CN109440484B - 一种软质无溶剂阻燃型聚氨酯合成革及其制备方法 - Google Patents

一种软质无溶剂阻燃型聚氨酯合成革及其制备方法 Download PDF

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CN109440484B
CN109440484B CN201811528216.XA CN201811528216A CN109440484B CN 109440484 B CN109440484 B CN 109440484B CN 201811528216 A CN201811528216 A CN 201811528216A CN 109440484 B CN109440484 B CN 109440484B
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layer
parts
synthetic leather
prepared
polyurethane synthetic
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CN109440484A (zh
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姚和平
宋远周
王燕武
孙心如
黄万里
王义峰
姚克俭
王锐林
王森
罗运东
陈永志
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Anhui Anli Material Technology Co Ltd
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Anhui Anli Material Technology Co Ltd
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Priority to PCT/CN2018/122060 priority patent/WO2020118746A1/zh
Priority to US17/311,695 priority patent/US11773302B2/en
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract

本发明公开了一种软质无溶剂阻燃型聚氨酯合成革及其制备方法，从上到下依次包括防污层、面层、中间层、粘接层及基布；所述的粘接层由A组分和异氰酸酯制备而成，所述异氰酸酯中‑NCO与A组分中‑OH的摩尔数比为0.85‑0.93；所述A组分是由多元醇、抑制型催化剂、阻燃剂、填料、粘度调整剂按重量份数构成。本发明制得的聚氨酯合成革具有生活防污性、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能，同时还具有优异的防污、耐刮和耐曲挠性能；并且生产过程简单高效、绿色环保，能够满足市场需求。

Description

一种软质无溶剂阻燃型聚氨酯合成革及其制备方法
技术领域
本发明涉及一种聚氨酯合成革，具体涉及一种软质无溶剂阻燃型聚氨酯合成革及其制备方法。
背景技术
随着当前环保要求的日益提高，环保型聚氨酯合成革研究十分活跃。其中无溶剂聚氨酯合成革具有环境友好、使用性能优等特点，成为近几年研究热门。此外，相对于水性聚氨酯合成革而言，无溶剂聚氨酯合成革在能耗、使用性能等方面具有一定的优势。
无溶剂聚氨酯材料是一种有机高分子材料，但是未经阻燃处理的聚氨酯不抗燃，遇火会燃烧并分解，并产生大量有毒烟雾和气体，危害人身财产安全。而目前市场上在售的溶剂型或无溶剂型阻燃聚氨酯合成革，普遍存在手感硬、塑胶感强、使用性能及阻燃效果差等缺陷，不能满足消费者需求。在这种形势下，研究开发具有耐用性好、手感柔软、亲肤感强、阻燃性能优且环保的聚氨酯合成革以满足市场对合成革产品功能性和多样性的要求。
发明内容
本发明旨在提供一种软质无溶剂阻燃型聚氨酯合成革及其制备方法，本发明制得的聚氨酯合成革具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能，且生产过程简单高效、绿色环保，能够满足市场需求。
为克服现有技术中的问题，实现上述目的，本发明采用如下技术方案：
一种软质无溶剂阻燃型聚氨酯合成革，从上到下依次包括防污层、面层、中间层、粘接层及基布；所述的粘接层由A组分和异氰酸酯制备而成，所述异氰酸酯中-NCO与A组分中-OH的摩尔数比为0.85-0.93；
所述A组分是由以下原料按重量份数构成：
Figure BDA0001905007240000011
Figure BDA0001905007240000021
进一步方案，所述抑制型催化剂是环保型有机锆催化剂；所述的阻燃剂为固乐科公司的GRPHOS 8815-10、GRPHOS 8815-57以及科莱恩公司的EXOLIT AP 462、EXOLIT RP-652中的至少两种；
