JPS63112636A - Pneumatic tire having improved side appearance - Google Patents
Pneumatic tire having improved side appearanceInfo
- Publication number
- JPS63112636A JPS63112636A JP61255789A JP25578986A JPS63112636A JP S63112636 A JPS63112636 A JP S63112636A JP 61255789 A JP61255789 A JP 61255789A JP 25578986 A JP25578986 A JP 25578986A JP S63112636 A JPS63112636 A JP S63112636A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- surface layer
- inner layer
- layer
- phenylenediamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 30
- 229920001971 elastomer Polymers 0.000 claims abstract description 28
- 239000005060 rubber Substances 0.000 claims abstract description 28
- 239000002344 surface layer Substances 0.000 claims abstract description 27
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 7
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 7
- 229920001194 natural rubber Polymers 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract 5
- 239000011324 bead Substances 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 230000003712 anti-aging effect Effects 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920003051 synthetic elastomer Polymers 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 238000002845 discoloration Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- 229920003244 diene elastomer Polymers 0.000 abstract 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KMFPSPFHUHOGOA-UHFFFAOYSA-N 1-N-phenyl-4-N-tridecan-2-ylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CCCCCCCCCCC)=CC=C1NC1=CC=CC=C1 KMFPSPFHUHOGOA-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CYIFVRUOHKNECG-UHFFFAOYSA-N tridecan-2-one Chemical compound CCCCCCCCCCCC(C)=O CYIFVRUOHKNECG-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IEDKVDCIEARIIU-UHFFFAOYSA-N 2-Nonadecanone Chemical compound CCCCCCCCCCCCCCCCCC(C)=O IEDKVDCIEARIIU-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- VJJYYGFAZVNHAZ-UHFFFAOYSA-N 4-n-(4-ethylphenyl)benzene-1,4-diamine Chemical compound C1=CC(CC)=CC=C1NC1=CC=C(N)C=C1 VJJYYGFAZVNHAZ-UHFFFAOYSA-N 0.000 description 1
- JQTYAZKTBXWQOM-UHFFFAOYSA-N 4-n-octan-2-yl-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CCCCCC)=CC=C1NC1=CC=CC=C1 JQTYAZKTBXWQOM-UHFFFAOYSA-N 0.000 description 1
- 241000254043 Melolonthinae Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- -1 N-(1,3-dimethylbutyl)-N'- (4'-ethylphenyl)-p-phenylenediamine Chemical compound 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゴム組成物、特に極めて長期間使用されるトラ
ック・バス用タイヤのサイドウオール部や、乗用車用タ
イヤのサイドウオール部に好適に使用されるゴム組成物
に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is suitable for use in rubber compositions, particularly in the sidewalls of truck and bus tires that are used for extremely long periods of time, and the sidewalls of passenger car tires. The present invention relates to a rubber composition.
（従来の技術）
自動車用タイヤの耐久性は益々改良され、特にトラック
・ハス用タイヤはトレッドの更生を２〜３回実施するこ
とは珍らしくなくなってきた。しかしながら、このよう
に更生を縁返して長期使用されるタイヤは必ずしも多い
とは言えず、使用中にカットによる故障やサイドウオー
ルのオゾンクラックによる廃品化といった問題も多くこ
れらの問題を解決し、更生比率を更に高めることは経済
的に極めて重要な問題である。(Prior Art) The durability of automobile tires has been improved more and more, and it is no longer uncommon for tires for trucks and lotuses in particular to undergo tread retreading two or three times. However, it cannot be said that there are many tires that can be used for a long time after being retreaded in this way, and there are many problems such as failure due to cuts during use or scrapping due to ozone cracks in the sidewall. Further increasing the ratio is an extremely important economic issue.
また乗用車用タイヤにおいては、丈夫て長持ちすること
を特に咀視されるのみではなく、自動車の高性脂化及び
高級化に伴ない、タイヤにもファツション性に富んだも
のか要求されるようになってきた。In addition, not only are tires for passenger cars required to be strong and long-lasting, but as automobiles become more highly oily and luxurious, tires are also required to be fashionable. It has become.
