TWI747001B - High-solid and low-viscosity resin composition containing acrylic copolymer and preparation method thereof - Google Patents
High-solid and low-viscosity resin composition containing acrylic copolymer and preparation method thereof Download PDFInfo
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Abstract
本發明涉及一種包含丙烯酸類共聚物的高固低黏的樹脂組合物,其中,所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度,並且所述丙烯酸類共聚物的主鏈具有懸掛的聚(氧亞烷基)片段。 The present invention relates to a high-solid, low-viscosity resin composition comprising an acrylic copolymer, wherein the resin composition has a solid content of at least about 80 wt% based on the weight of the acrylic copolymer and uses BROOKFIELD at 25°C. The viscometer measures a viscosity of 130,000 mPa.s or lower, and the main chain of the acrylic copolymer has pendant poly(oxyalkylene) segments.
Description
本發明涉及一種高固低黏的樹脂組合物,具體涉及一種包含丙烯酸類共聚物的樹脂組合物。本發明還涉及包含所述樹脂組合物的溶劑基塗料組合物。 The invention relates to a high-solid and low-viscosity resin composition, in particular to a resin composition containing an acrylic copolymer. The present invention also relates to a solvent-based coating composition containing the resin composition.
近年來,隨著人們對環境的關注,很多國家已制定了環境法律,並要求進一步降低允許塗料組合物,特別是溶劑型塗料組合物,向空氣中釋放的揮發性有機化合物(Volatile Organic Compounds,VOC)量。例如,在中國自2015年2月起,VOC含量超過420g/L的溶劑型塗料組合物將被徵收額外消費稅,稅率高達4%,這將大大增加了塗料公司的成本。因此,對於用於配製VOC含量不超過420g/L的溶劑型塗料組合物的高固低黏樹脂組合物的需求急劇增加。 In recent years, with people’s concern about the environment, many countries have enacted environmental laws and require further reductions in the amount of volatile organic compounds (Volatile Organic Compounds, VOC) amount. For example, in China since February 2015, solvent-based coating compositions with a VOC content of more than 420g/L will be levied an additional consumption tax, with a tax rate of up to 4%, which will greatly increase the cost of coating companies. Therefore, the demand for high-solids and low-viscosity resin compositions for formulating solvent-based coating compositions with a VOC content of not more than 420 g/L has increased sharply.
現有技術已經公開了兩種常用於製備高固低黏的丙烯酸類樹脂組合物的方法,一種方法是使用縮水甘油基化合物。例如CN102702438公開了使用叔碳酸縮水甘油酯來製備高固低黏的丙烯酸樹脂。然而,由此得到的產品僅僅可以達到約70%的固含量,而且仍然含有較大量的有機溶劑。另一種方法是通過添加超支化改性劑。例如CN103319666A公開了使用超支化改性劑製備丙烯酸樹脂水性分散體。然而,該產品適用於水性塗料體系,僅僅可以達到45%的固含量。與水基塗料組合物相比,低VOC含量要求對於溶劑基塗料組合物顯得更難以實現。 The prior art has disclosed two methods commonly used to prepare high-solid, low-viscosity acrylic resin compositions. One method is to use glycidyl compounds. For example, CN102702438 discloses the use of glycidyl tertiary carbonate to prepare high-solid, low-viscosity acrylic resins. However, the resulting product can only reach a solid content of about 70%, and still contains a relatively large amount of organic solvents. Another method is by adding hyperbranched modifiers. For example, CN103319666A discloses the use of hyperbranched modifiers to prepare aqueous acrylic resin dispersions. However, this product is suitable for water-based coating systems and can only achieve a solid content of 45%. Compared with water-based coating compositions, low VOC content requirements are more difficult to achieve for solvent-based coating compositions.
此外,業已公開了多種高固低黏的丙烯酸類樹脂的商品,例如來自Arkema的854BA80、來自Niupeisi樹脂的Setalux 1753以及來自Bayer的A-870。但是,這些產品仍不能滿足塗料工業的需求。 In addition, many high-solid, low-viscosity acrylic resin products have been disclosed, such as 854BA80 from Arkema, Setalux 1753 from Niupeisi resin, and A-870 from Bayer. However, these products still cannot meet the needs of the coating industry.
因此,為了滿足低於420g/L的VOC含量要求,塗料工業仍需要進一步改進的固含量高、黏度相對較低且適用於溶劑基塗料組合物的丙烯酸類樹脂組合物。 Therefore, in order to meet the VOC content requirement of less than 420g/L, the coating industry still needs to further improve the acrylic resin composition with high solid content, relatively low viscosity and suitable for solvent-based coating composition.
一方面,本發明提供了一種包含丙烯酸類共聚物的樹脂組合物,其中,所述丙烯酸類共聚物的主鏈上具有懸掛的聚(氧亞烷基)片段,並且其中所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度。 In one aspect, the present invention provides a resin composition comprising an acrylic copolymer, wherein the main chain of the acrylic copolymer has a pendant poly(oxyalkylene) segment, and wherein the resin composition has A solid content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130,000 mPa.s or lower measured at 25° C. using a BROOKFIELD viscometer.
另一方面,本發明涉及用於製備上述包含丙烯酸類共聚物的樹脂組合物的方法,所述方法包括:在相對於所述樹脂組合物的總重,用量不超過20wt%的有機溶劑和自由基引發劑的存在下,使包含作為第一單體的含有聚(氧亞烷基)片段的烯屬不飽和單體、不同於所述第一單體的丙烯酸類單體和附加的烯屬不飽和單體的反應混合物進行共聚,從而形成所述樹脂組合物。 In another aspect, the present invention relates to a method for preparing the above-mentioned acrylic copolymer-containing resin composition, the method comprising: relative to the total weight of the resin composition, an amount of organic solvent and free In the presence of the base initiator, an ethylenically unsaturated monomer containing a poly(oxyalkylene) segment as the first monomer, an acrylic monomer different from the first monomer, and additional ethylenic The reaction mixture of unsaturated monomers is copolymerized, thereby forming the resin composition.
另一方面,本發明涉及含有聚(氧亞烷基)片段的烯屬不飽和單體用於製備根據本發明的高固低黏樹脂組合物的用途。 In another aspect, the present invention relates to the use of ethylenically unsaturated monomers containing poly(oxyalkylene) fragments for preparing the high-solid low-viscosity resin composition according to the present invention.
另一方面,本發明涉及一種VOC排放量低於420g/L的溶劑基塗料組合物,其包含本發明的樹脂組合物。 In another aspect, the present invention relates to a solvent-based coating composition with a VOC emission amount of less than 420 g/L, which comprises the resin composition of the present invention.
