CN103260865B - 充气轮胎的制造方法 - Google Patents

充气轮胎的制造方法 Download PDF

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Publication number
CN103260865B
CN103260865B CN201180061404.6A CN201180061404A CN103260865B CN 103260865 B CN103260865 B CN 103260865B CN 201180061404 A CN201180061404 A CN 201180061404A CN 103260865 B CN103260865 B CN 103260865B
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China
Prior art keywords
thin slice
thermoplastic resin
layered product
resin composition
carry out
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Expired - Fee Related
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CN201180061404.6A
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English (en)
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CN103260865A (zh
Inventor
濑户秀树
原祐一
柴田宽和
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D3/00—Cutting work characterised by the nature of the cut made; Apparatus therefor
    • B26D3/003—Cutting work characterised by the nature of the cut made; Apparatus therefor specially adapted for cutting rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
    • B26F3/00—Severing by means other than cutting; Apparatus therefor
    • B26F3/06—Severing by using heat
    • B26F3/08—Severing by using heat with heated members
    • B26F3/12—Severing by using heat with heated members with heated wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/18—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated tools
    • B29C65/22—Heated wire resistive ribbon, resistive band or resistive strip
    • B29C65/221—Heated wire resistive ribbon, resistive band or resistive strip characterised by the type of heated wire, resistive ribbon, band or strip