一方一般にサイドウオール部は、オゾンクラックを受け
るために、耐オゾン性老化防止剤例えばＮ−（１，３−
ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジ
アミンやＮ−イソプロピル−Ｎ′−フェニル−ｐ−フェ
ニレンジアミン等が使用されている。しかしながら比較
的持続性が良いとされているＮ−（１，３−ジメチルブ
チル）−Ｎ′−フェニルーｐ−フェニレンジアミンても
、トラック・バス用タイヤにおいてはタイヤのｍ１次寿
命から１回更生後の第２次寿命の中期頃までにほとんど
消費されてしまい、使用末期においてはオゾンに対する
抵抗力が全く失われた状思で走行せざるを得ない、また
乗用車用タイヤにおいては上記老化防止剤は、タイヤ版
売店に在庫中、展示中あるいはタイヤ走行中、タイヤ表
面を茶色に変色させ、外観を著しく汚染し、特に展示中
にこのような変色が現れると、−遍に商品価値の低下を
招くといった欠点を有していた。On the other hand, generally sidewalls are treated with ozone-resistant anti-aging agents such as N-(1,3-
Dimethylbutyl)-N'-phenyl-p-phenylenediamine and N-isopropyl-N'-phenyl-p-phenylenediamine are used. However, even with N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, which is said to have relatively good durability, it is used in truck and bus tires after one retreading period from the tire's primary lifespan. Most of the anti-aging agent is consumed by the middle of the second life of the tire, and at the end of its life the driver is forced to drive as if it has completely lost its resistance to ozone. When the tire is in stock at a tire shop, on display, or while the tire is in motion, the tire surface turns brown, significantly contaminating the exterior, and especially when such discoloration appears during display, it can lead to a decline in product value. It had such drawbacks.
（発明が解決しようとする問題点）
上記のように、大型タイヤの使用末期までオゾンに対し
て充分抵抗力を有し、小型タイヤで問題となる茶色変色
がなく、オゾンに対する抵抗力も充分に有するサイドウ
オール部か現状では得られていないという問題点を解決
することを目的として鋭意検討した結果、本発明に到達
したものである。(Problems to be Solved by the Invention) As mentioned above, large tires have sufficient resistance to ozone until the end of their use, do not cause brown discoloration, which is a problem with small tires, and have sufficient resistance to ozone. The present invention was arrived at as a result of intensive studies aimed at solving the problem that sidewall parts are not currently available.
（［３１題点を解決するための手段）
本発明は特定のＰ−フェニレンジアミン系老化防１Ｌ剤
をサイドウオールの表面層と内部層に配合し、表面層中
の老化防止剤重量を少なくし、内部層中の老化防止剤重
量を多くすることにより、表面層中の老化防止剤でオゾ
ンクララフの発生が防止・遅延され、内部層中の老化防
止剤で老化防止剤が表面層に移行することてオゾンクラ
ックの成長を防止・遅延されること、かつ変色も改善さ
れることを見出したものである。(Means for Solving Problem 31) The present invention incorporates a specific P-phenylenediamine anti-aging agent into the surface layer and internal layer of the sidewall to reduce the weight of the anti-aging agent in the surface layer. By increasing the weight of the anti-aging agent in the inner layer, the anti-aging agent in the surface layer prevents and delays the generation of ozone clarification, and the anti-aging agent in the inner layer causes the anti-aging agent to migrate to the surface layer. It was discovered that the growth of ozone cracks can be prevented and delayed, and discoloration can also be improved.
即ち本発明は第１図に示すとおりサイドウオールの表面
層を構成するゴム組成物として、天然ゴム及びジエン系
合成ゴムよつなる群の中から選ばれた少なくとも１種の
ゴム１１）Ｏｉ開部に対し、老化防止剤として。That is, as shown in FIG. 1, the present invention uses at least one rubber selected from the group consisting of natural rubber and diene synthetic rubber as a rubber composition constituting the surface layer of the sidewall. However, as an anti-aging agent.
（Ｒ’及びＲは水素原子またはアルキル基であり、かつ
ＲとＲ′における炭素数の和は３〜１９である。）
ｐ−フェニレンシアミン系老化防止剤よりなる群の中か
ら選ばれた少なくとも１種の老化防ｌＩ：剤を０．１〜
１０屯量部のＷＡＩＭ内で配合してなるゴム組成物、ま
た内部層を構成するゴム組Ｊ＆物として天然ゴム及びジ
エン系合成ゴムよりなる群の中から選ばれた少なくとも
ｌ Ｊ４のゴム１００重量部に対し、老化防止剤として
。(R' and R are hydrogen atoms or alkyl groups, and the sum of the carbon numbers in R and R' is 3 to 19.) Selected from the group consisting of p-phenylenecyamine anti-aging agents. At least one anti-aging agent: 0.1~
A rubber composition compounded in 10 tonne parts of WAIM, and at least l J4 rubber selected from the group consisting of natural rubber and diene-based synthetic rubber as a rubber composition constituting the inner layer. as an anti-aging agent.
