CN104136137B - 具有包含至少两种不同聚酯的非水涂料制成的填料层的多层涂层 - Google Patents

具有包含至少两种不同聚酯的非水涂料制成的填料层的多层涂层 Download PDF

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Publication number
CN104136137B
CN104136137B CN201380010265.3A CN201380010265A CN104136137B CN 104136137 B CN104136137 B CN 104136137B CN 201380010265 A CN201380010265 A CN 201380010265A CN 104136137 B CN104136137 B CN 104136137B
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coating
polyester
weight
laminated
matrix
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CN104136137A (zh
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H·沃尼曼
M·奥博霍夫
M·里平
B·波得拉斯基-皮兹克
C·莫尔西洛鲁伊斯
M·哈通
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract

如下制备多层涂层的方法：i)将头二道混合底漆涂层(I)施涂于任选经预处理的基质上，ii)将头二道混合底漆涂层(II)固化，iii)将底涂层(II)施涂于固化的头二道混合底漆涂层(I)，iv)任选将底涂层(II)固化，v)将透明涂层(III)施涂于固化或未固化的底涂层(II)上，和vi)将透明涂层(III)或者如果底涂层在步骤iv)中未固化的话底涂层和透明涂层固化，其中头二道混合底漆涂层(I)通过施涂包含如下组分的非水溶剂基涂料(F)而得到：基于总涂料(F)为至少20重量％的至少一种有机溶剂，以及基于总涂料(F)为至少8重量％的至少一种第一聚酯(A1)，所述第一聚酯具有至少20℃的玻璃化转变温度和0-40mg？KOH/g的酸值；基于总涂料(F)为至少8重量％的至少一种不同于(A1)且玻璃化转变温度为不大于10℃的第二聚酯(A2)；至少一种交联剂(B)，和基于总涂料(F)为至少8重量％的一种或多种填料和/或颜料(C)。可通过该方法得到的多层涂层和涂有该涂层的基质。

Description

具有包含至少两种不同聚酯的非水涂料制成的填料层的多层涂层
发明领域
本发明涉及具有由基于聚酯的非水溶剂基涂料制成的头二道混合底漆涂层的多层涂层。本发明还涉及制备多层涂层的方法，和涂有该多层涂层的基质，更特别是汽车车体。
现有技术
已知基于聚酯的非水溶剂基(即“常规”)涂料用于生产涂饰层(涂层)。在汽车OEM涂饰以及在汽车修补中，通常使用可由例如电涂层、头二道混合底漆涂层、底涂层和透明涂层组成的多层涂层。多层涂层服从例如关于耐碎石性和对有害物质如鸟粪的抗性的确切要求。特别是头二道混合底漆涂层以及特征是良好喷砂打磨性、基质的有效精加工(良好的填充能力)和在基质和下层油漆涂层上的有效附着力，还必须贡献于非常好的耐碎石性和高耐鸟粪性。
作为多层涂层的一部分，已知类型的现有常规头二道混合底漆配制剂，例如来自“AutomotivePaintsandCoatings”(“PrimerSurfacer”；StreitbergerandWiley-VCH2008)的，满足大多数机动车厂商的常规碎石保护规格，但不同时满足耐鸟粪性方面的要求。来自鸟粪的侵蚀性物质能够通过上部油漆涂层透入头二道混合底漆涂层中，且用现有常规头二道混合底漆配制剂，通常导致头二道混合底漆涂层与底涂层之间的分层，以及因此油漆的剥落。
问题
因此，本发明解决的问题是提供包含头二道混合底漆涂层、底涂层和透明涂层的多层涂层，所述多层涂层显示出非常好的耐碎石性以及同时高耐鸟粪性。多层涂层更特别地适于汽车OEM涂饰。另外，得到头二道混合底漆涂层的涂料具有足够的贮藏寿命。
技术方案
该问题令人惊讶地通过多涂层油漆体系解决，所述多涂层油漆体系可通过包括如下步骤的生产方法得到：
i)将头二道混合底漆涂层(I)施涂于任选经预处理的基质上，
ii)将头二道混合底漆涂层(II)固化，
iii)将底涂层(II)施涂于固化的头二道混合底漆涂层(I)，
iv)任选将底涂层(II)固化，
