KR100843893B1 - Rubber composition for adhesion of steel cord of tire - Google Patents

Rubber composition for adhesion of steel cord of tire Download PDF

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Publication number
KR100843893B1
KR100843893B1 KR1020070022753A KR20070022753A KR100843893B1 KR 100843893 B1 KR100843893 B1 KR 100843893B1 KR 1020070022753 A KR1020070022753 A KR 1020070022753A KR 20070022753 A KR20070022753 A KR 20070022753A KR 100843893 B1 KR100843893 B1 KR 100843893B1
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South Korea
Prior art keywords
rubber
adhesion
rubber composition
steel cord
tire
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KR1020070022753A
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Korean (ko)
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박병철
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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
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic 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
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0843—Cobalt
    • 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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A rubber composition for adhesion of tire steel cords is provided to realize improved heat resistance and anti-aging property, and to improve the adhesion between steel cords and rubber during the long-term use under high temperature/humidity conditions. A rubber composition for adhesion of tire steel cords comprises base rubber, sulfur, zinc oxide and cobalt, and further comprises 0.5-5.0 parts by weight of an acrylate as an antioxidant based on 100 parts by weight of the base rubber. The base rubber includes natural rubber, synthetic rubber or a blend thereof. The rubber composition optionally further comprises conventional additives.

Description

타이어 스틸코드 접착용 고무 조성물{Rubber composition for adhesion of steel cord of tire}Rubber composition for adhesion of steel steel cords

본 발명은 타이어 스틸코드 접착용 고무 조성물에 관한 것으로, 더욱 상세하게는 고무의 내열노화특성을 개선시키고, 고온/습도에 장기간 사용시 접착용 고무의 가류도 감소를 억제함으로써 스틸코드와 고무간 접착력을 향상시켜 장기 내구성능을 개선시키는 스틸코드 접착용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for a tire steel cord adhesive, and more particularly, to improve the heat aging resistance of the rubber and to reduce the vulcanization degree of the adhesive rubber during long-term use at high temperature / humidity. The present invention relates to a rubber composition for adhering steel cords to improve long-term durability.

일반적으로 타이어에 사용하는 스틸코드는 구리(Cu)/아연(Zn)의 비가 62/38~68/32인 황동으로 피복하여 고무와의 접착성을 부여하는데, 기타 공정조제로서 황동에서의 탈아연화를 억제하고자 많은 양의 산화 아연을 사용하고, 레소시놀포름알데히드 레진과 헵사메톡시메틸멜라민(HMMM)을 사용하여 오랫동안 접착력을 유지하고 있다.In general, steel cords used for tires are coated with brass having a copper (Cu) / zinc (Zn) ratio of 62/38 to 68/32 to give adhesion to rubber. In order to suppress the large amount of zinc oxide is used, and resorcinol formaldehyde resin and hepsamethoxymethylmelamine (HMMM) is used to maintain the adhesion for a long time.

스틸코드의 황동내의 아연과 수분 및 산소와의 반응으로 아연/산화/수산화 층이 형성되는데, 과도한 조건에 의해 아연 산화/수산화 층이 두꺼워지면 구리 이온의 이동이 어려워 접착층이 형성되지 않아 접착력이 하락하거나 매우 딱딱한 아연 수산화물이 두껍게 존재하고, 또한 고무와 직접 접착을 하는 CuxS(접착층)층의 형성이 미흡해져 응력에 의한 파괴가 쉽게 발생한다.The zinc / oxidation / hydroxide layer is formed by the reaction of zinc with moisture and oxygen in the brass of the steel cord.If the zinc oxide / hydroxide layer becomes thick due to excessive conditions, the copper ions are difficult to move and the adhesion layer is not formed because the adhesion layer is not formed. Or very hard zinc hydroxide is present, and the formation of a CuxS (adhesive layer) layer which is directly bonded to rubber is insufficient, and breakage due to stress is easily generated.