（Ｒ’及びＲは水素原子またはアルキル基であり、かつ
ＲとＲ′における炭ｇａの和は３〜６である。）
ｐ−フェニレンジアミン系老化防止剤よりなる群の中か
ら選ばれた少なくともｌ稚の老化防止剤を０．１５〜１
５市量部の範囲内で配合してなるゴム組成物によって構
成し１表面層と内部層に配合される老化防ＩＥ剤の重量
比はｌ／１．５〜１１５てあり、表面層と内部層の厚さ
の比を３／】〜１／３とすることを特徴とする。(R' and R are a hydrogen atom or an alkyl group, and the sum of carbon ga in R and R' is 3 to 6.) At least one selected from the group consisting of p-phenylenediamine anti-aging agents. 0.15 to 1% of the anti-aging agent
The weight ratio of the anti-aging IE agent blended into the surface layer and the inner layer is 1/1.5 to 115, and the weight ratio of the anti-aging IE agent blended into the surface layer and the inner layer is 1/1.5 to 115. It is characterized by having a layer thickness ratio of 3/] to 1/3.
本発明にふいて使用するゴムとしては、天然ゴム、合成
ポリイソプレンゴム、ブチルゴム等てあり、これらのゴ
ムを中独もしくは２Ｊｉｉ以上併用できる。Rubbers used in the present invention include natural rubber, synthetic polyisoprene rubber, butyl rubber, etc., and these rubbers can be used in combination.
本発明においてサイドウオール部の表面層及び内部層に
配合する老化防止剤としては、特にＮ−イソプロピル＝
Ｎ′−フェニル−ｐ−フェニレンジアミン、Ｎ−（１，
３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレ
ンジアミン、Ｎ−（１−メチルへブチル）−Ｎ′−フェ
ニル−ｐ−フェニレンジアミン、Ｎ−（１，３−ジメチ
ルブチル）−Ｎ′−（４’−エチルフェニル）−ｐ−フ
ェニレンジアミン、Ｎ−（１，４−ジメチルへブチル）
−Ｎ′−フェニル−ｐ−フェニレンシアミン、Ｎ−（１
−メチルドデシル）−Ｎ′−フェニル−ｐ−フェニレン
ジアミン、Ｎ−（１−メチルオクタデシル）−Ｎ′−フ
ェニル−ｐ−フェニレンシアミン等であり、表面層での
配合量は［１，１〜１０屯賃部、内部層での配合量は０
．１５〜１５ ｍ ４１ｉ部である。In the present invention, the anti-aging agent to be added to the surface layer and inner layer of the sidewall portion is particularly N-isopropyl=
N'-phenyl-p-phenylenediamine, N-(1,
3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylhebutyl)-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'- (4'-ethylphenyl)-p-phenylenediamine, N-(1,4-dimethylhebutyl)
-N'-phenyl-p-phenylenecyamine, N-(1
-methyldodecyl)-N'-phenyl-p-phenylenediamine, N-(1-methyloctadecyl)-N'-phenyl-p-phenylenecyamine, etc., and the amount blended in the surface layer is [1,1- 10 tons, the amount blended in the inner layer is 0
．． 15-15 m 41i parts.
０．１重ＪＡ部未満ては添加の効果かなく、１５爪量部
を越えるとゴム組成物の機械的性質の悪化や、ゴム表面
の茶褐色変色か著しくなり好ましくない。If the amount is less than 0.1 weight JA parts, there will be no effect, and if it exceeds 15 weight parts, the mechanical properties of the rubber composition will deteriorate and the rubber surface will become noticeably brownish, which is undesirable.
また表面層と内部層の厚さの比は３／１・〜１／コてあ
り、好ましくはＩ／１〜１／３である。使用範囲か前記
範囲外ではサイドウオール部表面層と内部層にそれぞれ
配合された老化防止剤の相乗効果か期待できない。なお
本発明においてサイ１−ウオール部の範囲とは、第１図
に示しているゴムチェーファ−まで及んでもよい。The ratio of the thickness of the surface layer to the inner layer is 3/1 to 1/3, preferably I/1 to 1/3. If the usage range is outside the above-mentioned range, no synergistic effect can be expected between the anti-aging agents incorporated in the surface layer and the inner layer of the sidewall portion, respectively. In the present invention, the scope of the first wall portion may extend to the rubber chafer shown in FIG.
