JPH06157011A - Insoluble sulfur improved in high-temperature thermal stability and its production - Google Patents
Insoluble sulfur improved in high-temperature thermal stability and its productionInfo
- Publication number
- JPH06157011A JPH06157011A JP30725792A JP30725792A JPH06157011A JP H06157011 A JPH06157011 A JP H06157011A JP 30725792 A JP30725792 A JP 30725792A JP 30725792 A JP30725792 A JP 30725792A JP H06157011 A JPH06157011 A JP H06157011A
- Authority
- JP
- Japan
- Prior art keywords
- insoluble sulfur
- sulfur
- thermal stability
- rubber
- insoluble
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 94
- 239000011593 sulfur Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000007906 compression Methods 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 description 34
- 239000000047 product Substances 0.000 description 18
- 239000010734 process oil Substances 0.000 description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/12—Insoluble sulfur (mu-sulfur)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は流動性を改良した高温熱
安定性およびゴムへの分散性にすぐれた不溶性硫黄の製
造方法に関するものである。本発明の方法によって製造
された不溶性硫黄は、二硫化炭素をはじめとする全ての
溶剤に不溶であり、タイヤ製造工程においてゴムの加硫
剤として使用された場合、その製造工程でブルーミング
によるトラブルを防止することができることから特にス
チールラジアルタイヤの加硫剤として有用な物質であ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing insoluble sulfur having improved high temperature thermal stability with improved fluidity and excellent dispersibility in rubber. The insoluble sulfur produced by the method of the present invention is insoluble in all solvents including carbon disulfide, and when used as a vulcanizing agent for rubber in the tire manufacturing process, it causes troubles due to blooming in the manufacturing process. It is a substance that is particularly useful as a vulcanizing agent for steel radial tires because it can be prevented.
【０００２】[0002]
【従来の技術】不溶性硫黄は一般に高温の硫黄を急冷さ
せた時に生ずる高分子状の硫黄であり、古くから知られ
ているものである。近年、スチールラジアルタイヤの生
産量増加と共にその有用性が認識され、使用量も増加し
つつある。このように、工業的に有用な不溶性硫黄は、
通常、数十ミクロンあるいはそれ以下の微粒子からな
り、取扱い中に、粉塵が飛散しやすいことや静電気を帯
びやすく、作業上支障を来たすことが多かった。特に粉
塵爆発の危険性が大きく問題となっていた。2. Description of the Related Art Insoluble sulfur is a polymeric sulfur that is generally produced when high temperature sulfur is rapidly cooled and has been known for a long time. In recent years, the usefulness of the steel radial tires has been recognized as the production amount of the steel radial tires has increased, and the usage amount thereof has been increasing. In this way, industrially useful insoluble sulfur is
Usually, it is composed of fine particles of several tens of microns or less, and during handling, it is easy for dust to scatter and to be charged with static electricity, which often causes a trouble in work. Especially, the danger of dust explosion was a big problem.
【０００３】このような障害を防止するため、ゴム用の
プロセスオイルを硫黄粉末に対して一定量混合した製品
が開発されている。この処理により、静電気の発生はあ
る程度抑えられるが、粉塵の飛散防止に対してはまだ十
分ではなく、また流動性に対しても改善されていない。
従って、タイヤ製造工程において配管や容器の器壁に硫
黄の粉末が付着してトラブルの大きな原因となってい
た。In order to prevent such troubles, products have been developed in which a certain amount of process oil for rubber is mixed with sulfur powder. By this treatment, the generation of static electricity can be suppressed to some extent, but it is still not sufficient to prevent the scattering of dust, and the fluidity has not been improved.
Therefore, in the tire manufacturing process, sulfur powder adheres to the walls of pipes and containers, which is a major cause of trouble.
【０００４】これらの問題点を解決するために、例え
ば、特公平４−２０８４４号には不溶性硫黄をゴムプロ
セスオイルと共に、特開平４−２１９３０５号にはゴム
プロセスオイルおよびその他の有機溶剤と共に高速混合
機で混合して造粒物を製造する方法が提案されている。
しかしながら、これらの方法により製造された不溶性硫
黄は確かに流動性は改善され、ゴムへの分散性にも問題
はないものの、不溶性硫黄の最も重要な特性である高温
熱安定性が損なわれるという欠点があった。このように
高温熱安定性の損なわれた不溶性硫黄はタイヤ製造工程
においてブルーミングトラブルを引き起こし、ゴムとス
チールの間の接着性が低下するという重大な問題を引き
起こす。In order to solve these problems, for example, Japanese Patent Publication No. 4-20844 discloses high-speed mixing of insoluble sulfur with rubber process oil, and JP-A-4-219305 discloses high speed mixing with rubber process oil and other organic solvents. A method for producing a granulated product by mixing with a machine has been proposed.
