WO2019078068A1 - Composition de nbr hydrogéné - Google Patents

Composition de nbr hydrogéné Download PDF

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Publication number
WO2019078068A1
WO2019078068A1 PCT/JP2018/037772 JP2018037772W WO2019078068A1 WO 2019078068 A1 WO2019078068 A1 WO 2019078068A1 JP 2018037772 W JP2018037772 W JP 2018037772W WO 2019078068 A1 WO2019078068 A1 WO 2019078068A1
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WO
WIPO (PCT)
Prior art keywords
weight
hydrogenated nbr
parts
less
sealing material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/037772
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English (en)
Japanese (ja)
Inventor
慶 関口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nok Corp
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Nok Corp
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Publication date
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Application filed by Nok Corp filed Critical Nok Corp
Priority to JP2019549227A priority Critical patent/JP6843265B2/ja
Priority to CN201880025757.2A priority patent/CN110536923B/zh
Publication of WO2019078068A1 publication Critical patent/WO2019078068A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing

Definitions

  • the present invention relates to hydrogenated NBR compositions. More particularly, it relates to hydrogenated NBR compositions that can be used in R32 refrigerant contact applications and can provide seals that require high cold resistance.
  • hydrogenated NBR is excellent in oil resistance, heat resistance, chemical stability, mechanical properties and the like, it is widely used as a member for hoses, automobile seal members and the like.
  • the hydrogenated NBR is characterized in that various properties can be changed by changing the acrylonitrile [AN] content.
  • AN acrylonitrile
  • the hydrogenated NBR composition is in a relation that heat resistance deteriorates when cold resistance is improved, and it is difficult to impart high cold resistance while maintaining excellent heat resistance.
  • R32 HFC
  • sealing materials that can be used for applications that contact R32 refrigerant. It is rising.
  • An object of the present invention is to provide a sealing material which can be used in R32 refrigerant contact applications, and which has both excellent cold resistance and heat resistance, and which can sufficiently maintain sealability even in a low temperature environment of -40 ° C or less To provide a hydrogenated NBR composition.
  • the object of the present invention is to use 5 to 50 parts by weight of an ester plasticizer having a freezing point of -40.degree. C. or less and a molecular weight of 500 to 1000 and 100 parts by weight of hydrogenated NBR having an acrylonitrile content of 15 to 22%. This is achieved by a hydrogenated NBR composition comprising 1 to 10 parts by weight of oxide.
  • the present invention provides a sealing material that can be used in R32 refrigerant contact applications, and has both excellent cold resistance and heat resistance, and can maintain sealing performance sufficiently even in a low temperature environment of -40 ° C or less
  • An improved NBR composition is provided. This is because hydrogenated NBR having a specific AN content is used, and a specific amount of a specific ester plasticizer is compounded.
  • the hydrogenated NBR one having an AN content in the range of 15 to 22%, preferably 18 to 21% is used. There is no commercial product having a lower AN content, while a higher AN content leads to poor cold resistance and R32 refrigerant resistance.
  • the degree of hydrogenation is arbitrary.
  • the hydrogenated NBR is peroxide crosslinked.
  • an amine-vulcanizable hydrogenated NBR containing a carboxyl group or the like is used, as shown in Comparative Example 1 below, resistance to R32 refrigerant becomes inferior (see Patent Documents 1 and 2).
  • ester-based plasticizers those having a freezing point of -40 ° C. or less, preferably -45 ° C. or less and a molecular weight of 500 to 1000 are used in an amount of about 5 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight of hydrogenated NBR. Used in proportions by weight.
  • cold resistance will be poor, and if the molecular weight is smaller than this, cold resistance will be improved, but heat resistance will deteriorate, while if it is larger, viscosity will be high and handling will be difficult , Compatibility will also be worse. If the proportion is lower than this range, cold resistance will be poor. If more than this range, cold resistance will be improved, but heat resistance and R32 refrigerant resistance will be inferior, and kneading processability will also deteriorate.
  • ester-based plasticizers having such a freezing point and / or molecular weight
  • commercially available products such as Adeka products Adekasizer RS-700, RS-1000 (more than polyether ester based), C-9N (trimellitic acid isononyl ester) Etc. are used.
  • Examples of the organic peroxide used for peroxide crosslinking of hydrogenated NBR include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-di (tert-butylperoxy)- 3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 1,3-Di (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, n -Butyl-4,4'-di (tert-butylperoxy) valerate or the like is used
  • the amount of the organic peroxide is less than this, a vulcanized product having a sufficient crosslink density can not be obtained, while if it is used at a ratio higher than this, it can not be formed by foaming or vulcanization. Even in such cases, the rubber elasticity and the elongation will be reduced.
