CN113929953A - 高柔软性发泡鞋底材料及鞋底的制备方法 - Google Patents
高柔软性发泡鞋底材料及鞋底的制备方法 Download PDFInfo
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Abstract
本发明公开了高柔软性发泡鞋底材料,包括以下质量份数的原料制成:乙烯‑醋酸乙烯酯共聚物25~55份,复合型柔性热塑性弹性体20~35份,α‑烯烃类热塑性弹性体15~30份,滑石粉5~10份,耐磨剂2~15份,交联剂0.3~1.5份,发泡剂2.5~10份;其中,复合型柔性热塑性弹性体由苯乙烯‑乙烯‑苯乙烯嵌段共聚物、热塑性聚酯弹性体及液体橡胶按照质量比(5~15):(20~30):(20~45)共混而成。本发明还公开了采用上述材料的鞋底的制备方法。本发明的高柔软性发泡鞋底材料耐磨性好,同时质地柔软舒适,具有优异的回弹性能,轻便舒适。采用本发明鞋底的制备方法制备出的高柔软性发泡鞋底,制备工艺过程稳定,成品的良品率较高。
Description
技术领域
本发明涉及一种鞋底,具体为高柔软性发泡鞋底材料,以及鞋底的制备方法。
背景技术
运动鞋,可以简单的将其分为专业运动竞技和日常休闲运动鞋,专业运动鞋可以给足部足够的支撑和力学反馈,因此这类鞋底往往整体偏重、偏硬。
普通一次射出成型鞋底因为要全掌接触地面,为了改善中底耐磨性,一方面要增加硬度,另一方面要加入过多的耐磨剂或者粉剂,从而使中底***,其柔软舒适性能大幅度降低,给人不好的穿着体验。因此,为了解决一次射出成型鞋底偏硬,脚感较差的问题,有必要研发出一种高舒适性、柔软发泡的中底材料,可满足大部分运动爱好者的日常运动需求。
发明内容
本发明的目的在于提供一种高柔软性发泡鞋底材料,其制得的鞋底耐磨,且柔软性高,适宜在运动鞋上使用。为实现上述目的,本发明采用以下技术方案:
本发明公开了高柔软性发泡鞋底材料,包括以下质量份数的原料制成:乙烯-醋酸乙烯酯共聚物25~55份,复合型柔性热塑性弹性体20~35份,α-烯烃类热塑性弹性体15~30 份,滑石粉5~10份,耐磨剂2~15份,交联剂0.3~1.5份,发泡剂2.5~10份;其中,复合型柔性热塑性弹性体由苯乙烯-乙烯-苯乙烯嵌段共聚物、热塑性聚酯弹性体及液体橡胶按照质量比(5~15):(20~30):(20~45)共混而成。
优选的,还包括以下质量份数的原料:钛白粉2.5~3份,氧化锌2~2.5份,硬脂酸0.5~0.8份,硬脂酸锌0.8~1份。
进一步的,所述的乙烯-醋酸乙烯酯共聚物中VA的质量含量在22%-35%。所述的液体橡胶为相对分子量为1000~35000的液体橡胶。
其中,所述的液体橡胶为端羟基聚丁二烯、端巯基液体聚硫橡胶、液体丁腈橡胶、液体丁苯橡胶、液体硅橡胶及浇注型聚氨酯中的一种或多种。
其中,所述的α-烯烃类热塑性弹性体为乙烯-丁/辛烯无规共聚物、乙烯-丁/辛烯嵌段共聚物、乙烯-丙烯-非共轭二烯烃共聚物中的一种或多种。
优选的,所述的滑石粉的粒径为4000-6500目;所述耐磨剂为乙烯-醋酸乙烯酯共聚物和硅油复合而成的共混物;所述的交联剂为过氧化二异丙苯或1,4-双叔丁基过氧异丙基苯中的一种或两种;所述的发泡剂选自偶氮二甲酰胺、4,4'-氧代双苯磺酰肼、N,N'-二亚硝基五亚甲基四胺中的一种或几种。
本发明还公开了一种鞋底的制备方法,包括以下步骤:
S1.称取原料,按上述的高柔软性发泡鞋底材料的比例称取各个原料。
S2.胶料混炼,将除了交联剂和发泡剂的其余原料先进行密炼,温度升高至100℃~110℃时,加入交联剂和发泡剂进行混炼。
S3.胶料开炼,将混炼好的胶料加入开炼机进行开炼,开炼机前辊温度设定65℃~75℃;后辊温度设定35~45℃。
S4.造粒,将开炼后的胶料投入造粒机进行造粒,造粒机的温度为80℃~85℃。
S5.发泡,将造好的料子倒入发泡成型机内进行发泡和模具硫化成型,发泡的温度为 90℃~95℃,模具的温度为170~185℃;硫化时间为300-500s,得到成型好的鞋底。
S6.烘干,将成型好的鞋底进行烘干,热定型。
优选的,步骤S3中,调整开炼机的前辊和后辊间隙为5~10mm,将胶料通过辊轮碾压若干次,然后将前辊和后辊间隙调整为2~3mm,再将胶料通过辊轮碾压若干次;步骤S4中造粒机中料斗、螺杆加热区、模头的温度分别为80±5℃、80±5℃、85±5℃,螺杆转速调至40~50r/min,将切料机转速调至15~20r/min。
优选的,步骤S5中,发泡过程设置四个连续的发泡区域,四个区域的温度依次为95±2℃、95±2℃、90±2℃、90±2℃,四个区域的压力为90±5Bar;步骤S6中,烘干在烘箱中进行,所述的烘箱设置前段、中段、后段,温度分别设定为100±2℃、90±2℃、80 ±2℃,热定型的时间为30±5分钟。
由于采用了上述方案,本发明具有如下有益效果:本发明的高柔软性发泡鞋底材料耐磨性好,同时质地柔软舒适,具有优异的回弹性能,轻便舒适。采用本发明鞋底的制备方法制备出的高柔软性发泡鞋底为一次射出成型,制备工艺过程稳定,成品的良品率较高。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案,下面结合具体实施例对本发明作进一步详细的描述。
本发明公开了一种高柔软性发泡鞋底材料,按照质量份数,原料组分包括:乙烯-醋酸乙烯酯共聚物25~55份,复合型柔性热塑性弹性体20~35份,α-烯烃类热塑性弹性体15~ 30份,滑石粉5~10份,耐磨剂2~15份,交联剂0.3~1.5份,发泡剂2.5~10份,钛白粉2.5~3份,氧化锌2~2.5份,硬脂酸0.5~0.8份,硬脂酸锌0.8~1份。
其中,复合型柔性热塑性弹性体由苯乙烯-乙烯-苯乙烯嵌段共聚物、热塑性聚酯弹性体及液体橡胶按照质量比(5~15):(20~30):(20~45)共混而成。
根据原料组分进行具体材料的选型,如下表1所示。
表1原料组分的材料选型
根据原料的配比,可以进行表2的配比。
表2原料组分的配比(质量份数)
原料组分/实施组别 | A | B | C | D | E |
乙烯-醋酸乙烯酯共聚物(EVA) | 45 | 40 | 35 | 25 | 55 |
复合型柔性热塑性弹性体 | 25 | 30 | 35 | 20 | 30 |
α-烯烃类热塑性弹性体(TPO) | 30 | 30 | 30 | 25 | 15 |
滑石粉 | 5 | 5 | 5 | 8 | 10 |
耐磨剂 | 10 | 10 | 10 | 15 | 4 |
交联剂 | 1.5 | 1.6 | 1.7 | 0.8 | 0.3 |
发泡剂 | 3.5 | 3.4 | 3.8 | 5 | 2.5 |
钛白粉 | 2.5 | 2.5 | 2.5 | 3 | 2.8 |
氧化锌 | 2.1 | 2.1 | 2.5 | 2 | 2.4 |
硬脂酸 | 0.5 | 0.5 | 0.5 | 0.8 | 0.6 |
硬脂酸锌 | 0.8 | 1.0 | 1.0 | 0.8 | 0.8 |
本发明中复合型柔性热塑性弹性体的特点是软弹舒适,弹性优异,支撑性好、耐疲劳性好。本发明的复合型柔性热塑性弹性体由苯乙烯-乙烯-苯乙烯嵌段共聚物(SBS)、热塑性聚酯弹性体(TPEE)及复合液体橡胶共混物组成,其具有优异性能的原理如下详述:
(1)苯乙烯-乙烯-苯乙烯嵌段共聚物(SBS)的分子结构中聚丁二烯段充当软段,由于C=C双键的存在,使其分子链的旋转更加灵活,从而具有优异的柔韧性及弹性,分子两端为含有刚性基团(苯环)的聚苯乙烯,其分子内聚能较高,相互聚集形成物理连接点,从而使材料有一定的弹性及支撑性。
(2)热塑性聚酯弹性体(TPEE)又称聚酯橡胶,是一类含有PBT(聚对苯二甲酸丁二醇酯)聚酯硬段和脂肪族聚酯软段的线型嵌段共聚物,其具有较好的柔韧性和力学特性,可提高材料的加工性能,同时聚酯硬段和脂肪族聚酯软段相互结合,使得材料具有优异的耐疲劳特性,鞋底在长时间屈挠后依旧保持软弹特性。
(3)液体橡胶选用相对分子量在1000-35000范围的低分子量液体橡胶,其在室温下为黏稠状流动性液体,经过适当化学反应可形成三维网状结构,从而获得和普通硫化胶具有类似的物理机械性能的低聚物,由于相对分子量比较小,在复合过程中小分子链可以在其他大分子链段之间穿插,使大分子与大分子之间链段间距增大,从而更加有利于分子链的伸展与收缩,反馈到宏观上即表现出优异的软弹特性。
将三种原料按照质量比(5~15):(20~30):(20~45)共混后使材料的支撑性好,同时又不致于过硬,而保持一定的柔软性。
本发明中乙烯-乙烯酯共聚物(EVA)中VA质量含量在22%-35%,其VA质量含量较高。乙烯-醋酸乙烯酯共聚物主要有两部分组成,一部分是可结晶的聚乙烯硬段,其链结构规整度较高,结构对称,另一部分是含有酯基侧基且分子结构不对称的聚醋酸乙烯酯软段。可结晶的聚乙烯段作为物理缠结点,主要是起到交联的作用,使大分子链缠结更加紧密,张弛有度,不会使大分子过度滑移导致鞋底变形,赋予鞋底支撑性;含有酯基侧基的聚醋酸乙烯酯软段为柔性链,在大分子中主要以无规团聚形式存在,可以提高材料的柔软度及回弹性,给穿着者更好的穿着体验。
本发明中采用α-烯烃类热塑性弹性体,此类弹性体的分子结构特殊,C-C单键及侧甲基、侧乙烯基的存在使其具有优异的抗老化性能,同时硬段软段交替/嵌段的存在使大分子链相互缠绕,形成类似于线团一样的结构,使材料体现出优异的软弹性能,同时α-烯烃类热塑性弹性体相比于其他材料密度更轻,穿着起来更加轻便舒适。
本发明中加入硬脂酸,可以增加材料的流动性,防止制备时粘结机台,加入硬脂酸锌和氧化锌两种活性剂,可以促进制备中的发泡过程。
实施例一
本实施例公开了一种高柔软性发泡鞋底材料,按照质量份数,原料组分如下表3所示。
表3实施例一原料
按照如上表3的配方进行鞋底的制备,其制备步骤如下详述。
S1.称取原料
按照高柔软性发泡鞋底材料的比例称取各个原料。将原料分为两组:第一组为交联剂和发泡剂,第二组为其余原料,即:乙烯-醋酸乙烯酯共聚物、复合型柔性热塑性弹性体、α- 烯烃类热塑性弹性体、滑石粉、耐磨剂、钛白粉、氧化锌、硬脂酸、硬脂酸锌。
S2.胶料混炼
将第二组原料先进行密炼,倒入密炼机,并启动机器,降下防尘罩,然后降下压陀,待温度升高到85℃左右时打开防尘罩,清扫干净周围的粉末,待温度升到至100℃~110℃时,倒入第一组原料,密炼1分钟左右,打开压陀,清扫干净混炼室内腔的残留的无味DCP 和发泡剂;待温度升到115℃时,将混炼好的胶料倒出,进入下一步骤。
S3.胶料开炼
提前两小时将开炼机预热,开炼机前辊温度设定65℃~75℃,后辊温度设定35~45℃,开炼机的前辊和后辊间隙为5~10mm。将步骤S2中混炼好的胶料通过辊轮碾压2次,然后将前辊和后辊间隙调整为2~3mm,再将胶料通过辊轮碾压2次。胶料开炼的目的一方面是为了胶料混合的更加均匀,另一方面是为了降低胶料的温度,防止在造粒过程中提前发泡。
S4.造粒
提前打开温度开关将造粒机的机台预热,将料斗、螺杆加热区、模头温度分别调为: 80℃、80℃、85℃,将螺杆转速调至40~50r/min,将切料机转速调至15~20r/min,清理模头、螺杆及风筒内的积料准备造粒,将风筒末端套好袋子,锁紧模头准备造粒,造好粒子贴好标签备用。
将开炼后的胶料投入造粒机进行造粒。
S5.发泡
将步骤S4的造粒料倒入注塑发泡成型机进行发泡和模具硫化成型。
发泡过程设置四个连续的发泡区域,四个区域的温度依次为95±2℃、95±2℃、90±2℃、90±2℃,四个区域的压力为90±5Bar。设置温度梯度的原因是加热板温度会受到诸多因素影响,比如周围环境温度、模具薄厚等,通过设置温度梯度,使得螺杆加料区和压缩区温度高于均化区,这样有利于物料充分的熔融混合。
模具上下模板可调为:170~185℃。将料量和射速依据模具用量设定好,硫化时间设定为300-500秒。
S6.烘干
将成型好的鞋底放入烘箱进行烘干,热定型。烘箱设置前段、中段、后段,温度分别设定为100±2℃、90±2℃、80±2℃,热定型的时间为30±5分钟。烘干后得到成品。设置温度梯度主要是提高中底的尺寸稳定性,增加良品率,首先前段温度较高,大分子振动加剧,可以释放大分子链间的内应力,后端温度较低,主要是使大分子链振动趋于稳定,从而更好的定型。
实施例二
本实施例公开了一种高柔软性发泡鞋底材料,按照质量份数,原料组分如下表4所示。
表4实施例二原料
本实施例的制备过程与实施例一相同。
实施例三
本实施例公开了一种高柔软性发泡鞋底材料,按照质量份数,原料组分如下表5所示。
表5实施例三原料
本实施例的制备过程与实施例一相同。
以下针对本发明的效果进行实验论证。
为了验证本发明的效果,制备三组对照例:对照例一采用的配方与实施例一比较,采用普通的热塑性弹性体替代复合型柔性热塑性弹性体和α-烯烃类热塑性弹性体。对照例二采用的配方与实施例二比较,采用普通的热塑性弹性体替代复合型柔性热塑性弹性体和α- 烯烃类热塑性弹性体。对照例三采用的配方与实施例三比较,采用普通的热塑性弹性体替代复合型柔性热塑性弹性体和α-烯烃类热塑性弹性体。
将制得的三组实施例和三组对照例的鞋底进行性能检测,检测结果如下表6所示。
表6性能检测结果
从表6可知,对照例一至对照例三由于未采用本发明的复合型柔性热塑性弹性体和α- 烯烃类热塑性弹性体,其整体硬度都比较高,回弹率低。本发明的硬度在达标的情况下,回弹率高,具有一定的柔软性,且耐磨性好,适用于做为运动鞋的鞋底,可满足大部分运动爱好者的日常运动需求。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
1.高柔软性发泡鞋底材料,其特征在于,包括以下质量份数的原料制成:
乙烯-醋酸乙烯酯共聚物25~55份,
复合型柔性热塑性弹性体20~35份,
α-烯烃类热塑性弹性体15~30份,
滑石粉5~10份,
耐磨剂2~15份,
交联剂0.3~1.5份,
发泡剂2.5~10份;
其中,复合型柔性热塑性弹性体由苯乙烯-乙烯-苯乙烯嵌段共聚物、热塑性聚酯弹性体及液体橡胶按照质量比(5~15):(20~30):(20~45)共混而成。
2.如权利要求1所述的高柔软性发泡鞋底材料,其特征在于,还包括以下质量份数的原料:
钛白粉2.5~3份,
氧化锌2~2.5份,
硬脂酸0.5~0.8份,
硬脂酸锌0.8~1份。
3.如权利要求1或2所述的高柔软性发泡鞋底材料,其特征在于,所述的乙烯-醋酸乙烯酯共聚物中VA的质量含量在22%-35%。
4.如权利要求1或2所述的高柔软性发泡鞋底材料,其特征在于,所述的液体橡胶为相对分子量为1000~35000的液体橡胶。
5.如权利要求4所述的高柔软性发泡鞋底材料,其特征在于,所述的液体橡胶为端羟基聚丁二烯、端巯基液体聚硫橡胶、液体丁腈橡胶、液体丁苯橡胶、液体硅橡胶及浇注型聚氨酯中的一种或多种。
6.如权利要求1或2所述的高柔软性发泡鞋底材料,其特征在于,所述的α-烯烃类热塑性弹性体为乙烯-丁/辛烯无规共聚物、乙烯-丁/辛烯嵌段共聚物、乙烯-丙烯-非共轭二烯烃共聚物中的一种或多种。
7.如权利要求1或2所述的高柔软性发泡鞋底材料,其特征在于,所述的滑石粉的粒径为4000-6500目;所述耐磨剂为乙烯-醋酸乙烯酯共聚物和硅油复合而成的共混物;所述的交联剂为过氧化二异丙苯或1,4-双叔丁基过氧异丙基苯中的一种或两种;所述的发泡剂选自偶氮二甲酰胺、4,4'-氧代双苯磺酰肼、N,N'-二亚硝基五亚甲基四胺中的一种或几种。
8.一种鞋底的制备方法,其特征在于,包括以下步骤:
S1.称取原料
按权利要求1~7任一项所述的高柔软性发泡鞋底材料的比例称取各个原料;
S2.胶料混炼
将除了交联剂和发泡剂的其余原料先进行密炼,温度升高至100℃~110℃时,加入交联剂和发泡剂进行混炼;
S3.胶料开炼
将混炼好的胶料加入开炼机进行开炼,开炼机前辊温度设定65℃~75℃;后辊温度设定35~45℃;
S4.造粒
将开炼后的胶料投入造粒机进行造粒,造粒机的温度为80℃~85℃;
S5.发泡
将造好的料子倒入发泡成型机内进行发泡和模具硫化成型,发泡的温度为90℃~95℃,模具的温度为170~185℃;硫化时间为300-500s,得到成型好的鞋底;
S6.烘干
将成型好的鞋底进行烘干,热定型。
9.如权利要求8所述的鞋底的制备方法,其特征在于,步骤S3中,调整开炼机的前辊和后辊间隙为5~10mm,将胶料通过辊轮碾压若干次,然后将前辊和后辊间隙调整为2~3mm,再将胶料通过辊轮碾压若干次;步骤S4中造粒机中料斗、螺杆加热区、模头的温度分别为80±5℃、80±5℃、85±5℃,螺杆转速调至40~50r/min,将切料机转速调至15~20r/min。
10.如权利要求8所述的鞋底的制备方法,其特征在于,步骤S5中,发泡过程设置四个连续的发泡区域,四个区域的温度依次为95±2℃、95±2℃、90±2℃、90±2℃,四个区域的压力为90±5Bar;步骤S6中,烘干在烘箱中进行,所述的烘箱设置前段、中段、后段,温度分别设定为100±2℃、90±2℃、80±2℃,热定型的时间为30±5分钟。
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