KR100515654B1 - Compound Adhering Metal Reinforcement Improved Adhesion - Google Patents

Compound Adhering Metal Reinforcement Improved Adhesion Download PDF

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KR100515654B1
KR100515654B1 KR10-2003-0084685A KR20030084685A KR100515654B1 KR 100515654 B1 KR100515654 B1 KR 100515654B1 KR 20030084685 A KR20030084685 A KR 20030084685A KR 100515654 B1 KR100515654 B1 KR 100515654B1
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adhesion
rubber composition
metal
copper
cyclohexane
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KR20050051004A (en
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박중양
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금호타이어 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber

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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)
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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

본 발명은 접착력이 향상된 금속접착 고무조성물에 관한 것으로, 좀더 상세하게는 접착증진제로 copper(Ⅱ) cyclohexane alkyrate를 함유하여 소량 사용으로도 접착력이 향상되고 다양한 노화조건에서도 접착력이 감소되지 않는 금속이 접착된 고무조성물에 관한 것이다.The present invention relates to a metal adhesive rubber composition with improved adhesion, more specifically, a copper (II) cyclohexane alkyrate as an adhesion enhancer, the adhesion is improved even by using a small amount of adhesion and the adhesion is not reduced even under various aging conditions It relates to a rubber composition.

본 발명은 금속을 보강제로 사용하는 고무조성물에 있어서, 접착증진제로 copper(Ⅱ) cyclohexane alkyrate를 0.5∼5.0phr 함유하는 금속접착 고무조성물을 제공한다.The present invention provides a metal adhesive rubber composition containing 0.5 to 5.0 phr of copper (II) cyclohexane alkyrate as an adhesion promoter in a rubber composition using metal as a reinforcing agent.

Description

접착력이 향상된 금속접착 고무조성물{Compound Adhering Metal Reinforcement Improved Adhesion}Compound Adhering Metal Reinforcement Improved Adhesion

본 발명은 접착력이 향상된 금속접착 고무조성물에 관한 것으로, 좀더 상세하게는 접착증진제로 copper(Ⅱ) cyclohexane alkyrate를 함유하여 소량 사용으로도 접착력이 향상되고 다양한 노화조건에서도 접착력이 감소되지 않는 금속이 접착된 고무조성물에 관한 것이다.The present invention relates to a metal adhesive rubber composition with improved adhesion, more specifically, a copper (II) cyclohexane alkyrate as an adhesion enhancer, the adhesion is improved even by using a small amount of adhesion and the adhesion is not reduced even under various aging conditions It relates to a rubber composition.

각종 고무제품들은 종종 물성을 향상시키기 위하여 보강용 금속제를 사용하고 있는데, 이러한 금속을 보강제로 사용하는 고무제품은 고무와 금속간의 접착력이 매우 중요하기 때문에 고무와 보강용 금속과의 접착력을 유지하기 위하여 접착증진제를 사용하고 있다.Various rubber products often use reinforcing metals to improve their physical properties. Rubber products using these metals as reinforcing agents are important for maintaining adhesion between rubber and reinforcing metals because the adhesion between rubber and metal is very important. Adhesion promoters are used.

스틸 벨트(steel belt)를 사용하는 타이어의 경우 타이어용 고무조성물과 타이어용 금속 코드류와의 접착력은 결정적으로 중요한 인자라고 할 수 있는데, 특히 컨베이어 벨트(conveyor belt), 동력전달 벨트(power transmission belt) 및 금속으로 보강된 고무호스 등을 포함한 각종 고무제품에서의 고무와 금속간의 접착력은 그 제품의 성능과 직접적인 관련이 있다.In the case of tires using steel belts, the adhesion between rubber components for tires and metal cords for tires is a crucial factor, in particular for conveyor belts and power transmission belts. ) And the adhesion between rubber and metal in various rubber products, including rubber hoses reinforced with metal, are directly related to their performance.

