JP4573035B2 - Nitrile group-containing copolymer rubber composition and rubber vulcanizate - Google Patents
Nitrile group-containing copolymer rubber composition and rubber vulcanizate Download PDFInfo
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本発明はニトリル基含有共重合ゴム組成物に関し、さらに詳しくは、機械的強度、耐熱老化性および耐摩耗性に優れるゴム加硫物を与える、スコーチ安定性の高いニトリル基含有共重合ゴム組成物に関する。 TECHNICAL FIELD The present invention relates to a nitrile group-containing copolymer rubber composition, and more specifically, a nitrile group-containing copolymer rubber composition having high scorch stability, which gives a rubber vulcanizate excellent in mechanical strength, heat aging resistance and wear resistance. About.
アクリロニトリル−ブタジエンゴムなどの、α、β−エチレン性不飽和ニトリル−共役ジエン共重合体の炭素−炭素不飽和結合を水素化してなるニトリル基含有共重合体の加硫物は、耐油性の良さに加えて耐オゾン性及び耐熱老化性に顕著に優れるゴムとして、ガスケット、オイルシール、自動車用ホース、自動車用ベルトなどに使用されている。しかしながら、自動車用部品を始めとする多くの分野で、機械的強度、耐熱老化性、耐摩耗性など種々の特性の高度化が絶えず求められている。
特許文献１は、ヨウ素価８０以下のニトリル基含有共重合体にｐＨ８．５以上のシリカ系無機配合剤およびビニル系シランカップリング剤を配合してなるゴム組成物を加硫することにより耐熱性および耐油性が一層改善されることが記載されている。しかしながら、このゴム加硫物は、その後の更なる耐摩耗性向上の要求に応えられるものではなかった。特許文献２は、特定割合のアクリロニトリル、ブタジエンおよびイソプレンを共重合して得られるニトリル基含有共重合体の炭素−炭素二重結合の少なくとも８５％を有機溶媒中で特定量の金属等の存在下で水素化してなるニトリル基含有共重合ゴムを、また、特許文献３はブタジエン単位／イソプレン単位のモル比が３未満であるニトリル基含有共重合体を水素化してなるニトリル基含有共重合ゴムをそれぞれ提案した。これらの提案によるゴムの加硫物は特に低温での圧縮永久ひずみ特性や柔軟性は改善されるものの、機械的強度、耐熱老化性および耐摩耗性などの基本特性を総合的に引上げることは、依然として課題として残されている。また、成形、加硫工程以前の段階でゴム組成物の架橋が進行してしまうスコーチの問題も今なお改善が望まれている。
Patent Document 1 discloses heat resistance by vulcanizing a rubber composition obtained by blending a nitrile group-containing copolymer having an iodine value of 80 or less with a silica-based inorganic compounding agent having a pH of 8.5 or more and a vinyl-based silane coupling agent. And oil resistance is further improved. However, this rubber vulcanizate has not been able to meet the subsequent demand for further improvement in wear resistance. Patent Document 2 discloses that at least 85% of the carbon-carbon double bond of a nitrile group-containing copolymer obtained by copolymerizing a specific ratio of acrylonitrile, butadiene and isoprene in an organic solvent in the presence of a specific amount of metal or the like. A nitrile group-containing copolymer rubber obtained by hydrogenating a nitrile group-containing copolymer rubber, and Patent Document 3 discloses a nitrile group-containing copolymer rubber obtained by hydrogenating a nitrile group-containing copolymer having a butadiene unit / isoprene unit molar ratio of less than 3. Proposed each. Although these rubber vulcanizates have improved compression set characteristics and flexibility, especially at low temperatures, it is not possible to comprehensively improve basic characteristics such as mechanical strength, heat aging resistance and wear resistance. Still remains a challenge. Further, it is still desired to improve the problem of scorch where crosslinking of the rubber composition proceeds before the molding and vulcanization steps.
本発明の目的は、機械的強度、耐摩耗性および耐熱老化性に優れる加硫物を与えることのできる、スコーチ安定性の高いニトリル基含有共重合ゴム組成物を提供することにある。 An object of the present invention is to provide a nitrile group-containing copolymer rubber composition having high scorch stability and capable of providing a vulcanizate having excellent mechanical strength, wear resistance and heat aging resistance.
本発明者らは、上記課題を解決すべく鋭意研究した結果、特定割合のα、β−エチレン性不飽和ニトリル、イソプレンおよびブタジエンの共重合体を水素化して得られる、特定ヨウ素価を有するニトリル基含有共重合ゴムに、特定ｐＨのシリカ系無機配合物を配合することにより硫黄系加硫剤による加硫で上記目的にかなう加硫物が得られ、しかも加硫前のゴム組成物はスコーチ安定性が高いことを見出し、この知見に基づいて本発明を完成するに至った。
かくして本発明によれば、α、β−エチレン性不飽和ニトリル単位１０〜６０重量％、イソプレン単位５〜３５重量％およびブタジエン単位１０〜８０重量％からなるニトリル基含有共重合体の炭素−炭素不飽和結合を水素化してなるヨウ素価１５〜６５のニトリル基含有共重合ゴム１００重量部に対して、ｐＨ４．５〜８．５のシリカ系無機配合物１０〜１００重量部及び硫黄系加硫剤０．５〜２０重量部を含有してなるニトリル基含有共重合ゴム組成物、及び、該ゴム組成物を加硫してなるゴム加硫物が提供される。
As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a nitrile having a specific iodine value obtained by hydrogenating a copolymer of a specific proportion of α, β-ethylenically unsaturated nitrile, isoprene and butadiene. By adding a silica-based inorganic compound having a specific pH to the group-containing copolymer rubber, a vulcanized product satisfying the above-described purpose can be obtained by vulcanization with a sulfur-based vulcanizing agent. The inventors have found that the stability is high, and have completed the present invention based on this finding.
