CN111886272A - 含脲二酮基团的水性组合物及其制备方法 - Google Patents

含脲二酮基团的水性组合物及其制备方法 Download PDF

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Publication number
CN111886272A
CN111886272A CN201980021445.9A CN201980021445A CN111886272A CN 111886272 A CN111886272 A CN 111886272A CN 201980021445 A CN201980021445 A CN 201980021445A CN 111886272 A CN111886272 A CN 111886272A
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China
Prior art keywords
diisocyanate
acid
groups
uretdione
group
Prior art date
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Granted
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CN201980021445.9A
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CN111886272B (zh
Inventor
D·格雷茨塔-弗兰茨
S·博伊克
S·德尔
H-J·拉斯
N·尤瓦
H-D·格维斯
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Covestro Deutschland AG
Covestro LLC
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Covestro Deutschland AG
Covestro LLC
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Priority claimed from US15/933,495 external-priority patent/US11312881B2/en
Priority claimed from US15/933,500 external-priority patent/US10696775B2/en
Priority claimed from US15/933,507 external-priority patent/US20190292294A1/en
Priority claimed from US15/933,570 external-priority patent/US10731051B2/en
Priority claimed from US15/933,527 external-priority patent/US20190292296A1/en
Priority claimed from US15/933,487 external-priority patent/US20190292305A1/en
Priority claimed from US15/933,553 external-priority patent/US10633477B2/en
Priority claimed from US15/933,475 external-priority patent/US11008416B2/en
Priority claimed from US15/933,470 external-priority patent/US11292864B2/en
Priority claimed from EP18163621.8A external-priority patent/EP3543270A1/de
Priority claimed from EP18163620.0A external-priority patent/EP3543269A1/en
Priority claimed from EP18163625.9A external-priority patent/EP3543271A1/de
Priority claimed from US15/933,511 external-priority patent/US11440988B2/en
Priority claimed from EP18181877.4A external-priority patent/EP3590988A1/de
Priority claimed from EP18181876.6A external-priority patent/EP3590987A1/de
Application filed by Covestro Deutschland AG, Covestro LLC filed Critical Covestro Deutschland AG