그동안 세계의 많은 연구원들은 이러한 금속과 고무와의 접착력 향상을 위하여 다양한 각도에서 연구를 진행해 왔는데, 예컨대 금속 케이블(metal cable)에서는 케이블 와이어 필라멘트(cable wire filaments)의 구성 또는 구조를 변경하여 접착력을 향상시켰으며, 공기압 타이어의 보강용 스틸 코드(steel cord)에서는 스틸 필라멘트(steel filament)를 황동을 사용하여 전처리함으로써 고무조성물과의 접착력을 향상시켰다. In the meantime, many researchers around the world have been working from various angles to improve the adhesion between metal and rubber. For example, in metal cables, the structure or structure of cable wire filaments can be changed to improve adhesion. In the steel cord for reinforcement of pneumatic tires, the steel filament was pretreated with brass to improve adhesion to the rubber composition.

또한 금속과의 접착력 향상을 위해 고무조성물에 다양한 첨가제를 넣기도 하는데, 고무와 금속간의 접착력 향상을 위하여 가류되기 전의 고무조성물에 접착력을 향상시킬 수 있는 s-트리아진(s-triazines)을 넣어 접착력을 향상시키거나(미국특허 제3,894,903호), 금속으로 보강시킨 고무제품에 산화 카본블랙을 사용하여 황동표면을 보호함으로써 접착력을 향상시키는 기술(미국특허 제3,676,256호) 등이 개시되어 있다. In addition, various additives are added to the rubber composition to improve adhesion to the metal, and s-triazines can be added to the rubber composition before being vulcanized to improve adhesion between the rubber and the metal. A technique of improving adhesion (US Pat. No. 3,894,903) or improving adhesion by protecting a brass surface by using carbon black oxide on a rubber product reinforced with metal is disclosed (US Pat. No. 3,676,256).

한편, 종래에는 타이어 제조용 고무조성물과 스틸코드와의 접착력향상을 위해 접착증진제로 고무조성물에 코발트 보론 아세테이트(cobalt boron acetate)를 사용하여 왔는데, 최근 타이어의 사용 수명이 연장되고 일부 트럭이나 버스용 타이어는 재생하여 사용하고 있는 추세로서 장기사용에 따라 가혹한 조건에서도 접착력을 유지할 수 있는 타이어의 개발이 절실히 요구되고 있는 실정이다. On the other hand, in the past, cobalt boron acetate has been used in rubber compositions as adhesion promoters to improve adhesion between rubber compositions for tire production and steel cords. Recently, the service life of tires has been extended and some truck or bus tires have been used. As the trend of reusing and using, the development of a tire that can maintain the adhesion even in harsh conditions with the long-term use is urgently required.

본 발명자는 상기와 같은 문제점을 해결하기 위한 연구를 지속적으로 수행하여 소량의 접착증진제 사용으로도 고무조성물과 보강용 금속과의 접착력을 향상시킬 수 있는 특수한 접착증진제를 사용하여 이와 같은 문제점을 해결할 수 있음을 알아내고 본 발명을 완성하였다.The present inventors continue to research to solve the above problems by using a special adhesion promoter that can improve the adhesion between the rubber composition and the reinforcing metal even with the use of a small amount of adhesion promoter to solve such problems. It was found that the present invention was completed.

따라서, 본 발명의 목적은 소량의 점착증진제 사용으로도 접착력이 향상되고 다양한 노화조건에서도 접착력이 감소되지 않는 금속이 접착된 고무조성물을 제공함에 있다. Accordingly, it is an object of the present invention to provide a rubber composition in which a metal is adhered even when a small amount of an adhesion enhancer is used and adhesion is not reduced even under various aging conditions.

본 발명은 상기와 같은 목적을 달성하기 위한 수단으로 금속을 보강제로 사용하는 고무조성물에 있어서, 접착증진제로 copper(Ⅱ) cyclohexane alkyrate를 0.5∼5.0phr 함유하는 금속접착 고무조성물을 제공한다.The present invention provides a metal adhesive rubber composition containing 0.5 to 5.0 phr of copper (II) cyclohexane alkyrate as an adhesion promoter in a rubber composition using a metal as a reinforcing agent as a means for achieving the above object.