Thus, according to the present invention, the carbon-carbon of the nitrile group-containing copolymer comprising 10 to 60% by weight of α, β-ethylenically unsaturated nitrile unit, 5 to 35% by weight of isoprene unit and 10 to 80% by weight of butadiene unit. 10 to 100 parts by weight of a silica-based inorganic compound having a pH of 4.5 to 8.5 and sulfur-based vulcanization with respect to 100 parts by weight of a nitrile group-containing copolymer rubber having an iodine value of 15 to 65 obtained by hydrogenating unsaturated bonds There are provided a nitrile group-containing copolymer rubber composition containing 0.5 to 20 parts by weight of an agent, and a rubber vulcanizate obtained by vulcanizing the rubber composition.
本発明により、機械的強度、耐摩耗性および耐熱老化性に優れる加硫物を与えることのできる、スコーチ安定性の高いニトリル基含有共重合ゴム組成物が提供される。 According to the present invention, there is provided a nitrile group-containing copolymer rubber composition having high scorch stability and capable of giving a vulcanizate having excellent mechanical strength, abrasion resistance and heat aging resistance.
本発明のニトリル基含有共重合ゴム組成物は、α、β−エチレン性不飽和ニトリル単位１０〜６０重量％、イソプレン単位５〜３５重量％およびブタジエン単位１０〜８０重量％からなるニトリル基含有共重合体の炭素−炭素不飽和結合を水素化してなるヨウ素価１５〜６５のニトリル基含有共重合ゴム１００重量部に対して、ｐＨ４．５〜８．５のシリカ系無機配合物１０〜１００重量部及び硫黄系加硫剤０．５〜２０重量部を含有してなるものである。
The nitrile group-containing copolymer rubber composition of the present invention comprises a nitrile group-containing copolymer comprising 10 to 60% by weight of an α, β-ethylenically unsaturated nitrile unit, 5 to 35% by weight of an isoprene unit, and 10 to 80% by weight of a butadiene unit. 10 to 100 weight percent of silica-based inorganic compound having a pH of 4.5 to 8.5 with respect to 100 weight parts of nitrile group-containing copolymer rubber having an iodine value of 15 to 65 obtained by hydrogenating carbon-carbon unsaturated bonds of the polymer. Part and 0.5-20 weight part of sulfur-type vulcanizing agents.
本発明に用いるニトリル基含有共重合ゴムの水素化前のニトリル基含有共重合体（以下、「水素化前ニトリル基含有共重合体」と記すことがある。）は、α、β−エチレン性不飽和ニトリル単位１０〜６０重量％、好ましくは２０〜５０重量％、より好ましくは３０〜４５重量％と、イソプレン単位５〜３５重量％、好ましくは６〜２５重量％、より好ましくは８〜２０重量％と、ブタジエン単位１０〜８０重量％、好ましくは２０〜７０重量％、より好ましくは４０〜６０重量％を含有してなるゴムである。
The nitrile group-containing copolymer before hydrogenation of the nitrile group-containing copolymer rubber used in the present invention (hereinafter sometimes referred to as “pre-hydrogenated nitrile group-containing copolymer”) is α, β-ethylenic. 10-60% by weight of unsaturated nitrile units, preferably 20-50% by weight, more preferably 30-45% by weight, and 5-35% by weight of isoprene units, preferably 6-25% by weight, more preferably 8-20%. It is a rubber comprising 10% by weight and 10 to 80% by weight of butadiene units, preferably 20 to 70% by weight, and more preferably 40 to 60% by weight.
水素化前ニトリル基含有共重合体のα、β−エチレン性不飽和ニトリル単位の含有量が少なすぎると加硫物は耐油性が低下するおそれがあり、逆に多すぎると耐寒性に劣るおそれがある。また、イソプレンの含有量が少なすぎると加工性や耐熱性に劣るおそれがあり、逆に多すぎると機械的強度に劣る可能性がある。 If the content of the α, β-ethylenically unsaturated nitrile unit in the nitrile group-containing copolymer before hydrogenation is too small, the vulcanizate may be deteriorated in oil resistance, and conversely, if it is too much, the cold resistance may be inferior. There is. Moreover, when there is too little content of isoprene, there exists a possibility that it may be inferior to workability and heat resistance, and conversely, when there is too much, there exists a possibility that it may be inferior to mechanical strength.
上記α、β−エチレン性不飽和ニトリルとしては、ニトリル基を含有するα，β−エチレン性不飽和化合物であれば限定されず、例えば、アクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリルなどの炭素数３〜１０のニトリル基含有α，β−エチレン性不飽和化合物が挙げられ、なかでもアクリロニトリルが好ましい。
上記ブタジエンとしては、１，３−ブタジエンが好ましい。
The α, β-ethylenically unsaturated nitrile is not limited as long as it is an α, β-ethylenically unsaturated compound containing a nitrile group. For example, the number of carbon atoms such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc. Examples thereof include 3 to 10 nitrile group-containing α, β-ethylenically unsaturated compounds, among which acrylonitrile is preferable.
As the butadiene, 1, 3-butadiene is preferable.