本発明においては、上述の老化防止剤以外にゴム工業で
通常使用される配合剤、例えばワックス類、軟化剤、加
硫促進剤、加硫促進助剤、加硫剤等を必要に応して通常
の配合量の範囲内で配合することができる。In the present invention, in addition to the above-mentioned anti-aging agent, compounding agents commonly used in the rubber industry, such as waxes, softeners, vulcanization accelerators, vulcanization accelerators, vulcanizing agents, etc., may be used as necessary. It can be blended within the usual range of blending amounts.
また本発明のゴム組成物は、タイヤ特にサイドウオール
用として好適に使用できる。Further, the rubber composition of the present invention can be suitably used for tires, especially sidewalls.
（実施例）
以下１本発明を合成例、″：５施例及び比較例により詳
細に説明する。(Example) The present invention will be explained in detail below using 1 Synthesis Example, 5 Examples, and Comparative Example.
へ虞
ｐ−アミノジフェニルアミン１．：１８ ｇ （０，７
５モル）及び炭ぶ担持白金触媒２．８ｇを２−オクタノ
ン１４４ ｇ （１，１３モル）と共に攪拌機、水素導
入口及び脱気口を具備した高圧反応合憲に入れる。水素
を用い１反応容器内の酸素を脱気する。水素を導入し、
攪拌しながら徐々に加熱し水素を０．７５モル吸収させ
る。５０°Ｃまで冷却し、触媒を濾別する、 濾別シタ
慮液ヲ１７０ ’Ｃ，５ｍＪｇ！Ｔｅ１ｌｌｌシ、 Ｈ
縮残か目的とするＮ−（１−メチルヘプチル）−Ｎ′−
フェニル−ｐ−フェニレンシアミンである。収４：２１
９．９ ｇ、収率９９．１％。p-aminodiphenylamine 1. :18 g (0,7
5 mol) and 2.8 g of charcoal-supported platinum catalyst were placed together with 144 g (1.13 mol) of 2-octanone in a high-pressure reactor equipped with a stirrer, a hydrogen inlet and a degassing port. Oxygen in one reaction vessel is degassed using hydrogen. Introducing hydrogen,
While stirring, the mixture is gradually heated to absorb 0.75 mol of hydrogen. Cool to 50°C, filter out the catalyst, and filter the solution at 170'C, 5mJg! Tellll, H
Residue or target N-(1-methylheptyl)-N'-
It is phenyl-p-phenylenecyamine. 4:21 am
9.9 g, yield 99.1%.
合成例２ Ｎ−（１，４−ジメチルヘプチル）−Ｎ′
−フェニル−ｐ−フェニレンシア
旦２
合成例１にやじ２〜オクタノンの代りに５−メチル−２
−才クタノン１５９．８ ｇ （１，１：１モル）を用
い、反応、ｅａｔ、、Ｆｌ 的トｔ ルＮ −（１、４
−シ：１チＪレヘブチル）−Ｎ’−フェニル−ｐ−フェ
ニレンシアミンをｔｌ）た。収量２：１１．４ Ｋ、収
＋９ｇ、５％。Synthesis Example 2 N-(1,4-dimethylheptyl)-N'
-Phenyl-p-phenylenethiadan 2 Synthesis Example 1 Yaji 2 - 5-methyl-2 instead of octanone
Using 159.8 g (1,1:1 mol) of 159.8 g (1,1:1 mol), the reaction was carried out using 159.8 g (1,1:1 mol) of
-N'-phenyl-p-phenylenecyamine (tl). Yield 2: 11.4 K, yield +9g, 5%.
合成例１に準じ２−オクタノンの代りに２−トリデカノ
ン２２２．８ ｇ （１，１３モル）を用い１反応、ｅ
ｍし目的とするＮ−（１−メチルドデシルＮ′−フェニ
ル−ｐ−フェニレンジアミンを得た。収：誹２６１．９
ｇ、収率９５．４％。One reaction was carried out according to Synthesis Example 1 using 222.8 g (1.13 mol) of 2-tridecanone instead of 2-octanone, e.
