber composition for hose, and hose WO2019235073A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018108380A JP2019210390A (en) 2018-06-06 2018-06-06 Rubber composition for hose, and hose
JP2018-108380 2018-06-06

Publications (1)

Publication Number Publication Date
WO2019235073A1 true WO2019235073A1 (en) 2019-12-12

Family

ID=68769983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/016178 WO2019235073A1 (en) 2018-06-06 2019-04-15 Rubber composition for hose, and hose

Country Status (2)

Country Link
JP (1) JP2019210390A (en)
WO (1) WO2019235073A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04168135A (en) * 1990-10-31 1992-06-16 Toyoda Gosei Co Ltd Ethylene-propylene rubber composition
JP2002241552A (en) * 2001-02-15 2002-08-28 Toyoda Gosei Co Ltd Rubber composite material, method for producing the same and extrusion molding
JP2004083614A (en) * 2002-08-22 2004-03-18 Kyushu Hakusui Corp Colorable rubber and resin composition having conductivity
JP2006193621A (en) * 2005-01-13 2006-07-27 Toyo Tire & Rubber Co Ltd Vibration-proof rubber composition and vibration-proof rubber
JP2011174002A (en) * 2010-02-25 2011-09-08 Sumitomo Chemical Co Ltd Rubber composition for rubber hose, and rubber hose
CN104829895A (en) * 2015-05-08 2015-08-12 尉氏县久龙橡塑有限公司 Flame-retardant antistatic V-belt coating glue and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04168135A (en) * 1990-10-31 1992-06-16 Toyoda Gosei Co Ltd Ethylene-propylene rubber composition
JP2002241552A (en) * 2001-02-15 2002-08-28 Toyoda Gosei Co Ltd Rubber composite material, method for producing the same and extrusion molding
JP2004083614A (en) * 2002-08-22 2004-03-18 Kyushu Hakusui Corp Colorable rubber and resin composition having conductivity
JP2006193621A (en) * 2005-01-13 2006-07-27 Toyo Tire & Rubber Co Ltd Vibration-proof rubber composition and vibration-proof rubber
JP2011174002A (en) * 2010-02-25 2011-09-08 Sumitomo Chemical Co Ltd Rubber composition for rubber hose, and rubber hose
CN104829895A (en) * 2015-05-08 2015-08-12 尉氏县久龙橡塑有限公司 Flame-retardant antistatic V-belt coating glue and preparation method thereof

Also Published As

Publication number Publication date
JP2019210390A (en) 2019-12-12

Similar Documents

Publication Publication Date Title
US7758937B2 (en) Rubber composition and vulcanized rubber product using the same
AU646622B1 (en) Pneumatic tire having a multilayered innerliner
US4405756A (en) Co-vulcanizable rubber composition
DE102009032975A1 (en) A manufacturing method of a rubber composition and a rubber composition prepared by the method, and a tire using the rubber composition
WO2012043372A1 (en) Rubber composition for water hose, and water hose obtained using same
US6071582A (en) Rubber layer structure
JP5095093B2 (en) Method for producing rubber composition and rubber composition obtained thereby
US20190031862A1 (en) Rubber Composition for Refrigerant-Transporting Hose, and Refrigerant-Transporting Hose
JP4715362B2 (en) Inner liner for tire and pneumatic tire using the same
JP4543685B2 (en) Rubber composition for hose interlayer rubber and hose
EP3477177B1 (en) Rubber composition for refrigerant transporting hoses, and refrigerant transporting hose
WO2019235073A1 (en) Rubber composition for hose, and hose
EP3459999A1 (en) Rubber composition
US20090130358A1 (en) Water hose and composition for hose
JP2012017757A (en) Rubber composition for inner tube of hose, and hose
JP4294607B2 (en) Pneumatic radial tire
JP2008069276A (en) Rubber composition, fiber/rubber composite and hose
JP2005023246A (en) High-pressure hose
KR102628502B1 (en) Brine seal rubber compositions for an eco-friendly water purifier and a brine seal molded body manufactured therefrom
WO2024053261A1 (en) Rubber composition and hose
WO2012043097A1 (en) Rubber composition for water hose, and water hose obtained using same
JP4547727B2 (en) Refrigerant transport hose and manufacturing method thereof
CN117715966A (en) Rubber composition for hose inner pipe, laminate, and hose
JP2005024032A (en) High pressure hose
JPS61143458A (en) High-hardness rubber composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19814433

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19814433

Country of ref document: EP

Kind code of ref document: A1