CN111518509B - 无溶剂反应型粘结组合物及利用其的轮胎的制造方法 - Google Patents
无溶剂反应型粘结组合物及利用其的轮胎的制造方法 Download PDFInfo
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- CN111518509B CN111518509B CN201911078768.XA CN201911078768A CN111518509B CN 111518509 B CN111518509 B CN 111518509B CN 201911078768 A CN201911078768 A CN 201911078768A CN 111518509 B CN111518509 B CN 111518509B
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Abstract
本发明涉及无溶剂反应型粘结组合物及利用其的轮胎的制造方法,更详细地,涉及一种包含聚丁二烯多元醇;具有硫醇基的化合物;以及基团引发剂的无溶剂反应型粘结组合物及利用其的轮胎的制造方法。
Description
技术领域
本发明涉及无溶剂反应型粘结组合物及利用其的轮胎的制造方法,涉及用于化学结合非极性硫化橡胶和极性聚氨酯材料的无溶剂反应型粘结组合物及利用其的轮胎的制造方法。
背景技术
硫化橡胶是通常通过将使用硫的网络结构引入由二烯单体获得的高分子体系中来实现弹性的橡胶。由于硫化橡胶的弹性、耐久性及经济性优秀,因此广泛应用于各种轮胎、辊、鞋底和汽车零件等的材料。
在将这种硫化橡胶用于汽车零件、轮胎、鞋等的各种产品的情况下,它受限于用单一材料满足所需的性能,必须与其他材料零件一起复合,在这种情况下,需要使用粘结剂进行粘合。
硫化橡胶的原料有天然橡胶、苯乙烯-丁二烯共聚物橡胶、丁二烯橡胶、丙烯腈-丁二烯共聚物等,大多数具有极性低的非极性特征。
另一方面,用于弥补硫化橡胶的缺点的材料通常是诸如极性高的聚氨酯的材料。在使用为了粘合这些材料和硫化橡胶而利用表面的物理结合的普通粘结剂的情况下,存在难以实现所需性能的问题。
发明内容
因此,本发明的目的在于,提供一种无溶剂反应型粘结组合物,即使在苛刻条件下,也可以使粘合诸如硫化橡胶之类的非极性弹性体和诸如聚氨酯之类的极性弹性体的部件保持粘结力。
而且,本发明的另一目的在于,提供一种通过利用上述粘结组合物来化学键合用于硫化橡胶轮胎的胎面和聚氨酯材料的橡胶的轮胎的制造方法。
为了实现上述目的,本发明一实施方式的无溶剂反应型粘结组合物包含聚丁二烯多元醇;具有硫醇基的化合物;以及基团引发剂。
其中,上述无溶剂反应型粘结组合物可包含90至95重量份的上述聚丁二烯多元醇、5重量份至10重量份的上述具有硫醇基的化合物、0.1重量份至5重量份的上述基团引发剂。
而且,上述聚丁二烯多元醇可以为选自由顺式-1,4-聚丁二烯多元醇、反式-1,4-聚丁二烯多元醇、1,2-聚丁二烯多元醇及端羟基聚丁二烯组成的组中的一种或它们中的两种以上的混合物。
而且,上述具有硫醇基的化合物可以为脂肪族硫醇化合物或芳香族硫醇化合物。