    • B29C65/222—Heated wire resistive ribbon, resistive band or resistive strip characterised by the type of heated wire, resistive ribbon, band or strip comprising at least a single heated wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/14—Particular design of joint configurations particular design of the joint cross-sections the joint having the same thickness as the thickness of the parts to be joined
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
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Abstract

本发明提供充气轮胎的制造方法，以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与其硫化粘结的橡胶进行层压的层压体薄片，并将该层压体薄片的端部拼接头，进一步通过硫化成形形成轮胎，此时，构成内衬层的该热塑性树脂组合物薄片和与其硫化粘结的带状橡胶薄片之间，不会发生剥离，具有良好的耐久性。该轮胎制造方法具有下述工序：以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与其硫化粘结的橡胶进行层压的层压体薄片，并将该层压体薄片的端部拼接头，进一步通过硫化成形形成内衬层，其中，在以规定长度切割层压体薄片时，在所述热塑性树脂融点以上温度下进行热切割。

Description

充气轮胎的制造方法
技术领域
本发明涉及充气轮胎的制造方法。
进一步详细来说，涉及一种下述的充气轮胎的制造方法，该方法包括下述的形成内衬层的工序：以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与该热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片，并对层压体薄片进行拼接，进一步对其硫化成形，制造充气轮胎后，在拼接的层压体薄片的拼接部分附近，不会发生开裂，能够制造出耐久性优良的充气轮胎。
背景技术
近年来，被提出并研究有下述的技术方案：由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片状物使用于轮胎内衬层的方案（专利文献1）。
由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片状物实际使用于轮胎内衬层时，通常使用下述制造方法：将热塑性树脂和弹性体进行混合的热塑性树脂组合物薄片和与该热塑性树脂组合物薄片硫化粘结的橡胶（带状橡胶）薄片的层压体薄片卷绕在轮胎成形鼓上拼接头并进行硫化成形。
但是，将呈筒状的卷绕体来被卷绕的、由将热塑性树脂和弹性体进行混合的热塑性树脂组合物和带状橡胶构成的层压体薄片从该筒状体的卷绕体以所需长度卷出并切割后、卷绕在轮胎成形鼓上并在该鼓上进行拼接头、并进一步进行硫化成形来制造轮胎时，轮胎行使开始后，有时会发生构成内衬层的热塑性树脂组合物薄片和与该热塑性树脂组合物薄片硫化粘结的带状橡胶薄片被剥离的情况。
如果将该情况用附图进行说明，则如图2（a）所示，由将热塑性树脂和弹性体进行混合的热塑性树脂组合物2和带状橡胶层3构成的层压体薄片1例如按照下述方式被拼接：被刀具以所需尺寸（长度）进行切割，然后在轮胎成形鼓上，在其两端部设有拼接头部S的方式呈环状。另外，在使用一片该层压体薄片1时，按照其两端部被拼接而呈环状的方式形成，或者，在使用多片该层压体薄片1时，将它们层压体薄片相互的各端部被拼接而呈环状的方式形成。
