CN1217009A - 具有有机聚合物壳的预交联硅氧烷弹性体颗粒作为水性涂料配制料的配方成分 - Google Patents
具有有机聚合物壳的预交联硅氧烷弹性体颗粒作为水性涂料配制料的配方成分 Download PDFInfo
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- CN1217009A CN1217009A CN97194200A CN97194200A CN1217009A CN 1217009 A CN1217009 A CN 1217009A CN 97194200 A CN97194200 A CN 97194200A CN 97194200 A CN97194200 A CN 97194200A CN 1217009 A CN1217009 A CN 1217009A
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
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- C—CHEMISTRY; METALLURGY
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- 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
具有有机聚合物壳的预交联硅氧烷弹性体颗粒被用作配制基于水溶性或水稀释性粘结剂的水性漆组合物的成分。该硅氧烷弹性体颗粒含:(a)基于该共聚物总重量5-95wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核聚合物,其中x=5-99.5mol%,y=0.5-95mol%,z=0-30mol%,以及(b)基于该共聚物总重量5-95wt%的来自单-或多烯属不饱和单体的有机聚合物而制成的壳;且R表示相同或不同的具有1-6个碳原子的一价烷基或链烯基、芳基或取代烃基。
Description
本发明涉及具有有机聚合物壳的预交联硅氧烷弹性体颗粒作为在基于水溶性或水可稀释的水性涂料组合物中配方成分的用途。
水性涂料包括在水中可溶解或可稀释的粘结剂;水可稀释的粘结剂包括已经被乳化或赋予自乳化性能的树脂组分和树脂,和水分散体。水溶性粘结剂的例子是改性醇酸树脂,丙烯酸酯树脂,线性和支化的饱和聚酯树脂,环氧树脂,紫胶(shellac)和改性的酚醛树脂。水稀释性粘结剂的例子是一任意性地加以改性的-分散的或水可分散的,不饱和和饱和聚酯树脂,醇酸树脂乳化物,聚氨酯分散体,单组分环氧树脂乳化物,可乳化的双组分环氧树脂体系,可分散的醇酸树脂,酚醛树脂,蜜胺树脂和尿素树脂,(甲基)丙烯酸酯分散体,(甲基)丙烯酸酯共聚物分散体,聚苯乙烯和苯乙烯共聚物分散体,聚(乙烯基醚)分散体,和聚氯乙烯和聚偏氯乙烯分散体。
除水溶性或水可稀释的粘结剂外,水性涂料通常包括颜料,填料,水溶性交联剂和交联催化剂,以及其它添加剂如,流平助剂,脱挥发分助剂和润湿剂。
这些组合物以水性形式被涂敷到,例如金属基底,矿物基底,塑料,木材,纸张或玻璃上。在涂敷后,含水膜干燥成固体涂膜。在常温(室温)下干燥的膜,在空气中干燥后,任意性地在至多100℃的温度下进行热调理/后干燥。对于其它类型的水性涂料,如果后者需要两种或多种粘结剂组分的化学反应(后交联),则成膜需要更高的温度(120-220℃)。
所列举的水溶性和水可稀释的粘结剂主要包括热塑性或热固性聚合物,它们通常硬而不脆。因此,为了提高膜的性能,通常需要进行聚合物体系的冲击性改性。硅氧烷是已知的热塑性和热固性塑料的改性剂,而且是特别有用的,因为它们不但增加了热塑性或热固性有机聚合物体系的冲击强度而且改进了它们的低温柔软性,耐候稳定性,波动温度应力的稳定性和耐化学性。然而,通常不利的是硅氧烷与有机聚合物的基本不相溶性。不相容性导致在使用过程中的流动缺陷,同时硅氧烷的迁移导致附着力问题以及与再涂性有关的各种问题。
