JPH01229074A - Thermal type furnace carbon black - Google Patents
Thermal type furnace carbon blackInfo
- Publication number
- JPH01229074A JPH01229074A JP5273288A JP5273288A JPH01229074A JP H01229074 A JPH01229074 A JP H01229074A JP 5273288 A JP5273288 A JP 5273288A JP 5273288 A JP5273288 A JP 5273288A JP H01229074 A JPH01229074 A JP H01229074A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- dst
- value
- furnace carbon
- furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 53
- 238000004040 coloring Methods 0.000 claims abstract description 16
- 238000002834 transmittance Methods 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 238000004364 calculation method Methods 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 241000872198 Serjania polyphylla Species 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- ZUROCNHARMFRKA-UHFFFAOYSA-N 4,5-dibromo-1h-pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC(Br)=C(Br)N1 ZUROCNHARMFRKA-UHFFFAOYSA-N 0.000 claims 1
- 101100431668 Homo sapiens YBX3 gene Proteins 0.000 claims 1
- 102100022221 Y-box-binding protein 3 Human genes 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 16
- 239000005060 rubber Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 7
- 238000001556 precipitation Methods 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 43
- 150000001875 compounds Chemical class 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006244 Medium Thermal Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006234 thermal black Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【発明の詳細な説明】
［技術分野］
本発明はゴムならびにプラスチックへの分散性、非汚染
性ならびに配合物の屈曲亀裂発生低減性等にすぐれた新
規なサーマルタイプのファーネスカーボンブラックに関
するものである。[Detailed Description of the Invention] [Technical Field] The present invention relates to a novel thermal type furnace carbon black that has excellent dispersibility in rubber and plastics, non-staining properties, and ability to reduce the occurrence of flex cracks in compounds. .
［従来技術］
サーマルブラックとしては、従来から耐火れんがを内部
に積んだ分解炉中で天然ガスを断続的に熱分解して生産
されるＭＴ（Ｍｅｄｉｕｍ Ｔｈｅｒｍａｌ）ならびに
ＦＴ（Ｆｉｎｅ Ｔｈｅｒ＋＋＋ａｌ）級ブラックが知
られている。これらのサーマルブラックはベルト、ロー
ラー、各種シール、ガスケット、ホース類、チューブ、
モーターマウント、ウェザ−ストリップ、各種成型物、
ワイパーブレード、０−リング等のゴム部材ならびにプ
ラスチック（例えば紫外線劣化防止等）への補強剤ある
いは充填剤として利用されている。[Prior art] As thermal black, MT (Medium Thermal) and FT (Fine Ther+++al) class blacks, which are produced by intermittently thermally decomposing natural gas in a cracking furnace loaded with refractory bricks, have been known. It is being These thermal blacks are used for belts, rollers, various seals, gaskets, hoses, tubes,
Motor mounts, weather strips, various molded products,
It is used as a reinforcing agent or filler for rubber members such as wiper blades and O-rings, as well as plastics (for example, to prevent UV deterioration).
また連続生産できるオイルファーネス法による、サーマ
ルブラックに代替可能な廿−マルタイブの大粒子ファー
ネスブラック（ＵＮＩＴＥＤ ５Ｌ−９０等）も知られ
ている。Also known is a large-particle furnace black (UNITED 5L-90, etc.) made by an oil furnace method that allows continuous production and which can be substituted for thermal black.
これらの物理化学特性としては、例えばＲｕｂｂｅｒ
Ｗｏｒｌｄ １９７６年８月号”Ｃａａｒｂｏｎ Ｂｌ
ａｃｋｂｏａｒｄ”には下記の表−１のとおりの記載が
見られる。These physicochemical properties include, for example, Rubber
World August 1976 issue “Carbon Bl”
ackboard” contains the descriptions shown in Table 1 below.
表 −１
さらにファーネス法によるサーマルタイプのカーボンブ
ラックとしては、Ｒｕｂｂｅｒ Ｃｈｅｍｉｓｔｒｙａ
ｎｄ Ｔｅｃｈｎｏｌｏｇｙ、第４５巻、第１４５頁（
１９７２）にその物理化学特性として下記の表−２のも
のが知られている。Table 1 Furthermore, as a thermal type carbon black produced by the furnace method, Rubber Chemistrya
nd Technology, Volume 45, Page 145 (
1972), the physical and chemical properties shown in Table 2 below are known.
表 −２
さらにまた、我国におけるファーネス法によるサーマル
級カーボンブラックとして、ＣＡＲＢＯＮ［］ＬＡＣＫ
年鑑Ｎａ３１．１９８７（カーボンブラック協会昭和６
２年７月１日発行）によれば、下記の表−３のものが知
られている。Table 2 Furthermore, CARBON[]LACK is a thermal grade carbon black produced by the furnace method in Japan.