The desired N-(1-methyldodecylN'-phenyl-p-phenylenediamine) was obtained. Yield: 261.9
g, yield 95.4%.
合成例１に準じｐ−アミノジフェニルアミンの代りにＮ
−（４−エチルフェニル）−ｐ−フェニレンジアミン（
注１ ） ＩＳ９．Ｑ ｇ （０．７５モル）を用い、
また２−オクタノンの代りに４−メチル−２−ペンタノ
ン１１２．５ ｇ （１，１３モル）を用い反応。According to Synthesis Example 1, N was substituted for p-aminodiphenylamine.
-(4-ethylphenyl)-p-phenylenediamine (
Note 1) IS9. Using Q g (0.75 mol),
In addition, 112.5 g (1.13 mol) of 4-methyl-2-pentanone was used instead of 2-octanone.
濃縮し、目的とするＮ−（１，３−ジメチルブチル’）
−Ｎ’ −（４’エチルフエニル）−ｐ−フェニレンジ
アミンを得た。収量２２：１．Ｏｇ、収率１００％。Concentrate and obtain the desired N-(1,3-dimethylbutyl')
-N'-(4'ethylphenyl)-p-phenylenediamine was obtained. Yield 22:1. Og, yield 100%.
Ｐ−クロルニトロベンゼン２モル（＋ｔｓｇ）及びｐ−
エチルアニリン４モル（４８４ｇ）及び炭酸カリウム１
．１モル（１５１，８ｇ ）及びシアン化銅４ｇをキシ
レン３０ ａｎと共に、攪拌機、水分離器、還流冷却器
及び温度計をＡ愉した丸底フラスコ中に入れる。攪拌し
ながら徐々に加熱し、佛とうさせ、水を１９．５ ａｎ
流出させる。１００℃まで冷却し、性別し、沈殿物はト
ルエンで洗浄する。１！！別した鑓液とトルエン洗浄液
を一緒に共に真空ポンプを用い１９Ｇ’ｃ、７ ａｍ）
Ｉｇまで濃縮し、未反応のｐ−クロルニトロベンゼン及
びｐ−エチルアニリン、キシレン、トルエンを留去する
。ｅｉｍ物として４−エチル−４′−ニトロジフェニル
アミンが得られる。収量２４８ ｇ、収率５１．２％て
あった。この４−エチル−４′−二トロジフェニルアミ
ン１モル（２４２ｇ）を用い、ラネーニッケル触媒ｌｏ
ｇとイソプロピルアルコール：１５０ ｒａＬ；Ｌと
共に、攪拌機、水素導入口及び脱気口を備えた高圧反応
容器に入れる。水素を用い、反応容器の！＃素を脱気す
る。水素を導入し、攪拌しながら徐々に加熱し、水素３
モルを吸収させる。５０℃まで冷却し、触媒を諸別後、
吐液を濃縮し、２０２℃、４ａｕｓｌｔｇの条件で蒸留
し、目的とするＮ−（４−エチルアニリンΩＡ１
合成例１に準じ２−オクタノンの代りにメチルヘプタデ
シルケトン：１１８ ｇ （１，１３モル）を用い、反
応、濃縮し目的とするＮ−（１−メチルオクタデシル）
−Ｎ′−フェニル−ｐ−フェニレンジアミンを得た。収
Ｑ３３５ ｇ、収率９８．９％を得た。2 moles of p-chlornitrobenzene (+tsg) and p-
4 moles (484 g) of ethylaniline and 1 potassium carbonate
．． 1 mol (151.8 g) and 4 g of copper cyanide are placed together with 30 ann of xylene in a round bottom flask equipped with a stirrer, water separator, reflux condenser and thermometer. Gradually heat while stirring and boil water to 19.5 an
Let it flow. Cool to 100°C, strain, and wash the precipitate with toluene. 1! ! Combine the separated sintering liquid and toluene cleaning liquid together using a vacuum pump (19G'c, 7 am).
The mixture is concentrated to Ig, and unreacted p-chloronitrobenzene, p-ethylaniline, xylene, and toluene are distilled off. 4-ethyl-4'-nitrodiphenylamine is obtained as an eim product. The yield was 248 g, yield 51.2%. Using 1 mole (242 g) of this 4-ethyl-4'-nitrodiphenylamine, Raney nickel catalyst lo
g and isopropyl alcohol: 150 raL; L into a high-pressure reaction vessel equipped with a stirrer, a hydrogen inlet, and a degassing port. of a reaction vessel using hydrogen! # Degas the base. Introduce hydrogen and gradually heat while stirring until hydrogen 3
Absorb moles. After cooling to 50℃ and separating the catalyst,
The discharged liquid was concentrated and distilled under the conditions of 202°C and 4ausltg to obtain the desired N-(4-ethylaniline ΩA1.Methylheptadecylketone: 118 g (1.13 mol) in place of 2-octanone according to Synthesis Example 1. ) to react and concentrate the desired N-(1-methyloctadecyl).