在DE-A3922285(=GB-A2222167)(Dow Coming,公开于25.01.90)中,已知的硅氧烷与有机聚合物的不相容性被用于装饰;该文描述了一种由聚二有机基硅氧烷和成膜用聚合物材料的水分散体组成的涂料组合物,以获得锤纹表面效果。这种硅氧烷不适合水性涂料的冲击性改性,因为聚硅氧烷以乳化的形式作为液体存在于水相中而不是作为分散的颗粒存在。以用于冲击性改性的量使用,这些化合物会从涂膜体中渗出。
EP-A586048(Shin Etsu,公开于09.03.94)描述了二醇官能化硅油作为添加剂添加到水性涂料中以降低表面张力和改进基底润湿性;在该确定的用途中,这些硅氧烷比聚醚改性硅油显示出更好的流动性。这种硅氧烷,以乳化形式存在,不适合于冲击性改性。该文献继续描述了,所使用的量大于5wt%时,用这些化合物改性的聚合物膜的机械强度下降。
WO-A93/14169(Crompton Garland Ltd.,公开于22.07.93)描述了一种可交联水性酚醛树脂乳剂和硅氧烷树脂乳剂的配制料。在酚醛树脂组分的交联过程中,硅氧烷以化学键连接在酚醛树脂上,其结果硅氧烷组分作为增塑剂包含在酚醛树脂基质中。US-A4803233(DowComing,授权于07.02.89)描述了包括有机聚合物,硅氧烷树脂和三种不同非离子乳化剂的混合物的水性混合物。依聚合物体系和硅氧烷组分而定,所添加的硅氧烷树脂会导致-在某些情况下,只在均匀共混物的热处理后-涂料提高的拉伸强度,附着性和耐腐蚀性。
冲击强度的改进连同硬度的保留既没有描述在WO-A93/14169中也没有描述在US-A4803233中。其中没有受到控制的微相分离,因为所涉及的物质不是具有特定结构的有机聚合物相容改性剂。
EP-A541395(Takemoto,公开于12.05.93)描述了热塑性聚酯膜的水性涂料组合物,该组合物基于聚硅氧烷-聚乙烯基接枝共聚物的含水乳液。这些水性粘结剂体系改进了聚酯膜的表面性能,如光滑度,防粘性,和防水防油性。在此情况下,接枝共聚物不被用作水性涂料中有机聚合物防粘剂的改性剂而是作为水性涂料组合物被使用,在本申请文本中,有可能使用该水性涂料组合物来获得热塑性聚合物膜的特定的表面性能。
WO-A90/08810(ICI Australia Operations Proprietary Ltd.,公开于09.08.90)描述了基于含硅氧烷的聚合物的水性涂料组合物,所谓“多聚合物”颗粒。该“多聚合物颗粒”是通过将单体与硅氧烷聚合物的混合物进行聚合反应来制备的。在此情况下,硅氧烷组分必须在聚合物制备之前添加到单体/多种单体中,不能作为配方成分添加到(仅是任意的)水性粘结剂体系中。在该情况中所获得的的水可稀释的粘结剂体系中硅氧烷组分增强了,例如涂料的UV稳定性;但没有描述冲击强度的改进。再者,在该情况中,没有受到控制的微相分离,因为所使用的硅氧烷组分是不包括具有特定结构的有机聚合物相容性改性剂的液体或树脂。
本发明的目的是提供基于有机聚合物粘结剂的水性涂料组合物(即水性涂料)的改性剂,它们与有机聚合物粘结剂高度相容,而且使用该物质有可能改进由此获得的膜强度,与此同时,保留了现有的所需聚合物的性能,如硬度、尺寸稳定性和机械强度。
本发明提供了具有有机聚合物壳的预交联硅氧烷弹性体颗粒作为基于水溶性或水可稀释的粘结剂的水性涂料组合物中配制成分的用途,其中硅氧烷弹性体颗粒包括:
a)占共聚物总重量5-95wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核心聚合物,其中x=5-99.5mol%,y=0.5-95mol%,z=0-30mol%,和
b)占共聚物总重量5-95wt%的单或多烯属不饱和单体的有机聚合物的壳,且R表示相同或不同的具有1-6个碳原子的一价烷基或链烯基,芳基或取代烃基。
