CN103180128B - 轮胎的着色部的形成方法及通过该方法获得的轮胎 - Google Patents

轮胎的着色部的形成方法及通过该方法获得的轮胎 Download PDF

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CN103180128B
CN103180128B CN201180050726.0A CN201180050726A CN103180128B CN 103180128 B CN103180128 B CN 103180128B CN 201180050726 A CN201180050726 A CN 201180050726A CN 103180128 B CN103180128 B CN 103180128B
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S·科图尼奥
M·S·艾尔米
M·格鲁阿林
G·A·皮尔图西奥
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Abstract

本发明涉及轮胎的着色部的形成方法及通过所述方法获得的轮胎。所述方法包括：通过在轮胎的待着色部上沉积水性乳液来形成高度不渗透性保护层；和将着色层沉积在所述保护层上。所述水性乳液至少具有可交联聚合物类和分子式(I)的表面活性剂：(R1CONR2CHR3COO-)nXn+，其中：R1为C6-C23的脂族基，R2为H或C1-C8的脂族基，R3为H或C1-C8的脂族或芳族基，X为金属阳离子、优选碱金属阳离子，和n为1至3的整数。

Description

轮胎的着色部的形成方法及通过该方法获得的轮胎
技术领域
本发明涉及轮胎的着色部的形成方法。
背景技术
在轮胎工业中，出于各种原因，尤其是装饰性原因，过去几年间已出现了对着色的轮胎部的需求。
迄今为止已知的方法基于用适当颜料来着色橡胶混炼胶(rubber mix)。
最常用的方法基本上采用以下三层：轮胎内层上的连接层；由着色的混炼胶生产的着色层；和出售前除去的外部覆盖层。
这些方法的缺点在于主要由化学试剂从轮胎内层迁移至着色部所引起的着色部的过早劣化。为了延长着色部的保存，常规做法是增加着色层的厚度来减缓化学试剂的迁移，而这会造成生热增加、进而滚动阻力增加方面的其他问题。
发明内容
本发明的目的为提供一种轮胎的着色部的形成方法，用于消除已知技术的缺陷。
具体实施方式
根据本发明，提供一种轮胎的着色部的形成方法；所述方法包括以下步骤：
-通过在轮胎的待着色部上沉积水性乳液来形成高度不渗透性保护层；和
-将着色层沉积在所述保护层上；
所述方法的特征在于所述水性乳液至少包括可交联聚合物类(cross-linkable polymer base)和分子式(I)的表面活性剂
(R1CONR2CHR3COO-)n Xn+        (I)
其中：
R1为C6-C23的脂族基，
R2为H或C1-C8的脂族基，
R3为H或C1-C8的脂族或芳族基，
X为金属阳离子、优选碱金属阳离子，和
n为1至3的整数。
优选地，所述脂族基R1包括双键。
优选地，Xn+为Na+。
优选地，所述表面活性剂具有在包括以下分子式的组中的分子式：
CH3(CH2)7CHCH(CH2)7CONHCH2COO-X+
CH2CH(CH2)8CONHCH2COO-X+
优选地，所述填料在包括高岭土、粘土、云母、长石、硅石、石墨、膨润土、矾土和炭黑的组中。
优选地，所述可交联聚合物类包括Tg超过0℃的聚合物。
优选地，所述着色层由橡胶制成。
优选地，根据本发明的方法包括预压花步骤，在所述预压花步骤中使用激光压花所述轮胎的待着色部。
以下为非限制性实施例，用于更清楚地理解本发明。
实施例
以下为用于本发明保护层的混炼胶的描述。
所有这些混炼胶均通过采用高Tg聚合物和/或大量填料(在该情况下为粘土)而为高度不渗透性的。
高Tg聚合物和矿物填料的使用能够使混炼胶由包括至少一种分子式(I)的表面活性剂的水性乳液制备。事实上，在常规班伯里密炼机的方法中，分散组分如高Tg聚合物和矿物填料可造成严重问题，这通常通过增加混炼时间和温度来解决。然而，这不可避免地导致较高的能量消耗，并造成污染和成本方面的显著影响。另一方面，在乳液中混炼，根据本发明的所有混炼胶的能量消耗独立于所使用的组分类型。
因而通过将水性乳液沉积在轮胎的着色部如侧壁上；然后除去水来由获得的混炼胶生产保护层。
水性乳液均通过在水中分散并混炼混炼胶组分来生产。更具体地，通过将表I所示的所有成分同时分散在1升水中来生产乳液。将所得水性分散液(aqueous dispersion)机械搅拌30分钟，然后声波处理15分钟，从而形成水性乳液。
上述水性乳液制备过程决不构成对本发明的限制。
将乳液喷雾或刷涂在轮胎的侧壁上，然后除去水分来形成约0.3mm厚的保护层，向其施用商用的、厚度小于1mm的着色橡胶层-更具体地，已知由VENETADECALCOGOMME srl生产和销售的商品名为“Rubber Label ReelPalomino”的着色橡胶层。
