TWI625370B - Highly reflective coating - Google Patents
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Abstract
本發明提供具有優異的耐久性、高反射率和極低光澤度的塗料組合物。所述塗料組合物包含：至少包含第一樹脂組分的粘合劑體系、任選的一種或多種額外樹脂組分、交聯組分和產生紋理的組分。還提供其至少部分表面上塗覆有所述塗料組合物的塗佈製品。 The present invention provides a coating composition having excellent durability, high reflectance, and extremely low gloss. The coating composition comprises: a binder system comprising at least a first resin component, optionally one or more additional resin components, a cross-linking component, and a texture-forming component. A coated article having at least a portion of its surface coated with the coating composition is also provided.
Description
本發明係提供一種塗料組合物，特別是指一種具有優異的耐久性、高反射率和極低光澤度的塗料組合物。 The present invention provides a coating composition, and more particularly to a coating composition having excellent durability, high reflectance, and extremely low gloss.
聚合物塗料組合物通常被塗覆到基材上，尤其是金屬基材上。這樣的塗料出於下述各種原因而被使用，包括例如為了保護基材免於降解、為了美化基材(例如為了提供顏色、亮度等)和/或為了反射光線。 The polymeric coating composition is typically applied to a substrate, especially a metal substrate. Such coatings are used for a variety of reasons including, for example, to protect the substrate from degradation, to beautify the substrate (eg, to provide color, brightness, etc.) and/or to reflect light.
許多這樣的聚合物塗料組合物被塗覆到平面基材上(例如使用卷塗工藝)，隨後使其形成最終製品，包括用作外部建築材料的製品、燈具等。塗層還必須在長期暴露於各種條件(包括光、濕度、雨、波動溫度等)之後維持合適的美學外觀(光澤、顏色等)。 Many such polymeric coating compositions are applied to planar substrates (e.g., using a roll coating process) and subsequently formed into final articles, including articles, luminaires, and the like, for use as exterior building materials. The coating must also maintain a suitable aesthetic appearance (gloss, color, etc.) after prolonged exposure to various conditions including light, humidity, rain, fluctuating temperatures, and the like.
卷塗零件可用於製造反射表面。通常，當這種零件被用在照明設備中時，反射表面是高光澤度白色塗層或者鏡面銀色塗層。這種表面不僅提供高反射水準，還還產生高眩光水準，而高眩光水準最終將降低這些塗層的可用性。 Coiled parts can be used to make reflective surfaces. Typically, when such parts are used in a lighting device, the reflective surface is a high gloss white coating or a mirrored silver coating. This surface not only provides high levels of reflection, but also produces high levels of glare, which in turn will reduce the usability of these coatings.
因此，持續需要如下的卷材塗層和卷塗零件，當用在照明設備中時，其不僅能夠提供高反射率而且能夠提供顯著減少的眩光(glare)。 Accordingly, there is a continuing need for coil coatings and coiled parts that, when used in a lighting device, are capable of providing not only high reflectivity but also significantly reduced glare.
在一個實施方式中，本說明書提供由塗料組合物形成的固化塗層，其中所述固化塗層展示出高反射率和低光澤度。所述塗料組合 物包含粘合劑體系，所述粘合劑體系至少包含第一粘合劑樹脂組分。所述塗料組合物可包含其它成分，包括以下之中的一種或多種：(i)交聯劑、(ii)催化劑、(iii)一種或多種光散射組分、(iv)顏料、(v)產生紋理的添加劑、和/或(vi)流平劑，以及其它組分。所述組合物形成60°光澤度等級為約5且反射率為至少約90%的低光澤度塗層。 In one embodiment, the present specification provides a cured coating formed from a coating composition, wherein the cured coating exhibits high reflectivity and low gloss. The coating combination The composition comprises a binder system comprising at least a first binder resin component. The coating composition may comprise other ingredients, including one or more of the following: (i) a crosslinking agent, (ii) a catalyst, (iii) one or more light scattering components, (iv) a pigment, (v) Textured additives, and/or (vi) leveling agents, as well as other components. The composition forms a low gloss coating having a 60° gloss rating of about 5 and a reflectivity of at least about 90%.
在另一個實施方式中，本說明書提供了塗佈製品，通常是金屬基材，其中至少部分所述基材上佈置有由本文所述的塗料組合物形成的固化塗層。 In another embodiment, the present specification provides a coated article, typically a metal substrate, wherein at least a portion of the substrate is provided with a cured coating formed from the coating composition described herein.
在另一個實施方式中，本發明提供了由金屬基材生產製品的方法，其中所述基材的至少部分表面上佈置有由本文所述的塗料組合物形成的固化塗層。 In another embodiment, the invention provides a method of producing an article from a metal substrate, wherein at least a portion of the surface of the substrate is disposed with a cured coating formed from the coating composition described herein.
除非另外指明，本文中使用的如下術語具有下文提供的含義。 Unless otherwise indicated, the following terms as used herein have the meanings provided below.
預期在本文所述的塗料組合物中使用的聚酯和其它聚合物樹脂的有機基團上會有取代。為了簡化本申請通篇中使用的某些術語的討論和陳述，術語“基團”和“片段”被用於區分允許取代或可以被取代的化學物種與不允許取代或不可被取代的化學物種。因此，使用術語“基團”描述化學取代基時，所描述的化學材料包括未經取代的基團和下述基團，所述基團例如在鏈中(如在烷氧基中)具有O、N、Si或S原子以及具有羰基或其它常規取代。使用術語“片段”描述化合物或取代基時，僅旨在包括未經取代的化學材料。例如，短語“烷基基團”旨在不僅包括純開鏈飽和烴烷基取代基(例如甲基、乙基、丙基、叔丁基等等)，而且包括還帶有本領域已知的其它取代基(例如羥基、烷氧基、烷基磺醯基、鹵 素原子、氰基、硝基、氨基、羧基等等)的烷基取代基。因此，“烷基基團”包括醚基、鹵代烷基、硝基烷基、羧基烷基、羥基烷基、磺基烷基等等。另一方面，短語“烷基片段”僅限於包括純開鏈飽和烴烷基取代基，例如甲基、乙基、丙基、叔丁基等等。術語“烴基片段”指僅含氫和碳的未被取代的有機片段。本文中使用的術語“基團”意欲記述特定的片段以及記述含有該片段的更廣種類的被取代結構和未被取代結構。 It is contemplated that there will be substitutions on the organic groups of the polyesters and other polymeric resins used in the coating compositions described herein. To simplify the discussion and statements of certain terms used throughout this application, the terms "group" and "fragment" are used to distinguish between chemical species that are allowed to be substituted or that may be substituted, and chemical species that are not allowed or substituted. . Thus, when the term "group" is used to describe a chemical substituent, the chemical materials described include unsubstituted groups and groups such as O in the chain (eg, in an alkoxy group). , N, Si or S atoms as well as having a carbonyl group or other conventional substitution. When the term "fragment" is used to describe a compound or substituent, it is intended only to include unsubstituted chemical materials. For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents (eg, methyl, ethyl, propyl, t-butyl, and the like), but also include those known in the art. Other substituents (eg, hydroxy, alkoxy, alkylsulfonyl, halo) An alkyl substituent of a prime atom, a cyano group, a nitro group, an amino group, a carboxyl group, or the like. Thus, "alkyl group" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like. In another aspect, the phrase "alkyl fragment" is meant to include pure open-chain saturated hydrocarbon alkyl substituents such as methyl, ethyl, propyl, t-butyl, and the like. The term "hydrocarbyl fragment" refers to an unsubstituted organic moiety containing only hydrogen and carbon. The term "group" as used herein is intended to describe a particular fragment as well as to describe a broader variety of substituted and unsubstituted structures containing the fragment.