另外,本发明还提供了基于水溶性或水可稀释的粘结剂的水性涂料组合物,它包括作为配制料成分的、具有有机聚合物壳的预交联硅氧烷弹性体颗粒,其中硅氧烷弹性体颗粒包括:
a)占共聚物总重量5-95wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核心聚合物,其中x=5-99.5mol%,y=0.5-95mol%,z=0-30mol%,和
b)占共聚物总重量5-95wt%的单或多烯属不饱和单体的有机聚合物的壳,且R表示相同或不同的具有1-6个碳原子的一价烷基或链烯基,芳基或取代烃基。
被用作配方成分的具有有机聚合物壳的预交联硅氧烷弹性体颗粒和它们的制备方法被描述在EP-A492376(US-A5223586)中。预交联硅氧烷弹性体颗粒是指,在此情况下,这些颗粒通过按比例定量配合(RSiO3/2)和(SiO4/2)单元的方式被交联。
具有有机聚合物壳的硅氧烷弹性体颗粒优选包括:
a)占共聚物总重量20-80wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核心聚合物,其中x=50-99mol%,y=1-50mol%,z=0-20mol%,和
b)占共聚物总重量20-80wt%的单或多烯属不饱和单体的有机聚合物的壳,且R具有上述意义。
基团R优选是烷基如甲基,乙基,正丙基,异丙基,正丁基,仲丁基,戊基,己基;链烯基如乙烯基,烯丙基,丁烯基和1-己烯基;芳基如苯基;或取代的烃基如卤代烃基,巯基烷基,氰基烷基,氨基烷基,酰氧基烷基,羟基烷基。
特别优选的基团是甲基,乙基,丙基,苯基,乙烯基,烯丙基,1-己烯基,3-甲基丙烯酰基丙基(3-methacryloxypropyl),3-巯基丙基,其中在硅氧烷聚合物中,30mol%以下的基团是乙烯基,3-甲基丙烯酰基丙基或3-巯基丙基。
作为有机聚合物组分b)的单体,优选使用丙烯酸酯或甲基丙烯酸酯以及富马酸和马来酸与脂族醇类和具有1-10个碳原子的二醇类的单和二酯,丙烯酰胺和甲基丙烯酰胺,丙烯腈,苯乙烯,对-甲基苯乙烯,邻-甲基苯乙烯,二乙烯基苯,乙酸乙烯酯,丙酸乙烯酯,马来酰亚胺,氯乙烯,单和二乙烯基醚,乙烯,丁二烯,异戊二烯和氯丁二烯。特别优选的是苯乙烯和具有1-4个碳原子的脂族醇类的丙烯酸酯和甲基丙烯酸酯,例子是(甲基)丙烯酸甲酯,(甲基)丙烯酸丁酯和(甲基)丙烯酸缩水甘油酯。这些单体的均聚物和共聚物适合用作有机聚合物组分。
极细散的接枝共聚物优选具有10-300nm的平均粒径,特别优选30-150nm。粒度可以在上述范围内变化,优选具有多分散性指数不超过σ2=0.2的单峰型粒度分布。
聚硅氧烷接枝基础物是按乳化聚合反应方法通过将RaSi(OR′)4-a型单体硅烷,其中a=0,1或2,或若需要,通式(R2SiO)n型低分子量硅氧烷,其中n=3-8的相应混合物计量加入到搅拌的乳液/水混合物中来制备的。基团R具有上述意义。R′表示具有1-6个碳原子的烷基,芳基或取代的烃基;甲基,乙基和丙基是优选的。硅烷或硅烷混合物或硅烷/硅氧烷混合物以计量形式加入。乳液聚合反应是在30-90℃,优选60-85℃的温度和优选在大气压下进行的。聚合反应混合物的pH值是1-4,优选2-3。所使用的合适的乳化剂和其用量被描述在EP-A492376中。
为了获得单峰型粒度分布,优选在制备聚硅氧烷接枝基础物的过程中略去均化步骤。在进一步优选的实施方案中,在接枝基础物的聚合反应之后,通过蒸馏除去在该聚合反应中所形成的醇,和任何其它挥发性成分。
合适的硅烷的例子,对于通式R2Si(OR′)2的硅烷,是二甲基二乙氧基硅烷或二甲基二甲氧基硅烷;对于通式(R2SiO)n,其中n=3-8的低聚物,是八甲基环四硅氧烷或六甲基环三硅氧烷;对于通式RSi(OR′)3的硅烷,是甲基三甲氧基硅烷,苯基三乙氧基硅烷,3-氯丙基三甲氧基硅烷,3-巯基丙基三甲氧基硅烷,或甲基丙烯酰基丙基三甲氧基硅烷;和对于通式Si(OR′)4的硅烷,是四甲氧基硅烷或四乙氧基硅烷。
