JP2012158699A - Soft furnace carbon black and rubber composition - Google Patents
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- 239000006229 carbon black Substances 0.000 title claims abstract description 68
- 229920001971 elastomer Polymers 0.000 title claims description 38
- 239000005060 rubber Substances 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 11
- 239000011630 iodine Substances 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 230000035699 permeability Effects 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000001000 micrograph Methods 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract 1
- 238000004627 transmission electron microscopy Methods 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 60
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001125 extrusion Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 9
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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Abstract
Description
本発明は、ソフト系ファーネスカーボンブラック及びこのカーボンブラックをゴム成分に配合したゴム組成物に関する。 The present invention relates to a soft furnace carbon black and a rubber composition containing this carbon black in a rubber component.
カーボンブラックは、その主たる用途であるゴムへの特性、即ち加工性と補強性により分類されており、主なソフト系カーボンブラックとしては、半袖強性ファーネスカーボンブラック（Ｓｅｍｉ Ｒｅｉｎｆｏｒｃｉｎｇ Ｆｕｒｎａｃｅ−ＳＲＦ）、汎用ファーネスカーボンブラック（Ｇｅｎｅｒａｌ Ｐｕｒｐｏｓｅ Ｆｕｒｎａｃｅ−ＧＰＦ）、良押出性ファーネスカーボンブラック（Ｆａｓｔ Ｅｘｔｒｕｄｉｎｇ Ｆｕｒｎａｃｅ−ＦＥＦ）などがある。
上記の「ソフト系」という名称表現は、ゴム配合時において軟らかいゴム組成物を与えることから生じたものであり、作業性が良い、発熱が少ない、多量配合ができるなどの特徴を有し、タイヤカーカス用、チューブ用、ベルト、シート材、ウェザ−ストリップなどのゴム部材の充填補強剤として広く利用されている。
ところで、カーボンブラックの基本的特性としては、ヨウ素吸着量や窒素吸着比表面積などで評価される比表面積及びカーボンブラック粒子のつながりによる高次構造（ストラクチャー）があることは周知である。しかしなから、カーボンブラックのゴムに対する付与特性の評価は、上記二つの特性だけでは不可能であることが広く認識されるようになってきており、これらの特性だけでゴム特性を制御することは困難である。
Carbon black is classified according to its main application properties to rubber, that is, processability and reinforcement, and the main soft carbon black is short sleeve strong furnace carbon black (Semi Reinforming Furnace-SRF), general purpose There are furnace carbon black (General Purpose Furnace-GPF), good extruding furnace carbon black (Fast Extruding Furnace-FEF), and the like.
The name expression “soft” is derived from giving a soft rubber composition at the time of rubber compounding, and has characteristics such as good workability, low heat generation, and large amount compounding. Widely used as a reinforcing filler for rubber members such as carcass, tube, belt, sheet material, and weather strip.
By the way, it is well known that the basic characteristics of carbon black include a high-order structure (structure) due to the relationship between the specific surface area evaluated by iodine adsorption amount, nitrogen adsorption specific surface area, etc., and carbon black particles. However, it has been widely recognized that the evaluation of the imparting characteristics of carbon black to rubber is impossible only with the above two characteristics, and it is not possible to control the rubber characteristics only with these characteristics. Have difficulty.
このような状況に鑑み、本出願人は先願１（特許文献１参照）において、ヨウ素吸着量（ＩＡ）が１５〜２５ｍｇ／ｇ、ジブチルフタレート吸収量（ＤＢＰＡ）が１００〜１５０ｍｌ／１００ｇの特性を有するファーネスカーボンブラックにおいて、遠心沈降分析によるストークス相当径の最頻度値（Ｄｓｔ）が下記式１を満足し、かつ着色力が式２を満足するソフト系ファーネスカーボンブラックを提案した。
式１ Ｄｓｔ≧（ＤＢＰＡ）−７．５（ＩＡ）＋３５０
式２ 着色力≦（ＩＡ）＋２５
このソフト系ファーネスカーボンブラックは、カーボンブラック多量配合時の分散不良及びゴム配合物の押出特性の低下を改善すると共に、反発弾性、圧縮永久歪みなどの特性を向上させる効果がある。しかしながら、ヨウ素吸着量の範囲が従来のカーボンブラックよりも低い側にあるため、補強性、特に引張り特性が低下する傾向にあった。
In view of such circumstances, the applicant of the prior application 1 (see Patent Document 1) has a characteristic of iodine adsorption amount (IA) of 15 to 25 mg / g and dibutyl phthalate absorption amount (DBPA) of 100 to 150 ml / 100 g. A soft furnace carbon black in which the most frequent value (Dst) of the Stokes equivalent diameter by centrifugal sedimentation analysis satisfies the following formula 1 and the coloring power satisfies the formula 2 was proposed.