However, although the insoluble sulfur produced by these methods certainly has improved fluidity and has no problem in dispersibility in rubber, it has the drawback of impairing the high temperature thermal stability, which is the most important property of insoluble sulfur. was there. Thus, the insoluble sulfur having impaired high temperature thermal stability causes blooming troubles in the tire manufacturing process, and causes a serious problem that the adhesion between rubber and steel is deteriorated.
【０００５】従って、従来、高温熱安定性に優れ、同時
に流動性及び分散性に優れた成形された不溶性硫黄を製
造することはできなかった。Therefore, conventionally, it has not been possible to produce a molded insoluble sulfur which is excellent in high temperature thermal stability and is also excellent in fluidity and dispersibility.
【０００６】[0006]
【発明が解決しようとする課題】従って本発明は、高温
熱安定性およびゴムへの分散性にすぐれ、しかも流動性
の改善された不溶性硫黄の製造方法を提供するものであ
る。Accordingly, the present invention provides a method for producing insoluble sulfur which has excellent high temperature heat stability and dispersibility in rubber and which has improved fluidity.
【０００７】[0007]
【課題を解決するための手段】本発明者等は上記した欠
点を克服して、高温熱安定性およびゴムへの分散性にす
ぐれ、流動性の改善された不溶性硫黄を開発すべく種々
検討した結果、全硫黄中の不溶性硫黄分が９０％以上で
ある硫黄組成物をプレス式圧縮造粒装置で成形し、目開
きが０．２〜１．０mmの篩で処理し、残存する微粉を除
去することにより、圧潰強度が１０〜２０ｇの範囲にな
るように成形された不溶性硫黄は流動性およびゴムへの
分散性が同時に改善され、しかも驚くべきことに不溶性
硫黄の最も重要な性質である高温熱安定性が全く損なわ
れることがなく、従ってこの不溶性硫黄を用いたゴム組
成物のブルーミング性には全く問題が生じないというこ
とを見い出し本発明に到達した。ここで、高温熱安定性
は、不溶性硫黄残存率により表わすことができ、本発明
によれば、不溶性硫黄残存率が７０％以上の場合に十分
な高温熱安定性が得られる。DISCLOSURE OF THE INVENTION The present inventors have made various studies to overcome the above-mentioned drawbacks and develop an insoluble sulfur having excellent high temperature thermal stability and dispersibility in rubber and improved fluidity. As a result, a sulfur composition having an insoluble sulfur content of 90% or more in the total sulfur was molded by a press-type compression granulator and treated with a sieve having an opening of 0.2 to 1.0 mm to remove residual fine powder. By doing so, the insoluble sulfur molded so that the crush strength is in the range of 10 to 20 g has improved fluidity and dispersibility in rubber at the same time, and surprisingly, the most important property of the insoluble sulfur is high. The present inventors have found that the thermal stability is not impaired at all, and therefore the blooming properties of the rubber composition using this insoluble sulfur do not cause any problems. Here, the high temperature thermal stability can be represented by the insoluble sulfur residual rate, and according to the present invention, sufficient high temperature thermal stability can be obtained when the insoluble sulfur residual rate is 70% or more.
【０００８】従って本発明は、９０％以上の不溶性硫黄
を含有し、不溶性硫黄残存率が７０％以上であり、且つ
圧潰強度が１０〜２０ｇである成形された不溶性硫黄を
提供する。本発明はまた、全硫黄中の不溶性硫黄分が９
０％以上である硫黄組成物をプレス式圧縮造粒装置で成
形し、目開きが０．２〜１．０mmの篩で処理し、微粉を
除去することを特徴とする圧潰強度が１０〜２０ｇの範
囲になるように成形された不溶性硫黄の製造方法を提供
する。Accordingly, the present invention provides molded insoluble sulfur containing 90% or more of insoluble sulfur, residual insoluble sulfur of 70% or more, and crush strength of 10 to 20 g. The present invention also provides 9% total insoluble sulfur.