而且,上述基团引发剂可以为选自由光引发剂、过氧化物引发剂及偶氮化合物组成的组中的一种或它们中的两种以上的混合物。
另一方面,本发明另一实施方式的轮胎的制造方法,包括:S1步骤,在用于轮胎胎面的硫化橡胶的表面涂敷粘结组合物;S2步骤,在上述粘结组合物上形成聚氨酯预聚物;以及S3步骤,对上述S2步骤的产物进行加热,并且上述粘结组合物为前述的本发明的无溶剂反应型粘结组合物。
本发明的粘结组合物包含可与非极性硫化橡胶化学键合的聚丁二烯多元醇、可参与极性聚氨酯材料形成的硫醇化合物,因此在硫化橡胶与聚氨酯间的界面可通过化学键合来实现高粘结力。
并且,与现有的粘结组合物不同,由于不包含有机溶剂,因此环保。
附图说明
图1为示出本发明一实施例中聚丁二烯多元醇(Hydroxyl terminatedpolybutadiene,HTPB)和具有硫醇基的化合物通过基团引发剂(HS-CH2CH2OH)发生硫醇-烯链接反应的图。
图2为示出本发明一实施例中通过硫醇化合物的硫醇基与聚氨酯预聚物的化学反应来形成聚氨酯的反应图。
图3为示出本发明一实施例中通过包含羟基的化合物与聚氨酯预聚物的化学反应来形成聚氨酯的反应图。
具体实施方式
以下,进一步详细说明本发明。
本发明一实施方式的无溶剂反应型粘结组合物包含聚丁二烯多元醇;具有硫醇基的化合物;以及基团引发剂。
上述聚丁二烯多元醇可与非极性硫化橡胶化学键合。首先,聚丁二烯多元醇为通过聚合丁二烯来获得的低聚物,由于对硫化橡胶具有优秀的亲和性,因此可以很好地涂敷在被粘面,并且可以很好地润湿硫化橡胶。而且,即使在形成低聚物后,剩余的双键也能够与硫化橡胶的双键化学键合。并且,引入聚丁二烯多元醇中的羟基可具有用于与硫化橡胶粘合并可参与诸如聚氨酯之类的极性的弹性材料形成的反应性。由于被粘面之间的化学键合,这种多重反应性可实现高粘结力。
另一方面,通常上述聚丁二烯多元醇的重均分子量为10000g/mol以下,但是,因常温粘度高而难以单独使用,因此在本发明中还包含具有硫醇基的化合物。
上述具有硫醇基的化合物降低上述聚丁二烯多元醇的高粘度,同时可参与与聚丁二烯多元醇的反应,以及极性弹性材料的形成如聚氨酯。这种具有硫醇基的化合物可通过所谓的硫醇-烯链接(thiol-ene click)反应来形成双键和共价键,具有还可参与聚氨酯材料生成的反应性,并且粘度低以及具有与聚丁二烯多元醇相容性。
图1为示出聚丁二烯多元醇和具有硫醇基的化合物(HS-CH2CH2OH)通过基团引发剂发生硫醇-烯链接反应。为了发生这种硫醇-烯链接反应需要基团引发剂。
图2为通过硫醇化合物和聚氨酯预聚物的化学反应来形成聚氨酯的反应的图,图3为通过具有羟基的化合物与聚氨酯预聚物的化学反应来形成的聚氨酯的反应的图。通过如图2及图3的反应,在与极性的聚氨酯预聚物进行粘结的界面发生化学反应,从而可实现强粘结力。
此时,上述无溶剂反应型粘结组合物可包含90重量份至95重量份的上述聚丁二烯多元醇、5重量份至10重量份的上述具有硫醇基的化合物、0.5重量份至5重量份的上述基团引发剂。
若上述聚丁二烯多元醇的含量小于90重量份、上述具有硫醇基的化合物的含量大于10重量份,则可因聚丁二烯多元醇与具有硫醇基的化合物之间的相分离而成为问题,若上述聚丁二烯多元醇的含量大于95重量份且上述具有硫醇基的化合物的含量小于5重量份,则粘结强度可能低。
