TW201331273A - A crosslinkable composition cross-linkable by real Michael addition reaction and resins for use in said composition - Google Patents

Abstract

The invention relates to an RMA crosslinkable composition comprising at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups wherein the at least 2 reactive groups of component A are acidic protons (C-H) in activated methylene or methine groups and the at least 2 reactive groups of component B are activated unsaturated groups (C=C) anda base catalyst (C) which reactive components A and B crosslink by Real Michael Addition (RMA) reaction under action of the base catalyst, characterised in that the at least one crosslinkable component comprising reactive components A and B in the composition have a total hydroxy number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids. The invention further relates to specific resins A and B having a low hydroxy number for use in RMA cross-linkable compositions and to a process for the manufacture thereof.

Description

藉真實麥可加成反應可交聯之可交聯組成物以及用於該組成物之樹脂 a crosslinkable composition crosslinkable by a real 麦加加反应 reaction and a resin for the composition

本發明係關於一種可藉由真實麥可加成(real Michael addition，RMA)反應而交聯之可交聯組成物及用於該組成物之樹脂。真實麥可加成為其中具有至少2個活化不飽和基團之反應性組分B(下文亦稱為RMA受體)與具有至少2個於活化亞甲基或次甲基上之酸性質子C-H之反應性組分A(下文亦稱為RMA供體)在強鹼催化劑存在下反應的反應。 The present invention relates to a crosslinkable composition crosslinkable by a real Michael addition (RMA) reaction and a resin for the composition. Real micola is a reactive component B (hereinafter also referred to as RMA acceptor) having at least 2 activated unsaturated groups therein and having at least 2 acidic protons CH on an activated methylene or methine group The reaction of the reactive component A (hereinafter also referred to as RMA donor) in the presence of a strong base catalyst.

可調節RMA化學反應以在具有可接受或良好的適用期及良好材料性質之塗料組成物中得到極快固化的組成物(在較低固化溫度下亦然)，此使得該化學反應作為塗料組成物之基礎極具有吸引力。使用潛伏鹼交聯催化劑之RMA可交聯組成物之詳情由本申請案之發明人描述於WO2011/055463中，該文獻據此以引用的方式併入本文中。 The RMA chemical reaction can be adjusted to obtain an extremely fast curing composition in a coating composition having acceptable or good pot life and good material properties (also at lower curing temperatures), which allows the chemical reaction to be used as a coating composition The foundation of things is extremely attractive. The details of the RMA crosslinkable composition using a latent alkali crosslinking catalyst are described by the inventors of the present application in WO 2011/055463, which is incorporated herein by reference.

真實麥可加成係藉由強鹼活化。在鑒於達成所需乾燥特徵而調節塗料系統之反應性時，有不同要求要平衡。乾燥特徵(亦稱為反應特徵或固化特徵)為交聯反應隨著時間變化而進展的型態。需要乾燥特徵允許儘可能快速地形成機械性質，以有助於塗佈機之生產力。亦需要可交聯組成物，其與例如自T.Jung等人Farbe und Lacke 2003年10月得知之包含光潛伏胺催化劑之組成物相反，可在環境條件下簡單固化。 Real mega-addition is activated by strong bases. There are different requirements to balance when adjusting the reactivity of the coating system in view of achieving the desired drying characteristics. Drying characteristics (also known as reaction characteristics or curing characteristics) are types in which the crosslinking reaction progresses with time. The need for drying characteristics allows mechanical properties to be formed as quickly as possible to aid in the productivity of the coater. There is also a need for a crosslinkable composition which, in contrast to a composition comprising a photolatent amine catalyst known from T. Jung et al., Farbe und Lacke, October 2003, can be simply cured under ambient conditions.

另一方面，需要所得塗層具有良好外觀。此意味著，當固化塗料組成物以液體形式存在且能夠流平時，在塗覆後之最近時期期間需要足夠的該種流平性。此亦意味著，需要不存在以下人為製品，如溶劑夾雜物或氣體夾雜物或可能在固化極快速時，尤其在固化在表面處比層的較深處更快速時產生之其他表面不規則性，若固化在催化劑之溶劑蒸發或表面活化之時間標度時發生，則通常為此情況。膜硬度的形成在發生溶劑滯留(solvent entrapment)之情形下亦將受到影響。所述要求在一定程度上彼此相對。就快速固化特徵而言，高含量催化劑較佳，而同時該等高含量催化劑會不利地影響表面外觀及硬度發展。 On the other hand, the resulting coating is required to have a good appearance. This means that when the cured coating composition is present in liquid form and capable of leveling, sufficient leveling is required during the most recent period after coating. This also means that there is no need for artifacts such as solvent inclusions or gas inclusions or other surface irregularities that may occur when curing is extremely fast, especially when curing is faster at the surface than at deeper layers. This is usually the case if curing occurs on the time scale of solvent evaporation or surface activation of the catalyst. The formation of film hardness will also be affected in the event of solvent entrapment. The requirements are relative to each other to some extent. In terms of fast cure characteristics, high levels of catalyst are preferred, while at the same time such high levels of catalyst can adversely affect surface appearance and hardness development.

本發明之目標為提供改良型可交聯組成物，其提供最佳塗層性質，使此等明顯對立的需求得到極好的平衡，在具有高固體含量之可交聯組成物中尤其如此。特定言之，持續需要改良塗層之外觀及硬度，且難題在於提供產生具有改良外觀及硬度之塗層的RMA可交聯組成物。 It is an object of the present invention to provide improved crosslinkable compositions which provide optimum coating properties which provide an excellent balance of such apparently opposing requirements, particularly in crosslinkable compositions having a high solids content. In particular, there is a continuing need to improve the appearance and hardness of coatings, and the challenge is to provide RMA crosslinkable compositions that produce coatings with improved appearance and hardness.

根據本發明，提供一種RMA可交聯組成物，其包含：至少一種可交聯組分，該可交聯組分包含反應性組分A及B，其各包含至少2個反應基，其中組分A之至少2個反應基為於活化亞甲基或次甲基上之酸性質子(C-H)且組分B之至少2個反應基為活化不飽和基團(C=C)；及鹼催化劑(C)，該等反應性組分A與B在鹼催化劑作用下藉由真實麥可加成(RMA)反應而交聯，其特徵在於，該組成物中的 至少一種包含反應性組分A及B之可交聯組分的總羥基值為小於60、較佳小於40且更佳小於20 mg KOH/g固體。 According to the present invention, there is provided an RMA crosslinkable composition comprising: at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups, wherein the group At least 2 reactive groups of A are activated acid protons (CH) on the methylene or methine group and at least 2 reactive groups of component B are activated unsaturated groups (C=C); Catalyst (C), the reactive components A and B are crosslinked by a real Michael Additive (RMA) reaction under the action of a base catalyst, characterized in that in the composition The at least one crosslinkable component comprising reactive components A and B has a total hydroxyl number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids.

意外地發現，如實施例中所例示，包含具有極低羥基值之特殊可交聯組分之可交聯組成物展示顯著改良之硬度及改良之外觀。 It has been unexpectedly found that as exemplified in the examples, the crosslinkable composition comprising a particular crosslinkable component having a very low hydroxyl value exhibits a significantly improved hardness and improved appearance.

在可交聯組成物之一較佳具體實例中，催化劑C為如式X+ROCO2-之碳酸鹽，其中X+為非酸性陽離子，較佳為四級銨或鏻，且R為氫或經取代或未經取代之烷基、芳基或芳烷基。此潛伏鹼催化劑之詳情描述於WO2011/055463中，該文獻據此以引用的方式併入本文中。 In a preferred embodiment of the crosslinkable composition, the catalyst C is a carbonate of the formula X+ROCO2- wherein X+ is a non-acidic cation, preferably a quaternary ammonium or phosphonium, and R is hydrogen or substituted. Or unsubstituted alkyl, aryl or aralkyl. The details of this latent base catalyst are described in WO 2011/055463, which is hereby incorporated by reference herein.

反應性組分A及B可呈各別分子形式且各自獨立地呈聚合物、寡聚物、二聚體或單體形式。因此，「包含活性組分A之可交聯組分」在本文中有時亦稱為組分A。反應性組分A及B可組合於單一分子中。甚至催化劑C可視情況與反應性組分A及/或B組合於單一分子中。可交聯組成物較佳包含寡聚或聚合樹脂A，其包含反應性組分A。本發明亦關於寡聚或聚合樹脂A，其包含羥基值小於60、較佳小於40、更佳小於20且視情況甚至小於10 mg KOH/g固體之反應性組分A。 Reactive components A and B can be in the form of individual molecules and each independently in the form of a polymer, oligomer, dimer or monomer. Thus, "crosslinkable component comprising active ingredient A" is sometimes referred to herein as component A. Reactive components A and B can be combined in a single molecule. Even catalyst C may be combined with reactive component A and/or B as a single molecule. The crosslinkable composition preferably comprises an oligomeric or polymeric resin A comprising reactive component A. The invention also relates to oligomeric or polymeric resins A comprising reactive component A having a hydroxyl number of less than 60, preferably less than 40, more preferably less than 20 and optionally even less than 10 mg KOH/g solids.

本發明進一步關於寡聚或聚合樹脂B，其包含反應性組分B且羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。本發明進一步關於樹脂A或樹脂B或樹脂A與B之混合物之用途，其用於製備RMA可交聯組成物。 The invention further relates to oligomeric or polymeric resin B comprising reactive component B and having a hydroxyl number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids. The invention further relates to the use of Resin A or Resin B or a mixture of Resins A and B for the preparation of an RMA crosslinkable composition.

組分A Component A

含有活化亞甲基或次甲基之組分A之適合實例在此項技術中已為人熟知。較佳為寡聚及/或聚合組分，諸如在主鏈、側鏈或兩者中含有反應性組分A之聚酯、聚胺基甲酸酯、聚丙烯酸酯、環氧樹脂、聚醯胺及聚乙烯樹脂。聚合物較佳為聚酯、聚胺基甲酸酯或聚碳酸酯。 Suitable examples of component A containing an activated methylene or methine group are well known in the art. Preferred are oligomeric and/or polymeric components such as polyesters, polyurethanes, polyacrylates, epoxies, polyfluorenes containing reactive component A in the backbone, side chains or both. Amine and polyethylene resin. The polymer is preferably a polyester, a polyurethane or a polycarbonate.

包含反應性組分A之可交聯組分較佳為包含一或多種具有如式2之結構之反應性組分A的聚合物： The crosslinkable component comprising reactive component A is preferably a polymer comprising one or more reactive components A having the structure of formula 2:

其中R為氫或烷基、芳烷基或芳基取代基，且Y及Y'為相同或不同取代基，較佳為烷基、芳烷基或芳基(R*)、烷氧基(-OR*)或聚合物主鏈，或其中-C(=O)-Y及/或-C(=O)-Y'由CN或苯基置換，且該聚合物之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。在R為氫之情況下，CH2為活化亞甲基，且在R不為氫之情況下，C-H為活化次甲基。 Wherein R is hydrogen or an alkyl, aralkyl or aryl substituent, and Y and Y' are the same or different substituents, preferably an alkyl group, an aralkyl group or an aryl group (R*), an alkoxy group ( -OR*) or a polymer backbone, or wherein -C(=O)-Y and/or -C(=O)-Y' are replaced by CN or phenyl, and the hydroxyl value of the polymer is less than 60, Preferably less than 40 and more preferably less than 20 mg KOH/g solids. In the case where R is hydrogen, CH2 is an activated methylene group, and in the case where R is not hydrogen, C-H is an activated methine group.

當含活化C-H基團之組分A為丙二酸酯(在式1中Y及Y'為-OR*)或乙醯乙酸酯(在式1中Y為-OR*且Y'為-R*)時，可獲得良好結果。較佳可交聯組分中之反應性組分A的大於50、較佳60%、70%、80%、90%或95%為為丙二酸酯基。在同一分子中含有丙二酸酯及乙醯乙酸酯基兩者之 組分亦為適合的。另外，含丙二酸酯與乙醯乙酸酯基之組分的物理混合物為適合的。包含反應性組分A之可交聯組分較佳為每分子平均包含2至20、較佳4至10個活性C-H官能基之聚合物。 When component A containing an activated CH group is malonate (Y and Y' in formula 1 is -OR*) or acetamidine acetate (in the formula 1, Y is -OR* and Y' is - Good results are obtained when R*). More than 50, preferably 60%, 70%, 80%, 90% or 95% of the reactive component A in the preferred crosslinkable component is a malonate group. Containing both malonate and acetamidine acetate groups in the same molecule The components are also suitable. Additionally, physical mixtures of components comprising a malonate and an acetamidine acetate group are suitable. The crosslinkable component comprising reactive component A is preferably a polymer comprising an average of from 2 to 20, preferably from 4 to 10, active C-H functional groups per molecule.

在可交聯組成物之一個最佳具體實例中，組分A為含丙二酸酯之化合物。較佳的是，在可交聯組成物中，大多數活化C-H基團來自丙二酸酯，亦即可交聯組成物中之所有活化C-H基團的超過50%、較佳超過60%、更佳超過70%、最佳超過80%來自丙二酸酯。在另一具體實例中，交聯組成物包含組分A，例如聚合物，其中活化C-H基團的超過50%、較佳超過70%、更佳超過80%且最佳超過90%來自丙二酸酯；及各別組分，例如另一聚合物、寡聚物或單體，其包含不來自丙二酸酯之活化C-H基團，例如乙醯乙酸酯。 In a preferred embodiment of the crosslinkable composition, component A is a malonate-containing compound. Preferably, in the crosslinkable composition, most of the activated CH groups are derived from malonic esters, that is, more than 50%, preferably more than 60%, of all activated CH groups in the crosslinked composition. More preferably, more than 70%, and most preferably more than 80% is derived from malonic ester. In another embodiment, the cross-linking composition comprises component A, such as a polymer, wherein more than 50%, preferably more than 70%, more preferably more than 80%, and most preferably more than 90% of the activated CH groups are derived from propylene. An acid ester; and a separate component, such as another polymer, oligomer or monomer, comprising an activated CH group that is not derived from a malonate, such as acetamidine acetate.