The sulfur composition of 0% or more is molded by a press-type compression granulator, treated with a sieve having an opening of 0.2 to 1.0 mm, and fine powder is removed to obtain a crushing strength of 10 to 20 g. There is provided a method for producing insoluble sulfur molded so as to fall within the range.
【０００９】[0009]
【具体的な説明】本発明の成形された不溶性硫黄は、高
い高温熱安定性、良好な分散性及び良好な流動性を共に
有することを特徴としている。ここで、高温熱安定性と
は、熱に暴露された場合に不溶性硫黄が可溶化しない性
質を意味し、不溶性硫黄残存率として表わすことができ
る。ここで不溶性硫黄とは、硫黄粉末を二硫化炭素で抽
出して二硫化炭素に溶解した硫黄を除去した後、残る硫
黄である。被験硫黄サンプル中の不溶性硫黄の含有率を
求めるには、所定量、例えば５ｇの硫黄サンプルを１０
０mlの二硫化炭素により２０℃にて５分間抽出した後、
溶解しなかった硫黄の乾燥重量を求め、これを被験サン
プルの乾燥重量で除すことにより得られる。すなわち、
次の式により得られる。Detailed Description The shaped insoluble sulfur of the present invention is characterized by having both high high temperature thermal stability, good dispersibility and good flowability. Here, the high temperature thermal stability means a property that insoluble sulfur does not solubilize when exposed to heat, and can be expressed as a residual ratio of insoluble sulfur. Here, the insoluble sulfur is sulfur that remains after the sulfur powder is extracted with carbon disulfide to remove the sulfur dissolved in the carbon disulfide. In order to determine the content of insoluble sulfur in the test sulfur sample, a predetermined amount, for example, 5 g of sulfur sample
After extraction with 0 ml of carbon disulfide for 5 minutes at 20 ° C,
It is obtained by determining the dry weight of undissolved sulfur and dividing this by the dry weight of the test sample. That is,
It is obtained by the following formula.
【００１０】[0010]
【数１】 [Equation 1]
【００１１】また、不溶性硫黄残存率は、所定量の被験
サンプル中の不溶性硫黄の重量（ｇ）を前記の測定法に
より求め、他方同じ所定量の被験サンプルを１１０℃に
加熱されたパラフィンオイルに投入して１５分間加熱し
た後、前記と同じ方法により不溶性硫黄の重量（ｇ）を
求め、次の式により不溶性硫黄残存率を計算する。The insoluble sulfur residual ratio is obtained by determining the weight (g) of insoluble sulfur in a predetermined amount of the test sample by the above-mentioned measuring method, while the same predetermined amount of the test sample is added to paraffin oil heated to 110 ° C. After charging and heating for 15 minutes, the weight (g) of insoluble sulfur is obtained by the same method as described above, and the residual ratio of insoluble sulfur is calculated by the following formula.
【００１２】[0012]
【数２】 [Equation 2]
【００１３】本発明によれば、不溶性硫黄残存率が７０
％以上である場合に十分な高温熱安定性が得られる。な
お、これは不溶性硫黄含有量が９０％以上であることを
前提としている。本発明の成形された不溶性硫黄は、上
記のごとき高温熱安定性を有すると共に、良好な流動性
とゴムへの良好な分散性を有する。流動性は、硫黄を所
定の強度を有する粒状体にすることにより得られるが、
この粉状体は使用に際して崩壊してゴム中に均一に分散
しなければならない。従って、良好な流動性と良好な分
散性を同時に得るには、粒状体が所定の範囲の硬度を有
しなければならない。本発明によれば、圧潰強度が１０
〜２０ｇの場合に、良好な流動性と良好な分散性とが同
時に得られる。圧潰強度は、上皿天秤にサンプル粒子１
粒を置き、先端部の平らなガラス棒で押圧し、サンプル
粒子が破壊された時のグラム数で表わす。この測定をラ
ンダムに取り出した１２粒（１２回）について行い、最
高値と最低値を除いた１０回の平均値で圧潰強度を表
す。According to the present invention, the residual ratio of insoluble sulfur is 70.