v)将透明涂层(III)施涂于固化或未固化的底涂层(II)上，和
vi)将透明涂层(III)固化或者如果底涂层在步骤iv)中未固化的话将底涂层和透明涂层固化，
其中头二道混合底漆涂层(I)通过施涂包含如下组分的非水溶剂基涂料(F)而得到：
基于总涂料(F)为至少20重量％的至少一种有机溶剂，以及
A1)基于总涂料(F)为至少8重量％的至少一种第一聚酯(A1)，所述第一聚酯具有至少20℃的玻璃化转变温度和0-40mgKOH/g的酸值，
A2)基于总涂料(F)为至少8重量％的至少一种不同于(A1)且玻璃化转变温度为不大于10℃的第二聚酯(A2)，
B)至少一种交联剂(B)，和
C)基于总涂料(F)为至少8重量％的一种或多种填料和/或颜料(C)。
所得多层涂层更特别地适于汽车OEM涂饰。特别惊讶的是所得多层涂层同时具有非常好的耐碎石性和高耐鸟粪性。此外，涂料(F)的贮藏寿命是足够的。
因此，本发明提供用于制备多层涂层的上述方法，因此可得到的多层涂层以及涂有这些多层涂层的基质。
多层涂层
多层涂层包含至少一层头二道混合底漆涂层(I)、底涂层(II)和透明涂层(III)。
头二道混合底漆涂层(I)通过施涂稍后在下文中更详细地描述的非水溶剂基涂料(F)得到。
底涂层(II)通过施涂常规且已知的底涂料得到。底涂料为通常包含一种或多种基料、交联剂和颜料的有色涂料。合适的底涂料为汽车涂饰中常用的有色底涂料。不仅可使用水基底涂料，而且可使用常规溶剂基底涂料。底涂层(II)优选通过施涂水基底涂料得到。
透明涂层(III)通过施涂常规且已知的透明涂料而得到。透明涂料为产生透明涂层且通常不包含任何颜料或填料，至多仅包含染料或非常细碎的透明颜料的涂料。可使用溶剂基和水性透明涂料。可使用单组分和多组分透明涂料。
底涂层(II)和透明涂层(III)可根据常规且已知的技术，更特别是通过喷雾或喷射施涂。施涂优选以常用于汽车OEM涂饰的层厚度，例如干膜厚度10-80μm，更特别是20-70μm进行。
底涂层(II)和透明涂层(III)可分别或联合地固化。固化在技术方面不具有特性，而是可根据常规且已知的方法进行。例如，固化可热或者用光化辐射，或者热和光化辐射进行。如果底涂层(II)和透明涂层(III)联合地固化，则底涂层(II)可在施涂透明涂层(III)以前通过常规方法闪蒸，而不将底涂层(II)完全固化。
涂料(F)和头二道混合底漆涂层(I)
头二道混合底漆涂层(I)通过将非水溶剂基涂料(F)施涂于任选经预处理的基质上而得到。
非水涂料为包含基于总涂料为不大于1重量％的水的涂料。
涂料(F)为溶剂基的。这意指它包含每种情况下基于总涂料为至少20重量％，优选至少30重量％的至少一种有机溶剂。在本发明另一实施方案中，还可存在基于总涂料为至少40重量％的有机溶剂。合适的有机溶剂为已知且用于涂料中的常规有机溶剂。非常合适的有机溶剂的实例包括正丁醇和异丁醇、丁基二甘醇乙酸酯、乙酸正丁酯、溶剂石脑油和二甲苯。也可例如使用其它芳族烃、异丙基苯、乙苯、均三甲基苯、正丙基苯、1,2,4-三甲基苯、环己烷、甲醇、2-丁氧基乙醇、蒸馏碳酸亚丙酯、丁基乙二醇乙酸酯、甲苯磺酰氯、甲醛和/或萘作为有机溶剂。
涂料(F)的固体优选为58-68％，更优选60-66％。就喷涂而言，则将涂料(F)用合适的溶剂优选调整至5-16％，更优选8-12％。固体可通过用合适的有机溶剂稀释进行调整。涂料的固体作为在105℃下加热180分钟以后1g试样的非挥发物含量(％)测定。
涂料(F)的玻璃化转变温度通过DSC(差示扫描量热法)测量优选为至少35℃，更优选至少40℃。玻璃化转变温度通过DSC在初始湿膜厚度为50μm并在130℃下干燥60分钟的试样上测量。首先使干膜冷却至室温。然后将膜在DSC装置中冷却至-80℃，从该水平加热至+80℃，再次冷却至-80℃，最后再次加热至+80℃。加热和冷却速率每种情况下为10℃/分钟。评估第二加热程的中点，从此处可读出玻璃化转变温度Tg。
在涂料(F)的玻璃化转变温度相应地高时特别有效地满足耐鸟粪性方面的要求。
涂料(F)具有0.5-1.2，更优选0.7-0.9的填料和/或颜料(C):基料(A1、A2、B)重量比。它使用所用A1、A2、B和C的固体质量计算。A1、A2、B和C的固体每种情况下作为非挥发物含量确定并通过随着加入2ml二甲苯将在强制通风烘箱中在130℃下加热60分钟的盖上的约2g试样干燥而测量。
涂料(F)优选具有0.7-1.2，更优选0.9-1.1的聚酯(A1):聚酯(A2)重量比。它使用所用A1和A2的固体质量计算。A1和A2的固体每种情况下作为非挥发物含量测定并通过随着加入2ml二甲苯将在强制通风烘箱中在130℃下加热60分钟的盖上的约2g试样干燥而测量。
聚酯(A1)(具有高玻璃化转变温度)
