KR100356588B1 - Rubber vulcanizing agent composition controlling vulcanizing rate - Google Patents

Rubber vulcanizing agent composition controlling vulcanizing rate Download PDF

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KR100356588B1
KR100356588B1 KR1019950018919A KR19950018919A KR100356588B1 KR 100356588 B1 KR100356588 B1 KR 100356588B1 KR 1019950018919 A KR1019950018919 A KR 1019950018919A KR 19950018919 A KR19950018919 A KR 19950018919A KR 100356588 B1 KR100356588 B1 KR 100356588B1
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South Korea
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vulcanization
rubber
vulcanizing agent
vulcanizing
zinc oxide
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KR1019950018919A
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Korean (ko)
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KR960017690A (en
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안은경
최성신
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금호산업 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/26—Incorporating metal atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: Provided is a rubber vulcanizing agent composition controlling a vulcanizing rate by metal oxides having different bonding energies, which can prevent early vulcanization and non-vulcanization. CONSTITUTION: The rubber vulcanizing agent composition is produced by adding magnesium oxide and calcium oxide, as vulcanization delaying agents, having larger bonding energy than zinc oxide to a conventional vulcanizing agent comprising the zinc oxide and stearic acid or by adding magnesium stearate and calcium stearate to the zinc oxide except the stearic acid.

Description

가류속도를 조절하는 고무가류제 조성물Rubber vulcanizing agent to adjust the vulcanization rate

본 발명은 고무 가류공정에서 기존의 가류제인 산화아연과 스테아르산 외에 지연제로서 산화마그네슘과 산화칼슘을 함께 혼합한 가류제를 사용하거나, 기존의 가류제 조성물중 산화아연에 마그네슘 스테아레이트와 칼슘스테아레이트를 첨가하여 고무의 가류속도를 조절하는 고무가류제 조성물에 관한 것이다.The present invention uses a vulcanizing agent mixed with magnesium oxide and calcium oxide together as a retardant in addition to the existing vulcanizing agents zinc oxide and stearic acid in the rubber vulcanization process, or magnesium stearate and calcium stearate in zinc oxide in the conventional vulcanizing agent composition A rubber vulcanizing agent composition is added to control the vulcanization rate of rubber by adding a rate.

현재 널리 사용되고 있는 황, 산화아연, 가류활성제 및 가류촉진제를 이용하여 가류하는 가류공정은 다음과 같다.The vulcanization process which is currently vulcanized using sulfur, zinc oxide, vulcanization activator and vulcanization accelerator which are widely used are as follows.

황 + 산화아연 + 가류활성제 + 가류촉진제 → 황화복합물 → 가류예비제 → 초기가류 → 가류완료Sulfur + zinc oxide + vulcanization activator + vulcanization accelerator → sulfide complex → vulcanizing agent → initial vulcanization → complete vulcanization

산화아연과 스테아르산(stearic acid)이 반응하여 아연스테아레이트를 형성하여 가류활성제로 작용한다. 아연스테아레이트는 가류촉진제 및 황 등과 반응하여 황화 복합물을 형성하고 이 복합물은 고무와 반응하여 가교결합을 함으로써 고무는 탄성을 갖게 된다.Zinc oxide reacts with stearic acid to form zinc stearate, acting as a vulcanizing activator. Zinc stearate reacts with a vulcanization accelerator, sulfur and the like to form a sulfide complex, and the complex reacts with the rubber to crosslink to make the rubber elastic.

그러나 산화아연은 결합에너지가 작기 때문에 조기가류(scorch)를 유발시키게 되고, 또 가류공정 후반까지 가류활성제로서 역할을 못한다.However, zinc oxide causes early scorch because of its low binding energy, and does not act as a vulcanizing activator until the second half of the vulcanization process.

따라서 본 발명에서는 가류제의 조성을 달리하여 가류속도를 조절하기 위한 것으로서 이를 상세히 설명하면 다음과 같다.Therefore, the present invention is to control the vulcanization rate by changing the composition of the vulcanizing agent as follows.

산화아연과 스테아르산으로 되는 기존의 가류제에 산화아연보다 결합에너지가 큰 산화마그네슘과 산화칼슘을 함께 첨가하거나, 기존의 가류제 조성물중 스테아르산을 제외한 산화아연에 마그네슘스테아레이트 칼슘스테아레이트를 함께 첨가한 가류제를 고무가류시에 첨가하면 가류공정의 속도를 적절하게 조절할 수 있다.Magnesium stearate and calcium stearate are added to zinc oxide except for stearic acid in the conventional vulcanizing agent. When the added vulcanizing agent is added during rubber vulcanization, the speed of the vulcanization process can be properly adjusted.

즉, 상기 각 물질으 결합에너지는 다음과 같다.That is, the binding energy of each material is as follows.

