JP3724989B2 - Carbon black for rubber compounding functional parts and rubber composition thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、自動車内装用のドアパッキング材や窓枠シール材などをはじめ、ベルト、ホースなどの機能部品用ゴムに配合するカーボンブラック、及びこのカーボンブラックを配合した機能部品用ゴム組成物に関する。
【０００２】
【従来の技術】
ゴム補強用のカーボンブラックには具備特性に応じた多様の品種があり、これらの品種特性がゴムに配合した組成物の諸特性を決定付けるための主要な因子となることから、通常ゴムへの配合に当たっては部材用途に適合する品種特性のカーボンブラックを選定使用する手段が慣用されている。例えば、機能部品用ゴムに配合するカーボンブラックとしては、従来からＳＲＦやＧＰＦなどの粒子径の大きいソフト系のカーボンブラックが有用されている。
【０００３】
自動車内装用のドアパッキング材や窓枠シール材などの機能部品用ゴム部材には、長期間、安定に使用することが要求されるため、耐へたり性や耐疲労性が高く、耐久性に優れていることが必要である。そのため、これらの機能部品用ゴム部材の耐へたり性や耐疲労性を配合するカーボンブラックのコロイダル特性により改善する研究も盛んに行われている。
【０００４】
例えば、本出願人は、凝集体の遠心沈降法（ＤＣＦ法）により測定されるモード径（Ｄst）が１５０nm以上、前記モード径（Ｄst）とその半値幅（ΔＤst）の比（ΔＤst／Ｄst）が１．５０以上、着色力（Ｔ）とブラックネス（Ｂ）との比（Ｂ／Ｔ）が１．２０以上の特性を備える機能部品ゴム配合用カーボンブラック（特開平３−14848 号公報）、あるいは、窒素吸着比表面積（Ｎ2 ＳＡ）が４５〜６５m2/g、ＤＢＰ吸油量（Ｄ0)と圧縮ＤＢＰ吸油量（Ｄ1)の比（Ｄ0 ／Ｄ1)が１．１０〜１．２０の範囲にあり、かつ前記ＤＢＰ吸油量（Ｄ0)が６０〜８０ml/100g の特性要件を満たすことを特徴とする機能部品ゴム配合用カーボンブラック（特開平８−143784号公報）などを開発、提案している。
【０００５】
しかしながら、近年、生産性向上のために高周波（ＵＨＦ；Ultra High Freq-uency ）加硫（以下、「ＵＨＦ加硫」ともいう）が採用されてきており、へたり性が小さいばかりでなく、ＵＨＦ加硫時間の短縮化、すなわち、高周波誘導電流による発熱性に優れていることが必要となってきている。高周波による発熱効果はカーボンブラックの粒子径を小さくすることにより上昇するが、耐へたり性が低下するため、耐へたり性とＵＨＦ加硫時における高発熱性とを両立させることは困難である。
【０００６】
そのため、ＵＨＦ加硫における加硫時間の遅延を改善する目的で特開平６−１４５５５４号公報には、ＤＢＰ吸油量（ＤＢＰＡ）が１１０〜１４０ml/100g 、よう素吸着量（ＩＡ）が２５mg/gを超え３５mg/g未満という基本特性を有するカーボンブラックにおいて、窒素吸着比表面積（Ｎ2 ＳＡ）とＩＡとの比、Ｎ2 ＳＡ／ＩＡが０．８５〜１．００であり、遠心沈降分析によるストークス相当径の最多頻度値（Ｄst）が▲１▼式より大きく、かつ着色力が▲２▼式より小さいことを特徴とするカーボンブラックが提案されている。
▲１▼ Ｄst≧（ＤＢＰＡ）−７．５（ＩＡ）＋４０５
▲２▼ 着色力≦ＩＡ＋２０
【０００７】
【発明が解決しようとする課題】
本発明者らは、上記の特開平６−１４５５５４号公報とは異なる観点から、耐へたり性が高く、ＵＨＦ加硫における発熱効果に優れたカーボンブラックの開発について研究を進め、カーボンブラックの比表面積及び表面性状が大きく影響することを見出した。
【０００８】
本発明は、この知見により開発されたものであって、その目的は機能部品用のゴム部材として、配合ゴムに高位の耐へたり性を付与するとともにＵＨＦ加硫時における発熱性が高く、両特性を高位で両立化し得るカーボンブラック、及びこのカーボンブラックを配合した機能部品用ゴム組成物を提供することにある。
【０００９】
【課題を解決するための手段】
上記の目的を達成するための本発明による機能部品ゴム配合用カーボンブラックは、ＣＴＡＢ比表面積が２０〜４０m2/g、５０kg/cm2の圧力で圧縮した時の電気比抵抗が０．３Ω・cm以下、トルエン着色透過度（ＬＴ）が９５％以上の特性を有することを構成上の特徴とする。
【００１０】
また、本発明の機能部品用ゴム組成物は、天然ゴム、合成ゴム、またはこれらのブレンドゴム１００重量部に、前記の特性を有するカーボンブラックを２０〜２００重量部配合してなることを構成上に特徴とする。