涂料(F)包含基于总涂料为至少8重量％的至少一种具有通过DSC测量为至少20℃的玻璃化转变温度的第一聚酯(A1)。合适的聚酯(A1)可例如由二醇和/或多元醇与二羧酸和/或多羧酸反应而得到。也可使用一种或多种二醇和/或多元醇和一种或多种二羧酸和/或多羧酸的混合物。代替二羧酸和/或多羧酸，也可使用它们的酐或它们与挥发性醇的酯(更特别是对苯二甲酸二甲酯)。另外，也可使用单羧酸和/或单醇的部分。
合适的二醇例如为具有2-22个碳原子和伯和/或仲羟基的线性、环状和/或支化链烷二醇，例如乙二醇、1,2-丙二醇(丙二醇)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、1-甲基-2,3-丙二醇、新戊二醇、1,6-己二醇、1,4-环己烷二甲醇(任选为与它的1,3异构体的混合物)、三环癸烷二甲醇(TCDAlcoholDM)，以及其它线性、环状和/或支化链烷二醇；二羟基官能醚，例如二甘醇、三甘醇、其它聚乙二醇、二丙二醇、三丙二醇、其它聚丙二醇，或者具有芳族结构单元的混合聚亚乙基-聚亚丙基二醇，例如双酚A或双酚F；二羟基官能酯，例如羟基新戊酸的新戊二醇酯；以及支化单羧酸如Versatic酸的缩水甘油酯。
这些中，优选的二醇是具有优选3-14个碳原子的环状和支化二醇。特别优选的二醇为羟基新戊酸的新戊二醇酯和新戊二醇。
合适的多元醇为例如三元醇，例如三羟甲基丙烷、三羟甲基乙烷或甘油，以及更高氢-电(Hydricity)的醇，例如季戊四醇。
合适的二羧酸为例如具有3-22个碳原子的饱和或不饱和、线性或支化、脂环族或脂族二羧酸，以及芳族二羧酸，例如己二酸、癸二酸、链烯基琥珀酸如四丙烯基琥珀酸、十二碳烯基琥珀酸、邻苯二甲酸、间苯二甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸或对苯二甲酸。也可使用相应的酐，换言之，例如邻苯二甲酸酐、四丙烯基琥珀酸酐、十二碳烯基琥珀酸酐、四氢邻苯二甲酸酐或六氢邻苯二甲酸酐。
优选仅使用小部分的，优选基于用于制备聚酯(A1)的总二羧酸和/或多羧酸为0％-5重量％的线性脂族二羧酸。特别优选不使用任何线性脂族二羧酸制备聚酯(A1)。
优选的二羧酸及其酐为脂环族和芳族二羧酸，例如邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、四氢邻苯二甲酸、四氢邻苯二甲酸酐或对苯二甲酸。特别优选的二羧酸及其酐为邻苯二甲酸酐、间苯二甲酸和四氢邻苯二甲酸酐。
合适的多羧酸为例如偏苯三酸和其它多羧酸。也可使用相应的酐，换言之，例如偏苯三酸酐。优选的多羧酸及其酐为偏苯三酸和偏苯三酸酐。
二醇和/或多元醇与二羧酸和/或多羧酸反应制备聚酯(A1)可在一个阶段或者在两个或更多阶段中进行。特别优选的聚酯(A1)由羟基新戊酸的新戊二醇酯、新戊二醇、间苯二甲酸和四氢邻苯二甲酸酐的反应，以及产物与偏苯三酸酐和邻苯二甲酸酐的随后反应而得到。
聚酯(A1)包含能够进入与交联剂分子(B)的交联反应的官能团。这些基团更特别地包括异氰酸酯反应性基团，以及对氨基树脂呈反应性的基团。合适的官能团为例如羟基、环氧基、羧基、氨基和脲基团。聚酯(A1)的优选官能团为羟基。
聚酯(A1)优选具有每种情况下基于相应聚酯(A1)的固体(非挥发性部分)为50-150mgKOH/g，更优选80-120mgKOH/g的羟值，其在130℃下干燥60分钟以后测定。
聚酯(A1)具有每种情况下基于相应聚酯(A1)的固体(非挥发性部分)为0-40mgKOH/g，优选5-30mgKOH/g，更优选0-25mgKOH/g的酸值，其在130℃下干燥60分钟以后测定。如果所用聚酯(A1)的酸值太高，则不再确保涂料足够的贮藏寿命。在本发明上下文中，酸值根据DINENISO3682测定。
第一聚酯(A1)的数均分子量(Mn)优选为1000-10000g/mol，更优选1000-5000g/mol。
第一聚酯(A1)的重均分子量(Mw)优选为1000-50000g/mol，更优选2500-15000g/mol。
第一聚酯(A1)的多分散性(Mw/Mn)优选为5或以下，更优选3.5或以下。
数均和重均分子量通过凝胶渗透色谱法根据关于THF可溶性聚合物的DIN55672-1(2007-08版)使用四氢呋喃(+0.1％乙酸)作为洗脱剂在苯乙烯-二乙烯基苯柱组合(WatersHR4、HR3、HR2)上测定。校准通过聚苯乙烯标准进行。
第一聚酯(A1)的玻璃化转变温度通过DSC测量为至少20℃，优选至少25℃。
涂料(F)包含基于总涂料(F)优选为至少9重量％，更特别是至少10重量％的至少一种聚酯(A1)。聚酯(A1)的最大重量含量最后受存在于涂料中的其它组分的量限制。聚酯(A1)的重量含量例如为30重量％以下，更特别优选为20重量％以下。