本發明的發明人開創性地提供了一種包含丙烯酸類共聚物的樹脂組合物,其中,所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度,並且其中所述丙烯酸類共聚物的主鏈具有懸掛的聚(氧亞烷基)片段。與此同時,根據本發明的樹脂組合物包含,相對於所述樹脂組合物的總重,至多20wt%的有機溶劑。 The inventors of the present invention groundbreakingly provide a resin composition containing an acrylic copolymer, wherein the resin composition has a solid content of at least about 80 wt% based on the weight of the acrylic copolymer and a solid content at 25° C. A BROOKFIELD viscometer was used to measure a viscosity of 130,000 mPa.s or lower, and wherein the main chain of the acrylic copolymer has pendant poly(oxyalkylene) segments. At the same time, the resin composition according to the present invention contains at most 20 wt% of an organic solvent relative to the total weight of the resin composition.
本發明的發明人驚訝地發現,在本發明的樹脂組合物的製備過程中,通過含有聚(氧亞烷基)片段的烯屬不飽和單體與丙烯酸類單體和附加的烯屬不飽和單體的共聚,使柔軟的聚(氧亞烷基)片段懸掛在丙烯酸類共聚物的骨架上,該聚(氧亞烷基)片段的存在可以在保持樹脂組合物的固含量的同時顯著降低其 黏度,使得該樹脂組合物可以配製VOC排放量不超過420g/L的溶劑基塗料組合物,而不需要額外的稀釋劑。 The inventors of the present invention surprisingly found that in the preparation process of the resin composition of the present invention, an ethylenically unsaturated monomer containing a poly(oxyalkylene) segment is combined with an acrylic monomer and additional ethylenically unsaturated monomers. The copolymerization of monomers makes the soft poly(oxyalkylene) segment suspended on the backbone of the acrylic copolymer. The presence of the poly(oxyalkylene) segment can significantly reduce the solid content of the resin composition while maintaining the solid content of the resin composition. Its viscosity allows the resin composition to formulate a solvent-based coating composition with a VOC emission of no more than 420g/L without the need for additional diluents.
本發明的發明人進一步驚訝地發現,根據本發明的高固低黏樹脂組合物可以在有機溶劑含量非常低的情況下通過使含有聚(氧亞烷基)片段的烯屬不飽和單體與丙烯酸類單體和附加的烯屬不飽和單體的共聚來形成,這在本發明之前是難以預見的。 The inventors of the present invention have further surprisingly discovered that the high-solid and low-viscosity resin composition according to the present invention can be combined with ethylenically unsaturated monomers containing poly(oxyalkylene) segments with very low organic solvent content. The copolymerization of acrylic monomers and additional ethylenically unsaturated monomers is difficult to foresee before the present invention.
本發明的一個或多個實施方案的細節在以下的說明書中闡明。根據說明書和申請專利範圍,本發明其它特徵、目的和優點將變得清楚。 The details of one or more embodiments of the present invention are set forth in the following description. According to the specification and the scope of the patent application, other features, purposes and advantages of the present invention will become clear.
定義definition
在本文中使用時,除非另有說明,“一種”、“這種”、“至少一種”和“一種或多種”以及不使用數量詞的情形可互換使用。因此,例如包含“一種”添加劑的塗料組合物可以被解釋為表示該塗料組合物中包含“一種或多種”添加劑。除本文中另有說明外,本文中單數形式的使用還意在包括複數形式。 When used herein, unless otherwise stated, "a", "this", "at least one" and "one or more" and the situations where quantifiers are not used can be used interchangeably. Thus, for example, a coating composition containing "an" additive may be interpreted as meaning that the coating composition contains "one or more" additives. Unless otherwise stated herein, the use of the singular form herein is also intended to include the plural form.
在組合物被描述為包括或包含特定組分的情況下,預計該組合物中並不排除本發明未涉及的可選組分,並且預計該組合物可由所涉及的組分構成或組成,或者在方法被描述為包括或包含特定工藝步驟的情況下,預計該方法中並不排除本發明未涉及的可選工藝步驟,並且預計該方法可由所涉及的工藝步驟構成或組成。 Where the composition is described as including or containing specific components, it is expected that the composition does not exclude optional components not involved in the present invention, and it is expected that the composition may be composed or composed of the involved components, or Where a method is described as including or containing specific process steps, it is expected that the method does not exclude optional process steps not involved in the present invention, and it is expected that the method can be constituted or composed of the involved process steps.
當出現在本說明書和申請專利範圍中時,術語“包含”和“包括”及其變體不具有限制性含義。 When appearing in this specification and the scope of the patent application, the terms "including" and "including" and their variants do not have a restrictive meaning.
在涉及“樹脂組合物”使用時,術語“高固含量”是指該樹脂組合物的固含量為至少80wt%或更高,其中所述固含量是基於樹脂組合物中的樹脂組分 計算。 When referring to the use of "resin composition", the term "high solid content" means that the solid content of the resin composition is at least 80 wt% or higher, wherein the solid content is calculated based on the resin components in the resin composition.
在本發明的上下文中,術語“溶劑基塗料組合物”是指水含量小於2g/L,優選基本上不含,更優選基本上完全不含,還要更優選完全不含水的以有機溶劑作為分散介質的塗料組合物。 In the context of the present invention, the term "solvent-based coating composition" refers to a water content of less than 2g/L, preferably substantially free of water, more preferably substantially completely free of water, and even more preferably completely free of water as an organic solvent Dispersion medium coating composition.
當針對“溶劑型塗料組合物”使用時,術語“基本上不含”水是指,本發明的溶劑型塗料組合物包含小於1000份每百萬(ppm)的水;術語“本質上不含”水是指,本發明的溶劑型塗料組合物包含小於100ppm水;術語“本質上完全不含”水是指,本發明的溶劑型塗料組合物包含小於5ppm水;術語“完全不含”水是指,本發明的溶劑型塗料組合物包含小於20份每十億(ppb)水。 When used in reference to "solvent-based coating composition", the term "essentially free of water" means that the solvent-based coating composition of the present invention contains less than 1000 parts per million (ppm) of water; the term "essentially free of water" "Water means that the solvent-based coating composition of the present invention contains less than 100 ppm of water; the term "essentially completely free of" water means that the solvent-based coating composition of the present invention contains less than 5 ppm of water; the term "completely free of" water It means that the solvent-based coating composition of the present invention contains less than 20 parts per billion (ppb) of water.
在本發明的上下文中,術語“烯屬不飽和基團”是指,具有順式-或反式-構型的反應性碳-碳雙鍵不飽和基團,但不包括芳族不飽和基團、碳-碳三鍵、碳-雜原子不飽和基團。 In the context of the present invention, the term "ethylenically unsaturated group" refers to a reactive carbon-carbon double bond unsaturated group having a cis- or trans-configuration, but does not include aromatic unsaturated groups Groups, carbon-carbon triple bonds, carbon-heteroatom unsaturated groups.
在本發明的上下文中,術語“反應性混合物”是指,由具有反應性的單體構成的混合物,不包括未參與反應的溶劑。 In the context of the present invention, the term "reactive mixture" refers to a mixture composed of reactive monomers, excluding solvents that do not participate in the reaction.