而且,若上述基团引发剂小于0.1重量份,则因引发剂含量不足而可能无法顺利地进行反应,若大于5重量份,则因反应太快导致不能正确涂敷粘结剂。
另一方面,用于制备本发明的无溶剂反应型粘结组合物的上述聚丁二烯多元醇可以为选自由顺式-1,4-聚丁二烯多元醇、反式-1,4-聚丁二烯多元醇、1,2-聚丁二烯多元醇及端羟基聚丁二烯组成的组中的一种或它们中的两种以上的混合物。
而且,上述具有硫醇基的化合物可以为脂肪族硫醇化合物或芳香族硫醇化合物。
更具体地,作为上述硫醇化合物的非限定性例,可列举脂肪族硫醇化合物,如1,3-丙二硫醇、1,4-丁二硫醇、1,5-戊二硫醇、1,6-己二硫醇、1,7-庚二硫醇、1,8-辛二硫醇、2-巯基乙醇、氨基乙硫醇、2-(丁基氨基)乙硫醇、3-(甲硫基)丙胺、三甲醇丙烷三(3-巯基丙酸酯)、季戊四醇四(3-巯基丙酸酯)、四乙二醇(3-巯基丙酸酯)、季戊四醇六(3-巯基丙酸酯)、季戊四醇四(硫代乙醇酸酯)、三[(3-巯基丙氧基-乙基]-异氰脲酸酯)、1,4-双(3-巯基丁氧基)丁烷、1,3,5-三(3-巯基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、季戊四醇四(3-巯基丁酸酯)、2,2′-(乙二氧基)二乙硫醇等;以及芳香族硫醇化合物等。优选地,可以为具有约500g/mol以下的重均分子量的低分子量的硫醇化合物。
而且,上述基团引发剂可以为选自由通过紫外线激活的光引发剂、利用基于加热分解的过氧化物引发剂及偶氮化合物组成的组中的一种或它们中的两种以上的混合物。
作为上述光引发剂,包括安息香醚(例如,安息香甲醚或安息香丁醚)、苯乙酮衍生物(例如,2,2-二甲氧基-2-苯基苯乙酮或2,2-二乙氧基苯乙酮)、1-羟基环己基苯基酮、酰基氧化膦衍生物及酰基膦酸酯衍生物(例如,双(2,4,6-三甲基苯甲酰基)苯氧化膦、二苯基-2,4,6-三甲基苯甲酰氧化膦、异丙氧基苯-2,4,6-三甲基苯甲酰氧化膦或新戊酸二甲酯)。
而且,作为过氧化物引发剂可包括氢过氧化物(例如,异丙苯、叔丁基或叔戊基氢过氧化物)、过氧化二烷基(例如,过氧化二叔丁基、过氧化二枯基或过氧化环己基)、过氧酯(例如,过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化-3,5,5-三甲基己酸叔丁酯、单过氧化马来酸叔丁酯或过氧化邻苯二甲酸二叔丁酯)以及过氧化二酰(例如,过氧化苯甲酰或过氧化月桂)。
并且,可包括过氧化碳酸酯(例如,过氧化2-乙基己基碳酸叔丁酯、过氧化异丙基碳酸叔丁酯或过氧化二碳酸二(4-叔丁基环己基)酯及过氧化酮(例如,过氧化甲基乙基酮、1,1-二(叔丁基过氧)环己烷、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷及过氧化环己酮)。