본 발명에 의한 금속접착 고무조성물에 사용되는 접착증진제는 copper(Ⅱ) cyclohexane alkyrate로서 copper(Ⅱ) cyclohexane propyrate([C6H11(CH2 )2CO2]2Cu), copper(Ⅱ) cyclohexane butyrate([C6H11(CH2)3CO2 ]2Cu), copper(Ⅱ) cyclohexane pentyrate([C6H11(CH2)4CO2]2Cu) 또는 copper(Ⅱ) cyclohexane octyrate([C6H11(CH2)7CO2]2Cu)이 사용될 수 있다.The adhesion promoter used in the metal adhesive rubber composition according to the present invention is copper (II) cyclohexane alkyrate as copper (II) cyclohexane propyrate ([C 6 H 11 (CH 2 ) 2 CO 2 ] 2 Cu), copper (II) cyclohexane butyrate ([C 6 H 11 (CH 2 ) 3 CO 2 ] 2 Cu), copper (II) cyclohexane pentyrate ([C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu) or copper (II) cyclohexane octyrate ( [C 6 H 11 (CH 2 ) 7 CO 2 ] 2 Cu) can be used.

고무조성물과 금속을 접착함에 있어서 일반적으로 접착증진제는 0.05 ~ 10 phr 사용되나, 본 발명에 의한 금속접착 고무조성물에 사용되는 접착증진제의 양은 0.1∼5phr로서 소량 사용으로도 고무조성물과 보강용 금속간의 접착력을 향상시킬 수 있다.In the case of bonding the rubber composition and the metal, the adhesion promoter is generally used in the range of 0.05 to 10 phr, but the amount of the adhesion promoter used in the metal adhesive rubber composition according to the present invention is 0.1 to 5 phr. Adhesion can be improved.

또한 본 발명에 의한 금속접착 고무조성물에 사용되는 금속은 황동이 도금된 카본스틸 코드(carbon steel cord)로서, 스틸은 산화에 의한 부식이 용이하고 경미한 부식에도 고무와의 접착에 치명적인 영향을 미치기 때문에 보강용 스틸코드의 표면을 황동으로 처리하고 이때 사용되는 황동은 구리와 아연의 합금이다.In addition, the metal used in the metal-bonded rubber composition according to the present invention is a brass-plated carbon steel cord (carbon steel cord), because the steel is easy to corrode by oxidation and even a slight corrosion has a fatal effect on the adhesion to rubber. The surface of the reinforcing steel cord is treated with brass, and the brass used here is an alloy of copper and zinc.

이하 본 발명의 내용을 실시예 및 비교예를 통하여 구체적으로 설명한다. 그러나 다음의 실시예는 본 발명을 보다 상세하게 설명하기 위한 것으로, 본 발명의 권리범위를 이에 한정하고자 하는 것은 아니다.Hereinafter, the content of the present invention will be described in detail through Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not intended to be limited thereto.

<실시예 1><Example 1>

하기 표 1과 같이, 천연고무 100phr, 스테아린산 2phr, 산화아연 8phr, 산화방지제 1.5phr, 점착제로 페놀계 수지 1.5phr, 카본블랙 65phr, 공정오일 2phr, 가류제 5.2phr, 가류촉진제 0.65phr 및 접착증진제로 copper(Ⅱ) cyclohexane propyrate([C6H11(CH2)2CO2]2Cu) 1.0phr을 반바리 믹서에 첨가하여 배합하고 황동이 도금된 카본스틸 코드를 상기에서 배합한 미가류 상태의 고무혼합물에 넣고 150℃에서 45분간 가류시켜 금속접착 고무조성물을 제조하였다.As shown in Table 1 below, natural rubber 100phr, stearic acid 2phr, zinc oxide 8phr, antioxidant 1.5phr, phenolic resin 1.5phr, carbon black 65phr, process oil 2phr, vulcanizing agent 5.2phr, vulcanization accelerator 0.65phr and adhesion promoter Uncured state in which 1.0 phr of zero copper (II) cyclohexane propyrate ([C 6 H 11 (CH 2 ) 2 CO 2 ] 2 Cu) was added to a half-barrier mixer and the brass-plated carbon steel cord was formulated above. Into the rubber mixture of the mixture was vulcanized at 150 ℃ for 45 minutes to prepare a metal adhesive rubber composition.