為了簡便,本文僅明確地公開了一些數值範圍。然而,任意下限可以與任何上限組合形成未明確記載的範圍;以及任意下限可以與其它下限組合形成未明確記載的範圍,同樣任意上限可以與任意其它上限組合形成未明確記載的範圍。此外,儘管未明確記載,但是範圍端點間的每個點或單個數值都包含在該範圍內。因而,每個點或單個數值可以作為自身的下限或上限與任意其它點或單個數值組合或與其它下限或上限組合形成未明確記載的範圍。 For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range. In addition, although not explicitly stated, every point or single value between the end points of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit in combination with any other point or single numerical value or in combination with other lower or upper limits to form an unspecified range.
在本發明中,通過端點限定的數值範圍包括該範圍內的所有任何數值,例如1到5的範圍涵蓋了數值1、1.5、2、2.75、3、3.80、4、5等。而且,公開的數值範圍包括在該較寬範圍內的所有子集範圍,例如1到5的範圍包括了子範圍1到4、1.5到4.5、1到2等。 In the present invention, the numerical range defined by the endpoints includes all any numerical values within the range, for example, the range of 1 to 5 encompasses numerical values 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like. Moreover, the disclosed numerical range includes all the subset ranges within the wider range, for example, the range of 1 to 5 includes the subranges 1 to 4, 1.5 to 4.5, 1 to 2, and so on.
術語“優選的”和“優選地”是指在某些情況下可提供某些益處的本發明實施方案。然而,在相同或其他情況下,其他實施方案也可能是優選的。另外,一個或多個優選的實施方案的敘述不意味著其他實施方案是不可用的,並且 不旨在將其他實施方案排除在本發明範圍外。 The terms "preferred" and "preferably" refer to embodiments of the invention that can provide certain benefits under certain circumstances. However, under the same or other circumstances, other embodiments may also be preferred. In addition, the recitation of one or more preferred embodiments does not mean that other embodiments are unavailable, and is not intended to exclude other embodiments from the scope of the present invention.
根據本發明的第一方面,本發明提供了一種包含丙烯酸類共聚物的樹脂組合物,其中,所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度,並且所述丙烯酸類共聚物的主鏈上具有懸掛的聚(氧亞烷基)片段。 According to the first aspect of the present invention, the present invention provides a resin composition comprising an acrylic copolymer, wherein the resin composition has a solid content of at least about 80 wt% based on the weight of the acrylic copolymer and a solid content of 25 A BROOKFIELD viscometer is used to measure a viscosity of 130,000 mPa.s or lower at °C, and the acrylic copolymer has a pendant poly(oxyalkylene) segment on the main chain.
根據本發明的樹脂組合物不僅具有高固含量,而且具有非常低的黏度,因而可被用於配製溶劑型塗料組合物,而不會引入過量的VOC。在本發明的一個實施方式中,所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量。發明人驚訝地發現,本發明的樹脂組合物在保持高固含量的同時具有顯著更低的黏度。在本發明的一個實施方式中,所述樹脂組合物具有在25℃下利用BROOKFIELD黏度計測量60000mPa.s或更低的黏度,更優選10000mPa.s或更低的黏度。 The resin composition according to the present invention not only has a high solid content, but also has a very low viscosity, so it can be used to formulate a solvent-based coating composition without introducing excessive VOC. In one embodiment of the present invention, the resin composition has a solid content of at least about 80 wt% based on the weight of the acrylic copolymer. The inventor surprisingly found that the resin composition of the present invention has a significantly lower viscosity while maintaining a high solid content. In one embodiment of the present invention, the resin composition has a viscosity of 60000 mPa.s or lower measured with a BROOKFIELD viscometer at 25°C, more preferably a viscosity of 10000 mPa.s or lower.
根據本發明的樹脂組合物還包含相當少量的有機溶劑,例如包含,相對於所述樹脂組合物的總重,不超過20重量%的有機溶劑,優選不超過18重量%的有機溶劑。 The resin composition according to the present invention also contains a relatively small amount of organic solvent, for example, containing not more than 20% by weight, preferably not more than 18% by weight, relative to the total weight of the resin composition.
具有上述特性的樹脂組合物在被用於配製溶劑型塗料組合物時不需要添加大量的溶劑進行稀釋,甚至根本不需要添加溶劑作為稀釋劑,因此可以配製形成VOC排放量不超過420g/L的溶劑型塗料組合物。 The resin composition with the above characteristics does not need to add a large amount of solvent for dilution when used to formulate a solvent-based coating composition, or even does not need to add a solvent as a diluent at all, so it can be formulated to form a VOC emission of no more than 420g/L Solvent-based coating composition.
在根據本發明的樹脂組合物中,丙烯酸類共聚物的骨架上具有懸掛的聚(氧亞烷基)片段。在本發明的實施方式中,基於所述丙烯酸類共聚物的重量,所述聚(氧亞烷基)片段以15-60wt%的量存在,優選以20-50wt%的量存在。聚(氧亞烷基)片段懸掛在丙烯酸類共聚物的骨架上使得含有該丙烯酸類共聚物的樹脂組合物可以在保持高固含量的同時顯示顯著降低的黏度。 In the resin composition according to the present invention, the acrylic copolymer has pendant poly(oxyalkylene) segments on the backbone. In an embodiment of the present invention, based on the weight of the acrylic copolymer, the poly(oxyalkylene) segment is present in an amount of 15-60 wt%, preferably in an amount of 20-50 wt%. The poly(oxyalkylene) segment is suspended on the backbone of the acrylic copolymer so that the resin composition containing the acrylic copolymer can exhibit a significantly reduced viscosity while maintaining a high solid content.
根據本發明,所述聚(氧亞烷基)選自聚(氧亞乙基)片段、聚(氧亞丙基)片段、聚(氧亞丁基)片段、聚(氧亞戊基)片段及其任意組合的聚(氧亞烷基)片段。優選地,聚(氧亞烷基)片段選自由聚(氧亞乙基)片段、聚(氧亞丙基)片段及其組合組成的組。 According to the present invention, the poly(oxyalkylene) is selected from poly(oxyethylene) fragments, poly(oxypropylene) fragments, poly(oxybutylene) fragments, poly(oxypentylene) fragments and Any combination of poly(oxyalkylene) fragments. Preferably, the poly(oxyalkylene) segment is selected from the group consisting of poly(oxyethylene) segment, poly(oxypropylene) segment, and combinations thereof.
根據本發明,所述聚(氧亞烷基)片段衍生自具有下式I的含有聚(氧亞烷基)片段的烯屬不飽和單體,也被稱為含烯屬不飽和基團的聚醚,
根據本發明,其中的X為-(CH2)a-的上式I所示聚醚被稱為醚型聚醚,其中的X為-CO-或-(CH2)a-CO-的上式I所示聚醚被稱為酯型聚醚。 According to the present invention, the polyether represented by the above formula I in which X is -(CH 2 ) a -is called ether type polyether, wherein X is -CO- or -(CH 2 ) a -CO- The polyethers represented by formula I are called ester polyethers.