所述填料是指氢氧化铝、氮化硼和氧化锌混合料经干法改性后所得的改性填料，其中所述氢氧化铝、氮化硼和氧化锌的质量比40-60：10-20：20-40；
所述粘度调整剂为丙三醇三乙酸酯。
进一步方案，所述改性填料的制备方法如下：
1)将10-15g硅烷偶联剂、3.5-5g水、50-80g无水乙醇加入容器中，然后将容器密闭后置于25-35℃恒温水浴锅中水解10-30min得水解液；
2)将氢氧化铝、氮化硼和氧化锌按质量比40-60：10-20：20-40混合成混合料，然后取1-2kg混合料加入高速混合搅拌机中，所述高速混合搅拌机转速为500-800r/min、烘干温度设定为110-125℃；
3)将步骤(1)制得的水解液分三批加入步骤(2)的高速混合搅拌机中，每批加入间隔时间为5-8min，第一批加入量为水解液质量的30-50％，第二批加入量为水解液质量的20-40％，第三批为余量；
4)加入完毕后，在1200-2000r/min条件下高速搅拌10-20min，出料、冷却即得改性填料。
进一步方案，所述防污层由以下组分按重量份制备而成：
水性防污表处剂 100份
耐水解助剂 0.5-2份；
所述面层是由以下组分按重量份制备而成：
Figure BDA0001905007240000022
Figure BDA0001905007240000031
更优选的，所述水性防污表处剂为脂肪族水性聚氨酯，所述耐水解助剂为改性聚碳化二亚胺；
所述聚碳型聚氨酯树脂由NE-8875-30MF和ST-8630按重量比1.5：(1-1.5)混合而成，所述液体阻燃剂为无卤磷酸酯阻燃剂。
其中脂肪族水性聚氨酯选择建德市顺发化工助剂有限公司生产的水性亮面防涂鸦处理剂SF-6110，其固含量为25±2％，粘度为1500-3000CPS/25℃。
改性聚碳化二亚胺选择斯塔尔公司的XR-5580，其主要适用于水性丙烯酸，聚氨酯体系或其溶剂型产品的通用交联剂，可显著提高耐水，耐化学品和耐磨性能，同时可增强对基材的附着力。
无卤磷酸酯阻燃剂选择斯塔尔公司的FRA-9555，具有优良的水解稳定性、低挥发性及低雾化性。
NE-8875-30MF为大日精化(上海)化工有限公司产品，ResamineNE-8875-30MF作为人工皮革用素材而开发的二液型碳酸酯/醚类是有着优越性能的聚氨酯树脂溶液。使用时是利用ResamineNE-8875-30MF液型架桥剂架桥，形成弹性丰富的弹性体薄膜。
ST-8630为合肥安利聚氨酯新材料公司产品，ST-8630为芳香族面层聚氨酯树脂，该树脂成革具有手感柔和、丰满，表面触感湿蜡，耐水解性能优异等特点。其性能为：固形份28±1％、溶剂为DMF/DMC、100％定伸模量2.7±0.5MPa、断裂伸长率≥400％、抗张强度≥30.0MPa。
进一步方案，所述中间层是由以下组分按重量份制备而成：
Figure BDA0001905007240000032
优选的，所述聚醚聚碳型聚氨酯树脂为NES-9015-22；所述的可溶性阻燃剂为磷腈阻燃剂。
其中聚醚聚碳型聚氨酯树脂为NES-9015-22为大日精化(上海)化工有限公司的产品；所述磷腈阻燃剂选择日本艾迪科公司生产的SPB-100，其不含卤素和锑，磷含量高(13.4％)，其他磷酸盐含量为9-11％，氮含量6％；具有优异的疏水和耐水性、且耐高温。
进一步方案，所述基布为沛特阻燃型再生皮基布，其由真皮粉及全棉机织布按重量比55-65：35-45组成；其厚度为1.3±0.1mm、克重700±20g/cm2。
本发明的另一个发明目的是提供上述一种软质无溶剂阻燃型聚氨酯合成革的制备方法，其包括如下步骤：
(1)将面层浆料充分搅拌混合均匀后抽至真空，再均匀涂刮在离型纸的正面作为面层；再将中间层浆料进行充分搅拌混合均匀后抽真空，将其均匀涂刮在面层上制得中间层；
(2)将A组分和异氰酸酯搅拌混合成粘接层浆料，边混合边涂覆在中间层上，加热烘干，得到粘接层；
(3)在粘接层上贴合基布，烘干、熟化、剥离分卷，得到聚氨酯合成革半成品；
(4)将防污层浆料通过表处辊辊涂在步骤(3)中制得的合成革半成品的革面上，烘干即得合成革成品。
进一步方案，所述步骤(1)中面层浆料的涂覆厚度为0.05-0.08mm，中间层浆料的涂刮厚度为0.12-0.18mm，面层及中间层在110-115℃条件下鼓风干燥1-1.5min；
所述步骤(2)中粘接层浆料混合搅拌速度为3000-3500r/min，加热烘干温度为80-95℃，粘接层涂覆厚度为0.25-0.4mm；
所述步骤(3)中烘干温度为110-130℃，熟化时间为5-7min，贴合基布时的层压间隙为基布厚度的78-85％。
所述步骤(4)中烘干温度为140-150℃，所述表处辊为300目，车速为20-25m/min。
本申请中的环保型溶剂、耐磨助剂、可溶性阻燃剂、润湿剂、稳定剂、颜料色浆等均是本领域常用的一些助剂，本申请不作特殊的限制。
与现有技术相比，本发明的有益效果体现在：