【００１１】
【発明の実施の形態】
本発明のカーボンブラックの特性要件のうち、ＣＴＡＢ比表面積は配合ゴムのへたり性を高位に保持するための粒子径範囲の前提的要件となる特性要素であって、この値が４０m2/gを超えるとへたり性の劣化が著しくなる。一方、２０m2/gを下回る場合には表面性状を改質してもＵＨＦ加硫時の発熱性が低下して、加硫時間の短縮化を図ることが困難となる。
【００１２】
電気比抵抗は、カーボンブラック自体の導電性を示す指標であり、ＵＨＦ加硫時の発熱性、すなわち誘導電流による抵抗発熱特性に関与する特性であって、電気比抵抗が高くなると発熱性が低くなりＵＨＦ加硫時間の短縮化を図ることができなくなる。そこで、本発明は電気比抵抗として、５０kg/cm2の圧力で圧縮した時の電気比抵抗の値を０．３Ω・cm以下に設定することにより、ＵＨＦ加硫時の発熱性能の向上を図るものである。
【００１３】
トルエン着色透過度（ＬＴ）はカーボンブラック粒子表面に残留する未分解炭化水素量の程度を示すもので、残留する未分解炭化水素量が少ない程トルエン着色透過度（ＬＴ）の値は大きくなる。残留する未分解炭化水素はカーボンブラックの導電性を阻害する物質であり、本発明は導電性を阻害するこの未分解炭化水素量を規制するためにトルエン着色透過度（ＬＴ）の値を９５％以上と設定するものである。その結果、未加硫ゴム組成物の抵抗発熱性が高くなり、ＵＨＦ加硫時における発熱性能の向上、すなわち加硫時間の短縮化が図られる。
【００１４】
このように、本発明の機能部品ゴム配合用カーボンブラックは、ＣＴＡＢ比表面積、電気比抵抗、及びトルエン着色透過度（ＬＴ）を特定することにより、これらの特性が総合的に機能して、配合ゴムに高度の耐へたり性を付与することができるとともに未加硫ゴム組成物の導電性を高く保持して導電発熱性の向上を図り、ＵＨＦ加硫の時間短縮化に有効機能する。
【００１５】
上記の構成におけるカーボンブラックの各特性は、以下の測定方法によって得られる値が用いられる。
▲１▼ＣＴＡＢ比表面積（m2/g）；
ＡＳＴＭ Ｄ3765−80“Standard Test Methods for Carbon Black−CTAB(CETYL TRIMETHYL AMMONIUM BROMIDE)Surface Area”による。
▲２▼電気比抵抗（Ω・cm）；
ＪＩＳ Ｋ1469−84「アセチレンブラック」 5.6項による。
▲３▼トルエン着色透過度（％）；
ＪＩＳ Ｋ6221−82「ゴム用カーボンブラックの試験方法」 6.2.4項による。
【００１６】
本発明のカーボンブラックは、緩除に収斂、開口する鼓状絞り部をもつ広径の円筒型反応炉を用い、燃料油と空気または酸素を含む適宜な酸化剤とによる高温燃焼ガス中に原料油の霧化気流を二段に導入することにより製造される。
【００１７】
原料油にはクレオソート油、ＦＣＣ油、エチレンボトム油などの高芳香族系重質油が使用され、高温燃焼ガスとの良好な均質混合状態を得るために霧化噴射ノズルを介して充分な微粒子気流として導入する。霧化噴射ノズルは、例えば水冷外套を有し、炉軸方向に伸縮可能な外筒ノズルと、これに装着された伸縮自在な中軸筒ノズルからなる二重筒構造のものが使用され、燃焼バーナとは別に炉頭部に装着される。原料油は霧化空気とともに外筒ノズル及び中軸筒ノズルを介して二段に分割導入されるが、この際の原料油導入位置は外筒ノズルの進退と中軸ノズルの伸縮によって変更することができる。本発明のカーボンブラックは、上記の装置を用い、供給する空気量及び燃料油量、原料油の分割導入点、カーボンブラック生成ガス流の炉内滞留時間などを制御することにより製造することができる。
【００１８】
本発明の機能部品用ゴム組成物は、上記の特性を有するカーボンブラックを、ゴム成分１００重量部に対して、２０〜２００重量部の割合で配合したものである。ゴム成分としては、天然ゴムやスチレンブタジエンゴム、ポリブタジエンゴム、イソプレンゴム、クロロプレンゴム、アクリロニトリル−ブタジエンゴム、エチレン−プロピレンゴム、その他カーボンブラックにより補強可能な常用の各種合成ゴム、あるいはそれらを混合したブレンドゴムなどが例示される。
【００１９】
ゴム組成物は、これらのゴム成分にカーボンブラック、及び、常法に従って加硫剤、加硫促進剤、加硫助剤、老化防止剤、軟化剤、可塑剤等の必要成分とともに配合し、混練、加硫処理して目的とする機能部品用ゴム組成物が得られる。
【００２０】
【実施例】
以下、本発明の実施例を比較例と対比して具体的に説明する。
【００２１】
実施例１〜３、比較例１〜５
(1)カーボンブラックの製造；