Yearbook Na31.1987 (Carbon Black Association Showa 6
According to the publication published on July 1, 2013), the following Table 3 is known.
表 −３
上記各表から明らかな如く、本来のＦＴ（Ｎ８８０）や
ＭＴ （Ｎ９９０）はベンゼン着色透過度が著しく低く
。Table 3 As is clear from the above tables, the original FT (N880) and MT (N990) have extremely low benzene color transmittance.
すなわち、カーボン表面が未分解残留物質（この量が増
加すると、カーボンブラックの揮発分の割合が大きくな
る）で覆われているので配合物への汚染性が問題とされ
ていた。ファーネス法によるサーマルタイプのカーボン
ブラックでは、平均粒子径また粒子径の大小の尺度とし
てのよう素吸着量で対比してみると、ファーネス法によ
るものは典型的なサーマルブラックよりもよう素吸着量
が大きく（すなわち粒子径小）、かつ比着色力も高いの
でＦＴまたは１級ブラックの特徴である多量配合におけ
る分散性等についてやや難点があったばかりではなく、
作業性、成形性においても不満足なものであった。よう
素吸着量ならびにＤＢＰ吸油量において、従来のＦＴま
たはＭＴ級ジブラック近似する上記表−２のＸＣ−３１
カーボンは、後述の本発明にかかるカーボンブラックに
おいて理解されるとおり、例えば比着色力値が一定値以
下であっても、アクリゲートサイズ分布指数Ｓが一定値
を下回ると、上記表−２に示された特性値のみでは律し
きれないゴム配合特性、例えば分散性の低下と、これに
起因する耐屈曲亀裂性が劣るなどの問題がある。That is, since the carbon surface is covered with undecomposed residual substances (as the amount of these substances increases, the proportion of volatile components of carbon black increases), contamination of the compound has been a problem. Comparing the average particle size and the amount of iodine adsorbed as a measure of particle size, thermal type carbon black produced by the furnace method has a higher iodine adsorption amount than typical thermal black. Because it is large (i.e., small particle size) and has a high specific coloring power, it not only has some difficulties in terms of dispersibility in large amounts, which is a characteristic of FT or grade 1 black, but also
Workability and moldability were also unsatisfactory. XC-31 in Table 2 above, which is similar to conventional FT or MT class diblack in terms of iodine adsorption and DBP oil absorption.
As will be understood in the carbon black according to the present invention, which will be described later, even if the specific coloring power value is below a certain value, if the acrylate size distribution index S is below a certain value, carbon will have the following properties as shown in Table 2 above. There are problems with rubber compounding properties that cannot be controlled solely by the specified property values, such as a decrease in dispersibility and poor flex cracking resistance due to this.
ファーネス法によるサーマルタイプのカーボンブラック
の製造法としては、特公昭４９−４５０７５号（出願人
：旭カーボン株式会社）公報が知られているが、この先
行発明による製品として吸油量４０ｃｃ／ｌｏｏｇ、よ
う素吸着量１１．０■／ｇ、揮発分０゜６７％が紹介さ
れており、従来の典型的なサーマルブラックに近似した
特性を有していることが理解される。Japanese Patent Publication No. 49-45075 (Applicant: Asahi Carbon Co., Ltd.) is known as a method for producing thermal type carbon black using the furnace method. An elementary adsorption amount of 11.0 .mu./g and a volatile content of 0.67% are introduced, and it is understood that the material has characteristics similar to conventional typical thermal blacks.
しかし、揮発分（未分解物質）が熱分解ＦＴの０．９６
％に匹敵する程高い（すなわち、トルエン着色透過度が
低い）ために配合物への汚染性という問題があり、さら
にはアクリゲートサイズ分布指数Ｓが小さいために生じ
る分散性低下に対応するための改善が必要であった。However, the volatile content (undecomposed substances) is 0.96 of the thermal decomposition FT.
% (i.e., the toluene coloring transmittance is low), there is a problem of contamination of the formulation, and furthermore, in order to cope with the decrease in dispersibility caused by the small acrylate size distribution index S. Improvement was needed.