着色橡胶层通常包括亚层(sublayer)：第一粘合剂亚层(使用时涂布在保护层上)；第二阻挡亚层；和实际着色的第三橡胶亚层。尽管该着色橡胶层结构可安全地用于本发明，但粘合剂层和阻挡亚层是任选的。即，着色橡胶层可仅由实际着色的橡胶亚层来限定。
保护层和着色橡胶层可在硫化轮胎之时或之后交联，即，可采用着色以硫化轮胎或生轮胎。
测试色牢度从而评价本发明相对于已知技术的优势。
使用1976国际照明委员会(International Commission on Illumination)所制定的、并由下式来定义的褪色指数ΔE：
ΔE=[(ΔL)2+(Δa)2+(Δb)2]1/2
其中：
L为发光度；a为红-绿光感(light sensation)；和b为黄-蓝光感。使用MinolteCM2002分光光度计进行测量。
通过将形成着色部当天的颜色与人工老化(根据ASTM D4587、ISO2810和ISO2813)来模拟轮胎暴露于正常操作条件所产生的颜色进行比较来测试本发明的有效性。出于比较的目的，为了方便将表示100的值的ΔE值指定为完全无褪色。
还根据ASTM标准D621测试保护层对轮胎侧壁的粘着力。
在以下实施例中，使用分子式(I)组中的两种不同的表面活性剂(a、b)：
-分子式CH3(CH2)7CHCH(CH2)7CONHCH2COO-Na+的表面活性剂(a)
-分子式CH2CH(CH2)8CONHCH2COO-Na+的表面活性剂(b)。
表I示出由根据本发明的各乳液制备的五种混炼胶A-E以phr计的组成；以及各组成、相对褪色值ΔE和对轮胎侧壁的粘着力。在混炼胶A-E中，使用Tg越来越高的聚合物来改变聚合物类的组成。
表I
A B C D E F G
Cl-IIR 100 70 70 70 70 70 70
CR -- 30 -- -- -- -- --
NR -- -- 30 -- -- -- --
SBR -- -- -- 30 -- -- --
PMA -- -- -- -- 30 -- --
PEMA -- -- -- -- -- 30 --
ABS -- -- -- -- -- -- 30
炭黑 50 50 50 50 50 50 50
树脂 10 10 10 10 10 10 10
ZnO 1.5 1.5 1.5 1.5 1.5 1.5 1.5
硫磺 2.8 2.8 2.8 2.8 2.8 2.8 2.8
促进剂 1.5 1.5 1.5 1.5 1.5 1.5 1.5
表面活性剂(a) 2.0 2.0 2.0 2.0 2.0 2.0 2.0
ΔE 90 85 80 80 88 100 100
粘着力(N/mm) 1.2 3.8 4.5 4.1 3.2 2.8 2.5
Cl-IIR=氯化丁基橡胶；CR=氯丁二烯；SBR=苯乙烯-丁二烯橡胶；NR=天然橡胶；PMA=聚甲基丙烯酸酯；PEM=聚甲基丙烯酸乙酯；ABS=丙烯腈-丁二烯-苯乙烯三元共聚物。
如表I清楚地示出，根据本发明的方法提供极其良好的色牢度以及保护层对相关轮胎部的牢固粘着力。
表II示出由根据本发明的各乳液制备的三种混炼胶F-H以phr计的组成，和各组成、相对褪色值ΔE以及对轮胎侧壁的粘着力。在混炼胶F-H中，以递增量加入粘土。
表II
F G H
Cl-IIR 100 100 100
炭黑 50 50 50
粘土 30 70 110
树脂 10 10 10
ZnO 1.5 1.5 1.5
硫磺 2.8 2.8 2.8
促进剂 1.5 1.5 1.5
表面活性剂(b) 2.0 2.0 2.0
ΔE 92 95 97
粘着力(N/mm) 3.0 3.5 4.2
表II清楚地示出，同样，在该情况中，根据本发明的方法提供在色牢度以及对轮胎的粘着力方面有效着色的轮胎。
用于根据本发明的保护层的填料优选包括直径为0.2至2μm和长径比为5至30,000的矿物颗粒。
所述填料优选在包括高岭土、粘土、云母、长石、硅石、石墨、膨润土、矾土和蛭石的组中。
根据本发明的方法确定无疑比已知方法低廉。相对于使用班伯里密炼机，由水性乳液生产混炼胶，大大减少能量消耗，同时不管轮胎类型如何，均有效地分散乳液组分。
根据本发明的方法还提供仅使用非常薄的其他材料层来使轮胎着色，所述其他材料层对滚动阻力几乎没有影响。事实上，可将源自水性乳液并由高度不渗透性的混炼胶制备的保护层制备成如0.001至0.5mm薄。
如上所述，根据本发明的方法应用于生轮胎和硫化轮胎。
在用于着色硫化轮胎的本发明优选实施方案中，使轮胎的待着色部进行激光如CO2激光的预压花步骤，从而形成槽式图案，在所述槽式图案上沉积保护层和着色橡胶层，从而使它们固定，因而更牢固地确保对轮胎的着色。即，除了保护层与轮胎表面的化学粘着力以外，该机械固定(mechanicalfastening)也助于确保轮胎的着色。
根据本发明的方法优选包括精加工步骤，其中激光处理着色部，从而产生为了掩饰磨耗导致的橡胶褪色的几何和装饰效果。

