TW201247728A - Amino and hydroxyl functional polyesters - Google Patents

Abstract

The invention relates to amino and hydroxy-functional polyesters, wherein the amine is in the form of aspartic acid esters functionality, and wherein the amino and hydroxy-functional polyester has (a) a molecular weight (Mn) of at least about 500, (b) an acid value of about 5 or less, (c) a hydroxyl value of about 30 or more, and (d) an amine value of about 30 or more, and (e) an amine functionality of less than 1.8. Preferably, the compound comprises molecules having on the average: at least 1 secondary amino group as an aspartate, and/or at least 1 hydroxy group, and an average total functionality of about 1.8 or higher. More preferably, the molecular weight of the amino and hydroxy-functional polyesters is between 204 and 10, 000 and preferably between 482 and 5000.

Description

201247728 發明說明： 本發明係關於胺基及經基官能聚醋、包含該等聚西旨之 組成物、其用作黏合劑或用作黏合劑系統中之改質劑的用 2此等黏合劑或黏合劑系統尤其適用於與聚異氛酸醋化 &物交聯以產生交聯聚(脲/胺基甲酸賴)系統，該等系統適 用作塗料、黏著劑、密封劑或填縫材料。戈呈單組分•且成 物形式，但較佳呈雙組分聚(脲/胺基甲酸醋)混合塗料植成 物形式。本發明進-步係關於該等交聯系統及製造胺基多 元醇之方法。 基於丙烯酸及/或聚酯多元醇及異氰酸酯之高效耐用塗 料在汽車塗料及工業塗料市射為熟知的，對較低 VOC之需求增加使得需要降低多元醇分子量及/或使用低分 子量活性稀釋劑以增加塗料之固體含量。由於併入此等低 分子量多元醇，因此與習知介質或低含固量單組分或雙組 分胺基甲酸酯塗料相比，塗料之乾燥速度及早期硬度發展 受損。使用受阻二級胺化合物以及異氰酸酯硬化劑已由於 快速胺-NCO反應及在所得聚脲塗料中產生更硬且更具極性 之脲基而在一定程度上減輕早期固化問題。 U.S. 5’126，170及U.S· 5,236,741中已描述聚天冬胺酸 酯’其係用於藉由用含有聚異氰酸酯組分及含有至少一種 聚天冬胺酸酯之異氰酸酯活性組分的塗料組成物塗佈基板 且在100°C或低於100°C之溫度下固化該組成物來製備聚脲 201247728 塗1層。 EP l，〇38,897 A2揭示包含聚異氰酸酯組分、異氰酸酯 活性組分之聚脲塗料的製備，用塗料組成物塗佈基板且在 低於1 00°C之溫度下固化。異氰酸酯活性組分包含順丁烯二 酸二酯或反丁烯二酸二酯與多元胺之反應產物；多元胺具 有2個一級胺基及至少一個在低於1 〇〇°C之溫度下對異氰酸 酯具有反應性的其他官能基。 U.S. 5,5 96,044揭示衍生自胺基醇且含有乙内醯脲基前 驅物之預聚物及其在塗料組成物中之用途。 U.S. 7,166,748揭示一種包含聚異氰酸酯、具有羥基及 天冬胺酸酯官能基之異氰酸酯活性組分的塗料組成物，用 含有胺及/或羥基胺化合物之塗料組成物塗佈基板。 U.S. 5,633,389揭示一種用於製備乙内醯脲之熱可逆方 ;.法’其包含使不飽和聚酯與單官能胺反應以產生聚（天冬胺 酸酿），使該天冬胺酸酯與異氰酸酯反應以產生聚（酯脲）， 且加熱該聚（酯脲）以形成乙内醯脲化合物。 U.S. 5,561，214描述用於製造超支鏈聚天冬胺酸酯之組 成物及方法。 美國專利申請案2005/0059792 A1描述一種藉由併入 不飽和寡酯來製備可撓性聚天冬胺酸酯之方法，該寡酯由 用羥基官能化合物對α，β_不飽和酯進行酯基轉移且使酯基 轉移產物與一級二胺反應並且使剩餘一級胺基與α，卩不飽 和酯反應而製備。 先則技術ΕΡ0604814 (加拿大專利申請案第2，u1,927 201247728 號）描述一種製造胺基聚酯樹脂的方法，該胺基聚酯樹脂 係由不飽和聚酯樹脂與單胺反應得到《不飽和聚酯樹脂含 有至少兩個具有以下結構之順丁烯二酸酯或反丁烯二酸酯 單元： Ο II c—〇 〇201247728 DESCRIPTION OF THE INVENTION: The present invention relates to amine-based and trans-functionalized polyacetates, compositions comprising the same, which are used as binders or as modifiers in binder systems. Or the binder system is particularly suitable for cross-linking with polyisocyanates & amps to produce a cross-linked poly(urea/carbamate lysate) system suitable for use as a coating, adhesive, sealant or caulk material . It is in the form of a single component and in the form of a compound, but is preferably in the form of a two-component poly(urea/amino carboxylic acid vinegar) mixed coating plant. The present invention is directed to such cross-linking systems and methods of making the amine-based polyols. Efficient and durable coatings based on acrylic and/or polyester polyols and isocyanates are well known in automotive coatings and industrial coatings. The increased demand for lower VOCs necessitates lowering the molecular weight of the polyols and/or using low molecular weight reactive diluents. Increase the solids content of the coating. Due to the incorporation of such low molecular weight polyols, the drying speed and early hardness development of the coating is impaired compared to conventional media or low solids one-component or two-component urethane coatings. The use of hindered secondary amine compounds and isocyanate hardeners has alleviated early curing problems to some extent due to the fast amine-NCO reaction and the production of harder and more polar urea groups in the resulting polyurea coatings. Polyaspartate is described in U.S. Patent No. 5,236,741, which is incorporated by the use of a coating comprising a polyisocyanate component and an isocyanate active component comprising at least one polyaspartate. The substrate was coated and the composition was cured at a temperature of 100 ° C or lower to prepare a polyurea 201247728 coated layer. EP 1, 38, 897 A2 discloses the preparation of a polyurea coating comprising a polyisocyanate component, an isocyanate-reactive component, coating the substrate with a coating composition and curing at a temperature below 100 °C. The isocyanate-reactive component comprises the reaction product of maleic acid diester or fumaric acid diester and polyamine; the polyamine has two primary amine groups and at least one is at a temperature below 1 〇〇 ° C Isocyanates are reactive with other functional groups. U.S. Patent No. 5,5,96,044 discloses a prepolymer derived from an amino alcohol and containing a beta-ureganide-based precursor and its use in a coating composition. U.S. Patent No. 7,166,748 discloses a coating composition comprising a polyisocyanate, an isocyanate-reactive component having a hydroxyl group and an aspartate functional group, coated with a coating composition comprising an amine and/or a hydroxylamine compound. No. 5,633,389 discloses a thermoreversible formula for the preparation of intramethylene urea; a method comprising reacting an unsaturated polyester with a monofunctional amine to produce a poly(aspartic acid), the aspartate and The isocyanate reacts to produce a poly(esterurea), and the poly(esterurea) is heated to form a beta-urea compound. U.S. 5,561,214 describes compositions and methods for making hyperbranched polyaspartate. US Patent Application No. 2005/0059792 A1 describes a process for preparing flexible polyaspartic acid esters by incorporating an unsaturated oligoester which is esterified with a hydroxy-functional compound for an α,β-unsaturated ester The base is transferred and the transesterification product is reacted with a primary diamine and the remaining primary amine group is reacted with an alpha, an unsaturated ester. A method for producing an amine-based polyester resin which is obtained by reacting an unsaturated polyester resin with a monoamine to obtain an "unsaturated" method is described in U.S. Patent Application No. 0, 024, 044, to the patent application No. The polyester resin contains at least two maleic acid ester or fumarate units having the following structure: Ο II c-〇〇