<실시예 2><Example 2>

접착증진제로 copper(Ⅱ) cyclohexane butyrate([C6H11(CH2)3 CO2]2Cu)를 1.0phr 사용하는 것 이외에는 상기 실시예 1과 동일하게 실시하여 금속접착 고무조성물을 제조하였다.A metal adhesive rubber composition was prepared in the same manner as in Example 1 except that 1.0 phr of copper (II) cyclohexane butyrate ([C 6 H 11 (CH 2 ) 3 CO 2 ] 2 Cu) was used as an adhesion promoter.

<실시예 3><Example 3>

접착증진제로 copper(Ⅱ) cyclohexane pentyrate([C6H11(CH2)4 CO2]2Cu)를 1.0phr 사용하는 것 이외에는 상기 실시예 1과 동일하게 실시하여 금속접착 고무조성물을 제조하였다.A metal adhesive rubber composition was prepared in the same manner as in Example 1 except that 1.0 phr of copper (II) cyclohexane pentyrate ([C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu) was used as an adhesion promoter.

<실시예 4><Example 4>

접착증진제로 copper(Ⅱ) cyclohexane octyrate([C6H11(CH2)7 CO2]2Cu)를 1.0phr 사용하는 것 이외에는 상기 실시예 1과 동일하게 실시하여 금속접착 고무조성물을 제조하였다.A metal adhesive rubber composition was prepared in the same manner as in Example 1 except that 1.0 phr of copper (II) cyclohexane octyrate ([C 6 H 11 (CH 2 ) 7 CO 2 ] 2 Cu) was used as an adhesion promoter.

<비교예>Comparative Example

접착증진제를 사용하지 않는 것 이외에는 상기 실시예 1 내지 실시예 5와 같이 실시하여 금속접착 고무조성물을 제조하였다. Except not using the adhesion promoter was carried out in the same manner as in Example 1 to Example 5 to prepare a metal adhesive rubber composition.

<표 1> 접착증진제 사용량(단위:phr)<Table 1> Adhesion Promoter Usage (Unit: phr)

구분division 접착증진제Adhesion promoter 사용량usage 비교예Comparative example -- 00 실시예 1Example 1 [C6H11(CH2)2CO2]2Cu[C 6 H 11 (CH 2 ) 2 CO 2 ] 2 Cu 1.01.0 실시예 2Example 2 [C6H11(CH2)3CO2]2Cu[C 6 H 11 (CH 2 ) 3 CO 2 ] 2 Cu 1.01.0 실시예 3Example 3 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 1.01.0 실시예 4Example 4 [C6H11(CH2)7CO2]2Cu[C 6 H 11 (CH 2 ) 7 CO 2 ] 2 Cu 1.01.0

<실시예 5>Example 5

하기 표 2와 같이, 접착증진제로 copper(Ⅱ) cyclohexane pentyrate ([C6H11(CH2)4CO2]2Cu)의 사용량을 0.5phr로 하는 것 이외에는 상기 실시예 1과 동일하게 실시하여 금속접착 고무조성물을 제조하였다.As shown in Table 2, except that the amount of copper (II) cyclohexane pentyrate ([C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu) to 0.5phr as an adhesion promoter was carried out in the same manner as in Example 1 A metal adhesive rubber composition was prepared.

<실시예 6><Example 6>

접착증진제의 사용량을 1.0phr로 하는 것 이외에는 상기 실시예 5와 동일하게 실시하여 금속접착 고무조성물을 제조하였다. A metal adhesive rubber composition was prepared in the same manner as in Example 5 except that the amount of the adhesion promoter was 1.0 phr.

<실시예 7><Example 7>

접착증진제의 사용량을 1.5phr로 하는 것 이외에는 상기 실시예 5와 동일하게 실시하여 금속접착 고무조성물을 제조하였다. A metal adhesive rubber composition was prepared in the same manner as in Example 5 except that the amount of the adhesion promoter was 1.5 phr.

<실시예 8><Example 8>

접착증진제의 사용량을 2.0phr로 하는 것 이외에는 상기 실시예 5와 동일하게 실시하여 금속접착 고무조성물을 제조하였다. A metal adhesive rubber composition was prepared in the same manner as in Example 5 except that the amount of the adhesion promoter was 2.0 phr.