  • polyfunctional unsaturated compounds such as triallyl (iso) cyanurate, trimethylolpropane tri (meth) acrylate, and triallyl trimellitate are added in an amount of about 100 parts by weight of hydrogenated NBR. It is preferable to blend 10 parts by weight or less, preferably about 2 to 8 parts by weight.
  • the compounding of the polyfunctional unsaturated compound is effective to further improve the heat resistance and the compression set resistance. However, when it is used at a ratio higher than this, the rubber elasticity and elongation decrease.
  • (iso) cyanurate means cyanurate or isocyanurate
  • (meth) acrylate means acrylate or methacrylate.
  • reinforcing agents such as carbon black and white carbon
  • fillers such as talc, clay, graphite and calcium silicate
  • processing aids such as stearic acid, palmitic acid and paraffin wax, zinc oxide, magnesium oxide
  • acid acceptors such as hydrotalcite, anti-aging agents, and plasticizers other than the above-mentioned ester plasticizers
  • carbon black When carbon black is used alone, it is used in a proportion of about 20 to 150 parts by weight, preferably about 40 to 100 parts by weight, per 100 parts by weight of hydrogenated NBR, in which case the carbon black may be a single grade. Or as a mixture of multiple grades.
  • white carbon When white carbon is used alone, it is used in a proportion of about 20 to 150 parts by weight, preferably about 30 to 60 parts by weight, per 100 parts by weight of hydrogenated NBR. Both of these can be used in combination, in which case about 10 to about 140 parts by weight each per 100 parts by weight of hydrogenated NBR, and the total of these is about 20 to about 150 parts by weight.
  • silane coupling in an amount of about 0.1 part by weight or more, preferably about 0.5 to 3 parts by weight, per 100 parts by weight of hydrogenated NBR.
  • silane coupling agent any one which can be generally used for rubber can be used without limitation, and examples thereof include vinyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane Examples thereof include ⁇ -aminopropyltrimethoxysilane and ⁇ -mercaptopropyltrimethoxysilane.
  • the blending of the silane coupling agent contributes to the improvement of the heat resistance and the cold resistance.
  • Preparation of the composition is carried out by kneading using an intermix, kneader such as kneader or Banbury mixer, open roll, etc.
  • the vulcanization is carried out using an injection molding machine, a compression molding machine, a vulcanization press, etc.
  • secondary vulcanization is carried out by heating at about 150 to 200 ° C. for about 2 to 30 minutes, and if necessary, heating at about 120 to 200 ° C. for about 1 to 24 hours.
  • the sealing material molded from such a hydrogenated NBR composition has less foaming even when brought into contact with the R32 refrigerant under the conditions of 40 ° C. and 24 hours, and the TR-10 value in the low temperature elastic recovery test is -36. Because it is less than ° C, and the compression set after 70 hours at 120 ° C of G25 O-ring is 34% or less, it can be used for applications that contact R32 refrigerant, and used in a low temperature environment of -40 ° C or less Sealing material, for example, a seal for a refrigerant used in an air conditioner or the like.
  • Example 1 Hydrogenated NBR (Nippon Zeon product Zetpol 4310, AN content 18.6%) 100 parts by weight Carbon black (Tokai carbon product Seat GS) 95 ⁇ Ester-based plasticizer (ADEKA products Adekasizer RS-700 20 ⁇ Freezing point-53 ° C, molecular weight about 550) Dicumyl peroxide 6 ⁇ Processing aid (Miyoshi oil product Stearic acid TST) 1 ⁇ Anti-aging agent (Ouchi emerging chemical industry product Nocl CD) 1 1 1
  • the above components except for the crosslinking agent) are kneaded with a kneader, and then the crosslinking agent is added and kneaded using an open roll. The kneaded product (composition) was press-cured at 180 ° C. for 6 minutes and then oven-cured (secondary cure) at 150 ° C. for 1 hour.
  • Low-temperature elastic recovery test conforms to JIS K6261 corresponding to ISO 2921 TR if measured TR-10 value is -40 ° C or less, ⁇ if -39 to -36 ° C, ⁇ if -35 ° C or more
  • Compression set test evaluated Using a G25 O-ring specified in JIS B 2401-1 according to JIS K6262 corresponding to ISO 815-1, according to ISO 3601-1, the compression set after the test at 120 ° C.
  • Example 2 In Example 1, the amount of ester plasticizer was changed to 10 parts by weight.
  • Example 3 In Example 1, the amount of ester plasticizer was changed to 40 parts by weight.
  • Example 1 Comparative Example 1 In Example 1, the same amount (100 parts by weight) of Nippon Zeon product Zetpol 3610 (20.5% of AN content) was used as a hydrogenated NBR, and 2.5 parts by weight of hexamethylene diamine dicarbamate was used instead of dicumyl peroxide. . However, oven vulcanization was performed at 175 ° C. for 6 hours.
  • Comparative example 2 In Example 1, the same amount (100 parts by weight) of Nippon Zeon product Zetpol 3310 (24.6% of AN content) was used as a hydrogenated NBR.
  • Comparative example 4 In Example 1, 60 parts by weight of an ester plasticizer was used.
  • Comparative example 5 In Example 1, the same amount (20 parts by weight) of ADEKA product Adekasizer RS-735 (solidifying point -8 ° C., molecular weight about 850) was used as an ester-based plasticizer.
  • Comparative example 6 In Example 1, the same amount (20 parts by weight) of ADEKA product Adekasizer RS-107 (solidifying point-47 ° C, molecular weight 434) was used as an ester-based plasticizer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Gasket Seals (AREA)