［目 的コ
本発明の目的は、ゴムやプラスチックの配合物への多量
配合が可能である従来のＦＴならびに１級ブラック並の
大粒子径、すなわち、よう素吸着量（ＩＡ）値を低位に
維持しながらＤＢＰ吸油量（ＤＢＰＡ）を従来のＦＴな
らびに訂よりも若干高位に保持せしめ、さらに配合物の
汚染に関連するトルエン着色透過度を６０％以上にした
サーマルタイプのファーネスカーボンブラックを提供す
ることである。さらに、本発明の目的は、分散性に関連
する比着色力を後述の算出式−（１）で算出される値以
下の低位とし、さらにアグリゲートのストークス相当径
の最多頻度値（Ｄｓｔ）と、Ｄｓｔよりも大きな側にあ
って、かつＤｓｔの１／２の頻度を有するストークス相
当径（ＯＳ。）とにより算出される下記算出式−■のＳ
値を従来のサーマル級ファーネスカーボンブラックより
も大きい０．２０以上に保持せしめることにより、配合
物中への分散性、耐屈曲亀裂発生性を改善したサーマル
タイプファーネスカーボンブラックを提供することであ
る。[Purpose] The purpose of the present invention is to reduce the particle size of conventional FT and grade 1 black, which can be incorporated in large quantities into rubber and plastic compounds, that is, to reduce the iodine adsorption amount (IA) value. To provide a thermal type furnace carbon black that maintains DBP oil absorption (DBPA) at a slightly higher level than conventional FT and revision, and also has a toluene color transmittance related to contamination of the compound of 60% or more. That's true. Furthermore, it is an object of the present invention to reduce the specific coloring power related to dispersibility to a value below the value calculated by the calculation formula (1) described below, and further to reduce the most frequent value (Dst) of the Stokes equivalent diameter of the aggregate. , the Stokes equivalent diameter (OS) which is on the larger side than Dst and has a frequency of 1/2 of Dst.
It is an object of the present invention to provide a thermal type furnace carbon black which has improved dispersibility in a compound and resistance to flex cracking by keeping the value at 0.20 or more, which is larger than that of conventional thermal type furnace carbon black.
算出式−（１）：比着色力＝ ＩＡ ＋ ２０ここで、
比着色力はＪＩＳに６２２１−８２による測定値である
。Calculation formula - (1): Specific coloring power = IA + 20 where,
The specific tinting power is a value measured according to JIS 6221-82.
算出式−■： Ｓ＝０．８４９３２ＸＱｏｇ（吋。／Ｄ
ｓｔ）ここで、Ｄｓｔは遠心沈降分析によるカーボンブ
ラックアクリゲートのストークス相当径の最多頻度値（
Ｄｓｔ）であり、吋。はＤｓｔよりも大きな側にあって
、かつＤｓｔの１７２の頻度を有するストークス相当径
である。Calculation formula-■: S=0.84932XQog(吋./D
st) Here, Dst is the most frequent value of the Stokes equivalent diameter of carbon black acrylate determined by centrifugal sedimentation analysis (
Dst) and 吋. is a Stokes equivalent diameter which is on the larger side than Dst and has a frequency of 172 of Dst.
［目的を達成するための手段］
本発明者らは、上述の如きＩＡ、 ＤＢＰＡ、比着色力
ならびにトルエン着色透過度の基本特性値を有するファ
ーネスカーボンブラックにおいて、特に比較的大きなア
クリゲートサイズの分布広さの目安となり、算出式−（
２）で算出されるＳ値について、最多頻度アクリゲート
サイズ（Ｄｓｔ）よりも大きいアグリゲートの多寡すな
わちＳ値の大小が配合物への分散性に極めて大きな影響
を与えることを見出した。この指数Ｓは、上述の基本特
性値範囲のファーネスカーボンブラックでは通常０．１
８以下であり、このＳ値を０．２０以上という分布の広
い側に制御することにより、分散性にすぐれたカーボン
ブラックとなることが判明した。[Means for Achieving the Object] The present inventors have developed a furnace carbon black having the above-mentioned basic characteristic values of IA, DBPA, specific coloring power, and toluene color transmittance, in particular a relatively large acrylate size distribution. It is a guideline for the size, and the calculation formula - (
Regarding the S value calculated in 2), it has been found that the number of aggregates larger than the most frequently occurring acrylate size (Dst), that is, the size of the S value, has a very large effect on the dispersibility in the formulation. This index S is usually 0.1 for furnace carbon black within the basic characteristic value range mentioned above.
It was found that by controlling this S value to 0.20 or more, which is on the wide side of the distribution, carbon black with excellent dispersibility can be obtained.