水素化前ニトリル基含有共重合体は、さらに、α、β−エチレン性不飽和ニトリル、イソプレンおよびブタジエンと共重合可能なその他の単量体を、全単量体単位に占める単量体含有量で、通常、２０重量％以下、好ましくは１０重量％以下、より好ましくは５重量％以下含有してもよい。このようなその他の単量体としては、非共役ジエン、α−オレフィン、芳香族ビニル、フッ素含有ビニル、α、β−エチレン性不飽和モノカルボン酸及びそのエステル、α、β−エチレン性不飽和多価カルボン酸並びにそのモノエステル、多価エステル及びその無水物、架橋性単量体、共重合性老化防止剤などが挙げられる。
The pre-hydrogenated nitrile group-containing copolymer is further composed of a monomer content that accounts for α, β-ethylenically unsaturated nitrile, isoprene and other monomers copolymerizable with butadiene in the total monomer units. In general, it may be contained in an amount of 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less. Such other monomers include non-conjugated dienes, α-olefins, aromatic vinyls, fluorine-containing vinyls, α, β-ethylenically unsaturated monocarboxylic acids and esters, α, β-ethylenically unsaturated Examples thereof include polyvalent carboxylic acids and monoesters thereof, polyvalent esters and anhydrides thereof, crosslinkable monomers, and copolymerizable anti-aging agents.
非共役ジエンは、炭素数が５〜１２のものが好ましく、１，４−ペンタジエン、１，４−ヘキサジエン、ビニルノルボルネン、ジシクロペンタジエンなどが例示される。α−オレフィンは、炭素数が２〜１２のものが好ましく、エチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテンなどが例示される。芳香族ビニルとしては、例えば、スチレン、α−メチルスチレン、ビニルピリジンなどが挙げられる。フッ素含有ビニルとしては、例えば、フルオロエチルビニルエーテル、フルオロプロピルビニルエーテル、ｏ−トリフルオロメチルスチレン、ペンタフルオロ安息香酸ビニル、ジフルオロエチレン、テトラフルオロエチレンなどが挙げられる。 Non-conjugated dienes having 5 to 12 carbon atoms are preferred, and examples include 1,4-pentadiene, 1,4-hexadiene, vinylnorbornene, and dicyclopentadiene. The α-olefin preferably has 2 to 12 carbon atoms, and examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Examples of the aromatic vinyl include styrene, α-methylstyrene, vinyl pyridine and the like. Examples of the fluorine-containing vinyl include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
α、β−エチレン性不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、ケイ皮酸などが挙げられる。α，β−エチレン性不飽和モノカルボン酸エステルとしては、例えば、（メタ）アクリル酸エチル（アクリル酸エチル及びメタクリル酸エチルの意。以下同様。）、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシルなどが挙げられる。α、β−エチレン性不飽和多価カルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸などが挙げられる。α，β−エチレン性不飽和多価カルボン酸モノエステルとしては、例えば、マレイン酸モノメチル、マレイン酸モノエチル、イタコン酸モノエチルなどが挙げられる。α，β−エチレン性不飽和多価カルボン酸多価エステルとしては、例えば、マレイン酸ジメチル、フマル酸ジｎ−ブチル、イタコン酸ジメチル、イタコン酸ジ２−エチルヘキシルなどが挙げられる。α、β−エチレン性不飽和多価カルボン酸無水物としては、例えば、無水マレイン酸、無水イタコン酸などが挙げられる。 Examples of the α, β-ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid. Examples of the α, β-ethylenically unsaturated monocarboxylic acid ester include ethyl (meth) acrylate (meaning ethyl acrylate and ethyl methacrylate; the same applies hereinafter), butyl (meth) acrylate, and (meth) acrylic. Acid 2-ethylhexyl etc. are mentioned. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid include maleic acid, fumaric acid, itaconic acid and the like. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid monoester include monomethyl maleate, monoethyl maleate, monoethyl itaconate and the like. Examples of the α, β-ethylenically unsaturated polycarboxylic acid polyvalent ester include dimethyl maleate, di-n-butyl fumarate, dimethyl itaconate, di-2-ethylhexyl itaconate, and the like. Examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid anhydride include maleic anhydride and itaconic anhydride.
架橋性単量体としては、ジビニルベンゼンなどのジビニル化合物；エチレンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレートなどのジ（メタ）アクリル酸エステル類；トリメチロールプロパントリ（メタ）アクリレートなどのトリメタクリル酸エステル類；などの多官能エチレン性不飽和単量体のほか、Ｎ−メチロール（メタ）アクリルアミド、Ｎ，Ｎ′−ジメチロール（メタ）アクリルアミドなどの自己架橋性単量体などが挙げられる。 Examples of the crosslinking monomer include divinyl compounds such as divinylbenzene; di (meth) acrylates such as ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, and ethylene glycol di (meth) acrylate; trimethylolpropane tri In addition to polyfunctional ethylenically unsaturated monomers such as trimethacrylates such as (meth) acrylates; self-crosslinkable monomers such as N-methylol (meth) acrylamide and N, N'-dimethylol (meth) acrylamide Examples include masses.
共重合性老化防止剤としては、例えば、Ｎ−（４−アニリノフェニル）アクリルアミド、Ｎ−（４−アニリノフェニル）メタクリルアミド、Ｎ−（４−アニリノフェニル）シンナムアミド、Ｎ−（４−アニリノフェニル）クロトンアミド、Ｎ−フェニル−４−（３−ビニルベンジルオキシ）アニリン、Ｎ−フェニル−４−（４−ビニルベンジルオキシ）アニリンなどが挙げられる。 Examples of the copolymerizable anti-aging agent include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4- Anilinophenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
α、β−エチレン性不飽和ニトリル、イソプレン、ブタジエン及び必要に応じて加えられその他の単量体を共重合する重合方法は、特に限定されず公知の乳化重合法や溶液重合法によればよいが、工業的生産性の観点から乳化重合法による製造が好ましい。
The polymerization method for copolymerizing α, β-ethylenically unsaturated nitrile, isoprene, butadiene and other monomers added as necessary is not particularly limited, and may be a known emulsion polymerization method or solution polymerization method. However, production by an emulsion polymerization method is preferred from the viewpoint of industrial productivity.
