CN110983792A - 一种无溶剂免复合鞋用聚氨酯合成革及其制备方法 - Google Patents

一种无溶剂免复合鞋用聚氨酯合成革及其制备方法 Download PDF

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CN110983792A
CN110983792A CN201911067626.3A CN201911067626A CN110983792A CN 110983792 A CN110983792 A CN 110983792A CN 201911067626 A CN201911067626 A CN 201911067626A CN 110983792 A CN110983792 A CN 110983792A
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阚道俊
迟红梅
高建成
姚克俭
刘兵
胡国金
朱福检
陈泽
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Anhui Anli Material Technology Co Ltd
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Abstract

本发明公开了一种无溶剂免复合鞋用聚氨酯合成革,其由外至内依次包括面层、中间层、无溶剂发泡层和基布层,所述面层由水性脂肪族聚醚型聚氨酯浆料制成,所述中间层由第一水性聚醚型聚氨酯浆料制成,所述基布层为厚型涤纶针织布含浸第二水性聚醚型聚氨酯浆料制成。本发明中基布层采用含浸水性聚醚型聚氨酯浆料,从而使得制得半成品具有类似真皮背面绒面的感觉,在通过复合无溶剂发泡层、中间层和面层,解决了现有技术中合成革单薄、立体感不够、脚感差、需要复合内里的技术问题。

Description

一种无溶剂免复合鞋用聚氨酯合成革及其制备方法
技术领域
本发明属于聚氨酯合成革制造领域,具体涉及一种无溶剂免复合鞋用聚氨酯合成革及其制备方法。
背景技术
真皮由于具有优良的天然特性被人们广泛用于生产日用品和工业品,但随着需求量的日益增加和环保压力越来越大,真皮早已不能满足未来的发展需求。为解决这一矛盾,人造革、合成皮革,得到了长足的发展,特别近几年环保的水性无溶剂技术得到了广泛的应用,这些环保工艺制得的产品手感丰满,皱折细腻,物性好,普遍被看好是是未来合成革行业的发展趋势。
目前传统的制鞋行业,合成革背面基本都是起毛布基,一方面比较单薄,立体感不够,另一方面还存在脚感差、档次低的问题,所以一般都需要复合内里。
发明内容
有鉴于此,本发明有必要提供一种无溶剂免复合鞋用聚氨酯合成革及其制备方法,由于基布层采用含浸水性聚醚型聚氨酯浆料,从而使得制得半成品具有类似真皮背面绒面的感觉,在通过复合无溶剂发泡层、中间层和面层,解决了现有技术中合成革单薄、立体感不够、脚感差、需要复合内里的技术问题。
为了实现上述目的,本发明采用以下技术方案:
一种无溶剂免复合鞋用聚氨酯合成革,其由外至内依次包括面层、中间层、无溶剂发泡层和基布层,所述面层由水性脂肪族聚醚型聚氨酯浆料制成,所述中间层由第一水性聚醚型聚氨酯浆料制成,所述基布层为厚型涤纶针织布含浸第二水性聚醚型聚氨酯浆料制成。
进一步的,所述水性脂肪族聚醚型聚氨酯浆料由100份水性聚醚型聚氨酯树脂、1~3份水性固化剂、1~3份水性增稠剂、0.5-2份水性流平剂 、0.1-1份水性消泡剂和5-20份水性色浆按照质量份数制备而成;
所述第一水性聚醚型聚氨酯浆料由100份水性聚醚型聚氨酯树脂、1~3份水性固化剂、1~3份水性增稠剂、0.5-2份水性流平剂 、0.1-1份水性消泡剂 和5-20份水性色浆按照质量份数制备而成。