而且,例如,作为偶氮化合物可包括2,2′-偶氮二异丁腈、2,2′-偶氮双(2-甲基丁腈)、2,2′-偶氮双[2-甲基-N-(2-羟乙基)丙酰胺、1,1′-偶氮双(1-环己烷甲腈)、2,2′-偶氮二(2,4-二甲基戊腈)、偶氮二咪唑啉基丙烷及2,2′-偶氮二(2-脒基丙烷)二氯化氢,例如,有机过氧化物或无机过氧化物可包括过氧化二乙酰、过氧化二叔丁基、过氧化二甲酰、过氧化二辛酰、过氧化十二烷、过氧化二月桂酰、过氧化二苯甲酰、过氧化双(邻甲苯甲酰)、过氧化琥珀酰、过氧化乙酸叔丁酯、过氧化马来酸叔丁酯、过氧化异丁酸叔丁酯、过氧化碘酸叔丁酯、过氧化辛酸叔丁酯、过氧化癸酸叔丁酯、过氧化苯甲酸叔丁酯、过氧化叔丁基、叔丁基过氧化氢、异丙苯过氧化氢、过氧化-2-乙基己酸叔丁酯及过氧化二氨基甲酸二异丙酯。
一般而言,以单体的总量为基准,可使用0.1重量百分比至5重量百分比的量的这些基团引发剂,更优选地,以单体的总量为基准,可使用0.1重量百分比至3重量百分比的量。
另一方面,本发明另一实施方式的轮胎的制造方法的特征在于,包括:S1步骤,在用于轮胎胎面的硫化橡胶的表面涂敷粘结组合物;S2步骤,在上述粘结组合物上形成聚氨酯预聚物;以及S3步骤,对上述S2步骤的产物进行加热,并且上述粘结组合物为前述的本发明的无溶剂反应型粘结组合物。
根据这种方法,用于轮胎胎面的硫化橡胶与聚氨酯预聚物之间的化学键合可使两种材料之间具有完美的粘结力。
此时,在上述S1步骤之后,在S2步骤之前,可在110℃的温度下热处理30分钟,以使可通过粘结组合物进行硫醇-烯链接反应的反应。
而且,上述S3步骤可在110℃的温度下进行12小时,以用于固化聚氨酯。
另一方面,本发明的用于轮胎胎面的硫化橡胶的原料橡胶可以为选自由天然橡胶、合成橡胶及它们的组合组成的组中的一种。
上述天然橡胶可以为常规的天然橡胶或改性天然橡胶。
上述常规的天然橡胶可使用任何天然橡胶,只要是公知为天然橡胶的即可,并且原产地等不受限制。上述天然橡胶包含顺式-1,4-聚异戊二烯作为主剂,根据要求特性还可包含反式-1,4-聚异戊二烯。因此,上述天然橡胶除了包含顺式-1,4-聚异戊二烯作为主剂的天然橡胶之外,还可包含反式-1,4-异戊二烯作为主剂的天然橡胶,例如,作为南美山山榄科的橡胶之一的巴拉塔胶等。
上述改性天然橡胶是指改性或纯化上述常规天然橡胶的天然橡胶。例如,作为上述改性天然橡胶可列举环氧天然橡胶(ENR)、脱蛋白天然橡胶(DPNR)、氢化天然橡胶等。
而且,上述合成橡胶可以为选自由苯乙烯丁二烯橡胶(SBR)、改性苯乙烯丁二烯橡胶、丁二烯橡胶(BR)、改性丁二烯橡胶、丙烯腈-丁二烯橡胶及它们的组合组成的组中的一种。
其中,就使用原料橡胶的轮胎的耐磨性及燃油费心梗的改善效果而言,优选地,上述原料橡胶可包含苯乙烯-丁二烯橡胶(Styrene Butadiene Rubber,SBR)和丁二烯橡胶(Butadiene Rubber,BR)的混合物。
而且,作为增强性填充剂可使用炭黑、二氧化硅或它们的混合物。
另一方面,上述用于轮胎胎面的硫化橡胶组合物选择性地还可包含额外的各种添加剂,例如硫化剂、硫化促进剂、硫化促进助剂、抗老化剂、软化剂、阻滞剂或粘结剂等。上述各种添加剂可使用任何添加剂,只要是通常用于本发明所属领域的添加剂即可,它们的含量基于用于常规的轮胎胎面的橡胶组合物中使用的配比,并不受特别限制。
上述硫化剂优选地可使用硫磺类硫化剂。上述硫磺类硫化剂可使用无机硫化机,例如粉末硫(S)、不溶性硫(S)、沉淀硫(S)、胶体(colloid)硫等。具体地,上述硫磺类硫化剂可使用制备元素硫或硫的硫化剂,例如可使用二硫化胺(amine disulfide)、高分子硫等。