すなわち、本発明はよう素吸着量（ＩＡ）が８〜１５＋
ｎｇ／ｇ、 ＤＢＰ吸油量（ＤＢＰＡ）が３５〜４５ｄ
／１００ｇ、トルエン着色透過度（着色透過度は、カー
ボンブラック中の未分解物質を溶媒で抽出し、抽出され
た量を分光光度計で測定するものであるが、同じ芳香族
系溶媒であるベンゼンとトルエンの抽出能力に若干の差
異があり、通常トルエンの方が抽出能力が高く透過率と
しては低く測定される）が６０％以上の領域にあるファ
ーネスカーボンブラックにおいて、比着色力が前記算出
式−（１）で得られる値以下であり、かつ前記算出式−
（２）で得られるアクリゲートサイズ分布指数（Ｓ）が
０．２０以上である特性を有するサーマルタイプファー
ネスカーボンブラックである。That is, the present invention has an iodine adsorption amount (IA) of 8 to 15+
ng/g, DBP oil absorption (DBPA) is 35-45d
/100g, toluene colored transmittance (colored transmittance is measured by extracting undecomposed substances in carbon black with a solvent and measuring the extracted amount with a spectrophotometer. There is a slight difference in the extraction ability of toluene and toluene, and the specific coloring power of the furnace carbon black is in the range of 60% or more (usually toluene has a higher extraction ability and is measured as a lower transmittance), and the specific coloring power is calculated using the above formula. - less than or equal to the value obtained by (1), and the calculation formula -
This is a thermal type furnace carbon black having a characteristic that the acrylate size distribution index (S) obtained in (2) is 0.20 or more.
なお、ＩＡが８■／ｇを下回る場合はゴム配合物におい
て引張り強さ等が不満足となり、１５ｍｇ／ｇを上回る
場合は多量配合が困難となる。If the IA is less than 8 .mu./g, the tensile strength etc. of the rubber compound will be unsatisfactory, and if it exceeds 15 mg/g, it will be difficult to blend in a large amount.
また、ＤＢＰＡが３５ｍｌ／１００ｇを下回る場合には
、ゴムやプラスチックへの配合時の分散性が低下し、４
５ｄ／１００ｇを上回る場合には、ゴム配合物の硬さが
増大して柔軟性が低下し、屈曲亀裂発生試験における亀
裂発生までの屈曲回数が大幅に低下するために好ましく
ない。トルエン着色透過度は、６０％を下回るとゴムや
プラスチック配合物の汚染性を回避することが困難とな
り、できれば６５％、とくに７０％以上とするのが好適
である。In addition, if DBPA is less than 35ml/100g, the dispersibility during compounding into rubber or plastic will decrease, resulting in
If it exceeds 5d/100g, the hardness of the rubber compound increases, the flexibility decreases, and the number of times the rubber compound is bent until cracking occurs in the bending crack initiation test decreases significantly, which is not preferable. If the toluene color transmittance is less than 60%, it will be difficult to avoid contamination of rubber or plastic compounds, so it is preferably 65% or more, particularly 70% or more.
本発明カーボンブラックにおいて比着色力がＩＡ ＋
２０で算出する値を上回る大きな値になると配合物への
分散性が低下するので不適当である。The specific tinting strength of the carbon black of the present invention is IA +
If the value exceeds the value calculated in 20, the dispersibility in the formulation will decrease, which is inappropriate.
本発明の分散性にすぐれたカーボンブラックは、特に柔
軟性について要求される屈曲亀裂発生試験の屈曲回数を
格段に向上することができるが、Ｓ値をあまり大きくす
るとゴム等への配合の場合に補強性を低下する傾向にあ
るので、望ましくは０．３５以下、さらに望ましくは０
．３０以下とするのが本発明において好適である。The highly dispersible carbon black of the present invention can significantly improve the number of bends in the flex crack initiation test, which is particularly required for flexibility, but if the S value is too large, it may be difficult to incorporate into rubber etc. Since it tends to reduce reinforcing properties, it is preferably 0.35 or less, more preferably 0.
．． In the present invention, it is preferable that it is 30 or less.
本発明にかかるカーボンブラックの物理化学特性は次の
ようにして測定される。The physicochemical properties of the carbon black according to the present invention are measured as follows.
（１）よう素吸着量
ＪＩＳ Ｋ ６２２１（１９３２）６・１・１で測定さ
れる。(1) Amount of iodine adsorption Measured according to JIS K 6221 (1932) 6.1.1.
（２） ＤＢＰ吸油量Ａ法（機械法）
ＪＩＳ Ｋ ６２２１（１９８２）６・１・２で測定さ
れる。(2) DBP oil absorption A method (mechanical method) Measured according to JIS K 6221 (1982) 6.1.2.
（３）比着色力
ＪＩＳ Ｋ ６２２１（１９８２）６・ｌ・３で測定さ
れる。(3) Specific coloring power Measured according to JIS K 6221 (1982) 6.l.3.
（４）トルエン着色透過度
ＪＩＳ Ｋ ６２２１（１９８２）６・１・４で測定さ
れる。(4) Toluene color transmittance Measured according to JIS K 6221 (1982) 6.1.4.