<실시예 9>Example 9

접착증진제의 사용량을 5.0phr로 하는 것 이외에는 상기 실시예 5와 동일하게 실시하여 금속접착 고무조성물을 제조하였다. A metal adhesive rubber composition was prepared in the same manner as in Example 5 except that the amount of the adhesion promoter was 5.0 phr.

<표 2> 접착증진제 사용량(단위:phr)<Table 2> Concentration of Adhesion Promoter (Unit: phr)

구분division 접착증진제Adhesion promoter 사용량usage 실시예 5Example 5 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 0.50.5 실시예 6Example 6 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 1.01.0 실시예 7Example 7 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 1.51.5 실시예 8Example 8 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 2.02.0 실시예 9Example 9 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 5.05.0

<시험예 1><Test Example 1>

상기 실시예 1 내지 실시예 4 및 비교예에서 제조한 금속접착 고무조성물의 고무와 금속간의 접착력을 알아보기 위하여 ASTM-D2229-73에 준하여 초기 접착력과 습도, 염 및 열 노화접착력을 비교평가한 결과를 하기 표 3에 나타내었다. In order to determine the adhesive strength between the metal and the rubber of the metal adhesive rubber composition prepared in Examples 1 to 4 and Comparative Examples, the comparative evaluation of the initial adhesive strength and humidity, salt and heat aging adhesive strength in accordance with ASTM-D2229-73 It is shown in Table 3 below.

각각의 시료들은 다양한 조건에서 노화를 진행시켰는데, 습도 노화(humidity ageing)의 경우 85℃, 상대습도 85%에서 5일간 노화시켰고, 염 노화(salt ageing)은 상온의 15%-NaCl 수용액속에서 48 시간 동안 노화시켰고, 열 노화(thermal ageing)의 경우 95℃에서 5일간 노화시켰다. Each sample was subjected to aging under various conditions. Humidity aging was performed at 85 ° C. and 85% RH for 5 days. Salt aging was performed in a 15% NaCl solution at room temperature. Aging was performed for 48 hours and for 5 days at 95 ° C. for thermal aging.

<표 3> 노화접착력 측정결과(단위 : kgf)<Table 3> Aging Adhesion Measurement Results (Unit: kgf)

구분division 접착증진제Adhesion promoter 초기접착력Initial Adhesion 습도 노화Humidity aging 염 노화Salt aging 열 노화Heat aging 비교예Comparative example -- 115115 106106 7575 100100 실시예 1Example 1 [C6H11(CH2)2CO2]2Cu[C 6 H 11 (CH 2 ) 2 CO 2 ] 2 Cu 111111 103103 8080 9898 실시예 2Example 2 [C6H11(CH2)3CO2]2Cu[C 6 H 11 (CH 2 ) 3 CO 2 ] 2 Cu 129129 120120 119119 124124 실시예 3Example 3 [C6H11(CH2)4CO2]2Cu[C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu 139139 124124 134134 125125 실시예 4Example 4 [C6H11(CH2)7CO2]2Cu[C 6 H 11 (CH 2 ) 7 CO 2 ] 2 Cu 118118 116116 108108 9696

상기 표 3에서 보는 바와 같이, 접착증진제를 사용한 실시예 2 내지 실시예 4는 접착증진제를 사용하지 않은 비교예 보다 높은 접착력을 나타내었고, copper(Ⅱ) cyclohexane propyrate([C6H11(CH2)2CO2] 2Cu)를 사용한 실시예 1의 경우는 비교예 보다 다소 낮은 접착력을 보이고 있다.As shown in Table 3, Examples 2 to 4 using the adhesion promoter showed a higher adhesion than the comparative example without the adhesion promoter, copper (II) cyclohexane propyrate ([C 6 H 11 (CH 2 Example 1 using 2 CO 2 ] 2 Cu) shows a somewhat lower adhesive force than the comparative example.

4 종류의 접착증진제를 사용한 금속접착 고무조성물의 접착력은 copper(Ⅱ) cyclohexane pentyrate([C6H11(CH2)4CO2] 2Cu)를 사용한 것이 비교적 양호한 접착력을 얻을 수 있음을 알 수 있다.The adhesion strength of the metal adhesive rubber composition using the four types of adhesion promoters was found to be relatively good when the copper (II) cyclohexane pentyrate ([C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu) was used. have.