在制备方法的最后一步中,已经提到的烯属不饱和单体被接枝到聚硅氧烷接枝基础物上。接枝过程是在水溶性或单体可溶性自由基引发剂存在下,通过在EP-A492376中所述的程序,根据乳化聚合反应方法进行的。使用该程序,具有有机聚合物壳的预交联硅氧烷弹性体能够以它们的水分散体形式获得。优选确定水分散体的固体含量为10-60wt%,特别优选15-50wt%。
硅氧烷核的交联度决定了它的弹性性能,而且能够以熟练技术人员熟悉的方式通过适当选择起始组分、相应的烷氧基硅烷和/或硅氧烷以获得单元(RSiO3/2)或(SiO4/2)来确定。在随后的接枝聚合反应中,包括烯属不饱和双键的硅烷单元,例如乙烯基或3-甲基丙烯酰基丙基的硅烷单元的引入使得能够通过共价键将有机聚合物壳以化学键连接到硅氧烷核上。通过选择合适的合成有机聚合物壳b)所用的单体,有可能定制各种有机聚合物壳。
例如,通过将包括例如甲基丙烯酸甲酯(高玻璃化转变温度)和丙烯酸正丁酯(低玻璃化转变温度)的共聚物壳接枝到交联硅氧烷核上,有可能确定聚合物壳的软化温度,并由此准确地符合与水性涂料组分的加工和涂敷性能有关的要求。一方面,通过将包括例如甲基丙烯酸甲酯和甲基丙烯酸缩水甘油酯的共聚物壳接枝到交联硅氧烷核上,有可能通过甲基丙烯酸缩水甘油酯引入环氧官能团,在水性涂料组合物的改性剂颗粒和粘结剂树脂之间获得基质连接,另一方面,这些改性剂颗粒能够用作基于聚酯树脂的粘结剂中的交联剂。
因此,最优选的是具有包括(R2SiO2/2)x·(RSiO3/2)y(其中x=80-99mol%和y=1-20mol%,R可以相同或不同且R=甲基和/或3-甲基丙烯酰基丙基)的核和具有聚(甲基丙烯酸甲酯)的壳或包括甲基丙烯酸甲酯和丙烯酸丁酯和/或甲基丙烯酸缩水甘油酯的共聚物壳的交联硅氧烷弹性体颗粒。
核聚合物占共聚物总重量的比例特别优选为50-80wt%;因此,有机聚合物壳的比例特别优选为20-50wt%。这与25-100%的有机聚合物的接枝度相对应。
具有有机聚合物壳的预交联硅氧烷弹性体颗粒的添加特性和作为水分散体的引入的难易程度使得可以与水性涂料的所有普通的粘结剂体系一起使用。水性涂料的粘结剂的例子,对于水溶性粘结剂,是改性醇酸树脂,丙烯酸酯树脂,线性和支化饱和聚酯树脂,环氧树脂,紫胶(shellac)和改性的酚醛树脂。水可稀释的粘结剂的例子一任意性地改性的-分散的或水可分散的不饱和和饱和聚酯树脂,醇酸树脂乳液,聚氨酯分散体,单组分环氧树脂乳液,可乳化的双组分环氧树脂体系,可分散的醇酸树脂,酚醛树脂,蜜胺树脂和尿素树脂,(甲基)丙烯酸酯分散体,(甲基)丙烯酸酯共聚物分散体,聚苯乙烯和苯乙烯共聚物分散体,聚(乙烯基醚)分散体,和聚氯乙烯和聚偏氯乙烯分散体。
为了改性,具有有机聚合物壳的预交联硅氧烷弹性体优选以它们的水分散体形式,若需要作为分散体粉末,通常以0.5-50wt%、优选1.0-3.0wt%的量添加到水性涂料配制料中,在每种情况下,硅氧烷弹性体分数是以硅氧烷弹性体组分和粘结剂组分总重量为基础的。适合于水性涂料的配制料对熟练的技术人员是已知的,例如从H.Kittel(ed.),Lehrbuch der Lacke und Beschichtungen,VolumeIV,Verlag W.A.Colomb,Berlin,Oberschwandorf,1976中已知。
根据配制水性涂料的常规步骤,使用搅拌器或分散工具来进行添加。在此情况下,将具有有机聚合物壳的预交联硅氧烷弹性体的水分散体与水性涂敷配制料的组分如粘结剂,水,交联剂,催化剂,颜料,增稠剂,填料按照任何需要的次序混合。优选在+1至+90℃,特别+5至+60℃的温度下进行混合(配料)。
不管是普通的溶剂基涂料还是非改性水性涂料,原则上可以使用根据本发明改性的水性涂料。