1、本发明采用环保型有机锆催化剂，使得A组分和异氰酸酯搅拌混合成的粘接层浆料涂覆在中间层上，在室温(25℃)条件下，反应活性极低，具有良好的过刀性，当温度高于80℃后，反应活性大幅提高，缩短反应时间，提高生产效率。
2、本发明采用NE-8875-30MF和ST-8630为面层树脂，NES-9015-22为中间层树脂，这些树脂模量低且耐磨性能极优；另外，由于无溶剂粘接层物料中R值较小，为0.85-0.93，使制得合成革手感柔软、肤感强，同时具有超强耐磨性能、耐久用性能。
3、本发明粘接层中添加复配阻燃剂，利用其协同作用，提高阻燃效果，同时采用沛特阻燃型再生皮基布，因其成分为真皮粉和全棉机织布按重量比55-65：35-45组成，则可大幅提高合成革阻燃性能，在阻燃剂较低添加量下即可满足美标FMVSS302及英标BS5852:2006，5号火焰阻燃检测标准要求。
4、本发明面层采用液体阻燃剂，中间层中采用可溶于环保溶剂DEF或DMC的可溶性磷腈阻燃剂(SPB-100)，从而在提高了合成革阻燃性能的同时，不影响其曲挠、耐刮等各项物理性能。
5、本发明制得的聚氨酯合成革具有耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能(满足英标BS5852:2006，5号火焰检测要求)，且生产过程简单高效、绿色环保，能够满足市场需求。
6、本发明采用单组分、水性脂肪族水性聚氨酯作为防污表处剂，将其与改性聚碳化二亚胺混合后，可直接通过表处辊辊涂在半成品革的表面。其生产操作简单、高效环保，在涂覆量较低的情况下，即可获得良好的防污功能，同时具有优异的耐刮、耐曲挠性能。
7、本发明采用干法改性工艺对填料进行表面改性处理，在硅烷偶联剂添加量很少(填料粉体质量的0.5％-1％)的情况下即可使改性后的填料粉体的活化度≥97％。
具体实施方式
下面结合具体实施例，对本发明作进一步阐述。应该理解，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整，仍属于本发明的保护范围。下述实施例中份数均按质量份计。
下述实施例中各原料的来源为：
以下各实施例中，多元醇选择混合料Al-2010A，异氰酸酯为Al-2010B，均为合肥安利聚氨酯新材料公司产品；
所述的阻燃剂GRPHOS 8815-10、GRPHOS 8815-57为固乐科公司产品，EXOLIT AP-462、EXOLIT RP-652为科莱恩公司产品；
可溶性阻燃剂选择日本艾迪科公司生产的SPB-100；
所述硅烷偶联剂选择正丙基三甲氧基硅烷为荆州江汉精细化工产品；
所述粘度调整剂为丙三醇三乙酸酯，具体为伊士曼EASTMAN公司产品(上海凯茵化工代理)；
所述FRA-9555、XR-5580均为斯塔尔公司产品；
所述SF-6110为建德市顺发化工助剂有限公司；
所述BASF A料(CC6945-100C-A)、B料(CC6945-100C-B)、93540/93600均为巴斯夫公司产品；
所述无水乙醇为国药化学公司产品；
所述环保型溶剂选择DMC、DEF，均为合肥同创化工有限公司产品；
所述润湿剂选择LT-7110为合肥安利聚氨酯新材料公司产品；
所述稳定剂为抗氧剂、紫外吸收剂或受阻胺类稳定剂，其中抗氧剂为259、1222、1425或1081，为汽巴精化(Ciba SC)产品；紫外吸收剂为328、UV-2337、UV-5411、213或171，为汽巴精化(Ciba SC)产品；受阻胺类稳定剂为783、791、2030或2040，为汽巴精化(CibaSC)产品；
所述耐磨助剂为PTFE粉或3238，其中耐磨助剂3238为上海和氏璧化工有限公司产品；耐磨助剂PTFE为美国杜邦公司产品；
面层中聚碳型聚氨酯树脂由NE-8875-30MF和ST-8630按重量比1.5：(1-1.5)混合而成。NE-8875-30MF大日精化(上海)化工有限公司产品；ST-8630为合肥安利聚氨酯新材料公司产品；
聚醚聚碳型聚氨酯树脂NES-9015-22为大日精化(上海)化工有限公司产品；
抑制型催化剂HI-0199为大日精化(上海)化工有限公司产品。
采用沛特阻燃型再生皮基布，其由真皮粉及全棉机织布按重量比55-65：35-45组成；其厚度为1.3±0.1mm、克重700±20g/cm2。
实施例1
首先，将10g正丙基三甲氧基硅烷、3.8水、60g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于25℃恒温水浴锅中水解25min；将2kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为4:2:4)加入高速混合搅拌机中，转速设定为500r/min，烘干温度设定为110℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔5min，第一批为水解液质量的50％，第二批为水解液质量的30％，第三批为水解液质量的20％，加入完毕后，在1200r/min条件下高速搅拌20min，出料、冷却得改性填料。