进一步的,所述无溶剂发泡层由质量比为(1.5-2.5):1的A料和B料混合而成的无溶剂发泡浆料构成,其中,所述A料由100份聚酯多元醇 AL-1026A、30~60份CaCO3、0.01~0.1份催化剂DY-5508和0.01~0.1份发泡剂 DY-2958按照重量份数制备而成,所述B料为异氰酸酯预聚体AL-5040B。
进一步的,所述第二水性聚醚型聚氨酯浆料由20~50份水性聚醚型聚氨酯树脂3455、50~100份水、5~15份柔软剂LK-156和5~15份色浆按照质量份数制备而成。
进一步的,所述厚型涤纶针织布为厚度1.2~1.3mm的仿真皮的弹力涤纶针织布,其起毛短的一面为短毛面,与所述短毛面相背的一面为长毛面。
本发明还提供了一种无溶剂免复合鞋用聚氨酯合成革的制备方法,包括以下步骤:
S1、将厚型涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过挤压、烘干、卷曲制得半成品;
S2、采用离型纸转移法贴面制得面层,在所述面层上涂覆第一水性聚醚型聚氨酯浆料烘干后制得中间层,然后在中间层表面涂覆无溶剂发泡层,加热预反应后与所述半成品的短毛面贴合,烘干熟化后与离型纸剥离,常温熟化得到无溶剂免复合鞋用聚氨酯合成革。
进一步的,步骤S1中,所述烘干的温度为130-150℃。
进一步的,步骤S2中,所述面层制备的具体步骤为:在离型纸涂覆一层水性脂肪族聚醚型聚氨酯烘烤后作为面层,其中涂覆厚度为0.1-0.2mm,烘烤温度为100-130℃。
进一步的,步骤S2中,所述中间层的涂覆厚度为0.15~0.2mm,所述中间层的烘干温度为100~130℃。
进一步的,步骤S2中,所述无溶剂发泡层的涂覆厚度为0.2-0.3mm,所述无溶剂发泡层的烘干温度为80-110℃,所述熟化温度为125-140℃,所述常温熟化的时间为24-48h。
与现有技术相比,本发明中的无溶剂免复合鞋用聚氨酯合成革环保性能优,且由于使用水性含浸加上水性无溶剂离型纸转移贴面工艺,成品中DMF能够控制在20ppm以内(常规湿法PU合成革一般在1000~3000ppm),环保性能十分优异。
此外,本发明的无溶剂免复合鞋用聚氨酯合成革中采用了1.2-1.3mm厚型的仿真皮涤纶针织布起毛均匀细密,绒感强,在基布上再含浸少量水性聚醚型聚氨酯树脂,使得制得的半成品肉感强,起毛类似真皮背面,再通过离型纸转移贴面,制得的产品手感好、肉感强、厚度厚、经久耐用。
同时本发明中的无溶剂免复合鞋用聚氨酯厚度较厚,可以直接加工,无需复合内里,成本低,真皮感强,肉感强,穿着舒服轻便。
具体实施方式
为了便于理解本发明,下面将结合具体的实施例对本发明进行更全面的描述。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式。相反地,提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。
以下实施例中所用的第二水性聚醚型聚氨酯浆料中水性聚醚型聚氨酯树脂3455采用江苏华大新材料有限公司的产品,柔软剂LK-156为合肥蓝凯化工有限公司的产品;
水性脂肪族聚醚型聚氨酯浆料中水性聚醚型聚氨酯树脂JF-876HY和第一水性聚醚型聚氨酯浆料中的水性聚醚型聚氨酯树脂JF-745A为浙江华峰合成树脂有限公司的材料,水性增稠剂U-605采用中国烟台万华公司的产品,水性固化剂XR2500和水性流平剂LA-91-120采用的是斯塔尔精细涂料苏州有限公司的产品,水性消泡剂SY-210B采用的是江西三越新材料的产品;
无溶剂发泡层中所使用的聚酯多元醇AL-1026A和异氰酸预聚体AL-5040B为合肥安利聚氨酯新材料有限公司的产品,催化剂DY-5508和发泡剂DY-2958为德音化学有限公司的产品,水性色浆用的均是浙江深蓝科技有限公司的产品,其余均为市售产品。
实施例1
本实施例中的无溶剂免复合鞋用聚氨酯合成革采用以下步骤制备:
S1、首先选用1.2mm厚型仿真皮涤纶针织布作为基材,其起毛长的一面为长毛面,起毛短的一面为短毛面,将厚型仿真皮涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过轧辊挤压,于130℃烘干,卷曲制得半成品。含浸用的第二水性聚醚型聚氨酯浆料由以下组份按质量配制成:20份水性聚醚型聚氨酯树脂 3455、50份水、5份柔软剂LK-156和5份色浆制成;
S2、然后采用离型纸转移法贴面,先在离型纸涂覆一层厚度为0.1mm的水性脂肪族聚醚型聚氨酯于100℃烘干后作为面层,然后在面层上涂覆一层厚度为0.15mm的第一水性聚醚性聚氨酯于100℃烘干后作为中间层,然后再在中间层表面涂覆一层厚度为0.2mm的无溶剂发泡层,加热预反应后与半成品短毛面贴合,于110℃烘干后再于125℃熟化后与离型纸剥离,常温熟化24H后得到最终的成品;
其中,面层的水性脂肪族聚醚型聚氨酯浆料按以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-876HY、1份水性固化剂XR-5508、1份水性增稠剂U-605、0.5份水性流平剂LA-91-120、0.1份水性消泡剂 SY-210B和5份水性色浆;
中间层的第一水性聚醚型聚氨酯树脂浆料由以下组份按质量配制成:100份水性聚醚型聚氨酯树脂JF-745A、1份水性固化剂XR-5508、1份水性增稠剂U-605、0.5份水性流平剂LA-91-120、0.1份水性消泡剂 SY-210B 和5份水性色浆;
无溶剂发泡层由质量比为1.5:1的A料和B料混合而成无溶剂发泡浆料构成,其中,所述A料由以下组分按重量份数构成:100份聚酯多元醇 AL-1026A、60份CaCO3、0.01份催化剂DY-5508和0.01份发泡剂 DY-2958,所述B料为异氰酸酯预聚体AL-5040B。
经过本实例制成的无溶剂免复合鞋用聚氨酯合成革:在25℃时,曲折8万次不裂,在-10℃,2万次不裂,耐磨(H18*1KG)=800次不破,70℃*95%RH恒温恒湿检测2周不发雾,不粉化。
实施例2
本实施例中的无溶剂免复合鞋用聚氨酯合成革采用以下步骤制备:
S1、首先选用1.2mm厚型仿真皮涤纶针织布作为基材,其起毛长的一面为长毛面,起毛短的一面为短毛面,将厚型仿真皮涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过轧辊挤压,于140℃烘干,卷曲制得半成品。含浸用的第二水性聚醚型聚氨酯浆料由以下组份按质量配制成:30份水性聚醚型聚氨酯树脂 3455、70份水、6份柔软剂LK-156和10份色浆制成;
S2、然后采用离型纸转移法贴面,先在离型纸涂覆一层厚度为0.15mm的水性脂肪族聚醚型聚氨酯于110℃烘干后作为面层,然后在面层上涂覆一层厚度为0.15mm的第一水性聚醚性聚氨酯于110℃烘干后作为中间层,然后再在中间层表面涂覆一层厚度为0.25mm的无溶剂发泡层,加热预反应后与半成品短毛面贴合,于105℃烘干后再于130℃熟化后与离型纸剥离,常温熟化30H后得到最终的成品;
其中,面层的水性脂肪族聚醚型聚氨酯浆料按以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-876HY、1.5份水性固化剂XR-5508、1.5份水性增稠剂U-605、1份水性流平剂 LA-91-120、0.5份水性消泡剂 SY-210B和10份水性色浆;
中间层的第一水性聚醚型聚氨酯树脂浆料由以下组份按质量配制成:100份水性聚醚型聚氨酯树脂JF-745A、1.5份水性固化剂XR-5508、1.5份水性增稠剂U-605、1份水性流平剂LA-91-120、0.5份水性消泡剂 SY-210B 和10份水性色浆;
无溶剂发泡层由质量比为1.8:1的A料和B料混合而成无溶剂发泡浆料构成,其中,所述A料由以下组分按重量份数构成:100份聚酯多元醇 AL-1026A、50份CaCO3、0.06份催化剂DY-5508和0.03份发泡剂 DY-2958,所述B料为异氰酸酯预聚体AL-5040B。