關於用於本發明，尤其較佳的含丙二酸酯基之組分為含丙二酸酯基之寡聚或聚合酯類、醚類、胺基甲酸酯及環氧酯，其每分子含有1-50、更佳2-10個丙二酸酯基。在實踐中，聚酯及聚胺基甲酸酯較佳。該等含丙二酸酯基之組分之數目平均分子量(Mn)亦較佳在約100至約5000、更佳250-2500範圍內，且酸值為約2或更小。單丙二酸酯因其每分子具有2個反應性C-H而亦可使用。另外，單體丙二酸酯可用作反應稀釋劑。 With regard to the present invention, particularly preferred malonate group-containing components are malonate-containing oligomeric or polymeric esters, ethers, urethanes and epoxy esters per molecule It contains 1-50, more preferably 2-10, malonate groups. In practice, polyesters and polyurethanes are preferred. The number average molecular weight (Mn) of the components containing the malonate groups is also preferably in the range of from about 100 to about 5,000, more preferably from 250 to 2,500, and the acid value is about 2 or less. Monomalonates can also be used because they have two reactive C-H per molecule. Additionally, monomeric malonates can be used as the reactive diluent.

本發明亦關於一種聚合或寡聚樹脂A，其用於RMA可交聯組成物中，其包含一或多種具有如式2之結構之反應 性組分A： The invention also relates to a polymeric or oligomeric resin A for use in an RMA crosslinkable composition comprising one or more reactive components A having the structure of formula 2:

其中R為氫或烷基、芳烷基或芳基取代基，且Y及Y'為相同或不同取代基，較佳為烷基、芳烷基或芳基(R*)、烷氧基(-OR*)或聚合物主鏈，或其中-C(=O)-Y及/或-C(=O)-Y'由CN或苯基置換，且該聚合或寡聚樹脂A之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。聚合或寡聚樹脂較佳為包含反應性組分A之聚酯、聚醚、聚環氧樹脂、聚胺基甲酸酯或聚碳酸酯，更佳為聚醚、聚酯或聚胺基甲酸酯，較佳為丙二酸酯或乙醯乙酸酯，且較佳量為使得樹脂每分子平均包含2至20、較佳4至10個活化C-H官能基。較佳可交聯組分中之反應性組分A的大於50、較佳60%、70%、80%、90%或95%為為丙二酸酯基。含丙二酸酯之樹脂A較佳優於例如含乙醯乙酸酯之樹脂A，此係因為其提供改良適用期及塗層硬度。 Wherein R is hydrogen or an alkyl, aralkyl or aryl substituent, and Y and Y' are the same or different substituents, preferably an alkyl group, an aralkyl group or an aryl group (R*), an alkoxy group ( -OR*) or a polymer backbone, or wherein -C(=O)-Y and/or -C(=O)-Y' are replaced by CN or phenyl, and the hydroxyl value of the polymeric or oligomeric resin A Less than 60, preferably less than 40 and more preferably less than 20 mg KOH / g solids. The polymeric or oligomeric resin is preferably a polyester, polyether, polyepoxy, polyurethane or polycarbonate comprising reactive component A, more preferably a polyether, polyester or polyamine. The acid ester is preferably malonate or acetamidine acetate, and is preferably present in an amount such that the resin contains an average of 2 to 20, preferably 4 to 10, activated CH functional groups per molecule. More than 50, preferably 60%, 70%, 80%, 90% or 95% of the reactive component A in the preferred crosslinkable component is a malonate group. The malonate-containing resin A is preferably superior to, for example, the ethyl acetate-containing resin A because it provides an improved pot life and coating hardness.

樹脂A之典型數目分子量在100-20000公克/莫耳之間，較佳在250與10000公克/莫耳之間，且鑒於塗料組成物之流變學及所得塗層之機械性質，更佳在300與6000公克/莫耳之間，且較佳每反應性組分A之當量為100-2000公克/莫耳。樹脂酸值較佳小於4、較佳小於3、2或1毫克KOH/公克，此係因為高酸值將導致鹼催化劑之至少一部分滅活。 The typical number of molecular weights of Resin A is between 100 and 20,000 g/mole, preferably between 250 and 10,000 g/mole, and is preferred in view of the rheology of the coating composition and the mechanical properties of the resulting coating. Between 300 and 6000 grams per mole, and preferably equivalent to 100-2000 grams per mole of reactive component A. The acid value of the resin is preferably less than 4, preferably less than 3, 2 or 1 mg KOH per gram, since high acid numbers will result in at least a portion of the base catalyst being inactivated.

組分B Component B

組分B一般可為烯系不飽和組分，其中碳-碳雙鍵係藉由拉電子基團(例如α位置處之羰基)活化。適合組分B在此項技術中為已知的，例如為丙烯醯酯；丙烯醯胺；或者基於順丁烯二酸、反丁烯二酸及/或衣康酸之聚酯(及順丁烯二酸酐及衣康酸酐及聚酯)；聚胺基甲酸酯；聚醚；及/或含有側接活化不飽和基團之醇酸樹脂。丙烯酸酯、反丁烯二酸酯及順丁烯二酸酯較佳。組分B最佳為不飽和丙烯醯基官能組分。 Component B can generally be an ethylenically unsaturated component wherein the carbon-carbon double bond is activated by an electron withdrawing group such as a carbonyl group at the alpha position. Suitable components B are known in the art, for example propylene oxime ester; acrylamide; or polyester based on maleic acid, fumaric acid and/or itaconic acid (and cisplatin) Adipic anhydride and itaconic anhydride and polyester); polyurethane; polyether; and/or alkyd resin containing pendant activated unsaturated groups. Acrylates, fumarates and maleates are preferred. Component B is preferably an unsaturated propylene sulfhydryl functional component.

亦尤其較佳的是，含活化不飽和基團之組分(以及組成物中所用之其他組分中之任一者)之酸值足夠低，但不會實質上削弱催化劑之活化，因此較佳為小於約2 mg KOH/g，最佳為小於1 mg KOH/g。如由先前併入之文獻所例示，此等及其他含活化不飽和基團之組分及其製造方法一般為熟習此項技術者所知，且在此不需要作進一步說明。較佳地，官能性為2-20，當量(EQW：每反應性官能基之平均分子量)為100-2000，且數目平均分子量較佳為Mn 200-5000。 It is also particularly preferred that the acid value of the component containing the activated unsaturated group (and any of the other components used in the composition) is sufficiently low, but does not substantially impair the activation of the catalyst, and thus Preferably less than about 2 mg KOH/g, most preferably less than 1 mg KOH/g. Such and other components containing activated unsaturated groups and methods for their manufacture are generally known to those skilled in the art, as exemplified by the previously incorporated literature, and need not be further described herein. Preferably, the functionality is from 2 to 20, the equivalent (EQW: average molecular weight per reactive functional group) is from 100 to 2,000, and the number average molecular weight is preferably from Mn 200 to 5000.

本發明之優點在極其棘手的組成物中特別明顯，該等組成物不僅包含高固體含量而且旨在獲得高交聯密度、具有相對較高之官能基濃度及官能性，例如組分A為每聚合物鏈平均包含2至30個、較佳為4至20個且更佳為4-10個活化C-H之化合物、尤其為寡聚物或聚合物的情況。 The advantages of the present invention are particularly pronounced in extremely difficult compositions which not only contain high solids content but are also intended to achieve high crosslink density, relatively high functional group concentration and functionality, for example component A per The polymer chain comprises on average 2 to 30, preferably 4 to 20 and more preferably 4 to 10 activated CH compounds, especially oligomers or polymers.

典型地對組分A及B中之官能基之濃度及其相對化學 計算量進行選擇，以使得在有效使用此等官能基的情況下可預期在固化後獲得良好薄膜性質。典型地，化學計算量C-H/C=C經選定為0.1至10，較佳為0.5至3，更佳為0.7至3，最佳為0.8/1.5。 Typically the concentration of functional groups in components A and B and their relative chemistry The amount of calculation is selected such that good film properties can be expected to be obtained after curing in the case of effective use of such functional groups. Typically, the stoichiometric amount C-H/C=C is selected to be from 0.1 to 10, preferably from 0.5 to 3, more preferably from 0.7 to 3, most preferably from 0.8/1.5.

本發明亦關於一種聚合或寡聚樹脂B，其用於RMA可交聯組成物中，該可交聯組成物包含一或多種包含活化不飽和基團(C=C)之反應性組分B，較佳不飽和丙烯醯基或順丁烯二酸酯官能基(較佳丙烯醯基)或丙烯醯胺，且該聚合或寡聚樹脂之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。樹脂B較佳為聚酯、聚醚、聚環氧樹脂、聚胺基甲酸酯或聚碳酸酯，其包含反應性組分B且較佳數目分子量在300與20000公克/莫耳之間、較佳在300與10000公克/莫耳之間或6000公克/莫耳。先前技術通常使用分子量為296之TMPTA。樹脂B較佳每反應性組分A或B之當量為100-2000公克/莫耳且酸值小於4、較佳小於3、2或1毫克KOH/公克。 The invention also relates to a polymeric or oligomeric resin B for use in an RMA crosslinkable composition comprising one or more reactive components comprising an activated unsaturated group (C=C) Preferably, the unsaturated acrylonitrile or maleate functional group (preferably acrylonitrile) or acrylamide, and the polymeric or oligomeric resin has a hydroxyl number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solid. Resin B is preferably a polyester, a polyether, a polyepoxy resin, a polyurethane or a polycarbonate comprising reactive component B and preferably having a molecular weight between 300 and 20,000 g/mole, It is preferably between 300 and 10,000 g/mole or 6000 g/mole. The prior art typically uses TMPTA having a molecular weight of 296. The resin B preferably has an equivalent weight per reactive component A or B of from 100 to 2000 g/mole and an acid value of less than 4, preferably less than 3, 2 or 1 mg KOH/g.

本發明亦關於一種如上文所述之聚合或寡聚樹脂A與聚合或寡聚樹脂B之樹脂混合物，其用於RMA可交聯組成物中；及樹脂A或樹脂B或樹脂A與樹脂B之樹脂混合物之用途，其用作RMA可交聯組成物中之可交聯組分。在本文中，較佳樹脂A或樹脂B中之至少一者包含至少3個反應***聯基團以便形成三維交聯網狀結構，且樹脂A或樹脂B中之至少一者包含至少兩個反應***聯基團，且其中樹脂A或B或兩者每聚合物或寡聚物分子平均具有3-30個反應***聯基團。 The present invention also relates to a resin mixture of a polymeric or oligomeric resin A and a polymeric or oligomeric resin B as described above for use in an RMA crosslinkable composition; and Resin A or Resin B or Resin A and Resin B The use of a resin mixture for use as a crosslinkable component in an RMA crosslinkable composition. Herein, preferably at least one of the resin A or the resin B contains at least 3 reactive crosslinking groups to form a three-dimensional crosslinked network structure, and at least one of the resin A or the resin B contains at least two reactive sites. A linking group, and wherein the resin A or B or both have an average of from 3 to 30 reactive crosslinking groups per polymer or oligomer molecule.

製備本發明之RMA樹脂A及B之方法 Method for preparing RMA resins A and B of the present invention

本發明亦關於一種製備本發明之RMA樹脂A及B之方法，尤其一種製備樹脂A之方法，該方法包含使多元醇與呈羧酸酯形式(Y及Y'為烷氧基(-OR*))之反應性組分A發生轉酯反應；及一種製備樹脂B之方法，該方法包含使多元醇與呈羧酸酯形式之反應性組分B(較佳丙烯醯基)發生轉酯反應或藉由使多元醇與呈羧酸形式之反應性組分B發生直接酯化反應。 The invention also relates to a process for the preparation of the RMA resins A and B of the invention, in particular a process for the preparation of a resin A which comprises reacting a polyol with a carboxylate form (Y and Y' are alkoxy groups (-OR*) a) a transesterification reaction of the reactive component A; and a method of preparing the resin B, which comprises transesterifying the polyol with the reactive component B (preferably propylene sulfhydryl) in the form of a carboxylate Or by direct esterification of the polyol with the reactive component B in the form of a carboxylic acid.

尤其重要的是，在樹脂A或樹脂B之製備方法中，選擇反應混合物中之組分之相對量及反應時間以及反應溫度，以使得所得樹脂A或B具有小於60、較佳小於40且更佳小於20 mg KOH/g固體之所需低羥基值。在多元醇與反應性組分A之間的反應中，羥基值將在反應開始時較高且將隨多元醇之羥基與反應性組分A反應而逐漸降低。熟習此項技術者可計算所需組分量，以使得反應完成時所得樹脂A具有極低羥基值，且可藉由已知技術(諸如酸-鹼滴定)確定所得樹脂是否已反應得足夠久以將羥基值降低至所需水準以形成樹脂A或B。 It is especially important that in the preparation method of the resin A or the resin B, the relative amounts of the components in the reaction mixture and the reaction time and the reaction temperature are selected such that the obtained resin A or B has less than 60, preferably less than 40 and more. The desired low hydroxyl number is less than 20 mg KOH/g solids. In the reaction between the polyol and the reactive component A, the hydroxyl value will be higher at the beginning of the reaction and will gradually decrease as the hydroxyl group of the polyol reacts with the reactive component A. Those skilled in the art can calculate the desired amount of components such that the resulting resin A has a very low hydroxyl value upon completion of the reaction, and it can be determined by known techniques (such as acid-base titration) whether the resulting resin has reacted sufficiently long. The hydroxyl value is lowered to the desired level to form resin A or B.