When it is at least%, sufficient high temperature thermal stability can be obtained. This is based on the premise that the insoluble sulfur content is 90% or more. The molded insoluble sulfur of the present invention has high temperature thermal stability as described above, and also has good fluidity and good dispersibility in rubber. Flowability is obtained by forming sulfur into a granular material having a predetermined strength,
This powder must disintegrate during use and must be dispersed uniformly in the rubber. Therefore, in order to obtain good flowability and good dispersibility at the same time, the granular material must have a hardness within a predetermined range. According to the present invention, the crush strength is 10
In the case of -20 g, good fluidity and good dispersibility can be obtained at the same time. The crushing strength is 1
Grains are placed, pressed with a flat glass rod at the tip, and expressed in grams when the sample particles are broken. This measurement is performed on 12 particles (12 times) taken out at random, and the crush strength is expressed by the average value of 10 times excluding the highest value and the lowest value.
【００１４】圧潰強度が１０ｇより小さい場合は、成形
品の粒子強度が弱く、該製品の貯蔵、運搬等の過程で成
形品の破壊が起こり、原型である粉末に戻ってしまい、
本発明の目的を達成できない。また、２０ｇを越える場
合は、粒子強度が大きすぎ、この製品を用いてゴム組成
物を作った場合、ゴム混練中に原型の数十ミクロンまで
戻らず、ゴム中に硫黄の固まりが残存し、いわゆる分散
不良を生ずる。このようなゴム組成物を加硫した場合、
ゴムの機械的強度の異常点が発生し、物性低下の原因と
なり好ましくない。If the crushing strength is less than 10 g, the particle strength of the molded product is weak and the molded product is destroyed during the storage, transportation, etc. of the product, and the powder returns to the original powder.
The object of the present invention cannot be achieved. Further, when it exceeds 20 g, the particle strength is too large, and when a rubber composition is made using this product, the prototype does not return to several tens of microns during rubber kneading, and a lump of sulfur remains in the rubber, So-called poor dispersion occurs. When vulcanizing such a rubber composition,
An abnormal point of the mechanical strength of the rubber occurs, which causes deterioration of physical properties, which is not preferable.
【００１５】流動性は次に示すステンレス缶への硫黄組
成物の付着性で評価する。即ち、ステンレス製の円筒容
器（７０mmφ×９０mmH ）に試料５０ｇをとり、密閉し
た後、この容器を振とう機に取り付けて、振動幅４０m
m、振動数３００往復／分で１０分間振とうさせた後、
該容器を静かに振とう機から取り外し、蓋をはずし、水
平から４５°傾け容器を１回転させて試料を自然排出さ
せ、容器に付着残存した試料の重量を測定し、次式によ
り付着率を求める。この値が小さいほど流動性が良好な
ことを示す。The fluidity is evaluated by the following adhesion of the sulfur composition to a stainless steel can. That is, 50 g of a sample is placed in a cylindrical container (70 mmφ × 90 mmH) made of stainless steel, and after sealing the container, the container is attached to a shaker and the vibration width is 40 m.
After shaking for 10 minutes at a frequency of 300 reciprocations / minute,
Gently remove the container from the shaker, remove the lid, tilt the container 45 ° from the horizontal and rotate the container once to allow the sample to spontaneously discharge, and measure the weight of the sample remaining on the container. Ask. The smaller this value is, the better the fluidity is.
【００１６】[0016]
【数３】 [Equation 3]
【００１７】本発明においては、付着率が３０％以下で
あることが望ましい。ゴム組成物中での硫黄組成物の分
散性は次の様にして測定する。天然ゴム１００重量部あ
たり１．０重量部の酸化鉄を含んだマスターバッチを用
い、天然ゴム１００部あたり３０部の硫黄組成物を、表
面温度５０℃の加熱２本ロール上でゴム中に混練り分散
させる。この混練りゴムを分出し、シートから５０×３
０×５mmの小片を８枚切り出し、それらを重ねて５０×
３０×４０mmのブロックを作る。このブロックをカッタ
ーで切断し、その横断面積約２０cm2 の中に分散不良ま
たは凝集を起こしている直径０．１mm以上の硫黄粒子数
を数えた後、硫黄の分散性指数を求める。なお、上記分
散性指数は、成形前の硫黄組成物を用いた場合の直径
０．１mm以上の硫黄粒子数を１００として対比されるも
のであり、この値が小さいほど分散性が良好なことを示
す。In the present invention, the adhesion rate is preferably 30% or less. The dispersibility of the sulfur composition in the rubber composition is measured as follows. Using a masterbatch containing 1.0 part by weight of iron oxide per 100 parts by weight of natural rubber, 30 parts by weight of the sulfur composition per 100 parts by weight of natural rubber were mixed into the rubber on a two-roll roll heated at a surface temperature of 50 ° C. Knead and disperse. This kneaded rubber is dispensed and 50 × 3 from the sheet
Cut out 8 pieces of 0x5mm and stack them 50x
Make a 30 x 40 mm block. This block is cut with a cutter, and the number of sulfur particles having a diameter of 0.1 mm or more that are poorly dispersed or agglomerated in the cross-sectional area of about 20 cm 2 is counted, and then the dispersibility index of sulfur is determined. The above-mentioned dispersibility index is compared with the number of sulfur particles having a diameter of 0.1 mm or more in the case of using the sulfur composition before molding as 100, and the smaller this value is, the better the dispersibility is. Show.