Publication of CN111886272A publication Critical patent/CN111886272A/zh
Publication of CN111886272B publication Critical patent/CN111886272B/zh
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Abstract

本发明涉及含脲二酮基团的水性组合物,所述组合物包含或由以下组成,(A)至少一种基于脂族、脂环族、芳脂族和/或芳族多异氰酸酯的含脲二酮基团的固化剂,其不包含化学键合的亲水化基团;(B)至少一种包含羟基的多元醇,其包含至少一个化学键合的羧酸基团;(C)任选的溶剂;和(D)任选的助剂和添加剂;其中如此计量组分(A)和(B)的量比,使得固化剂(A)的作为脲二酮存在的NCO基团与多元醇(B)的NCO‑反应性基团的摩尔比为3:0.5至0.5:3,并且其中A和B作为物理混合物存在。此外,本发明涉及使用本发明的含脲二酮基团的水性组合物制备聚氨酯层的方法,由该方法获得的聚氨酯层,和用所述聚氨酯层涂覆或粘合的基材。

Description

含脲二酮基团的水性组合物及其制备方法
本发明涉及含脲二酮基团的水性组合物,其包含或由以下组分组成
(A) 至少一种基于脂族、脂环族、芳脂族和/或芳族多异氰酸酯的含脲二酮基团的固化剂,其不包含化学键合的亲水化基团;
(B) 至少一种包含羟基的多元醇,其包含至少一个化学键合的羧酸基团;
(C) 任选的溶剂;和
(D) 任选的助剂和添加剂;
其中如此计量组分(A)和(B)的量比,使得固化剂(A)的作为脲二酮存在的NCO基团与多元醇(B)的NCO-反应性基团的摩尔比为3:0.5至0.5:3,并且其中A和B作为物理混合物存在。
此外,本发明涉及使用本发明的含脲二酮基团的水性组合物制备聚氨酯层的方法,由该方法获得的聚氨酯层,和用所述聚氨酯层涂覆或粘合的基材。
近年来,由于对施加漆时释放的溶剂的排放准则越来越严格,因此水性的漆和涂层剂的重要性急剧提高。尽管对于许多应用领域而言,现在已经具有水性漆体系,但就溶剂耐受性和化学品耐受性或者弹性和机械负荷而言,它们经常不能达到常规的含溶剂的漆的高品质水平。特别是,迄今为止,尚未知晓充分满足实践中的高要求的可由水相加工的聚氨酯基涂层剂。此论断既适用于DE 4001783A1,其致力于特殊的阴离子改性的脂族多异氰酸酯,也适用于DE 2456469A1、DE 2814815A1、EP 0012348A1和EP 0424697A1的体系,它们描述了基于封闭型多异氰酸酯和有机多羟基化合物的水性单组分烤漆粘合剂。
近年来,已经实现了对基于封闭型多异氰酸酯的单组分烤漆粘合剂的进一步改进,例如记载在EP 0576952A中。
上述的相应于现有技术的基于封闭型多异氰酸酯的单组分烤漆粘合剂具有的缺点是,即使它们基本上不含溶剂,在烘烤这种漆粘合剂时,各自的封端剂被释放,这又导致排放。因此,长期以来市场上存在对于开发水性、无排放的单组分烤漆粘合剂的需求。不缺乏对于制备这种基于没有解离物(Abspalter)的、含脲二酮的多异氰酸酯的烤漆粘合剂的尝试。
根据EP 1687354A1,可以通过将固体脲二酮化合物与熔融的水分散性树脂合并,如果需要的话,将水分散性树脂盐化,并将该树脂混合物分散在水中,来制备含脲二酮的水性分散体涂料。该熔融的水分散性树脂可以具有对脲二酮化合物具有反应性的官能团,或者该涂料组合物可以包含另一种水分散性树脂,该水分散性树脂具有对脲二酮化合物具有反应性的官能团。然而,在实施例中,使用了环氧树脂。通常已知,环氧漆在大多数性能上劣于聚氨酯漆。根据EP 1687354A1,为制备这些分散体涂料还需要使用另外的乳化剂,这进一步损害了该分散体涂料的漆性能。此外,EP 1687354A1中描述的制备方法与对于脲二酮基团而言非常高的热负荷相关联,这在实践中最有可能导致脲二酮基团的损失。此外,EP1687354A1中描述的分散体在制备后立即直接施用。EP 1687354A1中缺乏关于这些分散体的稳定性的信息。
US 4496684 A描述了通过羟基封端的预聚物与二羧酸酐的反应制备的包含脲二酮基团的聚氨酯低聚物。该文献中没有水性组合物,其中含脲二酮基团的固化剂和多元醇作为物理混合物存在。
例如在DE 2538484 A1和DE 10 2005 036 654 A1中可找到可分散在水中的亲水性含脲二酮的多异氰酸酯的进一步实例。在这两个文献中,亲水化基团(即羧基)被直接并入含脲二酮的多异氰酸酯中。DE 2538484 A和DE 10 2005 036 654 A1都没有给出关于这些分散体的稳定性的信息。在此的区别还在于,不存在特定的含脲二酮基团的固化剂和特定的多元醇的物理混合物。
US 2015232609A1公开了可分散在水中的含脲二酮的亲水性多异氰酸酯,其可通过带有脲二酮基团的预聚物与含有可离子化基团的乳化剂的反应得到,其中该可离子化基团在室温下在水中的pKa值> 8或pKb> 8。这种含脲二酮的反应产物在室温下显示出8周的改进的储存稳定性,但是这对于工业中的实际应用而言仍然是不够的,在工业中经常必须要考虑到长途运输。