Formula 1 Dst ≧ (DBPA) −7.5 (IA) +350
Formula 2 Coloring power ≦ (IA) +25
This soft furnace carbon black has the effect of improving the properties such as rebound resilience and compression set, as well as improving the poor dispersion when carbon black is blended in large amounts and the extrusion characteristics of the rubber compound. However, since the range of iodine adsorption is on the lower side than that of conventional carbon black, the reinforcing property, particularly the tensile property, tends to be lowered.
この欠点を改良するため、本出願人は先願２（特許文献２参照）において、ヨウ素吸着量（ＩＡ）が３５〜５０ｍｇ／ｇであり、ジブチルフタレート吸収量（ＤＢＰＡ）が１２０ｍｌ／１００ｇを超え１４０ｍｌ／１００ｇ未満の範囲内にあり、△ＤＢＰＡ（ＤＢＰＡ−２４Ｍ４ＤＢＰＡ）が４０ｍｌ／１００ｇを超え５０ｍｌ／１００ｇ未満の範囲内にあり、かつ、遠心沈降分析によるカーボンブラックアゲリケードのストークス相当径の最多頻度値（Ｄｓｔ）が、
Ｄｓｔ≧｛（ＤＢＰＡ）２−（ＩＡ）２｝１／２＋８０
の関係を満足することを特徴とする、先願１のソフト系ファーネスカーボンブラックよりも表面積が大きいカーボンブラックの発明を開示し、ゴム組成物における分散性を著しく改良すると共に、ゴム組成物に対して優れた反発弾性と圧縮永久歪み特性を付与するソフト系カーボンブラックを提供した。
In order to remedy this drawback, in the prior application 2 (see Patent Document 2), the present applicant has an iodine adsorption amount (IA) of 35 to 50 mg / g and a dibutyl phthalate absorption amount (DBPA) of more than 120 ml / 100 g. It is in the range of less than 140 ml / 100 g, ΔDBPA (DBPA-24M4DBPA) is in the range of more than 40 ml / 100 g and less than 50 ml / 100 g, and the largest Stokes equivalent diameter of carbon black aged by centrifugal sedimentation analysis The frequency value (Dst) is
Dst ≧ {(DBPA) 2 − (IA) 2 } 1/2 +80
The invention of carbon black having a surface area larger than that of the soft furnace carbon black of the prior application 1 is disclosed, and the dispersibility in the rubber composition is remarkably improved. A soft carbon black that provides excellent rebound resilience and compression set properties is provided.
しかし、最近ではゴム組成物に配合するカーボンブラックにおける顧客の要求性能、特に引張り強さや弾性率などの機械的特性に関する要求は更に増大しており、その代表例として自動車の車内空間のシール材料として使用されるゴム部材に対する性能向上がある。
雨、風、埃の中を高速で走行する自動車には、車室や客室へ雨や埃が入り込まないように様々なゴム組成物が使用されている。例えば、窓ガラスを車体に密着させるウェザーストリップやドアシール部材、回転するエンジンやトランスミッションの軸を伝わって油の漏出を防止するオイルシール、ブレーキピストンでの油の漏出を防ぐブレーキキャップなどがある。これらのゴム組成物は過酷な環境で使用されるため、耐候性、耐油性、耐摩耗性、耐久性等が要求される。その中でもゴム組成物の安全性を高め、寿命を向上させる上でゴム組成物の機械的強度を上げることが最も重要な要求項目である。
ゴム組成物の機械的強度を向上させる方法としては、カーボンブラックの粒子径を小さくすることが提案されている。しかし、カーボンブラックの粒子径を小さくすると、配合ゴム組成物の粘度上昇や加硫時間の短縮が考えられ、加工性を損なう可能性がある。このため、粒子径範囲は従来とほぼ同等のままで、補強性等の機械的特性のみを向上させることは困難であった。この問題を解決するために開発されたのが前記先願発明であったが、前述したように従来のＦＥＦと同等の押出し特性や外観特性、圧縮永久歪み性を維持しながら、機械的強度を一層向上させることのできるソフト系ファーネスカーボンブラックへの要望が近年益々強くなり、この対応が急務となっている。
Recently, however, customer performance requirements for carbon blacks blended in rubber compositions, especially the demands on mechanical properties such as tensile strength and elastic modulus, are further increasing. There is a performance improvement over the rubber member used.
Various rubber compositions are used in automobiles that travel at high speed in rain, wind, and dust so that rain and dust do not enter the passenger compartment and cabin. For example, there are a weather strip and a door seal member that tightly attaches the window glass to the vehicle body, an oil seal that prevents oil leakage through the shaft of a rotating engine or transmission, and a brake cap that prevents oil leakage from the brake piston. Since these rubber compositions are used in a harsh environment, weather resistance, oil resistance, wear resistance, durability, and the like are required. Among them, the most important requirement is to increase the mechanical strength of the rubber composition in order to improve the safety of the rubber composition and improve the life.