【００１８】上記のごとき性質を有する成形された不溶
性硫黄は、全硫黄中の不溶性硫黄分が９０％以上である
硫黄組成物を、プレス式圧縮造粒装置で成形し、次に目
開きが０．２〜１．０mmの篩で処理して、通過する微粒
を除去することにより得られる。本発明に用いられる不
溶性硫黄は高温の気体または液体状の硫黄を急冷するこ
とによって得られるものであって全硫黄分中の不溶性硫
黄分の割合が９０％以上のものであればどのようなもの
でもよい。全硫黄分中の不溶性硫黄分の割合が９０％よ
り小さい場合はゴム組成物のブルーミングを生じさせな
いという本発明の目的が達成されないため好ましくな
い。ゴム用プロセスオイルおよび／またはその他の添加
剤を含んでいても本発明の方法に使用できる。The molded insoluble sulfur having the above-mentioned properties is formed by molding a sulfur composition having a total sulfur content of 90% or more with a press-type compression granulator, and then opening the mesh to 0. It is obtained by treating with a sieve of 2 to 1.0 mm to remove passing fine particles. The insoluble sulfur used in the present invention is obtained by rapidly cooling high-temperature gas or liquid sulfur, and any insoluble sulfur content in the total sulfur content is 90% or more. But it's okay. If the proportion of the insoluble sulfur content in the total sulfur content is less than 90%, the object of the present invention of not causing blooming of the rubber composition is not achieved, which is not preferable. Included with the process oil for rubber and / or other additives can be used in the process of the present invention.
【００１９】プレス式の圧縮造粒装置としては、例え
ば、ローラーコンパクター（ターボ工業社製）、ローラ
コンパクター（栗本鐵工所社製）、サニケット（太陽鉄
工社製）等のロールプレス式圧縮造粒装置が好ましく用
いられる。該装置のロール間のクリアランス、ロール
圧、ロールの回転数等を調節することにより、圧潰強度
が１０〜２０ｇの成形物を形成する。Examples of the press-type compression granulator include roll compactors (made by Turbo Kogyo Co., Ltd.), roller compactors (made by Kurimoto Iron Works Co., Ltd.), sanicket (made by Taiyo Iron Works Co., Ltd.) and the like. A device is preferably used. A molded product having a crushing strength of 10 to 20 g is formed by adjusting the clearance between rolls of the apparatus, the roll pressure, the number of rotations of the roll, and the like.
【００２０】このようにして成形された中間品は次に篩
工程にかけられるが、この場合目開き０．２〜１．０mm
のメッシュを備えた振動式の篩が好ましく用いられる。
この工程の目的は圧縮造粒工程で発生した、成形不十分
の粉末を除去して本発明の効果をより大きくするための
ものである。目開きが０．２mmより小さい場合は、篩目
に粉末が詰まり作業がスムースに進行しない。また１．
０mmより大きい場合は、折角成形された成形品まで除去
されてしまいロスが大きくなり好ましくない。該工程で
篩目を通過して除去された粉末状の硫黄組成物はリサイ
クルして、再び圧縮造粒工程に使用することができるこ
とは言うまでもない。The intermediate product thus formed is then subjected to a sieving process, in which case the mesh size is 0.2 to 1.0 mm.
A vibrating screen equipped with the above mesh is preferably used.
The purpose of this step is to remove the insufficiently shaped powder generated in the compression granulation step to enhance the effect of the present invention. If the opening is smaller than 0.2 mm, the powder is clogged in the sieve mesh and the work does not proceed smoothly. Also 1.
If it is larger than 0 mm, even a molded product formed by bending is removed, resulting in a large loss, which is not preferable. It goes without saying that the powdery sulfur composition removed by passing through the sieve mesh in this step can be recycled and used again in the compression granulation step.
