KR20010019162A - Non Discoloring White Sidewall Rubber Composition - Google Patents

Non Discoloring White Sidewall Rubber Composition Download PDF

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KR20010019162A
KR20010019162A KR1019990035444A KR19990035444A KR20010019162A KR 20010019162 A KR20010019162 A KR 20010019162A KR 1019990035444 A KR1019990035444 A KR 1019990035444A KR 19990035444 A KR19990035444 A KR 19990035444A KR 20010019162 A KR20010019162 A KR 20010019162A
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rubber
rubber composition
weight
parts
stabilizer
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KR1019990035444A
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Korean (ko)
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최윤희
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신형인
금호산업 주식회사
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Publication of KR20010019162A publication Critical patent/KR20010019162A/en

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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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • 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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A white sidewall rubber composition having non-discoloration ability is provided for increasing whiteness, physical property retaining ability by means of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate as UV stabilizer. CONSTITUTION: A white sidewall rubber composition having non-discoloration performance comprises alkyl ester phosphite as phosphites anti-oxidant instead of conventional BHT anti-oxidant and as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate as UV stabilizer to ensure discoloration-resistant property to be enhanced. The rubber composition contains 100 weight part of raw rubber consisting of natural rubber, EPDM rubber, butyl rubber, 0.5-7 weight part of alkyl ester phosphite and 0.01-5 weight part of UV stabilizer and other known filler, stearic acid or wax.

Description

비변색성 화이트 사이드월 고무조성물 {Non Discoloring White Sidewall Rubber Composition}Non Discoloring White Sidewall Rubber Composition

본 발명은 비변색성 화이트 사이드월 고무조성물에 관한 것으로 보다 상세하게는 종래에 사용되는 BHT 산화방지제 대신 포스파이트계 산화방지제인 알킬 에스터 포스파이트와 자외선 안정제인 비스(2,2,6,6-테트라메틸-4-피페리디닐)세바케이트를 첨가하여 내변색 특성을 향상시킨 화이트 사이드월 고무조성물에 관한 것이다.The present invention relates to a non-discolorable white sidewall rubber composition, and more specifically, an alkyl ester phosphite which is a phosphite-based antioxidant and a bis (2,2,6,6-ultraviolet stabilizer) instead of a conventional BHT antioxidant. The present invention relates to a white sidewall rubber composition in which tetramethyl-4-piperidinyl) sebacate is added to improve discoloration resistance.

종래의 화이트 사이드월의 고무조성물은 점착력을 향상시키기 위하여 파라옥틸계 페놀릭 레진을 사용하고 백색도 증진을 위해 충진제로 이산화티타늄 및 클레이를 사용하며, 노화방지를 위해 페놀계 산화방지제로 분자량이 작고 휘발성이 큰 BHT를 적용하는데 충진제인 이산화티타늄이 자외선에 의해 활성화되어 점착제의 분해를 촉진시켜 발색단을 생성시켜 배합물의 변색을 가속화하게 된다.The rubber composition of the conventional white sidewall uses paraoctyl phenolic resin to improve adhesion, uses titanium dioxide and clay as a filler to enhance whiteness, and has a low molecular weight and volatile phenolic antioxidant to prevent aging. In applying this large BHT, the filler, titanium dioxide, is activated by ultraviolet light, which accelerates the decomposition of the pressure-sensitive adhesive to generate chromophores, thus accelerating discoloration of the formulation.

타이어의 구성부위인 화이트 사이드월은 타이어의 외관품질과 직접적인 관련성을 갖고 있다. 타이어를 대기중에서 방치할 경우 대기중의 자외선이나 산소에 의해 충진제인 이산화티타늄의 산화에 의해 화이트 사이드월 고무의 변색이 심화되어 타이어의 외관 품질에 악영향을 미치기도 한다. 이러한 변색을 방지하기 위해 산화방지제인 BHT를 사이드월 고무조성물에 적용하여 사용하여 내변색 특성의 향상을 도모하고 있으나 BHT는 자외선 차단 및 흡수작용이 불가능하여 사이드월 고무의 내변색성에 대한 특성이 취약한 문제점이 있다.The white sidewalls that make up the tire are directly related to the appearance quality of the tire. When the tire is left in the air, the white sidewall rubber becomes discolored by the oxidation of titanium dioxide, a filler, by ultraviolet or oxygen in the air, which adversely affects the appearance quality of the tire. In order to prevent such discoloration, BHT, an antioxidant, is applied to the sidewall rubber composition to improve the discoloration resistance. However, BHT is incapable of blocking and absorbing UV rays, and thus is poor in discoloration resistance of the sidewall rubber. There is a problem.

