CN106903910B - 聚氨酯拉挤成型复合材料的涂装方法 - Google Patents

聚氨酯拉挤成型复合材料的涂装方法 Download PDF

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CN106903910B
CN106903910B CN201511007485.8A CN201511007485A CN106903910B CN 106903910 B CN106903910 B CN 106903910B CN 201511007485 A CN201511007485 A CN 201511007485A CN 106903910 B CN106903910 B CN 106903910B
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CN106903910A (zh
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唐军贞
陈湛
李志江
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Covestro Deutschland AG
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Priority to EP16825376.3A priority patent/EP3393766B1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/521Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/30Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B29C69/02Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/54Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08Glass

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  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Moulding By Coating Moulds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

本发明涉及一种聚氨酯拉挤成型复合材料的涂装方法,所述方法包括:a)通过聚氨酯拉挤成型工艺制备聚氨酯拉挤成型复合材料,所述聚氨酯拉挤成型工艺包括步骤:以聚氨酯树脂浸润纤维增强材料,再将浸润的纤维增强材料在模具中固化成型以提供聚氨酯拉挤成型复合材料;和b)牵引所述聚氨酯拉挤成型复合材料使其离开模具,然后在聚氨酯拉挤成型复合材料上温度为30‑90℃的部分在线施用水性涂料。本发明的方法可以实现对聚氨酯拉挤型材良好的涂装。