【００２１】[0021]
【実施例】次に、実施例により本発明をさらに具体的に
説明する。実施例 １． 全硫黄分中の不溶性硫黄分が９７．０％の
粉末状硫黄８０部およびナフテン系ゴム用プロセスオイ
ル２０部から成る不溶性硫黄組成物の高温熱安定性の評
価の目安である不溶性硫黄残存率（以下、ＨＴＳと略す
る。）は７５．０％、流動性評価の目安である付着率
（以下、付着率と略する。）は６０％であった。EXAMPLES Next, the present invention will be described more specifically by way of examples. Example 1. The insoluble sulfur residual ratio, which is a standard for evaluating the high temperature thermal stability of an insoluble sulfur composition consisting of 80 parts of powdery sulfur having 97.0% of total sulfur content and 20 parts of process oil for naphthenic rubber ( In the following, abbreviated as HTS) was 75.0%, and the adherence rate (hereinafter abbreviated as adherence rate), which is a measure of fluidity evaluation, was 60%.
【００２２】該不溶性硫黄組成物をロール間のクリアラ
ンス２．０mm、ロール間圧４kg／cm 2 、ロール回転数１
０rpm に調整された圧縮造粒装置のロール間に供給し、
成形した。次いで、目開き０．５mmの篩を備えた振動篩
装置を通過させ未成形の粉末を除去した。得られた造粒
物の圧潰強度は１８．４ｇ、付着率は１５％、ＨＴＳは
７５．０％、分散性指数は９４であった。The insoluble sulfur composition is applied to a clearer between rolls.
2.0 mm, pressure between rolls 4 kg / cm 2, Roll speed 1
Feeding between the rolls of a compression granulator adjusted to 0 rpm,
Molded. Then, a vibrating sieve equipped with a sieve having an opening of 0.5 mm.
It was passed through the device to remove unformed powder. Granulation obtained
The crush strength of the product is 18.4g, the adhesion rate is 15%, HTS is
The dispersibility index was 75.0% and 94.
【００２３】実施例 ２．実施例１において、粉末状硫
黄１００部、ナフテン系ゴム用プロセスオイル０部とし
た以外は実施例１と同様の操作を行って得られた結果は
次のようであった。成形前の不溶性硫黄組成物のＨＴＳ
は７５．０％、付着率は９３％であり、成形後の造粒物
の圧潰強度は１３．８ｇ、付着率は２８％、ＨＴＳは７
５％、分散性指数は９８であった。 Example 2. The results obtained by carrying out the same operations as in Example 1 except that 100 parts of powdered sulfur and 0 part of process oil for naphthenic rubber were used in Example 1, were as follows. HTS of insoluble sulfur composition before molding
Is 75.0%, the adhesion rate is 93%, the crushing strength of the granulated product after molding is 13.8 g, the adhesion rate is 28%, and the HTS is 7.
5%, dispersibility index was 98.
【００２４】実施例 ３．実施例１において、粉末状硫
黄９０部、ナフテン系ゴム用プロセスオイル１０部とし
た以外は実施例１と同様の操作を行って得られた結果は
次のようであった。成形前の不溶性硫黄組成物のＨＴＳ
は７５．０％、付着率は８０％であり、成形後の造粒物
の圧潰強度は１９．６ｇ、付着率は１８％、ＨＴＳは７
５％、分散性指数は９５であった。 Example 3. The results obtained by performing the same operations as in Example 1 except that 90 parts of powdered sulfur and 10 parts of process oil for naphthenic rubber were used in Example 1, were as follows. HTS of insoluble sulfur composition before molding
Is 75.0%, the adhesion rate is 80%, the crushing strength of the granulated product after molding is 19.6 g, the adhesion rate is 18%, and the HTS is 7%.
5% and dispersibility index was 95.
【００２５】比較例 １．実施例１において用いた粉末
状硫黄２０kgナフテン系ゴム用プロセスオイル５kgを全
容量８０リットルの高速攪拌混合機に入れ、２５００rp
m で攪拌させながら、ｎ−ヘキサン６リットルを添加し
て５分間攪拌を続けた。得られた造粒物を６０℃に設定
された棚段式乾燥器に入れ、２時間乾燥し、ｎ−ヘキサ
ンを揮散させた。この造粒物のＨＴＳを測定したとこ
ろ、６１％であり著しく高温熱安定性が損なわれてい
た。またこの造粒物を使用して作られたゴム組成物には
著しいブルーミングが見られた。 Comparative Example 1. 20 kg of powdery sulfur used in Example 1 and 5 kg of process oil for naphthenic rubber were placed in a high-speed stirring mixer having a total volume of 80 liters and 2500 rp.