水素化前ニトリル基含有共重合体のムーニー粘度（ＭＬ１＋４、１００℃）は、好ましくは１０〜１００、より好ましくは１５〜８０、特に好ましくは２０〜６０である。この範囲を外れると、水素化して得られるニトリル基含有共重合ゴムのムーニー粘度が不適切になるおそれがある。水素化前ニトリル基含有共重合体のムーニー粘度は、重合反応温度、重合開始剤濃度などの条件を適宜選定することにより調整することができる。 The Mooney viscosity (ML 1 + 4 , 100 ° C.) of the nitrile group-containing copolymer before hydrogenation is preferably 10 to 100, more preferably 15 to 80, and particularly preferably 20 to 60. Outside this range, the Mooney viscosity of the nitrile group-containing copolymer rubber obtained by hydrogenation may become inappropriate. The Mooney viscosity of the nitrile group-containing copolymer before hydrogenation can be adjusted by appropriately selecting conditions such as polymerization reaction temperature and polymerization initiator concentration.
本発明に用いるニトリル基含有共重合ゴムは、上記の水素化前ニトリル基含有共重合体の炭素−炭素不飽和結合を水素化してなり、ヨウ素価が１５〜８５、好ましくは１８〜６０、より好ましくは２０〜３０のものである。ヨウ素価が低すぎると加硫物はゴム弾性に劣るおそれがあり、逆に、高すぎると加硫物の耐熱老化性や耐オゾン性が低下する可能性がある。水素化前ニトリル基含有共重合体の炭素−炭素不飽和結合の水素化率を上げまたは下げることにより、ヨウ素価を小さくまたは大きくすることができる。 The nitrile group-containing copolymer rubber used in the present invention is formed by hydrogenating the carbon-carbon unsaturated bond of the nitrile group-containing copolymer before hydrogenation, and has an iodine value of 15 to 85, preferably 18 to 60, and more. Preferably it is 20-30. If the iodine value is too low, the vulcanizate may be inferior in rubber elasticity. Conversely, if the iodine value is too high, the heat aging resistance and ozone resistance of the vulcanizate may be lowered. The iodine value can be decreased or increased by increasing or decreasing the hydrogenation rate of the carbon-carbon unsaturated bond of the nitrile group-containing copolymer before hydrogenation.
水素化前ニトリル基含有共重合体の水素化において、ニトリル基まで水素化すると架橋物の耐油性を低下させるので、炭素−炭素不飽和結合のみを選択的に水素化する必要がある。かかる選択的水素化を行う方法は特に限定されず、公知の方法を採用すればよい。 In the hydrogenation of a nitrile group-containing copolymer before hydrogenation, hydrogenation to a nitrile group reduces the oil resistance of the cross-linked product. Therefore, it is necessary to selectively hydrogenate only the carbon-carbon unsaturated bond. A method for performing such selective hydrogenation is not particularly limited, and a known method may be employed.
水素化前ニトリル基含有共重合体を水素化して得られるニトリル基含有共重合ゴムは、ムーニー粘度（ＭＬ１＋４、１００℃）が好ましくは５０〜１３０、より好ましくは６０〜１００、特に好ましくは６５〜９０である。ムーニー粘度が低すぎると加硫物の機械的強度が低下するおそれがあり、逆に、高すぎると加工性に劣る可能性がある。ニトリル基含有共重合ゴムのムーニー粘度は、選択する水素化前ニトリル基含有共重合体のムーニー粘度により調整する。 The nitrile group-containing copolymer rubber obtained by hydrogenating the nitrile group-containing copolymer before hydrogenation has a Mooney viscosity (ML 1 + 4 , 100 ° C.) of preferably 50 to 130, more preferably 60 to 100, and particularly preferably 65. ~ 90. If the Mooney viscosity is too low, the mechanical strength of the vulcanizate may be reduced. Conversely, if the Mooney viscosity is too high, the processability may be inferior. The Mooney viscosity of the nitrile group-containing copolymer rubber is adjusted by the Mooney viscosity of the pre-hydrogenated nitrile group-containing copolymer.
本発明に用いるシリカ系無機配合物としては、シリカおよび天然ケイ酸化合物が挙げられる。シリカとしては、湿式製法による湿式シリカ（含水ケイ酸）、乾式製法による乾式シリカ（無水ケイ酸）のいずれでもよい。
天然ケイ酸化合物としてはカオリンクレー、焼成クレー、パイロフィライトクレー、タルク、マイカなどが挙げられる。シリカ系無機配合物として、これらを１種単独で、または２種以上併せて使用することができる。
Examples of the silica-based inorganic compound used in the present invention include silica and natural silicate compounds. Silica may be either wet silica (hydrous silicic acid) produced by a wet production method or dry silica (anhydrous silicic acid) produced by a dry production method.
Examples of natural silicic acid compounds include kaolin clay, calcined clay, pyrophyllite clay, talc and mica. As a silica type inorganic compound, these can be used individually by 1 type or in combination of 2 or more types.
本発明に用いるシリカ系無機配合剤のｐＨは、４．５〜８．５、好ましくは５．０〜８．３、より好ましくは５．５〜８．０である。ｐＨがこの範囲を外れると加工安定性や耐摩耗性に劣る可能性がある。
なお、シリカ系配合剤のｐＨは、２０℃において該配合剤４ｇを１００ｍｌの蒸留水に懸濁させてガラス電極ｐＨ計で測定して求められる。
The pH of the silica-based inorganic compounding agent used in the present invention is 4.5 to 8.5, preferably 5.0 to 8.3, and more preferably 5.5 to 8.0. If the pH is out of this range, the processing stability and wear resistance may be inferior.
The pH of the silica-based compounding agent is obtained by suspending 4 g of the compounding agent in 100 ml of distilled water at 20 ° C. and measuring with a glass electrode pH meter.
