TW202118837A - Resin coating - Google Patents
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本發明是有關於一種樹脂塗料,且特別是有關於一種含有經表面改質之碳的同素異形體之樹脂塗料。The present invention relates to a resin coating, and more particularly to a resin coating containing an allotrope of surface-modified carbon.
在室外環境中,通常使用樹脂塗料對物件設備(例如欄杆、管道或門窗等建材)進行塗布,以發揮保護或裝飾的作用。然而,當樹脂塗料長期暴露於室外環境時,在日曬的作用下,基於UV光對樹脂的破壞,可能縮短使用壽命,同時也存在安全風險。另一方面,在海洋塗料、儲槽塗料以及實驗室反應器塗料方面,也需要樹脂塗料具備更佳的耐化性及耐腐蝕性,以應用於惡劣環境及高腐蝕環境。In the outdoor environment, resin coatings are usually used to coat objects and equipment (such as railings, pipes, doors and windows and other building materials) to play a protective or decorative role. However, when the resin coating is exposed to the outdoor environment for a long time, under the action of the sun, based on the damage of UV light to the resin, the service life may be shortened, and there are also safety risks. On the other hand, in marine coatings, storage tank coatings and laboratory reactor coatings, resin coatings are also required to have better chemical resistance and corrosion resistance to be used in harsh and highly corrosive environments.
在現有的底漆-面漆複合塗層中,造成腐蝕的因素包括環境因素、工程因素或其他人為因素。環境因素例如是酸雨、海風(含鹽)、潮濕或強日照;工程因素例如是鐵件撞擊敲打、塗料附著力不佳、塗料阻水氣能力差、面漆耐候性差、底漆保護能力不足或表面處理不佳;其他人為因素例如是刮傷、撞擊或環境中存在其他具腐蝕性的化學物質。In the existing primer-finish composite coating, the factors that cause corrosion include environmental factors, engineering factors or other human factors. Environmental factors such as acid rain, sea breeze (with salt), humidity or strong sunlight; engineering factors such as iron impact knocking, poor paint adhesion, poor water and vapor resistance of the paint, poor weather resistance of the topcoat, insufficient primer protection, or Poor surface treatment; other human factors such as scratches, impacts or the presence of other corrosive chemicals in the environment.
基於上述,如何提升樹脂塗料的耐化性、抗UV特性、附著力以及耐腐蝕效能,為本領域技術發展的重要課題。Based on the above, how to improve the chemical resistance, UV resistance, adhesion, and corrosion resistance of resin coatings is an important topic for technical development in the field.
本發明提供一種樹脂塗料,具有更佳的耐化性、抗UV特性(吸光值提升)、抗腐蝕力、對金屬基材的高附著力及還原力,適合作為室外塗料、海洋塗料、儲槽塗料以及實驗室反應器塗料。The invention provides a resin coating which has better chemical resistance, UV resistance (increased light absorption value), corrosion resistance, high adhesion to metal substrates and reduction power, and is suitable for outdoor coatings, marine coatings, and storage tanks. Coatings and laboratory reactor coatings.
本發明的樹脂塗料,包括第一經表面改質之碳的同素異形體及第一樹脂。第一經表面改質之碳的同素異形體具有sp2結構且C:O比例為50:1至800:1,在320 nm至750 nm波長下的吸光值(Absorbance)為0.5至2.5。The resin coating of the present invention includes a first surface-modified carbon allotrope and a first resin. The allotrope of the first surface-modified carbon has an sp2 structure and a C:O ratio of 50:1 to 800:1, and an absorbance value (Absorbance) of 0.5 to 2.5 at a wavelength of 320 nm to 750 nm.
在本發明的一實施例中,以樹脂塗料的總重量計,第一經表面改質之碳的同素異形體的含量為0.05 wt%至1 wt%,第一樹脂的含量為10 wt%至25 wt%。In an embodiment of the present invention, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is 0.05 wt% to 1 wt%, and the content of the first resin is 10 wt% To 25 wt%.