As a method for improving the mechanical strength of a rubber composition, it has been proposed to reduce the particle size of carbon black. However, if the particle size of carbon black is reduced, the viscosity of the compounded rubber composition may be increased and the vulcanization time may be shortened, which may impair processability. For this reason, it has been difficult to improve only the mechanical properties such as the reinforcing property while the particle diameter range remains almost the same as the conventional one. The invention of the prior application was developed to solve this problem. As described above, while maintaining the extrusion characteristics, appearance characteristics, and compression set characteristics equivalent to those of conventional FEF, the mechanical strength is improved. In recent years, there has been an increasing demand for soft furnace carbon black that can be further improved, and this response has become an urgent issue.
本発明の目的は、ゴムに配合したとき、従来のＦＥＦ（Ｆａｓｔ Ｅｘｔｒｕｄｉｎｇ Ｆｕｒｎａｃｅ）級カーボンブラックと比べて、加工性を維持しながら機械的特性の向上を可能にするソフト系ファーネスカーボンブラック及びこれを配合したゴム組成物を提供することである。 An object of the present invention is to provide a soft furnace carbon black that can improve mechanical properties while maintaining processability as compared with conventional FEF (Fast Extracting Furnace) grade carbon black when blended with rubber, and It is to provide a compounded rubber composition.
上記課題は、次の１）〜２）の発明によって解決される。
１） 窒素吸着比表面積（Ｎ２ＳＡ）が３０〜５０ｍ２／ｇ、ジブチルフタレート吸収量（ＤＢＰＡ）が１００〜１４０ｍｌ／１００ｇ、トルエン着色透過度（ＴＴ）が８０％以上の領域にあるファーネスカーボンブラックであって、下記式（１）のＸが１．００〜１．２０、下記式（２）のＹが２４０〜３５０、かつ下記式（３）のＺが０．８０〜１．２０であることを特徴とするソフト系ファーネスカーボンブラック。
２） 天然ゴム及び／又は合成ゴム成分に対して、１）記載のソフト系ファーネスカーボンブラックを配合したことを特徴とするゴム組成物。
The above problems are solved by the following inventions 1) to 2).
1) Furnace carbon having a nitrogen adsorption specific surface area (N 2 SA) of 30 to 50 m 2 / g, a dibutyl phthalate absorption (DBPA) of 100 to 140 ml / 100 g, and a toluene color permeability (TT) of 80% or more. It is black, X of the following formula (1) is 1.00-1.20, Y of the following formula (2) is 240-350, and Z of the following formula (3) is 0.80-1.20. A soft furnace carbon black characterized by being.
2) A rubber composition comprising the soft furnace carbon black described in 1) with natural rubber and / or synthetic rubber component.
本発明によれば、ゴムに配合したとき、従来のＦＥＦ級カーボンブラックと比べて、加工性を維持しながら機械的特性の向上を可能にするソフト系ファーネスカーボンブラック及びこれを配合したゴム組成物を提供できる。
即ち、ゴムに配合したとき、従来のＦＥＦ級カーボンブラックと同等の押出し特性、黒色度や光沢度といった外観特性、圧縮永久歪み性を維持しながら、機械的強度を一層向上させることができるソフト系ファーネスカーボンブラックを提供できる。
また、スポンジ押出製品や低硬度ゴム製品などのように押出加工の難しい部材に配合した場合にも、優れた押出加工性と圧縮永久歪み特性を付与することができるソフト系カーボンブラックを提供できる。
According to the present invention, a soft furnace carbon black that can improve mechanical properties while maintaining processability as compared with conventional FEF-grade carbon black when blended with rubber, and a rubber composition containing the same Can provide.
That is, when blended with rubber, a soft system that can further improve the mechanical strength while maintaining the same extrusion characteristics, appearance characteristics such as blackness and glossiness, and compression set as with conventional FEF grade carbon black. Furnace carbon black can be provided.
In addition, soft carbon black that can impart excellent extrudability and compression set characteristics can be provided even when it is blended in a member that is difficult to extrude, such as a sponge extruded product or a low-hardness rubber product.
以下、上記本発明について詳しく説明する。
本発明者らは、従来のＦＥＦ級カーボンブラックと比べて、加工性、外観性、圧縮永久歪み性を維持しながら補強性を向上させることができるカーボンブラックについて鋭意研究を進めた結果、前記式（１）〜（３）の要件を満足するソフト系ファーネスカーボンブラックをゴムに配合すれば、前述した本出願人の先願に係る従来のＦＥＦ級カーボンブラックと同等の加硫ゴム物性を満足し、かつ機械的特性を向上させることができることを見出し、本発明に到達した。
なお、本発明が適用可能なゴムとしては天然ゴム、スチレン−ブタジエンゴム、イソプレンゴム、クロロプレンゴム、エチレン−プロピレン−ジエン共重合ゴム、ブチルゴム、ハロゲン化ブチルゴム、アクリルニトリル−ブタジエンゴムなどが挙げられ、これらを任意に組み合わせたブレンドゴムにも適用可能である。
Hereinafter, the present invention will be described in detail.