본 발명은 공지의 사이드월 고무조성물에 산화방지제인 알킬 에스터 포스파이트와 자외선 안정제인 비스(2,2,6,6-테트라메틸-4-피페리디닐)세바케이트를 첨가함으로써 상기에서 언급한 사이드월 고무의 문제점의 해결 및 백색도, 노화 후 물성 유지력을 향상시킨 화이트 사이드월 고무조성물을 제공하는 것을 목적으로 한다.The above-mentioned side is obtained by adding an alkyl ester phosphite as an antioxidant and a bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate as an ultraviolet stabilizer to a known sidewall rubber composition. It is an object of the present invention to provide a white sidewall rubber composition which can solve the problems of the wall rubber and improve the whiteness and physical property retention after aging.

본 발명의 내변색 특성을 향상시킨 화이트 사이드월 고무조성물은 천연고무, 이피디엠(EPDM) 고무, 부틸고무로 구성된 원료고무 100 중량부에 대하여 포스파이트계 산화방지제인 알킬 에스터 포스파이트 0.5∼7 중량부, 하기의 구조식 (Ⅰ)으로 나타내는 자외선 안정제인 비스(2,2,6,6-테트라메틸-4-피페리디닐) 세바케이트 (Bis(2,2,6,6-tetramethyl-4-piperidinyl)Sebacate) 0.01∼5 중량부 및 공지의 충진제, 아연화, 스테아린산, 왁스 등으로 구성한다.The white sidewall rubber composition having improved discoloration resistance of the present invention is 0.5 to 7 weight of alkyl ester phosphite, which is a phosphite-based antioxidant, based on 100 parts by weight of a raw material rubber composed of natural rubber, EPDM rubber, and butyl rubber. In addition, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Bis (2,2,6,6-tetramethyl-4-piperidinyl) which is an ultraviolet stabilizer represented by the following structural formula (I) Sebacate) 0.01 to 5 parts by weight and a known filler, zincated, stearic acid, wax and the like.

(Ⅰ)(Ⅰ)

이하 본 발명을 다음의 실시예, 비교예, 시험예에 의하여 설명한다. 그러나 이들이 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following examples, comparative examples and test examples. However, these do not limit the technical scope of the present invention.

＜실시예 ＞<Example>

천연고무 50 중량부, 이피디엠 고무 15 중량부, 부틸고무 35 중량부로 구성된 원료고무 100 중량부에 대하여 충진제로 클레이 45 중량부, 점착제 4 중량부, 아연화 5 중량부, 스테아린산 1.5 중량부, 왁스 3 중량부, 기타 4.25 중량부, 자외선 안정제 비스(2,2,6,6-테트라메틸-4-피페리디닐)세바케이트 2 중량부, 산화방지제 알킬 에스터 포스파이트 2 중량부, 촉진제 1.2 중량부, 가류제 2.75 중량부, 지연제 0.1 중량부를 밴부리믹서에서 5분 동안 배합하고 160℃의 온도에서 방출하여 본 발명의 화이트 사이드월 고무시편을 제조하였다. 한편 아래의 표 1에 고무조성물의 배합비를 나타내었다.45 parts by weight of clay, 4 parts by weight of pressure-sensitive adhesive, 4 parts by weight of zinc, 5 parts by weight of stearic acid, 1.5 parts by weight of wax, based on 100 parts by weight of the raw material rubber consisting of 50 parts by weight of natural rubber, 15 parts by weight of EPDM rubber and 35 parts by weight of butyl rubber. Parts by weight, other 4.25 parts by weight, UV stabilizer bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate 2 parts by weight, antioxidant alkyl ester phosphite 2 parts by weight, accelerator 1.2 parts by weight, 2.75 parts by weight of vulcanizing agent and 0.1 parts by weight of retardant were blended in a Banburi mixer for 5 minutes and released at a temperature of 160 ° C. to prepare a white sidewall rubber specimen of the present invention. Meanwhile, Table 1 below shows the mixing ratio of the rubber composition.