在本發明的一實施例中,第一經表面改質之碳的同素異形體包括石墨烯或奈米鑽石。In an embodiment of the present invention, the first surface-modified carbon allotrope includes graphene or nanodiamond.
在本發明的一實施例中,第一樹脂包括環氧樹脂(Epoxy)。In an embodiment of the present invention, the first resin includes epoxy resin (Epoxy).
在本發明的一實施例中,第一經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值為7.5至9的反應條件下進行還原反應,以使第一經表面改質之碳的同素異形體的C:O比例為50:1至800:1。In an embodiment of the present invention, the first surface modification method of the allotrope of surface-modified carbon includes: using a strong acid solution to break the π bond of the allotrope of carbon, and then oxidizing the carbon allotrope. The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to carry out a reduction reaction under the reaction condition of pH 7.5 to 9 to make the first surface-modified carbon homologous The C:O ratio of the plain body is 50:1 to 800:1.
在本發明的一實施例中,弱鹼溶液包括2%至8%的碳酸氫鈉水溶液。In an embodiment of the present invention, the weak base solution includes 2% to 8% sodium bicarbonate aqueous solution.
在本發明的一實施例中,強酸溶液包括硫酸水溶液或硝酸水溶液。In an embodiment of the present invention, the strong acid solution includes an aqueous sulfuric acid solution or an aqueous nitric acid solution.
在本發明的一實施例中,取代基包括羧基、羥基或醯胺基。In an embodiment of the present invention, the substituent includes a carboxyl group, a hydroxyl group or an amide group.
在本發明的一實施例中,樹脂塗料作為底漆使用,在底漆上設置面漆,面漆包括第二經表面改質之碳的同素異形體,其具有sp2結構且C:O比例為50:1至800:1,在320 nm至750 nm波長下的吸光值為0.5至3。In an embodiment of the present invention, the resin coating is used as a primer, and a topcoat is provided on the primer. The topcoat includes a second surface-modified carbon allotrope, which has an sp2 structure and a C:O ratio It is 50:1 to 800:1, and the absorbance value is 0.5 to 3 at a wavelength of 320 nm to 750 nm.
在本發明的一實施例中,在底漆及面漆之間設置中塗漆,中塗漆包括第三經表面改質之碳的同素異形體,其具有sp2結構且C:O比例為10:1至300:1,在320 nm至750 nm波長下的吸光值為0.5至3。In an embodiment of the present invention, a middle paint is provided between the primer and the top paint, and the middle paint includes a third surface-modified carbon allotrope, which has an sp2 structure and a C:O ratio of 10: 1 to 300:1, the absorbance value is 0.5 to 3 at a wavelength of 320 nm to 750 nm.
在本發明的一實施例中,第二經表面改質之碳的同素異形體包括石墨烯或奈米鑽石。In an embodiment of the present invention, the second surface-modified carbon allotrope includes graphene or nanodiamond.
在本發明的一實施例中,面漆更包括第二樹脂,所述第二樹脂包括環氧矽樹脂。In an embodiment of the present invention, the topcoat further includes a second resin, and the second resin includes epoxy silicone resin.
在本發明的一實施例中,第三經表面改質之碳的同素異形體包括石墨烯或奈米鑽石。In an embodiment of the present invention, the third surface-modified carbon allotrope includes graphene or nanodiamond.
在本發明的一實施例中,中塗漆更包括第三樹脂,第三樹脂包括環氧樹脂。In an embodiment of the present invention, the intermediate paint further includes a third resin, and the third resin includes an epoxy resin.
在本發明的一實施例中,第二經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值為7.5至9的反應條件下進行還原反應,以使第二經表面改質之碳的同素異形體的C:O比例為50:1至800:1。In an embodiment of the present invention, the second surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the carbon allotrope The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to carry out a reduction reaction under the reaction condition of pH 7.5 to 9 to make the second surface-modified carbon homologous The C:O ratio of the plain body is 50:1 to 800:1.