通过使用本发明的特定固化剂和多元醇的物理混合物,令人惊奇地能够解决上述问题。特别地,可以获得与现有技术中已知的组合物相比具有提高的储存稳定性的分散体。
本发明特别涉及:
1. 含脲二酮基团的水性组合物,其包含或由以下组分组成
(A) 至少一种基于脂族、脂环族、芳脂族和/或芳族多异氰酸酯的含脲二酮基团的固化剂,优选基于基于脂族、脂环族、和/或芳脂族多异氰酸酯,特别优选基于脂族和/或脂环族多异氰酸酯,其不包含化学键合的亲水化基团;
(B) 至少一种包含羟基的多元醇,其包含至少一个化学键合的羧酸基团;
(C) 任选的溶剂;和
(D) 任选的助剂和添加剂;
其中如此计量组分(A)和(B)的量比,使得固化剂(A)的作为脲二酮存在的NCO基团与多元醇(B)的NCO-反应性基团的摩尔比为3.0:0.5至0.5:3.0,优选2.5:1.0至1.0:2.5,特别优选2.0:2.0至1.0至1.0:2.0,并且其中(A)和(B)作为物理混合物存在。
2. 根据方面1的含脲二酮基团的水性组合物,其特征在于,
所述至少一种含脲二酮基团的固化剂(A)通过单体异氰酸酯的反应获得,所述单体异氰酸酯包含或由至少一种选自以下的单体异氰酸酯组成:四亚甲基二异氰酸酯,环己烷-1,3-二异氰酸酯和环己烷-1,4-二异氰酸酯,五亚甲基二异氰酸酯,六亚甲基二异氰酸酯(HDI),1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷 (异佛尔酮二异氰酸酯IPDI),二环己基甲烷-2,4’-二异氰酸酯和/或二环己基甲烷-4,4’-二异氰酸酯,四甲基苯二亚甲基二异氰酸酯 (TMXDI),三异氰酸根合壬烷,甲苯二异氰酸酯 (TDI),二苯基甲烷-2,4’-二异氰酸酯和/或二苯基甲烷-4,4’-二异氰酸酯 (MDI),三苯基甲烷-4,4’-二异氰酸酯或萘-1,5-二异氰酸酯或者它们的混合物,优选选自异佛尔酮二异氰酸酯,二环己基甲烷-2,4’-二异氰酸酯和/或二环己基甲烷-4,4’-二异氰酸酯或六亚甲基二异氰酸酯。
3. 根据方面1或2的含脲二酮基团的水性组合物,其特征在于,
使用含羟基的单体和/或聚合物作为所述至少一种含脲二酮基团的固化剂 (A)的原料。
4. 根据前述方面之一的含脲二酮基团的水性组合物,其特征在于,
所述至少一种含脲二酮基团的固化剂 (A)的游离NCO含量小于5重量%,脲二酮基团的含量为1至18重量%(作为C2N2O2计算,分子量为84 g/mol)。
5. 根据前述方面之一的含脲二酮基团的水性组合物,其特征在于,
所述水性组合物的酸值为1至100 mg KOH/g,优选2至50 mg KOH/g,特别优选5至30 mgKOH/g,优选根据DIN EN ISO 2114: 2002-06,用重量比为2:1的丙酮和乙醇作为溶剂来测量, 并且基于固体含量来计算。
6. 根据前述方面之一的含脲二酮基团的水性组合物,其特征在于
通过羟基羧酸或氨基羧酸的反应获得所述至少一种含羟基的多元醇(B),所述羟基羧酸或氨基羧酸包含或由选自下述的至少一种羧酸组成:2,2-二羟甲基乙酸、2,2-二羟甲基丁酸、2,2-二羟甲基戊酸、二羟基琥珀酸、α,Ω-二氨基戊酸或其混合物,优选选自二羟甲基丙酸或羟基新戊酸。
7. 根据前述方面之一的含脲二酮基团的水性组合物,其特征在于,
所述至少一种包含羟基的多元醇(B)的OH含量大于1重量% - 作为OH基团基于固体含量计算,分子量为17 g/mol – 和数均分子量Mn为500至20 000 g/mol。
8. 根据前述方面之一的水性脲二酮分散体,其特征在于,
所述溶剂选自丙酮,甲乙酮,乙酸乙酯,乙酸丁酯,二甲苯,重苯,如商购可得的Solvesso 100或Solvesso 150,丙二醇单正丁醚,二丙二醇二甲醚,乙酸甲氧基丙酯,二酯或者它们的混合物。
9. 根据前述方面之一的水性脲二酮分散体,其特征在于,
所述助剂和添加剂选自流平剂,例如有机硅聚合物(Polysilicone)或丙烯酸酯,光保护剂,例如空间位阻胺,催化剂,例如2-乙基己酸锡(II)或二月桂酸二丁基锡,填料和颜料,例如二氧化钛,或者它们的混合物。
10. 根据前述方面之一的含脲二酮基团的水性组合物,其特征在于,
(A)、(B)和(D)的重量比例之和为30至60重量%,基于整个水性组合物的固体含量计。
11. 制备聚氨酯层的方法,包括以下步骤
i) 提供根据方面1至10之一的含脲二酮基团的水性组合物;
ii) 将在i)中获得的混合物施加在基材上;
iii) 干燥得自步骤ii)的混合物,和
iv) 加热到40℃至180℃,至多180分钟,使得自步骤iii)的混合物固化。
12. 根据方面11的方法,其特征在于,所述含脲二酮基团的水性组合物通过在不存在水的情况下将所述含脲二酮基团的固化剂(A)与所述至少一种包含羟基的多元醇(B)混合,随后用水分散而得到。
13. 可以通过根据方面11或12的方法得到的聚氨酯层,特别是聚氨酯膜。
14. 用根据方面13的聚氨酯层涂覆或粘合的基材。