特别优选涂料(F)包含基于总涂料(F)为至少9重量％，更特别是至少10重量％的至少一种具有通过DSC测量为至少20℃，非常优选至少25℃的玻璃化转变温度的聚酯(A1)。
聚酯(A2)(具有较低玻璃化转变温度)
涂料(F)进一步包含基于总涂料(F)为至少8重量％的至少一种第二聚酯(A2)，所述第二聚酯不同于聚酯(A1)且具有通过DSC测量为不大于10℃的玻璃化转变温度。合适的聚酯(A2)可例如由二醇和/或多元醇与二羧酸和/或多羧酸的反应得到。也可使用一种或多种二醇和/或多元醇和一种或多种二羧酸和/或多羧酸的混合物。另外，也可使用单羧酸和/或单醇的部分。
合适的二醇例如为具有优选2-14个碳原子和伯和/或仲羟基的线性、环状和/或支化链烷二醇，例如乙二醇、1,2-丙二醇(丙二醇)、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-环己烷二甲醇(任选为与它的其它异构体的混合物)，以及其它线性、环状和/或支化链烷二醇；二羟基官能醚，例如二甘醇、三甘醇、其它聚乙二醇、二丙二醇、三丙二醇、其它聚丙二醇，或者具有芳族结构单元的混合聚亚乙基-聚亚丙基二醇，例如双酚A或双酚F；二羟基官能酯，例如羟基新戊酸的新戊二醇酯；以及“二聚二醇”，其通过二聚脂肪酸的还原而制备(例如来自Uniqema的2033)。
这些中，优选的二醇是具有4-8个碳原子的线性、环状和/或支化链烷二醇，例如新戊二醇或1,4-环己烷二醇，以及具有芳族结构单元的聚二醇，例如乙氧基化双酚A衍生物(例如BP40/240，4摩尔氧化乙烯与双酚A的加合物)。
特别优选的二醇为新戊二醇和乙氧基化双酚A衍生物。
合适的多元醇为例如三醇，例如三羟甲基丙烷、三羟甲基乙烷或甘油，以及更高氢-电(Hydricity)的醇，例如季戊四醇。优选的多元醇为三羟甲基丙烷。
合适的二羧酸为例如具有3-22个碳原子的饱和或不饱和、线性或支化、脂环族或脂族二羧酸，以及芳族二羧酸，例如己二酸、癸二酸、邻苯二甲酸、间苯二甲酸、四氢邻苯二甲酸或对苯二甲酸；以及植物基或动物基二聚脂肪酸，这可通过不饱和键的氢化改性和/或可通过蒸馏提纯改性，例如1010、1012或1022。也可使用相应的酐，换言之，例如邻苯二甲酸酐、间苯二甲酸酐或四氢邻苯二甲酸酐。优选的二羧酸及其酐为脂环族和芳族二羧酸，例如邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、间苯二甲酸酐、四氢邻苯二甲酸、四氢邻苯二甲酸酐、对苯二甲酸或对苯二甲酸酐。特别优选的二羧酸及其酐为邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、间苯二甲酸酐、四氢邻苯二甲酸和四氢邻苯二甲酸酐。
合适的多羧酸为例如偏苯三酸。也可使用相应的酐，换言之，例如偏苯三酸酐。
二醇和/或多元醇与二羧酸和/或多羧酸反应制备聚酯(A2)可在一个阶段或者在两个或更多阶段中进行。特别优选的聚酯(A2)由乙氧基化双酚A衍生物(例如可以以商品名BP40E由BASFSE得到)、新戊二醇和三羟甲基丙烷与己二酸和偏苯三酸酐反应而得到。聚酯(A2)还可在随后的步骤中通过与内酯，更特别是己内酯的加成反应而改性。这通常导致聚酯降低的玻璃化转变温度(Tg)。
聚酯(A2)包含能够进入与交联剂分子(B)的交联反应的官能团。这些基团更特别地包括异氰酸酯反应性基团，以及对氨基树脂呈反应性的基团。合适的官能团为例如羟基、环氧基、羧基、氨基或脲基团。聚酯(A2)的优选官能团为羟基。
聚酯(A2)优选具有每种情况下基于相应聚酯(A2)的固体(非挥发性部分)为60-130mgKOH/g，更优选70-110mgKOH/g，非常优选80-100mgKOH/g的羟基，其在130℃下干燥60分钟以后测定。
聚酯(A2)优选具有每种情况下基于相应聚酯(A2)的固体(非挥发性部分)为5-50mgKOH/g，非常优选5-20mgKOH/g的酸值，其在130℃下干燥60分钟以后测定。如果所用聚酯(A2)的酸值太高，则不再确保涂料足够的贮藏寿命。
第二聚酯(A2)的数均分子量(Mn)优选为1000-10000g/mol，更优选1000-5000g/mol。
第二聚酯(A2)的重均分子量(Mw)优选为5000-80000g/mol，更优选10000-60000g/mol。
第二聚酯(A2)的多分散性(Mw/Mn)优选为5或以上，更优选8或以上。
数均和重均分子量通过凝胶渗透色谱法根据关于THF可溶性聚合物的DIN55672-1(2007-08版)使用四氢呋喃(+0.1％乙酸)作为洗脱剂在苯乙烯-二乙烯基苯柱组合(WatersHR4、HR3、HR2)上测定。校准通过聚苯乙烯标准进行。