術語“交聯劑”是指，能夠在聚合物之間或同一聚合物的兩個不同區域之間形成共價鍵連接的分子。 The term "crosslinker" refers to a molecule capable of forming a covalent bond between polymers or between two different regions of the same polymer.
當在“塗料塗覆在表面或基材上”的上下文中使用時，術語“在......上”包括塗料直接或間接塗覆於表面或基材上。因此，例如，塗料塗覆在基材上的底漆層上表示塗料塗覆在該基材上。 When used in the context of "coating a coating on a surface or substrate", the term "on" includes coating applied directly or indirectly to a surface or substrate. Thus, for example, coating a coating on a primer layer on a substrate indicates that the coating is applied to the substrate.
除非另外指明，術語“聚合物”包括均聚物和共聚物(即兩種或更多種不同單體的聚合物)。類似地，除非另有聲明，指定聚合物種類的術語(例如“聚酯”)的使用旨在包括均聚物和共聚物(例如聚酯-聚氨酯聚合物)二者。 Unless otherwise indicated, the term "polymer" includes homopolymers and copolymers (ie, polymers of two or more different monomers). Similarly, the use of terms specifying a polymer species (eg, "polyester") is intended to include both homopolymers and copolymers (eg, polyester-polyurethane polymers) unless otherwise stated.
當在化合物的上下文中使用時，術語“不飽和的”是指，含有至少一個不是存在於芳族環中的雙鍵的化合物。 The term "unsaturated" when used in the context of a compound refers to a compound containing at least one double bond that is not present in the aromatic ring.
當在本文中使用時，術語“矽酮”是指，聚合的矽氧烷或聚矽氧烷，其是具有通用結構式[R2SiO]n的混合無機-有機聚合物，其中R是取代的或未經取代的C1-C12烷基、C1-C12烷氧基、C6-C10芳基等。當在本文中使用時，矽酮是羥基官能的聚矽氧烷或烷氧基官能的聚矽氧烷。 As used herein, the term "fluorenone" refers to a polymeric decane or polyoxyalkylene which is a mixed inorganic-organic polymer of the general formula [R 2 SiO] n wherein R is a substitution Or unsubstituted C1-C12 alkyl, C1-C12 alkoxy, C6-C10 aryl, and the like. When used herein, an anthrone is a hydroxy-functional polyoxane or an alkoxy-functional polyoxyalkylene.
在說明書和申請專利範圍中出現的術語“包含”及其變體沒有限制含義。 The term "comprising" and variations thereof appearing in the specification and claims are not limiting.
當在本文中使用時，術語“反射率”(relectance)是指，在特定的光波長下，從經塗佈的製品或零件的表面反射回到觀察者的垂直入射光的光的百分比。 As used herein, the term "relectance" refers to the percentage of light that is reflected back from the surface of a coated article or part to the observer's normally incident light at a particular wavelength of light.
當在本文中使用時，“柔軟的觸摸”(soft touch)或“摸起來柔軟”(soft to the tough)是指，具有模擬觸摸感的低光澤度絲絨樣外觀的塗佈表面。這些術語在本文中可與術語“觸覺的”(tactile)或“觸感”(tactile feel)互換使用。 As used herein, "soft touch" or "soft to the tough" refers to a coated surface having a low gloss velvet-like appearance that mimics the touch. These terms are used interchangeably herein with the terms "tactile" or "tactile feel."
術語“優選的”和“優選地”是指在某些情況下可提供某些有益效果的本發明的實施方式。然而，在相同情況或其它情況下，其它實施方式也可以是優選的。此外，一個或多個優選實施方式的表述並不意味著其它實施方式不可用，並且並非意圖將其它實施方式排除在本發明的範圍之外。 The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits in certain circumstances. However, other embodiments may also be preferred in the same or other circumstances. In addition, the expression of one or more preferred embodiments does not imply that other embodiments are not available, and is not intended to exclude other embodiments from the scope of the invention.
當在本文中使用時，不使用數量詞、“至少一種”和“一種或多種”可互換使用。因此，例如，包含添加劑的塗料組合物可被理解為是指該塗料組合物包含“一種或多種”添加劑。 When used herein, the terms "a", "the" Thus, for example, a coating composition comprising an additive can be understood to mean that the coating composition comprises "one or more" additives.
另外，在本文，通過端點表述的數值範圍包括該範圍內的所有數值(例如，1-5包含1、1.5、2、2.75、3、3.80、4、5等)。此外，一個範圍的公開包括較寬範圍內包括的所有子範圍的公開(例如1至5公開1至4、1.5至4.5、1至2等)。 In addition, the numerical range expressed by the endpoints herein includes all values within the range (eg, 1-5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Further, a range of disclosure includes disclosure of all subranges included within a broader scope (eg, 1 to 5 disclosures 1 to 4, 1.5 to 4.5, 1 to 2, etc.).