-N'-phenyl-p-phenylenediamine was obtained. A total weight of 335 g was obtained, with a yield of 98.9%.
実施例１〜２０ 比較例２１〜２４天然ゴム５０重
賃部とシス−１，４−ポリブタジェンゴム５０屯？部、
ＦＥＦカーボンブラウク５０重量部、ステアリン酸２−
１１１部、ミクロクリスタリンワックス２屯お部、亜鉛
層３重か部、Ｎ−オキシジエチレン−２−ベンゾチアゾ
ールスルフェンアミド１．０重量部、硫黄１．５重量部
に第１表に示した種々の老化防止剤を配合したゴム１ｉ
ｉＪ＆、！ｌｋをバンバリーミキサ−で混練して作成し
た。Examples 1 to 20 Comparative Examples 21 to 24 50 parts of natural rubber and 50 tons of cis-1,4-polybutadiene rubber? Department,
FEF Carbon Brauch 50 parts by weight, 2-stearic acid
111 parts of microcrystalline wax, 2 parts of microcrystalline wax, 3 parts of zinc layer, 1.0 parts by weight of N-oxydiethylene-2-benzothiazolesulfenamide, 1.5 parts by weight of sulfur, and various components shown in Table 1. Rubber 1i containing anti-aging agent
iJ &,! It was prepared by kneading lk in a Banbury mixer.
タイへ！サイズＩＧ５ ＳＲ１：ｌのサイドウオール部
を７分割して上記各種ゴム組成物をサイドウオール部に
使用し、第１図のごとく表面層と内部層の二層構造にし
て表面層と内部層の厚さの比を１７３にした乗用車用タ
イヤを作成した。このタイヤを屋外に設置した鉄製トラ
ムヒで速度ＳＯｋｍ／ｈの条件で５万ｋｍ、１０万ｋｍ
走行させた時のオゾンクラック性を１１視により観察し
、クラック程度を５段階（数字か小さい程良好）て評価
した。To Thailand! The sidewall part of size IG5 SR1:l was divided into seven parts, the various rubber compositions mentioned above were used for the sidewall part, and the thickness of the surface layer and the inner layer was changed to have a two-layer structure of a surface layer and an inner layer as shown in Fig. 1. A passenger car tire with a diameter ratio of 173 was created. This tire is installed outdoors on a steel tram vehicle with a speed of 50,000km and 100,000km at a speed of SOkm/h.
The ozone cracking property during running was observed under 11-scanning, and the degree of cracking was evaluated in five stages (the smaller the number, the better).
また同時にゴム表面の茶色変色度合も［１視により評価
し、やはり５段階（ａ字か小さい程良好）で評価した。At the same time, the degree of brown discoloration of the rubber surface was also evaluated by one viewing, and was also evaluated on a 5-level scale (the smaller the letter A, the better).
結果を第１表に示す。The results are shown in Table 1.
実施例２１〜３１ 比較例２５〜２日実施例１〜２０
と同じように、表面層と内部層の厚さの比による本発明
の結果を第２表に示す。Examples 21-31 Comparative Example 25-2 days Examples 1-20
Similarly, Table 2 shows the results of the present invention according to the ratio of the thickness of the surface layer and the inner layer.