涂料(F)包含基于总涂料优选为至少9重量％的至少一种聚酯(A2)。聚酯(A2)的最大重量含量最后受存在于涂料中的其它组分的量限制。聚酯(A2)的重量含量例如为30重量％以下，更特别优选为20重量％以下。
通过DSC测量的第二聚酯(A2)的玻璃化转变温度与第一聚酯(A1)的玻璃化转变温度的差为不大于10℃，优选不大于0℃，非常优选不大于-10℃。
如果第二聚酯(A2)的玻璃化转变温度太高，不再满足关于耐碎石性的要求。
交联剂(B)
涂料(F)进一步包含至少一种交联剂(B)。合适的交联剂(B)为能够进入与聚酯的官能团的交联反应的所有交联剂。交联剂(B)优选选自封端多异氰酸酯和氨基树脂。
封端多异氰酸酯为每分子具有两个或更多异氰酸酯基团的化合物，它们的异氰酸酯基团已经与常规且已知的封端剂反应。封端剂仅在升高的温度下再次消除，释放出异氰酸酯基团用于交联反应。
氨基树脂为由甲醛和具有伯和/或仲氨基的化合物形成的缩聚树脂，更特别是三聚氰胺-甲醛树脂、苯胍胺-甲醛树脂和脲-甲醛树脂。
涂料(F)优选包含至少两种不同交联剂(B)，优选包含至少一种封端多异氰酸酯和至少一种氨基树脂的组合。
合适的封端多异氰酸酯为例如脂族、脂环族、芳脂族和芳族封端多异氰酸酯。它们可例如由六亚甲基二异氰酸酯(HDI)、二聚或三聚HDI、异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、氢化MDI(H12MDI)或二甲苯二异氰酸酯(XDI)与合适的封端剂如酚、内酰胺、CH酸性化合物或肟反应而得到。优选的封端剂为甲基乙基酮肟、N-羟基邻苯二甲酰亚胺、1,2,4-三唑、己内酰胺、丙二酸二乙酯和3,5-二甲基吡唑。特别优选的封端剂为甲基乙基酮肟。优选使用具有2-5个异氰酸酯基团每分子的封端多异氰酸酯。
在封端多异氰酸酯中，特别优选脂族封端多异氰酸酯，更特别是基于HDI和IPDI的那些。尤其优选基于IPDI的脂族封端多异氰酸酯。它们可例如以名称BL4265市售。
合适的氨基树脂为例如三聚氰胺-甲醛树脂、苯胍胺-甲醛树脂和/或脲-甲醛树脂，这些树脂的羟甲基为游离的或者可以为部分或完全醚化的。适用于醚化的例如为短链链烷醇，例如甲醇、乙醇、丙醇、正丁醇或异丁醇，更特别是甲醇或正丁醇。
在氨基树脂中，优选三聚氰胺-甲醛和苯胍胺-甲醛树脂。特别优选用甲醇部分醚化的三聚氰胺-甲醛树脂(例如HM2608)、用正丁醇部分醚化的三聚氰胺-甲醛树脂(例如018BX)和用正丁醇醚化的苯胍胺-甲醛树脂(例如B017)。
涂料(F)包含基于总涂料优选为5-15重量％的至少一种交联剂(B)。进一步优选涂料(F)包含每种情况下基于基料(A1)和(A2)的固体总和为25-75重量％，更特别是35-60重量％的一种或多种交联剂(B)。在这些中，优选至少一种封端多异氰酸酯与至少一种氨基树脂的组合作为交联剂(B)。封端多异氰酸酯与氨基树脂之间的重量比优选为0.5-1.5，更优选0.8-1.2。在本发明另一实施方案中，涂料(F)包含基于基料(A1)和(A2)的固体总和为25-35重量％的一种或多种交联剂。在该实施方案中，至少一种封端多异氰酸酯与至少一种氨基树脂的组合也优选作为交联剂(B)，封端多异氰酸酯与氨基树脂之间的重量比优选为0.5-1.5，更优选0.8-1.2。
填料和/或颜料(C)
涂料(F)为头二道混合底漆组合物。
涂料(F)包含基于总涂料(F)为至少8重量％的一种或多种填料和/或颜料(C)。涂料(F)优选包含每种情况下基于总涂料(F)为至少11重量％，更优选至少15重量％的一种或多种填料和/或颜料(C)。填料和/或颜料(C)的最大重量含量最终受存在于涂料中的其它组分的量限制。重量含量例如为40重量％以下，更特别优选30重量％以下。
涂料(F)优选具有0.5-1.2，更优选0.7-0.9的填料和/或颜料(C):基料(A1、A2、B)重量比。它使用所用A1、A2、B和C的固体质量计算。A1、A2、B和C的固体每种情况下作为非挥发性部分测定并通过随着加入2ml二甲苯将在强制通风烘箱中在130℃下加热60分钟的盖上的约2g试样干燥而测量。
合适的填料和/或颜料(C)最终为就本文而言技术人员已知的所有填料和/或颜料，实例为适当地选自如下的那些：
-硅酸盐，例如硅酸镁水合物(例如滑石)、硅酸铝水合物(例如高岭土、瓷土)和硅酸钾铝水合物(例如白云母/云母)，
-碳酸钙(例如白垩、方解石、大理石)，
-碳酸钙镁(例如白云石)，
-碳酸钡，
-硫酸钡(例如Blancfixe、重晶石(barite)、重晶石(heavyspar))，
-硫酸钙，