シリカ系配合剤の粒子表面にあるシラノール基は親水性が大きいためシリカ系配合剤のゴムとの親和性を阻害したり、水分を吸着してゴム組成物のスコーチを早めたり、加硫促進剤を吸着してその作用を損ねたりするので、予め熱処理してシロキサン基に変換したり、グリコール類（例えばジエチレングリコール）、アミン化合物（例えばトリエタノールアミン）、シランカップリング剤などを添加してこれらをシラノール基に対して水分に優先して吸着させたりする、などの処置をして親水性を低減させて使用することが好ましい。 Silanol group on the particle surface of silica compounding agent has high hydrophilicity, which inhibits the affinity of silica compounding compound with rubber, adsorbs moisture and accelerates scorching of rubber composition, vulcanization accelerator Adsorption of the water will impair its action, so that it can be converted into a siloxane group by heat treatment in advance, or by adding glycols (eg diethylene glycol), amine compounds (eg triethanolamine), silane coupling agents, etc. It is preferable to reduce the hydrophilicity by using a treatment such as preferentially adsorbing moisture to the silanol group.
本発明のニトリル基含有共重合ゴム組成物のシリカ系無機配合剤の含有量は、ニトリル基含有共重合ゴム１００重量部に対して１０〜１００重量部、好ましくは１５〜９０重量部、より好ましくは２０〜７０重量部である。シリカ系無機配合剤の含有量は、また、水素化前ニトリル基含有共重合体１００重量部におけるイソプレン単位の重量部の好ましくは１５倍以下、より好ましくは１２倍以下、特に好ましくは１０倍以下である。
シリカ系無機配合剤の含有量が少なすぎると耐熱性や耐摩耗性に劣るおそれがあり、逆に多すぎると加工性に劣る可能性がある。
The content of the silica-based inorganic compounding agent in the nitrile group-containing copolymer rubber composition of the present invention is 10 to 100 parts by weight, preferably 15 to 90 parts by weight, more preferably 100 parts by weight of the nitrile group-containing copolymer rubber. Is 20 to 70 parts by weight. The content of the silica-based inorganic compounding agent is preferably not more than 15 times, more preferably not more than 12 times, particularly preferably not more than 10 times the weight part of the isoprene unit in 100 parts by weight of the nitrile group-containing copolymer before hydrogenation. It is.
If the content of the silica-based inorganic compounding agent is too small, the heat resistance and wear resistance may be inferior. On the other hand, if the content is too large, the processability may be inferior.
本発明に用いる硫黄系加硫剤としては、粉末硫黄、沈降硫黄などの硫黄；４，４’−ジチオモルホリン、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、高分子多硫化物など有機硫黄化合物；などが挙げられる。 Examples of the sulfur-based vulcanizing agent used in the present invention include sulfur such as powdered sulfur and precipitated sulfur; organic sulfur compounds such as 4,4′-dithiomorpholine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and polymer polysulfide; Can be mentioned.
本発明組成物の硫黄系加硫剤の含有量は、ニトリル基含有共重合ゴム１００重量部に対して、０．５〜２０重量部、好ましくは１〜１５重量部、より好ましくは１．５〜１０重量部である。加硫剤の含有量が少なすぎると加硫物は圧縮永久歪みが大きくなるおそれがあり、逆に、多すぎるとゴム弾性に劣る可能性がある。 The content of the sulfur-based vulcanizing agent in the composition of the present invention is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1.5 to 100 parts by weight of the nitrile group-containing copolymer rubber. -10 parts by weight. If the content of the vulcanizing agent is too small, the vulcanizate may have a large compression set. Conversely, if the content is too large, the rubber elasticity may be inferior.
本発明のニトリル基含有共重合ゴム組成物は、必要に応じて加硫促進剤、老化防止剤、補強剤（例えばカーボンブラック、アラミド繊維など）、充填剤（例えば炭酸カルシウム）、可塑剤、滑剤、粘着剤、潤滑剤、難燃剤、防黴剤、帯電防止剤、着色剤などの添加剤を含有することができる。 The nitrile group-containing copolymer rubber composition of the present invention includes a vulcanization accelerator, an anti-aging agent, a reinforcing agent (for example, carbon black, aramid fiber, etc.), a filler (for example, calcium carbonate), a plasticizer, and a lubricant as necessary. Further, additives such as an adhesive, a lubricant, a flame retardant, an antifungal agent, an antistatic agent and a colorant can be contained.
加硫促進剤としては、スルフェンアミド系加硫促進剤、グアニジン系加硫促進剤、チアゾール系加硫促進剤、チウラム系加硫促進剤、ジチオ酸塩系加硫促進剤などが挙げられる。加硫促進剤の使用量は特に限定されず、加硫物の用途、要求性能、硫黄加硫剤の種類、加硫促進剤の種類などに応じて決めればよい。 Examples of the vulcanization accelerator include a sulfenamide vulcanization accelerator, a guanidine vulcanization accelerator, a thiazole vulcanization accelerator, a thiuram vulcanization accelerator, and a dithioate vulcanization accelerator. The amount of the vulcanization accelerator used is not particularly limited, and may be determined according to the use of the vulcanizate, the required performance, the type of sulfur vulcanizing agent, the type of vulcanizing accelerator, and the like.
本発明のニトリル基含有共重合ゴム組成物を調製する方法に限定はないが、通常、加硫剤および熱に不安定な一部の加硫促進剤を除いた成分を、バンバリーミキサ、インターミキサ、ニーダなどの混合機で一次混練した後、ロールなどに移して加硫剤等を加えて二次混練する。 The method for preparing the nitrile group-containing copolymer rubber composition of the present invention is not limited, but usually the components excluding the vulcanizing agent and a part of the vulcanization accelerator which is unstable to heat are used as a Banbury mixer and an intermixer. Then, after primary kneading with a mixer such as a kneader, the mixture is transferred to a roll or the like, and a vulcanizing agent or the like is added to perform secondary kneading.