As a result of diligent research on carbon black capable of improving reinforcement while maintaining processability, appearance, and compression set as compared with conventional FEF class carbon black, If a soft furnace carbon black that satisfies the requirements (1) to (3) is blended with rubber, the physical properties of the vulcanized rubber equivalent to the conventional FEF-grade carbon black according to the prior application of the applicant mentioned above are satisfied. And the present inventors have found that the mechanical properties can be improved and have reached the present invention.
The rubber to which the present invention can be applied includes natural rubber, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, ethylene-propylene-diene copolymer rubber, butyl rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber, and the like. The present invention can also be applied to a blend rubber in which these are arbitrarily combined.
本発明のカーボンブラックにおいて、窒素吸着比表面積（Ｎ２ＳＡ）が３０ｍ２／ｇを下回ると、粘度が低下して押出し時の形状保持が困難となり、５０ｍ２／ｇを上回ると、粘度が上昇して押出しが困難となる。また、ジブチルフタレート吸収量（ＤＢＰＡ）が１００ｍｌ／１００ｇを下回ると、押出し後の収縮が大きくなり、１４０ｍｌ／１００ｇを上回ると、耐圧縮永久歪み性が低下する。また、トルエン着色透過度（ＴＴ）が８０％を下回ると、ゴム配合物からのカーボンブラック表面の未分解タール分の染み出しによる汚染性を回避することが困難となる。ＴＴは好ましくは８５％以上、より好ましくは９０％以上である。 In the carbon black of the present invention, when the nitrogen adsorption specific surface area (N 2 SA) is less than 30 m 2 / g, the viscosity decreases and it becomes difficult to maintain the shape during extrusion, and when it exceeds 50 m 2 / g, the viscosity increases. As a result, extrusion becomes difficult. On the other hand, when the dibutyl phthalate absorption (DBPA) is less than 100 ml / 100 g, shrinkage after extrusion increases, and when it exceeds 140 ml / 100 g, the compression set resistance decreases. On the other hand, when the toluene coloring transmittance (TT) is less than 80%, it becomes difficult to avoid contamination due to exudation of undecomposed tar on the surface of carbon black from the rubber compound. TT is preferably 85% or more, more preferably 90% or more.
更に本発明では、カーボンブラックの表面活性を表す指標として、Ｎ２ＳＡとヨウ素吸着量（ＩＡ）の比（Ｘ）を用いているが、この比（Ｘ）が１．００を下回ると、ポリマーとの相互作用が小さくなるので補強性が低下し本発明が求める補強性の向上が困難となる。逆にこの比（Ｘ）が１．２０を上回ると、カーボンブラック表面の未分解タール分が増加し、トルエン着色透過度が８０％を下回って、ゴム配合物の汚染性を回避することが困難となる。 Further, in the present invention, the ratio (X) of N 2 SA and iodine adsorption amount (IA) is used as an index representing the surface activity of carbon black. When this ratio (X) is less than 1.00, the polymer Therefore, the reinforcement is reduced and it is difficult to improve the reinforcement required by the present invention. Conversely, when this ratio (X) exceeds 1.20, the undecomposed tar content on the surface of carbon black increases, and the toluene color permeability is less than 80%, making it difficult to avoid the contamination of rubber compounds. It becomes.
また、本発明ではカーボンブラックの透過型電子顕微鏡像から得られる凝集体の複雑さを表す形状係数を指標として用いている。
一般に、ＤＢＰＡが同じでも生成条件によって凝集体の形状が変化することが知られている。そこで、カーボンブラックの凝集体の発達度合いをより精確に評価するために鋭意研究した結果、透過型電子顕微鏡像の画像解析で得られるアグリゲートの複雑さを表す形状係数（Ｙ）の値が、カーボンブラックのストラクチャーの発達度合いを表す指標として有用なことを見出した。（Ｙ）の値が１００の場合は完全な円であることを表す。ストラクチャーが発達するに伴い（Ｙ）の値が増加する。凝集体の形状と補強性の関係を研究した結果、（Ｙ）が２４０以上のとき、顕著な機械的特性の向上を確認した。一方、（Ｙ）が３５０を超えるとゴム配合物の外観の黒さを示す黒色度が低下してしまうので外観特性を維持することが困難となってくる。
In the present invention, a shape factor representing the complexity of the aggregate obtained from the transmission electron microscope image of carbon black is used as an index.