除非明确地另行规定,否则平均分子量根据本发明被定义为数均分子量Mn。在作为溶剂的四氢呋喃中,在23℃下,借助于凝胶渗透色谱法(GPC)测定Mn。如DIN 55672-1:2016-03: “凝胶渗透色谱法,第1部分-四氢呋喃为洗脱剂”(来自PSS Polymer Service的Security GPC 体系,流量1.0 ml)中所述般进行测量。
除非另有明确说明,否则本发明中的重量%是基于各自体系的总重量或各自组分的总重量计的。 例如,共聚物可以包含以重量%给出的特定单体,在这种情况下,重量百分比将基于该共聚物的总重量计。
除非另有明确说明,否则表述“至少一”是指化合物的种类,而不是单个分子。 例如,至少一种多元醇应理解为是指包含至少一个种类的多元醇,但是其以任意数目的分子含于组合物中。因此,也可能存在两个或更多个种类的多元醇,各自以任意数目存在,如果没有定义量的话。
在一个优选的实施方案中,所述含脲二酮基团的水性组合物基本上不含其他助乳化剂(除了组分(B)之外)。 根据本发明如此定义术语“基本上不含”,即包含的各自化合物的比例优选小于1重量%,更优选小于0.25重量%,甚至更优选小于0.1重量%,最优选小于0.01重量%,或者完全没有,各自基于含脲二酮基团的水性组合物的总重量计。
本发明的含脲二酮基团的水性组合物优选为基于聚氨酯的组合物。
适合作为用于组分(A)的起始化合物的包含脲二酮基团的多异氰酸酯是包含至少一个异氰酸酯基团和至少一个脲二酮基团的多异氰酸酯。它们通过合适的起始异氰酸酯(a1)的反应来制备,例如记载在WO 02/92657 A1或WO 2004/005364 A1中。在此,在催化作用下,例如用三唑盐或4-二甲基氨基吡啶(DMAP)作为催化剂,一部分异氰酸酯基团转化为脲二酮基团。构建含脲二酮的结构单元的异氰酸酯(a1)的实例是四亚甲基二异氰酸酯,环己烷-1,3-二异氰酸酯和环己烷-1,4-二异氰酸酯,五亚甲基二异氰酸酯,六亚甲基二异氰酸酯(HDI),1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯IPDI),二环己基甲烷-2,4'-二异氰酸酯和/或二环己基甲烷-4,4'-二异氰酸酯,四甲基苯二亚甲基二异氰酸酯(TMXDI),三异氰酸根合壬烷,甲苯二异氰酸酯(TDI),二苯基甲烷-2,4'-二异氰酸酯和/或二苯基甲烷-4,4'-二异氰酸酯(MDI),三苯基甲烷-4,4'-二异氰酸酯或萘-1,5-二异氰酸酯,以及此类异氰酸酯的任意混合物。优选异佛尔酮二异氰酸酯,二环己基甲烷-2,4′-二异氰酸酯和/或二环己基甲烷-4,4′-二异氰酸酯或六亚甲基二异氰酸酯。
除了异氰酸酯基团和脲二酮基团之外,组分(A)还可以具有异氰脲酸酯结构,缩二脲结构,脲基甲酸酯结构,氨基甲酸酯结构和/或脲结构。
这些带有脲二酮基团的多异氰酸酯转化成具有脲二酮基团的固化剂(A)包括上述多异氰酸酯的游离NCO基团与多元醇组分(b1)的反应,任选共同使用多元醇组分(b2)。
多元醇成分(b1)优选具有≥2的羟基官能度,分子量Mn为62至500 g/mol,优选62至400 g/mol,特别优选62至300 g/mol。多元醇组分(b1)优选包含分子量Mn为62至500 g/mol,优选62至400 g/mol,特别优选62至300 g/mol的2至6元多元醇组分。优选的多元醇组分(b1)例如是1,4-丁二醇和/或1,3-丁二醇,1,6-己二醇,2,2,4-三甲基-1,3-戊二醇,三羟甲基丙烷,平均分子量Mn小于或等于500 g/mol的聚酯多元醇和/或聚醚多元醇。
合适的线性双官能多元醇(b2)选自聚醚,聚酯,聚己内酯二醇和/或聚碳酸酯。多元醇组分(b2)优选包含至少一种包含酯基团的分子量Mn为350至4000 g/mol,优选350至2000 g/mol,特别优选350至1000 g/mol的二醇。这是可由羟值计算的平均分子量。酯二醇通常是混合物,在其中也可以以次要量存在具有低于或高于这些极限的分子量的个别成分。这些是本身已知的由二醇和二羧酸构建的聚酯二醇。
合适的二醇例如是1,4-二羟甲基环己烷,1,4-丁二醇或1,3-丁二醇,1,6-己二醇,新戊二醇,2,2,4-三甲基-1,3-戊二醇,三羟甲基丙烷以及季戊四醇,或这些二醇的混合物。合适的二羧酸例如是芳族二羧酸,如邻苯二甲酸,间苯二甲酸和对苯二甲酸;脂环族二羧酸,例如六氢邻苯二甲酸,四氢邻苯二甲酸;内亚甲基四氢邻苯二甲酸或其酸酐;和脂族二羧酸,这是优选使用的,如琥珀酸,戊二酸,己二酸,辛二酸,壬二酸和癸二酸或其酸酐。
基于己二酸,邻苯二甲酸,间苯二甲酸和四氢邻苯二甲酸的聚酯二醇优选用作组分(b2)。作为优选的二醇使用例如1,4-丁二醇或1,3-丁二醇,1,6-己二醇或三羟甲基丙烷及其混合物。
同样优选作为组分(b2)的是平均分子量为350至4000 g/mol,优选350至2000 g/mol,特别优选350至1000 g/mol的聚己内酯二醇,其以本身已知的方法由上述示例性提及类型的二醇或二醇混合物作为起始剂和内酯来制备,所述内酯例如是β-丙内酯,γ-丁内酯,γ-和δ-戊内酯,ε-己内酯,3,5,5-和3,3,5-三甲基己内酯,或这些内酯的任意混合物。特别优选的是通过ε-己内酯的聚合来制备的这种聚己内酯二醇。