（発明の効果）
サイ［・つオール部の表面層に配合する老化防止剤とし
てトｚ−イソプロピルーＮ′−フェニル−ｐ−フェニレ
ンジアミン、Ｎ−（１，：ｌ−ジメチルブチル）−Ｎ゛
−フェニル−ｐ−フェニレン・ジアミン、Ｎ−（１−メ
チルヘプチル）−Ｎ′−フェニル−Ｐ−フェニレンジア
ミン、 Ｎ−（１，：ｌ−ジメチルブチル）−Ｎ′ （
４−エチルフェニル）−ｐ−フェニレンジアミン、Ｎ−
（１−メチルドデシル）−Ｎ′−フェニル−ｐ−フェニ
レンジアミン、Ｎ−（１−メチルオクタデシル）−Ｎ′
−フェニル−ｐ−フェニレンジアミンからなる群より選
択された少なくとも１種の老化防止剤を内部層に配合す
る老化防止剤してＮ−イソプロピル＝Ｎ′−フェニル−
ｐ−フェニレンジアミン、Ｎ−（１，３−ジメチルブチ
ル）−Ｎ′−ツボニル−ｐ−フェニレンシアミンを表面
層に少なく内部層に多く配合した。ゴム組成物は耐オゾ
ン性に優れかつ、その効果が著しく長期間にわたって完
揮される、かつ老化防止剤を主要原因とする茶色変色か
極めて少なくなる。(Effect of the invention) As an anti-aging agent blended into the surface layer of the cy[-triol part, toz-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,:l-dimethylbutyl)-N' -Phenyl-p-phenylene diamine, N-(1-methylheptyl)-N'-phenyl-P-phenylenediamine, N-(1,:l-dimethylbutyl)-N' (
4-ethylphenyl)-p-phenylenediamine, N-
(1-methyldodecyl)-N'-phenyl-p-phenylenediamine, N-(1-methyloctadecyl)-N'
-Phenyl-p-phenylene diamine At least one anti-aging agent selected from the group consisting of p-phenylene diamine is blended into the inner layer.
A small amount of p-phenylenediamine and N-(1,3-dimethylbutyl)-N'-tubonyl-p-phenylenecyamine was blended in the surface layer and a larger amount in the inner layer. The rubber composition has excellent ozone resistance, exhibits its effects over a significantly long period of time, and has very little brown discoloration caused mainly by anti-aging agents.
第１図は本発明の乗用車用空気入りタイヤの周方向１部
半裁断面図である。
１：トレ・ンドFIG. 1 is a circumferential half-section view of a pneumatic tire for a passenger car according to the present invention. 1:Traindo
Claims (1)
気入りタイヤにおいて前記サイドウォール部を表面層・
内部層の二層構造にし、表面層を構成するゴム組成物と
して天然ゴム及びジエン系合成ゴムよりなる群の中から
選ばれた少なくとも１種のゴム１００重量部に対し、老
化防止剤として、 ▲数式、化学式、表等があります▼の構造式を持つ （Ｒ′及びＲは水素原子またはアルキル基であり、かつ
ＲとＲ′における炭素数の和は３〜１９である。） ｐ−フェニレンジアミン系老化防止剤よりなる群の中か
ら選ばれた少なくとも１種の老化防止剤を０．１〜１０
重量部の範囲内で配合してなるゴム組成物また内部層を
構成するゴム組成物として天然ゴム及びジエン系合成ゴ
ムよりなる群の中から選ばれた少なくとも１種のゴム１
００重量部に対し、老化防止剤として、 ▲数式、化学式、表等があります▼の構造式を持つ （Ｒ′及びＲは水素原子またはアルキル基であり、かつ
ＲとＲ′における炭素数の和は３〜６である。） ｐ−フェニレンジアミン系老化防止剤よりなる群の中か
ら選ばれた少なくとも１種の老化防止剤を０．１５〜１
５重量部の範囲内で配合してなるゴム組成物によって構
成し、 表面層と内部層に配合される老化防止剤の重量比は１／
１．５〜１／５であり、表面層と内部層の厚さの比を３
／１〜１／３とすることを特徴とするサイド外観が改良
された空気入りタイヤ。[Claims] In a pneumatic tire comprising a tread portion, a sidewall portion, and a bead portion, the sidewall portion is formed by forming a surface layer.
▲ As an anti-aging agent, to 100 parts by weight of at least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber as a rubber composition constituting a two-layer inner layer and a surface layer. There are mathematical formulas, chemical formulas, tables, etc.Having the structural formula ▼ (R' and R are hydrogen atoms or alkyl groups, and the sum of the carbon numbers in R and R' is 3 to 19.) p-phenylenediamine 0.1 to 10% of at least one antiaging agent selected from the group consisting of antiaging agents.
At least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber 1 as a rubber composition or a rubber composition constituting the inner layer, blended within the range of parts by weight.
00 parts by weight, as an anti-aging agent, it has the structural formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R' and R are hydrogen atoms or alkyl groups, and the sum of the carbon numbers in R and R' is 3 to 6.) At least one antioxidant selected from the group consisting of p-phenylenediamine antioxidants is added in an amount of 0.15 to 1.