在一個實施方式中，本說明書提供由熱固性塗料組合物形成的固化塗層，其展示出高反射率和低光澤度。所述塗料組合物通常包含粘合劑體系、交聯劑、催化劑、流平劑、一種或多種顏料、和光散射組分，連同紋理添加劑。粘合劑體系優選地至少包含第一樹脂組分，和任選的一種或多種額外樹脂組分。優選地，塗料組合物至少包含成膜量的粘合劑體系。雖然包含液態載體的塗料組合物目前是優選的，但預期本文所述的組合物可利用其它塗料塗覆技術(例如，粉末塗佈、擠出或層壓)。 In one embodiment, the present specification provides a cured coating formed from a thermosetting coating composition that exhibits high reflectivity and low gloss. The coating composition typically comprises a binder system, a crosslinking agent, a catalyst, a leveling agent, one or more pigments, and a light scattering component, along with a texturative additive. The binder system preferably comprises at least a first resin component, and optionally one or more additional resin components. Preferably, the coating composition comprises at least a film forming amount of a binder system. While coating compositions comprising a liquid carrier are presently preferred, it is contemplated that the compositions described herein may utilize other coating application techniques (e.g., powder coating, extrusion or lamination).
本文所述的粘合劑體系至少包含第一樹脂組分。第一樹脂組分優選地為聚酯樹脂，更優選地為耐久的聚酯樹脂。合適的聚酯包括，例如，通過具有反應性官能團的化合物(例如，具有羥基、羧基、酸酐、醯基或酯官能團的化合物)的反應形成的樹脂。已知羥基官能團在恰當條件下與酸、酸酐、醯基或酯官能團反應以形成聚酯鍵。適用於形成聚酯樹脂的合適化合物包括單官能化合物、二官能化合物和多官能化合物。目前優選二官能化合物。合適的化合物包括具有一種類型的反應性官能團的化合物(例如，單官能醇、二官能醇或多官能醇或者單官能酸、二官能酸或多官能酸)以及具有兩種或更多種不同類型官能團的化合物(例如，具有酸酐基團和酸基團二者的化合物或者具有醇基團和酸基團二者的化合物等)。粘合劑體系可包含一種或多種額外樹脂組分，所述額外樹脂組分與第一樹脂組分相同或不同。 The binder system described herein comprises at least a first resin component. The first resin component is preferably a polyester resin, more preferably a durable polyester resin. Suitable polyesters include, for example, resins formed by the reaction of a compound having a reactive functional group (for example, a compound having a hydroxyl group, a carboxyl group, an acid anhydride, a mercapto group or an ester functional group). Hydroxyl functional groups are known to react with acid, anhydride, sulfhydryl or ester functional groups under appropriate conditions to form polyester linkages. Suitable compounds suitable for forming the polyester resin include monofunctional compounds, difunctional compounds, and polyfunctional compounds. Difunctional compounds are presently preferred. Suitable compounds include compounds having one type of reactive functional group (for example, monofunctional alcohols, difunctional alcohols or polyfunctional alcohols or monofunctional acids, difunctional acids or polyfunctional acids) and having two or more different types A compound of a functional group (for example, a compound having both an acid anhydride group and an acid group or a compound having both an alcohol group and an acid group, etc.). The binder system can comprise one or more additional resin components that are the same or different than the first resin component.
在一個實施方式中，除了第一樹脂組分之外，粘合劑體系還包含第二聚酯樹脂組分。第二聚酯樹脂組分優選地為矽酮改性的或者矽化的聚酯樹脂。合適的矽化聚酯包括通過矽酮官能化合物與具有其它反應性官能團的化合物(例如，具有羥基、羧基、酸酐、醯基或酯官能團的化合物)的反應形成的那些。合適的矽酮官能化合物包括，例如，具有通式[R2SiO]n的聚合矽氧烷(又名有機-矽氧烷或有機聚矽氧烷)，其中R通常是C1-C12烷基(優選甲基或乙基)、C1-C12烷氧基(優選甲氧基或乙氧基)、芳基(優選苯基)等。在一個方面，聚合矽氧烷包含反應性官能團，例如，羥基、烷氧基、矽醇基等。本文中所使用的優選的矽化聚酯進一步描述在2015年1月9日提交的申請人的共同待決國際申請PCT/US2014/070096中。 In one embodiment, the binder system further comprises a second polyester resin component in addition to the first resin component. The second polyester resin component is preferably an anthrone-modified or deuterated polyester resin. Suitable deuterated polyesters include those formed by the reaction of an indolone functional compound with a compound having other reactive functional groups (e.g., compounds having hydroxyl, carboxyl, anhydride, sulfhydryl or ester functional groups). Suitable anthrone functional compounds include, for example, polymeric oxiranes of the general formula [R 2 SiO] n (also known as organic-p-oxanes or organopolyoxyalkylenes), wherein R is typically a C1-C12 alkyl group ( Methyl or ethyl), C1-C12 alkoxy (preferably methoxy or ethoxy), aryl (preferably phenyl) and the like are preferred. In one aspect, the polymeric oxirane comprises a reactive functional group, for example, a hydroxyl group, an alkoxy group, a decyl group, and the like. The preferred deuterated polyesters used herein are further described in the applicant's co-pending international application PCT/US2014/070096, filed on Jan. 9, 2015.
如果本文所述的粘合劑體系包含矽化聚酯，則基於粘合劑體系的總重量，矽化聚酯的量為優選地約5-60重量%、更優選地約10-55重量%。 If the binder system described herein comprises a deuterated polyester, the amount of deuterated polyester is preferably from about 5 to 60% by weight, more preferably from about 10 to 55% by weight, based on the total weight of the binder system.
基於本文所述塗料組合物的總重量，塗料組合物中粘合劑體系的量為優選地約1-65重量%、更優選地約15-50重量%、最優選地約20-40重量%。組合物中使用的粘合劑的量因所選擇的樹脂組分而異。 The amount of binder system in the coating composition is preferably from about 1 to about 65 weight percent, more preferably from about 15 to about 50 weight percent, and most preferably from about 20 to 40 weight percent, based on the total weight of the coating composition described herein. . The amount of binder used in the composition will vary with the resin component selected.