고무와 스틸코드와의 접착에 있어서, 고무와 스틸코드 사이에 형성되는 층을 세분하여 보면, 고무/CuxS(ZnS)/Zn(OH)2/ZnO(CuO)/Cu++(Zn++)/CuZn/Fe층으로 구분이 가능하다. 이러한 층들의 구분은 명확하지 않지만, CuxS층이 접착층으로 적당하게 형성되어야 고무와 스틸코드의 접착이 우수하다. CuxS층이 너무 많이 형성되거나 CuxS층이 너무 적으면 고무와 스틸코드와의 접착력이 매우 낮아지므로 황동 피복 스틸코드는 관리조건이 매우 까다로우며, 특히 수분 및 산소제거에 심혈을 기울여야 한다.In the bonding of rubber and steel cord, the layer formed between rubber and steel cord can be broken down into rubber / CuxS (ZnS) / Zn (OH) 2 / ZnO (CuO) / Cu ++ (Zn ++ ) It can be divided into / CuZn / Fe layers. Although the distinction between these layers is not clear, the adhesion of rubber and steel cord is excellent when the CuxS layer is properly formed as an adhesive layer. Too many CuxS layers or too few CuxS layers result in very low adhesion between rubber and steel cords. Brass-coated steel cords are very difficult to manage, especially in the removal of moisture and oxygen.

스틸코드와 접착하는 접착용 고무는 초기의 접착력을 오랫동안 유지하기 위해서 고무 혼합물에 과량의 유황을 사용하고, 접착증진제로 황동내의 구리이온을 활성화하여 고무와 접착이 쉽도록 하고, 계속적인 접착력을 유지하는 활성제 역할을 하도록 소량의 코발트염을 사용하는데, 유황과 코발트염의 분산이 원만하지 않으면 장기간 보관하거나 사용에 의해 고무의 열노화를 촉진하는 역할을 하여 고무의 수명단축의 원인이 되기도 한다. 고른 분산이 되지 않는 경우에는 유황이나 코발트염이 많이 존재하므로 고무부위에서 급속한 고무 물성하락이 나타나기 때문에 소량이 필요하나, 고른 분산을 고려하여 다소 많은 양을 사용하는 것이 현실로서, 종래 접착용 고무 조성물에서는 코발트염과 과량의 유황을 사용함에 따라 고무의 내열노화특성이 하락하고, 고온/습도에 장기간 사용시 스틸코드와 고무의 접착력이 하락하는 문제가 있었다.Adhesive rubber that bonds to the steel cord uses excessive sulfur in the rubber mixture to maintain the initial adhesive strength for a long time, and activates copper ions in brass as an adhesion promoter to facilitate adhesion with rubber, and maintains continuous adhesive strength. A small amount of cobalt salt is used to act as an activator, and if the dispersion of sulfur and cobalt salt is not smooth, it plays a role of promoting the thermal aging of rubber by long-term storage or use, which may cause a reduction in the life of rubber. If it is not evenly dispersed, there are many sulfur or cobalt salts, so a rapid decrease in rubber properties occurs in the rubber part. However, a small amount is required, but in consideration of even dispersion, a relatively large amount is used. In the case of using cobalt salt and excessive sulfur, there was a problem that the heat-aging characteristics of the rubber is reduced, and the adhesive strength of the steel cord and rubber is reduced when used for a long time at high temperature / humidity.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 과량의 유황과 접착증진제로서 코발트염을 사용하는 종래의 스틸코드 접착용 고무 조성물에 산화 보조제를 포함하므로써 고무의 내열노화특성을 개선시키고, 고온/습도에 장기간 사용시 스틸코드와 고무의 접착력을 향상시킬 수 있는 스틸코드 접착용 고무 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems, by including an oxidation aid in the conventional rubber cord adhesive rubber composition using an excess of sulfur and cobalt salt as an adhesion promoter to improve the heat aging characteristics of the rubber, An object of the present invention is to provide a rubber composition for adhering a steel cord that can improve the adhesion between the steel cord and rubber when used for a long time in humidity.