用於本發明中之聚酯樹脂可藉由使一或多種多元醇、一或多種多元酸及丙二酸及/或乙基乙醯乙酸之一或多種酯共聚來製備。製備本發明之聚酯之較佳方式為，在第一步驟中製備羥基官能聚酯，及在隨後步驟中用丙二酸或乙基乙醯乙酸與揮發性醇(較佳乙醇或甲醇)之酯將第一步驟之聚酯轉酯化。 The polyester resin used in the present invention can be produced by copolymerizing one or more polyols, one or more polybasic acids, and one or more esters of malonic acid and/or ethylacetamidineacetic acid. A preferred mode of preparing the polyester of the present invention is to prepare a hydroxy-functional polyester in the first step, and to use malonic acid or ethyl acetoacetic acid with a volatile alcohol (preferably ethanol or methanol) in a subsequent step. The ester is transesterified with the polyester of the first step.

羥基官能聚酯亦可藉由使羥基官能聚酯多元醇與增鏈劑(較佳內酯，諸如己內酯、戊內酯及γ-丁內酯)反應來製備。或者此羥基聚酯可藉由使兼具有羥基及酸基之聚酯與一或多種單或多官能環氧化合物反應來製備。適合單或多官能環氧化合物為(環)脂族或芳族羥基化合物(諸如烯丙醇、丁醇、環己醇、苯酚、丁基苯酚、癸醇、乙二醇、甘油、環己二醇、單核二或三官能苯酚、雙酚(諸如雙酚-A或雙酚-F)及多核苯酚)之單、二或聚縮水甘油醚。 Hydroxy-functional polyesters can also be prepared by reacting a hydroxy-functional polyester polyol with a chain extender, preferably a lactone such as caprolactone, valerolactone, and gamma-butyrolactone. Alternatively, the hydroxy polyester can be prepared by reacting a polyester having both a hydroxyl group and an acid group with one or more mono- or polyfunctional epoxy compounds. Suitable mono- or polyfunctional epoxy compounds are (cyclo)aliphatic or aromatic hydroxy compounds (such as allyl alcohol, butanol, cyclohexanol, phenol, butyl phenol, decyl alcohol, ethylene glycol, glycerol, cyclohexane) Mono, di or polyglycidyl ethers of alcohols, mononuclear di- or trifunctional phenols, bisphenols (such as bisphenol-A or bisphenol-F) and polynuclear phenols.

第一步驟之多元醇亦可藉由使第一步驟之羥基官能聚酯與單或多官能異氰酸酯化合物反應來製備。作為適合至少三官能異氰酸酯，可提及多種單體及寡聚多官能異氰酸酯。用於製備聚酯多元醇之聚羧酸較佳係選自非環狀或環狀聚羧酸、其酯或酐之群。環狀聚羧酸包括芳族聚羧酸及環脂族聚羧酸。此聚羧酸中包括脂肪酸、其酯、二聚體及更高寡聚物及其混合物。亦包括其酯或酐，諸如丙二酸之二甲酯及二乙酯、琥珀酸酐、辛烯基琥珀酸酐(4-辛烯基-5-氫-1,3-呋喃二酮之任何異構體或異構體之混合物)、十二烯基琥珀酸酐(4-十二烯基-5-氫-1,3-呋喃二酮之任何異構體或異構體之混合物)及其混合物。 The polyol of the first step can also be prepared by reacting the hydroxy-functional polyester of the first step with a mono- or polyfunctional isocyanate compound. As suitable at least trifunctional isocyanates, mention may be made of various monomers and oligomeric polyfunctional isocyanates. The polycarboxylic acid used to prepare the polyester polyol is preferably selected from the group consisting of acyclic or cyclic polycarboxylic acids, esters or anhydrides thereof. The cyclic polycarboxylic acid includes an aromatic polycarboxylic acid and a cycloaliphatic polycarboxylic acid. The polycarboxylic acid includes fatty acids, esters, dimers and higher oligomers thereof, and mixtures thereof. Also included are esters or anhydrides thereof, such as dimethyl and diethyl malonate, succinic anhydride, octenyl succinic anhydride (4-octenyl-5-hydro-1,3-furanedione, any isomerism) a mixture of isomers or isomers), dodecenyl succinic anhydride (any isomer or mixture of isomers of 4-dodecenyl-5-hydro-1,3-furanedione), and mixtures thereof.

視情況選用之共縮合單羧酸可為脂族、環脂族、芳族或其混合物。單羧酸較佳含有6至18個碳原子、最佳7至14個碳原子，諸如為辛酸、2-乙基己酸、異壬酸、癸酸、十二酸、苯甲酸、六氫苯甲酸及其混合物。多元醇較佳為具有2至15個碳原子之環脂族或脂族多元醇。至少一種選 自以下之多元醇與至少一種具有2至15個碳原子之二醇的混合物亦較佳：三羥甲基乙烷、三羥甲基丙烷、甘油、季戊四醇及二(三羥甲基)丙烷。較佳之二醇包括1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、3-甲基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、二羥甲基丙酸及1,4-環己烷二甲醇。適合單官能醇之實例包括具有6-18個碳原子之醇，諸如2-乙基己醇、十二醇、環己醇及三甲基環己醇。視情況選用之共縮合單羧酸可為脂族、環脂族、芳族或其混合物。單羧酸較佳含有6至18個碳原子、最佳7至14個碳原子，諸如為辛酸、2-乙基己酸、異壬酸、癸酸、十二酸、苯甲酸、六氫苯甲酸及其混合物。可使用之典型羥基酸包括二羥甲基丙酸、羥基特戊酸及羥基硬脂酸。適合單官能環氧化合物包括分支鏈單羧酸之縮水甘油酯，諸如來自Resolution之Cardura(R)E。聚胺基甲酸酯、聚醚多元醇可以已知方式使用如上文所述之適合單體來製備。 The co-condensed monocarboxylic acid selected as appropriate may be aliphatic, cycloaliphatic, aromatic or a mixture thereof. The monocarboxylic acid preferably has 6 to 18 carbon atoms, preferably 7 to 14 carbon atoms, such as octanoic acid, 2-ethylhexanoic acid, isophthalic acid, citric acid, dodecanoic acid, benzoic acid, hexahydrobenzene. Formic acid and mixtures thereof. The polyol is preferably a cycloaliphatic or aliphatic polyol having 2 to 15 carbon atoms. At least one choice Mixtures of the following polyols with at least one diol having from 2 to 15 carbon atoms are also preferred: trimethylolethane, trimethylolpropane, glycerol, pentaerythritol and bis(trimethylol)propane. Preferred diols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- Propylene glycol, dimethylolpropionic acid and 1,4-cyclohexanedimethanol. Examples of suitable monofunctional alcohols include alcohols having from 6 to 18 carbon atoms, such as 2-ethylhexanol, dodecanol, cyclohexanol, and trimethylcyclohexanol. The co-condensed monocarboxylic acid selected as appropriate may be aliphatic, cycloaliphatic, aromatic or a mixture thereof. The monocarboxylic acid preferably has 6 to 18 carbon atoms, preferably 7 to 14 carbon atoms, such as octanoic acid, 2-ethylhexanoic acid, isophthalic acid, citric acid, dodecanoic acid, benzoic acid, hexahydrobenzene. Formic acid and mixtures thereof. Typical hydroxy acids that can be used include dimethylolpropionic acid, hydroxypivalic acid, and hydroxystearic acid. Suitable monofunctional epoxy compounds include glycidyl esters of branched monocarboxylic acids such as Cardura(R)E from Resolution. Polyurethanes, polyether polyols can be prepared in a known manner using suitable monomers as described above.

較佳，鑒於自可交聯組成物製備之塗層之所要機械及外觀性質，選擇樹脂A之寡聚物或聚合物組分，以使得樹脂A之玻璃轉化溫度在-25與+25℃之間，更佳在-20與+20℃之間，且最佳在-20與+15℃之間。與該樹脂A組合之樹脂B之玻璃轉化溫度可經選為在較寬範圍之間，較佳在-50與+25℃之間。樹脂可為脂族或脂族與芳族組分之混合物，其中鑒於所設想應用來選擇芳族組分百分比。樹脂A及樹脂B以及樹脂A與樹脂B之混合物中之芳族化合物之量較佳為至多60 wt%(相對於樹脂或樹脂混合物之總重量)，較佳至 多40、20或10 wt%。在其中樹脂A及樹脂B為脂族樹脂(亦即實質上不包含芳族組分(至多5 wt%))之一個較佳具體實例中，獲得良好結果。鑒於RMA交聯活化，樹脂A及B之酸值較佳小於1 mg KOH/g固體。鑒於所得塗層之性質及反應動力學，分子量較佳較低，在300與6000公克/莫耳之間。鑒於達成良好乾燥及塗層硬度，羥基值較佳儘可能低；最佳小於20且視情況甚至小於10 mg KOH/g固體。即使分子量相對較低，但鑒於所得塗層之機械性質，樹脂亦必須具有足夠交聯官能性。較佳樹脂A及樹脂B之平均官能性為每聚合物或寡聚物分子具有3-30個反應***聯基團。就樹脂A而言，官能性較佳在5與30之間、更佳在10與30之間。適合組合可為具有相對較高官能性之樹脂A與具有相對較低官能性之樹脂B、尤其官能性在10與30之間的樹脂A與官能性為3-20或3-10之樹脂B之混合物。 Preferably, in view of the desired mechanical and appearance properties of the coating prepared from the crosslinkable composition, the oligomer or polymer component of Resin A is selected such that the glass transition temperature of Resin A is between -25 and +25 °C. More preferably, it is between -20 and +20 ° C, and most preferably between -20 and +15 ° C. The glass transition temperature of the resin B in combination with the resin A can be selected to be in a wide range, preferably between -50 and +25 °C. The resin may be a mixture of aliphatic or aliphatic and aromatic components, wherein the percentage of aromatic components is selected in view of the contemplated application. The amount of the aromatic compound in the mixture of the resin A and the resin B and the resin A and the resin B is preferably at most 60 wt% (relative to the total weight of the resin or resin mixture), preferably to More than 40, 20 or 10 wt%. In a preferred embodiment in which the resin A and the resin B are aliphatic resins (i.e., substantially free of aromatic components (up to 5 wt%)), good results are obtained. The acid value of the resins A and B is preferably less than 1 mg KOH/g solids in view of the activation of the RMA crosslinking. In view of the nature of the resulting coating and the kinetics of the reaction, the molecular weight is preferably lower, between 300 and 6000 grams per mole. In view of achieving good drying and coating hardness, the hydroxyl value is preferably as low as possible; optimally less than 20 and optionally less than 10 mg KOH/g solids. Even though the molecular weight is relatively low, the resin must have sufficient cross-linking functionality in view of the mechanical properties of the resulting coating. Preferably, the average functionality of Resin A and Resin B is from 3 to 30 reactive crosslinking groups per polymer or oligomer molecule. In the case of Resin A, the functionality is preferably between 5 and 30, more preferably between 10 and 30. Suitable combinations may be resin A having relatively high functionality and resin B having relatively low functionality, especially resin A having a functionality between 10 and 30 and resin B having a functionality of 3-20 or 3-10. a mixture.

組分C Component C

鹼催化劑C原則上可為適用於催化RMA反應之任何已知的催化劑。鑒於達成良好的適用期以及低溫固化行為，交聯組成物較佳包含包括由揮發性酸阻斷之強鹼之催化劑系統C，其係藉由蒸發此酸而活化。適合催化劑系統C包含由二氧化碳阻斷之強鹼，或經阻斷之催化物質具有式ROCO2-，R為視情況經取代之烷基，較佳為C1-C4自由基或氫，催化劑較佳包含阻斷鹼陰離子及四級銨或鏻陽離子。交聯催化劑較佳以範圍介於0.001與0.3毫當量/公克固體之間、較佳介於0.01與0.2毫當量/公克固體之間、更佳 介於0.02與0.1毫當量/公克固體之間的量使用(毫當量/公克固體被定義為鹼相對於可交聯組成物之不計微粒填料或顏料之總乾重的毫莫耳數)。或者，催化劑系統C係藉由使環氧基組分與三級胺或陰離子反應來活化。 The base catalyst C can in principle be any known catalyst suitable for catalyzing the RMA reaction. In view of achieving a good pot life and low temperature curing behavior, the crosslinked composition preferably comprises a catalyst system C comprising a strong base blocked by a volatile acid, which is activated by evaporation of the acid. Suitable catalyst system C comprises a strong base blocked by carbon dioxide, or the blocked catalytic substance has the formula ROCO2-, R is an optionally substituted alkyl group, preferably a C1-C4 radical or hydrogen, and the catalyst preferably comprises Blocking alkali anions and quaternary ammonium or phosphonium cations. Preferably, the crosslinking catalyst is in the range of between 0.001 and 0.3 meq/g solid, preferably between 0.01 and 0.2 meq/g solid, more preferably An amount between 0.02 and 0.1 meq/g solid is used (milli eq/g solid is defined as the millimoles of base relative to the crosslinkable composition excluding the total dry weight of the particulate filler or pigment). Alternatively, catalyst system C is activated by reacting an epoxy component with a tertiary amine or anion.