While stirring at m, 6 liters of n-hexane was added and stirring was continued for 5 minutes. The obtained granulated product was placed in a tray dryer set at 60 ° C. and dried for 2 hours to evaporate n-hexane. The HTS of this granulated product was measured and found to be 61%, which markedly impaired the high temperature thermal stability. Further, remarkable blooming was observed in the rubber composition produced by using this granulated product.
【００２６】比較例 ２．実施例１において用いた粉末
状硫黄２０kgナフテン系ゴム用プロセスオイル２．２kg
を全容量８０リットルの高速攪拌混合機に入れ、２５０
０rpm で攪拌させながら、イソプロパノール８．６リッ
トルを添加して５分間攪拌を続けた。得られた造粒物を
６０℃に設定された棚段式乾燥器に入れ、２時間乾燥
し、イソプロパノールを揮散させた。この造粒物のＨＴ
Ｓを測定したところ、５８％であり著しく高温熱安定性
が損なわれていた。またこの造粒物を使用して作られた
ゴム組成物には著しいブルーミングが見られた。 Comparative Example 2. Powdered sulfur used in Example 1 20 kg Process oil for naphthenic rubber 2.2 kg
Into a high speed stirring mixer with a total volume of 80 liters and
With stirring at 0 rpm, 8.6 liters of isopropanol was added and stirring was continued for 5 minutes. The obtained granulated product was placed in a tray dryer set at 60 ° C. and dried for 2 hours to volatilize isopropanol. HT of this granule
When S was measured, it was 58%, which markedly impaired the high temperature thermal stability. Further, remarkable blooming was observed in the rubber composition produced by using this granulated product.
【００２７】比較例 ３．実施例１において用いた粉末
状硫黄２０kgナフテン系ゴム用プロセスオイル５kgを全
容量８０リットルの高速攪拌混合機に入れ、２５００rp
m で攪拌させながら１０分間攪拌を続けた。得られた造
粒物のＨＴＳを測定したところ、６３％であり著しく高
温熱安定性が損われていた。またこの造粒物を使用して
作られたゴム組成物には著しいブルーミングが見られ
た。 Comparative Example 3. 20 kg of powdery sulfur used in Example 1 and 5 kg of process oil for naphthenic rubber were placed in a high-speed stirring mixer having a total volume of 80 liters and 2500 rp.
Stirring was continued for 10 minutes while stirring at m 2. The HTS of the obtained granulated product was measured and found to be 63%, which markedly impaired the high temperature thermal stability. Further, remarkable blooming was observed in the rubber composition produced by using this granulated product.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年１月１８日[Submission date] January 18, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】本発明によれば、不溶性硫黄残存率が７０
％以上である場合に十分な高温熱安定性が得られる。な
お、これは不溶性硫黄含有量が９０％以上であることを
前提としている。本発明の成形された不溶性硫黄は、上
記のごとき高温熱安定性を有すると共に、良好な流動性
とゴムへの良好な分散性を有する。流動性は、硫黄を所
定の強度を有する粒状体にすることにより得られるが、
この粒状体は使用に際して崩壊してゴム中に均一に分散
しなければならない。従って、良好な流動性と良好な分
散性を同時に得るには、粒状体が所定の範囲の硬度を有
しなければならない。本発明によれば、圧潰強度が１０
〜２０ｇの場合に、良好な流動性と良好な分散性とが同
時に得られる。圧潰強度は、上皿天秤にサンプル粒子１
粒を置き、先端部の平らなガラス棒で押圧し、サンプル
粒子が破壊された時のグラム数で表わす。この測定をラ
ンダムに取り出した１２粒（１２回）について行い、最
高値と最低値を除いた１０回の平均値で圧潰強度を表
す。According to the present invention, the residual ratio of insoluble sulfur is 70.