＜비교예 ＞<Comparative Example>

자외선 안정제를 제거하고 산화방지제로 BHT 1.5 중량부를 사용하는 것을 제외하고는 상기 실시예와 같은 방법으로 하여 화이트 사이드월 고무시편을 제조하였다.White sidewall rubber specimens were prepared in the same manner as in Example except that the UV stabilizer was removed and 1.5 parts by weight of BHT was used as an antioxidant.

표 1. 고무조성물의 배합비(단위: 중량부)Table 1. Mixing ratio of rubber composition (unit: parts by weight)

배 합 비Compound ratio 비교예Comparative example 실시예Example 천연고무Natural rubber 5050 5050 이피디엠 고무EPDM Rubber 1515 1515 부틸고무Butyl rubber 3535 3535 이산화티타늄Titanium dioxide 3535 3535 클레이Clay 4545 4545 점착제adhesive 44 44 아연화Zincification 55 55 스테아르산Stearic acid 1.51.5 1.51.5 왁스Wax 33 33 기타Etc 4.254.25 4.254.25 BHTBHT 1.51.5 -- 자외선 안정제UV stabilizer -- 22 포스파이트계 노방제Phosphite-based preservatives -- 22 촉진제accelerant 1.21.2 1.21.2 가류제Vulcanizing agent 2.752.75 2.752.75 지연제Retardant 0.10.1 0.10.1

＜시험예 ＞<Test Example>

상기 실시예 및 비교예의 방법으로 제조한 사이드월 고무시편에 대한 물성 및 백색도를 ASTM 규격에 준하여 시험하였고, 그 결과를 아래의 표 2, 표 3에 나타내었다.The physical properties and whiteness of the sidewall rubber specimens prepared by the methods of Examples and Comparative Examples were tested according to ASTM standards, and the results are shown in Tables 2 and 3 below.

표 2. 물성시험 결과표Table 2. Property Test Results Table

물 성Properties 비교예Comparative example 실시예Example 100℃ 점도스코치 타임(t5)가류시간(t90)인장물성(노화 전/후)경도(Shore A)300% 모듈러스(kg/cm2)인장강도(kg/cm2)신율(%)100 ° C Viscosity Scotch Time (t5) Curing Time (t90) Tensile Properties (Before / After Aging) Hardness (Shore A) 300% Modulus (kg / cm 2 ) Tensile Strength (kg / cm 2 ) Elongation (%) 35.315.911.651(52)35.5(48.3)127(86)634(480)35.315.911.651 (52) 35.5 (48.3) 127 (86) 634 (480) 36.614.310.549(48)31.2(41.3)124(97)663(565)36.614.310.549 (48) 31.2 (41.3) 124 (97) 663 (565)

표 3. 백색도 측정결과(Whiteness value)Table 3. Whiteness value

조 건Condition 비교예Comparative example 실시예Example InitialUV 6hrsUV 12hrsUV 24hrsUV 48hrsThermal 17 hrs+UV 17hrsThermal 34 hrs+UV 17hrsThermal 17 hrs+UV 34hrsThermal 34 hrs+UV 34hrsInitialUV 6hrsUV 12hrsUV 24hrsUV 48hrsThermal 17 hrs + UV 17hrsThermal 34 hrs + UV 17hrsThermal 17 hrs + UV 34hrsThermal 34 hrs + UV 34hrs 91.8490.1489.4689.5889.1889.8990.8789.0489.2091.8490.1489.4689.5889.1889.8990.8789.0489.20 93.4292.9892.6192.5991.7992.5192.6791.6791.393.4292.9892.6192.5991.7992.5192.6791.6791.3

* 백색도 측정방법* How to measure whiteness

시편크기: 5×5 cmSpecimen size: 5 × 5 cm

Whiteness value: 100에 가까울수록 백색도가 우수하고, 0에 가까울수록 흑색도가 우수하다.Whiteness value: The closer to 100, the better the whiteness. The closer to 0, the better the blackness.