另外，进一步被卷绕制造轮胎所需的部件（未示图），并在胶囊中被硫化成形。在被硫化成形后，如图2（b）所示，形成由将热塑性树脂和弹性体进行混合的热塑性树脂组合物2和带状橡胶层3构成的内衬层10，在拼接部S附近，热塑性树脂组合物2构成暴露的部分和被埋设在带状橡胶层中的部分。
尤其是，上述的热塑性树脂组合物2的薄片和被硫化粘结的带状橡胶层3进行剥离的现象会发生在如图2（b）所示的热塑性树脂组合物2的薄片暴露部分和其前端部附近4等上，首先会发生开裂，该开裂进一步进展而发展成薄片剥离现象。
现有技术文献：
专利文献
专利文献1：日本国特开2009-241855号公报
发明内容
鉴于上述问题，本发明的目的在于提供一种充气轮胎的制造方法，以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与该热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片，并对层压体薄片的端部进行拼接头，进一步通过硫化成形，制造充气轮胎，此时，在轮胎开始行使后，在构成内衬层的热塑性树脂组合物的薄片和与该热塑性树脂组合物的薄片被硫化粘结的带状橡胶薄片相互之间不会发生剥离，具有优良的耐久性。
为了达到上述目的，本发明的充气轮胎的制造方法，具有以下（1）的构成。
（1）一种充气轮胎的制造方法，其特征在于，该方法包括下述的形成内衬层的工序：以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与该热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片，并将该层压体薄片的端部拼接头，进一步通过硫化成形，形成内衬层，其中，在以规定长度切割所述层压体薄片时，在所述热塑性树脂融点以上温度下进行热切割。
另外，所涉及的本发明的充气轮胎的制造方法，优选具有以下（2）～（7）的任一种构成。
（2）根据上述（1）所述的充气轮胎的制造方法，其特征在于，进行所述热切割的同时，在所述热切割的切割面上，按照以该热切割的热使所述热塑性树脂流动，并用该热塑性树脂覆盖至少包括位于切割面上的弹性体的切割面整体的方式进行热切割。
（3）根据上述（1）或（2）所述的充气轮胎的制造方法，其特征在于，用热刀进行所述热切割。
（4）根据上述（3）所述的充气轮胎的制造方法，其特征在于，作为所述热刀，使用电热刀。
（5）根据上述（3）或（4）所述的充气轮胎的制造方法，其特征在于，用所述热刀进行所述热切割时，将该热刀在该层压体的侧面上按照跨过所述层压体薄片上方空间和下方空间而交叉的方式接触，且使该热刀朝向行进方向倾斜的状态下从所述层压体薄片的一端行进至另一端而进行所述热切割。
（6）根据上述（5）所述的充气轮胎的制造方法，其特征在于，使所述热刀行进时的所述倾斜状态是与该层压体薄片的垂线以10°～45°的倾斜角度倾斜的状态。
（7）根据上述（1）～（60任一项所述的充气轮胎的制造方法，其特征在于，所述热切割是伴随由所述热塑性树脂组合物构成的薄片前端部的侧面形状的前部锐化的处理，该前部锐化的侧面形状满足下述关系：向内侧进入（tx1/3）长度位置的厚度T（mm）为0.1t≤T≤0.8t，
在此，t表示由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片的非前部锐化处理部分的轮胎圆周方向平均厚度（mm），
T表示距由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片的前端向内侧进入（tx1/3）长度位置的薄片的厚度（mm）。
根据（1）所涉及的本发明，能够提供下述充气轮胎的制造方法：在轮胎开始行使后，在构成内衬层的热塑性树脂组合物的薄片和与该热塑性树脂组合物的薄片被硫化粘结的带状橡胶薄片相互之间不会发生剥离，具有优良的耐久性。
根据（2）～（6）任一项所涉及的本发明的充气轮胎的制造方法，具有上述（1）所涉及的本发明效果的同时，能够更加可靠且更加有效地获得该效果。