在一些實施方式中,所述含烯屬不飽和基團的聚醚為醚型聚醚。根據本發明的醚型聚醚的實例包括烯丙基聚醚(例如烯丙基聚氧乙烯醚、烯丙基聚氧丙烯聚氧乙烯聚醚)、甲基烯丙基聚醚等,這些都是可商購的,例如來自浙江皇馬的HMP-523B、HMS-239B、HMS-233B、HMP-517B等。 In some embodiments, the ethylenically unsaturated group-containing polyether is an ether type polyether. Examples of the ether type polyether according to the present invention include allyl polyether (for example, allyl polyoxyethylene ether, allyl polyoxypropylene polyoxyethylene polyether), methallyl polyether, etc. It is commercially available, such as HMP-523B, HMS-239B, HMS-233B, HMP-517B, etc. from Zhejiang Real Madrid.
在一些實施方式中,所述含烯屬不飽和基團的聚醚為酯型聚醚。根據本發明的酯型聚醚的實例包括丙烯醯氧基聚氧乙烯醚、丙烯醯氧基聚氧丙烯醚、甲基丙烯醯氧基聚氧乙烯醚、甲基丙烯醯氧基聚氧丙烯醚,這些都是可商購的。 In some embodiments, the ethylenically unsaturated group-containing polyether is an ester polyether. Examples of the ester type polyether according to the present invention include acryloxy polyoxyethylene ether, acryloxy polyoxypropylene ether, methacryloxy polyoxyethylene ether, methacryloxy polyoxypropylene ether , These are all commercially available.
在本發明的一些實施方式中,所述含烯屬不飽和基團的聚醚的數均分子量在100-10000之間,更優選地在200-6000之間,更優選在300-2000之間。所述數均分子量可以使用GPC來測定。 In some embodiments of the present invention, the number average molecular weight of the ethylenically unsaturated group-containing polyether is between 100-10000, more preferably between 200-6000, more preferably between 300-2000 . The number average molecular weight can be measured using GPC.
根據本發明,所述樹脂組合物是由包含如下的組分製成的:相對於反應混合物的總重,15-60wt%的含有聚(氧亞烷基)片段的 烯屬不飽和單體(此後稱為“第一單體”),相對於反應混合物的總重,35-60wt%的不同於第一單體的丙烯酸類單體,相對於反應混合物的總重,5-30wt%的附加的烯屬不飽和單體。 According to the present invention, the resin composition is made of the following components: relative to the total weight of the reaction mixture, 15-60 wt% of ethylenically unsaturated monomers containing poly(oxyalkylene) fragments ( Hereafter referred to as "first monomer"), relative to the total weight of the reaction mixture, 35-60wt% of acrylic monomers different from the first monomer, relative to the total weight of the reaction mixture, 5-30wt% of additional The ethylenically unsaturated monomer.
本發明的發明人驚訝地發現,根據本發明的樹脂組合物可以通過如下形成:在自由基引發劑和非常少量的有機溶劑的存在下使第一單體、不同於所述第一單體的丙烯酸類單體和附加的烯屬不飽和單體進行共聚合而沒有發生凝膠。優選地,所述有機溶劑以相對於所述樹脂組合物的總重,15-20wt%、優選15-18wt%、更優選15-17wt%的量存在。由此獲得樹脂組合物不僅具有高固含量而且具有顯著更低的黏度,例如所述樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度。 The inventors of the present invention surprisingly discovered that the resin composition according to the present invention can be formed by making the first monomer different from the first monomer in the presence of a radical initiator and a very small amount of organic solvent. Acrylic monomers and additional ethylenically unsaturated monomers are copolymerized without gelation. Preferably, the organic solvent is present in an amount of 15-20 wt%, preferably 15-18 wt%, more preferably 15-17 wt% relative to the total weight of the resin composition. The resin composition thus obtained not only has a high solid content but also has a significantly lower viscosity. For example, the resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer and a BROOKFIELD viscosity at 25°C. The meter measures the viscosity of 130000mPa.s or lower.
在根據本發明的樹脂組合物的製備中,第一單體是必需的。如上所述,發明人驚訝地發現,在樹脂組合物的製備過程中通過引入第一單體,即含有聚(氧亞烷基)片段的烯屬不飽和單體,可以在保持樹脂組合物的高固含量的同時顯著降低其黏度,使得該樹脂組合物可以配製VOC排放量不超過420g/L的溶劑基塗料組合物,而不需要額外的稀釋劑。 In the preparation of the resin composition according to the present invention, the first monomer is necessary. As described above, the inventor surprisingly found that by introducing the first monomer, that is, the ethylenically unsaturated monomer containing poly(oxyalkylene) fragments, during the preparation of the resin composition, the resin composition can be The high solid content also significantly reduces its viscosity, so that the resin composition can be formulated into a solvent-based coating composition with a VOC emission of not more than 420g/L without the need for additional diluents.
因此,本發明還涉及上述含有聚(氧亞烷基)片段的烯屬不飽和單體用於製備根據本發明的包含丙烯酸類共聚物的高固低黏樹脂組合物的用途。 Therefore, the present invention also relates to the use of the above-mentioned ethylenically unsaturated monomer containing poly(oxyalkylene) fragments for preparing the high-solid low-viscosity resin composition containing acrylic copolymer according to the present invention.
優選地,用於製備本發明的樹脂組合物的組分包含,相對於所述反應混合物的總重,15-55wt%的含有聚(氧亞烷基)片段的烯屬不飽和單體,優選20-50wt%的含有聚(氧亞烷基)片段的烯屬不飽和單體,更優選20-40wt%的含有聚(氧亞烷基)片段的烯屬不飽和單體。 Preferably, the components used to prepare the resin composition of the present invention comprise, relative to the total weight of the reaction mixture, 15-55 wt% of ethylenically unsaturated monomers containing poly(oxyalkylene) fragments, preferably 20-50 wt% of ethylenically unsaturated monomers containing poly(oxyalkylene) segments, more preferably 20-40 wt% of ethylenically unsaturated monomers containing poly(oxyalkylene) segments.
在根據本發明的樹脂組合物的製備中,還可以包括不同於第一單體的丙烯酸類單體。該單體的存在可被用於提供所得樹脂組合物的機械強度和成膜性能。在本發明的實施方式中,作為丙稀酸類單體的實例,可以使用(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯 酸2-乙基己酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丁酯、(甲基)丙烯酸羥丙酯、甲基丙烯酸2-(乙醯乙醯氧)乙酯、二丙酮丙烯醯胺、羥甲基(甲基)丙烯醯胺、丙烯腈、甲基丙烯酸烯丙基酯或其混合物。 In the preparation of the resin composition according to the present invention, an acrylic monomer different from the first monomer may also be included. The presence of the monomer can be used to provide the mechanical strength and film-forming properties of the resulting resin composition. In the embodiment of the present invention, as examples of acrylic monomers, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, ( 2-Ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-(acetylacetoxy)methacrylate Ethyl ester, diacetone acrylamide, hydroxymethyl (meth)acrylamide, acrylonitrile, allyl methacrylate or mixtures thereof.