相对于100重量份的上述原料橡胶,包含0.5重量份至4.0重量份的上述硫化剂时,作为适当的硫化效果,在原料橡胶对热不敏感且化学稳定方面优选。
上述硫化促进剂是指促进硫化速度或在初始硫化步骤中促进延迟作用的促进剂(accelerator)。
上述硫化促进剂可使用选自由亚磺酰胺类、噻唑类、秋兰姆类、硫脲类、胍类、二硫代氨基甲酸类、醛胺类、醛氨类、咪唑啉类、黄原酸酯类及它们的组合组成的组中的一种。
例如,上述亚磺酰胺类硫化促进剂可使用选自由N-环己基-2-苯并噻唑亚磺酰胺(CBS)、N-叔丁基-2-苯并噻唑亚磺酰胺(TBBS)、N,N-二环己基-2-苯并噻唑亚磺酰胺、N-氧二亚乙基-2-苯并噻唑亚磺酰胺、N,N-二异丙基-2-苯并噻唑亚磺酰胺及它们的组合组成的组中的一种亚磺酰胺类化合物。
例如,上述噻唑类硫化促进剂可使用选自由2-巯基苯并噻唑(MBT)、二苯并噻唑二硫化物(MBTS)、2-巯基苯并噻唑的钠盐、2-巯基苯并噻唑的锌盐、2-巯基苯并噻唑的铜盐、2-巯基苯并噻唑的环己胺盐、2-(2,4-二硝基苯基)巯基苯并噻唑、2-(2,6-二乙基4-吗啉代硫代)苯并噻唑及它们的组合组成的组中的一种噻唑类化合物。
例如,上述秋兰姆类硫化促进剂可使用选自由二硫化四甲基秋兰姆(TMTD)、二硫化四乙基秋兰姆、一硫化四甲基秋兰姆、二硫化二戊亚甲基秋兰姆、一硫化二戊亚甲基秋兰姆、二硫化二戊亚甲基秋兰姆、六硫化二戊亚甲基秋兰姆、二硫化四丁基秋兰姆、四硫化五亚甲基秋兰姆及它们的组合组成的组中的一种秋兰姆类化合物。
例如,上述硫脲类硫化促进剂可使用选自由硫脲、二乙硫脲、二丁基硫脲、三甲基硫脲、二甲酚基硫脲及它们的组合组成的组中的一种硫脲类化合物。
例如,上述胍类硫化促进剂可使用选自由二苯基胍、二甲酚基胍、三苯基胍、邻苯二酚双胍、邻苯二甲酸二苯胍及它们的组合组成的组中的一种胍类化合物。
例如,上述二硫代氨基甲酸类硫化促进剂可使用选自由乙基苯基二硫代氨基甲酸锌、丁基苯基二硫代氨基甲酸酯锌、二甲基二硫代氨基甲酸钠、二甲基二硫代氨基甲酸锌、二乙基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌、二戊基二硫代氨基甲酸锌、二丙基二硫代氨基甲酸锌、五亚甲基二硫代氨基甲酸锌和哌啶络盐、十六烷基异丙基二硫代氨基甲酸锌、十八烷基异丙基二硫代氨基甲酸锌、二苄基二硫代氨基甲酸锌、二乙基二硫代氨基甲酸钠、五亚甲基二硫代氨基甲酸哌啶、二甲基二硫代氨基甲酸酯硒、二乙基二硫代氨基甲酸酯碲、二甲基二硫代氨基甲酸镉及它们的组合组成的组中的一种二硫代氨基甲酸类化合物。
例如,上述醛胺类或醛氨类硫化促进剂可使用选自由乙醛苯胺反应物、丁醛苯胺缩合物、六亚甲基四胺、乙醛氨反应物及它们的组合组成的组中的醛胺类或醛氨类化合物。
例如,上述咪唑啉类硫化促进剂可使用2-巯基咪唑啉等咪唑啉类化合物,例如,上述黄原酸酯类硫化促进剂可使用二丁基黄原酸锌等黄原酸酯类化合物。
为了通过促进硫化速度来使生产性增加及橡胶物性增加最大化,相对于100重量份的上述原料橡胶,可包含0.5重量份至4.0重量份的上述硫化促进剂。