它们发现了许多用途,尤其用于涂敷大型钢结构的金属物,(例如桥梁,贮罐,起重机和传输设备,管路,矿物和油抽提设备,钢厂和化学厂的部件),用于涂覆汽车部件(透明漆层,面漆,内用末道漆,二道底漆,石击性保护漆和底部保护漆,如小汽车、卡车、客车、建设工地(building-site)和农业用车辆的修补漆)和轨道约束车辆中的金属,货物集装箱,飞机,船舶(在各种情况下为外用罩面漆),以及用于在家用电器(卧式冷冻柜,冰箱,洗碗机,洗衣机,电烤炉等)和金属包装材料(桶和容器等)的进一步处理(卷材涂覆)之前涂覆金属基底。它们还可以用于家具(木质家具,金属家具,灯具等)、室内和室外装饰组件(从木料、钢材、非铁金属和非铁合金、塑料、混凝土、灰浆、石膏制造,例如窗框,室外镶板,门,大门,檐槽,地板,楼梯,建筑物正面组件(facade components),墙体,天花板,加热器和辐射器,罐,线路),自行车,信号箱,轮缘的漆层中。
在实施例中的试验结果显示了,水性涂料的(冲击)韧性可以通过添加具有有机聚合物壳的预交联硅氧烷弹性体来加以改进,而对涂敷体系的附着力和它们的表面性能没有影响,只对涂敷体系的硬度稍有影响。从对比例可以看出,添加没有有机聚合物壳的硅氧烷弹性体颗粒,尽管也能够改进(冲击)韧性,然而对涂料的硬度和它们的表面性能有较大负面影响;因此,所需要的不仅是被控制的微相分离而且同时是改性剂颗粒与干燥涂膜中的聚合物基质之间具有良好的相容性。
在实施例中获得良好结果的原因是由于交联硅氧烷相的存在,本发明的冲击性改性剂以具有所限定的粒度和形态的单独、离散的微相形式引入热塑性或热固性体系中。只有完全的相分离才使得不存在聚合物基质的不希望有的软化,该软化作用将导致对聚合物基质的性能如硬度,尺寸稳定性和机械强度下降或对其产生负面的影响。此外,有机聚合物壳使得颗粒状改性剂与涂料粘结剂的聚合物基质具有良好的相容性。事实上,有机聚合物壳对分散体形式的预交联硅氧烷弹性体颗粒与水溶性或水可稀释的粘结剂的可混性/胶体相容性不是绝对必要的;然而,在干燥后,对颗粒与基质的聚合物相容性是必要的。颗粒结构和颗粒的聚合物相容性借助于粒径给出了改性剂相的畴尺寸的精确定义。因为预交联硅氧烷弹性体颗粒完全与有机聚合物壳接枝,所以不会产生污染问题,附着性问题,沉降问题和流动缺陷。所得的涂敷层是可再涂的。
以下的实施例用于说明本发明:实施例1-2,对比例1-3:
在实施例1和2以及对比例1-3中,制备具有表1所示组成的聚酯涂料配制料。
在根据本发明的实施例中,使用了分散体A。在对比例2和3中,使用了分散体B。对比例1的涂料配制料对应于普通的、未改性水性涂料。分散体A:
具有包括[R2SiO2/2]x·[R′SiO3/2]y,(x=95mol-%,y=5mol-%,R=甲基,R′=甲基和3-甲基丙烯酰基丙基)的核和聚甲基丙烯酸甲酯的壳(PMMA接枝度为50wt%)的硅氧烷颗粒的水分散体;初级粒径约100nm,具有有机聚合物壳的硅氧烷颗粒的固体含量为26.3%。分散体B:
由[R2SiO2/2]x·[RSiO3/2]y,(x=95mol-%,y=5mol-%,R=甲基)组成的硅氧烷颗粒水性分散体;初级粒径约100nm,硅氧烷颗粒的固体含量为19%。
为了制备列于表1的水性涂料配制料(实施例1-2,对比例1-3),其中指定的组分在常温下借助溶解器一起混合20-30分钟。
为了进行试验,借助螺旋刮膜刀(spiral film-drawing doctorblade),将水性涂料配制料涂敷到金属板上。在室温(22℃)下干燥,在板涂敷后让该试验进行三天。试验结果列于表1中。
使用了以下试验方法:表面性质:
通过膜表面的视觉评价来定性地估计表面性质。再涂性:
为了评价再涂性,用实施例1/2和对比例1-3的涂料配制料涂敷的金属板在各种情况下再次使用相同的涂料配制料进行再涂敷。由视觉观察来定性地估计再涂性。再涂敷后,涂层间附着力:
为了确定涂层间附着力,在干燥三天后,检查用铅笔刀能否将上层涂膜部分地除去。当发现没有除去时,涂层间附着力被评价为“良好”。反向冲击:
反向冲击是通过埃里克森落球冲击试验机304型的落球冲击试验来测定的。柯尼希摆杆硬度:
柯尼希摆杆硬度是根据DIN 53137来测试的。埃里克森压痕:
埃里克森压痕是根据DINISO 1520来测试的。交叉线(cross-hatch):
交叉线是由DIN 53151来确定的。
结果表明,通过添加本发明的具有PMMA壳的硅氧烷弹性体颗粒(实施例1和2),(冲击)韧性(反向冲击)显著地得到改进,膜硬度略微有所降低并且对膜的附着力和表面性能没有负面的影响。尽管当使用没有有机聚合物壳的硅氧烷弹性体颗粒(对比例2和3)时,(冲击)韧性可以改进到可比的程度,然而再涂敷后,膜硬度、表面性能和附着力明显受到了不利的影响。
表1:
实施例1 | 实施例2 | 对比例1 | 对比例2 | 对比例3 | |
组分[重量份]1、Halwedrol OX47-2/40Wa)(40%,在水中)2、Kronos TiO2-2130b)3、分散体A4、分散体B5、Reolate 255c) | 50.025.012.5-0.5 | 50.025.023.0-0.5 | 50.025.0--0.5 | 50.025.0-12.50.5 | 50.025.0-23.00.5 |
具有PMMA壳的硅氧烷弹性体颗粒占粘结剂的比例,(固体/固体),%硅氧烷弹性体颗粒占粘结剂的比例,(固体/固体),%硅氧烷组分占粘结剂的比例(固体/固体)干膜厚,μm | 16-1126 | 30-2026 | ---28 | -121232 | -222231 |
表1(续)
a)从Hüttenes-Albertus Lackrohstoffe得到的脂肪酸改性的聚酯树脂b)从Kronos-Titan得到的二氧化钛颜料c)从Kronos-Titan得到的聚丙烯酸酯基增稠剂实施例3和4,对比例4:
实施例1 | 实施例2 | 对比例1 | 对比例2 | 对比例3 | |
机械性能值反向冲击(in×1bs)柯尼希摆杆硬度埃里克森压痕(mm,钢板)交叉线表面 | 4056>6Gt0光滑 | 6054>6Gt0光滑 | 1267>6Gt0光滑 | 4646>6Gt0粗糙 | 6042>6Gt0粗糙 |
再涂性 | 是 | 是 | 是 | 是 | 是 |
再涂敷后,涂层间附着力 | 良好 | 良好 | 良好 | 中等 | 中等 |
该方法类似于实施例1/2和对比例1-3,所不同的是,对基于双组分环氧树脂涂料的水性涂料进行了试验。在根据本发明的实施例3和4中,分散体A再次用于改性。对比例4的涂料配制料没有被改性。
为了制备列于表2(实施例3-4,对比例4)的水性涂料配制料,其中指定的组分在常温下借助溶解器一起混合20-30分钟。借助螺旋刮膜刀,将水性涂料配制料涂敷到铝板和金属板上。在室温(22℃)下干燥。在板涂敷后,按照与上述试验说明中类似的方式进行三天试验。试验结果列于表2中。
结果表明,通过添加本发明的具有PMMA壳的硅氧烷弹性体颗粒(实施例3和4),(冲击)韧性(反向冲击)显著地得到改进,膜硬度仅略有降低。
表2
a)从Air Products得到的,基于双酚A/F的双组分环氧树脂涂敷材料b)从Borchers得到的,基于脂肪酸酯的流平剂c)从Kronos-Titan得到的二氧化钛颜料d)从Sachtleben得到的基于硫酸钡的填料e)从Air Products得到的,聚胺加合物硬化剂
实施例3 | 实施例4 | 对比例4 | |
组分[重量份]1、Epires ER8(100%)a)2、Borchigol VL73 Sb)3、Kronos TiO2-2160c)4、分散体A5、Blanc Fix Microd)6、软化水7、Epilink DP700(55%,在水中)e) | 43.50.245.015.2510.0约2066.7 | 43.50.245.030.5010.0约2066.7 | 43.50.245.0-10.0约2066.7 |