在本發明的一實施例中,第三經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值為7.5至9的反應條件下進行還原反應,以使第三經表面改質之碳的同素異形體的C:O比例為10:1至300:1。In an embodiment of the present invention, the third surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidize the carbon allotrope. The broken π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to carry out a reduction reaction under the reaction condition of pH 7.5 to 9 to make the third surface-modified carbon homologous The C:O ratio of the plain body is 10:1 to 300:1.
在本發明的一實施例中,弱鹼溶液包括2%至8%的碳酸氫鈉水溶液。In an embodiment of the present invention, the weak base solution includes 2% to 8% sodium bicarbonate aqueous solution.
基於上述,本發明的樹脂塗料作為底漆使用,具有導電性,可增加鋅粉的還原能力及樹脂的附著力。在底漆上設置的面漆具有優良吸光能力及耐候能力,使樹脂不粉化或劣化,進而有效保護底漆及中塗漆。底漆及面漆之間設置的中塗漆可使水氣無法順利透過到達基材表面。Based on the above, the resin coating of the present invention is used as a primer, has conductivity, and can increase the reduction ability of zinc powder and the adhesion of the resin. The top coat set on the primer has excellent light absorption and weather resistance, so that the resin will not powder or deteriorate, thereby effectively protecting the primer and intermediate paint. The middle coat paint set between the primer and the top coat prevents water vapor from passing through to the surface of the substrate smoothly.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例作詳細說明如下。In order to make the above-mentioned features and advantages of the present invention more obvious and comprehensible, the following specific embodiments are described in detail as follows.
在本文中,由「一數值至另一數值」表示的範圍,是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此,某一特定數值範圍的記載,涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍,如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。> 底漆 > In this article, the range represented by "a value to another value" is a general way to avoid listing all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are clearly written in the specification The scope is the same. > Primer >
本發明提供一種樹脂塗料,包括第一經表面改質之碳的同素異形體及樹脂。第一經表面改質之碳的同素異形體具有sp2結構且C:O比例例如是50:1至800:1,在320 nm至750 nm波長下的吸光值(Absorbance)例如是0.5至2.5。此外,透過BET檢驗,第一經表面改質之碳的同素異形體之比表面積例如是10 m2 /g至30 m2 /g;利用FTIR檢驗,其中存在CO、OH、COOH等官能基團。第一經表面改質之碳的同素異形體之粒徑例如是1μm至20μm,利用拉曼檢驗所得ID/IG比例例如是0.0至0.3。如此一來,當樹脂塗料作為底漆使用時,具有導電性及陰極防護作用,供應電子避免腐蝕,且可增加鋅粉的還原能力及樹脂的附著力。The invention provides a resin coating comprising a first surface-modified carbon allotrope and resin. The allotrope of the first surface-modified carbon has an sp2 structure and the C:O ratio is, for example, 50:1 to 800:1, and the absorbance (Absorbance) at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 2.5 . In addition, through BET inspection, the specific surface area of the first surface-modified carbon allotrope is, for example, 10 m 2 /g to 30 m 2 /g; using FTIR inspection, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the first surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by the Raman test is, for example, 0.0 to 0.3. In this way, when the resin paint is used as a primer, it has conductivity and cathodic protection, supplies electrons to avoid corrosion, and can increase the reduction ability of zinc powder and the adhesion of the resin.
在本實施例中,第一經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值例如是7.5至9的反應條件下進行還原反應,以使第一經表面改質之碳的同素異形體的C:O比例例如是50:1至800:1。更詳細而言,弱鹼溶液可包括2%至8%的碳酸氫鈉水溶液,強酸溶液可包括硫酸水溶液或硝酸水溶液,取代基可包括羧基、羥基或醯胺基。In this embodiment, the first surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the broken carbon allotrope. The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to perform a reduction reaction under a reaction condition of pH 7.5 to 9, for example, to make the first surface-modified carbon allotrope The C:O ratio of the body is, for example, 50:1 to 800:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group, or an amide group.