-氢氧化铝、氢氧化镁，
-炭黑，
-二氧化钛，和
-二氧化硅(例如石英、Aerosil)。
在这些中，优选的填料和/或颜料为二氧化硅(例如Aerosil)、二氧化钛和Blancfixe。在这些中，特别优选的填料和/或颜料为二氧化硅和Blancfixe。
其它组分
涂料(F)可进一步包含常规涂料量的不同于组分(A1)、(A2)、(B)和(C)的其它常规涂料组分(D)，这些是技术人员已知的。合适的其它常规涂料组分(D)的实例为不同于(A1)和(A2)的其它基料、不同于(C)的色彩和/或效果颜料、可热固化和/或热固化和用光化辐射固化的活性稀释剂、UV吸收剂、光稳定剂、自由基清除剂、交联催化剂、除气剂、滑爽添加剂、消泡剂、乳化剂、润湿剂、分散剂、粘合促进剂、流动控制剂、流挂控制剂(SCA)、流变助剂、阻燃剂、催干剂和腐蚀抑制剂。
涂料(F)的制备和头二道混合底漆涂层(I)的制备
涂料(F)的制备不具有特性，而是可通过将组分根据常规且已知的技术混合而进行。
涂料(F)的贮藏寿命优选使得在40℃下储存4星期时粘度上升至在制备以后立即测定的初始值的不大于两倍。粘度使用Afnor流杯(4mm)在23℃下测量(以秒报告)。
为制备头二道混合底漆涂层(I)，将涂料(F)施涂于任选经预处理的基质上。预处理可遵循常规且已知的待涂覆基质的表面预处理措施，例如清洗、活化和/或预涂覆。可例如将基质用电涂层预涂覆。基质优选为金属基质，更优选汽车车体或其部件。
涂料(F)在基质上的施涂可例如用常规且已知的施涂技术如喷涂进行。涂料优选通过喷涂而施涂于基质上。
涂料(F)可以以常规且已知膜厚度施涂于基质上，优选使得产生30-60μm，更优选35-50μm的干膜厚度。
基质上涂料(F)的固化在其方法方面也不具有特性，而是可根据常规且已知的技术进行。涂料(F)例如是热固化的。在固化以前，优选可将涂料(F)简短地闪蒸。闪蒸可例如在室温下进行数分钟。
下面通过实施例阐述本发明，而不意味着本发明主题应限于实施例。
实施例
测量方法
除非另外指出，粘度使用来自Brookfield的装配有CAP-03心轴的Cap2000粘度计测量，测量在23℃下以5000s-1的剪切速率进行(除非另外指出)。
各聚酯(A1)和(A2)和填料和/或颜料(C)的非挥发性部分(NVF)通过随着加入2ml二甲苯将在强制通风烘箱中在130℃下加热60分钟的盖上的约2g试样干燥而测量。
涂料的固体作为在105℃加热180分钟以后1g试样的非挥发性部分(以％表示)测定。
玻璃化转变温度(Tg)如上文已述通过DSC测量。用于测定涂料(F)的Tg的测量条件先前已描述于上文中。为测定基料的Tg，换言之更特别是聚酯(A1)和(A2)的Tg，程序如下。Tg在基于DIN51005“热分析(TA)-Terms”和DIN53765“热分析-动态扫描量热法(DSC)”的方法中测定。在该方法中，称出10mg试样放入试样盘中并引入DSC仪器中。将它冷却至起始温度，然后以50ml/min的惰性气体流(N2)，以10K/min的加热速率进行第一和第二测量程，在测量程之间再次冷却至起始温度。测量通常在从比预期玻璃化转变温度低约50℃至比玻璃化转变温度高约50℃的温度范围内进行。玻璃化转变温度根据DIN53765，第8.1部分确定为获得比热容变化的一半(0.5Δcp)时的第二测量程中的温度。它由DSC图(热流相对于温度的图)测定，且为测量曲线上在玻璃化转变以前与以后的外插基线之间的中线插入点的温度。
数均和重均分子量通过凝胶渗透色谱法根据关于THF可溶性聚合物的DIN55672-1(2007-08版)使用四氢呋喃(+0.1％乙酸)作为洗脱剂在苯乙烯-二乙烯基苯柱组合(WatersHR4、HR3、HR2)上测定。校准通过聚苯乙烯标准进行。
制备实施例1a：
具有高玻璃化转变温度Tg的聚酯树脂溶液(A1)的制备
顶上存在具有相分离容器的塔以使共沸物生成剂再循环的搅拌罐在第一阶段中用于在0.8重量％环己烷作为共沸物生成剂的存在下由9.07重量％的羟基新戊酸新戊二醇酯、21.692重量％新戊二醇、11.439重量％间苯二甲酸和11.043重量％四氢邻苯二甲酸酐合成具有根据DINENISO3682的酸值为9.0-12.0mgKOH/g且在丁基乙二醇中70％稀释物的粘度为390-450mPas的聚酯。粘度计的剪切速率为10000s-1。在加热过程中，注意保持塔顶部温度不超过85℃。
使因此所得的前体在第二阶段中与6.735重量％偏苯三酸酐和3.27重量％邻苯二甲酸酐在180℃下反应直至酸值为22.0-25.0mgKOH/g且在丁基乙二醇中60％稀释时的粘度为700-1200mPas。