附图说明
图1为用于说明覆盖将热塑性树脂和弹性体进行混合的热塑性树脂组合物薄片的热切割面的热塑性树脂层的模式侧视图；
图2（a）表示以规定长度切割将由热塑性树脂组合物构成的薄片和与热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片、并将该层压体薄片卷绕在轮胎成形鼓上、使该层压体薄片的两端部拼接的状态的模式图，图2（b）表示以图2（a）所示的状态进行硫化成形后的状态的模式图；
图3（a）模式地表示使用热刀对层压体薄片1进行热切割时尤其可优选使用的切割方法的立体图，图3（b）模式地表示通过该切割方法获得的热塑性树脂组合物2薄片的前端部9形态的图；
图4为用于说明通过本发明制造的充气轮胎形态的图，表示在被供给轮胎硫化成形工序后，热塑性树脂组合物2薄片的前端部9的薄片侧面的侧视图；
图5为表示通过本发明制造的充气轮胎方式的一例的部分破损的立体图。
附图标号说明
1层压体薄片
2将热塑性树脂和弹性体进行混合的热塑性树脂组合物
3带状橡胶层
4热塑性树脂组合物2薄片的前端部附近
5弹性体
6热塑性树脂
7覆盖热切割面的热塑性树脂的覆盖层
8热刀
9热塑性树脂组合物2薄片的前端部（热切割后）
10内衬层
11胎面部
12胎侧部
13胎圈
14胎体层
15带束层
D热刀行进方向
L层压体薄片的垂线
S拼接头部
具体实施方式
下面，进一步详细说明本发明的充气轮胎的制造方法。
本发明的充气轮胎的制造方法，其特征在于，该方法包括下述的形成内衬层的工序：以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与该热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片，并对该层压体薄片的端部进行拼接头，进一步对其硫化成形，其中，在以规定长度切割层压体薄片时，通过所述热塑性树脂的融点以上的温度进行热切割。
本发明的发明人针对现有方法中存在的不适合的问题、即，在构成内衬层的该热塑性树脂组合物的薄片和与该热塑性树脂组合物的薄片被硫化粘结的带状橡胶薄片相互之间发生剥离的原因，经过各种研究，结果得到了如下的见解：
即，在通过通常的刀具对现有方法的上述层压体薄片进行切割并将其供给轮胎制造时，可以想到暴露在层压体薄片切割面（境界面）而存在的热塑性树脂组合物中的丁基橡胶等的弹性体会阻碍硫化粘结，会降低热塑性树脂组合物2薄片和带状橡胶薄片3之间的硫化粘结力。
对此，根据本发明方法，如图1所示，在以规定长度切割层压体薄片1时，通过所述热塑性树脂6的融点以上的温度进行热切割，使该热塑性树脂6熔融并流动，形成覆盖位于热切割截面上的丁基等弹性体5的覆盖层7，由此，能够不让发生因该弹性体5暴露存在而使热塑性树脂组合物2薄片和带状橡胶薄片3之间的硫化粘结力的不利情况。
热切割优选在被该热切割的热熔融流动的热塑性树脂6能够充分覆盖在切割面上的整个弹性体的条件下进行热切割。具体而言，优选在（热塑性树脂的融点+30℃）～（热塑性树脂的融点+180℃）的范围内的切割温度。在切割温度比该温度范围低的情况下，有时难以使热塑性树脂流动，难以充分进行对弹性体的覆盖。另外，在切割温度比该温度范围高的情况下，会使热塑性树脂组合物或带状橡胶薄片劣化，因此不优选。
热切割优选使用热刀进行，或者使用激光进行。作为热刀，使用电热刀进行的比较简单，因此优选。
另外，可以加热的同时进行加压来进行切割。另外，只要是在被加热的状态下能够进行切割，也可以使用机械刀具。