另一方面,上述硫化促进助剂是为了通过与上述硫化促进剂组合使用来使其促进效果完整而使用的配合剂,可使用选自由无机类硫化促进助剂、有机类硫化促进助剂及它们的组合组成的组中的一种。
上述无机类硫化促进助剂可使用选自由氧化锌(ZnO)、碳酸锌(zinc carbonate)、氧化镁(MgO)、氧化铅(lead oxide)、氢氧化钾及它们的组合组成的组中的一种。上述有机类硫化促进助剂可使用选自由硬脂酸、硬脂酸锌、棕榈酸、亚油酸、油酸、月桂酸、油酸二丁铵(dibutyl ammonium oleate)、它们的衍生物及它们的组合组成的组中的一种。
尤其,上述硫化促进助剂可一同使用上述氧化锌和上述硬脂酸,在此情况下,将上述氧化锌溶解在上述硬脂酸中以与上述硫化促进剂形成有效的复合物(complex),从而通过在硫化反应期间产生有利的硫来易于进行交联反应。
在将上述氧化锌和上述硬脂酸一起使用的情况下,为了用作合适的硫化促进助剂,相对于100重量份的上述原料橡胶,分别可使用1重量份至5重量份及0.5重量份至3重量份。在上述氧化锌和上述硬脂酸的含量小于上述范围的情况下,由于硫化速度慢,因此生产性可能下降,在大于上述范围的情况下,由于发生焦烧,因此物性可能下降。
另一方面,上述抗老化剂是为了终止轮胎因氧自动氧化的连锁反应而使用的添加剂。上述抗老化剂可适当选择使用选自由胺类、苯酚类、喹啉类、咪唑类、氨基甲酸金属盐、蜡及它们的组合组成的组中的一种。
上述胺类抗老化剂可使用选自由N-苯基-N′-(1,3-二甲基)-对苯二胺、N-(1,3-二甲基丁基)-N′-苯基-对苯二胺、N-苯基-N′-异丙基-对苯二胺、N,N′-二苯基-对苯二胺、N,N′-二芳基-对苯二胺、N-苯基-N′-环己基对苯二胺、N-苯基-N′-辛基-对苯二胺及它们的组合组成的组中的一种胺类抗老化剂。上述苯酚类抗老化剂可使用选自由作为苯酚类的2,2′-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2′-异丁烯-双(4,6-二甲基苯酚)、2,6-二叔丁基对甲酚及它们的组合组成的组中的一种苯酚类抗老化剂。上述喹啉类抗老化剂可使用选自由2,2,4-三甲基-1,2-二氢喹啉及其衍生物,具体地,可使用选自由6-乙氧基-2,2,4-三甲基-1,2-二氢喹啉、6-苯胺基-2,2,4-三甲基-1,2-二氢喹啉、6-十二烷基-2,2,4-三甲基-1,2-二氢喹啉及它们的组合组成的组中的一种。优选地,上述蜡可使用蜡状烃。
而且,除了具有抗老化作用之外,当考虑应对橡胶的溶解度大、挥发性低、应对橡胶呈非活性以及不抑制硫化等条件时,相对于100重量份的上述原料橡胶,可包含1重量份至10重量份的上述抗老化剂。
另一方面,上述软化剂是为了赋予橡胶可塑性以使易于加工或降低硫化橡胶的硬度而添加到橡胶组合物中,是指配合橡胶或制备橡胶时所使用的油类其他材料。上述软化剂是指加工油(Process oil)或其他包含在橡胶组合物中的油类。上述软化剂可使用选自由石油类油、植物油脂及它们的组合组成的组中的一种,但并不限定于此。
上述石油类油可使用选自由石蜡类油、环烷烃类油、芳香族类油及它们的组合组成的组中的一种。