在一個實施方式中，塗料組合物還包含交聯劑(也被稱為交聯試劑)。交聯劑可用於促進塗料的固化和建立期望的物理性質。當交聯劑存在時，其量將因多種因素而異，所述因素包括，例如，預期的最終用途和交聯劑的類型。典型地，基於樹脂固體的總重量，一種或多種交聯劑在塗料組合物中的存在量將高於約0.01重量%、更優選地從約5重量%到約50重量%、甚至更優選地從約10重量%到約30重量%、最優選地從約15重量%到約20重量%。 In one embodiment, the coating composition further comprises a crosslinking agent (also referred to as a crosslinking agent). Crosslinkers can be used to promote curing of the coating and to establish desired physical properties. When a crosslinking agent is present, the amount will vary depending on a number of factors including, for example, the intended end use and the type of crosslinking agent. Typically, the one or more crosslinkers will be present in the coating composition in an amount greater than about 0.01% by weight, more preferably from about 5% by weight to about 50% by weight, even more preferably based on the total weight of the resin solids. From about 10% by weight to about 30% by weight, most preferably from about 15% by weight to about 20% by weight.
具有羥基的聚酯可通過羥基固化。合適的羥基反應***聯劑可包括，例如，氨基塑膠，其通常是這樣的低聚物，所述低聚物是醛類(特別是甲醛)的反應產物；攜帶氨基或醯胺基(amido)的物質(例如，三聚氰胺、脲、雙氰胺、苯並胍胺和甘脲)；封閉異氰酸酯或其組合。 The polyester having a hydroxyl group can be cured by a hydroxyl group. Suitable hydroxy-reactive cross-linking agents may include, for example, aminoplasts, which are typically oligomers which are the reaction product of aldehydes, particularly formaldehyde; carrying an amino or amido group Substances (eg, melamine, urea, dicyandiamide, benzoguanamine, and glycoluril); blocked isocyanates or combinations thereof.
合適的交聯劑包括用具有1-4個碳原子的鏈烷醇改性的氨基塑膠。在許多情況下，適合應用氨基塑膠的前體例如六羥甲基三聚氰胺、二羥甲基脲、六甲氧基甲基三聚氰胺，和其它的醚化形式。因此，可以使用多種市售氨基塑膠及其前體。合適的商業氨基交聯劑包括由Cytek以商品名CYMEL出售的那些(例如，CYMEL 301、CYMEL 303和CYMEL 385烷基化三聚氰胺-甲醛樹脂或者這些樹脂的混合物是有用的)或者由Solutia以商品名RESIMENE出售的那些。 Suitable crosslinking agents include aminoplasts modified with alkanols having from 1 to 4 carbon atoms. In many cases, precursors suitable for the application of aminoplasts such as hexamethylol melamine, dimethylol urea, hexamethoxymethyl melamine, and other etherified forms are suitable. Therefore, a variety of commercially available aminoplasts and precursors thereof can be used. Suitable commercial amino crosslinkers include those sold under the tradename CYMEL by Cytek (for example, CYMEL 301, CYMEL 303 and CYMEL 385 alkylated melamine-formaldehyde resins or mixtures of these resins are useful) or by Solutia under the trade name Those sold by RESIMENE.
合適的交聯劑還可包括封閉型異氰酸酯，例如，如美國專利號5,246,557中所述。封閉型異氰酸酯是這樣的異氰酸酯，其中異氰酸酯基團已經與保護劑或封閉劑反應以形成衍生物，所述衍生物在加熱後將解離以移除保護劑或封閉劑並釋放反應性異氰酸酯基團。適用於多異氰 酸酯的封閉劑的一些實例包括脂族、脂環族或芳烷基一元醇、羥胺和酮肟。目前優選的封閉型多異氰酸酯在約160℃的溫度下解離。催化劑的存在對於提高釋放的多異氰酸酯和含活性氫的化合物(例如，羥基官能聚酯)之間的反應的速率是優選的。催化劑可以是任何合適的催化劑，例如，二月桂酸二丁基錫或三亞乙基二胺。 Suitable crosslinking agents can also include blocked isocyanates, for example, as described in U.S. Patent No. 5,246,557. Blocked isocyanates are isocyanates in which isocyanate groups have been reacted with a protecting or blocking agent to form a derivative which will dissociate upon heating to remove the protecting or blocking agent and release the reactive isocyanate groups. Suitable for polyisocyanate Some examples of blocking agents for acid esters include aliphatic, cycloaliphatic or aralkyl monohydric alcohols, hydroxylamines and ketoximes. The currently preferred blocked polyisocyanates dissociate at a temperature of about 160 °C. The presence of a catalyst is preferred for increasing the rate of reaction between the released polyisocyanate and the active hydrogen-containing compound (e.g., hydroxy-functional polyester). The catalyst can be any suitable catalyst, for example, dibutyltin dilaurate or triethylenediamine.
合適的交聯劑還包括未封閉異氰酸酯。未封閉異氰酸酯是具有與脂族、脂環族、芳基、芳脂族和/或芳族片段相連的遊離異氰酸酯基團的二官能異氰酸酯或多官能異氰酸酯。實例包括但不限於，四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、1,4-二異氰酸酯環己烷、3,5,5-三甲基環己基異氰酸酯、異佛爾酮二異氰酸酯等。 Suitable crosslinking agents also include unblocked isocyanates. Unblocked isocyanates are difunctional isocyanates or polyfunctional isocyanates having free isocyanate groups attached to aliphatic, cycloaliphatic, aryl, araliphatic and/or aromatic moieties. Examples include, but are not limited to, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanate cyclohexane, 3,5,5-trimethylcyclohexyl isocyanate , isophorone diisocyanate, and the like.
在一些實施方式中，紫外線固化交聯劑或電子束固化交聯劑可以是合適的。合適的此類交聯劑的實例可以包括1,6-己二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯或者其混合物。 In some embodiments, an ultraviolet curing crosslinking agent or an electron beam curing crosslinking agent may be suitable. Examples of suitable such crosslinking agents may include 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, trimethylolpropane triacrylate, or mixtures thereof.