图3（a）表示在使用热刀进行层压体1的热切割时特别优选被采用的切割方法，优选的热切割方法是，将热刀8在层压体薄片1的侧面上按照跨过层压体薄片上方空间和下方空间而交叉的方式接触，且使热刀8朝向行进方向D以倾斜角θ倾斜的状态下从层压体薄片1的一端E1行进至另一端E2而进行热切割。根据本发明的发明人见解，在使用该方法时，在使热刀8行进时，倾斜热刀8的程度优选做成与层压体薄片1的垂线L以10°～45°的倾斜角度θ倾斜的状态。这样使热刀8从一端E1朝向另一端E2交叉前进来进行切割的方式与将热刀在层压体薄片1的整个面上挤压接触一次而进行热切割的情况相比，流失热的情况较少，能够以可靠美观的切割面状态进行切割，因此优选的。而且，通过在将热刀8以倾斜角θ倾斜的状态下行进，由此热塑性树脂组合物2的薄片会以连其前端部都与带状橡胶层3良好粘结的切割端的状态被切割，能够进一步扩大本发明能够获得的通过热切割的效果，因此是优选的。
根据本发明的发明人的见解，用该方式获得的切割端的状态，如图3（b）模式图所示，热塑性树脂组合物2薄片的前端部9通常弯曲至带状橡胶3薄片层的前端侧而围绕。这可以认为是，通过使以倾斜角θ倾斜的状态下行进，使热塑性树脂组合物2薄片的前端部受到向下方（带状橡胶层存在的方向）的挤压作用的同时被熔融并被切割。另外，根据本发明的发明人的见解，即使是如该图3（b）所示热塑性树脂组合物2薄片的前端部呈多少有些弯曲形态，在其被供给轮胎硫化成形工序的情况下，由于在该工序中会被硫化胶囊挤压，因此弯曲最终会变成几乎直的层压体薄片。
在上述切割后，在使用一片该层压体薄片1时，按照其两端部被拼接而呈环状的方式形成，或者，在使用多片该层压体薄片1时，将它们层压体薄片相互的各端部被拼接头而呈环状的方式形成。该拼接头可以在轮胎成形鼓上卷绕层压体薄片来进行，或者，将事先进行拼接头而形成为环状的物体被覆在轮胎成形鼓上。
图5为表示通过本发明制造的充气轮胎方式的一例的部分破损的立体图。
充气轮胎T按照在胎面部11的左右连接有胎侧部12和胎圈部13的方式设置。在轮胎的内侧，作为轮胎骨骼的胎体层14按照在轮胎宽度方向上跨过左右胎圈13、13的方式设置。与胎面部11相对应的胎体层14的外周一侧设有由钢丝构成的两层带束层15。箭头D表示轮胎圆周方向。
在胎体层14的内侧配置有内衬层10，拼接头部S沿着轮胎宽度方向延伸而存在。根据本发明的方法，在轮胎内周面上能够抑制过去在该拼接头部S附近容易发生的开裂、形成内衬层10的热塑性树脂组合物2和带状橡胶层3之间发生开裂、发生剥离，由此显著提高耐久性。拼接头部S的重叠长度根据轮胎规格不同而不同，但是优选的7～20mm程度，更优选的是8～15mm程度。这是因为如果重叠长度过于长，则轮胎的均匀性会变差，相反，如果重叠长度过于短，则会有在成形时拼接部开裂的担忧。
另外，如上所述，即使如图3（b）所示那样热塑性树脂组合物2薄片的前端部9呈多少有弯曲的形态，根据本发明的发明人的见解，在其被供给轮胎硫化成形工序的情况下，由于在该工序中会被硫化胶囊挤压，因此弯曲最终会变成几乎直的层压体薄片。在图4中表示该状态的热塑性树脂组合物2薄片前端部9的薄片侧面的形状例子。如此，在薄片2前端附近，形成有朝向前端逐渐变细的前部锐化的部分9。
在本发明的充气轮胎的制造方法，优选使用如图4所示在其前端附近形成有前部锐化部分9的薄片2。由此，在上下成对存在的刚性大的热塑性树脂组合物薄片2的厚度会在图2（b）前端部附近4变薄，且，由于热塑性树脂组合物薄片2和橡胶部3的界面面积变大，因此应力会分散，因这些理由，在被薄片2夹住的橡胶部3上发生的应力会变小且分散而缓解。这在开始使用轮胎后，能够防止该热塑性树脂组合物薄片2和硫化粘结的带状橡胶薄片3之间发生相互剥离现象。
该前部锐化的部分9的、前部锐化而朝向前端逐渐变细的形状在前端附近可以是带有“弧形”的程度，仅仅形成有这样的具有弧形的形状，就显著地被认可防止发生开裂、发生剥离的效果。该薄片2的前端中的前端前部锐化形状在硫化前和硫化后能够实质地维持其前部锐化形状，在开始作为轮胎使用后能够有效地发挥防止发生开裂、发生剥离的效果。