In general, it is known that the shape of the aggregate changes depending on the production conditions even when the DBPA is the same. Therefore, as a result of earnest research to more accurately evaluate the degree of carbon black aggregate development, the value of the shape factor (Y) representing the complexity of the aggregate obtained by image analysis of a transmission electron microscope image is It was found useful as an index indicating the degree of carbon black structure development. A value of (Y) of 100 represents a complete circle. As the structure develops, the value of (Y) increases. As a result of investigating the relationship between the shape of the aggregate and the reinforcing property, when (Y) is 240 or more, a remarkable improvement in mechanical properties was confirmed. On the other hand, when (Y) exceeds 350, the blackness indicating the blackness of the appearance of the rubber compound is lowered, so that it is difficult to maintain the appearance characteristics.
これらの指標に加えて、本発明ではカーボンブラックのアグリゲートサイズ分布を遠心沈降法で測定されたモード径（Ｄｍｏｄｅ）に対する半値幅（ΔＤ−５０）の比（Ｚ）で表しており、この分布指数（Ｚ）の値が０．８０を下回ると、粘度が上昇して押出しが困難となり、逆に１．２０を上回ると、配合ゴム組成物の機械的特性が低下し、この為に本発明で求めるレベルの維持が困難となる。本発明の目標である加工性を維持しつつ補強性を向上させるためには、上記（Ｘ）（Ｙ）及び（Ｚ）の３つの特性を満たす必要がある。 In addition to these indicators, in the present invention, the aggregate size distribution of carbon black is represented by the ratio (Z) of the full width at half maximum (ΔD-50) to the mode diameter (Dmode) measured by the centrifugal sedimentation method. When the index (Z) value is less than 0.80, the viscosity increases and extrusion becomes difficult. On the other hand, when the index (Z) value exceeds 1.20, the mechanical properties of the compounded rubber composition are lowered. It becomes difficult to maintain the required level. In order to improve the reinforceability while maintaining the workability that is the target of the present invention, it is necessary to satisfy the above three characteristics (X), (Y), and (Z).
以下、実施例及び比較例を示して本発明を更に詳しく説明するが、本発明は、これらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in more detail, this invention is not limited by these Examples.
実施例１〜５、比較例１〜８
［製造例］
図１、図２に示す構造のオイルファーネス炉（特開平０７−３１６４６０号公報参照）を用いてカーボンブラックを製造した。原料油の性状は表１に示す通りである。
[Production example]
Carbon black was produced using an oil furnace having the structure shown in FIGS. 1 and 2 (see Japanese Patent Application Laid-Open No. 07-316460). The properties of the feed oil are as shown in Table 1.
カーボンブラックの製造条件を表２に示す。
なお、各実施例及び比較例のカーボンブラックの物理化学特性の制御は上記の各種製造条件を調整して行ったが、具体的には（Ｘ）、（Ｙ）及び（Ｚ）の３つの特性は次のようにして調整した。
＜Ｎ２ＳＡとヨウ素吸着量（ＩＡ）の比（Ｘ）の調整＞は、導入総空気量に対する原料油供給量を調節すること及び急冷位置までの距離を短くすることにより行った。
＜複雑さを表す形状係数（Ｙ）の調整＞は、反応室に導入する空気量を調節することにより行った。
＜アグリゲートサイズ分布指数（Ｚ）＞の調整は、可燃性流体導入室への導入総空気量の制御により行った。
In addition, although control of the physicochemical characteristics of the carbon black of each Example and Comparative Example was performed by adjusting the above various production conditions, specifically, the three characteristics (X), (Y), and (Z) Was adjusted as follows.
<Adjustment of the ratio (X) of N 2 SA and iodine adsorption amount (IA)> was performed by adjusting the feed amount of the feed oil relative to the total introduced air amount and shortening the distance to the quenching position.
<Adjustment of the shape factor (Y) representing complexity> was performed by adjusting the amount of air introduced into the reaction chamber.
The <aggregate size distribution index (Z)> was adjusted by controlling the total amount of air introduced into the combustible fluid introduction chamber.
表２に示す製造条件により得られたカーボンブラックの物理化学特性を表３に示す。
なお、実施例１〜５は本発明に係るファーネスカーボンブラックであり、比較例１〜８は本発明の請求項１に規定した何れかの要件を満たさないカーボンブラックである。また対照例は一般的なＦＥＦ級カーボンブラックの例である「旭＃６０Ｇ：旭カーボン社製」の値を示す。
Examples 1 to 5 are furnace carbon blacks according to the present invention, and Comparative Examples 1 to 8 are carbon blacks that do not satisfy any of the requirements defined in claim 1 of the present invention. Further, the control example shows a value of “Asahi # 60G: manufactured by Asahi Carbon Co., Ltd.” which is an example of general FEF grade carbon black.