在一些實施方式中,丙稀酸類單體可以包含至少一種含活性氫的單體,以使所獲得的最終樹脂組合物具有活性氫官能度,例如來自羥基、胺和酸官能度的那些官能度。優選地,基於反應混合物的總重量,所述含活性氫的丙烯酸類單體以5-20wt%的量存在,優選以10-15wt%的量存在。這種含活性氫的丙烯酸類單體的存在,確保了所得到的根據本發明的包含丙烯酸類共聚物的樹脂組合物可被用於配製雙組分溶劑型塗料組合物。 In some embodiments, the acrylic monomer may include at least one active hydrogen-containing monomer, so that the final resin composition obtained has active hydrogen functionality, such as those derived from hydroxyl, amine, and acid functionality . Preferably, based on the total weight of the reaction mixture, the active hydrogen-containing acrylic monomer is present in an amount of 5-20 wt%, preferably in an amount of 10-15 wt%. The presence of this active hydrogen-containing acrylic monomer ensures that the obtained resin composition containing the acrylic copolymer according to the present invention can be used to formulate a two-component solvent-based coating composition.
優選地,用於製備本發明的樹脂組合物的組分包含,相對於反應混合物的總重量,以至少35wt%的量存在,優選以至少40wt%的量,更優選以至少45wt%的量存在,最優選以至少50wt%的量存在的丙烯酸類單體。更優選地,基於反應混合物的總重量,所述丙烯酸類單體以至多60wt%的量存在,更優選以至多56wt%的量存在。 Preferably, the components used to prepare the resin composition of the present invention comprise, relative to the total weight of the reaction mixture, present in an amount of at least 35 wt%, preferably in an amount of at least 40 wt%, more preferably in an amount of at least 45 wt% , Most preferably acrylic monomers present in an amount of at least 50% by weight. More preferably, the acrylic monomer is present in an amount of up to 60% by weight based on the total weight of the reaction mixture, more preferably in an amount of up to 56% by weight.
在根據本發明的樹脂組合物的製備中,還可以包括附加的烯屬不飽和單體。該單體可被用於調節所得樹脂組合物的機械強度。在本發明的實施方式中,所述附加的烯屬不飽和單體選自苯乙烯、乙烯基甲苯、乙酸乙烯酯或其混合物。 In the preparation of the resin composition according to the present invention, additional ethylenically unsaturated monomers may also be included. The monomer can be used to adjust the mechanical strength of the resulting resin composition. In an embodiment of the present invention, the additional ethylenically unsaturated monomer is selected from styrene, vinyl toluene, vinyl acetate or a mixture thereof.
優選地,用於製備本發明的樹脂組合物的組分包含,相對於反應混合物的總重量,以15-30wt%的量存在的附加的烯屬不飽和單體。 Preferably, the components used to prepare the resin composition of the present invention include an additional ethylenically unsaturated monomer present in an amount of 15-30 wt% relative to the total weight of the reaction mixture.
在根據本發明的樹脂組合物的製備中,可以包含有機溶劑以調節體系黏度。合適的溶劑包括芳烴,如苯、甲苯和二甲苯等;醇,如乙醇、異丙醇、正丁醇、叔丁醇和乙基己醇等;酯,如乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯等。其它適用的溶劑包括酮,如甲基乙基酮、甲基戊基酮、甲基異丁基酮等;二醇,如丙二醇和二乙基二醇;二醇醚,如丙二醇單甲基醚、乙二醇單甲基醚。當然,可以使用溶劑的各種混合物。根據本發明,有機溶劑的量可以非常低,例如 低於20wt%、低於19wt%、低於18wt%、低於17wt%、低於15wt%,而並不會影響丙烯酸類共聚物的形成,其中該用量是相對於樹脂組合物的總重計算的,這在本發明之前是難以想像的。如CN1201809所記載的,在常規樹脂組合物的製備期間降低使用的溶劑量實際上是有限的,通常不低於反應混合物總重量的20wt%。若試圖再降低溶劑,則所得樹脂組合物變得過黏,甚至凝膠,從而無法用於塗料組合物的配製。 In the preparation of the resin composition according to the present invention, an organic solvent may be included to adjust the viscosity of the system. Suitable solvents include aromatic hydrocarbons, such as benzene, toluene, and xylene; alcohols, such as ethanol, isopropanol, n-butanol, tert-butanol, and ethylhexanol, etc.; esters, such as ethyl acetate, propyl acetate, and butyl acetate Ester, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Other suitable solvents include ketones, such as methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, etc.; glycols, such as propylene glycol and diethyl glycol; glycol ethers, such as propylene glycol monomethyl ether , Ethylene glycol monomethyl ether. Of course, various mixtures of solvents can be used. According to the present invention, the amount of organic solvent can be very low, for example, less than 20wt%, less than 19wt%, less than 18wt%, less than 17wt%, less than 15wt%, without affecting the formation of acrylic copolymers, The amount is calculated relative to the total weight of the resin composition, which was unimaginable before the present invention. As described in CN1201809, reducing the amount of solvent used during the preparation of conventional resin compositions is actually limited, usually not less than 20wt% of the total weight of the reaction mixture. If an attempt is made to reduce the solvent, the resulting resin composition will become too viscous, or even gel, and thus cannot be used for the formulation of coating compositions.
因此,本發明還涉及一種用於製備根據本發明的包含丙烯酸類共聚物的樹脂組合物的方法,所述方法包括:在相對於所述樹脂組合物的總重,用量不超過20wt%的有機溶劑和自由基引發劑的存在下,使包含作為第一單體的含有聚(氧亞烷基)片段的烯屬不飽和單體、不同於所述第一單體的丙烯酸類單體和附加的烯屬不飽和單體的反應混合物進行共聚,從而形成所述樹脂組合物。 Therefore, the present invention also relates to a method for preparing a resin composition containing an acrylic copolymer according to the present invention, the method comprising: relative to the total weight of the resin composition, an amount of not more than 20wt% of organic In the presence of a solvent and a radical initiator, an ethylenically unsaturated monomer containing a poly(oxyalkylene) segment as the first monomer, an acrylic monomer different from the first monomer, and an additional The reaction mixture of ethylenically unsaturated monomers is copolymerized to form the resin composition.
上述反應的適當條件取決於各種因素,包括含有聚(氧亞烷基)片段的烯屬不飽和單體和丙烯酸類單體的類型、溶劑存在與否、以及引發劑的類型等等,這些可由本領域技術人員以經驗確定。並不希望束縛於任何理論,發明人提供如下解釋,以使本發明能夠被更好地理解。 The appropriate conditions for the above reaction depend on various factors, including the types of ethylenically unsaturated monomers and acrylic monomers containing poly(oxyalkylene) fragments, the presence or absence of solvents, and the type of initiator, etc. These can be Those skilled in the art can determine it empirically. Without wishing to be bound by any theory, the inventors provide the following explanations so that the present invention can be better understood.
