KR100751828B1 - Synthetic rubber based cement composition - Google Patents

Synthetic rubber based cement composition Download PDF

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KR100751828B1
KR100751828B1 KR1020060093253A KR20060093253A KR100751828B1 KR 100751828 B1 KR100751828 B1 KR 100751828B1 KR 1020060093253 A KR1020060093253 A KR 1020060093253A KR 20060093253 A KR20060093253 A KR 20060093253A KR 100751828 B1 KR100751828 B1 KR 100751828B1
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rubber
cement composition
synthetic rubber
weight
based cement
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KR1020060093253A
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Korean (ko)
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박성수
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

Provided is a synthetic rubber-based cement composition which is improved in processing property and performance such as tensile strength, binding strength and crack resistance. A synthetic rubber-based cement composition comprises 100 parts by weight of a binder which comprises a natural rubber, an isoprene rubber, a solution polymerization styrene-butadiene rubber, an emulsion polymerization styrene-butadiene rubber and a butadiene rubber in a ratio of 5-20 : 5-20 : 30-45 : 5-20 by weight; and 3-5 parts by weight of a modified phenol-formaldehyde resin. Preferably the cement composition is used in a form of a solution obtained by mixing the cement composition with an aliphatic solvent and stirring the cement composition.

Description

합성고무계 타이어 시멘트 고무 조성물{SYNTHETIC RUBBER BASED CEMENT COMPOSITION}Synthetic rubber-based tire cement rubber composition {SYNTHETIC RUBBER BASED CEMENT COMPOSITION}

본 발명은 합성고무계 시멘트 조성물에 관한 것으로서, 좀더 상세하게는 시멘트 조성물 중의 바인더의 조성을 최적화하고 고성능 레진을 도입하므로써, 가공 공정성 및 성능을 개선할 수 있는 합성고무계 시멘트 조성물에 관한 것이다.The present invention relates to a synthetic rubber-based cement composition, and more particularly, to a synthetic rubber-based cement composition that can improve processing processability and performance by optimizing the composition of the binder in the cement composition and introducing a high performance resin.

최근 들어 고무산업에서는 고기능성 합성고무나 보강제로서 카본블랙 대신 실리카를 도입하고 있으나, 실리카의 함유량이 높아짐에 따라 고무 반제품의 점착성이 하락하고, 고무간 계면 강도가 급격히 감소하는 문제점이 발생하고 있어, 이러한 문제점을 개선하는데 더욱 관심이 많아지고 있다. 또한 고무 제품의 동적 유동시 계면의 강도가 약해지는 현상으로 인해 보강의 필요성이 더 한층 요구되고 있다.Recently, the rubber industry has introduced silica instead of carbon black as a high performance synthetic rubber or reinforcing agent. However, as the silica content increases, the adhesion of semi-finished rubber products decreases, and the interfacial strength between rubbers decreases rapidly. There is a growing interest in improving these problems. In addition, due to the phenomenon that the strength of the interface weakens during the dynamic flow of rubber products, the need for reinforcement is further required.

따라서, 고무간의 접착에 사용되는 시멘트 조성물은 고무 반제품의 고무간 계면 접착성 및 가교후 접착강도를 높일 수 있는 특성을 갖추어야만 한다.Therefore, the cement composition used for the adhesion between the rubber should have the property to increase the interfacial adhesion between the rubber semi-finished product and the adhesive strength after crosslinking.

종래에는 일반적으로 천연고무계 시멘트 조성물이 사용되고 있으나, 천연고무계 시멘트 조성물은 합성고무 제품에 적용할 경우 점착성은 양호하지만, 천연고 무와 합성고무간의 상용성이 나빠서 가류후 계면강도가 약해서 고무 특성의 하락을 유발하는 문제점이 있다.Conventionally, natural rubber-based cement compositions are generally used, but natural rubber-based cement compositions have good adhesiveness when applied to synthetic rubber products, but the compatibility between natural rubber and synthetic rubber is poor, and the interfacial strength after vulcanization is weak. There is a problem that causes.

한편, 종래의 합성고무계 시멘트 조성물의 경우에는 계면 강도는 높아지나, 그린 점착력이 하락되는 문제점이 있다.On the other hand, in the case of the conventional synthetic rubber-based cement composition, the interface strength is high, but there is a problem that the green adhesive strength is lowered.