본 발명에 따른 타이어 스틸코드 접착용 고무 조성물은, 원료고무, 유황, 산화아연 및 코발트를 포함하여 이루어지는 타이어 스틸코드 접착용 고무에 있어서, 상기 원료고무 100중량부에 대하여 산화 보조제 0.5~5.0중량부를 더 포함하는 것을 특징으로 한다.The rubber composition for tire steel cord bonding according to the present invention is a rubber for tire steel cord bonding comprising a raw material rubber, sulfur, zinc oxide and cobalt, and 0.5 to 5.0 parts by weight of an oxidizing aid based on 100 parts by weight of the raw material rubber. It further comprises.

본 발명에서 사용되는 원료고무는 그 종류에 특별히 한정이 없고, 천연고무, 합성고무 또는 이들의 혼합고무를 사용할 수 있는데, 예로서, 천연고무, 스티렌부타디엔고무, 부타디엔고무를 단독 또는 이들의 혼합물로 된 혼합고무를 사용하는 것이 바람직하고, 혼합고무의 경우, 천연고무, 스티렌부타디엔고무 및 부타디엔고무의 혼합비율에는 특별히 한정이 없다.The raw material rubber used in the present invention is not particularly limited in its kind, and natural rubber, synthetic rubber or mixed rubber thereof may be used, for example, natural rubber, styrene butadiene rubber, butadiene rubber alone or as a mixture thereof. It is preferable to use the mixed rubber, and in the case of mixed rubber, the mixing ratio of natural rubber, styrene butadiene rubber and butadiene rubber is not particularly limited.

본 발명에 사용되는 산화 보조제의 구체적인 예로는 아크릴레이트 코에이젼트(Acrylate coagent)로서, 아크릴산 에스테르가 있으며, 이것의 함량은 0.5~5.0중량부를 사용하는 것이 바람직한데, 0.5중량부 미만이면 산화 방지효과가 없어 바람직하지 않고, 5.0중량부를 초과하면 지나친 가류속도 지연이 발생하므로 바람직하 지 않다.A specific example of the oxidation aid used in the present invention is an acrylate coagent, which is an acrylic ester, and its content is preferably used in an amount of 0.5 to 5.0 parts by weight. It is not preferable because it is not preferable, and if it exceeds 5.0 parts by weight, excessive vulcanization rate delay occurs.

그 밖에 본 발명의 스틸코드 접착용 고무 조성물은 통상의 스틸코드 접착용 고무 조성물에 사용되는 기타 첨가제 및 배합제를 포함할 수 있음은 물론이다.In addition, the steel cord adhesive rubber composition of the present invention may include other additives and compounding agents used in conventional rubber cord adhesive rubber composition.

본 발명은 하기 실시예와 비교예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예는 본 발명을 예시하기 위한 것에 지나지 않으며, 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples and comparative examples, the following examples are only for illustrating the present invention, and are not intended to limit the protection scope of the present invention.

비교예Comparative example 및  And 실시예Example

하기 표 1의 조성에 따라 각 성분들을 밴버리 믹서에서 배합하여 160℃에서 25분 동안 가류하여 고무 조성물을 제조한 후, 이로써 스틸코드용 고무 시편을 제조하였다.According to the composition of Table 1, each component was blended in a Banbury mixer and vulcanized at 160 ° C. for 25 minutes to prepare a rubber composition, thereby preparing rubber specimens for steel cords.

표 1 (단위 : 중량부) Table 1 (Unit: parts by weight)

구 분division 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 천연고무Natural rubber 100100 100100 100100 100100 아크릴산 에스테르Acrylic ester -- 1One 22 33 산화아연Zinc oxide 1010 1010 1010 1010 유황brimstone 55 55 55 55 CoCo 0.40.4 0.40.4 0.40.4 0.40.4 Cu/Zn 혼합재료 (Cu/Zn 중량비:65/35)Cu / Zn Mixed Material (Cu / Zn Weight Ratio: 65/35) 1212 1212 1212 1212 가황촉진제DZ(DCBS)Vulcanization accelerator DZ (DCBS) 0.70.7 0.70.7 0.70.7 0.70.7 레소시놀포름알데하이드레진Lesosinol Formaldehyde Resin 22 22 22 22 헥사메톡시메틸멜라민Hexamethoxymethylmelamine 3.73.7 3.73.7 3.73.7 3.73.7