이상의 본원발명 가류제 조성물을 사용하여 고무를 가류하게 되면 산화마그네슘의 결합에너지가 산화칼슘보다 훨씬 작기 때문에 가류공정 초기에는 식(I)과 같이 진행될 것이다. 즉 산화마그네슘이 스테아르산과 반응하여 마그네슘스테아레이트를 만든 다음 산화아연과 반응하여 아연스테아레이트를 형성하여 가류활성제로서 작용하게 된다.When the rubber is vulcanized using the vulcanizing agent composition of the present invention, since the binding energy of magnesium oxide is much smaller than that of calcium oxide, it will proceed as shown in Formula (I) at the beginning of the vulcanization process. That is, magnesium oxide reacts with stearic acid to form magnesium stearate, and then reacts with zinc oxide to form zinc stearate to act as a vulcanizing activator.

여기에서 스테아르산을 첨가하지 않은 상태에서 산화아연에 기존의 화합물인 스테아르산 마그네슘을 직접 넣는 다면 (1)의 반응은 생략된 채 (1')의 반응이 직접 일어 나게 된다.Here, if magnesium stearate, which is an existing compound, is directly added to zinc oxide in the absence of stearic acid, the reaction of (1) is omitted and the reaction of (1 ') occurs directly.

가류공정 후기에는 결합에너지가 큰 산화칼슘과 스테아르산이 반응하여 칼슘스테아레이트를 형성한 후 다시 산화아연과 반응하여 아연스테아레이트가 가류활성제로서 작용케 하는 것이다.In the latter part of the vulcanization process, calcium oxide having a high binding energy and stearic acid react to form calcium stearate, and then react with zinc oxide to allow zinc stearate to act as a vulcanizing activator.

여기에서도 스테아르산이 첨가되지 않은 상태에서 산화아연에 기존의 화합물인 칼슘스테아레이트를 직접 넣는 다면 (2)의 반응은 생략되고 (2')의 반응이 직접 일어나게 된다.In this case, if the stearic acid is not added directly to the zinc oxide, calcium stearate, which is an existing compound, the reaction of (2) is omitted and the reaction of (2 ') occurs directly.

즉, 금속 산화물들간의 결합에너지 차에 의하여 가류활성제인 아연스테아레이트 양이 조절됨으로써 가류공정속도를 다단계로 조정하게 되는 것이다.That is, the amount of zinc stearate as a vulcanization activator is controlled by the difference in binding energy between metal oxides, thereby adjusting the vulcanization process speed in multiple stages.

이상과 같이 구성되는 본 발명 가류제조성물은 결합에너지가 다른 금속산화물에 의하여 가류속도를 조절할 수 있는 효과가 있고, 따라서 고무의 조기가류 및 미가류를 막을 수 있는 효과를 얻게 된다.The vulcanization composition of the present invention configured as described above has the effect of controlling the vulcanization rate by the binding energy of other metal oxides, and thus, the effect of preventing pre- and vulcanization of rubber can be obtained.

Claims (1)

고무가류 공정에 있어서, 기존의 산화아연과 스테아르산으로 구성되는 가류제에 지연제로 산화마그네슘과 산화칼슘을 첨가함을 특징으로한 가류속도를 조절하는 고무가류제 조성물.In the rubber vulcanization process, a rubber vulcanizing composition for controlling the vulcanization rate, characterized in that the addition of magnesium oxide and calcium oxide as a retardant to the conventional vulcanizing agent consisting of zinc oxide and stearic acid.
KR1019950018919A 1994-11-11 1995-06-30 Rubber vulcanizing agent composition controlling vulcanizing rate KR100356588B1 (en)

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KR19940029559 1994-11-11
KR1019940029559 1994-11-11
KR94-29559 1994-11-11

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KR100356588B1 true KR100356588B1 (en) 2003-01-24

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KR100450638B1 (en) * 2001-11-26 2004-10-01 한국타이어 주식회사 Rubber composition containing vulcanization retarder for insoluble sulfur master batch

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3644247A (en) * 1970-08-17 1972-02-22 Us Navy Encapsulating elastomeric compound
US4144154A (en) * 1977-02-22 1979-03-13 Zapp Robert L Polythiol accelerated radiation crosslinking of olefinically unsaturated polymers
US4246375A (en) * 1979-03-01 1981-01-20 Vulnax International Limited Vulcanization process and compositions for use therein

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3644247A (en) * 1970-08-17 1972-02-22 Us Navy Encapsulating elastomeric compound
US4144154A (en) * 1977-02-22 1979-03-13 Zapp Robert L Polythiol accelerated radiation crosslinking of olefinically unsaturated polymers
US4246375A (en) * 1979-03-01 1981-01-20 Vulnax International Limited Vulcanization process and compositions for use therein

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
대한민국특허공보 특92-9호(1992.01.06 등록) 사본 1부. *

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