본 발명의 목적은 상기와 같은 문제점을 개선하기 위한 것으로, 합성고무 반제품의 고무간 계면 점착성을 높이고, 가교후 접착강도를 증진시킬 수 있는 합성고무계 시멘트 조성물을 제공하는 것이다.An object of the present invention is to improve the above problems, to provide a synthetic rubber-based cement composition that can improve the interfacial adhesion between the rubber of the synthetic rubber semi-finished product, and improve the adhesive strength after crosslinking.

본 발명에 따른 합성고무계 시멘트 조성물은 천연고무:이소프렌고무:용액중합 스티렌 부타디엔 고무:유화중합 스티렌 부타디엔 고무:부타디엔고무가 5∼20:5∼20:30∼45:30∼45:5∼20의 중량비로 이루어진 바인더 100중량부에 대하여 변성 페놀-포름알데히드 레진 3∼5중량부를 포함하는 것을 특징으로 한다.Synthetic rubber-based cement composition according to the present invention is a natural rubber: isoprene rubber: solution polymerization styrene butadiene rubber: emulsion polymerization styrene butadiene rubber: butadiene rubber 5 to 20: 5 to 20: 30 to 45: 30 to 45: 5 to 20 It is characterized by including 3 to 5 parts by weight of the modified phenol-formaldehyde resin based on 100 parts by weight of the binder consisting of a weight ratio.

본 발명의 시멘트 조성물에 있어서, 상기 바인더의 고무 성분들의 배합비가 상기 범위를 벗어나는 경우에는 고무 요소간 계면 접착력이 하락하게 되고, 특히 고스티렌계 고무 배합물에 사용할 경우 혼화성이 떨어지고 계면의 초기 및 지속적인 점착성이 크게 하락하여 바람직하지 않다. In the cement composition of the present invention, when the blending ratio of the rubber components of the binder is out of the above range, the interfacial adhesion between the rubber elements is reduced, in particular, when used in a high styrene-based rubber compound, the miscibility is reduced and the initial and continuous Tackiness is greatly reduced and is not preferable.

본 발명에서 사용되는 변성 페놀-포름알데히드 레진의 함량은 3∼5중량부인 것이 바람직한데, 3중량부 미만인 경우에는 고무 바인더와의 용해도, 혼화성 및 점착성(초기 및 노화후)이 크게 미흡하게 되어 바람직하지 않고, 5중량부를 초과하는 경우에는 그린 점착성과 물성(노화후)이 하락하여 바람직하지 않다.The content of the modified phenol-formaldehyde resin used in the present invention is preferably 3 to 5 parts by weight, but less than 3 parts by weight, the solubility, miscibility and adhesion with the rubber binder (initial and post-aging) are greatly insufficient. Undesirably, when it exceeds 5 weight part, green adhesiveness and a physical property (after aging) fall, and it is unpreferable.

본 발명의 시멘트 조성물에는 상기 성분들 이외에 일반적으로 시멘트 조성물에 첨가되는 통상의 첨가제들, 예컨대 카본블랙, 산화아연, 스테아린산, 프로세스 오일, 노화방지제, 유황, 촉진제 등을 통상의 사용량으로 배합할 수 있다.In addition to the above components, the cement composition of the present invention may be formulated with conventional additives generally added to the cement composition, such as carbon black, zinc oxide, stearic acid, process oils, antioxidants, sulfur, accelerators, and the like, in conventional amounts. .

본 발명의 시멘트 조성물은 합성고무 제품에 적용할 수 있으며, 특히 타이어의 트레드부에 유용하게 적용할 수 있다.The cement composition of the present invention can be applied to synthetic rubber products, and particularly useful for tread portions of tires.

구체적인 사용예로서, 본 발명의 시멘트 조성물을 타이어 트레드의 압출시 트레드 압출물의 끝부위 및 하단부에 도포하므로써 타이어 성형시 트레드 접합부의 벌어짐 방지와 타이어의 다른 부위(예를 들어, 벨트)와의 점착력 및 접착력을 향상시킬 수 있고, 결과적으로 최종 타이어의 유니포미티(uniformity) 및 내구력을 향상시킬 수 있다.As a specific use example, the cement composition of the present invention is applied to the end and the lower end of the tread extrudates when the tire tread is extruded, thereby preventing the tread joint from spreading and the adhesion and adhesion to other parts of the tire (for example, a belt) when the tire is formed. Can be improved, and consequently, the uniformity and durability of the final tire can be improved.