炉頭部に接線方向空気供給口を備えたウインドボックスと下流側出口が緩やかに収斂する燃焼室（内径 700mm、長さ1200mm）を設置し、該燃焼室と同軸的に連結する狭径部（内径 400mm、長さ 200mm）、及びこれに引き続き開拡するするテーパー状反応室（内径 900mm、長さ9000mm）とからなるオイルファーネス炉において、炉頭から炉中心軸に沿って二重筒構造の原料油霧化噴射ノズルを挿着し、その周辺に４本の燃焼バーナを設置した。原料油噴射ノズルは、上流側の原料油導入点（外筒ノズルの噴出口）が収斂部位に、下流側原料油導入点は狭径部位にそれぞれ位置するように調整した。
【００２２】
上記のオイルファーネス炉により、表１に示す性状の原料油及び燃料油を用いて、表２に示す発生条件を適用してカーボンブラックを製造した。得られたカーボンブラックの特性を測定して、その結果も表２に併載した。
【００２３】
【表１】
【表２】
(2)ゴム組成物の作製；
これらの各カーボンブラック試料を表３に示す配合割合でＥＰＤＭゴムに配合した。なお、カーボンブラックの配合量は、配合ゴムの硬度(JIS) が７０となるように変量とした。
【００２６】
【表３】
(3)ゴム物性の測定；
配合物を１５０℃の温度で３０分間加硫して、得られた各ゴム組成物についてＪＩＳ Ｋ6301「加硫ゴム物理試験方法」によりゴム物性を測定した。なお、ＵＨＦ加硫時の発熱性、及び圧縮永久歪みの測定は下記によった。
【００２８】
▲１▼ＵＨＦ加硫時の発熱性の評価
未加硫のゴム配合物を試験片として、横河・ヒューレット・パッカード（株）製、ＱＭＥＴＥＲ(4342 A)を用いて、周波数；２０MHz 、温度；室温、の条件で誘電率（ε）及び損失係数（Ｄ）を測定した。ＵＨＦ加硫時の発熱性は、誘電率（ε）×損失係数（Ｄ）の値を指標として評価することができ、この値が大きい程、ＵＨＦ加硫時の発熱性が高く、短時間でＵＨＦ加硫を行うことができる。
▲２▼圧縮永久歪み（％）の測定
ＪＩＳ Ｋ6301「加硫ゴム物理試験方法」に準じて、７０℃、７０時間の条件にて測定した。なお、この値が小さい程、耐へたり性が高いことを示す。
【００２９】
測定したゴム物性値、及び誘電率（ε）×損失係数（Ｄ）の算出値を表４に示した。また、測定結果のうち、耐へたり性（繰り返し応力を与えたときに生じる永久的な歪み現象に耐え得る抗力）の指標となる圧縮永久歪みと、ＵＨＦ加硫時の発熱特性の指標となる誘電率（ε）×損失係数（Ｄ）値との関係グラフを、図１に示した。
【００３０】
【表４】
表４及び図１から本発明の特性要件を全て充足するカーボンブラックを配合した実施例１〜３のゴム組成物は、本発明の特性要件の少なくとも１つが外れるカーボンブラックを配合した比較例１〜５のゴム組成物に比べて、耐へたり性の指標となる圧縮永久歪みに対して、ＵＨＦ加硫時の発熱特性の指標となる（誘電率ε×損失係数Ｄ）値が高く、耐へたり性とＵＨＦ加硫時の発熱性とが高位に両立化されていることが判る。
【００３２】
すなわち、比較例１は電気比抵抗が高いためＵＨＦ加硫時の発熱性が低く、比較例２ではトルエン着色透過度（ＬＴ）が低いために同様にＵＨＦ加硫時の発熱性が低くなっている。また、ＣＴＡＢ比表面積及びＬＴが低い比較例３も圧縮永久歪みに対する（誘電率ε×損失係数Ｄ）値が低く、ＵＨＦ加硫時の発熱性が劣ることが認められる。同様に比較例４、５でも一定圧縮永久歪み当たりの（誘電率ε×損失係数Ｄ）値が低く、耐へたり性とＵＨＦ加硫時の発熱性との両立化が不充分であることが判る。
【００３３】
【発明の効果】
以上のとおり、本発明の機能部品ゴム配合用カーボンブラック及びそのカーボンブラックを配合したゴム組成物によれば、配合ゴムに高位の耐へたり性が付与されるとともにＵＨＦ加硫時の発熱性能に優れ、両特性の両立化が可能となる。すなわち、機能部品用ゴム部材として耐へたり性に優れ、またＵＨＦ加硫時の発熱性が高いので加硫時間の短縮化が可能となり、生産性の向上を図ることができる。したがって、自動車内装用のドアパッキング材や窓枠シール材などをはじめとして、ベルト、ホースなどの機能部品用ゴムに配合するカーボンブラック、及び機能部品用ゴム組成物として極めて有用である。
【図面の簡単な説明】
【図１】実施例と比較例による圧縮永久歪みと、（誘電率ε×損失係数Ｄ）値との関係グラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a carbon black blended in a rubber for functional parts such as a belt and a hose, as well as a door packing material and a window frame sealing material for automobile interior, and a rubber composition for functional parts blended with the carbon black.