在本實施例中,以樹脂塗料的總重量計,第一經表面改質之碳的同素異形體的含量例如是0.05 wt%至1 wt%,第一樹脂的含量例如是10 wt%至25 wt%。第一經表面改質之碳的同素異形體可包括石墨烯或奈米鑽石,第一樹脂可包括環氧樹脂(Epoxy)。更詳細而言,本發明的樹脂塗料可製成油性底漆或水性底漆,且配方組成因而有所不同。無論是油性底漆或水性底漆,配方皆不使用重金屬鉛,且盡可能降低鋅粉的使用量,以減少成本。In this embodiment, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 1 wt%, and the content of the first resin is, for example, 10 wt% to 10 wt%. 25 wt%. The first surface-modified carbon allotrope may include graphene or nanodiamond, and the first resin may include epoxy. In more detail, the resin coating of the present invention can be made into an oil-based primer or a water-based primer, and the formula composition is therefore different. Regardless of whether it is an oil-based primer or a water-based primer, the formula does not use heavy metal lead, and the amount of zinc powder used is as low as possible to reduce costs.
在油性底漆中,以樹脂塗料的總重量計,第一經表面改質之碳的同素異形體的含量例如是0.05 wt%至1 wt%(以增加抗腐蝕力),第一樹脂的含量例如是10 wt%至15 wt%(成膜作用相關),增稠劑的含量例如是0.2 wt%至1 wt%(增加黏稠度),二甲苯溶劑的含量例如是10 wt%至15 wt%,異丁醇溶劑的含量例如是3 wt%至10 wt%,分散劑的含量例如是0.2 wt%至5 wt%(可增加塗層潤濕度),流平劑的含量例如是0.5 wt%至5 wt%(使塗刷平整),鋅粉的含量例如是50 wt%至80 wt%(還原能力相關),固化劑(交聯劑)的含量例如是8 wt%至15 wt%。In the oil-based primer, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 1 wt% (to increase corrosion resistance). The content is, for example, 10 wt% to 15 wt% (related to film formation), the content of thickener is, for example, 0.2 wt% to 1 wt% (increasing viscosity), and the content of xylene solvent is, for example, 10 wt% to 15 wt. %, the content of isobutanol solvent is, for example, 3 wt% to 10 wt%, the content of dispersant is, for example, 0.2 wt% to 5 wt% (which can increase the wettability of the coating), and the content of leveling agent is, for example, 0.5 wt. % To 5 wt% (to make the painting smooth), the content of zinc powder is, for example, 50 wt% to 80 wt% (reducing ability related), and the content of curing agent (crosslinking agent) is, for example, 8 wt% to 15 wt%.
在水性底漆中,以樹脂塗料的總重量計,第一經表面改質之碳的同素異形體的含量例如是0.05 wt%至0.8 wt%(以增加抗腐蝕力),第一樹脂的含量例如是15 wt%至25 wt%,分散劑的含量例如是5 wt%至10 wt%(可增加塗層潤濕度),流平劑的含量例如是0.5 wt%至2 wt%(使塗刷平整),鋅粉的含量例如是50 wt%至85 wt%(還原能力相關),防沉劑的含量例如是5 wt%至10 wt%(避免沉澱),固化劑(交聯劑)的含量例如是5 wt%至15 wt%。> 面漆 > In the water-based primer, based on the total weight of the resin coating, the content of the first surface-modified carbon allotrope is, for example, 0.05 wt% to 0.8 wt% (to increase corrosion resistance). The content is, for example, 15 wt% to 25 wt%, the content of dispersant is, for example, 5 wt% to 10 wt% (which can increase the wettability of the coating), and the content of leveling agent is, for example, 0.5 wt% to 2 wt% (to make Brushing smoothly), the content of zinc powder is, for example, 50 wt% to 85 wt% (reducing ability related), the content of anti-settling agent is, for example, 5 wt% to 10 wt% (to avoid precipitation), curing agent (crosslinking agent) The content of is, for example, 5 wt% to 15 wt%. > Topcoat >