Description

聚氨酯拉挤成型复合材料的涂装方法
技术领域
本发明涉及一种聚氨酯拉挤成型复合材料的涂装方法,其通过聚氨酯拉挤成型复合材料上选择合适的部位施用涂料,特别是水性聚氨酯涂料。本发明的方法可以提供具有良好涂装的聚氨酯拉挤成型复合材料。
背景技术
聚氨酯拉挤成型复合材料拉伸强度高、耐腐蚀,故在具有腐蚀性的环境中是取代钢材的最佳产品,广泛应用于交通运输、电工、电气、电气绝缘、化工、矿山、海洋、船艇、腐蚀性环境及生活、民用各个领域。聚氨酯拉挤成型复合材料存在耐候性不足的问题,尤其在长期户外曝晒中,其表面的树脂层容易粉化、变色,甚至纤维曝露,影响聚氨酯拉挤复合材料的外观和性能。
因此聚氨酯拉挤成型复合材料通常都需要涂装,现有的涂装方法是在型材成型完成后,通过离线喷涂生产线工艺对聚氨酯拉挤复合材料进行涂装防护,现有的离线喷涂工艺上漆率低,涂装工序多,费时费工,造成涂装成本居高不下。加之目前适用的涂料多为溶剂型产品,带来了新的环保问题。因此本领域技术人员一直期望开发一种在线并且环保的涂装工艺。
美国专利US5492583A公开了一种拉挤成型复合材料在线涂装方法和装置,该方法在拉挤模具后添加了涂装模具对拉挤型材进行在线涂装,经过烘干装置进行涂层固化。该所述模具内含冷却装置先对型材进行表面冷却,再进行涂装,然后通过烘箱固化。由于聚氨酯拉挤型材在高温下固化将影响其尺寸稳定性,因此该方法不适用于聚氨酯拉挤型材。
因此本领域中仍需要一种聚氨酯拉挤型材的在线涂装工艺。
发明概述
本发明提供了一种聚氨酯拉挤成型复合材料的涂装方法,所述方法 包括:
a)通过聚氨酯拉挤成型工艺制备聚氨酯拉挤成型复合材料,所述聚氨酯拉挤成型工艺包括步骤:以聚氨酯树脂浸润纤维增强材料,再将浸润的纤维增强材料在模具中固化成型以提供聚氨酯拉挤成型复合材料;和
b)牵引所述聚氨酯拉挤成型复合材料使其离开模具,然后在聚氨酯拉挤成型复合材料上温度为30-90℃的部分在线施用水性涂料。
在本发明一个实施例中,所述水性涂料选自水性聚氨酯涂料、水性氟烯烃-乙烯基醚涂料和聚偏氟乙烯涂料。优选地,所述水性涂料选自水性双组分聚氨酯涂料。更优选地,所述水性双组分聚氨酯涂料的在常温下表干时间为30秒-30分钟,在50℃下的表干时间为30秒-10分钟。
在本发明另一个实施例中,其中所述水性涂料选择单组份聚氨酯涂料。优选地,所述水性单组份聚氨酯涂料的在常温下的表干时间为30秒-10分钟,在50℃下的表干时间为30-5分钟。
在本发明另一个实施例中,所述纤维增强材料选自:玻璃纤维、碳纤维、聚酯纤维、天然纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合。
在本发明又一个实施例中,其中所述聚氨酯拉挤成型复合材料选自:聚氨酯拉挤管箱、桥架、防眩板、门窗型材、太阳能板边框、鱼尾板、枕木和货架。
具体实施方式
本发明提供了一种聚氨酯拉挤成型复合材料的涂装方法,所述方法通过在拉挤型材离开模具后,选择合适的部位直接于其上在线施用水性涂料,涂料由于余热自然固化或者适当加热固化,从而完成对拉挤型材的涂装。本发明提供的方法操作简单,无需底涂可直接施用于拉挤型材上,并且涂层对拉挤型材具有良好的附着力。
本发明的方法包括步骤:
a)通过聚氨酯拉挤成型工艺制备聚氨酯拉挤成型复合材料,所述 聚氨酯拉挤成型工艺包括步骤:以聚氨酯树脂浸润纤维增强材料,再将浸润的纤维增强材料在模具中固化成型以提供聚氨酯拉挤成型复合材料;和
b)牵引所述聚氨酯拉挤成型复合材料使其离开模具,然后在聚氨酯拉挤成型复合材料上温度为30-90℃的部分在线施用水性涂料。
在步骤a)中所称的聚氨酯拉挤成型工艺和聚氨酯拉挤成型复合材料具有本领域中所公知的含义。美国专利US 3960629和US4935279公开了聚氨酯拉挤成型工艺,将这两篇专利的全部内容以引用的方式合并入本文。在聚氨酯拉挤成型工艺中,通常将玻璃纤维从纱架上引出,穿过导纱板,进入注胶盒,穿过模腔。将穿过模腔的玻璃纤维纱用牵引装置牵引拉顺;开启模具加温系统及模口冷却系统。启动注胶机,将树脂泵送至注胶盒,使纤维纱充分浸透。被注胶盒树脂浸透的纤维纱经牵引装置连续地拉过模具,经过加热的模具时,树脂纤维逐步固化后被继续地拉出模具,形成连续的聚氨酯拉挤成型复合材料,这些材料经切割后可获得的聚氨酯拉挤成型复合材料。
可用于本发明的纤维增强材料选自:玻璃纤维、碳纳米管、碳纤维、聚酯纤维、天然纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合。在本发明一些优选的实施例中,所述增强材料选自玻璃纤维,所述增强材料的含量为60-85wt.%,基于所述聚氨酯拉挤成型复合材料的总重量按100wt.%计。
在所述步骤b)中,从步骤a)获得的聚氨酯拉挤成型复合材料被继续地拉出模具,并沿着牵引方向继续前进。在聚氨酯拉挤工艺中,模具的温度通常设置为3个区,其中1区温度60-140℃,2区温度160-190℃,3区温度150-190℃,而连续的型材在被拉出模具时温度为80-150℃,在沿着牵引方向继续前进的过程中,其可以自然降温,也可通过吹风等方式使其加速降温。
在所述连续的聚氨酯拉挤成型复合材料上选取温度为30-90℃的部分,在该部分处在线施用水性涂料,水性涂料在此余热下快速固化从而对型材实施了涂装。在本发明一些实施例中,在所述连续的聚氨酯拉挤 成型复合材料上选取温度为40-80℃的部分施用水性涂料。所述水性涂料可以采用本领域中常用的方式施用于聚氨酯拉挤成型复合材料上,例如旋涂法、刀涂法、微凹版涂布法、直接凹版涂布法、胶印凹版法、反转凹版法、逆转辊涂布法、棒涂法、模具涂布法、喷涂法或浸涂法。
可用于本发明的水性涂料可以选自氟烯烃-乙烯基醚(FEVE)涂料、聚偏氟乙烯(PVDF)涂料和聚氨酯涂料。在本发明优选的实施例中,可用于本发明的水性涂料选自聚氨酯涂料,这些水性涂料用于本发明时,无需底涂,就与型材具有良好的附着力。水性涂料施用之后,可以常温固化从而实现涂装,也可以在升高的温度下使涂料固化。
可用于本发明聚氨酯水性涂料可以是双组分涂料,其固含量为10%-70%,优选20%-60%;其中A组分与B组分混合之后的粘度范围DIN4杯10秒-10分钟,优选DIN4杯10秒-3分钟;常温表干时间1-30分钟,50℃时,30秒-10分钟即可表干。
可用于本发明聚氨酯水性涂料可以是单组份水性聚氨酯涂料,其固含量30%-60%,优选35%-55%,其常温下粘度5-500mpa.s,优选20-200mpa.s,常温表干30秒-10分钟,50℃时,30秒-5分钟即可表干。
聚氨酯拉挤成型复合材料经涂装后被牵引至切割装置,被切割成所需的长度从而制备期望的涂装的聚氨酯拉挤成型复合材料。
在本发明实施例中,所述聚氨酯拉挤成型复合材料选自:聚氨酯拉挤管箱、桥架、防眩板、门窗型材、太阳能板边框、鱼尾板、枕木和货架。
实施例
将262根玻璃纤维纱CPIC469P-2400Tex以及上下各1片300g/m2玻璃纤维针织毡EMC 300g/m2从纱架上引出,穿过三级导纱板,进入注 胶盒,穿过模腔。将穿过模腔的玻璃纤维纱用牵引绳绑牢再开启履带牵 引装置向前牵引至纱全部拉顺;开启模具加温系统加热模具同时开启模 口冷却系统,模温从入口到出口控制为:20℃/60℃/190℃/170℃。启动注胶机,将聚氨酯树脂连续泵送至静态混合头,经混合头混合后将注胶 盒注满同时使纤维纱被充分浸透。被注胶盒浸透的纤维纱被履带牵引装 置连续地拉过模具,经加热的模具固化后成为平板被连续地拉出模具。
在离出模口1.1m到1.2m时,型材温度在80-90℃左右,选用滚筒涂刷涂料,测试7天后涂料附着力。其中环境温度13℃,湿度56RH%,生产线牵引速度0.65m/min。涂料选自水性双组分聚氨酯涂料,其中A组份为Bayhydrol XP 2546和2542,B组份为Bayhydrur XP2547。另一种涂料为FC-W200,双组分氟碳涂料,可购自上海衡峰氟碳材料有限公司。
将获得的制品根据GBT9286-1998测试涂料粘附力,以百格法测试 涂层与复合材料的粘附力,其中0-5的数值代表意义如表1所示。在该 方法中,以百格刀在样板上形成10*10的100格的正方形,然后将透明 力敏胶带粘附于正方形上,再以瞬间的力道将胶带撕起,记录脱落的面 积并按照表1所示标准给予等级。
对双组分水性聚氨酯涂料的附着力测试结果为0,对氟碳涂料的附着力测试结果为5。由此可见使用本发明的方法可以对聚氨酯拉挤型材实现良好的涂装,特别是使用了水性聚氨酯涂料时,涂装更为良好。
表1:百格法测试结果意义
Figure BSA0000125287890000051