[0002]
[Prior art]
There are various varieties of carbon black for rubber reinforcement depending on the characteristics of the equipment, and these varieties are the main factors for determining the properties of the composition blended with rubber. In blending, a means of selecting and using carbon black having a variety characteristic suitable for the member application is commonly used. For example, soft carbon black having a large particle size, such as SRF and GPF, has been conventionally used as a carbon black to be blended with rubber for functional parts.
[0003]
Rubber parts for functional parts such as door packing materials and window frame seal materials for automobile interiors are required to be used stably for a long period of time, so they have high sag resistance and fatigue resistance and are durable. It must be excellent. For this reason, researches are being actively conducted to improve the colloidal characteristics of carbon black, which combines the sag resistance and fatigue resistance of these functional component rubber members.
[0004]
For example, the present applicant has a mode diameter (Dst) measured by a centrifugal sedimentation method (DCF method) of an aggregate of 150 nm or more, and a ratio (ΔDst / Dst) between the mode diameter (Dst) and its half-value width (ΔDst). Black for functional component rubber compounding having a characteristic of 1.50 or more and a ratio (B / T) of coloring power (T) to blackness (B) of 1.20 or more (Japanese Patent Laid-Open No. 3-14848) or a nitrogen adsorption specific surface area (N 2 SA) 45~65m 2 / g, DBP oil absorption amount (D 0) and the compression DBP absorption (D 1) the ratio of (D 0 / D 1) is 1.10 Carbon black for functional component rubber (JP-A-8-143784), etc., characterized in that it is in the range of 1.20 and the DBP oil absorption (D 0 ) satisfies the characteristic requirement of 60-80 ml / 100 g Developed and proposed.