具有PMMA壳的硅氧烷弹性体颗粒占粘结剂的比例,(固体/固体),%干膜厚(金属板),μm干膜厚(铝板),μm | 5.02423 | 10.02624 | -3333 |
机械性能值反向冲击(in×1bs)(金属板)反向冲击(in×1bs)(铝板)柯尼希摆杆硬度(金属板)柯尼希摆杆硬度(铝板) | 66408988 | >80468983 | 44118108 |
Claims (9)
1、具有有机聚合物壳的预交联硅氧烷弹性体颗粒作为在基于水溶性或水可稀释性粘结剂的水性涂料组合物中的配制成分的应用,其中硅氧烷弹性体颗粒包括:
a)占共聚物总重量5-95wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核聚合物,其中x=5-99.5mol%,y=0.5-95mol%,z=0-30mol%,和
b)占共聚物总重量5-95wt%的单或多烯属不饱和单体的有机聚合物的壳,且R表示相同或不同的具有1-6个碳原子的一价烷基或链烯基,芳基或取代烃基。
2、根据权利要求1的应用,其中具有有机聚合物壳的预交联硅氧烷弹性体颗粒以它们的水分散体形式使用,该水分散体的固体含量为10-60wt%。
3、基于水溶性或水可稀释性粘结剂的水性涂料组合物,它包括作为配方成分的具有有机聚合物壳的预交联硅氧烷弹性体颗粒,其中硅氧烷弹性体颗粒包括:
a)占共聚物总重量5-95wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核聚合物,其中x=5-99.5mol%,y=0.5-95mol%,z=0-30mol%,和
b)占共聚物总重量5-95wt%的单或多烯属不饱和单体的有机聚合物的壳,且R表示相同或不同的具有1-6个碳原子的一价烷基或链烯基,芳基或取代烃基。
4、根据权利要求1-3的组合物,其中具有有机聚合物壳的预交联硅氧烷弹性体颗粒包括:
a)占共聚物总重量20-80wt%的通式(R2SiO2/2)x·(RSiO3/2)y·(SiO4/2)z的核聚合物,其中x=50-99mol%,y=1-50mol%,z=0-20mol%,和
b)占共聚物总重量20-80wt%的单或多烯属不饱和单体的有机聚合物的壳,且R具有上述意义。
5、权利要求1-4的组合物,其中预交联硅氧烷弹性体颗粒包括(R2SiO2/2)x·(RSiO3/2)y的核,其中x=80-99mol%和y=1-20mol%,R可以相同或不同且R=甲基和/或3-甲基丙烯酰基丙基,和聚(甲基丙烯酸甲酯)的壳或甲基丙烯酸甲酯和丙烯酸丁酯和/或甲基丙烯酸缩水甘油酯的共聚物壳。
6、根据权利要求1-5的组合物,其中具有有机聚合物壳的预交联硅氧烷弹性体颗粒具有10-300nm的平均粒径。
7、根据权利要求1-6的组合物,其中具有有机聚合物壳的预交联硅氧烷弹性体颗粒具有多分散性指数不超过σ2=0.2的单峰型粒度分布。
8、根据权利要求1-7的组合物,其中具有有机聚合物壳的预交联硅氧烷弹性体颗粒以占硅氧烷弹性体组分和粘结剂组分总重量0.5-50wt%的量用于包括粘结剂、水、交联剂、催化剂、颜料、增稠剂、填料的该水性涂料配制料中。
9、根据权利要求1-8的组合物,其中粘结剂是从改性醇酸树脂、丙烯酸树脂、线性和支化的饱和聚酯树脂、环氧树脂、紫胶和改性的酚醛树脂中选择的水溶性树脂,或从不饱和和饱和聚酯树脂、醇酸树脂乳化物、聚氨酯分散体、单组分环氧树脂乳化物、可乳化的双组分环氧树脂体系、可分散的醇酸树脂、酚醛树脂、蜜胺树脂和尿素树脂、(甲基)丙烯酸酯分散体、(甲基)丙烯酸酯共聚物分散体、聚苯乙烯和苯乙烯共聚物分散体、聚(乙烯基醚)分散体、和聚氯乙烯及聚偏氯乙烯分散体中选择的水稀释性粘结剂。
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-