본 발명의 시멘트 조성물은 지방족 용제, 바람직하게는 탄소수 6∼8의 지방족 용제와 혼합, 교반한 용액으로서 적용할 수 있으며, 이때 최종 용액중의 본 발명의 시멘트 조성물의 함량은 에어 건으로 사용시 분사가 가능하도록 적합한 점도와 분산 균일성 등을 고려하여 10∼15중량%인 것이 바람직하다.The cement composition of the present invention can be applied as a solution which is mixed and stirred with an aliphatic solvent, preferably an aliphatic solvent having 6 to 8 carbon atoms, wherein the content of the cement composition of the present invention in the final solution can be sprayed when used as an air gun. It is preferably 10 to 15% by weight in consideration of suitable viscosity, dispersion uniformity, and the like.

상기 용액에는 필요에 따라 분산성 향상을 위해 비이온계 계면활성제를 0.2∼0.7중량% 포함시킬 수 있다. If necessary, the solution may contain 0.2 to 0.7 wt% of a nonionic surfactant to improve dispersibility.

이하, 실시예를 통하여 본 발명을 더욱 상세하게 설명하지만, 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

실시예Example 및  And 비교예Comparative example

하기 표 1의 조성대로 실시예 및 비교예의 시멘트 조성물을 제조하여, ASTM 규격에 따라 그 물성을 측정하고, 그 결과를 표 2에 나타내었다. The cement compositions of Examples and Comparative Examples were prepared according to the compositions of Table 1 below, the physical properties thereof were measured according to ASTM standards, and the results are shown in Table 2.

(단위:중량부)                                                                (Unit: weight part) 항목Item 비교예Comparative example 실시예Example 천연고무Natural rubber 3030 1010 이소프렌 고무Isoprene rubber 1010 1010 용액중합 스티렌-부타디엔 고무Solution Polymerized Styrene-Butadiene Rubber -- 3535 유화중합 스티렌-부타디엔 고무Emulsion Polymerization Styrene-Butadiene Rubber 5050 3535 부타디엔 고무Butadiene rubber 1010 1010 카본블랙 N330Carbon black N330 4040 4040 변성 페놀-포름알데히드 레진Modified phenol-formaldehyde resins -- 44 산화아연Zinc oxide 33 33 스테아린산Stearic acid 22 22 공정오일Process oil 22 22 유황brimstone 22 33 CZCZ 0.40.4 22 DPGDPG -- 0.50.5 PVIPVI 0.050.05 --

- CZ : 시클로헥실 벤조티아졸 설펜아미드(cyclohexyl benzothiazol sulfenamide, Flexsis사제 : 1차 촉진제)-CZ: cyclohexyl benzothiazol sulfenamide (manufactured by Flexsis: primary accelerator)

- DPG : 디페닐 구아니딘(diphenyl guanidine , Akrochem사제 : 2차 촉진제)-DPG: diphenyl guanidine (diphenyl guanidine, manufactured by Akrochem: secondary accelerator)

- PVI : N-시클로헥실티오프탈이미드PVI: N-cyclohexylthioptalimide

시험항목Test Items 비교예Comparative example 실시예Example 레오메타 가교도 Tmin(160℃) Tmax(160℃) T40(분) E.C(분)Rheometer Crosslinking Degree Tmin (160 ° C) Tmax (160 ° C) T40 (minutes) E.C (minutes) 14.5(Nm) 36.5(Nm) 6.82 12.50 14.5 (Nm) 36.5 (Nm) 6.82 12.50 3.21(Nm) 49(Nm) 4.10 10.20 3.21 (Nm) 49 (Nm) 4.10 10.20 경도(JIS)Longitude (JIS) 6363 6565 300% 모듈러스300% modulus 9595 9898 인장강도The tensile strength 250250 288288 신장율Elongation 535535 540540 인열강도Tear strength 8080 9898 크랙성장율(mm) (5000사이클 후/초기)Crack growth rate (mm) (after 5000 cycles / initial stage) 10.3/9.5 10.3 / 9.5 8.3/6.5 8.3 / 6.5 마모 손실량(mg)Abrasion Loss (mg) 0.0290.029 0.0270.027 점탄성 특성 0℃ 탄델타 값 60℃탄델타 값Viscoelastic Properties 0 ℃ Tan Delta Value 60 ℃ Tan Delta Value 0.180 0.089 0.180 0.089 0.183 0.086 0.183 0.086 Bound 고무량(%)Bound rubber amount (%) 38.938.9 41.541.5 무늬점도(100℃)Pattern viscosity (100 ℃) 68.268.2 69.369.3 HEAT BUILD UP(℃)HEAT BUILD UP (℃) 15.215.2 15.815.8 레올로지 전단점도Rheological Shear Viscosity 4.2×104 4.2 × 10 4 4.3×104 4.3 × 10 4 그린 점착력 초기 7일 노화후Green adhesive force 7 days after aging 35 12.5 35 12.5 32.5 17.5 32.5 17.5 가류후 계면결합력 초기 7일 노화후7 days after aging 30 22.5 30 22.5 35 27.5 35 27.5