就CO2去阻斷催化劑系統而言，意外地發現，可在其中組分A為丙二酸酯之組成物中達成顯著更佳的適用期，該組成物進一步包含0.1-10 wt%、較佳為0.1-5、更佳為0.2-3且最佳為0.5-2 wt%之水(相對於塗料組成物之總重量而言)。較佳對水之量進行選擇，其有效量可使膠凝時間與不具有水之相同組成物相比增加至少15分鐘，較佳為至少30分鐘，更佳為至少1小時，甚至更佳為至少5小時且最佳為至少24小時、48小時；或至少10%、50%或100%。 With regard to the CO2 deblocking catalyst system, it has been surprisingly found that a significantly better pot life can be achieved in a composition in which component A is a malonate, the composition further comprising from 0.1 to 10% by weight, preferably It is from 0.1 to 5, more preferably from 0.2 to 3 and most preferably from 0.5 to 2% by weight of water (relative to the total weight of the coating composition). Preferably, the amount of water is selected such that the effective amount increases the gel time by at least 15 minutes, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably, compared to the same composition without water. At least 5 hours and most preferably at least 24 hours, 48 hours; or at least 10%, 50% or 100%.

組分D Component D

可交聯組成物可包含含X-H基團之組分(D)作為添加劑以改良塗層之外觀及/或硬度，其亦為可在催化劑C作用下與組分B反應之麥可加成供體，其中X為C、N、P、O或S，較佳為C、N或P，較佳以相對於由組分C產生之鹼至少50莫耳%且小於組分A之C-H活性基團的30莫耳%之量存在。 The crosslinkable composition may comprise an XH group-containing component (D) as an additive to improve the appearance and/or hardness of the coating, which is also a Michael addition which can react with the component B under the action of the catalyst C. Where X is C, N, P, O or S, preferably C, N or P, preferably at least 50 mol% relative to the base produced by component C and less than the CH reactive group of component A The amount of 30 moles of the group exists.

如催化之RMA可交聯組成物中所述之組分D可產生包含以下之反應性特徵：在初始誘導時間內在塗覆及活化系統之後反應速率立刻降低，隨後在稍後階段中反應性相對增加。可調節此誘導時間，以允許延長「開放時間」，即允許流動且允許溶劑及滯留氣泡逸出之時期。誘導時間允許 顯著更多量之系統之流動及流平，從而避免可能由在無此等添加劑之情況下極快速固化引起的表面缺陷，且因溶劑滯留減少而有更佳的硬度形成型態，同時在此誘導時間以外仍獲益於催化劑之全部潛力，因而在稍後階段中加速反應，從而以比將在簡單使用較低催化劑含量時可見要高之速率完成交聯。亦避免了較低催化劑含量針對偶然存在之酸污染之高敏感度。 Component D, as described in the catalyzed RMA crosslinkable composition, can produce reactive characteristics that include a reduction in the rate of reaction immediately after application and activation of the system during the initial induction period, followed by a later reactivity in a later stage. increase. This induction time can be adjusted to allow for an extension of the "open time", a period that allows flow and allows solvent and trapped bubbles to escape. Allowance time allowed Significantly more flow and leveling of the system, thereby avoiding surface defects that may be caused by extremely fast curing without such additives, and having a better hardness formation due to reduced solvent retention, while The full potential of the catalyst is still benefited beyond the induction time, so that the reaction is accelerated in a later stage to complete the crosslinking at a higher rate than would be seen when simply using a lower catalyst content. The high sensitivity of the lower catalyst content to the occasional acid contamination is also avoided.

儘管本發明之優點在具有正常厚度之層中顯而易見，但本發明之可交聯組成物尤其適用於製造厚層。厚層被認為是固化乾燥厚度為至少50或大於70微米之層。在厚層應用中，空氣及溶劑夾雜物之風險更高。此在10至60℃範圍內之低溫下固化之RMA可交聯組成物中特別顯著，其中樹脂更黏滯且難以流平。 While the advantages of the present invention are apparent in layers having a normal thickness, the crosslinkable compositions of the present invention are particularly useful for making thick layers. The thick layer is considered to be a layer that cures to a dry thickness of at least 50 or greater than 70 microns. In thick applications, the risk of air and solvent inclusions is higher. This is particularly pronounced in RMA crosslinkable compositions which cure at low temperatures in the range of 10 to 60 ° C where the resin is more viscous and difficult to level.

組分D中之X-H基團之酸性比組分A中之C-H基團高，較佳其特徵在於，組分D之pKa(於水性環境中定義)比組分A之pKa小至少一個單位、較佳為兩個單位。組分D中之X-H基團之pKa較佳低於13，較佳低於12，更佳低於11，最佳低於10。酸性過大會給催化劑系統中之組分帶來問題；因此pKa較佳高於7，更佳高於7.5，且視情況高於8。酸性差異確保，在塗覆塗層時，組分D優先於組分A被活化(去質子化)。 The acidity of the XH group in component D is higher than the CH group in component A, preferably characterized by the pKa of component D (defined in the aqueous environment) being at least one unit less than the pKa of component A, It is preferably two units. The pKa of the X-H group in component D is preferably less than 13, preferably less than 12, more preferably less than 11, most preferably less than 10. Excessive acidity poses a problem for the components of the catalyst system; therefore the pKa is preferably above 7, preferably above 7.5, and optionally above 8. The acid difference ensures that component D is activated (deprotonated) in preference to component A when the coating is applied.

組分D較佳係選自一或多種來自包含於活化亞甲基或次甲基上之C-H酸性質子(X為C)之化合物D1及包含N-H酸性化合物(X為N)之化合物D2之群的化合物。適 合組分D2為氮雜酸性化合物(X為N)，其較佳包含含有N-H作為基團Ar-NH-(C=O)-、-(C=O)-NH-(C=O)-或基團-NH-(O=S=O)-之一部分的分子；或雜環，其中N-H基團之氮含於雜環中，組分D2更佳為醯亞胺衍生物，較佳為(視情況經取代之)琥珀醯亞胺或戊二醯亞胺。其他適合組分D2為乙內醯脲衍生物，例如5,5-二甲基乙內醯脲；磺醯胺，例如芳族磺醯胺，如苯磺醯胺或甲苯磺醯胺；或雜環化合物，例如***或吡唑或尿嘧啶衍生物。 Component D is preferably selected from one or more compounds D1 derived from a CH acid proton (X is C) contained on an activated methylene or methine group and a compound D2 comprising an NH acidic compound (X is N). Group of compounds. suitable Component D2 is an aza-acidic compound (X is N), which preferably contains NH as a group Ar-NH-(C=O)-, -(C=O)-NH-(C=O)- Or a molecule of the group -NH-(O=S=O)-; or a heterocyclic ring wherein the nitrogen of the NH group is contained in the heterocyclic ring, and the component D2 is more preferably a quinone imine derivative, preferably (Substituted as appropriate) amber imine or pentaneimine. Other suitable component D2 is a carbendazole derivative such as 5,5-dimethylhydantoin; a sulfonamide such as an aromatic sulfonamide such as benzenesulfonamide or toluenesulfonamide; Ring compounds such as triazole or pyrazole or uracil derivatives.

在可交聯組成物中，組分D中之X-H基團係以對應於相對於將欲由催化劑C產生之鹼之量至少50莫耳%、較佳至少100莫耳%、最佳至少150莫耳%之量存在。適當量主要由組分D相對於組分A之酸鹼特徵及相應陰離子相對於B之反應性決定，因此在不同系統中可能不同。應注意，改良開放時間之效應在一些情況下可在極少量之組分D下獲得，此極為有利，因為該種少量不會或不會顯著地影響所得固化組成物之性質；例如塗層之化學及機械性質。組分D中之X-H基團典型地係以對應於相對於組分A之C-H供體基團不超過30莫耳%、較佳不超過20、視情況不超過10莫耳%之量存在。組分D之X-H官能性(每分子之基團數)較佳較低，較佳為小於4，更佳小於2，最佳為1。 In the crosslinkable composition, the XH group in component D is at least 50 mol%, preferably at least 100 mol%, optimally at least 150, relative to the amount of base to be produced from catalyst C. The amount of moles exists. The appropriate amount is primarily determined by the acid-base character of component D relative to component A and the reactivity of the corresponding anion relative to B, and thus may differ in different systems. It should be noted that the effect of improving the open time can be obtained in a small amount of component D in some cases, which is extremely advantageous because the small amount does not or does not significantly affect the properties of the resulting cured composition; for example, a coating Chemical and mechanical properties. The X-H group in component D is typically present in an amount corresponding to no more than 30 mole percent, preferably no more than 20, and optionally no more than 10 mole percent, relative to the C-H donor group of component A. The X-H functionality of component D (number of groups per molecule) is preferably lower, preferably less than 4, more preferably less than 2, most preferably 1.

緊跟著一或多種不同組分D，可交聯組成物可包含包含於活化亞甲基或次甲基上之酸性質子(C-H)之組分D1，其酸性比組分A高且亦具有朝向組分B之反應性。該組分D1亦可促成改良開放時間之效應，然而為了具有顯著效 應，D1典型地應以10-40莫耳%(相對於全部RMA C-H)之間的量存在，其為比組分D顯著要高之量。 Following the one or more different components D, the crosslinkable composition may comprise component D1 comprising an acidic proton (CH) on the activated methylene or methine group, which is more acidic than component A and Has reactivity towards component B. This component D1 can also contribute to the effect of improving the open time, but in order to be effective Should, D1 should typically be present in an amount between 10-40 mole % (relative to all RMA C-H), which is a significant amount higher than component D.

較佳對兩種C-H酸性組分A與D1之酸性差異進行選擇，以便其中組分D1之pKa比組分A之pKa低0.5至6個單位，較佳為1至5個單位且更佳為1.5至4個單位。較佳地，組分A為含丙二酸酯之組分且組分D1為含乙醯乙酸酯或乙醯丙酮之組分，較佳具有低C-H官能性(較佳小於10、更佳小於5、最佳不超過2)。適合組分D及A2之pKa值列為如下： Preferably, the acid difference between the two CH acidic components A and D1 is selected such that the pKa of component D1 is 0.5 to 6 units lower than the pKa of component A, preferably 1 to 5 units and more preferably 1.5 to 4 units. Preferably, component A is a malonate-containing component and component D1 is a component containing acetamidine acetate or acetamidine acetone, preferably having a low CH functionality (preferably less than 10, more preferably Less than 5, best not more than 2). The pKa values suitable for components D and A2 are listed below:

本發明亦關於如上文所述之組分D之用途，其用作RMA可交聯組成物之添加劑。改良外觀及改良硬度之優點可無關於層厚度而獲得，但尤其在乾燥厚度為至少50、較佳至少60、75、100且更佳至少125微米之厚塗層中顯而易見，其用於改良可交聯組成物之開放時間，且用於改良所得固化組成物、尤其塗層之外觀及硬度。 The invention also relates to the use of component D as described above for use as an additive to an RMA crosslinkable composition. The advantages of improved appearance and improved hardness can be obtained without regard to layer thickness, but are particularly evident in thick coatings having a dry thickness of at least 50, preferably at least 60, 75, 100 and more preferably at least 125 microns. The open time of the cross-linking composition is used to improve the appearance and hardness of the resulting cured composition, especially the coating.

在可交聯組成物中，選擇組分D之性質及量，從而在所選塗覆及固化條件下，當與不具有組分D之相同組成物相比時，使得達至30%轉化水準之時間增加至少3分鐘、較佳為5分鐘、更佳為10分鐘分鐘、較佳為不到60分鐘、更佳為不到30分鐘。 In the crosslinkable composition, the nature and amount of component D is selected such that, under selected coating and curing conditions, up to 30% conversion level is achieved when compared to the same composition without component D The time is increased by at least 3 minutes, preferably 5 minutes, more preferably 10 minutes, preferably less than 60 minutes, more preferably less than 30 minutes.

溶劑組分 Solvent component

可交聯組成物可在不具有任何其他溶劑下使用。當組成物中之可交聯組分具有足夠低黏度且所有組分一起形式溶液時，將典型為此情況。可添加溶劑，從而例如在高固體含量之相對高黏度的組分之情況下降低黏度，或在組成物含有某些需要溶劑之添加劑之情況下介導反應動力學。溶劑可為水或可為有機溶劑或其混合物。最佳使用有機溶劑。有機溶劑可(實質上)不含有水。然而，有時鑒於增加適用期，除有機溶劑之外，較佳亦添加相對少量、較佳0.1與10 wt%(相對於可交聯組成物之總重量)之間的水。 The crosslinkable composition can be used without any other solvent. This is typically the case when the crosslinkable component of the composition has a sufficiently low viscosity and all of the components are together in the form of a solution. Solvents may be added to, for example, reduce the viscosity in the case of relatively high viscosity components of relatively high viscosity, or to mediate reaction kinetics in the presence of certain additives requiring solvents. The solvent may be water or may be an organic solvent or a mixture thereof. The best use of organic solvents. The organic solvent may (substantially) contain no water. However, sometimes in view of increasing the pot life, it is preferred to add water in a relatively small amount, preferably 0.1 and 10% by weight (relative to the total weight of the crosslinkable composition), in addition to the organic solvent.

就CO2去阻斷催化劑系統而言，本發明人進一步發現，若在可交聯組成物中，溶劑之至少一部分為一級醇溶劑，則可在適用期方面達成優勢。溶劑可為非醇溶劑與醇 溶劑之混合物。醇較佳以相對於可交聯組成物之總重量至少1、較佳為2、更佳為3、最佳為至少5、甚至更佳為至少10 wt%之量存在，且鑒於VOC限制，較佳為至多45，較佳為至多40 wt%，最佳為小於30 wt%。 With regard to the CO2 deblocking catalyst system, the inventors have further found that if at least a portion of the solvent is a primary alcohol solvent in the crosslinkable composition, an advantage can be achieved in terms of pot life. The solvent can be a non-alcohol solvent and an alcohol a mixture of solvents. The alcohol is preferably present in an amount of at least 1, preferably 2, more preferably 3, most preferably at least 5, even more preferably at least 10 wt%, relative to the total weight of the crosslinkable composition, and in view of VOC limitations, It is preferably at most 45, preferably at most 40% by weight, most preferably less than 30% by weight.