[0005]
However, in recent years, in order to improve productivity, high frequency (UHF) vulcanization (hereinafter also referred to as “UHF vulcanization”) has been adopted. It has become necessary to shorten the vulcanization time, that is, to have excellent heat generation due to high-frequency induced current. The heat generation effect due to the high frequency is increased by reducing the particle size of the carbon black. However, since the sag resistance is reduced, it is difficult to achieve both sag resistance and high heat generation during UHF vulcanization. .
[0006]
Therefore, for the purpose of improving the delay of vulcanization time in UHF vulcanization, JP-A-6-145554 discloses that the DBP oil absorption (DBPA) is 110 to 140 ml / 100 g and the iodine adsorption (IA) is 25 mg / g. In carbon black having a basic characteristic of more than 35 mg / g and less than 35 mg / g, the ratio of nitrogen adsorption specific surface area (N 2 SA) to IA, N 2 SA / IA is 0.85 to 1.00. Carbon black has been proposed in which the most frequent value (Dst) of the Stokes equivalent diameter is larger than the formula (1) and the coloring power is smaller than the formula (2).
(1) Dst ≧ (DBPA) −7.5 (IA) +405
(2) Coloring power ≦ IA + 20
[0007]
[Problems to be solved by the invention]
The present inventors have advanced research on the development of carbon black having high sag resistance and excellent exothermic effect in UHF vulcanization from a viewpoint different from the above-mentioned JP-A-6-145554. It has been found that the surface area and surface properties have a great influence.
[0008]
The present invention has been developed based on this finding, and its purpose is to provide a high-level sag resistance to a compounded rubber as a rubber member for a functional component, and has high exothermicity during UHF vulcanization. An object of the present invention is to provide a carbon black capable of achieving high compatibility in properties and a rubber composition for functional parts containing the carbon black.
[0009]
[Means for Solving the Problems]
The carbon black for functional component rubber compounding according to the present invention for achieving the above object has a CTAB specific surface area of 20 to 40 m 2 / g and an electrical specific resistance of 0.3Ω · when compressed at a pressure of 50 kg / cm 2. It is a structural feature that it has a characteristic of cm or less and a toluene coloring transmittance (LT) of 95% or more.
[0010]
In addition, the rubber composition for functional parts of the present invention is constituted by blending 20 to 200 parts by weight of carbon black having the above characteristics with 100 parts by weight of natural rubber, synthetic rubber or blended rubber thereof. It is characterized by.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Among the characteristic requirements of the carbon black of the present invention, the CTAB specific surface area is a characteristic element which is a precondition for the particle diameter range for maintaining the sagability of the compounded rubber at a high level, and this value is 40 m 2 / g. If it exceeds, the deterioration of drooping property becomes significant. On the other hand, if it is less than 20 m 2 / g, even if the surface properties are modified, the exothermic property at the time of UHF vulcanization is lowered, and it becomes difficult to shorten the vulcanization time.
[0012]
The electrical resistivity is an index indicating the conductivity of the carbon black itself, and is a property related to the heat generation during UHF vulcanization, that is, the resistance heat generation due to the induced current, and the heat generation decreases as the electrical specific resistance increases. Therefore, the UHF vulcanization time cannot be shortened. Therefore, the present invention aims to improve the heat generation performance during UHF vulcanization by setting the value of the electrical specific resistance when compressed at a pressure of 50 kg / cm 2 to 0.3 Ω · cm or less as the electrical specific resistance. Is.
[0013]
The toluene color permeability (LT) indicates the degree of the amount of undecomposed hydrocarbons remaining on the surface of the carbon black particles, and the value of the toluene color permeability (LT) increases as the amount of the remaining undecomposed hydrocarbons decreases. The remaining undecomposed hydrocarbon is a substance that inhibits the conductivity of carbon black, and in the present invention, the value of toluene coloring transmittance (LT) is set to 95% in order to regulate the amount of undecomposed hydrocarbon that inhibits the conductivity. The above is set. As a result, the resistance exotherm of the unvulcanized rubber composition is increased, and the heat generation performance during UHF vulcanization is improved, that is, the vulcanization time is shortened.
[0014]
Thus, the carbon black for blending functional parts rubber of the present invention is characterized by the comprehensive functioning of these characteristics by specifying the CTAB specific surface area, electrical resistivity, and toluene color permeability (LT). The rubber can be imparted with a high degree of sag resistance, and the conductivity of the unvulcanized rubber composition is kept high to improve the conductive heat generation, which effectively functions to shorten the time of UHF vulcanization.