調製されたニトリル基含有共重合ゴム組成物を用いてゴム加硫物を得るには、所望の形状に対応した成形機、例えば押出機、射出成形機、圧縮機、ロールなどにより成形を行い、形状を固定化するために加硫物とする。予め成形した後に加硫しても、成形と加硫を同時に行ってもよい。成形温度は、通常、１０〜２００℃、好ましくは２５〜１２０℃である。加硫温度は、通常、１００〜２００℃、好ましくは１３０〜１９０℃であり、加硫時間は、通常、１分〜１２時間、好ましくは２分〜５時間である。 In order to obtain a rubber vulcanizate using the prepared nitrile group-containing copolymer rubber composition, molding is performed with a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc. A vulcanized product is used to fix the shape. It may be vulcanized after being molded in advance, or molding and vulcanization may be performed simultaneously. The molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C. The vulcanization temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C., and the vulcanization time is usually 1 minute to 12 hours, preferably 2 minutes to 5 hours.
また、ゴム加硫物の形状、大きさなどによっては、表面が加硫していても、内部まで十分に加硫していない場合があるので、さらに加熱して二次加硫を行ってもよい。 Also, depending on the shape and size of the rubber vulcanizate, the surface may be vulcanized, or it may not be sufficiently vulcanized to the inside. Good.
本発明のニトリル基含有共重合ゴム組成物はスコーチ安定性が高く、また、これを加硫して得られる本発明のゴム加硫物は、機械的強度、耐摩耗性および耐熱老化性それぞれがバランスよく向上している。
本発明のゴム加硫物の用途としては、ホース、ベルト、シール及びロールなどの工業部品の材料として好適に用いられる。具体的には、燃料ホース、歯付きベルト、パッキン、オイルシール、ＯＡロール、自動車内装部材、燃料系のシール、ガスケットなどの材料として好適である。
The nitrile group-containing copolymer rubber composition of the present invention has high scorch stability, and the rubber vulcanizate of the present invention obtained by vulcanizing this has mechanical strength, abrasion resistance and heat aging resistance. The balance is improving.
The rubber vulcanizate of the present invention is suitably used as a material for industrial parts such as hoses, belts, seals and rolls. Specifically, it is suitable as a material for fuel hoses, toothed belts, packing, oil seals, OA rolls, automobile interior members, fuel seals, gaskets, and the like.
以下に実施例、比較例を挙げて、本発明を具体的に説明する。ただし本発明は、これらの実施例に限定されるものではない。以下の配合において、〔部〕及び〔％〕は、特に断わりのない限り重量基準である。
試験、評価は下記によった。
The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the following formulations, [parts] and [%] are based on weight unless otherwise specified.
The test and evaluation were as follows.
（１）共重合組成
水素化前ニトリル基含有共重合体を重水素クロロホルムに溶解し、ＮＭＲ分析により共重合組成を算出した。
（２）ヨウ素価
ヨウ素価は、ＪＩＳ K ６２３５に準じて測定した。
（３）ムーニー粘度
ムーニー粘度（ＭＬ1+4、１００℃）は、ＪＩＳ Ｋ ６３００に準じて測定した。
（４）ムーニースコーチ時間（ｔ５）
ニトリル基含有共重合ゴム組成物のムーニースコーチ時間（ｔ５）は、ＪＩＳ
Ｋ６３００に従って１２５℃でＬロータを用いて測定した。ムーニースコーチ時間ｔ５の値が大きいほどスコーチが遅く、スコーチ安定性に優れる。
(1) Copolymer composition The nitrile group-containing copolymer before hydrogenation was dissolved in deuterium chloroform, and the copolymer composition was calculated by NMR analysis.
(2) Iodine value The iodine value was measured according to JIS K 6235.
(3) Mooney viscosity Mooney viscosity (ML 1 + 4 , 100 ° C.) was measured according to JIS K 6300.
(4) Mooney scorch time (t5)
The Mooney scorch time (t5) of the nitrile group-containing copolymer rubber composition is JIS
Measured using an L rotor at 125 ° C. according to K6300. The larger the Mooney scorch time t5, the slower the scorch and the better the scorch stability.
（５）常態物性（引張強さ、伸び）
ニトリル基含有共重合ゴム組成物を縦１５ｃｍ、横１５ｃｍ、厚さ０．２ｃｍの金型に入れ、加圧しながら、１６０℃で２０分間プレス成形した後、１５０℃２時間２次処理をおこないシート状加硫物を得た。得られたシート状加硫物を３号形ダンベルで打ち抜いて試験片を作製した。これらの試験片を用いて、ＪＩＳ
Ｋ ６２５１に従い、加硫物の引張強さおよび伸びを測定した。
(5) Normal properties (tensile strength, elongation)
A nitrile group-containing copolymer rubber composition is placed in a 15 cm long, 15 cm wide, 0.2 cm thick mold, press-molded at 160 ° C. for 20 minutes under pressure, and then subjected to a secondary treatment at 150 ° C. for 2 hours. A vulcanizate was obtained. The obtained sheet-like vulcanizate was punched with a No. 3 type dumbbell to prepare a test piece. Using these specimens, JIS
The tensile strength and elongation of the vulcanizate were measured according to K6251.