醇溶劑較佳為一或多種一級醇，更佳為具有1至20個、較佳為1-10個、更佳為1-6個碳原子之單醇，較佳選自乙醇、正丙醇、正丁醇、正戊醇及丁二醇之群。 The alcohol solvent is preferably one or more primary alcohols, more preferably a monoalcohol having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms, preferably selected from the group consisting of ethanol and n-propanol. , a group of n-butanol, n-pentanol and butanediol.

總之，本發明之可交聯組成物包含：a. 5與95 wt%之間的樹脂A，其具有包含至少2個於活化亞甲基或次甲基上之酸性質子C-H之反應性組分A，該樹脂A之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體，及b. 5與95 wt%之間的樹脂B，其具有含至少2個活化不飽和基團之反應性組分B(wt%相對於可交聯組成物之總重量)，該樹脂B之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體，及c.較佳含量為0.0001與0.5毫當量/公克固體組分之催化劑系統C，其含有或能夠產生能夠活化組分A與B之間的RMA反應之鹼性催化劑，d.視情況選用之含X-H基團之組分(D)，其亦為可在催化劑C作用下與組分B反應之麥可加成供體，其中X為C、N、P、O或S，較佳為C、N或P，較佳以相對於由組分C產生之鹼至少50莫耳%且小於組分A之C-H活化基團的30莫耳%之量存在， e.視情況選用之0.1與80 wt%之間的溶劑、較佳有機溶劑，其較佳含有至少1 wt%一級醇及視情況選用之至少0.1-10 wt%水，其中上文所提及之組分之總和為100重量百分比，且其中組成物中之樹脂A及B之總羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。 In summary, the crosslinkable composition of the present invention comprises: between 5 and 95 wt% of Resin A having a reactive group comprising at least 2 acid protons CH on an activated methylene or methine group. Substrate A, the resin A having a hydroxyl value of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids, and b. 5 and 95 wt% of resin B having at least 2 activation unsaturations a reactive component B of the group (wt% relative to the total weight of the crosslinkable composition) having a hydroxyl value of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids, and c. Catalyst system C having a solid content of 0.0001 and 0.5 meq/g of solid component, which contains or is capable of producing a basic catalyst capable of activating the RMA reaction between components A and B, d. optionally containing XH groups a component (D) which is also a methacrylic addition donor capable of reacting with component B under the action of catalyst C, wherein X is C, N, P, O or S, preferably C, N or P, preferably present in an amount of at least 50 mole % relative to the base produced by component C and less than 30 mole % of the CH activating group of component A, e. optionally between 0.1 and 80 wt% of a solvent, preferably an organic solvent, preferably containing at least 1 wt% of a primary alcohol and optionally at least 0.1 to 10 wt% of water, as mentioned above The sum of the components is 100% by weight, and the total hydroxyl value of the resins A and B in the composition is less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solid.

考慮到可交聯組成物為僅在實際使用之前不久形成之2K組成物，本發明亦關於一種部分之套組，其用於製造本發明之組成物，該套組包括包含組分A及B之部分1及包含組分C及D之部分2；或者包含組分A、B及D之部分1及包含組分C之部分2。一種部分之套組，其用於製造如申請專利範圍第1項之組成物，該套組包括包含具有反應性組分A及/或B但無C之可交聯組分之部分1及包含組分C之部分2。 In view of the fact that the crosslinkable composition is a 2K composition formed only shortly before actual use, the invention also relates to a kit for the manufacture of a composition of the invention comprising a component A and B Part 1 and part 2 comprising components C and D; or part 1 comprising components A, B and D and part 2 comprising component C. A kit of parts for the manufacture of a composition as claimed in claim 1, the kit comprising a portion 1 comprising a crosslinkable component having reactive components A and/or B but no C and comprising Part 2 of component C.

本發明亦關於本發明之交聯組成物於製造塗料組成物、薄膜或油墨之方法中之用途；及包含本發明之交聯組成物及其他塗覆定向添加劑(例如一或多種塗料添加劑，如顏料、共黏合劑、溶劑等)之塗料組成物、油墨或膜。 The invention also relates to the use of the crosslinked composition of the invention in a method of making a coating composition, film or ink; and comprising the crosslinked composition of the invention and other coating oriented additives (eg one or more coating additives, such as A coating composition, ink or film of a pigment, a co-binder, a solvent, or the like.

本發明亦關於一種製造塗層之方法，該塗層之完全固化乾燥厚度為至少70、75、80或100且更佳至少125微米且具有所得固化組成物之良好表面外觀及硬度，該方法包含在使用之前不久將組分A、B與催化劑C混合以形成本發明之塗料組成物，將塗料組成物層塗覆於基材上，且使其在0與60℃之間的溫度下固化。 The invention also relates to a method of making a coating having a fully cured dry thickness of at least 70, 75, 80 or 100 and more preferably at least 125 microns and having a good surface appearance and hardness of the resulting cured composition, the method comprising Components A, B and Catalyst C were mixed shortly before use to form the coating composition of the present invention, the coating composition layer was applied to the substrate, and allowed to cure at a temperature between 0 and 60 °C.

上面對本發明所作之較為籠統的論述將利用以下特定實施例來作進一步說明，該等實施例僅為例示性的。 The more general description of the present invention will be further described by the following specific embodiments, which are merely illustrative.

分子量係藉由GPC於THF中來量測，且以聚苯乙烯當量表示。 The molecular weight is measured by GPC in THF and expressed in terms of polystyrene equivalent.

帕索茲硬度(Persoz hardness)量測：帕索茲擺錘硬度係在氣候調節室中在23℃及55+/-5%相對濕度下量測。硬度係根據帕索茲如ASTM D 4366中所述用擺錘量測。 Persoz hardness measurement : The Pasozis pendulum hardness was measured in a climate chamber at 23 ° C and 55 +/- 5% relative humidity. The hardness is measured by a pendulum according to Pasoz as described in ASTM D 4366.

乾燥時間係藉由將拇指緊緊地按壓於漆膜中來測定。當無可見痕跡留於漆膜中時，記錄下時間。 The drying time was determined by pressing the thumb tightly into the paint film. When no visible traces remain in the paint film, record the time.

本發明之樹脂實施例：製備丙二酸酯聚酯樹脂I Resin Example of the Invention: Preparation of Malonate Polyester Resin I

向具有填充有拉西環之蒸餾柱之反應器中引入4.691莫耳新戊二醇、2.173莫耳六氫鄰苯二甲酸酐及0.0012莫耳丁基錫酸。使混合物在氮氣下在240℃下聚合至酸值為0.2 mg KOH/g。將混合物冷卻至130℃且添加2.819莫耳丙二酸二乙酯。將反應混合物加熱至170℃且在減壓下移除乙醇。將幾乎無色之物質冷卻，且用178 g乙酸丁酯稀釋至85%固體含量。最終樹脂之酸值為0.3 mg KOH/g固體，OH值為8 mg KOH/g固體。用乙酸丁酯將樹脂稀釋至85%固體。 4.691 Moen neopentyl glycol, 2.173 mol hexahydrophthalic anhydride and 0.0012 mol butyl stannic acid were introduced into a reactor having a distillation column packed with a Raschig ring. The mixture was polymerized under nitrogen at 240 ° C to an acid value of 0.2 mg KOH / g. The mixture was cooled to 130 ° C and 2.819 moles of diethyl malonate was added. The reaction mixture was heated to 170 ° C and the ethanol was removed under reduced pressure. The almost colorless material was cooled and diluted to 8% solids with 178 g of butyl acetate. The final resin had an acid value of 0.3 mg KOH/g solids and an OH value of 8 mg KOH/g solids. The resin was diluted to 85% solids with butyl acetate.

本發明之樹脂實施例：製備丙二酸酯聚酯樹脂II Resin Example of the Invention: Preparation of Malonate Polyester Resin II

以與(I)類似之方式將4.521莫耳新戊二醇、2.095莫耳六氫鄰苯二甲酸酐、0.232莫耳丁基乙基丙二醇及0.0011莫耳丁基錫酸引入反應器中。使混合物在氮氣下在240℃下聚合至酸值為0.2 mg KOH/g。將混合物冷卻至130℃且添加2.717莫耳丙二酸二乙酯。將反應混合物加熱至170℃且在 減壓下移除乙醇。將幾乎無色之物質冷卻，且用178 g乙酸丁酯稀釋至85%固體含量。最終樹脂之酸值為0.3 mg KOH/g固體，OH值為約30 mg KOH/g固體。用乙酸丁酯將樹脂稀釋至85%固體。 In a similar manner to (I), 4.521 moles of neopentyl glycol, 2.095 moles of hexahydrophthalic anhydride, 0.232 moles of butyl ethyl propylene glycol, and 0.0011 moles of butyl stannate were introduced into the reactor. The mixture was polymerized under nitrogen at 240 ° C to an acid value of 0.2 mg KOH / g. The mixture was cooled to 130 ° C and 2.718 moles of diethyl malonate was added. The reaction mixture is heated to 170 ° C and The ethanol was removed under reduced pressure. The almost colorless material was cooled and diluted to 8% solids with 178 g of butyl acetate. The final resin had an acid value of 0.3 mg KOH/g solids and an OH value of about 30 mg KOH/g solids. The resin was diluted to 85% solids with butyl acetate.

比較性樹脂實施例：製備比較丙二酸酯聚酯樹脂III Comparative Resin Example: Preparation of Comparative Malonate Polyester Resin III

以與(I)類似之方式將4.341莫耳新戊二醇、2.011莫耳六氫鄰苯二甲酸酐、0.464莫耳丁基乙基丙二醇及0.0011莫耳丁基錫酸引入反應器中。使混合物在氮氣下在240℃下聚合至酸值為0.2 mg KOH/g。將混合物冷卻至130℃且添加2.609莫耳丙二酸二乙酯。將反應混合物加熱至170℃且在減壓下移除乙醇。將幾乎無色之物質冷卻，且用178 g乙酸丁酯稀釋至85%固體含量。最終樹脂之酸值為0.3 mg KOH/g固體，OH值為約60 mg KOH/g固體。用乙酸丁酯將樹脂稀釋至85%固體。 4.341 Moen neopentyl glycol, 2.011 mole hexahydrophthalic anhydride, 0.464 mole butyl ethyl propylene glycol, and 0.0011 moles of butyl stannate were introduced into the reactor in a similar manner to (I). The mixture was polymerized under nitrogen at 240 ° C to an acid value of 0.2 mg KOH / g. The mixture was cooled to 130 ° C and 2.609 moles of diethyl malonate was added. The reaction mixture was heated to 170 ° C and the ethanol was removed under reduced pressure. The almost colorless material was cooled and diluted to 8% solids with 178 g of butyl acetate. The final resin had an acid value of 0.3 mg KOH/g solids and an OH value of about 60 mg KOH/g solids. The resin was diluted to 85% solids with butyl acetate.

製備油漆 Preparation of paint

根據表中之組成製備油漆。用高剪切力攪拌器將顏料分散於Disperbyk與Sartomer(其為可交聯組分B：DiTMPTA為二-三羥甲基丙烷-四丙烯酸酯)之混合物中15分鐘。隨後在攪拌下添加其他成分。在塗覆之前添加催化劑溶液。 The paint was prepared according to the composition in the table. The pigment was dispersed in a mixture of Disperbyk and Sartomer (which is a crosslinkable component B: DiTMPTA is di-trimethylolpropane-tetraacrylate) for 15 minutes using a high shear mixer. Additional ingredients are then added with stirring. The catalyst solution was added prior to coating.

製備催化劑溶液 Preparation of catalyst solution

如下形成催化劑溶液：向8.03 g 55%氫氧化四丁銨溶液中添加11.05 g碳酸二乙酯及6.74 g異丙醇。 A catalyst solution was formed by adding 11.05 g of diethyl carbonate and 6.74 g of isopropanol to 8.03 g of a 55% tetrabutylammonium hydroxide solution.

以上實施例顯示，塗料組成物之硬度強烈視樹脂之羥基值而定。60或更大之羥基值將導致不可接受之長乾燥時間及極緩慢硬度形成。 The above examples show that the hardness of the coating composition is strongly dependent on the hydroxyl value of the resin. A hydroxyl value of 60 or greater will result in unacceptably long drying times and very slow hardness formation.

先前技術比較性樹脂實施例 Prior art comparative resin embodiment

WO 2011/055463在實施例4中描述由丙二酸酯聚酯組分A-1及TMPA(作為可交聯組分B-1)及不同催化劑製得之調配物。丙二酸酯聚酯A-1之OH值為83.2 mg KOH/g。除羥基值之外，丙二酸酯聚酯A-1與上述丙二酸酯聚酯I及II類似。所用催化劑C-5(乙基碳酸四丁銨)為以上油漆調配物中所用之催化劑。帕索茲硬度在1個月固化時間之後為65，而具有低羥基值之本發明之樹脂在3天固化時間之後已具有顯著更高硬度(88)。 WO 2011/055463 describes in Formulation 4 formulations prepared from malonate polyester components A-1 and TMPA (as crosslinkable component B-1) and different catalysts. The OH value of the malonate polyester A-1 was 83.2 mg KOH/g. In addition to the hydroxyl value, the malonic ester polyester A-1 is similar to the above malonic ester polyesters I and II. The catalyst C-5 (tetrabutylammonium ethyl carbonate) used was the catalyst used in the above paint formulation. The Pasoz hardness was 65 after a one month cure time, while the resin of the present invention having a low hydroxyl value had a significantly higher hardness (88) after a 3 day cure time.

將藉由以下特定實施例來進一步說明本發明，該等實施例僅為例示性的。 The invention will be further illustrated by the following specific examples, which are merely illustrative.