如上所述，薄片2的前端的前端前部锐化处理以带有弧形程度也能发挥效果，如果特别稳定地要获得高效果，则优选的是，前端前部锐化满足下述关系：距由在所述热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片2的前端向内侧进入（t×1/3）长度位置的厚度T（mm）为0.1t≤T≤0.8t。图4是表示该关系的图，表示距前端向内侧进入（t/3）位置的厚度水平的关系，优选为0.2t≤T≤0.6t。在此，t表示由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片2的非前端前部锐化部分的轮胎圆周方向平均厚度（mm），T表示距由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片2的前端向内侧进入（t×1/3）长度位置的薄片2的厚度（mm）。
另外，前端前部锐化部分（图4中9）的长度L优选为L=（1.0～20）×t（mm），即，优选距前端向内侧进入至该长度L位置为前端前部锐化处理部。更优选的是L=（1.0～10）×t（mm），进一步更优选的是L=（1.0～2.5）×t（mm）。
作为本发明中可使用的热塑性树脂，例如可优选使用聚酰胺树脂[例如，尼龙6（N6）、尼龙66（N66）、尼龙46（N46）、尼龙11（N11）、尼龙12（N12）、尼龙610（N610）、尼龙612（N612）、尼龙6/66共聚物（N6/66）、尼龙6/66/610共聚物（N6/66/610）、尼龙MXD6（MXD6）、尼龙6T、尼龙9T、尼龙6/6T共聚物、尼龙66/PP共聚物、尼龙66/PPS共聚物]以及它们的N-烷氧烷基化物，例如，尼龙6的甲氧基甲基化物，尼龙6/610共聚物的甲氧基甲基化物，尼龙612的甲氧基甲基化物，、聚酯树脂[例如，聚对苯二甲酸丁二醇酯（PBT）、聚对苯二甲酸乙二醇酯（PET）、聚间苯二甲酸乙二醇酯（PEI）、PET/PEI共聚物、聚芳酯（PAR）、聚萘二甲酸丁二醇酯（PBN）、液晶聚酯、聚氧化亚烷基二亚胺酸/聚对苯二甲酸丁二醇酯共聚物等芳香族聚酯]、聚腈树脂[例如，聚丙烯腈（PAN）、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物（AS）、甲基丙烯腈/苯乙烯共聚物、（甲基）丙烯腈/苯乙烯/丁二烯共聚物]、聚甲基丙烯酸树脂[例如，聚甲基丙烯酸甲酯（PMMA）、聚甲基丙烯酸乙酯]、聚乙烯树脂[例如，醋酸乙烯酯、聚乙烯醇（PVA）、乙烯醇/乙烯共聚物（EVOH）、聚偏二氯乙烯（PVDC）、聚氯乙烯（PVC）、氯乙烯/偏二氯乙烯共聚物、偏二氯乙烯/甲基丙烯酸共聚物、偏二氯乙烯/丙烯腈共聚物（ETFE）]、纤维素树脂[例如，醋酸纤维素、醋酸丁酸纤维素]、氟树脂[例如，聚偏氟乙烯（PVDF）、聚氟乙烯（PVF）、聚三氟氯乙烯（PCTFE）、四氟乙烯/乙烯共聚物]、酰亚胺树脂[例如，芳香族聚酰亚胺（PI）]等。
作为在本发明中可使用的弹性体，例如可优选使用二烯橡胶及其氢加成物[例如，天然橡胶（NR）、异戊二烯（IR）、环氧化天然橡胶、苯乙烯丁二烯橡胶（SBR）、丁二烯橡胶（BR、高顺式BR和低顺式BR）、丁腈橡胶（NBR）、氢化NBR、氢化SBR]、烯烃橡胶[例如，乙烯丙烯橡胶（EPDM、EPM）、马来酸改性乙烯丙烯橡胶（M-EPM）、丁基橡胶（IIR）、异丁烯和乙烯基芳香族或二烯单体共聚物、丙烯橡胶（ACM）、离聚物]、含卤素橡胶[例如，Br-IIR、Cl-IIR、溴化异丁烯对甲基苯乙烯共聚物（BIMS）、氯丁橡胶（CR）、氯醚橡胶（CHR）、氯磺化聚乙烯（CSM）、氯化聚乙烯（CM）、马来酸改性氯化聚乙烯（M-CM）]、硅橡胶[例如，甲基乙烯基硅橡胶、二甲基硅橡胶、甲基苯基乙烯基硅橡胶]、含硫橡胶[例如，聚硫橡胶]、氟橡胶[例如，聚偏氟乙烯橡胶、含氟乙烯基醚橡胶、四氟乙烯-丙烯橡胶、含氟硅橡胶、含氟磷氮烯橡胶]、热塑性弹性体[例如，苯乙烯弹性体、烯烃弹性体、聚酯弹性体、聚氨酯弹性体、聚酰胺弹性体]等。