经过本实例制成的无溶剂免复合鞋用聚氨酯合成革:在25℃时,曲折10万次不裂,在-10℃,3万次不裂,耐磨(H18*1KG)=1000次不破,70℃*95%RH恒温恒湿检测2周不发雾,不粉化。
实施例3
本实施例中的无溶剂免复合鞋用聚氨酯合成革采用以下步骤制备:
S1、首先选用1.2mm厚型仿真皮涤纶针织布作为基材,其起毛长的一面为长毛面,起毛短的一面为短毛面,将厚型仿真皮涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过轧辊挤压,于140℃烘干,卷曲制得半成品。含浸用的第二水性聚醚型聚氨酯浆料由以下组份按质量配制成:35份水性聚醚型聚氨酯树脂 3455、70份水、10份柔软剂LK-156和10份色浆制成;
S2、然后采用离型纸转移法贴面,先在离型纸涂覆一层厚度为0.15mm的水性脂肪族聚醚型聚氨酯于120℃烘干后作为面层,然后在面层上涂覆一层厚度为0.18mm的第一水性聚醚性聚氨酯于120℃烘干后作为中间层,然后再在中间层表面涂覆一层厚度为0.25mm的无溶剂发泡层,加热预反应后与半成品短毛面贴合,于100℃烘干后再于130℃熟化后与离型纸剥离,常温熟化36h后得到最终的成品;
其中,面层的水性脂肪族聚醚型聚氨酯浆料按以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-876HY、2份水性固化剂XR-5508、2份水性增稠剂U-605、1份水性流平剂LA-91-120、0.5份水性消泡剂 SY-210B和15份水性色浆;
中间层的第一水性聚醚型聚氨酯树脂浆料由以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-745A 、2份水性固化剂XR-5508、2份水性增稠剂U-605、1份水性流平剂LA-91-120、0.5份水性消泡剂 SY-210B 和12份水性色浆;
无溶剂发泡层由质量比为2.1:1的A料和B料混合而成无溶剂发泡浆料构成,其中,所述A料由以下组分按重量份数构成:100份聚酯多元醇 AL-1026A、40份CaCO3、0.06份催化剂DY-5508和0.06份发泡剂 DY-2958,所述B料为异氰酸酯预聚体AL-5040B。
经过本实例制成的无溶剂免复合鞋用聚氨酯合成革:在25℃时,曲折12万次不裂,在-10℃,4万次不裂,耐磨(H18*1KG)=1200次不破,70℃*95%RH恒温恒湿检测3周不发雾,不粉化。
实施例4
本实施例中的无溶剂免复合鞋用聚氨酯合成革采用以下步骤制备:
S1、首先选用1.2mm厚型仿真皮涤纶针织布作为基材,其起毛长的一面为长毛面,起毛短的一面为短毛面,将厚型仿真皮涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过轧辊挤压,于150℃烘干,卷曲制得半成品。含浸用的第二水性聚醚型聚氨酯浆料由以下组份按质量配制成:50份水性聚醚型聚氨酯树脂 3455、100份水、15份柔软剂LK-156和15份色浆制成;
S2、然后采用离型纸转移法贴面,先在离型纸涂覆一层厚度为0.2mm的水性脂肪族聚醚型聚氨酯于130℃烘干后作为面层,然后在面层上涂覆一层厚度为0.2mm的第一水性聚醚性聚氨酯于130℃烘干后作为中间层,然后再在中间层表面涂覆一层厚度为0.3mm的无溶剂发泡层,加热预反应后与半成品短毛面贴合,于80℃烘干后再于140℃熟化后与离型纸剥离,常温熟化48h后得到最终的成品;
其中,面层的水性脂肪族聚醚型聚氨酯浆料按以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-876HY、3份水性固化剂XR-5508、3份水性增稠剂U-605、2份水性流平剂LA-91-120、1份水性消泡剂 SY-210B和20份水性色浆;