作为线性多元醇组分(b2),也可以使用由环氧乙烷、环氧丙烷和/或四氢呋喃制成的(共)聚醚,其由少于30mol%的环氧乙烷单元构成。优选的是平均分子量Mn为500至2000g/mol的聚醚,例如聚环氧丙烷或聚四氢呋喃二醇。
适合作为(b2)的也是含羟基的聚碳酸酯,优选平均分子量Mn为400至4000 g/mol,优选400至2000 g/mol,例如己二醇聚碳酸酯以及聚酯碳酸酯。
作为制备具有脲二酮基团的固化剂(A)中的多元醇组分(b2)也可以使用具有低分子量酯基团的二醇,所述二醇的可由官能度和羟值计算的平均分子量为134至349 g/mol,优选176至349 g/mol。这些例如是本身已知的具有酯基团的二醇或这些二醇的混合物,例如其可以通过醇与亚化学计量量的二羧酸、相应的二羧酸酐、相应的低级醇的二羧酸酯或内酯的反应来制备。合适的酸的实例是琥珀酸,己二酸,癸二酸,邻苯二甲酸,间苯二甲酸,邻苯二甲酸酐,四氢邻苯二甲酸,马来酸,马来酸酐,对苯二甲酸二甲酯和对苯二甲酸双乙二醇酯。适合用于制备这些酯二醇的内酯例如是β-丙内酯,γ-丁内酯,γ-和δ-戊内酯,ε-己内酯,3,5,5-和3,3,5-三甲基己内酯或这些内酯的任意混合物。
在制备具有脲二酮基团的固化剂(A)时也可以使用氨基官能化合物。合适的低分子量氨基官能化合物的实例是脂族和脂环族胺以及具有伯和/或仲键合的氨基的氨基醇,例如环己胺,2-甲基-1,5-戊二胺,二乙醇胺,单乙醇胺,丙胺,丁胺,二丁胺,己胺,单异丙醇胺,二异丙醇胺,乙二胺,1,3-二氨基丙烷,1,4-二氨基丁烷,异佛尔酮二胺,二亚乙基三胺,乙醇胺,氨基乙基-乙醇胺,二氨基环己烷,六亚甲基二胺,甲基亚氨基双丙胺,亚氨基双丙胺,双(氨基丙基)哌嗪,氨基乙基哌嗪,1,2-二氨基环己烷,三亚乙基四胺,四亚乙基五胺,双(4-氨基环己基)甲烷,双(4-氨基-3-甲基环己基)甲烷,双(4-氨基-3,5-二甲基环己基)甲烷,双(4-氨基-2,3,5-三甲基环己基)甲烷,1,1-双(4-氨基环己基)丙烷,2,2-双(4-氨基环己基)丙烷,1,1-双(4-氨基环己基)乙烷,1,1-双(4-氨基环己基)丁烷,2,2-双(4-氨基环己基)丁烷,1,1-双(4-氨基-3-甲基环己基)乙烷,2,2-双(4-氨基-3-甲基环己基)丙烷,1,1-双(4-氨基-3,5-二甲基环己基)乙烷,2,2-双(4-氨基-3,5-二甲基环己基)丙烷,2,2-双(4-氨基-3,5-二甲基环己基)丁烷,2,4-二氨基二环己基甲烷,4-氨基环己基-4-氨基-3-甲基环己基甲烷,4-氨基-3,5-二甲基环己基-4-氨基-3-甲基环己基甲烷和2-(4-氨基环己基)-2-(4-氨基-3-甲基环己基)甲烷。
在制备具有脲二酮基团的固化剂(A)时可以任选地使用溶剂。作为用于具有脲二酮基团的固化剂(A)的溶剂合适的是不与其他内容物反应的所有液体物质,例如丙酮,甲乙酮,乙酸乙酯,乙酸丁酯,二甲苯,重苯,如商购可得的Solvesso 100和Solvesso 150,丙二醇单正丁醚,二丙二醇二甲醚,乙酸甲氧基丙酯,二酯或者它们的混合物。
具有脲二酮基团的固化剂(A)基本上不含离子型或非离子型化学键合的亲水化化合物。离子型亲水化基团被本领域技术人员理解为是指能够形成阴离子或阳离子的基团。能够形成阴离子或阳离子的基团是那些可以通过化学反应,特别是通过中和,转化成阴离子或阳离子基团的那些。
具有脲二酮基团的固化剂(A)优选不含能够形成阴离子的含羧基的多元醇或二醇,例如二羟基羧酸,如α,α-二羟烷基链烷酸,特别是α,α-二羟甲基链烷酸,如2,2-二羟甲基乙酸,2,2-二羟甲基丙酸,2,2-二羟甲基丁酸,2,2-二羟甲基戊酸,二羟基琥珀酸或多羟基酸如葡糖酸。另外,具有脲二酮基团的固化剂(A)优选不含能够形成阴离子的含有氨基的化合物,例如α,Ω-二氨基戊酸或2,4-二氨基甲苯磺酸。具有脲二酮基团的固化剂(A)同样优选不含能够形成阴离子的磺酸基团。
此外,具有脲二酮基团的固化剂(A)优选不含选自叔氨基化合物或铵化合物的能够形成阳离子的化合物,例如三(羟基烷基)胺,N,N'-双(羟基烷基)烷基胺,N-羟基烷基二烷基胺,三氨基烷基胺,N,N′-双氨基烷基烷基胺,N-氨基烷基二烷基胺及其混合物。
具有脲二酮基团的固化剂(A)此外优选不含非离子性亲水化化合物,例如聚环氧烷聚醚醇或聚环氧烷聚醚胺。特别地,具有脲二酮基团的固化剂(A)优选不含聚环氧乙烷聚醚或混合的聚环氧烷聚醚,其环氧烷单元至少30mol%由环氧乙烷单元组成。
优选的具有脲二酮基团的固化剂(A)的游离NCO含量小于5重量%,脲二酮基团的含量为1至18重量%(作为C2N2O2计算,分子量84 g/mol)。除了脲二酮基团以外,固化剂(A)还可以具有异氰脲酸酯-、缩二脲-、脲基甲酸酯-、氨基甲酸酯-和/或脲结构。
该组合物同样包含至少一种包含羟基的多元醇,所述多元醇包含至少一个化学键合的羧酸基团(组分(B))。
合适的多元醇(B)可选自聚酯多元醇、聚醚多元醇、聚氨酯醚多元醇、聚氨酯酯多元醇、聚己内酯多元醇、聚醚酯多元醇、聚碳酸酯多元醇、具有至少两个羟基的C2-10烃或其混合物,只要这样的多元醇具有至少一个化学键合的羧酸基团。优选地,合适的多元醇(B)选自聚氨酯醚多元醇、聚氨酯酯多元醇、聚己内酯多元醇或聚碳酸酯多元醇,特别优选的是由以下制成的聚氨酯酯多元醇(B):5至80重量%,优选10至60重量%的异氰酸酯(a1),