固体树脂作为熔体溶于21.273重量％贫萘Solvesso150中，用14.728重量％丁基乙二醇稀释。用丁基乙二醇将最终产物调整至59-61％的NVF和600-1000mPas的粘度。
基料(聚酯A1)具有约+30℃的玻璃化转变温度、2110g/mol的数均分子量(Mn)和5480g/mol的重均分子量(Mw)以及基于固体(非挥发性部分)96mgKOH/g的羟值，其在130℃下干燥60分钟以后测定。
制备实施例1b：
具有高玻璃化转变温度Tg和过度酸值的聚酯树脂溶液的制备
顶上存在具有相分离容器的塔以使共沸物生成剂再循环的搅拌罐在第一阶段中用于在0.8重量％环己烷作为共沸物生成剂的存在下由8.63重量％羟基新戊酸新戊二醇酯、20.64重量％新戊二醇、10.6重量％间苯二甲酸和10.51重量％四氢邻苯二甲酸酐合成根据DINENISO3682的酸值为9.0-12.0mgKOH/g且当在丁基乙二醇中70％稀释时的粘度为390-450mPas的聚酯。粘度计的剪切速率为10000s-1。在加热过程中，注意保持塔顶部温度不超过85℃。
使前体在第二阶段中与10.41重量％偏苯三酸酐在180℃下反应直至酸值为49.0-54.0mgKOH/g且在丁基乙二醇中60％稀释时的粘度为700-1200mPas。
固体树脂作为熔体溶于21.273重量％贫萘Solvesso150中，用14.728重量％丁基乙二醇稀释。用丁基乙二醇将最终产物调整至59-61％的非挥发性部分(NVF)和1000-1300mPas的粘度。
基料具有约+40℃的玻璃化转变温度、1440g/mol的数均分子量(Mn)和4650g/mol的重均分子量(Mw)以及基于固体(非挥发性部分)98mgKOH/g的羟值，其在130℃下干燥60分钟以后测定。
制备实施例2：
具有低玻璃化转变温度Tg的聚酯树脂溶液(A2)的制备
顶上存在具有相分离容器的塔以使共沸物生成剂再循环的搅拌罐用于在220℃下在0.7重量％环己烷作为共沸物生成剂的存在下由7.338重量％PluriolBP40E(具有平均4个乙氧基的双酚A的乙氧基化衍生物，来自BASFSE)、1.785重量％三羟甲基丙烷、24.576重量％新戊二醇、19.9重量％己二酸和5.912重量％偏苯三酸酐合成聚酯，直至酸值为8-12mgKOH/g且粘度为620-720mPas。
固体树脂溶于25.994重量％Solvesso100中并在100℃以下用6.45重量％丁基乙二醇乙酸酯稀释。将聚酯溶液用Solvesso100调整至64-66％的NVF和以2500s-1的粘度计剪切速率测量为1600-2100mPas的粘度。
玻璃化转变温度为约-15℃。数均分子量(Mn)为2730g/mol。重均分子量(Mw)为22000g/mol。羟值基于固体(非挥发性部分)为84mgKOH/g，其在130℃下干燥60分钟以后测定。
涂料：本发明实施例1、本发明实施例2以及对比例C1和C2
根据下表制备满足本发明标准的两种涂料(F)(本发明实施例1,本发明实施例2)以及两种非本发明涂料(对比例C1和C2)：
数字每种情况下以重量份表示。环氧树脂溶液为在二甲苯与丁基乙二醇乙酸酯的比例为3:1的混合物中，环氧当量为475-505g/mol的环氧树脂的60％稀释物。
涂料的玻璃化转变温度Tg如下：
对比例C1 本发明实施例1 本发明实施例2 对比例C2
Tg 35℃ 43℃ 58℃ 58℃
来自实施例1、2、C1和C2的涂料的贮藏寿命
所制备的涂料的贮藏寿命通过对比a)在涂料的制备以后立即测量的初始粘度与b)在40℃下储存4星期以后的最终粘度而确定。粘度使用Afnor流杯(4mm)在23℃下测量(以秒报告)。
涂料的初始和最终粘度如下：
来自本发明实施例1和2的涂料具有与对比例C2相比明显更好的贮藏寿命。
多层涂层的制备
多层涂层如下由本发明实施例1、本发明实施例2、对比例C1和对比例C2的涂料制备：
每种情况下以45μm的干膜厚度通过喷涂将根据本发明实施例1、本发明实施例2、对比例1或对比例2的涂料施涂于电涂覆(500)金属基质上，然后在20℃下闪蒸5分钟并在30℃下固化150分钟，其后作为其它涂层(60-65μm)施涂商业水基底涂层和商业单组分透明涂层，其后在130℃下联合固化30分钟。
然后使用来自Atlas的Xenotest1200CPS仪器根据用户说明书使涂层体系在50±3℃和升高的湿度下并使用氙灯(290nm，60±3W/m2)用UV辐射经受老化试验。
多层涂层的性能
1)根据用户说明书的耐鸟粪性
施涂于老化以后所得多层涂层上的试验材料为阿拉伯胶溶液(在去离子水中50％)，其中施涂在各自2cm直径的至少3个测量部位上进行，施涂的阿拉伯胶溶液的量为每测量部位3滴，其后在室温下干燥30分钟。