（５）沈降分析によるカーボンブラック凝集体サイズ分
析法で測定される。(5) Determined by carbon black aggregate size analysis method using sedimentation analysis.
使用機器
Ｄｉｓｋ Ｃｅｎｔｒｉｆｕｇｅ（Ｐｈｏｔｏ ｓｅｄ
ｉｍｅｎｔｏｎ＋ｅｔｅｒ）（ＤＣＦ）（英） Ｊｏｙ
ｃａ Ｌｏｅｂ１社製
測定法
若干の界面活性剤を加えた３０％メタノール水溶液中に
、０．０２〜０．０６重量％のカーボンブラックを加え
、超音波処理を施して完全に分散せしめる。２５ｖ／ｖ
％グリセリン水溶液の沈降液（スピン液）２０〜３０−
を性態した回転ディスク（ｄｉｓｋ）の回転数を６００
０ｒｐ＋ｉとし、上記分散液０．０２〜０゜０３−を性
態する。Equipment used: Disk Centrifuge (Photo sed)
imenton+eter) (DCF) (English) Joy
Measurement method manufactured by ca Loeb 1 0.02 to 0.06% by weight of carbon black is added to a 30% methanol aqueous solution containing some surfactant and completely dispersed by ultrasonication. 25v/v
% glycerin aqueous solution sedimentation solution (spin solution) 20-30-
The rotation speed of the rotating disk (disk) is 600.
0rp+i, and the above dispersion is 0.02 to 0°03-.
分散液の性態と同時に記録計を動作せしめ、回転ディス
クの外周近傍の一定点を沈降によって通過するカーボン
ブラックアクリゲートの量を光学的に測定して、その量
を時間に対するヒストグラムとして記録する。A recorder is operated at the same time as the properties of the dispersion liquid, and the amount of carbon black acrylate that passes through a certain point near the outer periphery of the rotating disk due to sedimentation is optically measured, and the amount is recorded as a histogram against time.
沈降時間を、下記の式（ストークスの式の一般型）によ
りストークス相当径に換算し、力−ボンブラックアグリ
ゲートのストークス相当径とその頻度のヒストグラムを
得る。The sedimentation time is converted into a Stokes equivalent diameter using the following formula (general form of Stokes' equation) to obtain a histogram of the Stokes equivalent diameter of the force-bomb black aggregate and its frequency.
ｄ＝−（１）
式（１）において、ｄは沈降開始後の時間ｔで回転ディ
スクの光学的測定点を通過するカーボンブラックアクリ
ゲートのストークス相当径である。d=-(1) In equation (1), d is the Stokes equivalent diameter of the carbon black acrylate that passes through the optical measurement point of the rotating disk at time t after the start of sedimentation.
定数には、測定時のスピン液の量、粘度およびカーボン
ブラックとの密度差（カーボンブラックの真密度を１
、１１６ｇ／ ｍｌとする）、さらに回転ディスクの回
転数によって決定せられる定数である０例えば、スピン
液として２５Ｖ／Ｖ％グリセリン水溶液２２．５１を用
い、測定温度２０℃でディスク回転数６０００ｒｐ＋ｍ
とした場合のに値は７５２．０となり、ｄはｎ＋ｓ、
ｔは分で表示される。The constants include the amount of spin liquid at the time of measurement, the viscosity, and the density difference with carbon black (the true density of carbon black is 1
, 116 g/ml), and a constant determined by the rotational speed of the rotating disk.
In this case, the value is 752.0, and d is n+s,
t is expressed in minutes.
ＤｓｔおよびＳの定義
上記測定操作によって得られるアグリゲートのストーク
ス相当径のヒストグラムにおいて、最多頻度（実際には
、光学的測定を行なっているので最大吸光度である）を
与えるストークス相当径をＤｓｔ（Ｍｏｄｅ）と称し、
カーボンブラックアクリゲートの平均的大きさの目安と
する。Definition of Dst and S In the histogram of the Stokes equivalent diameter of the aggregate obtained by the above measurement operation, the Stokes equivalent diameter that gives the highest frequency (actually, it is the maximum absorbance because optical measurement is performed) is defined as Dst (Mode ),
Use this as a guideline for the average size of carbon black acrylate.
また、当該ヒストグラムにおいて、Ｄｓｔの示す頻度（
吸光度）の二分の−の頻度（吸光度）を示し、かつＤｓ
ｔよりも大なるストークス相当径を吋。とじたとき、ア
クリゲートサイズ分布指数Ｓは、
Ｓ ＝ ０．８４９３２ Ｘ １２ｏｇ（ＤＦｏ／Ｄｓ
ｔ）で定義される。これは、比較的大きなアクリゲート
サイズの分布広さの目安となる。In addition, in the histogram, the frequency (
Ds
The Stokes equivalent diameter is larger than t. When closed, the acrylate size distribution index S is: S = 0.84932 x 12og (DFo/Ds
t). This is a measure of the distribution width of relatively large acrylate sizes.