本發明的樹脂塗料作為底漆使用,且更可在底漆上設置面漆,面漆包括第二經表面改質之碳的同素異形體及第二樹脂。第二經表面改質之碳的同素異形體具有sp2結構且C:O比例例如是50:1至800:1,在320 nm至750 nm波長下的吸光值例如是0.5至3。此外,透過BET檢驗,第二經表面改質之碳的同素異形體之比表面積例如是5 m2 /g至30 m2 /g;利用FTIR檢驗,其中存在CO、OH、COOH等官能基團。第二經表面改質之碳的同素異形體之粒徑例如是1μm至20μm,利用拉曼檢驗所得ID/IG比例例如是0.0至0.3。如此一來,本發明的面漆吸光能力強且具備耐候能力,可使樹脂不粉化或劣化,進而有效地保護底漆及中塗漆。The resin coating of the present invention is used as a primer, and a topcoat can be provided on the primer. The topcoat includes a second surface-modified carbon allotrope and a second resin. The allotrope of the second surface-modified carbon has an sp2 structure and the C:O ratio is, for example, 50:1 to 800:1, and the absorbance at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 3. In addition, through BET inspection, the specific surface area of the second surface-modified carbon allotrope is, for example, 5 m 2 /g to 30 m 2 /g; using FTIR inspection, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the second surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by the Raman test is, for example, 0.0 to 0.3. In this way, the top coat of the present invention has strong light absorption and weather resistance, which can prevent the resin from powdering or deterioration, thereby effectively protecting the primer and middle coat.
在本實施例中,第二經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值例如是7.5至9的反應條件下進行還原反應,以使第二經表面改質之碳的同素異形體的C:O比例例如是50:1至800:1。更詳細而言,弱鹼溶液可包括2%至8%的碳酸氫鈉水溶液,強酸溶液可包括硫酸水溶液或硝酸水溶液,取代基可包括羧基、羥基或醯胺基。In this embodiment, the second surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidize the broken carbon allotrope. The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to perform a reduction reaction under a reaction condition of pH 7.5 to 9, for example, to make the second surface-modified carbon allotrope The C:O ratio of the body is, for example, 50:1 to 800:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group, or an amide group.
在本實施例中,第二經表面改質之碳的同素異形體可包括石墨烯或奈米鑽石,第二樹脂可包括環氧矽樹脂。以面漆組成物的總重量計,第二經表面改質之碳的同素異形體的含量例如是0.1 wt%至1 wt%(以增加抗腐蝕力),第二樹脂的含量例如是25 wt%至32 wt%(成膜作用相關),增稠劑的含量例如是0.1 wt%至5 wt%(增加黏稠度),二甲苯溶劑的含量例如是10 wt%至20 wt%,異丁醇溶劑的含量例如是3 wt%至8 wt%,分散劑的含量例如是0.5 wt%至2 wt%(可增加塗層潤濕度),流平劑的含量例如是0.5 wt%至1.5 wt%(使塗刷平整),鈦白粉的含量例如是5 wt%至10 wt%(耐候抗UV白色顏料),硫酸鋇填充粉的含量例如是8 wt%至15 wt%,磷酸鋅填充粉的含量例如是1 wt%至3 wt%,矽麗粉填充粉的含量例如是20 wt%至30 wt%,防沉劑的含量例如是3 wt%至10 wt%(避免沉澱),交聯劑的含量例如是3 wt%至10 wt%。> 中塗漆 > In this embodiment, the second surface-modified carbon allotrope may include graphene or nanodiamond, and the second resin may include epoxy silicone resin. Based on the total weight of the topcoat composition, the content of the second surface-modified carbon allotrope is, for example, 0.1 wt% to 1 wt% (to increase corrosion resistance), and the content of the second resin is, for example, 25 wt% to 32 wt% (related to film formation), the content of thickener is, for example, 0.1 wt% to 5 wt% (increasing viscosity), the content of xylene solvent is, for example, 10 wt% to 20 wt%, isobutyl The content of alcohol solvent is, for example, 3 wt% to 8 