作为上述石蜡类油的代表性例可列举Mi Chang Oil株式会社的P-1、P-2、P-3、P-4、P-5、P-6等,作为上述环烷烃类油的代表性例可列举Mi Chang Oil株式会社的N-1、N-2、N-3等,作为上述芳香族类油的代表性例可列举Mi Chang Oil株式会社的A-2、A-3等。
然而,近年来,随着环保意识的提高,已知包含在上述芳香族类油中多环芳香族(Polycyclic Aromatic Hydrocarbons,以下被称为PAHs)的含量为3重量百分比以上时,致癌的可能性高,优选地,可使用TDAE(经过处理的馏分芳族提取物(treated distillatearomatic extract))油、MES(温和提取溶剂(mild extraction solvate))油、RAE(残余芳族提取物(residual aromatic extract))油或重环烷油。
尤其,相对于上述油总含量,用作上述软化剂的油优选地可使用多环芳烃(PAHs)成分的总含量为3重量百分比以下,动粘度为95以上(210°F SUS),软化剂中的芳香族成分为15重量百分比至25重量百分比,环烷烃类成分为27重量百分比至37重量百分比及石蜡类成分为38重量百分比至58重量百分比的TDAE油。
上述TDAE油具有包括上述TDAE油在内的轮胎胎面的低温特性、优化燃油费性能并对多环芳烃的致癌因素也有利的特性。
上述植物油脂可使用选自由蓖麻油、棉籽油、亚麻油、菜籽油、大豆油、棕榈油、椰子油、花生油、松油、松焦油、妥尔油、玉米油、米糠油、红花油、芝麻油、橄榄油、葵花籽油、棕榈仁油、山茶油、荷荷巴油、澳洲坚果油、酸花油、煤油及它们的组合组成的组中的一种。
从提高原料橡胶的加工性的观点出发,优选地,相对于100重量份的上述原料橡胶,使用0重量份至20重量份的上述软化剂。
另一方面,上述阻滞剂可使用选自由邻苯二甲酸酐、水杨酸、醋酸钠、N-环己基硫代邻苯二甲酰亚胺及它们的组合组成的组中的一种。相对于100重量份的上述原料橡胶,上述阻滞剂可以为0.1重量份至0.5重量份。
而且,上述粘结剂进一步提高橡胶与橡胶之间的粘结(tack)性能,通过改善其他添加剂如填充剂的混合性、分散性及加工性来有助于提高橡胶组合物的物性。
上述粘结剂可使用天然树脂类粘结剂,如松香(rosin)类树脂或萜烯(terpene)类树脂和合成树脂类粘结剂,如石油树脂、煤焦油(coal tar)或烷基酚醛类树脂等。
上述松香类树脂可以为选自由松香树脂、松香酯树脂、氢化松香酯树脂、它们的衍生物及它们的组合组成的组中的一种。上述萜烯类树脂可以为选自由萜烯树脂、萜烯酚醛树脂及它们的组合组成的组中的一种。
上述石油树脂可使用选自由脂肪族类树脂、酸改性脂肪族类树脂、脂环族类树脂、氢化脂环族类树脂、芳香族类(C9)树脂、氢化芳香族类树脂、C5-C9共聚合树脂、苯乙烯树脂、苯乙烯共聚合树脂及它们的组合组成的组中的一种。
上述煤焦油可以为香豆酮-茚树脂(coumarone-indene resin)。
上述烷基酚醛树脂可以为对叔烷基苯酚甲醛树脂或间苯二酚甲醛树脂,上述对叔烷基苯酚甲醛树脂可以为对叔丁基苯酚甲醛树脂、对叔辛基苯酚甲醛及它们的组合组成的组中的一种。