1996
- 1996-04-30 DE DE19617379A patent/DE19617379A1/de not_active Withdrawn
-
1997
- 1997-04-24 KR KR1019980708663A patent/KR100301382B1/ko not_active IP Right Cessation
- 1997-04-24 JP JP9538560A patent/JPH11508641A/ja active Pending
- 1997-04-24 AU AU27697/97A patent/AU710726B2/en not_active Ceased
- 1997-04-24 CA CA002251692A patent/CA2251692A1/en not_active Abandoned
- 1997-04-24 EP EP97921738A patent/EP0882105B1/de not_active Expired - Lifetime
- 1997-04-24 US US09/155,370 patent/US6147142A/en not_active Expired - Fee Related
- 1997-04-24 ES ES97921738T patent/ES2142162T3/es not_active Expired - Lifetime
- 1997-04-24 WO PCT/EP1997/002093 patent/WO1997041183A1/de active IP Right Grant
- 1997-04-24 DE DE59700758T patent/DE59700758D1/de not_active Expired - Fee Related
- 1997-04-24 CN CN97194200A patent/CN1217009A/zh active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105189116A (zh) * | 2013-04-23 | 2015-12-23 | 阿肯马法国公司 | 氟化膜 |
CN114846115A (zh) * | 2019-12-17 | 2022-08-02 | 瓦克化学股份公司 | 细分的颗粒稳定的水性皮克林乳液和由其制备的颗粒 |
CN114539836A (zh) * | 2021-10-27 | 2022-05-27 | 深圳市深赛尔股份有限公司 | 一种高硬度、高弹性水性风电叶片涂料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH11508641A (ja) | 1999-07-27 |
WO1997041183A1 (de) | 1997-11-06 |
DE59700758D1 (de) | 1999-12-30 |
KR100301382B1 (ko) | 2001-11-22 |
AU2769797A (en) | 1997-11-19 |
EP0882105A1 (de) | 1998-12-09 |
ES2142162T3 (es) | 2000-04-01 |
CA2251692A1 (en) | 1997-11-06 |
EP0882105B1 (de) | 1999-11-24 |
KR20000065082A (ko) | 2000-11-06 |
US6147142A (en) | 2000-11-14 |
AU710726B2 (en) | 1999-09-30 |
DE19617379A1 (de) | 1997-11-06 |
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