wt%, the content of dispersant is, for example, 0.5 wt% to 2 wt% (which can increase the wettability of the coating), and the content of leveling agent is, for example, 0.5 wt% to 1.5 wt. % (To make the painting smooth), the content of titanium dioxide is, for example, 5 wt% to 10 wt% (weather-resistant UV white pigment), the content of barium sulfate filler powder is, for example, 8 wt% to 15 wt%, zinc phosphate filler powder The content is, for example, 1 wt% to 3 wt%, the content of silica filler powder is, for example, 20 wt% to 30 wt%, and the content of anti-settling agent is, for example, 3 wt% to 10 wt% (to avoid precipitation), crosslinking agent The content of is, for example, 3 wt% to 10 wt%. > Intermediate paint >
本發明可在底漆及面漆之間設置中塗漆,中塗漆包括第三經表面改質之碳的同素異形體及第三樹脂。第三經表面改質之碳的同素異形體具有sp2結構且C:O比例例如是10:1至300:1,在320 nm至750 nm波長下的吸光值例如是0.5至3。此外,透過BET檢驗,第三經表面改質之碳的同素異形體之比表面積例如是10 m2 /g至50 m2 /g;利用FTIR檢驗,其中存在CO、OH、COOH等官能基團。第三經表面改質之碳的同素異形體之粒徑例如是1μm至20μm,利用拉曼檢驗所得ID/IG比例例如是0.0至0.3。如此一來,中塗漆可有效地使水氣無法順利通過到達基材表面。In the present invention, an intermediate paint can be arranged between the primer and the top paint, and the intermediate paint includes a third surface-modified carbon allotrope and a third resin. The allotrope of the third surface-modified carbon has an sp2 structure and the C:O ratio is, for example, 10:1 to 300:1, and the absorbance at a wavelength of 320 nm to 750 nm is, for example, 0.5 to 3. In addition, through the BET test, the specific surface area of the third surface-modified carbon allotrope is, for example, 10 m 2 /g to 50 m 2 /g; using FTIR test, there are functional groups such as CO, OH, COOH, etc. group. The particle size of the third surface-modified carbon allotrope is, for example, 1 μm to 20 μm, and the ID/IG ratio obtained by the Raman test is, for example, 0.0 to 0.3. In this way, the intermediate paint can effectively prevent moisture from passing through to the surface of the substrate.
在本實施例中,第三經表面改質之碳的同素異形體的表面改質方法包括:使用強酸溶液打斷碳的同素異形體的π鍵,再以氧化作用於經打斷的π鍵上鍵結能夠與水形成氫鍵的取代基;以及使用弱鹼溶液在pH值例如是7.5至9的反應條件下進行還原反應,以使第三經表面改質之碳的同素異形體的C:O比例例如是10:1至300:1。更詳細而言,弱鹼溶液可包括2%至8%的碳酸氫鈉水溶液,強酸溶液可包括硫酸水溶液或硝酸水溶液,取代基可包括羧基、羥基或醯胺基。In this embodiment, the third surface modification method of the surface-modified carbon allotrope includes: using a strong acid solution to break the π bond of the carbon allotrope, and then oxidizing the broken carbon allotrope. The π bond is bonded to a substituent that can form a hydrogen bond with water; and a weak base solution is used to perform a reduction reaction at a pH of, for example, 7.5 to 9 to make the third surface-modified carbon allotrope The C:O ratio of the body is, for example, 10:1 to 300:1. In more detail, the weak base solution may include a 2% to 8% sodium bicarbonate aqueous solution, the strong acid solution may include an aqueous sulfuric acid solution or an aqueous nitric acid solution, and the substituent may include a carboxyl group, a hydroxyl group, or an amide group.