可通過本領域技術人員已知的常規方法來生產本文所述的塗料組合物。在一個實施方式中，通過使用聚合助劑或加工助劑(例如，催化劑)來製備塗料組合物。合適的加工助劑包括但不限於，金屬催化劑(例如，草酸亞錫、氯化亞錫、丁基錫酸、二丁基氧化錫、鈦酸四丁酯或鋯酸四丁酯)，抗氧化劑(例如，對苯二酚、單叔丁基-對苯二酚、苯醌、1,4-萘醌、2,5-二苯基-對苯醌或者對叔丁基鄰苯二酚)，未封閉的和封閉的酸催化劑(例如，二壬基萘磺酸、二壬基萘二磺酸、十二烷基苯磺酸鈉、對甲苯磺酸、磷酸酯、及其混合物或組合)和它們的混合物。催化劑的量取決於反應物的量和性質，但基於樹脂固體的總重量，優選地最多約5重量%、更優選地最多約2重量%。 The coating compositions described herein can be produced by conventional methods known to those skilled in the art. In one embodiment, the coating composition is prepared by using a polymerization aid or processing aid (eg, a catalyst). Suitable processing aids include, but are not limited to, metal catalysts (eg, stannous oxalate, stannous chloride, butyl stannate, dibutyl tin oxide, tetrabutyl titanate or tetrabutyl zirconate), antioxidants (eg, , hydroquinone, mono-tert-butyl-hydroquinone, benzoquinone, 1,4-naphthoquinone, 2,5-diphenyl-p-benzoquinone or p-tert-butyl catechol, not blocked And blocked acid catalysts (for example, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, sodium dodecylbenzenesulfonate, p-toluenesulfonic acid, phosphates, and mixtures or combinations thereof) and their mixture. The amount of catalyst depends on the amount and nature of the reactants, but is preferably up to about 5% by weight, more preferably up to about 2% by weight, based on the total weight of the resin solids.
本領域已知的其它添加劑可包含在本文所述的塗料組合物中。這些添加劑包括但不限於消光劑、流動或粘度調節劑、提供紋理的添加劑、蠟和/或可包含或分散在塗料組合物中的其它粘合劑。 Other additives known in the art can be included in the coating compositions described herein. These additives include, but are not limited to, matting agents, flow or viscosity modifiers, texturizing additives, waxes, and/or other binders that may be included or dispersed in the coating composition.
在一個實施方式中，本文所述的塗層是極低光澤度塗層。這種低光澤度塗層是有用的，因為它們能夠覆蓋基材表面上的缺陷，並且當用在例如反射體、照明設備等中時，可以幫助減少或者消除眩光。在一個優選的方面，由本文所述組合物形成的固化塗層展示出約10、優選地1-5、更優選地小於5的鏡面60°光澤度(通過手持型光澤度儀測量)。 In one embodiment, the coatings described herein are very low gloss coatings. Such low gloss coatings are useful because they can cover defects on the surface of the substrate and can help reduce or eliminate glare when used in, for example, reflectors, lighting fixtures, and the like. In a preferred aspect, the cured coating formed from the compositions described herein exhibits a specular 60° gloss (measured by a hand-held gloss meter) of about 10, preferably 1-5, more preferably less than 5.
按照慣例，通過在塗料組合物中包含一種或多種消光劑來製備低光澤度塗層。合適的消光劑包括，例如，二氧化矽、二氧化矽基材料、或者具有已知提供易分散性的顆粒的其它材料。消光劑的量取決於固化塗層的期望光澤度或反射率。基於組合物中樹脂固體的總重量，典型的低光澤度塗料組合物可包含最多約6重量%、優選地1重量%-5重量%的二氧化矽或二氧化矽基消光劑。 Conventionally, low gloss coatings are prepared by including one or more matting agents in the coating composition. Suitable matting agents include, for example, ceria, cerium oxide based materials, or other materials having particles known to provide easy dispersibility. The amount of matting agent depends on the desired gloss or reflectance of the cured coating. A typical low gloss coating composition may comprise up to about 6% by weight, preferably from 1% to 5% by weight, based on the total weight of the resin solids in the composition, of a ceria or cerium oxide based matting agent.
然而，為了產生60°光澤度低至本文所述(即，優選地小於5)的塗層，塗料組合物必須包含顯著過量的消光劑，但在這種高消光劑水準下，組合物的有益機械性能將損失。 However, in order to produce a coating having a 60° gloss as low as described herein (i.e., preferably less than 5), the coating composition must contain a significant excess of matting agent, but at such high matting agent levels, the composition is beneficial. Mechanical properties will be lost.
出乎意料地，本文所述的組合物展示出極低的60°光澤度，但不包含顯著過量的消光劑並沒有顯示出有益機械性能損失。在一個實施方式中，本文所述的組合物由於形成了微紋理表面形貌或微褶皺表面形貌，所以產生極低光澤度的固化塗層。不限於理論，人們認為：由於從塗層的不規則表面的光散射和子散射(subscattering)，這種微褶皺表面形貌引起漫反射。 Unexpectedly, the compositions described herein exhibited an extremely low 60° gloss, but did not contain a significant excess of matting agent and did not exhibit a beneficial loss of mechanical properties. In one embodiment, the compositions described herein produce a very low gloss cured coating due to the formation of a microtextured surface topography or a micropleated surface topography. Without being bound by theory, it is believed that such micro-pleated surface topography causes diffuse reflection due to light scattering and sub-scattering from the irregular surface of the coating.
為了形成微紋理塗層表面或微褶皺塗層表面，本文所述的塗料組合物包含產生紋理的添加劑，當塗層固化時，所述產生紋理的添加劑旨在產生微褶皺表面。因此，在一個實施方式中，本文所述的塗料組合物包含胺類添加劑以產生微褶皺表面形貌。不限於理論，人們認為：胺類傾向於在塗料組合物固化時揮發並因此形成表面褶皺。 To form a microtextured coating surface or a micropleated coating surface, the coating compositions described herein comprise a texturing additive that is intended to create a micropleated surface when the coating is cured. Thus, in one embodiment, the coating compositions described herein comprise an amine additive to create a micropleated surface topography. Without being bound by theory, it is believed that the amines tend to volatilize as the coating composition cures and thus form surface wrinkles.
在一個實施方式中，產生紋理的添加劑是具有通式(I)的胺類：NR1R2R3 (I) In one embodiment, the texturing additive is an amine having the general formula (I): NR 1 R 2 R 3 (I)
在式(I)中，R1、R2和R3可各自獨立地為-H；未被取代的C1-C10烷基；經取代的C1-C10烷基，其中取代基包括C1-C10烷基、烯基、芳基、鹵化物、羥基等；未被取代的和經取代的C4-C10支化烷基；未被取代的芳基；經取代的芳基，其中取代基包括C1-C10烷基、烯基、芳基、鹵化物、羥基等；C1-C10酮；C1-C10醛；C1-C10醚；芳基酮；芳基醛；芳基醚等，及其混合物或組合。 In formula (I), R 1 , R 2 and R 3 may each independently be -H; unsubstituted C1-C10 alkyl; substituted C1-C10 alkyl, wherein the substituent includes C1-C10 alkane Alkyl, alkenyl, aryl, halide, hydroxy, etc.; unsubstituted and substituted C4-C10 branched alkyl; unsubstituted aryl; substituted aryl, wherein the substituent includes C1-C10 Alkyl, alkenyl, aryl, halide, hydroxy, etc.; C1-C10 ketone; C1-C10 aldehyde; C1-C10 ether; aryl ketone; aryl aldehyde; aryl ether and the like, and mixtures or combinations thereof.