［実 施 例コ 以下に実施例を示し、本発明をさらに詳しく説明する。[Implementation example] EXAMPLES The present invention will be explained in more detail with reference to Examples below.
［製造例］
特公昭４９−４５０７５号公報記載の円筒型製造炉と同
様な構造の第１図に示したオイルファーネス炉（直径６
００ｎｙａ、長さ５０００ｎｗｍ）の炉頭部中心軸方向
から炉内に原料油噴霧ノズル１を挿入設置し、炉の接線
方向に上下一対に設けられた第１空気孔グループＡ、第
２空気孔グループＢならびに第３空気孔グループＣより
適宜の空気を導入し、各空気孔グループからの導入空気
量ならびに原料油供給量を変化することにより、物理化
学特性値の異なるサーマルタイプ・ファーネスカーボン
ブラックを製造した。なお、ＤＢＰＡの制御については
通常の調整剤を適宜利用した。[Production Example] The oil furnace shown in Fig. 1 (diameter 6
The raw material oil spray nozzle 1 is inserted into the furnace from the central axis direction of the furnace head with a length of 5,000 nwm), and a first air hole group A and a second air hole group are provided in a pair of upper and lower air holes in the tangential direction of the furnace. By introducing appropriate air from B and the third air hole group C and changing the amount of air introduced from each air hole group and the amount of feedstock oil supplied, thermal type furnace carbon black with different physicochemical property values is manufactured. did. Note that for the control of DBPA, a common regulator was used as appropriate.
使用原料油の性状を表−４に示し、製造したカーボンブ
ラックの製造条件と物理化学特性を表−５にそれぞれ示
した。The properties of the raw material oil used are shown in Table 4, and the manufacturing conditions and physicochemical properties of the produced carbon black are shown in Table 5.
表−４
（以下余白）
［ゴム配合例コ
表−５に示したカーボンブラックを表−６に示す配合割
合でゴムに配合し、１４５℃で３０分間加硫してゴム特
性を測定した。ゴム特性をとりまとめて表−７に示した
。Table 4 (blank below) [Rubber compounding example] The carbon black shown in Table 5 was compounded into rubber at the compounding ratio shown in Table 6, and the rubber properties were measured by vulcanization at 145° C. for 30 minutes. The rubber properties are summarized in Table 7.
表−６
配 合 物 重量部
Ｓ Ｂ Ｒ＃１５００ １００カーボンブ
ラツク ８０
アロマ系プロセスオイル ３０
ステアリン酸 ｌ
亜鉛華 ５
促進剤（ＣＺ） １．７５硫黄
１．５
［発明の効果］
製造例Ｎα１，２．３および４は本発明によるカーボン
ブラックであり、製造例Ｎｕ ５は前述した表−２のＸ
Ｃ−３１類似のカーボンブラックであり、比着色力は本
発明要件を満足するが、ＤＢＰＡならびにＳが本発明か
ら逸脱するカーボンブラックであって、カーボンブラッ
ク分散度が低位で屈曲亀裂発生性において劣る。Table-6 Compound Weight Part S B R#1500 100 Carbon Black 80 Aromatic Process Oil 30 Stearic Acid 1 Zinc White 5 Accelerator (CZ) 1.75 Sulfur
1.5 [Effect of the invention] Production examples Nα1, 2.3 and 4 are carbon blacks according to the present invention, and production example Nu 5 is the carbon black of the above-mentioned Table 2.
It is a carbon black similar to C-31, and the specific coloring strength satisfies the requirements of the present invention, but it is a carbon black in which DBPA and S deviate from the present invention, and the carbon black dispersion is low and the flex cracking resistance is poor. .
製造例Ｈａ ６のカーボンブラックはＤＢＰＡにおいて
、また製造例ＮＱ７のカーボンブラックはＳ値において
それぞれ本発明から逸脱するカーボンブラックである。The carbon black of production example Ha 6 deviates from the present invention in DBPA, and the carbon black of production example NQ7 deviates from the present invention in S value.
そして、Ｎａ ６力−ボンブラツク使用ゴム配合物は分
散度においては本発明カーボンブラックと同等であるが
、耐屈曲亀裂発生性において不満足なものとなる。また
、Ｎ１１７カーボンブラツクでは分散度ならびに耐屈曲
亀裂発生性の両者において不満足なものとなる。Although the rubber compound using Na6-bon black is equivalent to the carbon black of the present invention in terms of dispersion, it is unsatisfactory in terms of resistance to flex cracking. Furthermore, N117 carbon black is unsatisfactory in both its dispersion and resistance to flex cracking.