将0.4份3238、0.2份LT-7110、0.1份1425、0.2份UV-5411、0.2份2030、1份FRA-9555、45份ST-8630与45份NE-8875-30MF一起溶于60份DMC中，再加入8份颜料色浆进行充分搅拌混合均匀后抽真空成浆料，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.05mm；
再将0.5份3238、0.2份LT-7110、0.3份1425、0.2份UV-5411、0.2份2030、1份SPB-100与90份NES-9015-22一起溶于50份DMC中，再加入10份颜料色浆进行充分搅拌混合均匀后抽真空成浆料，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.13mm；面层及中间层在110℃条件下鼓风干燥1min。
其次，将43份异氰酸酯Al-2010B加入储料罐中，再将105份多元醇Al-2010A、0.015份HI-1099、8份改性填料、2份8815-10、2份462和3份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边涂覆在成型的中间层上，涂刮厚度为0.25mm，制备粘接层。
然后，粘接层在85℃温度条件下烘1.2min，贴合沛特阻燃型再生皮基布，贴合层压为1.1mm，再进行高温熟化，在110℃的温度条件下，熟化7min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在105℃条件下，以20m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
实施例2
首先，将15g正丙基三甲氧基硅烷、5g水、70g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于25℃恒温水浴锅中水解20min；将2kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为4:2:4)加入高速混合搅拌机中，转速设定为700r/min，烘干温度设定为120℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔5min，第一批为水解液质量的40％，第二批为水解液质量的40％，第三批为水解液质量的20％，加入完毕后，在1200r/min条件下高速搅拌20min，出料、冷却改性填料。
将0.6份3238、0.3份LT-7110、0.2份1222、0.3份UV-2337、0.2份791、1.2份FRA-9555、50份ST-8630和70份NE-8875-30MF一起溶于65份DMC中，再加入10份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.06mm；
再将0.3份3238及1.0份PTFE、0.2份LT-7110、0.4份1081、0.2份UV-5411、0.2份2030、4份SPB-100、与120份NES-9015-22一起溶于60份DEF中，再加入10份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.15mm；面层及中间层在110℃条件下鼓风干燥1.5min。
其次，将46份异氰酸酯加入储料罐，再将110份多元醇，0.02份HI-1099，15份改性填料，5份阻燃剂，3.5份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边浇注在成型的面层及中间层浆料层上，涂刮厚度为0.3mm，制备粘接层。
然后，粘接层在90℃温度条件下烘1min，贴合沛特阻燃型再生皮基布，贴合层压为1.15mm，再进行高温熟化，在120℃的温度条件下，熟化6min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在110℃条件下，以22m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
实施例3
首先，将15g正丙基三甲氧基硅烷、5g水、60g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于28℃恒温水浴锅中水解15min；将1.5kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为6:2:2)加入高速混合搅拌机中，转速设定为600r/min，烘干温度设定为115℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔6min，第一批为水解液质量的50％，第二批为水解液质量的40％，第三批为水解液质量的10％，加入完毕后，在1400r/min条件下高速搅拌15min，出料、冷却改性填料。