在一個實施方式中，基於本文所述的塗料組合物的總重量，組合物包含量為優選地約0.001重量%-5重量%、更優選地0.1重量%-2重量%的胺類添加劑。 In one embodiment, the composition comprises an amine additive in an amount of preferably from about 0.001% to 5% by weight, more preferably from 0.1% to 2% by weight, based on the total weight of the coating composition described herein.
在一個實施方式中，本文所述的塗料組合物包含一種或多種光散射劑或光散射組分。這種光散射劑通常是呈顆粒形式的多孔材料，所述顆粒的粒徑為至少約100μm、優選地120-150μm、更優選地160-180μm。光散射組分的合適實例包括但不限於，聚合物顆粒、大孔聚合物顆粒、顏料顆粒、玻璃薄片、金屬薄片、雲母等。在優選的方面，光散射組分可以是顏料，優選地是呈金紅石或銳鈦礦形式的二氧化鈦(TiO2)。 In one embodiment, the coating compositions described herein comprise one or more light scattering agents or light scattering components. Such light scattering agents are typically porous materials in the form of particles having a particle size of at least about 100 μm, preferably from 120 to 150 μm, more preferably from 160 to 180 μm. Suitable examples of light scattering components include, but are not limited to, polymer particles, macroporous polymer particles, pigment particles, glass flakes, metal flakes, mica, and the like. In a preferred aspect, the light scattering component can be a pigment, preferably titanium dioxide (TiO 2 ) in the form of rutile or anatase.
經塗佈的製品或表面的顏色取決於所使用的顏料。例如，如果塗料組合物包含TiO2作為顏料和光散射劑，則所產生的塗層是亮白色塗層。 The color of the coated article or surface depends on the pigment used. For example, if the coating composition comprises TiO 2 as a pigment and a light scattering agent, the resulting coating is a bright white coating.
在一個方面，顏料和/或光散射組分優選地分散在塗料組合物的三聚氰胺交聯劑中或者矽化聚酯組分中。在另一個方面，可以使用可商購的色漿或者將其與其它顏料組合並摻入塗料組合物中以獲得期望的 顏色或明暗度。在另一個方面，本文所述的一種或多種顏料可以是光散射組分。 In one aspect, the pigment and/or light scattering component is preferably dispersed in the melamine crosslinking agent of the coating composition or in the deuterated polyester component. In another aspect, a commercially available colorant can be used or combined with other pigments and incorporated into the coating composition to achieve the desired Color or shade. In another aspect, one or more of the pigments described herein can be a light scattering component.
在一些實施方式中，塗料組合物的顏料：粘合劑重量比為優選地至少0.02：1至約1.4：1。在某些實施方式中，顏料：粘合劑重量比不超過約1.4：1。 In some embodiments, the pigment:binder weight ratio of the coating composition is preferably at least 0.02:1 to about 1.4:1. In certain embodiments, the pigment:binder weight ratio does not exceed about 1.4:1.
在一個實施方式中，本文所述的塗料組合物包含一種或多種流動調節劑。這些流動或粘度調節劑通常用於說明空氣釋放和改善組合物的流動以允許塗覆到基材上。合適的流動調節劑包括，例如，矽酮基化合物、芳族羧酸(例如，未經取代的水楊酸、未經取代的萘甲酸、烷基-或芳烷基-取代的水楊酸、烷基-或芳烷基-取代的萘甲酸等)的金屬鹽、芳族羥基官能羧酸(例如，2-羥基-3-萘甲酸、烷基取代的2-羥基-3-萘甲酸等)的金屬鹽等。在一個優選的方面，流動調節劑是矽酮基化合物且基於組合物中樹脂固體的總重量，以約1重量%、優選地0.01重量%-0.5重量%的量存在。 In one embodiment, the coating compositions described herein comprise one or more flow regulators. These flow or viscosity modifiers are typically used to illustrate air release and improve the flow of the composition to allow for application to the substrate. Suitable flow regulators include, for example, anthrone-based compounds, aromatic carboxylic acids (eg, unsubstituted salicylic acid, unsubstituted naphthoic acid, alkyl- or aralkyl-substituted salicylic acid, a metal salt of an alkyl- or aralkyl-substituted naphthoic acid or the like, an aromatic hydroxy-functional carboxylic acid (for example, 2-hydroxy-3-naphthoic acid, alkyl-substituted 2-hydroxy-3-naphthoic acid, etc.) Metal salt, etc. In a preferred aspect, the flow regulator is an anthrone-based compound and is present in an amount of about 1% by weight, preferably 0.01% to 0.5% by weight, based on the total weight of the resin solids in the composition.
在一個實施方式中，本文所述的塗料組合物包含一種或多種蠟。蠟通常用於在塗覆之前說明處理塗料組合物，並且還可用於減少或防止固化塗層的磨損。合適的蠟包括，例如，天然存在的蠟(例如，棕櫚蠟等)、聚合物蠟(例如，聚乙烯-聚乙酸乙烯酯蠟、聚乙二醇蠟等)等。在一個優選的方面，本文所述的塗料組合物包含聚合物蠟，例如PTFE蠟或聚乙烯蠟且基於組合物中樹脂固體的總重量，蠟以最多約15重量%、優選地約1.5重量%-10重量%的量存在。 In one embodiment, the coating compositions described herein comprise one or more waxes. Waxes are commonly used to illustrate the treatment of coating compositions prior to coating and can also be used to reduce or prevent abrasion of the cured coating. Suitable waxes include, for example, naturally occurring waxes (e.g., palm wax, etc.), polymeric waxes (e.g., polyethylene-polyvinyl acetate wax, polyethylene glycol wax, etc.), and the like. In a preferred aspect, the coating compositions described herein comprise a polymeric wax, such as a PTFE wax or a polyethylene wax, and the wax is up to about 15% by weight, preferably about 1.5% by weight, based on the total weight of the resin solids in the composition. An amount of -10% by weight is present.