（６）常態物性（硬さ）
上記（５）と同様にして得たシート状加硫物につき、ＪＩＳ Ｋ ６２５３に従い、デュロメータ硬さ試験機タイプＡを用いて加硫物の硬さを測定した。
（７）耐熱老化性（空気加熱老化試験）
上記（５）と同様にして作製した試験片４枚／試料をＪＩＳ Ｋ ６２５７のノーマルオーブン法に従って１５０℃に７２時間置いてから取り出して（５）と同様にして引張強さおよび伸びを測定し、それらの上記（５）の常態物性からの変化率を求めた。絶対値が小さい方が大きいものより耐熱老化性が良いことを示す。
(6) Normal physical properties (hardness)
About the sheet-like vulcanizate obtained in the same manner as in the above (5), the hardness of the vulcanizate was measured using a durometer hardness tester type A according to JIS K 6253.
(7) Heat aging resistance (air heat aging test)
Four test pieces / sample prepared in the same manner as in (5) above were taken out after being placed at 150 ° C. for 72 hours in accordance with the normal oven method of JIS K 6257, and the tensile strength and elongation were measured in the same manner as in (5). The change rate from the normal physical properties of the above (5) was determined. A smaller absolute value indicates better heat aging resistance than a larger absolute value.
（８）耐摩耗性（アクロン耐摩耗性試験）
ＪＩＳ Ｋ６２６４のアクロン摩耗試験法に従って、リング状試験片の摩耗量を求めた。
摩耗減量が少ない方が耐摩耗性に優れる。
(8) Abrasion resistance (Akron abrasion resistance test)
The amount of wear of the ring-shaped test piece was determined according to the Akron abrasion test method of JIS K6264.
Less wear loss results in better wear resistance.
実施例および比較例の実験に用いた各種重合体（水素化前ニトリル基含有共重合体）の組成、水素化後のニトリル基含有共重合体のヨウ素価およびムーニー粘度を表１に示す。 Table 1 shows the compositions of various polymers (nitrile group-containing copolymers before hydrogenation) used in the experiments of Examples and Comparative Examples, the iodine value and Mooney viscosity of the nitrile group-containing copolymers after hydrogenation.
（製造例１〜４）
通常の乳化重合により共重合割合の異なる４種のアクリロニトリル−ブタジエン−イソプレン共重合ゴムを作製した。これらのゴムの単量体単位の含有量を表１に示す。これらを別々にメチルイソブチルケトンに溶解し、パラジウム／シリカ触媒を用いて耐圧容器内で各ゴム中のブタジエン単位部分を部分水素化し、４種の水素化ニトリル基含有共重合ゴムを得た。（以下、ＨＮＢＩＲ１、同２、同３、同４と記すことがある。）
なお、ＨＮＢＲ（表１において＊１を付記）は、水素化ニトリルブタジエンゴム（製品名Ｚｅｔｐｏｌ ２０２０、日本ゼオン社製；アクリロニトリル単位３６％、ヨウ素価２８、ムーニー粘度７８）である。
(Production Examples 1-4)
Four types of acrylonitrile-butadiene-isoprene copolymer rubbers having different copolymerization ratios were prepared by ordinary emulsion polymerization. Table 1 shows the content of monomer units of these rubbers. These were separately dissolved in methyl isobutyl ketone, and a butadiene unit portion in each rubber was partially hydrogenated in a pressure vessel using a palladium / silica catalyst to obtain four types of hydrogenated nitrile group-containing copolymer rubbers. (Hereafter, it may be written as HNBIR1, 2, 3, and 4.)
HNBR (added * 1 in Table 1) is a hydrogenated nitrile butadiene rubber (product name Zetpol 2020, manufactured by Nippon Zeon Co., Ltd .; acrylonitrile unit 36%, iodine value 28, Mooney viscosity 78).
実施例１
１００部のニトリル基含有共重合ゴム１（ＨＮＢＩＲ１）、湿式シリカ（ニプシルＶＮ３、日本シリカ工業社製、ｐＨ５．５〜６．５）４０部、酸化亜鉛５部、ステアリン酸０．５部、老化防止剤の２−メルカプトベンズイミダゾール亜鉛（ノクラックＭＢＺ，大内新興化学工業社製）１部およびアミン系老化防止剤（ナウガード４４５、ユニロイヤル社製）１部、活性剤のジエチレングリコール１部、並びに、シランカップリング剤のγ−メルカプトプロピルトリメトキシシラン１部をバンバリーミキサにて５０℃で混合した後、オープンロールに移して、硫黄０．５部、並びに、加硫促進剤のテトラメチルチウラムジスルフィド（ノクセラーＴＴ、大内新興社製）１．５部および２−メルカプトベンゾチアゾール（ノクセラーＭ、大内新興社製）０．５部を加えて５０℃にて１０分間混練してニトリル基含有共重合ゴム組成物を得た。該組成物について行ったムーニースコーチ；並びに；該組成物の加硫物について行った常態物性、耐熱老化性および耐摩耗性の試験の結果を表２に記す。
Example 1
100 parts of nitrile group-containing copolymer rubber 1 (HNBIR1), 40 parts of wet silica (Nipsil VN3, manufactured by Nippon Silica Kogyo Co., Ltd., pH 5.5 to 6.5), 5 parts of zinc oxide, 0.5 part of stearic acid, aging 2-mercaptobenzimidazole zinc (NOCRACK MBZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as an inhibitor and 1 part of an amine-based anti-aging agent (Naugard 445, manufactured by Uniroyal), 1 part of diethylene glycol as an activator, and After mixing 1 part of γ-mercaptopropyltrimethoxysilane as a silane coupling agent at 50 ° C. with a Banbury mixer, it was transferred to an open roll, and 0.5 parts of sulfur and tetramethylthiuram disulfide as a vulcanization accelerator ( Noxeller TT, made by Ouchi Shinsei Co., Ltd.) 1.5 parts and 2-mercaptobenzothiazole (Noxeller M, Ouchi Shin Company, Ltd.) was added 0.5 parts were kneaded for 10 minutes at 50 ° C. to give a nitrile group-containing copolymer rubber composition. Table 2 shows the results of Mooney scorch performed on the composition; and tests of normal properties, heat aging resistance and abrasion resistance performed on the vulcanizates of the composition.