＜各特性の測定＞
カーボンブラックの物理化学特性は次のようにして測定した。
（１）ＤＢＰ吸収量（ＤＢＰＡ）
ＪＩＳ Ｋ６２１７−４：２００１に記載の方法による、１００ｇ当たりに吸収されるＤＢＰの容積（ｍｌ／１００ｇ）を示した。
（２）窒素吸着比表面積（Ｎ２ＳＡ）
ＪＩＳ Ｋ６２１７−２：２００１に記載の方法による、単位重量当たりに吸着される窒素表面積（ｍ２／ｇ）を示した。
（３）ヨウ素吸着量（ＩＡ）
ＪＩＳ Ｋ６２１７−１：２００８に記載の方法による、単位重量当たりに吸着されるヨウ素量（ｍｇ／ｇ）を示した。
（４）トルエン着色透過度
ＪＩＳ Ｋ６２１８−４：２００５に記載の方法による、カーボンブラックから抽出される物質によってトルエンが着色される程度を、トルエンのブランク値を１００とした透過度（％）で示した。
（５）複雑さの形状係数（Ｙ）
ＡＳＴＭ Ｄ ３８４９−０７：２００８に記載の方法により最終倍率５，０００倍で表示された画像をニレコ社製の画像解析装置ＬＵＺＥＸ―ＦＳを用いて周囲長（ＰＭ）と投影面積（Ａ）から下記の式を用いて算出した。
ＪＩＳ Ｋ６２１７−６：２００８に記載の方法によるストークス径のモード径（Ｄｍｏｄｅ）に対する半値幅（ΔＤ−５０）の比を示した。
<Measurement of each characteristic>
The physicochemical properties of carbon black were measured as follows.
(1) DBP absorption (DBPA)
The DBP volume (ml / 100 g) absorbed per 100 g according to the method described in JIS K6217-4: 2001 was shown.
(2) Nitrogen adsorption specific surface area (N 2 SA)
The surface area of nitrogen adsorbed per unit weight (m 2 / g) according to the method described in JIS K6217-2: 2001 was shown.
(3) Iodine adsorption amount (IA)
The amount of iodine adsorbed per unit weight (mg / g) by the method described in JIS K6217-1: 2008 was shown.
(4) Toluene coloring transmittance The degree to which toluene is colored by a substance extracted from carbon black according to the method described in JIS K6218-4: 2005 is indicated by the transmittance (%) where the blank value of toluene is 100. It was.
(5) Complexity shape factor (Y)
An image displayed at a final magnification of 5,000 times according to the method described in ASTM D 3849-07: 2008, using an image analysis apparatus LUZEX-FS manufactured by Nireco, from the perimeter (PM) and the projection area (A) This was calculated using the following formula.
The ratio of the half width (ΔD-50) to the mode diameter (Dmode) of the Stokes diameter by the method described in JIS K6217-6: 2008 was shown.
＜ゴム配合特性＞
表３に示したカーボンブラックを表４に示した割合でＥＰＤＭ（エチレンプロピレンゴム）に配合してゴム組成物とし、各種特性を測定した。結果を表５に纏めて示す。
＊１ 商品名：ＥＰ−２４〔ＪＳＲ社製〕
＊２ 商品名：ＰＷ−３８０〔出光興産社製〕
＊３ 商品名：ホワイトンＰ−３０〔白石工業社製〕
＊４ 商品名：ノクセラーＭ〔大内新興化学工業社製〕
＊５ 商品名：ノクセラーＴＴ〔大内新興化学工業社製〕
＊６ 商品名：ノクセラーＴＲＡ〔大内新興化学工業社製〕
＊７ 商品名：ノクセラーＢＺ〔大内新興化学工業社製〕
<Rubber compounding characteristics>
Carbon black shown in Table 3 was blended with EPDM (ethylene propylene rubber) at the ratio shown in Table 4 to obtain a rubber composition, and various properties were measured. The results are summarized in Table 5.
* 1 Product name: EP-24 [manufactured by JSR]
* 2 Product name: PW-380 [made by Idemitsu Kosan Co., Ltd.]
* 3 Product name: Whiten P-30 [Shiraishi Kogyo Co., Ltd.]
* 4 Product name: Noxeller M [Ouchi Shinsei Chemical Co., Ltd.]
* 5 Product name: Noxeller TT [Ouchi Shinsei Chemical Co., Ltd.]
* 6 Product name: Noxeller TRA [manufactured by Ouchi Shinsei Chemical Co., Ltd.]
* 7 Product name: Noxeller BZ [Ouchi Shinsei Chemical Co., Ltd.]