[0015]
Values obtained by the following measuring methods are used for the characteristics of the carbon black in the above configuration.
(1) CTAB specific surface area (m 2 / g);
According to ASTM D3765-80 “Standard Test Methods for Carbon Black-CTAB (CETYL TRIMETHYL AMMONIUM BROMIDE) Surface Area”.
(2) Electric resistivity (Ω · cm);
According to JIS K1469-84 “Acetylene Black”, paragraph 5.6.
(3) Toluene color permeability (%);
According to JIS K6221-82 “Testing method for carbon black for rubber” in Section 6.2.4.
[0016]
The carbon black of the present invention uses a wide-diameter cylindrical reactor having a drum-shaped throttle portion that converges and opens slowly, and is used as a raw material in a high-temperature combustion gas composed of fuel oil and an appropriate oxidizing agent containing air or oxygen. Manufactured by introducing an oil atomizing air stream in two stages.
[0017]
High-aromatic heavy oils such as creosote oil, FCC oil, and ethylene bottom oil are used as the feedstock oil, and sufficient to obtain a good homogeneous mixing state with the high-temperature combustion gas is sufficient through the atomization injection nozzle. Introduced as a fine particle stream. The atomizing spray nozzle has a water-cooled mantle, for example, and has a double cylinder structure comprising an outer cylinder nozzle that can be expanded and contracted in the furnace axis direction, and an expandable / retractable middle-axis cylinder nozzle that is attached to the nozzle. Separately attached to the furnace head. The feedstock oil is divided and introduced in two stages together with the atomized air through the outer cylinder nozzle and the middle shaft nozzle, but the feed oil introduction position at this time can be changed by the advancement / retraction of the outer cylinder nozzle and the expansion / contraction of the middle shaft nozzle . The carbon black of the present invention can be produced by controlling the amount of air and fuel oil to be supplied, the split introduction point of the raw material oil, the residence time in the furnace of the carbon black product gas flow, etc. .
[0018]
The rubber composition for functional parts of the present invention is obtained by blending carbon black having the above characteristics in a proportion of 20 to 200 parts by weight with respect to 100 parts by weight of the rubber component. Rubber components include natural rubber, styrene butadiene rubber, polybutadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, and other various synthetic rubbers that can be reinforced with carbon black, or a blend of these. Examples thereof include rubber.
[0019]
The rubber composition is compounded with these rubber components together with carbon black and necessary components such as a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, an anti-aging agent, a softening agent, and a plasticizer according to a conventional method. The desired rubber composition for functional parts is obtained by vulcanization treatment.
[0020]
【Example】
Examples of the present invention will be specifically described below in comparison with comparative examples.
[0021]
Examples 1-3, Comparative Examples 1-5
(1) Production of carbon black;
A wind box with a tangential air supply port at the furnace head and a combustion chamber (inner diameter 700mm, length 1200mm) where the downstream outlet converges gently, and a narrow-diameter part (coaxially connected to the combustion chamber) In an oil furnace having an inner diameter of 400 mm and a length of 200 mm, and a tapered reaction chamber (inner diameter of 900 mm and length of 9000 mm) that subsequently expands, a double cylinder structure is formed along the furnace center axis from the furnace head. A raw material oil atomization injection nozzle was inserted, and four combustion burners were installed around it. The feedstock injection nozzle was adjusted so that the upstream feedstock introduction point (outlet of the outer cylinder nozzle) was located at the convergent part and the downstream feedstock introduction point was located at the narrow diameter part.
[0022]
Carbon black was produced by the above-described oil furnace using the raw material oil and fuel oil having the properties shown in Table 1 and applying the generation conditions shown in Table 2. The characteristics of the obtained carbon black were measured, and the results are also shown in Table 2.
[0023]
[Table 1]
[Table 2]
(2) Production of rubber composition;
Each of these carbon black samples was blended with EPDM rubber at the blending ratio shown in Table 3. The blending amount of carbon black was varied so that the hardness (JIS) of the blended rubber was 70.