相对于100重量份的上述原料橡胶,可包含2重量份至4重量份的上述粘结剂。相对于100重量份的上述原料橡胶,若上述粘结剂的含量小于2重量份,则粘结性能可能变差,若大于4重量份,则橡胶物性可能下降。
另一方面,本发明的轮胎可以为小轿车用轮胎、赛车用轮胎、飞机轮胎、农业机械用轮胎、越野(off-the-road)轮胎、卡车轮胎或公共汽车轮胎等。并且,上述轮胎可以为午线(radial)轮胎或斜交(bias)轮胎。
以下,详细说明本发明的实施例,使得本发明所属领域的普通技术人员可以容易地实施本发明。但是,可以以各种不同的形态实现本发明,但并不限定于在此说明的实施例。
制备例:粘结组合物的制备
以下述表1所示的组成制备粘结组合物。下述的粘结组合物不包含有机溶剂。
表1
(单位:重量比)
实验例:测定粘结力
为了测定根据在上述实施例中制备的粘结组合物的粘结力,测定了用作轮胎胎面用材料的典型的硫化合成橡胶与邵氏A(Shore A)硬度为95的聚氨酯弹性体之间的粘结力。
首先,将具有上述组成的粘结组合物以0.001g/in2涂敷于橡胶后,将粘结组合物在硫化橡胶中充分润湿,并在110℃的温度下热处理30分钟以使可以进行硫醇-烯链接反应。
接着,涂敷异氰酸酯含量为8.5重量百分比的酯类的聚氨酯预聚物和1,4-丁二烯混合物,为了固化此而在110℃的温度下保持12小时后,测定聚氨酯与硫化橡胶之间的粘结剂力并在下述表2中示出。
表2
从上述表2中可以确认,可通过本申请的粘结组合物来实现高粘结力,尤其,当评价粘结力时,在界面处未发生破坏,而硫化橡胶处发生破坏,从而可确认在界面处已完全粘合。
以上,对本发明优选的实施例进行了详细说明,但本发明的发明要求保护范围并不限定于此,利用在上述的发明要求保护范围中限定的本发明的基本概念的本领域技术人员的各种变形及改进也属于本发明的发明要求保护范围之内。
Claims (5)
1.一种无溶剂反应型粘结组合物,其特征在于,包含:
聚丁二烯多元醇;
具有硫醇基的化合物;以及
基团引发剂,
其中,所述无溶剂反应型粘结组合物包含90重量份至95重量份上述聚丁二烯多元醇、5重量份至10重量份的上述具有硫醇基的化合物、0.1重量份至5重量份的上述基团引发剂。
2.根据权利要求1所述的无溶剂反应型粘结组合物,其特征在于,上述聚丁二烯多元醇为选自由顺式-1,4-聚丁二烯多元醇、反式-1,4-聚丁二烯多元醇、1,2-聚丁二烯多元醇及端羟基聚丁二烯组成的组中的一种或它们中的两种以上的混合物。
3.根据权利要求1所述的无溶剂反应型粘结组合物,其特征在于,上述具有硫醇基的化合物为脂肪族硫醇化合物或芳香族硫醇化合物。
4.根据权利要求1所述的无溶剂反应型粘结组合物,其特征在于,上述基团引发剂为选自由光引发剂、过氧化物引发剂及偶氮化合物组成的组中的一种或它们中的两种以上的混合物。
5.一种轮胎的制造方法,其特征在于,
包括:
S1步骤,在用于轮胎胎面的硫化橡胶的表面涂敷粘结组合物;
S2步骤,在上述粘结组合物上形成聚氨酯预聚物;以及
S3步骤,对上述S2步骤的产物进行加热,
上述粘结组合物为权利要求1至4中任一项所述的无溶剂反应型粘结组合物。
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