中间层的第一水性聚醚型聚氨酯树脂浆料由以下组份按质量配制成:100份水性聚醚型聚氨酯树脂 JF-745A 、3份水性固化剂XR-5508、3份水性增稠剂U-605、2份水性流平剂LA-91-120、1份水性消泡剂 SY-210B 和20份水性色浆;
无溶剂发泡层由质量比为2.5:1的A料和B料混合而成无溶剂发泡浆料构成,其中,所述A料由以下组分按重量份数构成:100份聚酯多元醇 AL-1026A、30份CaCO3、0.1份催化剂DY-5508和0.1份发泡剂 DY-2958,所述B料为异氰酸酯预聚体AL-5040B。
经过本实例制成的无溶剂免复合鞋用聚氨酯合成革:在25℃时,曲折15万次不裂,在-10℃,5万次不裂,耐磨(H18*1KG)=1500次不破,70℃*95%RH恒温恒湿检测4周不发雾,不粉化。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。

Claims (10)

1.一种无溶剂免复合鞋用聚氨酯合成革,其特征在于,其由外至内依次包括面层、中间层、无溶剂发泡层和基布层,所述面层由水性脂肪族聚醚型聚氨酯浆料制成,所述中间层由第一水性聚醚型聚氨酯浆料制成,所述基布层为厚型涤纶针织布含浸第二水性聚醚型聚氨酯浆料制成。
2.如权利要求1所述的无溶剂免复合鞋用聚氨酯合成革,其特征在于,所述水性脂肪族聚醚型聚氨酯浆料由100份水性聚醚型聚氨酯树脂、1~3份水性固化剂、1~3份水性增稠剂、0.5-2份水性流平剂 、0.1-1份水性消泡剂和5-20份水性色浆按照质量份数制备而成;
所述第一水性聚醚型聚氨酯浆料由100份水性聚醚型聚氨酯树脂、1~3份水性固化剂、1~3份水性增稠剂、0.5-2份水性流平剂 、0.1-1份水性消泡剂 和5-20份水性色浆按照质量份数制备而成。
3.如权利要求1所述的无溶剂免复合鞋用聚氨酯合成革,其特征在于,所述无溶剂发泡层由质量比为(1.5-2.5):1的A料和B料混合而成的无溶剂发泡浆料构成,其中,所述A料由100份聚酯多元醇 AL-1026A、30~60份CaCO3、0.01~0.1份催化剂DY-5508和0.01~0.1份发泡剂 DY-2958按照重量份数制备而成,所述B料为异氰酸酯预聚体AL-5040B。
4.如权利要求1所述的无溶剂免复合鞋用聚氨酯合成革,其特征在于,所述第二水性聚醚型聚氨酯浆料由20~50份水性聚醚型聚氨酯树脂、50~100份水、5~15份柔软剂和5~15份色浆按照质量份数制备而成。
5.如权利要求1所述的无溶剂免复合鞋用聚氨酯合成革,其特征在于,所述厚型涤纶针织布为厚度1.2~1.3mm的仿真皮的弹力涤纶针织布,其起毛短的一面为短毛面,与所述短毛面相背的一面为长毛面。
6.如权利要求1-5任一项所述的无溶剂免复合鞋用聚氨酯合成革的制备方法,其特征在于,包括以下步骤:
S1、将厚型涤纶针织布含浸第二水性聚醚型聚氨酯浆料,然后经过挤压、烘干、卷曲制得半成品;
S2、采用离型纸转移法贴面制得面层,在所述面层上涂覆第一水性聚醚型聚氨酯浆料烘干后制得中间层,然后在中间层表面涂覆无溶剂发泡层,加热预反应后与所述半成品的短毛面贴合,烘干熟化后与离型纸剥离,常温熟化得到无溶剂免复合鞋用聚氨酯合成革。
7.如权利要求6所述的制备方法,其特征在于,步骤S1中,所述烘干的温度为130-150℃。
8.如权利要求6所述的制备方法,其特征在于,步骤S2中,所述面层制备的具体步骤为:在离型纸涂覆一层水性脂肪族聚醚型聚氨酯烘烤后作为面层,其中涂覆厚度为0.1-0.2mm,烘烤温度为100-130℃。
9.如权利要求6所述的制备方法,其特征在于,步骤S2中,所述中间层的涂覆厚度为0.15~0.2mm,所述中间层的烘干温度为100~130℃。
10.如权利要求6所述的制备方法,其特征在于,步骤S2中,所述无溶剂发泡层的涂覆厚度为0.2-0.3mm,所述无溶剂发泡层的烘干温度为80-110℃,所述熟化温度为125-140℃,所述常温熟化的时间为24-48h。
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