以上のように本発明によれば、分散度において優れ、耐
屈曲亀裂発生性においても格段に優れたカーボンブラッ
クが得られる。As described above, according to the present invention, carbon black which is excellent in dispersion degree and extremely excellent in flex cracking resistance can be obtained.
第１図は本発明カーボンブラックを製造するために使用
した一例の製造炉の縦断正面図である。
１・・・原料油噴霧ノズル
Ａ・・・第１空気孔グループ（２，２’）Ｂ・・・第２
空気孔グループ（３，３’）Ｃ・・・第３空気孔グルー
プ（４，４’）特許出願人 旭カーボン株式会社FIG. 1 is a longitudinal sectional front view of an example of a production furnace used to produce the carbon black of the present invention. 1... Raw oil spray nozzle A... 1st air hole group (2, 2') B... 2nd
Air hole group (3, 3') C...Third air hole group (4, 4') Patent applicant Asahi Carbon Co., Ltd.
Claims (1)
Ｐ吸油量（ＤＢＰＡ）が３５〜４５ｍｌ／１００ｇ、ト
ルエン着色透過度が６０％以上の領域にあるファーネス
カーボンブラックにおいて、比着色力が下記算出式−（
１）で得られる値以下であり、かつ下記算出式−（２）
で得られるアクリゲートサイズ分布指数（Ｓ）が０．２
０以上である特性を有するサーマルタイプファーネスカ
ーボンブラック。 算出式−（１）：比着色力＝ I Ａ＋２０ 算出式−（２）：Ｓ＝０．８４９３２×ｌｏｇ（Ｄ＾Ｌ
＿５＿０／Ｄｓｔ）ここで、Ｄｓｔは遠心沈降分析によ
るカーボンブラックアクリゲートのストークス相当径の
最多頻度値（Ｄｓｔ）であり、Ｄ＾Ｌ＿５＿０はＤｓｔ
よりも大きな側にあって、かつＤｓｔの１／２の頻度を
有するストークス相当径である。[Claims] 1. Iodine adsorption amount (IA) is 8 to 15 mg/g, DB
For furnace carbon black with a P oil absorption (DBPA) of 35 to 45 ml/100g and a toluene color transmittance of 60% or more, the specific coloring power is calculated using the following formula - (
It is less than or equal to the value obtained in 1), and the following calculation formula - (2)
The acrylate size distribution index (S) obtained with is 0.2
A thermal type furnace carbon black having a characteristic of 0 or more. Calculation formula - (1): Specific coloring power = I A + 20 Calculation formula - (2): S = 0.84932 x log (D^L
_5_0/Dst) Here, Dst is the most frequent value (Dst) of the Stokes equivalent diameter of carbon black acrylate determined by centrifugal sedimentation analysis, and D^L_5_0 is Dst
It is a Stokes equivalent diameter which is on the larger side and has a frequency of 1/2 of Dst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5273288A JP2708448B2 (en) | 1988-03-08 | 1988-03-08 | Thermal type furnace carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5273288A JP2708448B2 (en) | 1988-03-08 | 1988-03-08 | Thermal type furnace carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01229074A true JPH01229074A (en) | 1989-09-12 |
| JP2708448B2 JP2708448B2 (en) | 1998-02-04 |
Family
ID=12923100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5273288A Expired - Lifetime JP2708448B2 (en) | 1988-03-08 | 1988-03-08 | Thermal type furnace carbon black |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2708448B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04294374A (en) * | 1991-03-22 | 1992-10-19 | Tokai Rubber Ind Ltd | Fluorine rubber composition |
| WO1994005732A2 (en) | 1992-08-27 | 1994-03-17 | Cabot Corporation | Carbon blacks |
| WO1995023196A1 (en) * | 1994-02-25 | 1995-08-31 | Cabot Corporation | Carbon blacks |
| WO1995029953A1 (en) * | 1994-05-03 | 1995-11-09 | Cabot Corporation | Low permeabilitly rubber compositions |
| JPH08199105A (en) * | 1995-01-20 | 1996-08-06 | Orient Chem Ind Ltd | Black ink composition for writing board |
| US5688317A (en) * | 1992-08-27 | 1997-11-18 | Cabot Corporation | Carbon blacks |
| JP2011098995A (en) * | 2009-11-04 | 2011-05-19 | Asahi Carbon Kk | Soft furnace carbon black to be compounded into vibration-proof rubber, and vibration-proof rubber composition comprising the same |
| JP2011126953A (en) * | 2009-12-16 | 2011-06-30 | Asahi Carbon Kk | Soft furnace carbon black and rubber composition comprising the same |
| WO2014125992A1 (en) * | 2013-02-15 | 2014-08-21 | 三菱瓦斯化学株式会社 | Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring |
| CN114181546A (en) * | 2021-12-01 | 2022-03-15 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
-
1988