10至80重量%,优选40至70重量%的多元醇(b2)和/或具有至少400 g/mol的平均分子量Mn的氨基官能化合物;
2至15重量%,优选3至10重量%的具有至少一个化学键合的羧酸基团的起始组分(b3),
0至20重量%,优选1-10%的多元醇(b1),
0至20重量%的单官能或包含不同反应性的活性氢的化合物,
0至20重量%的不同于(b1)、(b2)和(b3)并包含至少两个对NCO基团呈反应性的基团的化合物。
作为用于多元醇(B)的具有至少一个化学键合的羧酸基团的起始组分(b3),合适的是每分子包含至少一个羧酸基团,通常1至3个羧酸基团的多元醇,优选二元醇。对此的实例是二羟基羧酸,如α,α-二羟烷基链烷酸,特别是α,α-二羟甲基链烷酸,如2,2-二羟甲基乙酸、2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基戊酸、二羟基琥珀酸以及多羟基酸,如葡糖酸或氨基羧酸,例如α,Ω-二氨基戊酸和2,4-二氨基甲苯磺酸。也可使用上述化合物的混合物。
作为用于多元醇(B)的具有至少一个化学键合的羧酸基团的起始组分(b3),特别优选的是2,2-二羟甲基丙酸。或者,也可使用具有至少一个羧酸基团的单羟基官能化合物,例如羟基新戊酸或羟基癸酸。
合适的多元醇(B)是优选具有大于1重量%的OH含量(作为OH基团基于固体含量计算,分子量17 g/mol)并优选具有500至20 000 g/mol,优选500至10 000 g/mol,特别优选500至5000 g/mol的数均分子量Mn的多元醇。
根据本发明使用的聚氨酯树脂优选以这样的方式来制备,即,将多元醇(B)的非水性树脂前体与至少一种基于脂族、(环)脂族、芳脂族和/或芳族的多异氰酸酯的不包含化学键合的亲水化基团的含脲二酮基团的固化剂(A)在非水性体系中均匀混合。随后,用合适的中和剂将多元醇(B)中存在的羧酸基团中和到优选至少50%,更优选80%至120%,特别优选95至105%,随后用去离子水分散。可在分散步骤之前、之中或之后进行中和。但是优选在添加水之前中和。
合适的中和剂例如是三乙胺,二甲基氨基乙醇,二甲基环己胺,三乙醇胺,甲基二乙醇胺,二异丙醇胺,乙基二异丙胺,二异丙基环己胺,N-甲基吗啉,2-氨基-2-甲基-1-丙醇,氨或其他常规中和剂或其中和混合物。优选的是叔胺,例如三乙胺和二异丙基己胺,特别优选的是二甲基乙醇胺。
根据本发明,中和剂应包括在助剂和添加剂(D)的组中。
作为(C)下的溶剂合适的是不与其他内容物反应的所有液体物质。优选丙酮,甲乙酮,乙酸乙酯,乙酸丁酯,二甲苯,重苯,如商购可得的Solvesso 100和Solvesso 150,丙二醇单正丁醚,二丙二醇二甲醚,乙酸甲氧基丙酯,二酯或者它们的混合物。随后,任选可以蒸馏除去所使用的溶剂。
根据本发明,可以以优选0.05至5重量%的总量包含在漆-和粘合剂技术中常用的添加剂(D),如流平剂,例如有机硅聚合物或丙烯酸酯, 光保护剂,例如空间位阻胺, 催化剂,例如2-乙基己基辛酸锡(II)或二月桂酸二丁基锡,或其它助剂,例如在EP 0 669 353中描述的那些。填料和颜料例如二氧化钛可以以至多50重量%的量添加到该水性组合物中。
在一个优选实施方案中,所述含脲二酮基团的水性组合物包含或由以下组成
基于A+B的总和计10-50重量%,优选20-40重量%的A)
基于A+B的总和计10-80重量%,优选40-70重量%的B)
基于A+B+D的总和计0至20重量%,优选1至15重量%的C)
基于A+B+D计0-70重量%,优选2-50重量%的D)。
实施例:
所用原材料:
聚酯1: 由1419克三羟甲基丙烷、4773克新戊二醇、3093克己二酸、4101克间苯二甲酸和267克1,2-丙二醇制备的脂族聚酯,具有< 3 mg KOH/g的酸值和181 mg KOH/g的OH值。
所用分析方法:
所有粘度测量用来自Anton Paar Germany GmbH (DE)的Physica MCR 51流变仪根据DIN EN ISO 3219:1994-10进行。
根据DIN EN ISO 11909:2007-05滴定测定NCO含量。
根据DIN EN ISO 4629-2:2015-02滴定测定OH值。
根据DIN EN ISO 2114:2002-06滴定测定酸值。
根据DIN EN ISO 3251:2008-06,方法B,借助于循环空气烘箱测定固体含量。
用来自Malvern (DE)的Zetasizer Nano根据DIN ISO 13321:2004-10测定平均粒度(MTG)。
用pH计根据DIN ISO 976:2008-07用蒸馏水以1:4的稀释测定pH值。
根据DIN EN ISO 10283通过使用内标的气相色谱法测量残留单体含量。
摆锤硬度根据DIN EN ISO 1522:2007-04,用König摆锤,在标准化的线圈测试板上(线圈涂层黑色-CS 200570,Heinz Zanders Prüf-Blech-Logistik)测量。