在根據本發明的包含丙烯酸類共聚物的樹脂組合物中,丙稀酸類共聚物主鏈上懸掛有適量的聚(氧亞烷基)片段,由於聚(氧亞烷基)片段的柔韌性,有助於提高丙稀酸類共聚物的分子活動性,從而達到顯著降低黏度的目的。此外,懸掛在主鏈上的非極性側基弱化了分子鏈間的作用力,進一步提高了丙烯酸類共聚物在溶劑中的溶解性,從而使得根據本發明的含有丙烯酸類共聚物的樹脂組合物的製備可以在非常少量的有機溶劑的存在下進行,而不會發生凝膠或硬化。 In the resin composition containing the acrylic copolymer according to the present invention, an appropriate amount of poly(oxyalkylene) segments are suspended on the main chain of the acrylic copolymer. Due to the flexibility of the poly(oxyalkylene) segments, It helps to improve the molecular mobility of acrylic copolymers, so as to achieve the purpose of significantly reducing the viscosity. In addition, the non-polar side groups suspended on the main chain weaken the force between the molecular chains and further improve the solubility of the acrylic copolymer in the solvent, thereby making the acrylic copolymer-containing resin composition according to the present invention The preparation can be carried out in the presence of a very small amount of organic solvents without gel or hardening.
由於具有高固含量和低黏度,根據本發明的包含丙烯酸類共聚物的樹脂組合物適用於配製低VOC的溶劑基塗料組合物,例如可以配製VOC排放量不超過420g/L的溶劑基塗料組合物。 Due to its high solid content and low viscosity, the resin composition containing acrylic copolymer according to the present invention is suitable for formulating low-VOC solvent-based coating compositions, for example, solvent-based coating compositions with VOC emissions not exceeding 420g/L can be formulated Things.
因此,本發明的另一方面提供了一種VOC排放量不超過420g/L的溶劑基塗料組合物,其包含本文所公開的包含丙烯酸類共聚物的樹脂組合物 和可選的附加添加劑。具體地,所述溶劑基塗料組合物,包含,相對於所述塗料組合物的總重,(i)30至99.5重量份包含聚醚改性的聚酯的樹脂組合物;(ii)0.5至70重量份的可選的附加添加劑。 Therefore, another aspect of the present invention provides a solvent-based coating composition with a VOC emission of no more than 420 g/L, which comprises the resin composition containing the acrylic copolymer disclosed herein and optional additional additives. Specifically, the solvent-based coating composition includes, relative to the total weight of the coating composition, (i) 30 to 99.5 parts by weight of a resin composition containing a polyether-modified polyester; (ii) 0.5 to 70 parts by weight of optional additional additives.
根據本發明,本文所述的包含丙烯酸類共聚物的樹脂組合物的含量,相對於溶劑基塗料組合物的總重,在30至99.5重量份的範圍內,優選在40至90重量份的範圍內,更優選在50至85重量份的範圍內。 According to the present invention, the content of the resin composition containing the acrylic copolymer described herein, relative to the total weight of the solvent-based coating composition, is in the range of 30 to 99.5 parts by weight, preferably in the range of 40 to 90 parts by weight Within, it is more preferably in the range of 50 to 85 parts by weight.
如果需要,本發明的塗料組合物可選包含其他添加劑,這些添加劑不會不利地影響塗料組合物或由其得到的固化塗層。適當的添加劑包括例如會改善組合物的加工性能或製造性能、增強組合物的美感、或改善塗料組合物或由其得到的固化組合物的特定功能性質或特性(諸如對基材的黏附性)的那些試劑。可以包含的添加劑是溶劑、載劑、附加聚合物、顏料、金屬粉末或膏體、填料、抗遷移助劑、抗菌劑、增量劑、潤滑劑、消泡劑、生物殺滅劑、增塑劑、增稠劑、著色劑、蠟、抗氧化劑、防腐蝕劑、流動控制劑、觸變劑、分散劑、UV穩定劑、或其組合。各個可選成分的含量足以起到其意欲達到的目的,但優選地,這樣的含量不會不利地影響塗料組合物或由其得到的固化塗層。適用於該塗料組合物的附加添加劑的實例包括增塑劑、顏料、填料、增稠劑、消泡劑、潤濕劑、分散劑、溶劑或其組合。 If necessary, the coating composition of the present invention may optionally contain other additives, which do not adversely affect the coating composition or the cured coating obtained therefrom. Appropriate additives include, for example, can improve the processing performance or manufacturing performance of the composition, enhance the aesthetics of the composition, or improve the specific functional properties or characteristics of the coating composition or the cured composition obtained therefrom (such as adhesion to the substrate) Those reagents. The additives that can be included are solvents, carriers, additional polymers, pigments, metal powders or pastes, fillers, anti-migration aids, antibacterial agents, extenders, lubricants, defoamers, biocides, plasticizers Agents, thickeners, colorants, waxes, antioxidants, corrosion inhibitors, flow control agents, thixotropic agents, dispersants, UV stabilizers, or combinations thereof. The content of each optional component is sufficient to achieve its intended purpose, but preferably, such content does not adversely affect the coating composition or the cured coating obtained therefrom. Examples of additional additives suitable for the coating composition include plasticizers, pigments, fillers, thickeners, defoamers, wetting agents, dispersants, solvents, or combinations thereof.
附加添加劑的含量,相對於溶劑基塗料組合物的總重,在0.5至70重量份的範圍內,或者更優選在1至50重量份的範圍內。 The content of the additional additives is in the range of 0.5 to 70 parts by weight, or more preferably in the range of 1 to 50 parts by weight, relative to the total weight of the solvent-based coating composition.
除了配製以上VOC排放量不超過420g/L的溶劑基塗料組合物以外,根據本發明的樹脂組合物還可用於配製雙組份的溶劑基塗料組合物。因此,本發明另一方面包括一種雙組份的VOC排放量不超過420g/L的溶劑基塗料組合物,其包含成膜樹脂組合物a),所述成膜樹脂組合物包含上述本文所公開的包含丙烯酸類共聚物的樹脂組合物和可選的附加添加劑;和交聯劑b)。 In addition to formulating the above solvent-based coating composition with a VOC emission amount not exceeding 420 g/L, the resin composition according to the present invention can also be used to formulate a two-component solvent-based coating composition. Therefore, another aspect of the present invention includes a two-component solvent-based coating composition with a VOC emission of no more than 420g/L, which comprises a film-forming resin composition a), the film-forming resin composition comprising the above-mentioned disclosed herein The resin composition containing acrylic copolymer and optional additional additives; and crosslinking agent b).
合適的交聯劑組分的例子為多異氰酸酯。 Examples of suitable crosslinker components are polyisocyanates.