※１ 試験片加硫条件：１５０℃×１５ｍｉｎ
※２ 試験片加硫条件：１５０℃×２０ｍｉｎ
※３ 試験条件：７０℃×２２ｈｒ
※４ 旭＃６０Ｇ対比指数（数が大きい方が黒い）
※５ 旭＃６０Ｇ対比指数（数が大きい方が光沢がある）
※６ 押出１ヶ月後の未加硫試料表面のブリードの有無
* 1 Test piece vulcanization conditions: 150 ° C x 15 min
* 2 Test piece vulcanization conditions: 150 ° C x 20 min
* 3 Test conditions: 70 ° C x 22 hours
* 4 Asahi # 60G contrast index (the larger number is black)
* 5 Asahi # 60G contrast index (the larger the number, the more shiny)
* 6 Presence of bleed on the surface of the unvulcanized sample after one month of extrusion
上記実施例及び比較例のカーボンブラックをＥＰＤＭに配合した表５のゴム特性の結果から、本発明のカーボンブラックの効果について説明する。なお、上記各特性は次の方法で測定した。
・ムーニー・スコーチ… ＪＩＳ Ｋ６３００−１：２００１に記載の方法
・押出特性 …ＡＳＴＭ Ｄ２２３０−９６：２００２に記載の方法
・硬さ …ＪＩＳ Ｋ６２５３：２００７に記載の方法
・引張試験 …ＪＩＳ Ｋ６２５１：２００４に記載の方法でダンベル状１号形試験片
の引張特性を測定
・反発弾性 …ＪＩＳ Ｋ６２５５：１９９６に記載の方法
・黒色度 …ＪＩＳ Ｚ８７２９：２００４に記載の方法
・光沢度 …ＪＩＳ Ｚ８７４１：１９９７に記載の方法で６０°の光沢度を測定
・ブリードの有無…押出特性で用いた試験片表面のブリードの有無を目視で観察
The effect of the carbon black of the present invention will be described from the results of rubber characteristics shown in Table 5 in which the carbon blacks of the above examples and comparative examples were blended with EPDM. The above characteristics were measured by the following methods.
・ Mooney scorch: Method described in JIS K6300-1: 2001 ・ Extrusion characteristics: Method described in ASTM D2230-96: 2002 ・ Hardness: Method described in JIS K6253: 2007 ・ Tensile test: JIS K6251: 2004 Dumbbell-shaped No. 1 test piece as described
・ Rebound resilience: Method described in JIS K6255: 1996 ・ Blackness: Method described in JIS Z8729: 2004 ・ Glossiness: Glossiness measured by the method described in JIS Z8741: 1997 ・Presence of bleed: Visual observation of bleed on the surface of the test piece used for extrusion characteristics
上記測定結果から以下のようなことが分かる。
（ｉ）補強性（引張強さ）について
表面積、ＤＢＰ吸収量、トルエン着色透過度などの物理化学特性がほぼ類似し、アグリゲートの複雑さを表す形状係数（Ｙ）が大きく異なる実施例１〜３と比較例１〜３〔形状係数（Ｙ）がいずれも本発明の範囲を下回る〕について、窒素吸着比表面積ＶＳ引張強さでプロットした結果を図３に示す。
図３から、一般的に引張強さの性能は、表面積とＤＢＰ吸収量の組合せにより決定されるが、これらの特性に加えて複雑さを表す形状係数（Ｙ）を本発明の数値範囲に制御することにより、従来よりも数％高い特性を示し、制御要因としての有効性は明らかである。なお、実施例１〜３では押出特性や硬さの特性については略同等である。
また、Ｎ２ＳＡ／ＩＡの比（Ｘ）が本発明の範囲を下回る比較例４、及びアグリゲート分布特性のΔＤ−５０／Ｄｍｏｄｅ（Ｚ）が本発明の範囲を上回る比較例７においては、１００％モジュラス値及び引張強さが従来のＦＥＦ（対照例）よりも低下した。
なお、実施例１の引張強さは対照例よりも低いが、これは、この特性に関与する要因が比表面積であるためであり、略同等の比表面積を有する実施例２と対照例とを対比すれば本発明の有位性は明らかである。
The following can be understood from the measurement results.
(I) Reinforcing property (tensile strength) Examples 1 to 3 having substantially similar physicochemical properties such as surface area, DBP absorption, and toluene coloring permeability, and having greatly different shape factors (Y) representing the complexity of the aggregate FIG. 3 shows the results of plotting the nitrogen adsorption specific surface area VS tensile strength for No. 3 and Comparative Examples 1 to 3 (the shape factor (Y) is below the range of the present invention).
From FIG. 3, the tensile strength performance is generally determined by the combination of the surface area and DBP absorption. In addition to these characteristics, the shape factor (Y) representing complexity is controlled within the numerical range of the present invention. By doing so, the characteristic is several percent higher than before, and the effectiveness as a control factor is clear. In Examples 1 to 3, the extrusion characteristics and hardness characteristics are substantially the same.
In Comparative Example 4 in which the ratio (X) of N 2 SA / IA is less than the range of the present invention, and in Comparative Example 7 in which ΔD-50 / Dmode (Z) of the aggregate distribution characteristic is greater than the range of the present invention, The 100% modulus value and tensile strength were lower than the conventional FEF (control example).