Claims (3)

1.一种聚氨酯拉挤成型复合材料的涂装方法,所述方法包括:
a)通过聚氨酯拉挤成型工艺制备聚氨酯拉挤成型复合材料,所述聚氨酯拉挤成型工艺包括步骤:以聚氨酯树脂浸润纤维增强材料,再将浸润的纤维增强材料在模具中固化成型以提供聚氨酯拉挤成型复合材料;和
b)牵引所述聚氨酯拉挤成型复合材料使其离开模具,然后在聚氨酯拉挤成型复合材料上温度为30-90℃的部分在线施用水性涂料;
其中,所述水性涂料选自水性聚氨酯涂料、水性氟烯烃-乙烯基醚涂料和聚偏氟乙烯涂料;
所述水性聚氨酯涂料选自水性双组分聚氨酯涂料或水性单组分聚氨酯涂料,所述水性双组分聚氨酯涂料的在常温下表干时间为30秒-30分钟,在50℃下的表干时间为30秒-10分钟;和所述水性单组份聚氨酯涂料的在常温下的表干时间为30秒-10分钟,在50℃下的表干时间为30-5分钟。
2.根据权利要求1所述的涂装方法,其中所述纤维增强材料选自:玻璃纤维、碳纤维、聚酯纤维、天然纤维、芳香族聚酰胺纤维、尼龙纤维、玄武岩纤维、硼纤维、碳化硅纤维、石棉纤维、晶须、硬质颗粒、金属纤维或其组合。
3.根据权利要求1所述的涂装方法,其中所述聚氨酯拉挤成型复合材料选自:聚氨酯拉挤管箱、桥架、防眩板、门窗型材、太阳能板边框、鱼尾板、枕木和货架。
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