<시험예 2><Test Example 2>

상기의 시험예 1에서 비교적 양호한 접착력 효과를 보인 copper(Ⅱ) cyclohexane pentyrate([C6H11(CH2)4CO2] 2Cu)의 사용량에 따른 접착력 효과를 알아보기 위하여 상기 실시예 5 내지 실시예 9에서 제조한 금속접착 고무조성물을 시험예 1 과 동일한 방법으로 하여 초기 접착력과 습도, 염 및 열 노화접착력을 비교평가한 결과를 하기 표 4에 나타내었다.In order to determine the effect of the adhesive strength according to the amount of the copper (II) cyclohexane pentyrate ([C 6 H 11 (CH 2 ) 4 CO 2 ] 2 Cu) showing a relatively good adhesive effect in Test Example 1 to Example 5 to The metal adhesive rubber composition prepared in Example 9 was tested in the same manner as in Test Example 1, and the results of comparing and evaluating the initial adhesive strength and humidity, salt, and heat aging adhesive strength are shown in Table 4 below.

<표 4> 노화접착력 측정결과(단위 : kgf)<Table 4> Aging Adhesion Measurement Results (Unit: kgf)

구분division 초기접착력Initial Adhesion 습도 노화Humidity aging 염 노화Salt aging 열 노화Heat aging 실시예 5Example 5 110110 106106 8080 9999 실시예 6Example 6 139139 124124 131131 125125 실시예 7Example 7 145145 143143 135135 149149 실시예 8Example 8 133133 128128 125125 119119 실시예 9Example 9 130130 129129 127127 120120

상기 표 4에서 보는 바와 같이, 0.5∼5.0phr의 소량의 접착증진제 사용으로도 우수한 접착력을 유지할 수 있음을 알 수 있다. As shown in Table 4, it can be seen that even using a small amount of adhesion promoter of 0.5 to 5.0 phr can maintain excellent adhesion.

본 발명에 의하면 황동이 도금된 카본스틸 코드와 고무조성물간의 접착력 향상을 위하여 새로운 접착증진제를 사용함으로써 소량 사용으로도 접착력이 우수하고 다양한 노화조건에서도 접착력 하락이 경미한 금속접착 고무조성물을 제공할 수 있다. According to the present invention, by using a new adhesion promoter to improve the adhesion between the brass-plated carbon steel cord and the rubber composition, it is possible to provide a metal adhesive rubber composition having excellent adhesion even in a small amount of use and having a slight drop in adhesion even under various aging conditions. .

Claims (3)

금속을 보강제로 사용하는 고무조성물에 있어서,In a rubber composition using a metal as a reinforcing agent, 접착증진제로 copper(Ⅱ) cyclohexane alkyrate를 0.5∼5.0phr 함유하는 금속접착 고무조성물.Metal-bonded rubber composition containing 0.5-5.0 phr of copper (II) cyclohexane alkyrate as an adhesion promoter. 제 1항에 있어서, The method of claim 1, copper(Ⅱ) cyclohexane alkyrate는 copper(Ⅱ) cyclohexane propyrate, copper(Ⅱ) cyclohexane butyrate, copper(Ⅱ) cyclohexane pentyrate 또는 copper(Ⅱ) cyclohexane octyrate 임을 특징으로 하는 금속접착 고무조성물.Copper (II) cyclohexane alkyrate is a metal-bonded rubber composition characterized by copper (II) cyclohexane propyrate, copper (II) cyclohexane butyrate, copper (II) cyclohexane pentyrate or copper (II) cyclohexane octyrate. 제 1항에 있어서, The method of claim 1, 금속은 황동이 도금된 카본스틸코드 임을 특징으로 하는 금속접착 고무조성물.Metal is a metal adhesive rubber composition, characterized in that the brass is plated carbon steel cord.
KR10-2003-0084685A 2003-11-26 2003-11-26 Compound Adhering Metal Reinforcement Improved Adhesion KR100515654B1 (en)

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