Abstract

L'invention concerne une composition de NBR hydrogéné qui est obtenue par mélange de 5 à 50 parties en poids d'un plastifiant à base d'ester qui présente un point de congélation égal ou inférieur à -40 °C et un poids moléculaire de 500 à 1 000, et de 1 à 10 parties en poids d'un peroxyde organique pour 100 parties en poids d'un NBR hydrogéné présentant une teneur en acrylonitrile de 15 à 22 %. Cette composition de NBR hydrogéné fournit un matériau d'étanchéité qui est approprié pour des applications en contact avec le réfrigérant R32, tout en présentant un bon équilibre entre une excellente résistance au froid et une excellente résistance à la chaleur, et qui est capable de conserver des propriétés d'étanchéité suffisantes même dans un environnement à basse température, de l'ordre de -40 °C ou moins. Un matériau d'étanchéité, formé à partir de cette composition de NBR hydrogéné, présente une valeur TR-10 de -36 °C ou moins lors d'un test de récupération élastique à basse température, et un joint torique G25 à base de ce matériau présente une compression rémanente égale ou inférieure à 34 % après 70 heures à 120 °C.
PCT/JP2018/037772 2017-10-17 2018-10-10 Composition de nbr hydrogéné Ceased WO2019078068A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019549227A JP6843265B2 (ja) 2017-10-17 2018-10-10 シール材
CN201880025757.2A CN110536923B (zh) 2017-10-17 2018-10-10 氢化nbr组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-201172 2017-10-17
JP2017201172 2017-10-17

Publications (1)

Publication Number Publication Date
WO2019078068A1 true WO2019078068A1 (fr) 2019-04-25

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PCT/JP2018/037772 Ceased WO2019078068A1 (fr) 2017-10-17 2018-10-10 Composition de nbr hydrogéné

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JP (2) JP6843265B2 (fr)
CN (1) CN110536923B (fr)
WO (1) WO2019078068A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026055300A1 (fr) * 2024-09-06 2026-03-12 Green, Tweed Technologies, Inc. Articles comprenant des compositions élastomères non pfas et leurs procédés de préparation