適當的多異氰酸酯交聯劑包括脂族多異氰酸酯、芳族多異氰酸酯或其任意組合。本文使用的術語“脂族多異氰酸酯”指異氰酸酯基直接連接到脂族 鏈或環上的多異氰酸酯化合物。本文使用的術語“芳族多異氰酸酯”指異氰酸酯基直接連接到芳族環上的多異氰酸酯化合物。 Suitable polyisocyanate crosslinkers include aliphatic polyisocyanates, aromatic polyisocyanates, or any combination thereof. The term "aliphatic polyisocyanate" as used herein refers to a polyisocyanate compound in which an isocyanate group is directly connected to an aliphatic chain or ring. The term "aromatic polyisocyanate" as used herein refers to a polyisocyanate compound in which an isocyanate group is directly connected to an aromatic ring.
用於本發明的合適的異氰酸酯包括脂族二異氰酸酯,如三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、八亞甲基二異氰酸酯、十亞甲基二異氰酸酯、亞丁基-1,2-二異氰酸酯、亞丁基-1,3-二異氰酸酯、亞乙基二異氰酸酯;環脂族二異氰酸酯,如環亞己基二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、2,2,4-三甲基六甲基二異氰酸酯、二聚體酸二異氰酸酯、3-異氰酸根合甲基-3,5,5-三甲基環己基異氰酸酯;和芳族二異氰酸酯,如2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、氯化甲苯二異氰酸酯、間亞苯基二異氰酸酯、氯化間亞苯基二異氰酸酯、鄰亞苯基二異氰酸酯、溴化間-亞苯基二異氰酸酯、間亞二甲苯基二異氰酸酯、對亞二甲苯基二異氰酸酯、亞萘基-1,4-二異氰酸酯、亞萘基-1,5-二異氰酸酯、亞萘基-2,7-二異氰酸酯、4',4-亞聯苯基二異氰酸酯、3,3'-二氯-4,4'-亞聯苯基二異氰酸酯、3,3'-二甲基-4,4'-亞聯苯基二異氰酸酯、3,3'-二甲氧基-4,4'-亞聯苯基二異氰酸酯、2,2',5,5'-四甲基-4,4'-亞聯苯基二異氰酸酯、2-硝基-4,4'-亞聯苯基二異氰酸酯、3,3'-二苯基-4,4'-亞聯苯基二異氰酸酯、4,4'-亞甲基-雙(苯基異氰酸酯)、4,4'-亞甲基-雙(2-甲苯基異氰酸酯)、4,4'-異亞丙基-雙(苯基異氰酸酯)和芴二異氰酸酯;三異氰酸酯,如六亞甲基二異氰酸酯縮二脲、4,4',4"-三苯基甲烷三異氰酸酯和甲苯-2,4,6-三異氰酸酯;異氰尿酸酯,如那些基於六亞甲基二異氰酸酯或3-異氰酸根合甲基-3,5,5-三甲基環己基異氰酸酯的異氰尿酸酯;四異氰酸酯及其混合物。 Suitable isocyanates for use in the present invention include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, ten methylene diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, ethylene diisocyanate; cycloaliphatic diisocyanates, such as cyclohexylene diisocyanate, 4,4 '- Methylene bis(cyclohexyl isocyanate), 2,2,4-trimethylhexamethyl diisocyanate, dimer acid diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl Cyclohexyl isocyanate; and aromatic diisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, chlorinated toluene diisocyanate, m-phenylene diisocyanate, chlorinated m-phenylene diisocyanate, o Phenylene diisocyanate, brominated meta-phenylene diisocyanate, meta-xylylene diisocyanate, p-xylylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5 -Diisocyanate, naphthylene-2,7-diisocyanate, 4 ' ,4-biphenylene diisocyanate, 3,3 ' -dichloro-4,4 ' -biphenylene diisocyanate, 3,3 '- dimethyl - 4,4' - biphenylene diisocyanate, 3,3 '- dimethoxy -4,4' - biphenylene diisocyanate, 2,2 ', 5,5' - Tetramethyl-4,4 ' -biphenylene diisocyanate, 2-nitro-4,4 ' -biphenylene diisocyanate, 3,3 ' -diphenyl-4,4 ' -biphenylene yl diisocyanate, 4,4 '- methylene - bis (phenyl isocyanate), 4,4' - methylene - bis (2-methylphenyl isocyanate), 4,4 '- isopropylidene - bis ( Phenyl isocyanate) and fluorene diisocyanate; triisocyanates such as hexamethylene diisocyanate biuret, 4,4 ' ,4 " -triphenylmethane triisocyanate and toluene-2,4,6-triisocyanate; isocyanate; Cyanurates, such as those based on hexamethylene diisocyanate or 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; tetraisocyanates and mixtures thereof.
特別適用的異氰酸酯是基於六亞甲基二異氰酸酯(HDI)的多官能脂族異氰酸酯。一些市購HDI包括Tolonate®HDT或Tolonate®HDT LV,購自Rhone-Poulenc Inc.(有機化學分公司),Monmouth Junction,NJ,或Desmodur®N-3300或Desmodur®N-3390異氰酸酯,購自Bayer AG,Pittsburgh,PA。 Particularly suitable isocyanates are multifunctional aliphatic isocyanates based on hexamethylene diisocyanate (HDI). Some commercially available HDIs include Tolonate®HDT or Tolonate®HDT LV, available from Rhone-Poulenc Inc. (organic chemistry branch), Monmouth Junction, NJ, or Desmodur®N-3300 or Desmodur®N-3390 isocyanate, available from Bayer AG, Pittsburgh, PA.
根據本發明,所述溶劑基塗料組合物可以通過本領域普通技術人員已知的常規塗覆方法進行塗布。所述塗覆方法包括浸塗、旋塗、噴塗、簾塗、刷塗、輥塗以及本領域已知的其他塗覆方法。 According to the present invention, the solvent-based coating composition can be coated by conventional coating methods known to those of ordinary skill in the art. The coating method includes dip coating, spin coating, spray coating, curtain coating, brush coating, roll coating, and other coating methods known in the art.
可以利用常規塗覆技術將低VOC的溶劑基塗料組合物塗覆到各種 不同基材上。適當基材的實例包括木材、水泥、水泥纖維板、木材-塑膠複合物、瓦片、金屬、塑膠、玻璃和纖維玻璃。 The low-VOC solvent-based coating composition can be coated on a variety of different substrates using conventional coating techniques. Examples of suitable substrates include wood, cement, cement fiberboard, wood-plastic composites, tiles, metal, plastic, glass, and fiberglass.
測試方法 Test Methods
除非另外指出,以下實施例中利用下述測試方法。 Unless otherwise indicated, the following test methods are used in the following examples.
固含量Solid content
根據GB/T1725-2007標準進行測定。 Measured according to GB/T1725-2007 standard.
黏度Viscosity
按照ASTMD 2196測定(通過旋轉(Brookfield)黏度計測定非牛頓材料的流變性能)。 Measured in accordance with ASTM D 2196 (measurement of rheological properties of non-Newtonian materials by means of a Brookfield viscometer).