分子量係藉由GPC於THF中來量測，且以聚苯乙烯當量表示。用TA儀器(TA Instruments)AR2000流變計，使用錐板式配置(圓錐4 cm 1°)在1 Pa應力下量測黏度。 The molecular weight is measured by GPC in THF and expressed in terms of polystyrene equivalent. The viscosity was measured under a 1 Pa stress using a TA Instruments AR2000 rheometer using a cone and plate configuration (cone 4 cm 1 °).

用於測定適用期之管與球方法：以20 ml油漆填充攜帶兩個相隔5 cm之標記的平底試管(內徑15 mm，長度12.5 cm)。添加直徑為8 mm之鋼球，且用彈扣蓋(snap cap)將管封閉。以10°之角度固持管且使鋼球在試管壁上滾動。在兩個標記之間滾動所需之時間被視為黏度之量度。黏度倍增所需之時間被視為適用期。若需要，則此時間係藉由在兩個量測之間進行線性內插來計算。此方法用於著色調配物。就澄清調配物而言，用12 mm直徑之不鏽鋼球及欲研究之調配物填充玻璃試管(長度12 cm，直徑13 mm)，留下極有限的頂部空間，且將其封閉。記錄當垂直傾斜管時球下落且通過5 cm距離之時間。對2次量測取平均值。 Tube and ball method for determining pot life : A flat-bottomed test tube (inner diameter 15 mm, length 12.5 cm) carrying two markers 5 cm apart was filled with 20 ml of paint. A steel ball having a diameter of 8 mm was added and the tube was closed with a snap cap. The tube was held at an angle of 10° and the steel ball was rolled over the tube wall. The time required to scroll between the two markers is considered a measure of viscosity. The time required for viscosity multiplication is considered to be the pot life. If desired, this time is calculated by linear interpolation between the two measurements. This method is used for color matching. For clarification of the formulation, a glass tube (12 cm in length, 13 mm in diameter) was filled with a 12 mm diameter stainless steel ball and the formulation to be studied, leaving a very limited headspace and closing it. Record the time the ball fell and passed a distance of 5 cm when tilting the tube vertically. The average of the two measurements was taken.

乾燥記錄器乾燥時間：就測定記錄器乾燥時間而言，用具有90 μ間隙之刮刀將油漆塗覆於玻璃面板上。用設定週期時間為60分鐘之DT-5020型Gardco電子乾燥時間記錄器量測乾燥時間。乾燥時間被記錄為記錄針不再在膜上留下可見痕跡之時間。 Dry Recorder Drying Time : For the determination of the recorder drying time, the paint was applied to the glass panel with a doctor blade having a gap of 90 μ. The drying time was measured with a DT-5020 Gardco electronic drying time recorder set to a cycle time of 60 minutes. The drying time is recorded as the time at which the recording needle no longer leaves visible marks on the film.

TNO棉球乾燥時間：脫塵乾燥及不黏著時間(tack-free time)係根據所謂TNO方法用棉毛團塊量測。脫塵乾燥時間意謂在團塊落於塗層表面後且使其保留在此處10秒鐘 後，在吹走團塊後塗層上無棉毛殘餘物黏附於表面上所需之時間。對於不黏著時間，保持相同，但現在將1 kg之重量負載施加於團塊上10秒。 TNO cotton ball drying time : dust drying and tack-free time are measured by cotton wool mass according to the so-called TNO method. The dust removal drying time means the time required for the cotton wool residue to adhere to the surface after the agglomerate has been left on the surface of the coating for 10 seconds. For the non-sticking time, keep the same, but now a weight load of 1 kg is applied to the mass for 10 seconds.

就梯度層厚度面板而言，在不同點處量測硬度且量測相應層厚度。若需要，則某一層厚度下之硬度係藉由對兩個不同層厚度下之量測值進行線性內插來計算。層厚度係用Fischer Permascope MP40E-S量測。 For a gradient layer thickness panel, the hardness is measured at different points and the corresponding layer thickness is measured. If desired, the hardness at a layer thickness is calculated by linearly interpolating the measurements at two different layer thicknesses. The layer thickness was measured using a Fischer Permascope MP40E-S.

光學評估噴塗之著色油漆：用特威噴槍(devilbiss spraygun)、噴嘴FF-1.4在3.5巴之空氣壓力下噴塗油漆。將油漆以連續層形式噴塗於55×10 cm鋼板之整個表面上。自距右邊緣10 cm開始，噴塗一連續層。堆積數層，向右移，以使得自左向右形成層厚度梯度。使膜在23℃、45% RH下水平地乾燥。層厚度係用Fischer Permascope MP40E-S量測。在100 μ層厚度下，用配備有數位攝影機之Olympus SZX10顯微鏡(1X放大率)拍攝圖像。 Optical evaluation of the painted paint : spray paint with a devilbiss spraygun, nozzle FF-1.4 at an air pressure of 3.5 bar. The paint was sprayed in a continuous layer on the entire surface of a 55 x 10 cm steel plate. Spray a continuous layer starting at 10 cm from the right edge. Stack several layers and move to the right so that a layer thickness gradient is formed from left to right. The film was allowed to dry horizontally at 23 ° C, 45% RH. The layer thickness was measured using a Fischer Permascope MP40E-S. Images were taken at 100 μ layer thickness using an Olympus SZX10 microscope (1X magnification) equipped with a digital camera.

波掃描分析：使用Byk儀器之Wavescan II來分析如上文所述之面板。使用來自Byk之Autochart軟體儲存資料。在垂直於厚度梯度之方向上進行分析。在此儀器中，藉由樣品表面以60°之角度反射小雷射二極體之光，且以光澤角度(相反60°)偵測反射光。在量測期間，在大約10 cm之掃描長度上移動「波掃描」橫過樣品表面，每0.027 mm記錄一資料點。樣品之表面結構調節雷射二極體之光。將信號分為0.1-30 mm範圍內之5個波長範圍，且藉由數學濾波來處理。就5個範圍內之每一者而言，計算特徵值(Wa 0.1-0.3 mm，Wb 0.3-1.0 mm，Wc 1.0-3.0 mm，Wd 3.0-10 mm，We 10-30 mm)以及典型波掃描值長波(LW，大約1-10 mm)及短波(SW，大約0.3-1 mm)。低值意謂光滑表面結構。另外，LED光源安裝於波掃描DOI中且在通過光圈之後以20度照亮表面。偵測散射光且量測所謂遲鈍度值(du，<0.1 mm)。藉由使用3個短波範圍Wa、Wb及du之值，計算DOI值。(參見Osterhold等人，Progress in Organic Coatings,2009，第65卷，第4期，第440-443頁)。 Wave Scan Analysis : The Wavescan II of the Byk instrument was used to analyze the panels as described above. Use the Autochart software from Byk to store data. The analysis was performed in a direction perpendicular to the thickness gradient. In this instrument, the light of the small laser diode is reflected by the surface of the sample at an angle of 60°, and the reflected light is detected at a gloss angle (reverse 60°). During the measurement, a "wave scan" was moved across the surface of the sample over a scan length of approximately 10 cm, and a data point was recorded every 0.027 mm. The surface structure of the sample modulates the light of the laser diode. The signal is divided into 5 wavelength ranges in the range of 0.1-30 mm and processed by mathematical filtering. For each of the five ranges, calculate eigenvalues (Wa 0.1-0.3 mm, Wb 0.3-1.0 mm, Wc 1.0-3.0 mm, Wd 3.0-10 mm, We 10-30 mm) and typical wave scans Long wave (LW, about 1-10 mm) and short wave (SW, about 0.3-1 mm). A low value means a smooth surface structure. In addition, the LED light source is mounted in the wave scan DOI and illuminates the surface at 20 degrees after passing through the aperture. Detect scattered light and measure the so-called retardation value (du, <0.1 mm). The DOI value is calculated by using the values of the three short wave ranges Wa, Wb, and du. (See Osterhold et al., Progress in Organic Coatings, 2009, Vol. 65, No. 4, pp. 440-443).

對實驗中所用之化學品使用以下縮寫：DiTMPTA為二-三羥甲基丙烷-四丙烯酸酯(獲自Aldrich(MW=466 g/mol))或以Sartomer SR355(由Sartomer商業供應)形式使用；Disperbyk 163為由Byk商業供應之分散劑；Byk 310及315為由Byk商業供應之添加劑；Kronos 2310為由Kronos商業供應之TiO2顏料；TBAH為氫氧化四丁銨；BuAc為乙酸丁酯；MEK為甲基乙基酮(2-丁酮)；EtAcAc為乙醯乙酸乙酯；DEC為碳酸二乙酯；IPA為異丙醇；RT為室溫。 The following abbreviations were used for the chemicals used in the experiments: DiTMPTA was di-trimethylolpropane-tetraacrylate (available from Aldrich (MW = 466 g/mol)) or used as Sartomer SR355 (commercially supplied by Sartomer); Disperbyk 163 is a commercial dispersant supplied by Byk; Byk 310 and 315 are commercially available additives from Byk; Kronos 2310 is a TiO2 pigment commercially available from Kronos; TBAH is tetrabutylammonium hydroxide; BuAc is butyl acetate; MEK is Methyl ethyl ketone (2-butanone); EtAcAc is ethyl acetate; DEC is diethyl carbonate; IPA is isopropanol; RT is room temperature.

製備本發明之丙二酸酯聚酯A Preparation of the malonate polyester A of the present invention

向具有填充有拉西環(Raschig ring)之蒸餾柱之反應器中引入17.31 mol新戊二醇、8.03 mol六氫鄰苯二甲酸酐及0.0047 mol丁基錫酸。使混合物在氮氣下在240℃下聚合至酸值為0.2 mg KOH/g。將混合物冷卻至130℃且添加10.44 mol丙二酸二乙酯。將反應混合物加熱至170℃且在減壓下移除乙醇。將幾乎無色之物質冷卻，且用420 g乙酸丁酯稀釋至90%固體含量。最終樹脂之酸值為0.3 mg KOH/g固 體，OH值為20 mg KOH/g固體，且重量平均分子量為3400 Da。 17.31 mol of neopentyl glycol, 8.03 mol of hexahydrophthalic anhydride and 0.0047 mol of butyl stannic acid were introduced into a reactor having a distillation column packed with a Raschig ring. The mixture was polymerized under nitrogen at 240 ° C to an acid value of 0.2 mg KOH / g. The mixture was cooled to 130 ° C and 10.44 mol of diethyl malonate was added. The reaction mixture was heated to 170 ° C and the ethanol was removed under reduced pressure. The almost colorless material was cooled and diluted to 420% solids with 420 g of butyl acetate. The final acid value of the resin is 0.3 mg KOH / g solid The OH value was 20 mg KOH/g solid and the weight average molecular weight was 3400 Da.

催化劑溶液C1 Catalyst solution C1

藉由使59.4 g TBAH溶液(40%水溶液)與13.5 g DEC反應(在室溫下反應隔夜)，以14.5 g異丙醇作為共溶劑，之後生成相應乙基碳酸鹽物質，來製備催化劑溶液。滴定指示，阻斷完成且受阻斷之鹼之濃度為0.83毫當量/公克溶液。 A catalyst solution was prepared by reacting 59.4 g of a TBAH solution (40% aqueous solution) with 13.5 g of DEC (reaction at room temperature overnight) with 14.5 g of isopropanol as a co-solvent, followed by formation of the corresponding ethyl carbonate material. Titration indicated that the blocking was complete and the concentration of the blocked base was 0.83 meq/g solution.

催化劑溶液C2 Catalyst solution C2

向43.6 g 45% TBAH水溶液中添加36.6 g異丙醇及60 g DEC。在靜置隔夜之後，經紙過濾混合物。滴定顯示，催化劑含有0.52毫當量阻斷鹼/公克溶液。 To 43.6 g of a 45% TBAH aqueous solution was added 36.6 g of isopropanol and 60 g of DEC. After standing overnight, the mixture was filtered through paper. Titration showed that the catalyst contained 0.52 milliequivalents of blocking base per gram of solution.

No-D實施例調配物1、實施例調配物1-4 No-D Example Formulation 1, Example Formulations 1-4

基於丙二酸酯供體樹脂A、DiTMPTA(作為丙烯醯基供體樹脂)及指示量之琥珀醯亞胺來製備調配物，且用MEK/BuAc按體積計1：1之混合物使其變稀至黏度為160 mPas。將此與一定量之催化劑溶液C1混合。表A中所列為總體組成之詳情。催化劑量為50毫當量/公克固體，水含量為1.8 wt%，異丙醇為0.7 wt%，乙醇含量估計為0.2 wt%。 Formulations were prepared based on malonate donor resin A, DiTMPTA (as propylene sulfhydryl donor resin) and the indicated amount of amber quinone imine, and diluted with a 1:1 mixture of MEK/BuAc by volume. The viscosity is 160 mPas. This was mixed with a certain amount of catalyst solution C1. Details of the overall composition are listed in Table A. The amount of the catalyst was 50 meq/g solid, the water content was 1.8 wt%, the isopropanol was 0.7 wt%, and the ethanol content was estimated to be 0.2 wt%.

在此等調配物中，用TNO棉球乾燥測試來追蹤產生約70-75 mu之乾燥膜厚度的薄膜在室溫下之乾燥特性，且測定帕索茲擺錘硬度發展情況；此等結果亦列於表B中。 In these formulations, the TNO cotton ball drying test was used to track the drying characteristics of the film which produced a dry film thickness of about 70-75 mu at room temperature, and the development of the Pasozi pendulum hardness was measured; Listed in Table B.