将0.8份3238、0.3份LT-7110、0.4份1222、0.4份UV-1425、0.3份2040、1.5份FRA-9555、55份ST-8630和90份NE-8875-30MF一起溶于85份DMC中，再加入15份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.08mm；
再将0.5份3238及1.5份PTFE、0.3份LT-7110、0.5份1081、0.4份UV-5411、0.5份2030、6份SPB-100、与140份NES-9015-22一起溶于65份DEF中，再加入13份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.18mm；面层及中间层在115℃条件下鼓风干燥1min。
其次，将47.5份Al-2010B加入储料罐，再将115份Al-2010A，0.03份HI-1099，25份改性填料，10份阻燃剂，4份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边浇注在成型的面层及中间层浆料层上，涂刮厚度为0.4mm，制得粘接层。
然后，粘接层在95℃温度条件下烘1min，贴合沛特阻燃型再生皮基布，贴合层压为1.15mm，再进行高温熟化，在110℃的温度条件下，熟化7min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在120℃条件下，以25m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
实施例4
首先，将12g正丙基三甲氧基硅烷、4.5g水、55g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于30℃恒温水浴锅中水解18min；将1.5kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为6:1:3)加入高速混合搅拌机中，转速设定为650r/min，烘干温度设定为120℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔5.5min，第一批为水解液质量的30％，第二批为水解液质量的40％，第三批为水解液质量的30％，加入完毕后，在2000r/min条件下高速搅拌17min，出料、冷却改性填料。
将1份3238、0.4份LT-7110、0.2份1222、0.6份UV-1425、0.3份2040、1.8份FRA-9555、60份ST-8630和95份NE-8875-30MF一起溶于85份DMC中，再加入15份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.08mm；
再将1.0份3238及1.0份PTFE、0.5份LT-7110、0.4份1081、0.4份UV-5411、0.5份2030、6份SPB-100、与150份NES-9015-22一起溶于65份DEF中，再加入13份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.18mm；面层及中间层在115℃条件下鼓风干燥1min。
其次，将46.5份Al-2010B加入储料罐，再将115份Al-2010A，0.03份HI-1099，25份改性填料，10份阻燃剂，4份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边浇注在成型的面层及中间层浆料层上，涂刮厚度为0.4mm，制得粘接层。
然后，粘接层在95℃温度条件下烘1min，贴合沛特阻燃型再生皮基布，贴合层压为1.15mm，再进行高温熟化，在110℃的温度条件下，熟化7min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在120℃条件下，以25m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
对比例1
首先，将12g正丙基三甲氧基硅烷、4g水、50g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于30℃恒温水浴锅中水解30min；将1.3kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为6:1:3)加入高速混合搅拌机中，转速设定为750r/min，烘干温度设定为125℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔8min，第一批为水解液质量的45％，第二批为水解液质量的35％，第三批为水解液质量的20％，加入完毕后，在1800r/min条件下高速搅拌14min，出料、冷却改性填料。