[0026]
[Table 3]
(3) Measurement of rubber properties;
The compound was vulcanized at a temperature of 150 ° C. for 30 minutes, and the rubber physical properties of each rubber composition obtained were measured according to JIS K6301 “Vulcanized Rubber Physical Test Method”. In addition, the exothermic property at the time of UHF vulcanization and the measurement of compression set were as follows.
[0028]
(1) Evaluation of exothermic property during UHF vulcanization Using an unvulcanized rubber compound as a test piece, QMETER (4342 A) manufactured by Yokogawa Hewlett-Packard Co., frequency: 20 MHz, temperature; The dielectric constant (ε) and the loss factor (D) were measured at room temperature. The exothermic property during UHF vulcanization can be evaluated using the value of dielectric constant (ε) × loss coefficient (D) as an index. The larger this value, the higher the exothermic property during UHF vulcanization, and in a short time. UHF vulcanization can be performed.
(2) Measurement of compression set (%) The measurement was carried out in accordance with JIS K6301 “Physical test method for vulcanized rubber” at 70 ° C. for 70 hours. In addition, it shows that sag-proof property is so high that this value is small.
[0029]
Table 4 shows the measured physical property values of rubber and calculated values of dielectric constant (ε) × loss coefficient (D). In addition, among the measurement results, compression permanent strain that is an index of sag resistance (drag that can withstand a permanent strain phenomenon that occurs when repeated stress is applied) and an index of heat generation characteristics during UHF vulcanization. A relationship graph between dielectric constant (ε) × loss coefficient (D) value is shown in FIG.
[0030]
[Table 4]
The rubber compositions of Examples 1 to 3 blended with carbon black satisfying all the characteristic requirements of the present invention from Table 4 and FIG. Compared to the rubber composition of No. 5, the compression set, which is an index of sag resistance, has a higher value (dielectric constant ε × loss coefficient D) which is an index of heat generation characteristics during UHF vulcanization and is resistant to heat. It can be seen that there is a high balance between the warmth and the exothermicity during UHF vulcanization.
[0032]
In other words, Comparative Example 1 has a high electrical specific resistance and thus low exothermicity during UHF vulcanization, and Comparative Example 2 has a low toluene coloring permeability (LT) and thus similarly exhibits low exothermicity during UHF vulcanization. Yes. Further, Comparative Example 3 having a low CTAB specific surface area and LT also has a low value of (dielectric constant ε × loss coefficient D) with respect to compression set, and it is recognized that heat generation during UHF vulcanization is inferior. Similarly, in Comparative Examples 4 and 5, the value of (dielectric constant ε × loss factor D) per fixed compression set is low, and it is insufficient to achieve both the sag resistance and the heat generation during UHF vulcanization. I understand.
[0033]
【The invention's effect】
As described above, according to the carbon black for blending functional parts rubber of the present invention and the rubber composition blended with the carbon black, a high level of sag resistance is imparted to the blended rubber, and heat generation performance during UHF vulcanization is achieved. It is excellent and both characteristics can be made compatible. That is, it is excellent in sag resistance as a rubber member for functional parts, and has high exothermic property during UHF vulcanization, so that the vulcanization time can be shortened and productivity can be improved. Therefore, it is extremely useful as a carbon black and a rubber composition for functional parts to be blended in rubbers for functional parts such as belts and hoses, including door packing materials and window frame sealing materials for automobile interiors.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between compression set and (dielectric constant ε × loss coefficient D) value according to an example and a comparative example.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22489999A JP3724989B2 (en) | 1999-08-09 | 1999-08-09 | Carbon black for rubber compounding functional parts and rubber composition thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22489999A JP3724989B2 (en) | 1999-08-09 | 1999-08-09 | Carbon black for rubber compounding functional parts and rubber composition thereof |
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| Publication Number | Publication Date |
|---|---|
| JP2001049028A JP2001049028A (en) | 2001-02-20 |
| JP3724989B2 true JP3724989B2 (en) | 2005-12-07 |
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| JP22489999A Expired - Fee Related JP3724989B2 (en) | 1999-08-09 | 1999-08-09 | Carbon black for rubber compounding functional parts and rubber composition thereof |
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| JP4947515B2 (en) * | 2006-10-20 | 2012-06-06 | 東海カーボン株式会社 | Carbon black for compounding functional rubber parts |
| EP4129713A4 (en) * | 2020-03-23 | 2023-09-13 | Bridgestone Corporation | Rubber composition and tire |
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