可以看出，儘管No-D實施例1展示極其快速的乾燥，但實際帕索茲硬度水準據推測因溶劑滯留於系統中而較低。此外，此No-D實施例1之外觀不佳。在添加低量琥珀醯亞胺(略高於催化劑用量)後，可觀察到乾燥有一定的延遲，但仍認為乾燥時間快速；然而，亦可觀測到，帕索茲硬度發展得到很大改良。同時，具有琥珀醯亞胺之實施例膜展現比No-D實施例1更佳之外觀。 It can be seen that although No-D Example 1 exhibits extremely fast drying, the actual Pasozz hardness level is presumably low due to solvent retention in the system. Further, the appearance of this No. 1 Example 1 was poor. After the addition of a low amount of amber succinimide (slightly higher than the amount of catalyst), a certain delay in drying was observed, but the drying time was still considered to be fast; however, it was also observed that the development of Pasoz hardness was greatly improved. Meanwhile, the film of the example having amber imine exhibited a better appearance than No. 1 Example 1.

製備實施例調配物5-7及No-D實施例調配物2-3作為具有表C中所表列之組成(量以公克為單位)的著色油漆。 PREPARATION EXAMPLES Formulations 5-7 and No-D Examples Formulations 2-3 were used as colored paints having the composition listed in Table C (in grams).

量測此等著色油漆之適用期，且用乾燥記錄器測定拉延於玻璃面板上之此等油漆的乾燥時間。亦藉由噴塗將此等油漆塗覆於鋼板上以獲得梯度膜厚度面板。測定24小時室溫固化後50 mu乾燥膜厚度下之帕索茲硬度；在大約100 mu乾燥膜厚度下拍攝此等面板上之所得塗層之顯微鏡圖像(附錄：像片)。亦量測此等油漆之適用期。結果包括於表C中。 The pot life of these pigmented paints was measured and the drying time of such paints drawn on the glass panels was measured using a dry recorder. These paints were also applied to the steel sheets by spraying to obtain a gradient film thickness panel. The Pasolz hardness at a dry film thickness of 50 mu after 24 hours of room temperature curing was measured; a microscope image of the resulting coating on these panels was taken at a dry film thickness of about 100 mu (Appendix: Photograph). The pot life of these paints is also measured. The results are included in Table C.

可自No-D實施例3與實施例6及7之比較而觀測到，添加琥珀醯亞胺至調配物中在帕索茲硬度形成方面產生明顯的優勢，且在適用期上有一定優勢。具有較高含量琥珀醯亞胺之實施例7展示乾燥時間有顯著增加，然而44分鐘值仍可視為可接受至良好的值。如可自比較顯微鏡像片而判斷出，來自實施例6及7之面板之外觀比來自No-D實施 例3之面板之外觀好得多，No-D實施例3展示更多缺陷(附錄：像片)。 It can be observed from the comparison of No-D Example 3 with Examples 6 and 7 that the addition of amber imine to the formulation produces significant advantages in the formation of Passoz hardness and has certain advantages over the pot life. Example 7 with a higher level of amber imine showed a significant increase in drying time, however the 44 minute value was still considered acceptable to good values. It can be judged from the comparison of the microscope image that the appearance of the panels from Examples 6 and 7 is from No-D implementation. The panel of Example 3 looks much better, and No. 3 Embodiment 3 shows more defects (Appendix: Photo).

現基於除丙二酸酯之外還包括有乙醯乙酸酯作為RMA供體基團之調配物，可自No-D實施例2與實施例5之比較得出類似結論。實施例5(添加有琥珀醯亞胺)與No-D實施例2(不含有琥珀醯亞胺)相比展現更高帕索茲硬度、更佳適用期及更佳外觀(附錄：像片)。 Based on the inclusion of acetamidine acetate as the RMA donor group in addition to the malonate, a similar conclusion can be drawn from the comparison of No. 2 Example 2 with Example 5. Example 5 (addition of amber succinimide) exhibited higher Pasolz hardness, better pot life and better appearance than No-D Example 2 (without amber succinimide) (Appendix: Photo) .

以與如上文關於實施例5-7所論述類似之方式製備且評估實施例8，組成及結果如下於表D中給出(量以公克為單位)。可以看出，額外存在1,2,4-***(當與實施例6相比時)使得適用期有顯著改良，而其他優勢則保留。 Example 8 was prepared and evaluated in a manner similar to that discussed above with respect to Examples 5-7, and the composition and results are given below in Table D (in grams). It can be seen that the additional presence of 1,2,4-triazole (when compared to Example 6) results in a significant improvement in pot life while other advantages remain.

沿著類似路線調配實施例調配物9及10及No-D實施例調配物4及5且加以評估(現亦包括波掃描分析)，以得到外觀品質之定量示度。組成及結果於表E中給出(量以公克為單位)。 The Example Formulations 9 and 10 and the No-D Example Formulations 4 and 5 were formulated along similar routes and evaluated (now also including wave scanning analysis) to obtain a quantitative indication of the quality of appearance. The composition and results are given in Table E (in grams).

可將實施例調配物9與No-D調配物實施例4相比，可將實施例調配物10與No-D調配物實施例5相比，差別在於存在低量琥珀醯亞胺。自兩個比較均可推斷，存在琥珀醯亞胺，除改良帕索茲硬度之外，還使得長波及短波粗糙度、遲鈍度及DOI值有顯著改良。 Example Formulation 9 can be compared to No-D Formulation Example 4, and Example Formulation 10 can be compared to No-D Formulation Example 5, with the difference that a low amount of amber imine is present. It can be inferred from both comparisons that the presence of amber quinone imine, in addition to the improved Pasotz hardness, also significantly improved the long-wave and short-wave roughness, retardation and DOI values.

實施例11：對轉化動力學之影響 Example 11: Effect on conversion kinetics

可藉由FTIR聚焦於丙烯醯基之809 cm-1譜帶特徵來追蹤系統中丙烯醯基之轉化。由此可使所添加之琥珀醯亞胺對總體轉化之影響變得可見。調配兩個系統(根據No-D實施例1(不具有琥珀醯亞胺)及實施例調配物1(相對於固體具有150%琥珀醯亞胺)之組成)。圖1比較了此等系統在塗覆於ATR晶體之頂部上後之轉化，其中IR光束探測接近基材之最深層。不具有琥珀醯亞胺之調配物之初始轉化快速，此亦為溶劑滯留及潛在外觀問題之原因。可以看出，即使以此等極低含量添加琥珀醯亞胺，亦使得初始轉化有顯著延遲；同時說明，在此初始延遲時期之後，轉化速率加速，以使得向更高轉化率之固化速率在此初始延遲之後仍然快速。 The conversion of propylene sulfhydryl groups in the system can be tracked by FTIR focusing on the 809 cm-1 band characteristics of the acrylonitrile group. This makes it possible to influence the effect of the added amber quinone imine on the overall conversion. Two systems were formulated (according to No-D Example 1 (without amber quinone imine) and Example Formulation 1 (with a composition of 150% amber succinimide relative to solids)). Figure 1 compares the conversion of such systems after application to the top of an ATR crystal where the IR beam is detected near the deepest layer of the substrate. The initial conversion of the formulation without amber imine is rapid, which is also the cause of solvent retention and potential appearance problems. It can be seen that even the addition of amber imine at such very low levels causes a significant delay in the initial conversion; it also shows that after this initial delay period, the conversion rate is accelerated so that the cure rate to higher conversions is This initial delay is still fast.

實施例12.測定琥珀醯亞胺之麥可加成反應性 Example 12. Determination of the methic acid addition reactivity of amber imine

將5公克琥珀醯亞胺(50.5毫莫耳)溶解於42公克丙烯酸丁酯與42公克甲醇之混合物中，且按原樣或在添加強鹼(9.82公克之1.12毫當量/公克的氫氧化四丁銨之甲醇溶液，11毫當量)之後維持於室溫下。隨後，藉由獲取樣品，用已知過量之HCl水溶液中和且用KOH溶液回滴定，來隨時間變化測定琥珀醯亞胺之濃度。在不用鹼起始之情況下，在兩週內未觀測到此溶液中之琥珀醯亞胺N-H有顯著損失。如以下表F中所說明，在添加鹼之情況下，可觀察到琥珀醯亞胺濃度隨時間降低。琥珀醯亞胺濃度係以基於所用量相對於理論含量之%表示。 5 g of amber succinimide (50.5 mmol) was dissolved in a mixture of 42 g of butyl acrylate and 42 g of methanol, and as it was or after the addition of a strong base (9.82 g of 1.12 meq/g of tetrabutyl hydroxide) The ammonium methanol solution, 11 meq, was maintained at room temperature. Subsequently, the concentration of amber imine was determined over time by taking a sample, neutralizing with a known excess of aqueous HCl and back titrating with a KOH solution. No significant loss of amber quinone imine N-H in this solution was observed within two weeks without starting with a base. As indicated in Table F below, in the case of addition of a base, amber amidine concentration was observed to decrease with time. The amber imine concentration is expressed as % based on the amount used relative to the theoretical content.

在此催化劑含量([琥珀醯亞胺]/[鹼]=5)下，失去欲消耗之琥珀醯亞胺酸性質子的25%需要花費約一小時。在此等條件下，丙二酸二甲酯(替代琥珀醯亞胺)將與丙烯酸酯反應得快速得多。 At this catalyst content ([ammonium imine] / [base] = 5), it takes about one hour to lose 25% of the amber imidate protons to be consumed. Under these conditions, dimethyl malonate (instead of amber succinimide) will react much more rapidly with acrylate.

Claims (33)