将1份3238、0.4份LT-7110、0.2份1222、0.6份UV-1425、0.3份2040、1.5份FRA-9555、55份ST-8630和90份NE-8875-30MF一起溶于85份DMC中，再加入15份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.08mm；
再将1.0份3238及1.0份PTFE、0.5份LT-7110、0.4份1081、0.4份UV-5411、0.5份2030、6份SPB-100、与130份NES-9015-22一起溶于50份DEF中，再加入13份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.18mm；面层及中间层在115℃条件下鼓风干燥1min。
其次，将58份异氰酸酯BASF B料加入储料罐，再将100份多元醇BASF A料，0.03份93540，0.04份93600，15份改性填料，10份阻燃剂，4份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边浇注在成型的面层及中间层浆料层上，涂刮厚度为0.4mm，制得粘接层。
然后，粘接层在95℃温度条件下烘1min，贴合沛特阻燃型再生皮基布，贴合层压为1.15mm，再进行高温熟化，在110℃的温度条件下，熟化7min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在115℃条件下，以20m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
对比例2
首先，将15g正丙基三甲氧基硅烷、5g水、55g无水乙醇加入三口烧瓶中，将三口烧瓶密闭后置于30℃恒温水浴锅中水解25min；将1kg混合料(氢氧化铝、氮化硼和氧化锌的质量比为6:1:3)加入高速混合搅拌机中，转速设定为800r/min，烘干温度设定为115℃；将正丙基三甲氧基硅烷水解液分三批加入高速混合机中，每批间隔7min，第一批为水解液质量的35％，第二批为水解液质量的35％，第三批为水解液质量的30％，加入完毕后，在1600r/min条件下高速搅拌14min，出料、冷却改性填料。
将1份3238、0.4份LT-7110、0.2份1222、0.6份UV-1425、0.3份2040、1.6份FRA-9555、40份ST-8630和105份NE-8875-30MF一起溶于85份DMC中，再加入15份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在离型纸的正面作为面层，其面层浆料层的涂刮厚度为0.08mm；
再将1.0份3238及1.0份PTFE、0.5份LT-7110、0.4份1081、0.4份UV-5411、0.5份2030、6份SPB-100、与150份NES-9015-22一起溶于70份DEF中，再加入13份颜料色浆进行充分搅拌混合均匀后抽真空，再均匀涂刮在面层上制备中间层，中间层浆料层的涂刮厚度为0.18mm；面层及中间层在115℃条件下鼓风干燥1min。
其次，将52份异氰酸酯BASF B料加入储料罐，再将100份多元醇BASF A料，0.03份93540，0.04份93600，12份改性填料，5份阻燃剂，4份丙三醇三乙酸酯加入另一储料罐中，通过调节计量泵将搅拌均匀的A、B料按照设定比例输送至混合头处，边快速混合边浇注在成型的面层及中间层浆料层上，涂刮厚度为0.4mm，制得粘接层。
然后，粘接层在95℃温度条件下烘1min，贴合沛特阻燃型再生皮基布，贴合层压为1.1mm，再进行高温熟化，在110℃的温度条件下，熟化7min后剥离、分卷，制得聚氨酯合成革半成品。
最后，在聚氨酯合成革半成品的表面上，在110℃条件下，以20m/min的车速、300目的表处辊辊涂由水性防污表处剂SF-6110和改性聚碳化二亚胺XR-5580混合而成的防污层浆料，即可制得具有防污、耐用性好、手感柔软、亲肤感强及非常优越的阻燃性能的软质无溶剂阻燃型聚氨酯合成革。
本发明中改性填料是由干法改性工艺制备而成的，其活化度均大于97％，在粘接层A组分中具有防沉降作用。
对比例3
选择市场上的市售聚氨酯合成革产品，其采用聚酯、聚醚类聚氨酯树脂为面层或面层及中间层，BASF CC6945-100C系列、旭川化学XCS系列或华峰JF-NS系列为无溶剂粘接层，采用两刀或三刀干法工艺贴合涤、涤棉布基制备而成。
分别测试上述实施例1-6和对比例制备的聚氨酯合成革性能，如下表所示，其中柔软度是按HGT3053橡胶或塑料涂覆织物柔软性的测定20％扁环法进行检测的。
Figure BDA0001905007240000131
从上表可看，本发明实施例1-4制得的聚氨酯合成革具有防污(防污性能≥4级)、耐用性好、手感柔软(柔软度≥7.0mm)、亲肤感强、超强耐磨性能(满足威士博检测，马丁达尔检测))及非常优越的阻燃性能(满足英标BS5852:2006，5号火焰检测要求，美标FMVSS302)，且生产过程简单高效、绿色环保，能够满足市场需求。各项性能远优于对比例3市场上现有无溶剂聚氨酯合成革产品。