Claims (12)

1.一种轮胎的着色部的形成方法；所述方法包括以下步骤：
-通过在轮胎的待着色部上沉积水性乳液来形成高度不渗透性保护层；和
-将着色层沉积在所述保护层上；
所述方法的特征在于所述水性乳液至少包括可交联聚合物类和分子式(I)的表面活性剂
(R1CONR2CHR3COO-)n Xn+              (I)
其中：
R1为C6-C23的脂族基，
R2为H或C1-C8的脂族基，
R3为H或C1-C8的脂族或芳族基，
X为金属阳离子，和
n为1至3的整数。
2.根据权利要求1所述的方法，其特征在于，所述脂族基R1包括双键。
3.根据权利要求1所述的方法，其特征在于，Xn+为Na+。
4.根据权利要求1所述的方法，其特征在于，所述表面活性剂具有在包括以下分子式的组中的分子式：
CH3(CH2)7CHCH(CH2)7CONHCH2COO-X+
CH2CH(CH2)8CONHCH2COO-X+。
5.根据权利要求1所述的方法，其特征在于，所述水性乳液包括矿物填料，所述矿物填料包括直径为0.2至2μm和长径比为5至30,000的颗粒。
6.根据权利要求5所述的方法，其特征在于，所述矿物填料在包括高岭土、粘土、云母、长石、硅石、石墨、膨润土、矾土和蛭石的组中。
7.根据权利要求1所述的方法，其特征在于，所述可交联聚合物类至少包括Tg超过0℃的聚合物。
8.根据权利要求1所述的方法，其特征在于，所述着色层由橡胶制成。
9.根据权利要求8所述的方法，其特征在于，所述着色层依次包括接触所述保护层的第一粘合剂亚层；第二阻挡亚层；和第三着色橡胶亚层。
10.根据权利要求1所述的方法，其特征在于，包括预压花步骤，在所述预压花步骤中激光压花所述轮胎的待着色部；所述预压花步骤形成在上面沉积所述保护层的槽式图案。
11.根据权利要求1所述的方法，其特征在于包括精加工步骤，在所述精加工步骤中，激光处理所述着色部。
12.一种轮胎，其特征在于包括根据权利要求1所述的方法所形成的着色部。
CN201180050726.0A 2010-10-20 2011-10-20 轮胎的着色部的形成方法及通过该方法获得的轮胎 Expired - Fee Related CN103180128B (zh)

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ITTO2010A000850A IT1402988B1 (it) 2010-10-20 2010-10-20 Metodo per la realizzazione di porzioni colorate su di un pneumatico
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IT1402988B1 (it) 2013-09-27
ITTO20100850A1 (it) 2012-04-21
JP2013540065A (ja) 2013-10-31
US20130273282A1 (en) 2013-10-17
WO2012052966A1 (en) 2012-04-26

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