一種RMA可交聯組成物，其包含：至少一種可交聯組分，該可交聯組分包含反應性組分A及B，其各包含至少2個反應基，其中組分A之該等至少2個反應基為於活化亞甲基或次甲基上之酸性質子(C-H)且組分B之該等至少2個反應基為活化不飽和基團(C=C)；及鹼催化劑(C)，該等反應性組分A與B在該鹼催化劑作用下藉由真實麥可加成(RMA)反應而交聯，其特徵在於，該組成物中的該至少一種包含反應性組分A及B之可交聯組分的總羥基值為小於60、較佳小於40且更佳小於20 mg KOH/g固體。 An RMA crosslinkable composition comprising: at least one crosslinkable component comprising reactive components A and B each comprising at least 2 reactive groups, wherein component A At least 2 reactive groups are activated acid protons (CH) on the methylene or methine group and at least 2 reactive groups of component B are activated unsaturated groups (C=C); and a base catalyst (C), the reactive components A and B are crosslinked by a real Michael Addition (RMA) reaction under the action of the base catalyst, characterized in that the at least one of the components comprises a reactive group The crosslinkable components of Parts A and B have a total hydroxyl number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids. 如申請專利範圍第1項之可交聯組成物，其中該催化劑C為如式X⁺ROCO₂ ^-之碳酸鹽，其中X⁺為非酸性陽離子，較佳為四級銨或鏻，且R為氫或經取代或未經取代之烷基、芳基或芳烷基。 The crosslinkable composition of claim 1, wherein the catalyst C is a carbonate of the formula X ⁺ ROCO ₂ ^- wherein X ^{+ is a} non-acidic cation, preferably a quaternary ammonium or ruthenium, and R is Hydrogen or substituted or unsubstituted alkyl, aryl or aralkyl. 如申請專利範圍第1項或第2項之可交聯組成物，其中反應性組分A及B係在各別分子中且各自獨立地呈聚合物、寡聚物、二聚體或單體形式，或其中組分A及B以及視情況選用之C組合於一分子中。 A crosslinkable composition according to claim 1 or 2, wherein the reactive components A and B are in separate molecules and are each independently a polymer, oligomer, dimer or monomer Form, or component A and B, and optionally C, are combined in one molecule. 如申請專利範圍第1項至第3項之可交聯組成物，其中包含反應性組分A之該可交聯組分為包含一或多種具有如式2之結構之反應性組分A的聚合物： 其中R為氫或烷基、芳烷基或芳基取代基，且Y及Y'為相同或不同取代基，較佳為烷基、芳烷基或芳基(R*)、烷氧基(-OR*)或聚合物主鏈，或其中-C(=O)-Y及/或-C(=O)-Y'由CN或苯基置換，且該聚合物之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。 The crosslinkable composition of claim 1 to 3, wherein the crosslinkable component comprising reactive component A is one or more reactive components A having a structure of formula 2 polymer: Wherein R is hydrogen or an alkyl, aralkyl or aryl substituent, and Y and Y' are the same or different substituents, preferably an alkyl group, an aralkyl group or an aryl group (R*), an alkoxy group ( -OR*) or a polymer backbone, or wherein -C(=O)-Y and/or -C(=O)-Y' are replaced by CN or phenyl, and the hydroxyl value of the polymer is less than 60, Preferably less than 40 and more preferably less than 20 mg KOH/g solids. 如申請專利範圍第4項之可交聯組成物，其中該聚合物為聚酯、聚胺基甲酸酯或聚碳酸酯。 The crosslinkable composition of claim 4, wherein the polymer is a polyester, a polyurethane or a polycarbonate. 如申請專利範圍第1項至第5項之可交聯組成物，其中該含活化C-H基團之組分A為丙二酸酯(在式1中Y及Y'為-OR*)或乙醯乙酸酯(在式1中Y為-OR*且Y'為-R*)。 The crosslinkable composition of claim 1 to 5, wherein the component A containing an activated CH group is a malonate (Y and Y' in the formula 1 is -OR*) or B Indole acetate (Y is -OR* and Y' is -R* in Formula 1). 如申請專利範圍第1項至第6項之可交聯組成物，其中包含組分A之該可交聯組分為每分子平均包含2至20個、較佳為4至10個活性C-H官能基之聚合物。 The crosslinkable composition of claim 1 to 6, wherein the crosslinkable component comprising component A comprises from 2 to 20, preferably from 4 to 10, active CH functional groups per molecule. Base polymer. 如申請專利範圍第1項至第7項之交聯組成物，其中該可交聯組分中之該等反應性組分A中有超過50%、較佳為60%、70%、80%、90%或95%為丙二酸酯基。 The cross-linking composition of claim 1 to 7, wherein the reactive component A of the crosslinkable component has more than 50%, preferably 60%, 70%, 80% 90% or 95% is a malonate group. 如申請專利範圍第1項至第8項之可交聯組成物，其中該組分B包含不飽和丙烯醯基或順丁烯二酸酯官能基，較佳為丙烯醯基或丙烯醯胺。 The crosslinkable composition of claims 1 to 8 wherein the component B comprises an unsaturated propylene fluorenyl or maleate functional group, preferably an acrylonitrile or acrylamide. 如申請專利範圍第1項至第9項之可交聯組成物，其中組分A中之活化反應性酸性質子(C-H)之數目與組分B中之活化不飽和基團(C=C)之數目的比率在10與0.1之間、更佳在5與0.2之間、甚至更佳在2與0.5之間的範圍內。 The crosslinkable composition of claim 1 to claim 9, wherein the number of activated reactive acid protons (CH) in component A and the activated unsaturated group in component B (C=C) The ratio of the number is between 10 and 0.1, more preferably between 5 and 0.2, even more preferably between 2 and 0.5. 如申請專利範圍第1項至第23項中任一項之可交聯組成物，其包含：a. 5與95 wt%之間的可交聯組分，其包含具有至少2個於活化亞甲基或次甲基上之酸性質子C-H之組分A，及b. 5與95 wt%之間的可交聯組分，其包含具有至少2個活化不飽和基團之組分B(wt%，相對於該可交聯組成物之總重量而言)，及c.較佳含量為0.0001與0.5毫當量/公克固體組分之催化劑系統C，其含有或能夠產生能夠活化組分A與B之間的該RMA反應之鹼性催化劑，d.視情況選用之含X-H基團之組分(D)，其亦為可在催化劑C作用下與組分B反應之麥可加成供體，其中X為C、N、P、O或S，較佳為C、N或P，較佳以相對於由組分C產生之鹼至少50莫耳%且小於組分A之C-H活性基團的30莫耳%之量存在，e.視情況選用之0.1與80 wt%之間的溶劑，較佳為有機溶劑，其較佳含有至少1 wt%一級醇及視情況選用之至少0.1-10 wt%水，其中該等上文所提及之組分之總和為100重量百分比，且其中該組成物中的包含反應性組分A及B之該至少一種可交聯組分的總羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。 The crosslinkable composition according to any one of claims 1 to 23, which comprises: between 5 and 95 wt% of a crosslinkable component comprising at least 2 in activating sub- Component A of the acidic proton CH on the methyl or methine group, and b. 5 and 95 wt% of a crosslinkable component comprising component B having at least 2 activated unsaturated groups ( Wt%, relative to the total weight of the crosslinkable composition), and c. Catalyst system C having a preferred content of 0.0001 and 0.5 meq/g of solid component, which contains or is capable of producing activating component A a basic catalyst for the RMA reaction with B, d. optionally an XH group-containing component (D), which is also a Michael addition reaction which can react with component B under the action of catalyst C. Where X is C, N, P, O or S, preferably C, N or P, preferably at least 50 mol% relative to the base produced by component C and less than the CH reactive group of component A 30 摩尔% of the mass is present, e. optionally between 0.1 and 80 wt% of the solvent, preferably an organic solvent, preferably containing at least 1 wt% of the primary alcohol and optionally at least 0.1- 10 wt% water, of which The sum of the components mentioned herein is 100% by weight, and wherein the at least one crosslinkable component comprising reactive components A and B in the composition has a total hydroxyl value of less than 60, preferably less than 40 and More preferably less than 20 mg KOH/g solids. 一種部分之套組，其用於製造如申請專利範圍第1 項之組成物，該套組包括包含具有反應性組分A及/或B之該等可交聯組分但無C之部分1及包含組分C之部分2。 a partial kit for manufacturing as claimed in claim 1 The composition of the item, the kit comprising a portion 1 comprising the crosslinkable components having reactive components A and/or B but no C and a portion 2 comprising component C. 一種聚合或寡聚樹脂A，其用於如申請專利範圍第1項至第11項之RMA可交聯組成物中，該樹脂A包含一或多種具有如式2之結構之反應性組分A： 其中R為氫或烷基、芳烷基或芳基取代基，且Y及Y'為相同或不同之取代基，較佳為烷基、芳烷基或芳基(R*)、烷氧基(-OR*)或聚合物主鏈，或其中該-C(=O)-Y及/或-C(=O)-Y'由CN或苯基置換，且該聚合或寡聚樹脂A之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。 A polymeric or oligomeric resin A for use in an RMA crosslinkable composition according to items 1 through 11 of the patent application, the resin A comprising one or more reactive components A having the structure of Formula 2 : Wherein R is hydrogen or an alkyl, aralkyl or aryl substituent, and Y and Y' are the same or different substituents, preferably an alkyl group, an arylalkyl group or an aryl group (R*), an alkoxy group. (-OR*) or a polymer backbone, or wherein the -C(=O)-Y and/or -C(=O)-Y' is replaced by CN or a phenyl group, and the polymerized or oligomerized resin A The hydroxyl value is less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids. 如申請專利範圍第13項之樹脂A，其中該聚合或寡聚樹脂為包含反應性組分A之聚酯、聚醚、聚環氧樹脂、聚胺基甲酸酯或聚碳酸酯，較佳為聚醚、聚丙烯酸酯、聚酯或聚胺基甲酸酯。 The resin A of claim 13 wherein the polymeric or oligomeric resin is a polyester, a polyether, a polyepoxy resin, a polyurethane or a polycarbonate comprising the reactive component A, preferably. It is a polyether, polyacrylate, polyester or polyurethane. 如申請專利範圍第13項或第14項之樹脂A，其中反應性組分A中之該活化C-H基團為丙二酸酯基(在式1中Y及Y'為-OR*)或乙醯乙酸酯基(在式1中Y為-OR*且Y'為-R*)。 The resin A of claim 13 or 14, wherein the activated CH group in the reactive component A is a malonate group (Y and Y' in the formula 1 is -OR*) or B Anthracene acetate group (Y is -OR* and Y' is -R* in Formula 1). 如申請專利範圍第13項至第15項之樹脂A，其中 該組分A為每分子包含2至20個、較佳為4至10個活性C-H官能基之聚合物。 For example, Resin A of Articles 13 to 15 of the patent application, in which This component A is a polymer comprising from 2 to 20, preferably from 4 to 10, active C-H functional groups per molecule. 如申請專利範圍第13項至第16項之樹脂A，其中該可交聯組分中之該等反應性組分A中有超過50%、較佳為60%、70%、80%、90%或95%為丙二酸酯基。 The resin A of claim 13 to 16, wherein the reactive component A of the crosslinkable component has more than 50%, preferably 60%, 70%, 80%, 90 % or 95% is a malonate group. 如申請專利範圍第13項至第17項之樹脂A，其數目分子量在100-20000公克/莫耳之間，較佳在250與10000公克/莫耳之間，甚至更佳在300與6000公克/莫耳之間。 Resin A, as claimed in claims 13 to 17, has a molecular weight of from 100 to 20,000 g/mole, preferably between 250 and 10,000 g/mole, and even more preferably between 300 and 6,000 g. / between Mo and. 如申請專利範圍第13項至第18項之樹脂A，其每一反應性組分A之當量為100-2000公克/莫耳。 Resin A of claims 13 to 18 of the patent application has an equivalent weight of 100-2000 g/mole per reactive component A. 如申請專利範圍第13項至第19項之樹脂A，其酸值小於4、較佳小於3、2或1毫克KOH/公克。 Resin A according to items 13 to 19 of the patent application has an acid value of less than 4, preferably less than 3, 2 or 1 mgKOH/g. 一種聚合或寡聚樹脂B，其用於如申請專利範圍第1項至第12項之RMA可交聯組成物中，該可交聯組成物包含一或多種包含活化不飽和基團(C=C)之反應性組分B，該等活化不飽和基團較佳為不飽和丙烯醯基或順丁烯二酸酯官能基(較佳為丙烯醯基)或丙烯醯胺，且該聚合或寡聚樹脂之羥基值小於60、較佳小於40且更佳小於20 mg KOH/g固體。 A polymeric or oligomeric resin B for use in an RMA crosslinkable composition according to items 1 through 12 of the patent application, the crosslinkable composition comprising one or more activated unsaturated groups (C= C) a reactive component B, which is preferably an unsaturated acryl oxime or maleate functional group (preferably acryl oxime) or acrylamide, and the polymerization or The oligomeric resin has a hydroxyl number of less than 60, preferably less than 40 and more preferably less than 20 mg KOH/g solids. 如申請專利範圍第21項之樹脂B，其中該聚合或寡聚樹脂B為包含反應性組分B之聚酯、聚醚、聚環氧樹脂、聚胺基甲酸酯或聚碳酸酯。 Resin B according to claim 21, wherein the polymeric or oligomeric resin B is a polyester, a polyether, a polyepoxy resin, a polyurethane or a polycarbonate comprising the reactive component B. 如申請專利範圍第21項至第22項之樹脂B，其數目分子量在300與20000公克/莫耳之間，較佳在300與 10000或6000公克/莫耳之間。 For example, the resin B of claim 21 to 22 has a molecular weight of between 300 and 20,000 g/mole, preferably at 300. Between 10,000 or 6,000 g/mole. 如申請專利範圍第21項至第23項之樹脂B，其每一反應性組分A或B之當量為100-2000公克/莫耳。 Resin B of claims 21 to 23 of the patent application has an equivalent weight of 100-2000 g/mole per reactive component A or B. 如申請專利範圍第21項至第24項之樹脂B，其酸值小於4、較佳小於3、2或1毫克KOH/公克。 Resin B, as claimed in claims 21 to 24, has an acid value of less than 4, preferably less than 3, 2 or 1 mg KOH per gram. 一種如申請專利範圍第13項至第25項之聚合或寡聚樹脂A與聚合或寡聚樹脂B之樹脂混合物，其用於如申請專利範圍第1項至第12項之RMA可交聯組成物中。 A resin mixture of a polymeric or oligomeric resin A and a polymeric or oligomeric resin B according to claims 13 to 25 of the patent application, which is used in the RMA crosslinkable composition according to items 1 to 12 of the patent application scope. In. 一種如申請專利範圍第13項至第25項之樹脂A或樹脂B或如申請專利範圍第26項之樹脂A與樹脂B之樹脂混合物的用途，其用作如申請專利範圍第1項至第12項中任一項之RMA可交聯組成物中之可交聯組分。 A use of a resin A or a resin B as claimed in claims 13 to 25 or a resin mixture of resin A and resin B as claimed in claim 26, which is used as the first to the first The RMA of any of the 12 items crosslinks the crosslinkable component of the composition. 一種如申請專利範圍第26項之用途，其中樹脂A或樹脂B中之至少一者包含至少3個反應***聯基團，且樹脂A或樹脂B中之至少一者包含至少2個反應***聯基團，且其中樹脂A或B或兩者每一聚合物或寡聚物分子平均具有3-30個反應***聯基團。 A use according to claim 26, wherein at least one of Resin A or Resin B comprises at least 3 reactive crosslinking groups, and at least one of Resin A or Resin B comprises at least 2 reactive crosslinks a group, and wherein the resin A or B or both have an average of from 3 to 30 reactive crosslinking groups per polymer or oligomer molecule. 一種製備如申請專利範圍第13項至第20項之樹脂A之方法，該方法包含使多元醇與呈羧酸酯形式(Y及Y'為烷氧基(-OR*))之反應性組分A發生轉酯反應。 A process for the preparation of Resin A according to Clauses 13 to 20 of the patent application, which comprises reacting a polyol with a carboxylic acid ester form (Y and Y' are alkoxy groups (-OR*)) A transesterification reaction occurs in sub-A. 一種製備如申請專利範圍第21項至第25項之樹脂B之方法，該方法包含使多元醇與呈羧酸酯形式之反應性組分B、較佳為丙烯醯基發生轉酯反應，或藉由使多元醇與呈羧酸形式之反應性組分B發生直接酯化反應來進行。 A process for preparing a resin B according to claim 21 to claim 25, which comprises subjecting a polyol to a transesterification reaction with a reactive component B, preferably a propylene thiol group, in the form of a carboxylate, or This is carried out by direct esterification of the polyol with the reactive component B in the form of a carboxylic acid. 一種如申請專利範圍第1項至第12項中任一項之交聯組成物之用途，其用於製造塗料組成物、薄膜或油墨。 A use of a crosslinked composition according to any one of claims 1 to 12 for the manufacture of a coating composition, film or ink. 一種塗料組成物，其包含如申請專利範圍第1項至第12項中任一項之交聯組成物且進一步包含一或多種塗料添加劑，如顏料、共黏合劑、溶劑等。 A coating composition comprising the crosslinked composition of any one of claims 1 to 12 and further comprising one or more coating additives such as a pigment, a co-binder, a solvent, and the like. 一種製造塗層之方法，該塗層具有良好表面外觀及硬度，該方法包含：在塗覆該塗層之前不久，製備如申請專利範圍第1項至第12項中任一項之可交聯組成物或如申請專利範圍第32項之塗料組成物，此係藉由使包含該等活性組分A及B之該等可交聯組分與催化劑C接觸而達成；及將一層該塗料組成物塗覆於一基材上，及使其較佳在10與60℃之間的溫度下固化。 A method of making a coating having a good surface appearance and hardness, the method comprising: preparing a crosslinkable according to any one of claims 1 to 12 shortly before applying the coating a composition or a coating composition according to claim 32, which is achieved by contacting the crosslinkable components comprising the active components A and B with the catalyst C; and forming a layer of the coating The article is applied to a substrate and is preferably cured at a temperature between 10 and 60 °C.