It is composed of a rubber composition containing 5 parts by weight of an anti-aging agent, and the weight ratio of the anti-aging agent blended into the surface layer and the inner layer is 1/1.
1.5 to 1/5, and the ratio of the thickness of the surface layer to the inner layer is 3.
A pneumatic tire with an improved side appearance, characterized in that the size is 1/1 to 1/3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61255789A JPH0764954B2 (en) | 1986-10-29 | 1986-10-29 | Pneumatic tire with improved side appearance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61255789A JPH0764954B2 (en) | 1986-10-29 | 1986-10-29 | Pneumatic tire with improved side appearance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112636A true JPS63112636A (en) | 1988-05-17 |
| JPH0764954B2 JPH0764954B2 (en) | 1995-07-12 |
Family
ID=17283651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61255789A Expired - Fee Related JPH0764954B2 (en) | 1986-10-29 | 1986-10-29 | Pneumatic tire with improved side appearance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764954B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7082976B2 (en) * | 2001-12-11 | 2006-08-01 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire having tread portion formed of two layers |
| JP2009220692A (en) * | 2008-03-14 | 2009-10-01 | Bridgestone Corp | Tire |
| JP2010188955A (en) * | 2009-02-20 | 2010-09-02 | Sumitomo Rubber Ind Ltd | Tire |
| CN112074423A (en) * | 2018-06-18 | 2020-12-11 | 横滨橡胶株式会社 | Pneumatic tire |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632528A (en) * | 1979-08-24 | 1981-04-02 | Sumitomo Rubber Ind Ltd | Air tire having improved crack failure resistance |
-
1986
- 1986-10-29 JP JP61255789A patent/JPH0764954B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632528A (en) * | 1979-08-24 | 1981-04-02 | Sumitomo Rubber Ind Ltd | Air tire having improved crack failure resistance |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7082976B2 (en) * | 2001-12-11 | 2006-08-01 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire having tread portion formed of two layers |
| JP2009220692A (en) * | 2008-03-14 | 2009-10-01 | Bridgestone Corp | Tire |
| JP2010188955A (en) * | 2009-02-20 | 2010-09-02 | Sumitomo Rubber Ind Ltd | Tire |
| CN112074423A (en) * | 2018-06-18 | 2020-12-11 | 横滨橡胶株式会社 | Pneumatic tire |
| CN112074423B (en) * | 2018-06-18 | 2023-02-17 | 横滨橡胶株式会社 | Pneumatic tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764954B2 (en) | 1995-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0478274B1 (en) | Rubber composition | |
| KR100429351B1 (en) | Tires with tread reinforced with silica | |
| WO2013046804A1 (en) | Sidewall rubber composition and tire using same | |
| JP4086359B2 (en) | Pneumatic tire | |
| JP5480781B2 (en) | Rubber composition for pneumatic tread and pneumatic tire | |
| EP1022306B1 (en) | Rubber composition | |
| WO2019235526A1 (en) | Rubber composition and tire | |
| JP4321894B2 (en) | Pneumatic tire | |
| JPS63112636A (en) | Pneumatic tire having improved side appearance | |
| JP2009107435A (en) | Tire | |
| WO2019156093A1 (en) | Rubber composition and tire | |
| JPS63162738A (en) | Improved rubber composition | |
| JPS63112635A (en) | Pneumatic tire having improved side appearance | |
| JPS6310646A (en) | Rubber composition | |
| EP0969038B1 (en) | Rubber composition for tyre tread | |
| EP2013273B1 (en) | Antiozonant blends | |
| WO2021132496A1 (en) | Rubber composition, method for preparing same, and tire for construction vehicle | |
| CA1167068A (en) | N,n'-bis(1-cyclohexyl-1-ethyl)-p-phenylenediamine, and rubber compounds containing the same | |
| KR100778547B1 (en) | Tire tread rubber composition improved anti-abrasion properties | |
| JP2001098111A (en) | Rubber composition | |
| JPH05112674A (en) | Rubber composition with excellent rolling resistance | |
| JPH07278352A (en) | Pneumatic tire | |
| JP6927398B2 (en) | Rubber composition, its manufacturing method and tires for construction vehicles | |
| JPH059339A (en) | Improved rubber compositon | |
| JPH05140115A (en) | Sulfonamide compound and rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |