CN105694364B - 一种手柄高能胶、制备方法及其用途 - Google Patents

一种手柄高能胶、制备方法及其用途 Download PDF

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Publication number
CN105694364B
CN105694364B CN201610089002.1A CN201610089002A CN105694364B CN 105694364 B CN105694364 B CN 105694364B CN 201610089002 A CN201610089002 A CN 201610089002A CN 105694364 B CN105694364 B CN 105694364B
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energy rubber
handle high
product
energy
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CN105694364A (zh
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蔡锦云
官江全
李卫平
谢容泉
李步龙
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XIAMEN HOWER MATERIAL CO Ltd
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XIAMEN HOWER MATERIAL CO Ltd
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Priority to CN201610089002.1A priority Critical patent/CN105694364B/zh
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Priority to PCT/CN2017/070727 priority patent/WO2017140192A1/zh
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Priority to US16/004,911 priority patent/US20180291167A1/en
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Abstract

本发明公开了一种手柄高能胶、制备方法及其用途。由20‑80重量份热固性树脂;5‑50重量份发泡剂;5‑50重量份填料;0‑60重量份稀释剂制备得到。所述手柄高能胶可用于制备网球拍、羽毛球拍、壁球拍、PK拍、沙滩拍、柔力拍、球杆、球棒等多种运动器材的手柄。所制备得到的手柄外观完整,手感优良,100‑160℃后加温没有二次膨胀现象,硬度为SHORE D 60‑95。

Description

一种手柄高能胶、制备方法及其用途
技术领域
本发明涉及运动器材领域,尤其涉及一种手柄高能胶、制备方法及其用途。
背景技术
目前生产网球拍、羽毛球拍、壁球拍、PK拍、沙滩拍、柔力拍、球杆、球棒的手柄,需要做成聚氨酯PU握把柄的形态,都是采用先成型一个粗胚大概的形状,经过多次加工后,再重新装入发泡模具里面,利用灌注机将两液型的PU发泡料灌入模具内使之成型为所要的尺寸规格,这种工艺流程长,设备投入大,能耗高,不良率高,以球拍为例:灌注PU的工序,从准备配重到灌注完成,一般要3-5天较长的工期;设备投入,需要一台精密灌注机,一条自动运转加热流水线,一台高压空压机以及不同型号不同尺寸的灌注模;能耗高,只要处在灌注中,所有的加热设备、机台都要运转;由于在作业中受设备及工艺的制约,往往会造成表面搓痕搓伤3-5%,使不良率高,返修增加,造成成本上升。
发明人蔡锦云等人,从2012年开始,公开了与高能胶相关的专利及专利申请201220387938.X、201310098800.7、201320386747.6、201220111085.7。其中CN201220387938.X公开的是碳纤高能胶结构,包括一轻质结构层,覆盖在所述的轻质结构层上的可增压发泡的若干高能胶涂覆层,及覆盖在所述的高能胶涂覆层外的保护层;CN201320386747.6公开的是碳纤高能胶结构,包括一塑料薄膜载体,涂覆在所述的塑料薄膜载体上的可增压发泡的高能胶涂覆层,及位于高能胶涂覆层上的植绒层;CN201220111085.7公开的是球拍月眉结构,包括碳纱外层,所述的碳纱外层内中间设有一PU支撑体,所述的PU支撑体与碳纱外层间填充有经过发泡膨胀后的发泡胶。保护的都是高能胶的结构。中国专利ZL201310098800.7公开的是一种高能胶配方,配方为(千克重量)热塑性橡胶15-25;乙酸乙酯10-25;发泡剂6-20;丁酮30-60;塑化剂0.5-3;防老剂0.5-2.5;硬脂酸0.5-2;交联剂2-3.5和聚酯纤维3-10;所得高能胶能够增强制品的强度和韧性,增加减震的功能;在加热条件下,能够发泡膨胀至自身倍率的40-80倍;但是操作性能仍有待提高,膨胀后制品表面粉化现象严重,破坏环境卫生;另外纤维复材制品成型后一般都有80-150℃后加温处理过程,这种高能胶产品在后加温过程中会产生二次失控膨胀,造成制品爆裂报废,从而不良率升高。
发明内容
本发明的目的在于提供一种一体成型,在后加温过程中不会二次膨胀的新型手柄专用高能胶。
为实现上述目的,本发明提供一种手柄高能胶,其特征在于,由如下重量份的成分制备得到,
进一步,由如下重量份的成分制备得到,
进一步,所述热固性树脂为高Tg(玻璃化转变温度)热固性树脂,温度为120-350℃。
进一步,所述发泡剂的膨胀温度为50-180℃。
进一步,所述填料为碳纤维粉末、石墨粉、碳纳米管、氧化铝、氧化镁、碳酸钙或滑石粉。
进一步,所述稀释剂为反应型稀释剂或非反应型稀释剂;
优选的,所述反应型稀释剂为丁基缩水甘油醚、苯基缩水甘油醚、C12-14脂肪缩水甘油醚、1,4-丁二醇二缩水甘油醚;
所述非反应型稀释剂为丙酮、丁酮、二甲苯、乙酸乙酯、乙酸丁酯。
进一步,所述手柄高能胶厚度为0.4-10mm;优选的,厚度为2-5mm。
进一步,制备方法为,将热固性树脂加入到稀释剂中,搅拌混合后,再依次加入发泡剂和填料,充分搅拌均匀,涂布在支撑材料上;或者将热固性树脂加热到软化温度以上,再加入发泡剂和填料,充分搅拌均匀,涂布在支撑材料上;视配方是否含有溶剂采取合适的干燥方式,根据实际情况裁切尺寸;
优选的,所述支撑材料为无纺布、玻纤毡布、珍珠棉或棉布。
本发明还公开所述手柄高能胶用于制备手柄的用途;优选的,所述手柄为网球拍、羽毛球拍、壁球拍、PK拍、沙滩拍、柔力拍、球杆、球棒的手柄。
所述工艺为:
按运动器材结构设计规格尺寸,裁切纤维复材布和手柄高能胶并整理好待用;
卷制品:按照具体运动器材结构,卷制纤维复材制品;
预型:将卷好的制品,放在室温-80℃加热台上预热3-60min,尽可能挤压排除层间气体,压平顺,将裁切好的手柄高能胶包裹在器材的柄部位置,然后将制品放入预型模内,按预型模设计的形状预型;
入模成型:将预型好的制品,放入35-75℃预热烤箱内预热3-60min,然后取出放入成型模具内,合模盖紧;将模具送入热压成型台,加热程序作用下使手柄高能胶膨胀致使手柄成型完成(高能胶成型膨胀后能很好的与纤维复材结合,不会产生剥离);优选的,所述加热程序中加热温度为80-180℃,时间为10-120min,外部压力为80-120kg/cm2,内部压力为5-15kg/cm2
冷却脱模,将成型好的模具送入冷却台冷却降温,再送入脱模台,开模取出制品即可;优选的,所述冷却降温中的冷却温度为15-45℃,冷却时间为3-10min,冷却外部压力为70-105kg/cm2
其中所述内部压力,可以是风压,也可以是热膨胀材料所提供的压力。
本发明所得成型后手柄高能胶的硬度为SHORE D 60-95。
本发明所得成型后的手柄,再进行后续加温处理,温度范围100-160℃,处理时间10-60min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于1%,优选小于0.1%。
本发明所述热固性树脂起到发泡剂载体支架的固定作用,主要提供高能胶膨胀成型后的强度和硬度,并能通过高Tg提高耐温的稳定性。如果热固性树脂含量低于20重量份,会造成高能胶膨胀成型后的强度和硬度过低,致使制品脱离模具后的高温处理时的束缚力不足;而如果含量高于80重量份,首先相对发泡剂的比例就会减少,影响膨胀效果,其次会造成高能胶膨胀成型后的硬度过高,手柄起不到减震的作用。所述热固性树脂的Tg温度的选择应与使用环境的耐热温度匹配,大于等于潜在使用环境的温度即可稳定使用。
所述发泡剂主要依靠其膨胀特性,提供合适的膨胀倍力。如果发泡剂含量低于5重量份,会造成膨胀倍率太小,不能填充手柄部位空间;而如果含量高于50重量份,会造成膨胀倍率太大,致使挤压内部纤维制品导致内部凹陷变形改变制品的对称性进而影响球拍的手感和击打性能,还有一种可能是导致制品脱离模具后的高温处理时再次失控膨胀爆裂制品。所述发泡剂的膨胀温度与模具温度一致即可。
本发明所述稀释剂的主要作用是用来调节体系粘度,方便高能胶产品不同的涂布方式。如果稀释剂为0,可能需要采用热熔涂布方式;如果添加有稀释剂,可以采用一般的涂布方式,但可能要增加后续的溶剂烘干过程。
本发明所述手柄高能胶平方克重为200-1000g/m2,优选500-600g/m2
应用领域范围:网球拍、羽毛球拍、壁球拍、PK拍、沙滩拍、柔力拍、球杆、球棒的柄部成型。
本发明与现有方案的工艺流程不同之处在于:
本发明:
制品预型—-》包手柄高能胶---》成型---》打磨---》喷漆---》组装---》成品包装。
现有方案:
制品预型---》成型---》打磨---》喷漆---》调重---》装模---》灌PU料---》成型---》削边打磨---》组装---》成品包装。
从以上流程可以看出,本发明流程明显比现有方案的流程简单、设备少、效率高。
优点:
(1)本发明创造性的取代了传统PU灌注手柄成型工艺,采用包裹手柄专用高能胶一次连续成型到位,真正实现连续化生产,极大缩短了原来3-5天的加工流程,提升10-15%的效率。
(2)本发明涉及的高能胶具有发泡倍率5-20倍产生合适的压力,并且在后续的加热过程中不会发生二次膨胀。本发明所得成型后手柄高能胶的硬度为SHORE D 60-95,所得成型后的手柄,再进行后续加温处理,温度范围100-160℃,处理时间10-60min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于1%,优选小于0.1%。实施例3-5实验表明,所制备得到的球拍手柄在100-160℃加温没有二次膨胀现象,硬度为SHORE D81-90。
(3)本发明涉及的高能胶成型膨胀后能很好的与纤维复材结合,不会产生剥离。
(4)减少传统PU灌注生产线设备的投入,降低能耗。
(5)避免返修,降低不良率3-5%,提升品质的稳定性,增强产品市场竟争力。
附图说明
图1是本发明所述手柄高能胶制备成球拍手柄的工艺流程图。
具体实施方式
下面详细描述本发明的实施例,所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的,旨在用于解释本发明,而不能理解为对本发明的限制。实施例中未注明具体技术或条件者,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
以下实施例中,所述热固性树脂为双马来酰亚胺改性环氧树脂。
所述发泡剂为偶氮化合物,磺酰肼类化合物,亚硝基化合物,碳酸钙、碳酸镁或碳酸氢钠。
所述填料为碳纤维粉末、石墨粉、碳纳米管、氧化铝、氧化镁、碳酸钙或滑石粉。
所述稀释剂为反应型稀释剂或非反应型稀释剂;所述反应型稀释剂为丁基缩水甘油醚、苯基缩水甘油醚、C12-14脂肪缩水甘油醚、1,4-丁二醇二缩水甘油醚;所述非反应型稀释剂为丙酮、丁酮、二甲苯、乙酸乙酯、乙酸丁酯。
表1实施例1-6各成分用量(重量份数)
实施例1:手柄高能胶的制备
原料:见表1
制备方法:将双马来酰亚胺改性环氧树脂加热到软化点温度,再加入发泡剂和填料,充分搅拌均匀,涂布在无纺布上,厚度为0.4mm;平方克重为500g/m2,产生的倍率为0-20,产生的压力0-3kg/cm2。将所得再进行后续加温处理,温度100℃,处理时间60min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
实施例2:手柄高能胶的制备
原料:见表1
制备方法:将热固性树脂加入到稀释剂中,搅拌溶解后,再依次加入发泡剂和填料,充分搅拌均匀,涂布在玻纤毡布上,厚度为2mm。涂布在无纺布上,厚度为2mm;平方克重为600g/m2,产生的倍率为0-20,产生的压力0-2kg/cm2。将所得再进行后续加温处理,温度160℃,处理时间10min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
实施例3:手柄高能胶的制备
原料:见表1
制备方法:同实施例2,涂布在玻纤毡布上,厚度为4mm。涂布在无纺布上,厚度为4mm;平方克重为200g/m2,产生的倍率为0-20,产生的压力0-12kg/cm2。将所得再进行后续加温处理,温度范围120℃,处理时间40min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
实施例4:手柄高能胶的制备
原料:见表1
制备方法:同实施例2,涂布在玻纤毡布上,厚度为3.5mm。涂布在无纺布上,厚度为3.5mm;平方克重为1000g/m2,产生的倍率为0-20,产生的压力0-10kg/cm2。将所得再进行后续加温处理,温度140℃,处理时间20min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
实施例5:手柄高能胶的制备
原料:见表1
制备方法:同实施例2,涂布在玻纤毡布上,厚度为5mm。涂布在无纺布上,厚度为5mm;平方克重为550g/m2,产生的倍率为0-20,产生的压力0-8kg/cm2。将所得再进行后续加温处理,温度范围150℃,处理时间20min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
实施例6:手柄高能胶的制备
原料:见表1
制备方法:同实施例2,涂布在玻纤毡布上,厚度为10mm。涂布在无纺布上,厚度为10mm;平方克重为900g/m2,产生的倍率为0-20,产生的压力0-5kg/cm2。将所得再进行后续加温处理,温度范围110℃,处理时间50min,不会出现再次膨胀,制品尺寸保持稳定,膨胀体积倍率(膨胀后的体积比膨胀前的体积)小于0.1%。
以下实施例参照图1的工艺流程。
实施例7:羽毛球拍手柄的制备
按结构设计规格,卷制网球拍制品,然后放在80℃加热台上预热3min,预型,然后在网球拍柄部包裹厚度为0.4mm厚的实施例1所得的手柄高能胶。然后将预型好的制品放入75℃预热烤箱内预热3min,取出放入成型模具内,合模盖紧。将模具送入温度为180℃热压成型台,时间10min,外部压力120kg/cm2,内部压力为5kg/cm2。然后用15℃冷却台冷却10min,冷却外部压力为90kg/cm2,,成型脱模后外观完整无缺,用100℃后加温30min,膨胀体积倍率为0.01%,硬度为SHORE D 81。
实施例8:网球拍手柄的制备
按结构设计规格,卷制网球拍制品,然后放在60℃加热台上预热10min,预型,然后在网球拍柄部包裹厚度为2mm厚的实施例2所得的手柄高能胶。然后将预型好的制品放入60℃预热烤箱内预热5min,取出放入成型模具内,合模盖紧。将模具送入温度为150℃热压成型台,时间17min,外部压力100kg/cm2,内部压力为10-12kg/cm2。然后用30℃冷却台冷却4min,冷却外部压力为70kg/cm2,成型脱模后外观完整无缺。用120℃后加温30min,膨胀体积倍率为0.09%,硬度为SHORE D 90。
实施例9:球棒和球杆手柄的制备
按结构设计规格,卷制网球拍制品,然后放在25℃加热台上预热60min,预型,然后在球棒和球杆预型料柄部一圈包裹厚度为5mm厚的实施例5所得的手柄高能胶。然后将预型好的制品放入35℃预热烤箱内预热60min,取出放入成型模具内,合模盖紧。将模具送入温度为80℃热压成型台,时间120min,外部压力80kg/cm2,内部压力为15kg/cm2。然后用45℃冷却台冷却3min,冷却外部压力为105kg/cm2,成型脱模后外观完整无缺,用160℃后加温60min,膨胀体积倍率为0.09%,硬度为SHORE D 90。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (10)

1.一种手柄高能胶,其特征在于,所述手柄高能胶厚度为0.4-10mm,制备方法为,将热固性树脂加入到稀释剂中,搅拌混合后,再依次加入发泡剂和填料,充分搅拌均匀,涂布在支撑材料上;或者将热固性树脂加热到软化温度以上,再加入发泡剂和填料,充分搅拌均匀,涂布在支撑材料上;视配方是否含有溶剂采取合适的干燥方式,根据实际情况裁切尺寸;其中各组分的用量按重量份分别为,
120-350℃;发泡剂的膨胀温度为50-180℃;所述填料为碳纤维粉末、石墨粉、碳纳米管、氧化铝、氧化镁、碳酸钙或滑石粉。
2.如权利要求1所述手柄高能胶,其特征在于,所述支撑材料为无纺布、玻纤毡布、珍珠棉或棉布。
3.如权利要求1所述手柄高能胶,其特征在于,其中各组分的用量按重量份分别为,
4.如权利要求1所述手柄高能胶,其特征在于,所述稀释剂为反应型稀释剂或非反应型稀释剂。
5.如权利要求4所述手柄高能胶,其特征在于,所述反应型稀释剂为丁基缩水甘油醚、苯基缩水甘油醚、C12-14脂肪缩水甘油醚、1,4-丁二醇二缩水甘油醚;
所述非反应型稀释剂为丙酮、丁酮、二甲苯、乙酸乙酯、乙酸丁酯。
6.如权利要求1所述手柄高能胶,其特征在于,所述手柄高能胶厚度为2-5mm。
7.权利要求1所述手柄高能胶的用途,其特征在于,所述手柄高能胶用于制备手柄。
8.如权利要求7所述手柄高能胶的用途,其特征在于,所述手柄为网球拍、羽毛球拍、壁球拍、PK拍、沙滩拍、柔力拍、球杆、球棒的手柄;
所述手柄的制备工艺为:
按运动器材结构设计规格尺寸,裁切纤维复材布和手柄高能胶并整理好待用;
卷制品:按照具体运动器材结构,卷制纤维复材制品;
预型:将卷好的制品,放在室温-80℃加热台上预热3-60min,尽可能挤压排除层间气体,压平顺,将裁切好的手柄高能胶包裹在器材的柄部位置,然后将制品放入预型模内,按预型模设计的形状预型;
入模成型:将预型好的制品,放入35-75℃预热烤箱内预热3-60min,然后取出放入成型模具内,合模盖紧;将模具送入热压成型台,加热程序作用下使手柄高能胶膨胀致使手柄成型完成;
冷却脱模,将成型好的模具送入冷却台冷却降温,再送入脱模台,开模取出制品即可。
9.如权利要求8所述手柄高能胶的用途,其特征在于,所述加热程序中加热温度为80-180℃,时间为10-120min,外部压力为80-120kg/cm2,内部压力为5-15kg/cm2
10.如权利要求8所述手柄高能胶的用途,其特征在于,所述冷却降温中的冷却温度为15-45℃,冷却时间为3-10min,冷却外部压力为70-105kg/cm2
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