将这样制备的油漆体系在烘箱中在60℃下保温3天。然后在60-65℃的流水下除去阿拉伯胶溶液，并使油漆体系在室温下干燥30分钟。
油漆涂层的附着力随后通过胶粘带脱除验证。这通过将一片胶粘带(例如Tesafilm)压在测量部位上，并以快速移动将它再次撕开而进行。
评估根据以下标准目测进行：
0＝无缺陷
1＝小裂纹
2＝裂纹和轻微的附着力损失
3＝裂纹和附着力损失
4＝严重的附着力损失
5＝极严重的附着力损失
平均值由油漆体系上的所有测量部位形成。
2)微针入度硬度
在老化以后，根据DINENISO14577在25.6mN下测量微针入度硬度(万能硬度；Martens硬度)。
3)耐碎石性
在老化以后，根据用户说明书测定耐碎石性(在2巴下以2×500g多石块冲击；随后胶粘带脱除)。评估通过损害部位的尺寸和数目目测进行，并使用0(无损害部位)至8(非常大量的大损害部位)的等级评定报告。
多层涂层的结果如下：
所得结果清楚地显示通过与对比例C1对比，本发明多层涂层(使用来自本发明实施例1和2的涂料制备)显示出改进的微针入度硬度和改进的耐鸟粪性而不具有耐碎石性的损失。

Claims (16)

1.制备多层涂层的方法，其包括步骤：
i)将头二道混合底漆涂层(I)施涂于任选经预处理的基质上，
ii)将头二道混合底漆涂层(I)固化，
iii)将底涂层(II)施涂于固化的头二道混合底漆涂层(I)，
iv)任选将底涂层(II)固化，
v)将透明涂层(III)施涂于固化或未固化的底涂层(II)上，和
vi)将透明涂层(III)固化或者如果底涂层在步骤iv)中未固化的话将底涂层和透明涂层固化，
其特征是头二道混合底漆涂层(I)通过施涂包含如下组分的非水溶剂基涂料(F)而得到：
基于涂料(F)总重量为至少20重量％的至少一种有机溶剂，以及
A1)基于涂料(F)总重量为至少8重量％的至少一种第一聚酯(A1)，其具有至少20℃的玻璃化转变温度和0-40mgKOH/g的酸值，
A2)基于涂料(F)总重量为至少8重量％的至少一种不同于第一聚酯(A1)且玻璃化转变温度为不大于10℃的第二聚酯(A2)，
B)至少一种交联剂(B)，和
C)基于涂料(F)总重量为至少8重量％的一种或多种填料和/或颜料(C)。
2.根据权利要求1的方法，其特征在于任选经预处理的基质为金属基质。
3.根据权利要求1或2的方法，其特征在于任选经预处理的基质为车体或其部件。
4.可通过根据权利要求1的方法得到的多层涂层。
5.根据权利要求4的多层涂层，其特征在于涂料(F)的玻璃化转变温度为至少35℃。
6.根据权利要求4的多层涂层，其特征在于涂料(F)具有0.7-1.2的第一聚酯(A1):第二聚酯(A2)重量比。
7.根据权利要求5的多层涂层，其特征在于涂料(F)具有0.7-1.2的第一聚酯(A1):第二聚酯(A2)重量比。
8.根据权利要求4-7中任一项的多层涂层，其特征在于第一聚酯(A1)具有0-30mgKOH/g的酸值。
9.根据权利要求4-7中任一项的多层涂层，其特征在于第一聚酯(A1)的多分散性(Mw/Mn)为5或以下，且第二聚酯(A2)的多分散性(Mw/Mn)为5或以上。
10.根据权利要求4-7中任一项的多层涂层，其特征在于交联剂(B)选自封端多异氰酸酯、三聚氰胺-甲醛树脂和苯胍胺-甲醛树脂。
11.根据权利要求4-7中任一项的多层涂层，其特征在于涂料(F)包含至少一种封端异氰酸酯和至少一种氨基树脂作为交联剂(B)。
12.根据权利要求4-7中任一项的多层涂层，其特征在于涂料(F)具有填料和/或颜料(C):(第一聚酯(A1)+第二聚酯(A2)+交联剂(B))＝0.5-1.2的填料和/或颜料(C):基料(第一聚酯(A1)+第二聚酯(A2)+交联剂(B))重量比。
13.根据权利要求4-7中任一项的多层涂层，其特征在于填料和/或颜料(C)选自硅酸盐、碳酸钙、碳酸钙镁、碳酸钡、炭黑、硫酸钡、硫酸钙、氢氧化铝、氢氧化镁、二氧化钛和二氧化硅。
14.涂有根据权利要求4-13中任一项的多层涂层的基质。
15.根据权利要求14的基质，其特征在于它为金属基质。
16.根据权利要求14或15的基质，其特征在于它为汽车车体或其部件。
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EP2817103B1 (de) 2016-04-20
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MX355138B (es) 2018-04-06
EP2817103A1 (de) 2014-12-31
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