在用上述特定的热塑性树脂和上述特定的弹性体组合进行混合时，如果其相容性不同，可以使用适当的相容剂作为第三成分以使两者相融化。通过在混合物中混合相容剂，由此降低热塑性树脂和弹性体之间的界面张力，其结果，形成分散层的弹性体粒子径会变微小，由此两成分的特性会更加有效地体现。作为这样的相容剂，可以是具有通常热塑性树脂和弹性体的两者或者其中之一结构的共聚物，或者与热塑性树脂或弹性体可进行反应的具有环氧基、羰基、卤素基、氨基、噁唑啉、羟基等的共聚物结构。这些可以是根据被混合的热塑性树脂和弹性体的种类选择，但是通常使用的是苯乙烯-乙烯/丁烯基嵌段共聚物（SEBS）以及该马来酸改性物、EPDM、EPM、EPDM/苯乙烯或者EPDM/丙烯腈接枝共聚物以及该马来酸改性物、苯乙烯/马来酸共聚物、反应性苯氧化物等。对所使用的相容剂的配合量没有特别的限定，但是优选的是，相对于100重量份聚合物成分（热塑性树脂和弹性体的合计）使用0.5～10重量份。
在热塑性弹性体组合物中，特定的热塑性树脂和弹性体的组合比没有特别的限定，只要是具有热塑性树脂和弹性体中弹性体以不连续相分散的结构，就可以适当地确定，其重量比优选的范围是90/10～30/70。
在本发明中，对热塑性树脂和弹性体进行混合的热塑性树脂组合物中，在不损害作为内衬层的必要特性的范围内，可以混合相容剂等其它聚合物。混合其它聚合物的目的是为了改善热塑性树脂和弹性体的相容性、提高材料的成形加工性、提高耐热性、降低成本等，作为该目的使用的材料例如可以举例聚乙烯（PE）、聚丙烯（PP）、聚苯乙烯（PS）、ABS、SBS、聚碳酸酯（PC）等。另外，只要是不损害作为内衬层的必要特性，可以任意混合通常混合于聚合物混合物中的填充剂（碳酸钙、氧化钛、氧化铝等）、碳黑、白碳黑等增强剂、软化剂、塑化剂、加工助剂、颜料、燃料、抗老化剂等。
热塑性树脂组合物具有在热塑性树脂的基质中弹性体作为不连续相分散的结构。通过该结构，在作为内衬层的充分柔韧性和连续相的树脂层效果的基础上，同时赋予充分的刚性，且与弹性体的多少无关地在成形时能够获得与热塑性树脂同等的成形加工性。
另外，因此下述技术构思发挥效果，即，特别是在本发明方法中通过采用热切割，由此用流动的热塑性树脂对在切割面上暴露的该弹性体进行覆盖。
热塑性树脂和弹性体的杨氏系数并没有特别限定，但是优选为1～500MPa、更优选为50～500MPa。
实施例
实施例1～9、比较例1
下面，根据实施例说明本发明充气轮胎的制造方法。
另外，对充气轮胎的评价是将在各测试轮胎内腔的内衬层的拼接部附近的开裂发生、剥离发生情况与除此之外的部分的情况相比较来进行的。
作为测试轮胎，使用了215/70R1598H规格轮胎，并每个实施例、比较例各制造了两条轮胎，将其安装在JATMA(JapanAutomobileTireManufacturersAssociation:日本汽车轮胎协会)所规定的标准轮辋15X6.5JJ上，并将轮胎内压做成JATMA所规定的最大气压（240kPa）。
构成内衬层的热塑性树脂组合物制作了如表1所示地将N6/66作为热塑性树脂、将BIMS作为弹性体以50/50的质量比进行混合的厚度为0.13mm的薄片，同样构成内衬层的粘结带状橡胶制作了如表2所示的厚度为0.7mm的橡胶，并准备了将这些进行层压的层压薄片的筒状卷绕体。其中，热塑性树脂的融点为190℃。
在轮胎成形鼓上将该层压体薄片拼接头而卷绕时，按所需长度进行切割时，针对实施例1是使用热刀（电热刀、直径0.6mm）以热切割方式（切割温度为300℃）并按照图3（a）所示的倾斜角θ=20°来进行的，针对比较例1是对上述层压体薄片以室温使用刀刃式刀具进行的。
对实施例1和比较例1的各层压体薄片的切割端面使用了X光电子能谱分析（XPS）进行观察的结果，在实施例1中确认了下述形态：位于切割端面的弹性体BIMS被熔融流动的热塑性树脂N6/66完全覆盖，且热塑性树脂组合物的薄片前端如图3（b）所示地与带状橡胶层紧贴并在带状橡胶层的前端侧弯曲而多少呈包住的形态。在比较例1中确认了位于切割端面的弹性体BIMS按原来状态被暴露。另外，比较例1中的热塑性树脂组合物的薄片前端部并没有特别地呈与带状橡胶层紧贴的形态。
作为实施例2～9，与实施例1同样地如表3所示地变化电热刀具的直径、切割温度、倾斜角θ，与实施例1同样地进行了对层压体薄片的切割。其各条件表示在表3里。在成形鼓上对各层压体薄片以重叠长度10mm的方式进行拼接头，其它的按照通常的轮胎硫化成形方法制造了各充气轮胎。