光澤度Gloss
該測試測量固化塗層的光澤度。根據ASTM D523來評估光澤。 This test measures the gloss of the cured coating. The gloss is evaluated according to ASTM D523.
鉛筆硬度Pencil hardness
該測試用於測量固化塗層的硬度。使用ASTM D3363來評估鉛筆硬度。資料被報告為在塗層破裂前最後一次成功進行測試的鉛筆硬度。因此,例如,如果用2H鉛筆測試時,塗層不破裂,但用3H鉛筆進行測試時破裂,則塗層被報告為具有2H的鉛筆硬度。 This test is used to measure the hardness of cured coatings. Use ASTM D3363 to evaluate pencil hardness. The data is reported as the pencil hardness of the last successful test before the coating cracked. Therefore, for example, if the coating does not break when tested with a 2H pencil, but does break when tested with a 3H pencil, the coating is reported as having a pencil hardness of 2H.
黏附性Adhesion
進行黏附性測試以評估塗層是否黏附到經塗布的基材上。該黏附性測試根目錄據ASTM D 3359-測試方法B進行。黏附性通常被分為0-5B的等級,其中5B表示最優的黏附性。 An adhesion test is performed to evaluate whether the coating adheres to the coated substrate. The adhesion test root list is carried out according to ASTM D 3359-Test Method B. Adhesion is usually divided into 0-5B grade, where 5B represents the best adhesion.
實施例Example
下面,通過實施例更具體地描述本發明公開的內容。這些實施例僅僅用於闡述性說明,並且不能解釋為限制本發明的保護範圍,因為在本發明公開內容的範圍內進行各種修正和變化對本領域技術人員來說是明顯的。 Hereinafter, the disclosure of the present invention will be described in more detail through examples. These embodiments are only used for explanatory description, and cannot be construed as limiting the protection scope of the present invention, because various modifications and changes within the scope of the disclosure of the present invention are obvious to those skilled in the art.
除非另有聲明,以下實施例中所報導的所有份、百分比和比值都是 基於重量計,而且實施例中使用的所有試劑都可商購並且可直接使用而無需進一步處理。 Unless otherwise stated, all parts, percentages and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available and can be used directly without further processing.
材料Material
所使用的材料列於下表1中。 The materials used are listed in Table 1 below.
包含丙烯酸類共聚物的樹脂組合物的製備Preparation of resin composition containing acrylic copolymer
按下表2所示的成分來製備包含丙烯酸類共聚物的樹脂組合物。具體步驟為:(1)稱取各原料;(2)在用氮氣吹掃將Part 3裝入燒瓶,然後加熱至140℃;(3)將燒瓶的反應溫度保持在140℃,並在3-3.5小時的時間內依次將Part 1和Part 2加入反應燒瓶中;(4)單體加料結束後,在140℃下保持1小時; (5)將Part 4在1小時內加入反應燒瓶中,然後在140℃下保持2小時;(6)冷卻至室溫,得到包含丙烯酸類共聚物的樹脂組合物。 The resin composition containing the acrylic copolymer was prepared according to the ingredients shown in Table 2 below. The specific steps are: (1) Weigh each raw material; (2) Purge Part 3 into the flask with nitrogen, and then heat it to 140°C; (3) Keep the reaction temperature of the flask at 140°C and keep it at 3- Add Part 1 and Part 2 to the reaction flask in sequence within 3.5 hours; (4) After the monomer feed is completed, keep it at 140°C for 1 hour; (5) Add Part 4 to the reaction flask within 1 hour, and then Keep it at 140°C for 2 hours; (6) Cool to room temperature to obtain a resin composition containing an acrylic copolymer.
測定所得樹脂組合物的固含量和黏度,結果如下表3所示:
從上述結果可以看出,在丙烯酸類共聚物的製備中,引入含有聚(氧亞烷基)片段的烯屬不飽和單體可以形成含有丙烯酸類共聚物的高固低黏樹脂組合物,該樹脂組合物具有基於所述丙烯酸類共聚物的重量至少約80wt%的固含量以及在25℃下利用BROOKFIELD黏度計測量130000mPa.s或更低的黏度。與之相比,採用不含具有聚(氧亞烷基)片段的烯屬不飽和單體的單體混合物製備得到的丙烯酸類共聚物是硬固體,根本不能用於配製溶劑基塗料組合物。 It can be seen from the above results that in the preparation of acrylic copolymers, the introduction of ethylenically unsaturated monomers containing poly(oxyalkylene) segments can form high-solid and low-viscosity resin compositions containing acrylic copolymers. The resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer and a viscosity of 130,000 mPa.s or lower measured with a BROOKFIELD viscometer at 25°C. In contrast, acrylic copolymers prepared from monomer mixtures that do not contain ethylenically unsaturated monomers with poly(oxyalkylene) segments are hard solids and cannot be used to formulate solvent-based coating compositions at all.
低VOC的溶劑基塗料組合物的製備Preparation of low-VOC solvent-based coating composition
按照下面表4的配比來製備低VOC溶劑基塗料組合物,在攪拌下將顏料、填料、增稠劑、消泡劑、潤濕分散劑和溶劑加入根據上面得到的包含丙烯酸類共聚物的樹脂組合物中,從而形成溶劑基塗料組合物。然後,將由此形成的溶劑基塗料組合物用塗膜塗布器施於裸鋼板上,如此得到0.05mm(2±0.1mil)幹膜厚度的塗層。將該塗層在室溫下固化兩周,然後獲得下表中給出的測量值 Prepare the low-VOC solvent-based coating composition according to the following Table 4 ratio. Under stirring, add the pigment, filler, thickener, defoamer, wetting and dispersing agent and solvent to the acrylic copolymer-containing acrylic copolymer obtained above. In the resin composition, thereby forming a solvent-based coating composition. Then, the solvent-based coating composition thus formed was applied on the bare steel plate with a coating film applicator, thus obtaining a coating with a dry film thickness of 0.05 mm (2±0.1 mil). The coating was cured at room temperature for two weeks, and then the measured values given in the table below were obtained
從上述結果可以看出,根據本發明的包含丙烯酸類共聚物的樹脂組合物可以直接用於配製低VOC(VOC排放量低於420g/L)的溶劑基塗料組合物,而且由其形成的塗層具有良好的塗層性質。 It can be seen from the above results that the resin composition containing the acrylic copolymer according to the present invention can be directly used to formulate low VOC (VOC emissions less than 420g/L) solvent-based coating composition, and the coating formed therefrom The layer has good coating properties.
儘管本發明參照大量實施方式和實施例進行描述,但是本領域普通技術人員根據本發明公開的內容能夠認識到可以設計其它實施方式,這並未脫離本發明的保護範圍和精神。 Although the present invention is described with reference to a large number of embodiments and examples, those of ordinary skill in the art can recognize that other embodiments can be designed based on the disclosure of the present invention, which does not depart from the protection scope and spirit of the present invention.
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