存在於本文所述塗料組合物中的固體的總量可因多種因素而異，所述因素包括例如，期望的塗覆方法。對於卷塗應用，塗料組合物通常包含約30-約65重量%的固體。在一些實施方式中，塗料組合物可包含多達80重量%或者更多的固體。 The total amount of solids present in the coating compositions described herein can vary depending on a variety of factors including, for example, the desired coating method. For roll coating applications, the coating composition typically comprises from about 30 to about 65 weight percent solids. In some embodiments, the coating composition can comprise up to 80% by weight or more of solids.
在一個實施方式中，本文所述的塗料組合物提供具有柔軟觸感的固化塗層。不限於理論，微紋理表面形貌或微褶皺表面形貌提供模擬觸摸感的極低光澤度表面。 In one embodiment, the coating compositions described herein provide a cured coating having a soft touch. Without being bound by theory, the microtextured surface topography or micro-pleated surface topography provides a very low gloss surface that mimics the touch.
本發明的優選固化塗料組合物具有優異的粘附性、硬度、柔韌性，並展示出高反射率。當塗層被用在反射體、照明設備等中時，低光澤度和提高的反射率這些性質的組合提供相較於現有技術明顯的優勢，特別地減少或者消除眩光的量。 The preferred cured coating compositions of the present invention have excellent adhesion, hardness, flexibility, and exhibit high reflectivity. The combination of low gloss and increased reflectivity provides a significant advantage over the prior art when coatings are used in reflectors, lighting fixtures, etc., particularly to reduce or eliminate the amount of glare.
按照慣例，為了使可用光最大化，將照明設備設計為以特定方向反射和重定向光，同時限制該設備或者該設備的零件所吸收的光的量。通常，將高光澤度塗層塗覆到該設備的反射表面，且塗層往往具有亮白色外觀或鏡面銀色外觀。這種塗層通常平滑、光澤度高，且具有足夠的鏡面反射率以使可用光最大化，從而改善照明效率。當入射光以與入射角相同的角度被反射時發生鏡面反射。光因此以受控方式被引出照明設備。但在某些情形下，鏡面反射產生顯著的眩光，較低了照明效率和照明設備的可用性。 Conventionally, in order to maximize available light, the illumination device is designed to reflect and redirect light in a particular direction while limiting the amount of light absorbed by the device or parts of the device. Typically, a high gloss coating is applied to the reflective surface of the device, and the coating tends to have a bright white appearance or a mirrored silver appearance. Such coatings are generally smooth, have high gloss, and have sufficient specular reflectance to maximize available light to improve illumination efficiency. Specular reflection occurs when incident light is reflected at the same angle as the angle of incidence. The light is thus led out of the lighting device in a controlled manner. However, in some cases, specular reflection produces significant glare, which reduces lighting efficiency and the availability of lighting equipment.
令人驚訝地，本文所述的塗層是具有高反射率和極低光澤度的亮白色塗層。不限於理論，這是因為由本文所述塗層提供的高Lambertian散射表面。塗層的微紋理性質或微褶皺性質呈現出近理想的無光表面(matte)或漫反射表面，其中表面的所有部分在所有方向同等反射光。因此，塗層展示出高反射率，但不具有在常規塗層中觀察到的高鏡面光澤度水準。來自塗佈表面的眩光被顯著減少或者消除，從而使可用光最大化。 Surprisingly, the coatings described herein are bright white coatings with high reflectivity and very low gloss. Not limited to theory, this is due to the high Lambertian scattering surface provided by the coatings described herein. The microtexture properties or micro-pleated properties of the coating exhibit near-ideal matte or diffuse reflective surfaces where all portions of the surface reflect light equally in all directions. Thus, the coating exhibits high reflectivity but does not have the high specular gloss level observed in conventional coatings. Glare from the coated surface is significantly reduced or eliminated, maximizing the available light.
因此，在一個實施方式中，由所述塗料組合物獲得的固化塗層展示出大於85%、優選地約90%、更優選地約93%的反射率，所述反射率是使用CapY方法在Hunter Lab Scan儀器上測量的。 Thus, in one embodiment, the cured coating obtained from the coating composition exhibits a reflectivity of greater than 85%, preferably about 90%, more preferably about 93%, which is achieved using the CapY method. Measured on the Hunter Lab Scan instrument.
當塗覆在基材上並固化時，本文所述塗料組合物優選地展示出耐久性和在低光澤度下的高反射率。不限於理論，人們認為這是塗層的微褶皺表面形貌的結果。這導致Lambertian散射表面或漫反射表面，且聯合光散射組分，提供亮白色、高反射率、低光澤度的塗層，所述塗層展示出來自塗層的眩光顯著減少或消除。 When applied to a substrate and cured, the coating compositions described herein preferably exhibit durability and high reflectivity at low gloss. Without being bound by theory, this is believed to be the result of the micro-pleated surface topography of the coating. This results in a Lambertian scattering or diffuse surface, and in combination with the light scattering component, provides a bright white, high reflectivity, low gloss coating that exhibits a significant reduction or elimination of glare from the coating.
除了耐久性和高反射率之外，本文所述的固化塗層還可展示出其它有用的性能特徵例如，鉛筆硬度、柔韌性、高反射率等。 In addition to durability and high reflectivity, the cured coatings described herein may exhibit other useful performance characteristics such as pencil hardness, flexibility, high reflectivity, and the like.
可通過本領域技術人員已知的各種方法塗覆本文所述的塗料組合物。在一個實施方式中，利用卷塗工藝將所述組合物塗覆到平面金屬表面。優選地，塗層被塗覆為薄膜，厚度在優選地0.1-5密耳、更優選地0.5-2密耳、甚至更優選地約1-1.2密耳範圍內。 The coating compositions described herein can be applied by a variety of methods known to those skilled in the art. In one embodiment, the composition is applied to a planar metal surface using a roll coating process. Preferably, the coating is applied as a film having a thickness in the range of preferably from 0.1 to 5 mils, more preferably from 0.5 to 2 mils, even more preferably from about 1 to 1.2 mils.