观察硫化成形后的薄片2前端部时，在实施例1～9的轮胎中，在上述的热塑性树脂组合物的薄片弯曲前端在轮胎硫化成形工序后，由于在该工序中被硫化囊挤压，所以前端弯曲的状态会消除，被前部锐化的同时，呈几乎直线的前部锐化形状且在前部锐化附近紧贴的状态。关于该前部锐化形状（硫化后），分别测量了如图4所示的薄片2的厚度T（mm）、前端形状T/t、前端前部锐化处理部分的长度L。其结果一同表示在表3中。
这样获得的充气轮胎在7.35kN的负荷下行使20，000km，然后，对在各测试轮胎内腔的内衬层的拼接部附近的开裂发生、是否发生有剥离的调查与除此之外部分的情况相比较来进行的。
其结果，在比较例1中，行使行使20，000km后，在拼接部附近发生了开裂，进而在累积行使50，000km后，该开裂发展成热塑性树脂组合物和带状橡胶之间的剥离。此时，在拼接部附近以外没有特别地发生问题，状态良好。
另一方面，在本发明的实施例1～9中，即使行使行使50，000km后在拼接部附近和除此之外的地方均都没有特别地发生问题。
表1
备注：a）溴化异丁烯对甲基苯乙烯共聚物
b）马来酸酐改性乙烯-丙烯酸乙酯共聚物
表2
表3

Claims (7)

1.一种充气轮胎的制造方法，其特征在于，该方法包括下述的形成内衬层的工序：以规定的长度进行切割由将热塑性树脂和弹性体进行混合的热塑性树脂组合物构成的薄片和与该热塑性树脂组合物硫化粘结的橡胶进行层压的层压体薄片，并将该层压体薄片的端部拼接头，进一步通过硫化成形，形成内衬层，其中，在以规定长度切割所述层压体薄片时，在所述热塑性树脂融点以上温度下进行热切割，
进行所述热切割的同时，在所述热切割的切割面上，按照以该热切割的热使所述热塑性树脂流动，并用该热塑性树脂覆盖至少包括位于切割面上的弹性体的切割面整体的方式进行热切割，
用热刀进行所述热切割。
2.根据权利要求1所述的充气轮胎的制造方法，其特征在于，作为所述热刀，使用电热刀。
3.根据权利要求1所述的充气轮胎的制造方法，其特征在于，用热刀进行所述热切割时，将该热刀在该层压体薄片的侧面上按照跨过所述层压体薄片上方空间和下方空间而交叉的方式接触，且使该热刀朝向行进方向倾斜的状态下从所述层压体薄片的一端行进至另一端而进行所述热切割。
4.根据权利要求2所述的充气轮胎的制造方法，其特征在于，用热刀进行所述热切割时，将该热刀在该层压体薄片的侧面上按照跨过所述层压体薄片上方空间和下方空间而交叉的方式接触，且使该热刀朝向行进方向倾斜的状态下从所述层压体薄片的一端行进至另一端而进行所述热切割。
5.根据权利要求3所述的充气轮胎的制造方法，其特征在于，使所述热刀行进时的所述倾斜状态是与该层压体薄片的垂线以10°～45°的倾斜角度倾斜的状态。
6.根据权利要求4所述的充气轮胎的制造方法，其特征在于，使所述热刀行进时的所述倾斜状态是与该层压体薄片的垂线以10°～45°的倾斜角度倾斜的状态。
7.根据权利要求1～6任一项所述的充气轮胎的制造方法，其特征在于，所述热切割是伴随由所述热塑性树脂组合物构成的薄片前端部的侧面形状的前部锐化的处理，该前部锐化的侧面形状满足下述关系：向内侧进入t×1/3长度位置的厚度T(mm)为0.1t≦T≦0.8t，
在此，t表示由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片的非前部锐化处理部分的轮胎圆周方向平均厚度(mm)，
T表示距由在热塑性树脂中混合弹性体的热塑性树脂组合物构成的薄片的前端向内侧进入t×1/3长度位置的薄片的厚度(mm)。
CN201180061404.6A 2010-12-22 2011-12-22 充气轮胎的制造方法 Expired - Fee Related CN103260865B (zh)

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US20130276971A1 (en) 2013-10-24
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