* 코드/인장강도 시편 : 160℃ 25분/30분 가교, 코드구조:3*0.30HT* Code / tensile strength specimen: 160 ℃ 25 minutes / 30 minutes crosslinking, code structure: 3 * 0.30HT

싱기 비교예 및 실시예에 의해 제조된 고무 시편의 초기 강도와 70℃ 오븐에서 3주간 노화시킨 후, 강도를 측정하여 그 결과를 하기의 표 2에 나타내었다.After the initial strength of the rubber specimens prepared by Comparative Examples and Examples and aged for 3 weeks in 70 ℃ oven, the strength was measured and the results are shown in Table 2 below.

표 2TABLE 2

항목Item 비교예Comparative example 실시예1Example 1 실시예2Example 2 실시예3Example 3 고무의 초기강도(kgf)Initial strength of rubber (kgf) 180180 197197 206206 205205 T-Test 초기(kgf/%)T-Test Initial (kgf /%) 49/9049/90 58/9058/90 53/9553/95 61/9061/90 노화(kgf/%)1 ) Aging (kgf /%) 1 ) 41/7041/70 45/8045/80 48/9048/90 44/9544/95 노화(kgf/%)2 ) Aging (kgf /%) 2 ) 20/5020/50 20/6520/65 26/8526/85 23/9023/90

주) 1)노화: 70℃의 오븐에서 7일 노화.Note 1) Aging: 7 days aging in an oven at 70 ° C.

2) 노화: 70℃의 오븐에서 21일 노화.2) Aging: 21 days of aging at 70 ° C. in an oven.

이상에서 볼 수 있는 바와 같이, 본 발명에 의해 제조된 고무 조성물은 장기간 사용에 의해서도 균일한 접착력을 유지하므로써 타이어의 장기 주행능력을 향상시키는 효과를 갖는다.As can be seen from the above, the rubber composition produced by the present invention has the effect of improving the long-term running ability of the tire by maintaining a uniform adhesion even after long-term use.

Claims (2)

원료고무, 유황, 산화아연 및 코발트를 포함하여 이루어지는 타이어 스틸코드 접착용 고무 조성물에 있어서, 상기 원료고무 100중량부에 대하여 산화 보조제로서 아크릴산 에스테르 0.5~5.0중량부를 더 포함하는 것을 특징으로 하는 타이어 스틸코드 접착용 고무 조성물.In a rubber composition for tire steel cord bonding comprising raw material rubber, sulfur, zinc oxide and cobalt, the tire steel further comprising 0.5 to 5.0 parts by weight of acrylic ester as an oxidizing aid based on 100 parts by weight of the raw material rubber. Rubber composition for cord bonding. 삭제delete
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR930016258A (en) * 1992-01-13 1993-08-26 카알 에이취. 크루코우 Binder for Wirecoat / Belt Compounds
KR19980073806A (en) 1997-03-19 1998-11-05 홍건희 Rubber composition for tire cord adhesion with excellent water resistance
KR19990008548A (en) 1997-07-02 1999-02-05 홍건희 Rubber composition for rubber / steel cord bonding of radial tires for passenger cars
KR20020016193A (en) * 2000-08-24 2002-03-04 신형인 Adhesive rubber composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR930016258A (en) * 1992-01-13 1993-08-26 카알 에이취. 크루코우 Binder for Wirecoat / Belt Compounds
KR19980073806A (en) 1997-03-19 1998-11-05 홍건희 Rubber composition for tire cord adhesion with excellent water resistance
KR19990008548A (en) 1997-07-02 1999-02-05 홍건희 Rubber composition for rubber / steel cord bonding of radial tires for passenger cars
KR20020016193A (en) * 2000-08-24 2002-03-04 신형인 Adhesive rubber composition

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