本發明的塗料組合物在多種應用中具有實用性。本發明的塗料組合物可被塗覆例如作為中間塗層、作為頂塗層、或其任意組合。塗料組合物可以通過噴塗、浸塗或刷塗塗覆到片材金屬上，諸如其被用於照明設備(例如，反射體、發光體、引導標示、日光應用等)、建築金屬外皮(例如溝槽板(gutter stock)、百葉窗、壁板和窗框等)，但該塗料組合物特別適於卷塗操作，其中，組合物在片材從卷軸上解繞時被塗覆到片材上，然後隨著片材向著收取卷材繞線機移動而被烘乾。還可想到，本發明的塗料組合物在各種其它終端應用(包括工業塗料應用，例如家用電器塗料；包裝塗料應用；內部或外部鋼建築產品；HVAC應用；農業金屬產品；木材塗料等)中也可以具有實用性。在一個優選的實施方式中，本文所述的固化塗層用作用於照明設備等的內部塗層。 The coating compositions of the present invention have utility in a variety of applications. The coating compositions of the present invention can be coated, for example, as an intermediate coating, as a topcoat, or any combination thereof. The coating composition can be applied to the sheet metal by spraying, dip coating or brushing, such as it is used in lighting equipment (eg, reflectors, illuminants, guiding signs, daylight applications, etc.), building metal skins (eg, trenches) Gutter stock, louvers, siding and sashes, etc., but the coating composition is particularly suitable for a coating operation wherein the composition is applied to the sheet as it is unwound from the reel, It is then dried as the sheet moves toward the take-up web winder. It is also contemplated that the coating compositions of the present invention are also useful in a variety of other end applications including industrial coating applications such as household appliance coatings; packaging coating applications; interior or exterior steel construction products; HVAC applications; agricultural metal products; wood coatings, etc. Can be practical. In a preferred embodiment, the cured coatings described herein are used as internal coatings for lighting equipment and the like.
可由其表面上塗覆本發明的塗料組合物而受益的金屬基材的非限制性實例包括，熱軋鋼、冷軋鋼、熱浸鍍鋅板、電鍍鋅板、鋁板、錫板、各種等級的不銹鋼、和鋁-鋅合金塗佈的鋼板(例如GALVALUME鋼板)。 Non-limiting examples of metal substrates that may benefit from the surface coating of the coating composition of the present invention include, hot rolled steel, cold rolled steel, hot dip galvanized sheet, electrogalvanized sheet, aluminum sheet, tin sheet, various grades of stainless steel, And aluminum-zinc alloy coated steel sheets (eg GALVALUME steel sheets).
塗層通常在約200-500℃、更優選約270-470℃的加熱的溫度環境下固化或硬化。對於卷塗操作來說，塗層通常被烘烤8秒-25秒至約200-250℃的峰值金屬溫度(PMT)。 The coating is typically cured or hardened in a heated temperature environment of from about 200 to 500 ° C, more preferably from about 270 to 470 ° C. For roll coating operations, the coating is typically baked for a period of 8 seconds-25 seconds to a peak metal temperature (PMT) of about 200-250 °C.
通過如下實施例闡述本發明。應當理解，特定實例、材料、用量和過程根據本文所闡述的本發明的範圍和精神進行廣義解釋。除非另有聲明，所有份和百分比都以重量計，所有分子量都是重均分子量。除非另有聲明，所使用的所有化學品都商購自例如Sigma-Aldrich,St.Louis,Missouri。 The invention is illustrated by the following examples. It should be understood that the specific examples, materials, amounts, and processes are construed broadly in accordance with the scope and spirit of the invention as set forth herein. Unless otherwise stated, all parts and percentages are by weight and all molecular weights are weight average molecular weights. All chemicals used were commercially available, for example, from Sigma-Aldrich, St. Louis, Missouri, unless otherwise stated.
如下所述來製備表1中所示的塗料組合物(#1到#3)：將包含聚酯樹脂的粘合劑體系與三聚氰胺固化劑組合。利用本領域已知的標準混合技術將樹脂和交聯劑共混在一起，連同TiO2顏料和最低水準的流平劑以促進卷塗工藝期間空氣釋放。摻入消光劑以提供高光澤度(塗層#1)或低光澤度(塗層#2)。對於塗層#3，摻入提供紋理的胺類添加劑以產生極低光澤度塗層。將塗料組合物與一種或多種顏料組合以產生如表1中所示的塗層。利用標準塗覆方法將塗料組合物塗覆在金屬板上，並在約200°-250℃的峰值金屬溫度下烘烤。 The coating compositions (#1 to #3) shown in Table 1 were prepared as follows: A binder system comprising a polyester resin was combined with a melamine curing agent. The resin and crosslinker are blended together using standard mixing techniques known in the art, along with TiO 2 pigments and a minimum level of leveling agent to promote air release during the roll coating process. A matting agent is incorporated to provide high gloss (Coating #1) or low gloss (Coating #2). For coating #3, a textured amine additive was incorporated to produce a very low gloss coating. The coating composition was combined with one or more pigments to produce a coating as shown in Table 1. The coating composition is applied to a metal panel using standard coating methods and baked at a peak metal temperature of from about 200° to about 250°C.
將實施例1的塗料組合物塗覆在試驗板上並烘烤以形成固化塗層。利用手持型光澤度儀(Byk Gardner)以60°角度測量每個板的光澤度等級，並利用CapY方法使用Hunter Lab Scan儀器測量反射率。觀察到如表2中所示的光澤度等級和反射率值。 The coating composition of Example 1 was coated on a test panel and baked to form a cured coating. The gloss level of each panel was measured at 60° using a hand-held gloss meter (Byk Gardner) and the reflectance was measured using the Hunter Lab Scan instrument using the CapY method. Gloss grades and reflectance values as shown in Table 2 were observed.
儘管已經描述了本發明的優選實施方式，但是本領域技術人員將容易認識到，本文中找到的教導內容可應用於本發明的申請專利範圍內的其它實施方式。所有專利、專利文獻和出版物的全部公開內容通過引用以單獨併入的方式併入本文。 While the preferred embodiment of the present invention has been described, it will be readily understood by those skilled in the art that the teachings herein may be applied to other embodiments within the scope of the invention. The entire disclosures of all patents, patent documents, and publications are hereby incorporated by reference in their entirety in their entirety.
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| CN103189456A (en) * | 2010-11-02 | 2013-07-03 | 阿克佐诺贝尔国际涂料股份有限公司 | Matte textured powder monocoat coating compositions |
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| CN103189456A (en) * | 2010-11-02 | 2013-07-03 | 阿克佐诺贝尔国际涂料股份有限公司 | Matte textured powder monocoat coating compositions |
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