化学品耐受性在标准化的线圈测试板上(线圈涂层黑色-CS 200570,HeinzZanders Prüf-Blech-Logistik)测量。 将浸有测试物质(二甲苯或水)的棉球放在漆表面上,并盖上表面皿。在给定的负荷时间之后,除去浸有测试物质的棉花,将负荷的位置擦干并立即检查。 评估漆表面的软化或变色。所述评估根据DIN EN ISO 4628-1如下进行:
0 无,即无明显损坏
1 非常少,即小的,刚好显著数量的损坏
2 少,即小的,但显著数量的损坏
3 中等多的损坏
4 相当多数量的损坏
5 非常多的损坏。
除非另有明确说明,否则所有%数据均指重量百分比。
制备包含脲二酮基团的交联剂(交联剂1, 制备实施例)
在室温下,在干燥的氮气和搅拌下,向1000 g(4.50 mol)的异佛尔酮二异氰酸酯(IPDI)中依次掺入10 g(1%)的亚磷酸三异癸酯和20 g(2%)的4-二甲基氨基吡啶(DMAP)作为催化剂。 20小时后,借助于薄膜蒸发器,在160℃的温度和0.3 mbar的压力下,将NCO含量为28.7%(相当于具有21.8%的低聚度)的反应混合物除去挥发性成分,而没有事先添加催化剂毒物。得到浅黄色的脲二酮多异氰酸酯,其游离NCO基团含量为17.0%,计算确定的脲二酮基团含量为20.8%,单体IPDI含量为0.4%,粘度大于200 000 mPas。
在室温下,在干燥的氮气下将337 g 1,4-丁二醇,108 g 2-乙基己醇和569 g e-己内酯混合,掺入0.3 g辛酸锡(II),并在160℃下搅拌5小时,随后冷却至室温。 然后在30分钟内向该混合物中加入加热至80℃的1850g前述基于IPDI的含脲二酮基团的多异氰酸酯。 将反应混合物在最高100℃的温度下搅拌,直至在7至8小时后该反应混合物的NCO含量降至0.8%的值。为了使其凝固,将反应混合物倒在金属板上,粉碎,然后溶解在丙酮中,从而产生具有70重量%固体比例的溶液。
实施例1-3(根据本发明)
实施例1
表1
称量(g)
部分1: 聚酯1 875
二羟甲基丙酸 55
2-乙基己酸锡(II) 1.4
丙酮 471
部分2: 六亚甲基二异氰酸酯 169
部分3: 交联剂1(70%在丙酮中) 458
部分4: 二甲基乙醇胺 36
部分5: 蒸馏水 1384
在氮气下,将来自表1的部分1称量到搅拌装置中并在60℃下均化1小时。然后在55℃下计量加入部分2,从而由于放热产生回流。将反应混合物保持在回流下直至NCO含量降到低于0.05%。然后将反应混合物冷却到50℃,并加入部分3且在50℃下搅入1小时。然后加入部分4并搅拌30分钟。最后,在15分钟时间内搅入部分5并在真空下蒸馏出丙酮。
得到具有以下特征数据的分散体:
固体含量 49.8重量%
酸值(100%的) 20mgKOH/g
OH含量(100%的,计算值) 1.9重量%
平均粒度 143nm
粘度 640mPas
pH值 7.8。
分散体在23℃下稳定保持14个月。
实施例2
实施例2如实施例1般来制备,区别是,使用718克交联剂1溶液和38克二甲基乙醇胺。所得分散体具有下列特征数据:
固体含量 42.6重量%
酸值(100%的) 18mgKOH/g
OH含量(100%的,计算值) 1.7重量%
平均粒度 180nm
粘度 850mPas
pH值 8.0。
该分散体在23℃下稳定保持14个月。
实施例3
实施例3如实施例1般来制备,区别是,使用下表2中所示的量的架构。
表2
重量(g)
部分1: 聚酯1 759
二羟甲基丙酸 60
2-乙基己酸锡(II) 1.3
丙酮 667
部分2: 六亚甲基二异氰酸酯 181
部分3: 交联剂1(70%在丙酮中) 1043
部分4: 二甲基乙醇胺 42
部分5: 蒸馏水 1690
如此得到的分散体具有以下特征数据:
固体含量 40.0重量%
酸值(100%) 17mgKOH/g
OH含量(100%,计算值) 1.2重量%
平均粒度 261nm
粘度 320mPas
pH值 7.6。
分散体在23℃下稳定保持10个月。
实施例4(对比)
在室温下,在干燥的氮气和搅拌下,向1000 g(4.50 mol)的异佛尔酮二异氰酸酯(IPDI)中依次掺入10 g(1%)的亚磷酸三异癸酯和20 g(2%)的4-二甲基氨基吡啶(DMAP)作为催化剂。 20小时后,借助于薄膜蒸发器,在160℃的温度和0.3 mbar的压力下,将NCO含量为28.7%(相当于具有21.8%的低聚度)的反应混合物除去挥发性成分,而没有事先添加催化剂毒物。
得到浅黄色的脲二酮多异氰酸酯,其游离NCO基团含量为17.0%,并且粘度大于200 000 mPas。
使219 g前述的基于IPDI的具有17.0%的游离异氰酸酯基团含量和20.8%的脲二酮基团计算含量的含脲二酮基团的多异氰酸酯在干燥的氮气下达到80℃,在氮气下称量到搅拌装置中并在室温下溶解在849 g丙酮中。然后将22.9 g二羟甲基丙酸和2.11 g 2-乙基己酸锡(II)计量加入到该均匀溶液中,从而通过放热产生回流。将反应混合物保持在回流下直至达到2.2%的NCO含量。然后向反应混合物中加入265.9 g聚酯1,并在回流下搅拌至反应混合物的NCO含量降到低于0.1%的值,冷却到50℃。在冷却到23℃后,将16.8 g二甲基乙醇胺添加到反应混合物中并搅拌30分钟。最后,在15分钟内搅入1451 g蒸馏水,并在真空下蒸馏出丙酮。得到具有以下特征数据的分散体:
固体含量 37.62重量%
平均粒度 91 nm
粘度 30 mPas
pH值 8.0。
在23℃下6个月后,该分散体显示出沉降物,并在40℃下储存6天后完全胶凝。
漆技术测试:
实施例5-7(根据本发明)
由以下组合物制备透明清漆(所有称量以g为单位):
表3
实施例 5 6 7
来自实施例1的组合物 10.00
来自实施例2的组合物 10.00
来自实施例3的组合物 10.00
将分散体在Speed Mixer中以2000转/分钟混合1分钟,用刮刀以180μm(湿)的层厚度施加在线圈-金属板上。将具有施加的湿漆的板在室温下通风干燥5分钟,随后在180℃下烘烤30分钟,并在室温下储存4天。对储存的膜的应用技术方面进行评估(表4)。
表4
实施例 5 6 7
漆的外观(视觉检查) 满意 满意 满意
膜厚度(干,µ) 50 60 50
摆锤硬度 (s) 95 145 200
二甲苯耐受性 (5 分钟) 3 3 3
去离子水(1小时) 1 1 0
从表4中可以看出,根据本发明的含脲二酮的分散体产生了硬的且耐受的漆。

Claims (14)

1.含脲二酮基团的水性组合物,其包含或由以下组分组成
(A) 至少一种基于脂族、脂环族、芳脂族和/或芳族多异氰酸酯的含脲二酮基团的固化剂,其不包含化学键合的亲水化基团;
(B) 至少一种包含羟基的多元醇,其包含至少一个化学键合的羧酸基团;
(C) 任选的溶剂;和
(D) 任选的助剂和添加剂;
其中如此计量组分(A)和(B)的量比,使得固化剂(A)的作为脲二酮存在的NCO基团与多元醇(B)的NCO-反应性基团的摩尔比为3.0:0.5至0.5:3.0, 并且其中A和B作为物理混合物存在。
2.根据权利要求1的组合物,其特征在于,
所述至少一种含脲二酮基团的固化剂(A)通过单体异氰酸酯的反应获得,所述单体异氰酸酯包含或由至少一种选自以下的单体异氰酸酯组成:四亚甲基二异氰酸酯,环己烷-1,3-二异氰酸酯和环己烷-1,4-二异氰酸酯,五亚甲基二异氰酸酯,六亚甲基二异氰酸酯(HDI),1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷 (异佛尔酮二异氰酸酯IPDI),二环己基甲烷-2,4’-二异氰酸酯和/或二环己基甲烷-4,4’-二异氰酸酯,四甲基苯二亚甲基二异氰酸酯 (TMXDI),三异氰酸根合壬烷,甲苯二异氰酸酯 (TDI),二苯基甲烷-2,4’-二异氰酸酯和/或二苯基甲烷-4,4’-二异氰酸酯 (MDI),三苯基甲烷-4,4’-二异氰酸酯或萘-1,5-二异氰酸酯或者它们的混合物。
3.根据权利要求1或2的组合物,其特征在于,
使用含羟基的单体和/或聚合物作为所述至少一种含脲二酮基团的固化剂 A的原料。
4.根据前述权利要求中任一项的组合物,其特征在于,
所述至少一种含脲二酮基团的固化剂 A的游离NCO含量小于5重量%,脲二酮基团的含量为1至18重量%(作为C2N2O2计算,分子量为84 g/mol)。
5.根据前述权利要求中任一项的组合物,其特征在于,
所述水性组合物的酸值为1至100 mg KOH/g。
6.根据前述权利要求中任一项的组合物,其特征在于,
通过羟基羧酸或氨基羧酸的反应获得所述至少一种包含羟基的多元醇(B),所述羟基羧酸或氨基羧酸包含或由选自下述的至少一种羧酸组成:2,2-二羟甲基乙酸、2,2-二羟甲基丁酸、2,2-二羟甲基戊酸、二羟基琥珀酸、α,Ω-二氨基戊酸或其混合物,优选选自二羟甲基丙酸或羟基新戊酸。
7.根据前述权利要求中任一项的组合物,其特征在于,
所述至少一种包含羟基的多元醇(B)的OH含量大于1重量%,作为OH基团基于固体含量计算,分子量17 g/mol,和数均分子量Mn为500至20 000 g/mol。
8.根据前述权利要求中任一项的组合物,其特征在于,所述溶剂选自丙酮,甲乙酮,乙酸乙酯,乙酸丁酯,二甲苯,重苯,丙二醇单正丁醚,二丙二醇二甲醚,乙酸甲氧基丙酯,二酯或者它们的混合物。
9.根据前述权利要求中任一项的组合物,其特征在于,所述助剂和添加剂选自流平剂,光保护剂,催化剂,填料,和颜料或者它们的混合物。
10.根据前述权利要求中任一项的组合物,其特征在于,(A)、(B)和(D)的重量比例之和为30至60重量%,基于整个水性组合物的固体含量计。
11.制备聚氨酯层的方法,包括以下步骤
i) 提供根据权利要求1至10中任一项的含脲二酮基团的水性组合物;
ii) 将在i)中获得的混合物施加在基材上;
iii) 干燥得自步骤ii)的混合物,和
iv) 加热到40℃至180℃,至多180分钟,使得自步骤iii)的混合物固化。
12.根据权利要求11的方法,其特征在于,所述含脲二酮基团的水性组合物通过在不存在水的情况下将所述含脲二酮基团的固化剂A与所述至少一种含羟基的多元醇B混合,随后用水分散而得到。
13.可通过根据权利要求11或12的方法得到的聚氨酯层,特别是聚氨酯膜。
14.用根据权利要求13的聚氨酯层涂覆或粘合的基材。
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