When it is at least%, sufficient high temperature thermal stability can be obtained. This is based on the premise that the insoluble sulfur content is 90% or more. The molded insoluble sulfur of the present invention has high temperature thermal stability as described above, and also has good fluidity and good dispersibility in rubber. Flowability is obtained by forming sulfur into a granular material having a predetermined strength,
The grain-shaped body must disintegrate uniformly dispersed in the rubber in use. Therefore, in order to obtain good flowability and good dispersibility at the same time, the granular material must have a hardness within a predetermined range. According to the present invention, the crush strength is 10
In the case of -20 g, good fluidity and good dispersibility can be obtained at the same time. The crushing strength is 1
Grains are placed, pressed with a flat glass rod at the tip, and expressed in grams when the sample particles are broken. This measurement is performed on 12 particles (12 times) taken out at random, and the crush strength is expressed by the average value of 10 times excluding the highest value and the lowest value.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水本 敏之 茨城県鹿島郡波崎町大字砂山１番地 アク ゾ・カシマ株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshiyuki Mizumoto No.1 Sunayama, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Akzo Kashima Co., Ltd.
Claims (2)
性硫黄残存率が７０％以上であり且つ圧潰強度が１０〜
２０ｇである成形された不溶性硫黄。1. An insoluble sulfur content of 90% or more, a residual insoluble sulfur content of 70% or more, and a crush strength of 10 to 10.
20 g of shaped insoluble sulfur.
ある硫黄組成物をプレス式圧縮造粒装置で成形し、目開
きが０．２〜１．０mmの篩で処理し、微粉を除去するこ
とを特徴とする圧潰強度が１０〜２０ｇの範囲になるよ
うに成形された不溶性硫黄の製造方法。2. A sulfur composition having an insoluble sulfur content of 90% or more in total sulfur is molded by a press-type compression granulator and treated with a sieve having an opening of 0.2 to 1.0 mm to obtain fine powder. A method for producing insoluble sulfur molded to have a crushing strength of 10 to 20 g, which is characterized in that it is removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4307257A JP2619591B2 (en) | 1992-11-17 | 1992-11-17 | Insoluble sulfur having improved high-temperature thermal stability and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4307257A JP2619591B2 (en) | 1992-11-17 | 1992-11-17 | Insoluble sulfur having improved high-temperature thermal stability and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157011A true JPH06157011A (en) | 1994-06-03 |
| JP2619591B2 JP2619591B2 (en) | 1997-06-11 |
Family
ID=17966930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4307257A Expired - Fee Related JP2619591B2 (en) | 1992-11-17 | 1992-11-17 | Insoluble sulfur having improved high-temperature thermal stability and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619591B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572483A (en) * | 2017-01-16 | 2018-01-12 | 赵西营 | Technique that is a kind of while producing carbon disulfide, sulphur and insoluble sulfur |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS509755A (en) * | 1973-06-01 | 1975-01-31 | ||
| JPS5556003A (en) * | 1978-10-18 | 1980-04-24 | Courtaulds Ltd | Method of stabilizing insoluble sulfur |
| JPS5622336A (en) * | 1979-07-30 | 1981-03-02 | Stauffer Chemical Co | Oil treatment of insoluble sulfur |
| JPS62246810A (en) * | 1986-04-18 | 1987-10-28 | Shikoku Chem Corp | Production of oil-treated insoluble sulfur with improved fluidity |
| JPH04219305A (en) * | 1990-08-28 | 1992-08-10 | Shikoku Chem Corp | Production of granular insoluble sulfur having improved fluidity and rubber composition |
-
1992
- 1992-11-17 JP JP4307257A patent/JP2619591B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS509755A (en) * | 1973-06-01 | 1975-01-31 | ||
| JPS5556003A (en) * | 1978-10-18 | 1980-04-24 | Courtaulds Ltd | Method of stabilizing insoluble sulfur |
| JPS5622336A (en) * | 1979-07-30 | 1981-03-02 | Stauffer Chemical Co | Oil treatment of insoluble sulfur |
| JPS62246810A (en) * | 1986-04-18 | 1987-10-28 | Shikoku Chem Corp | Production of oil-treated insoluble sulfur with improved fluidity |
| JPH04219305A (en) * | 1990-08-28 | 1992-08-10 | Shikoku Chem Corp | Production of granular insoluble sulfur having improved fluidity and rubber composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107572483A (en) * | 2017-01-16 | 2018-01-12 | 赵西营 | Technique that is a kind of while producing carbon disulfide, sulphur and insoluble sulfur |
| CN107572483B (en) * | 2017-01-16 | 2020-04-21 | 赵西营 | Process for simultaneously producing carbon disulfide, sulfur and insoluble sulfur |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2619591B2 (en) | 1997-06-11 |
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