In addition, although the tensile strength of Example 1 is lower than the control example, this is because the factor related to this characteristic is a specific surface area, and Example 2 and a control example which have a substantially equivalent specific surface area are compared. In contrast, the superiority of the present invention is clear.
（ii）加工性について
ほぼ拮抗した物理化学特性を持つ実施例１〜３及び比較例１〜３を対比すると、押出速度において実施例の方がいずれも高い数値を示しており、またダイスウェルの値も改良されていることが分かる。
（iii）外観性について
黒色度に関しては、実施例１〜５と比較例１〜４、６〜８は従来のＦＥＦと同等であるといえるが、複雑さを表す形状係数（Ｙ）が本発明の範囲を上回る比較例５は従来のＦＥＦよりも黒色度が低下した。一方で光沢度に関しては、複雑さを表す形状係数（Ｙ）が大きくなる程、大きくなる傾向があることが分かった。
（iv）ゴム組成物の表面汚染性について
トルエン着色透過度（％）が本発明の範囲を外れた比較例８では、同時にＮ２ＳＡ／ＩＡ（Ｘ）も本発明範囲を上回る側に外れ、このカーボンブラック配合ゴム組成物では表面への未熱分解タール分の染み出し（ステイニング）が発生し、ブリードとして観察された。
（ｖ）まとめ
上記（ｉ）〜（iii）から、本発明のソフト系ファーネスカーボンブラックは加工性、外観性、圧縮永久歪み性を損なうことなく補強性が向上することが分かる。
(Ii) Processability When comparing Examples 1 to 3 and Comparative Examples 1 to 3 having almost antagonistic physicochemical properties, the Examples all show higher numerical values in terms of extrusion speed. It can be seen that the value has also been improved.
(Iii) Appearance Regarding blackness, Examples 1 to 5 and Comparative Examples 1 to 4 and 6 to 8 can be said to be equivalent to the conventional FEF, but the shape factor (Y) representing complexity is the present invention. In Comparative Example 5 exceeding the range, the blackness was lower than that of the conventional FEF. On the other hand, it has been found that the glossiness tends to increase as the shape factor (Y) representing complexity increases.
(Iv) About the surface contamination property of the rubber composition In Comparative Example 8 in which the toluene coloring transmittance (%) is out of the range of the present invention, N 2 SA / IA (X) is also out of the range of the present invention. In this carbon black compounded rubber composition, exudation (staining) of unthermally decomposed tar to the surface occurred and was observed as bleeding.
(V) Summary From the above (i) to (iii), it can be seen that the soft furnace carbon black of the present invention has improved reinforceability without impairing workability, appearance, and compression set.
１ カーボンブラック反応装置
２ 可燃性流体導入室
３ 酸素含有ガス導入管
４ 酸素含有ガス導入用円筒
５ 整流板
７ 燃料油噴霧装置
８ 収れん室
９ バーナータイル
１０ 原料油噴霧装置
１１ 原料油導入室
１２ 反応室
１３ 反応室継続兼急冷室
１４ 収れん帯域を定める部材
１５ 酸素含有ガス導入管
ａ 急冷水圧入噴霧装置
ｂ 急冷水圧入噴霧装置
ｃ 急冷水圧入噴霧装置
ｄ 急冷水圧入噴霧装置
ｅ 急冷水圧入噴霧装置
ｆ 急冷水圧入噴霧装置
ｇ 急冷水圧入噴霧装置
ｈ 急冷水圧入噴霧装置
DESCRIPTION OF SYMBOLS 1 Carbon black reaction apparatus 2 Flammable fluid introduction chamber 3 Oxygen containing gas introduction pipe 4 Oxygen containing gas introduction cylinder 5 Current plate 7 Fuel oil spraying device 8 Converging chamber 9 Burner tile 10 Raw material
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011020172A JP5647534B2 (en) | 2011-02-01 | 2011-02-01 | Soft furnace carbon black and rubber composition |
Applications Claiming Priority (1)
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| JP2014088501A (en) * | 2012-10-30 | 2014-05-15 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| WO2015011796A1 (en) * | 2013-07-24 | 2015-01-29 | 東海カーボン株式会社 | Carbon black, method for producing carbon black, and rubber composition |
| WO2019130803A1 (en) * | 2017-12-26 | 2019-07-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition, pneumatic tire, production method for wet rubber masterbatch, and production method for rubber composition |
| JP2019112585A (en) * | 2017-12-26 | 2019-07-11 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
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| JP2014088501A (en) * | 2012-10-30 | 2014-05-15 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
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| JPWO2015011796A1 (en) * | 2013-07-24 | 2017-03-02 | 東海カーボン株式会社 | Carbon black, method for producing carbon black, and rubber composition |
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| JP2019112585A (en) * | 2017-12-26 | 2019-07-11 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
| JP7154008B2 (en) | 2017-12-26 | 2022-10-17 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
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