- 1988-03-08 JP JP5273288A patent/JP2708448B2/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04294374A (en) * | 1991-03-22 | 1992-10-19 | Tokai Rubber Ind Ltd | Fluorine rubber composition |
| EP0911371A1 (en) * | 1992-08-27 | 1999-04-28 | Cabot Corporation | Carbon blacks |
| WO1994005732A2 (en) | 1992-08-27 | 1994-03-17 | Cabot Corporation | Carbon blacks |
| WO1994005732A3 (en) * | 1992-08-27 | 1994-07-21 | Cabot Corp | Carbon blacks |
| KR100296566B1 (en) * | 1992-08-27 | 2001-12-01 | 마싸 앤 피네간 | Carbon black |
| US5688317A (en) * | 1992-08-27 | 1997-11-18 | Cabot Corporation | Carbon blacks |
| WO1995023196A1 (en) * | 1994-02-25 | 1995-08-31 | Cabot Corporation | Carbon blacks |
| WO1995029953A1 (en) * | 1994-05-03 | 1995-11-09 | Cabot Corporation | Low permeabilitly rubber compositions |
| CN1097609C (en) * | 1994-05-03 | 2003-01-01 | 卡伯特公司 | Low permeabilitly rubber compositions |
| JPH08199105A (en) * | 1995-01-20 | 1996-08-06 | Orient Chem Ind Ltd | Black ink composition for writing board |
| JP2011098995A (en) * | 2009-11-04 | 2011-05-19 | Asahi Carbon Kk | Soft furnace carbon black to be compounded into vibration-proof rubber, and vibration-proof rubber composition comprising the same |
| JP2011126953A (en) * | 2009-12-16 | 2011-06-30 | Asahi Carbon Kk | Soft furnace carbon black and rubber composition comprising the same |
| WO2014125992A1 (en) * | 2013-02-15 | 2014-08-21 | 三菱瓦斯化学株式会社 | Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring |
| US10546665B2 (en) | 2013-02-15 | 2020-01-28 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for high dielectric constant materials, molded article containing same, and master batch for coloring |
| CN114181546A (en) * | 2021-12-01 | 2022-03-15 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
| CN114181546B (en) * | 2021-12-01 | 2023-01-10 | 青岛黑猫炭黑科技有限责任公司 | Method and system for adjusting carbon black production process based on powdery carbon black sampling result |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2708448B2 (en) | 1998-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100377074B1 (en) | Low Permeability Rubber Composition | |
| EP0985713A2 (en) | Hard-type high-structure carbon black and rubber composition comprising same | |
| EP0799866A2 (en) | Carbon black and process for its manufacture | |
| JPH01229074A (en) | Thermal type furnace carbon black | |
| JP4452407B2 (en) | Carbon black, its production method and use | |
| US5100637A (en) | Carbon black for compounding into tire tread rubber | |
| US4786677A (en) | Rubber composition containing a carbon black particles having two modal diameters in the aggregate | |
| JP3782200B2 (en) | Carbon black for tire tread | |
| JPS6147759A (en) | Soft type carbon black | |
| DE60017668T2 (en) | Rubber composition and tire | |
| JPS62277446A (en) | Highly reinforcing furnace carbon black for rubber | |
| US20080095696A1 (en) | Carbon black for functional rubber component | |
| KR930002761B1 (en) | Cavan Black for Tire Treads | |
| JPH0689268B2 (en) | Soft carbon black | |
| JPH08259733A (en) | Rubber composition | |
| JPS62277443A (en) | Improved rubber composition | |
| JP2994157B2 (en) | Hard high structure carbon black | |
| JPS6134072A (en) | Reinforcing furnace carbon black | |
| JP3827256B2 (en) | Carbon black for compounding functional parts rubber and rubber composition for functional parts containing the same | |
| JP2506951B2 (en) | Soft system carbon black | |
| JPH0689266B2 (en) | Soft carbon black | |
| JP3283942B2 (en) | Rubber composition | |
| JP2945220B2 (en) | Hard high structure carbon black | |
| JPH0643522B2 (en) | Farnes car bomb rack for rubber reinforcement | |
| JPH0693136A (en) | Rubber composition for tire tread |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071017 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081017 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081017 Year of fee payment: 11 |