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0967471A (ja) * 1995-08-31 1997-03-11 Mitsubishi Cable Ind Ltd シール材用組成物およびシール材
JP2006001970A (ja) * 2004-06-15 2006-01-05 Yokohama Rubber Co Ltd:The 自動車部品用熱可塑性樹脂組成物
WO2014024698A1 (fr) * 2012-08-09 2014-02-13 Nok株式会社 Composition de caoutchouc nbr
WO2016035892A1 (fr) * 2014-09-05 2016-03-10 日本ゼオン株式会社 Composition de caoutchouc nitrile fortement saturé et matériau de caoutchouc réticulé
WO2016190214A1 (fr) * 2015-05-26 2016-12-01 日本ゼオン株式会社 Caoutchouc à base d'un copolymère fortement saturé, contenant un groupe nitrile
WO2017022598A1 (fr) * 2015-08-05 2017-02-09 日本ゼオン株式会社 Caoutchouc de copolymère hautement saturé contenant un groupe nitrile, composition de caoutchouc réticulable et caoutchouc réticulé
WO2017047571A1 (fr) * 2015-09-17 2017-03-23 日本ゼオン株式会社 Composition de caoutchouc de nitrile, composition de caoutchouc de nitrile réticulable et caoutchouc réticulé
WO2017086358A1 (fr) * 2015-11-20 2017-05-26 日本ゼオン株式会社 Matériau de caoutchouc réticulé
WO2017159623A1 (fr) * 2016-03-18 2017-09-21 日本ゼオン株式会社 Composition de caoutchouc nitrile et produit réticulé de caoutchouc

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4773059B2 (ja) * 2004-03-30 2011-09-14 ニチアス株式会社 燃料電池用セパレータ用ゴムガスケット
RU2658042C2 (ru) * 2013-11-28 2018-06-19 Зэон Корпорейшн Композиция высоконасыщенного сополимерного каучука, содержащего нитрильные группы, и сшитый каучук
CN106574080B (zh) * 2014-08-20 2018-10-30 日本瑞翁株式会社 交联性腈橡胶组合物和橡胶交联物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0967471A (ja) * 1995-08-31 1997-03-11 Mitsubishi Cable Ind Ltd シール材用組成物およびシール材
JP2006001970A (ja) * 2004-06-15 2006-01-05 Yokohama Rubber Co Ltd:The 自動車部品用熱可塑性樹脂組成物
WO2014024698A1 (fr) * 2012-08-09 2014-02-13 Nok株式会社 Composition de caoutchouc nbr
WO2016035892A1 (fr) * 2014-09-05 2016-03-10 日本ゼオン株式会社 Composition de caoutchouc nitrile fortement saturé et matériau de caoutchouc réticulé
WO2016190214A1 (fr) * 2015-05-26 2016-12-01 日本ゼオン株式会社 Caoutchouc à base d'un copolymère fortement saturé, contenant un groupe nitrile
WO2017022598A1 (fr) * 2015-08-05 2017-02-09 日本ゼオン株式会社 Caoutchouc de copolymère hautement saturé contenant un groupe nitrile, composition de caoutchouc réticulable et caoutchouc réticulé
WO2017047571A1 (fr) * 2015-09-17 2017-03-23 日本ゼオン株式会社 Composition de caoutchouc de nitrile, composition de caoutchouc de nitrile réticulable et caoutchouc réticulé
WO2017086358A1 (fr) * 2015-11-20 2017-05-26 日本ゼオン株式会社 Matériau de caoutchouc réticulé
WO2017159623A1 (fr) * 2016-03-18 2017-09-21 日本ゼオン株式会社 Composition de caoutchouc nitrile et produit réticulé de caoutchouc

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026055300A1 (fr) * 2024-09-06 2026-03-12 Green, Tweed Technologies, Inc. Articles comprenant des compositions élastomères non pfas et leurs procédés de préparation

Also Published As

Publication number Publication date
JPWO2019078068A1 (ja) 2020-01-16
JP6843265B2 (ja) 2021-03-17
JP2021042388A (ja) 2021-03-18
CN110536923A (zh) 2019-12-03
JP7016938B2 (ja) 2022-02-07
CN110536923B (zh) 2021-09-14

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