* E.C(End Cure) : 가교가 완결되는 최종 시간* E.C (End Cure): Final time when crosslinking is completed

* 그린 점착력 : 미가교된 최종 고무 배합물의 가공에 따른 고무 고유의 점착성 값으로서, 고무간 점착시 떨어지는 힘을 말한다. 이 값이 클수록 그린 점착성이 우수함을 의미한다.* Green Adhesion: The inherent adhesion value of rubber according to the processing of uncrosslinked final rubber compound. Larger value means better green adhesiveness.

상기 결과로부터 알 수 있는 바와 같이, 본 발명에 따른 실시예의 합성고무계 시멘트 조성물은 인장물성과 결합강도 및 내크랙성이 향상되었음을 나타내며, 동적 점탄성에서도 저온과 고온에서도 요구되는 물성이 유리함을 나타내었다. 특히 초기 및 지속 점착성 결과 비교예에 비하여 향상되며, 가류후 계면 결합력에서도 우수함을 알 수 있었다. As can be seen from the above results, the synthetic rubber-based cement composition of the embodiment according to the present invention showed that the tensile properties, the bonding strength and the crack resistance were improved, and the physical properties required at the low temperature and the high temperature in the dynamic viscoelasticity were shown to be advantageous. In particular, the initial and sustained tack result is improved compared to the comparative example, it was found that also excellent in interfacial bond strength after vulcanization.

본 발명의 합성고무계 시멘트 조성물은 기존의 천연고무계 시멘트 조성물 대비 합성고무의 반제품 고무간 계면 점착성을 높이고, 가교후 접착강도를 증진시키는 효과가 있으며, 보다 환경 친화적 재료로 구성하여 사용하므로써 인체 유해성 측면에서도 개선된 효과를 나타낸다.Synthetic rubber-based cement composition of the present invention has the effect of improving the interfacial adhesion between the semi-finished rubber of synthetic rubber compared to the existing natural rubber-based cement composition, and improves the adhesive strength after crosslinking, in terms of human hazards by using a more environmentally friendly material It shows an improved effect.

Claims (2)

천연고무:이소프렌고무:용액중합 스티렌-부타디엔 고무:유화중합 스티렌-부타디엔 고무:부타디엔고무가 5∼20:5∼20:30∼45:30∼45:5∼20의 중량비로 이루어진 바인더 100중량부에 대하여 변성 페놀-포름알데히드 레진 3∼5중량부를 포함하는 합성고무계 시멘트 조성물.Natural rubber: Isoprene rubber: Solution polymerization Styrene-butadiene rubber: Emulsification polymerization Styrene-butadiene rubber: Butadiene rubber 100 weight part of binder which consists of 5-20: 5-20: 30-45: 30-45: 5-20 Synthetic rubber-based cement composition comprising 3 to 5 parts by weight of modified phenol-formaldehyde resin. 제 1항에 있어서, 상기 시멘트 조성물은 지방족 용제와 혼합, 교반하여 얻어진 용액의 형태로 사용되는 것을 특징으로 하는 합성고무계 시멘트 조성물.The synthetic rubber-based cement composition according to claim 1, wherein the cement composition is used in the form of a solution obtained by mixing and stirring with an aliphatic solvent.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990031480A (en) * 1997-10-13 1999-05-06 홍건희 Rubber composition for tire tread
KR20050115650A (en) * 2004-06-04 2005-12-08 금호타이어 주식회사 Tread rubber composition of wear improvement for pcr tire
KR20060104180A (en) * 2005-03-29 2006-10-09 금호타이어 주식회사 Cement composition for tire tread adhesion
KR20070009165A (en) * 2005-07-15 2007-01-18 금호타이어 주식회사 Synthetic rubber based cement composition for tire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990031480A (en) * 1997-10-13 1999-05-06 홍건희 Rubber composition for tire tread
KR20050115650A (en) * 2004-06-04 2005-12-08 금호타이어 주식회사 Tread rubber composition of wear improvement for pcr tire
KR20060104180A (en) * 2005-03-29 2006-10-09 금호타이어 주식회사 Cement composition for tire tread adhesion
KR20070009165A (en) * 2005-07-15 2007-01-18 금호타이어 주식회사 Synthetic rubber based cement composition for tire

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