在本實施例中,第三經表面改質之碳的同素異形體可包括石墨烯或奈米鑽石,第三樹脂可包括環氧樹脂。以中塗漆組成物的總重量計,第三經表面改質之碳的同素異形體的含量例如是0.1 wt%至2 wt%,第三樹脂的含量例如是20 wt%至30 wt%(成膜作用相關),增稠劑的含量例如是3 wt%至5 wt%(增加黏稠度),二甲苯溶劑的含量例如是5 wt%至10 wt%,異丁醇溶劑的含量例如是3 wt%至10 wt%,甲基異丁基酮(MIBK)溶劑的含量例如是3 wt%至10 wt%,分散劑的含量例如是0.1 wt%至2 wt%(可增加塗層潤濕度),流平劑的含量例如是0.1 wt%至2 wt%(使塗刷平整),Al/Zr表面處理TiO2 的含量例如是3 wt%至8 wt%(作為色粉、填料),硫酸鋇填充粉的含量例如是5 wt%至10 wt%,磷酸鋅填充粉的含量例如是1 wt%至5 wt%,功能性填充劑的含量例如是5 wt%至20 wt%,交聯劑的含量例如是5 wt%至15 wt%。In this embodiment, the third surface-modified carbon allotrope may include graphene or nanodiamond, and the third resin may include epoxy resin. Based on the total weight of the middle coating composition, the content of the third surface-modified carbon allotrope is, for example, 0.1 wt% to 2 wt%, and the content of the third resin is, for example, 20 wt% to 30 wt% ( Related to film formation), the content of thickener is, for example, 3 wt% to 5 wt% (increasing viscosity), the content of xylene solvent is, for example, 5 wt% to 10 wt%, and the content of isobutanol solvent is, for example, 3. wt% to 10 wt%, the content of the methyl isobutyl ketone (MIBK) solvent is, for example, 3 wt% to 10 wt%, and the content of the dispersant is, for example, 0.1 wt% to 2 wt% (which can increase the wettability of the coating ), the content of leveling agent is, for example, 0.1 wt% to 2 wt% (to make the painting smooth), the content of Al/Zr surface treatment TiO 2 is , for example, 3 wt% to 8 wt% (as toner and filler), sulfuric acid The content of barium filler powder is, for example, 5 wt% to 10 wt%, the content of zinc phosphate filler powder is, for example, 1 wt% to 5 wt%, and the content of functional filler is, for example, 5 wt% to 20 wt%. Crosslinking agent The content of is, for example, 5 wt% to 15 wt%.
在本發明的底漆、中塗漆及面漆複合塗料系統中,底漆、中塗漆及面漆的總塗層厚度例如是240μm。底漆的厚度例如是80μm至120μm,中塗漆的厚度例如是0μm至80μm,面漆的厚度例如是60μm至120μm。當面漆的厚度夠厚時,可以不用配置中塗漆。舉例而言,當底漆的厚度例如是120μm,面漆的厚度例如是120μm時,中塗漆的厚度例如是0μm,亦即,可以不用塗佈中塗漆。In the primer, middle coat and top coat composite coating system of the present invention, the total coating thickness of the primer, middle coat and top coat is, for example, 240 μm. The thickness of the primer is, for example, 80 μm to 120 μm, the thickness of the middle coating is, for example, 0 μm to 80 μm, and the thickness of the top coat is, for example, 60 μm to 120 μm. When the thickness of the top coat is thick enough, it is not necessary to configure the middle coat. For example, when the thickness of the primer is 120 μm and the thickness of the top paint is 120 μm, the thickness of the intermediate paint is, for example, 0 μm, that is, the intermediate paint may not be applied.