実施例２〜４、比較例１〜６
実施例１において、表２に示す成分および部数を用いた他は実施例１と同様に行ってニトリル基含有共重合ゴム組成物を得た。実施例１と同様の項目につき試験、評価した結果を表２に記す。
ただし、比較例６においては加硫剤として、硫黄０．５部に代えて１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン４０％品（バルカップ４０ＫＥ、ＧＥＯ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ Ｉｎｃ製、有機過酸化物）８部を用い、また、シランカップリング剤のγ−メルカプトプロピルトリメトキシシランに代えてγ−メタクリロキシプロピルトリメトキシシランを同部数使用した。
Examples 2-4, Comparative Examples 1-6
A nitrile group-containing copolymer rubber composition was obtained in the same manner as in Example 1 except that the components and parts shown in Table 2 were used. Table 2 shows the results of tests and evaluations on the same items as in Example 1.
However, in Comparative Example 6, as a vulcanizing agent, instead of 0.5 part of sulfur, 1,3-bis (t-butylperoxyisopropyl) benzene 40% product (Valcup 40KE, manufactured by GEO Specialty Chemicals Inc., organic peroxide) 8 parts were used, and the same number of γ-methacryloxypropyltrimethoxysilane was used instead of γ-mercaptopropyltrimethoxysilane as a silane coupling agent.
注
＊１：カープレックス＃６７は塩野義製薬社製の湿式シリカ。ｐＨ７〜８。
＊２：ハードトップクレーは白石カルシウム社製のカオリンクレー。ｐＨ６。
＊３：アエロジル２００は日本アエロジル社製の乾式シリカ。ｐＨ３．６〜４．３。
＊４：カープレックス＃１１２０は塩野義製薬社製の湿式シリカ。ｐＨ１０．４〜１０．９。
* 1: Carplex # 67 is wet silica manufactured by Shionogi & Co. pH 7-8.
* 2: Hard top clay is kaolin clay manufactured by Shiraishi Calcium. pH 6.
* 3: Aerosil 200 is dry silica manufactured by Nippon Aerosil Co., Ltd. pH 3.6-4.3.
* 4: Carplex # 1120 is a wet silica manufactured by Shionogi & Co. pH 10.4 to 10.9.
表２が示すように、本発明で規定するニトリル基含有共重合ゴムおよびシリカ系無機配合剤、および、硫黄をそれぞれ規定量用いてなるニトリル基含有共重合ゴム組成物は、ムーニースコーチ時間が長くてスコーチ安定性が高かった。また、該組成物の加硫物は、常態での引張強度および伸びが十分に大きく、空気加熱老化試験で物性低下が小さくて耐熱老化性に優れ、また、顕著な耐摩耗性を示した（実施例１〜４）。
一方、ｐＨが低すぎるシリカおよび高すぎるシリカをそれぞれ用いたニトリル基含有共重合ゴム組成物は、共にスコーチが早く、加硫物は耐摩耗性が劣るものだった（比較例１および２）。イソプレン単位の含有量が多すぎる水素化前ニトリル基含有共重合体を水素化して得たＨＮＢＩＲ３を用いたニトリル基含有共重合ゴム組成物は、常態での引っ張り強さが小さく、耐摩耗性に欠けるゴム加硫物を与えた（比較例３）。イソプレン単位を有さないアクリロニトリル−ブタジエン共重合体の水素化物を用いたニトリル基含有共重合ゴム組成物は、スコーチがやや早く、その加硫物は耐熱老化性の劣るものとなった（比較例４）。ヨウ素価が低すぎるＨＮＢＩＲ４を用いたニトリル基含有共重合ゴム組成物を加硫すると、常態での引っ張り強さが小さく、また、耐摩耗性に欠けた（比較例５）。加硫系を硫黄加硫から有機過酸化物系に変更すると、ゴム組成物のスコーチ安定性は極めて良好であるが、加硫物は常態での引張強さおよび伸びに劣り、耐摩耗性が大きく低下した（比較例６）。
As shown in Table 2, the nitrile group-containing copolymer rubber and the silica-based inorganic compounding agent specified in the present invention and the nitrile group-containing copolymer rubber composition using a specified amount of sulfur each have a long Mooney scorch time. Scorch stability was high. Further, the vulcanizate of the composition had sufficiently large tensile strength and elongation in the normal state, small deterioration in physical properties in the air heat aging test, excellent heat aging resistance, and remarkable wear resistance ( Examples 1-4).
On the other hand, both the nitrile group-containing copolymer rubber composition using silica having a pH too low and silica too high were both scorched quickly, and the vulcanizates were inferior in wear resistance (Comparative Examples 1 and 2). A nitrile group-containing copolymer rubber composition using HNBIR3 obtained by hydrogenating a pre-hydrogenated nitrile group-containing copolymer having a too large content of isoprene units has a low tensile strength in the normal state and a high wear resistance. A missing rubber vulcanizate was provided (Comparative Example 3). The nitrile group-containing copolymer rubber composition using the hydride of acrylonitrile-butadiene copolymer having no isoprene unit has a slightly faster scorch, and the vulcanizate has poor heat aging resistance (Comparative Example). 4). When a nitrile group-containing copolymer rubber composition using HNBIR4 having an iodine value that was too low was vulcanized, the tensile strength in the normal state was small and the wear resistance was poor (Comparative Example 5). When the vulcanization system is changed from sulfur vulcanization to an organic peroxide system, the scorch stability of the rubber composition is very good, but the vulcanizate is inferior to the tensile strength and elongation in the normal state and wear resistance. It was greatly reduced (Comparative Example 6).
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