자외선 파장(UV Wavelength): 254mmUV Wavelength: 254mm

열처리 조건(thermal): 70℃ 열 챔버Thermal Treatment: 70 ° C Thermal Chamber

상기 표 2는 물성측정에 대한 결과로 가류특성은 비교예 대비 실시예는 동등 수준을 보이고 있으며, 기본물성의 경우 노화후의 300% 모듈러스의 물성 유지력(노화전 모듈러스/노화후 모듈러스 ×100)은 비교예에 비해 향상되었다. 특히 표 3에서 보는 바와 같이 BHT를 적용한 비교예 보다 비스(2,2,6,6-테트라메틸-4-피페리디닐)세바케이트와 알킬 에스터 포스파이트를 적용한 실시예에서의 백색도가 자외선 조사 시간에 관계없이 현저히 개선됨을 알 수 있다.Table 2 shows the vulcanization characteristics as compared to the comparative example as a result of the measurement of the physical properties, and in the case of the basic properties, the physical properties of the 300% modulus after aging (modulus before aging / modulus after aging × 100) is compared Improvement compared to the example. In particular, as shown in Table 3, the whiteness in the examples in which bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and alkyl ester phosphite were applied was compared to the comparative example in which BHT was applied. It can be seen that it is significantly improved regardless.

본 고무조성물의 경우 기존의 화이트 사이드월에 산화방지제인 BHT를 삭제하고 충진제인 이산화티타늄과 파라옥틸페놀계 레진 점착제의 자외선에 의한 분해를 억제하는 자외선 안정제와 산화방지 효과가 더 우수한 포스파이트계 산화방지제를 적용하여 타이어 백테의 노화전후의 백색도가 현저히 개선된다.This rubber composition removes BHT, an antioxidant, from the existing white sidewalls, and is a UV stabilizer that suppresses decomposition of UV-filled fillers such as titanium dioxide and paraoctylphenol-based resin adhesives. By applying the inhibitor, the whiteness of the tire bag frame before and after aging is remarkably improved.

Claims (1)

사이드월 고무조성물에 있어서, 천연고무, 이피디엠 고무 및 부틸고무로 구성된 원료고무 100 중량부에 대하여 아래의 구조식 (Ⅰ)으로 나타내는 자외선 안정제인 비스(2,2,6,6-테트라메틸-4-피페리디닐)세바케이트 0.01∼5 중량부, 산화방지제로 알킬 에스터 포스파이트 0.5∼7 중량부를 사용하는 것을 특징으로 하는 비변색성 화이트 사이드월 고무조성물In the sidewall rubber composition, bis (2,2,6,6-tetramethyl-4), which is an ultraviolet stabilizer represented by Structural Formula (I) below, based on 100 parts by weight of a raw material rubber composed of natural rubber, EPDM rubber and butyl rubber. Piperidinyl) sebacate 0.01-5 parts by weight, non-discolorable white sidewall rubber composition, characterized in that 0.5-7 parts by weight of alkyl ester phosphite is used as an antioxidant (Ⅰ)(Ⅰ)
KR1019990035444A 1999-08-25 1999-08-25 Non Discoloring White Sidewall Rubber Composition KR20010019162A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259227A (en) * 1979-09-21 1981-03-31 E. I. Du Pont De Nemours And Company Polyurethane compositions for tire sidewalls and composite articles
KR900018241A (en) * 1989-05-26 1990-12-20 존 제이. 마혼 Dynamically Vulcanized Composition with Improved Stiffness / Impact Balance
US5246990A (en) * 1990-11-22 1993-09-21 Sumitomo Chemical Company, Limited Cured ethylene.α-olefin copolymer-based rubber composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259227A (en) * 1979-09-21 1981-03-31 E. I. Du Pont De Nemours And Company Polyurethane compositions for tire sidewalls and composite articles
KR900018241A (en) * 1989-05-26 1990-12-20 존 제이. 마혼 Dynamically Vulcanized Composition with Improved Stiffness / Impact Balance
US5246990A (en) * 1990-11-22 1993-09-21 Sumitomo Chemical Company, Limited Cured ethylene.α-olefin copolymer-based rubber composition

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