而对比例1-2的粘接层由于采用BASF A、B料体系，使得制成的合成革整体物性均低于本发明1-4实施例；其中对比例1根据BASF公司提供A、B配方比例，成革手感硬，塑胶感强，对比例2将BASF体系中R值调低，手感变软，但耐用性显著下降(3-4周无溶剂粘接层发粘，革面破损)。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。

Claims (8)

1.一种软质无溶剂阻燃型聚氨酯合成革，其从上到下依次包括防污层、面层、中间层、粘接层及基布；其特征在于：所述的粘接层是由A组分和异氰酸酯制备而成，所述异氰酸酯中-NCO与A组分中-OH的摩尔数比为0.85-0.93；
所述A组分是由以下原料按重量份数构成：
Figure FDA0003153045560000011
所述多元醇选择混合料Al-2010A，异氰酸酯为Al-2010B；
所述抑制型催化剂是环保型有机锆催化剂；
所述填料是指氢氧化铝、氮化硼和氧化锌混合料经干法改性后所得的改性填料；
所述改性填料的制备方法如下：
1)将10-15g硅烷偶联剂、3.5-5g水、50-80g无水乙醇加入容器中，然后将容器密闭后置于25-35℃恒温水浴锅中水解10-30min得水解液；
2)将氢氧化铝、氮化硼和氧化锌按质量比40-60：10-20：20-40混合成混合料，然后取1-2kg混合料加入高速混合搅拌机中，所述高速混合搅拌机转速为500-800r/min、烘干温度设定为110-125℃；
3)将步骤(1)制得的水解液分三批加入步骤(2)的高速混合搅拌机中，每批加入间隔时间为5-8min，第一批加入量为水解液质量的30-50％，第二批加入量为水解液质量的20-40％，第三批为余量；
4)加入完毕后，在1200-2000r/min条件下高速搅拌10-20min，出料、冷却即得改性填料；
所述面层是由以下组分按重量份制备而成：
Figure FDA0003153045560000012
Figure FDA0003153045560000021
所述中间层是由以下组分按重量份制备而成：
Figure FDA0003153045560000022
2.如权利要求1所述的一种软质无溶剂阻燃型聚氨酯合成革，其特征在于：所述的阻燃剂为固乐科公司的GRPHOS 8815-10、GRPHOS 8815-57以及科莱恩公司的EXOLIT AP 462、EXOLIT RP-6520中的至少两种；
所述粘度调整剂为丙三醇三乙酸酯。
3.如权利要求1所述的一种软质无溶剂阻燃型聚氨酯合成革，其特征在于：所述防污层由以下组分按重量份制备而成：
水性防污表处剂 100份
耐水解助剂 0.5-2份。
4.如权利要求3所述的一种软质无溶剂阻燃型聚氨酯合成革，其特征在于：所述水性防污表处剂为脂肪族水性聚氨酯，所述耐水解助剂为改性聚碳化二亚胺；
所述聚碳型聚氨酯树脂是由NE-8875-30MF和ST-8630按重量比1.5：(1-1.5)混合而成；
所述液体阻燃剂为无卤磷酸酯阻燃剂。
5.如权利要求1所述的一种软质无溶剂阻燃型聚氨酯合成革，其特征在于：所述聚醚聚碳型聚氨酯树脂为NES-9015-22；所述的可溶性阻燃剂为磷腈阻燃剂。
6.如权利要求1所述的一种软质无溶剂阻燃型聚氨酯合成革，其特征在于：所述基布为沛特阻燃型再生皮基布，其由真皮粉及全棉机织布按重量比55-65：35-45组成；其厚度为1.3±0.1mm、克重700±20g/cm2。
7.如权利要求1-6任一项所述的一种软质无溶剂阻燃型聚氨酯合成革的制备方法，其特征在于：包括如下步骤：
(1)将面层浆料充分搅拌混合均匀后抽至真空，再均匀涂刮在离型纸的正面作为面层；再将中间层浆料进行充分搅拌混合均匀后抽真空后，将其均匀地涂刮在面层上制得中间层；
(2)将A组分和异氰酸酯搅拌混合成粘接层浆料，边混合边涂覆在中间层上，加热烘干，得到粘接层；
(3)在粘接层上贴合基布，烘干、熟化、剥离分卷，得到聚氨酯合成革半成品；
(4)将防污层浆料通过表处辊辊涂在步骤(3)中制得的合成革半成品的革面上，烘干即得合成革成品。
8.如权利要求7所述的制备方法，其特征在于：
所述步骤(1)中面层浆料的涂覆厚度为0.05-0.08mm，中间层浆料的涂刮厚度为0.12-0.18mm，面层及中间层在110-115℃条件下鼓风干燥1-1.5min；
所述步骤(2)中粘接层浆料混合搅拌速度为3000-3500r/min，加热烘干温度为80-95℃，粘接层涂覆厚度为0.25-0.4mm；
所述步骤(3)中烘干温度为110-130℃，熟化时间为5-7min，贴合基布时的层压间隙为基布厚度的78-85％；
所述步骤(4)中烘干温度为140-150℃，所述表处辊为300目，车速为20-25m/min。
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