本發明的底漆、中塗漆及面漆複合塗料系統具有良好的耐候能力,測試結果△E為0.061。附著性的評估方法採用百格附著性測試,測試方法是用百格刀在測試樣本(玻璃材料)表面劃10×10個(100個)1 mm×1 mm小網格,每一條劃線深及塗料的底層。之後,用毛刷將測試區域的碎片刷乾淨,再用3M 600號膠紙或等同效力的膠紙牢牢黏住被測試小網格,並用橡皮擦用力擦拭膠帶,以加大膠帶與被測區域的接觸面積及力度。接著,用手抓住膠帶一端,在垂直方向(90°)迅速扯下膠紙,同一位置進行2次相同試驗。本發明的底漆、中塗漆及面漆複合塗料系統之百格附著性測試結果為4B,具有良好附著力。The primer, middle coat and top coat composite coating system of the present invention has good weather resistance, and the test result ΔE is 0.061. The adhesion evaluation method adopts the 100-grid adhesion test. The test method is to use a 100-grid knife to draw 10×10 (100) 1 mm×1 mm small grids on the surface of the test sample (glass material), each of which is deep And the bottom layer of the paint. After that, use a brush to clean the debris in the test area, then use 3M 600 adhesive tape or equivalent adhesive tape to firmly stick the small grid to be tested, and wipe the tape with an eraser to enlarge the tape and the tested area. The contact area and intensity of the area. Then, grab one end of the tape with your hand, quickly pull off the tape in the vertical direction (90°), and perform the same test twice at the same position. The 100 grid adhesion test result of the primer, middle coat and top coat composite coating system of the present invention is 4B, which has good adhesion.
以下,藉由實驗例來詳細說明上述實施例所提出的底漆、中塗漆及面漆複合塗料系統。然而,下述實驗例並非用以限制本發明。實驗例 Hereinafter, experimental examples are used to describe in detail the primer, intermediate paint, and topcoat composite coating systems proposed in the foregoing embodiments. However, the following experimental examples are not intended to limit the present invention. Experimental example
為了證明將本發明的底漆、中塗漆及面漆複合塗料系統具有優良耐化性、抗UV特性(吸光值提升)、抗腐蝕力、對金屬基材的附著力及還原力,以下特別作此實驗例。鹽水防鏽測試 In order to prove that the primer, midcoat and topcoat composite coating system of the present invention has excellent chemical resistance, UV resistance (increased absorbance), corrosion resistance, adhesion to metal substrates and reducing power, the following special This experimental example. Salt water anti-rust test
將本發明的底漆、中塗漆及面漆複合塗料系統以不同厚度進行塗佈,再進行720小時的鹽水噴霧加速測試以評估防鏽能力,實驗結果列於以下表1中。如下方表1所示,本發明的底漆、中塗漆及面漆複合塗料系統進行720小時的鹽水噴霧加速測試的結果,均呈現不生鏽的實驗結果,因此,可得知本發明的底漆、中塗漆及面漆複合塗料系統具有良好的防鏽效果。
表1
綜上所述,本發明的樹脂塗料作為底漆使用,具有導電性,可增加鋅粉的還原能力及樹脂的附著力。在底漆上設置的面漆具有優良吸光能力及耐候能力,使樹脂不粉化或劣化,進而有效保護底漆及中塗漆。底漆及面漆之間設置的中塗漆可使水氣無法順利透過到達基材表面。此外,經百格附著性測試結果,驗證了本發明的底漆、中塗漆及面漆複合塗料系統具有良好附著力,經鹽水防鏽測試結果,更驗證了本發明的底漆、中塗漆及面漆複合塗料系統具有優良的防鏽能力。In summary, the resin coating of the present invention is used as a primer, has conductivity, and can increase the reduction ability of zinc powder and the adhesion of the resin. The top coat set on the primer has excellent light absorption and weather resistance, so that the resin will not powder or deteriorate, thereby effectively protecting the primer and intermediate paint. The middle coat paint set between the primer and the top coat prevents water vapor from passing through to the surface of the substrate smoothly. In addition, the results of the 100 grid adhesion test verify that the primer, midcoat and topcoat composite coating systems of the present invention have good adhesion, and the salt water anti-rust test results further verify that the primer, midcoat and topcoat of the present invention have good adhesion. The top coat composite coating system has excellent anti-rust ability.
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