II -〇—c一CH=CH- 氮重量百分比（重量％)為0.01 %至9.0%，且羥基重量 百分比（％ OH)為0至1 〇%。 雖然先前技術使用天冬胺酸酯製造塗料，但其他關於 可橈性、黏著、耐久性組合平衡固化速度之性質的改良仍 然具有挑戰性。 【發明内容】 在第一具體實例中，本發明係關於胺基及羥基官能聚 酯’其中該胺基官能基為呈天冬胺酸酯形式之二級胺，且 其中該胺基及羥基官能聚酯具有： (a)至少約500之分子量（Mn); (b )約5或5以下之酸值； (c) 約30或30以上之經值； (d) 約30或30以上之胺值； (e )羥基為位阻一級羥基及/或二級羥基。 該聚酯之胺基及羥基官能分子較佳平均具有： (Ο至少一個呈天冬胺酸酯形式之二級胺盖； (g )及/或至少一個羥基； 201247728 (h)每分子1.8或ι·8以上之平均總二級胺基及羥基 官能度。 在本發明之第二具體實例中，本發明係關於低分子量 胺基及羥基官能聚酯，其係由不飽和募酯與單一級胺反應 獲得。不飽和聚酯平均具有至少一個且最多丨.8個反丁烯二 酸酯或順丁烯二酸酯單元。胺基官能度為每分子〇 8至i. 8 個基團，其呈天冬胺酸酯形式之二級胺形式。羥基官能度 之最小值為每分子1個羥基且最大值為每分子丨2個羥基。 胺基及經基官能聚酯之數量平均分子量為204至1〇,〇〇〇， 且更佳為482至5000。胺基及羥基官能聚酯含有〇」重量0/〇 至7重量％呈天冬胺酸酯基形式之二級胺形式的氮及〇.1〇/〇 至10%—級羥基及/或二級羥基。較佳〇H基團為二級羥基 及/或受阻一級羥基。胺基及羥基官能聚酯之最大酸值為2 且較佳小於1。 此外’本發明係關於包含該胺基及羥基官能聚酯及聚 異氰酸醋之可固化組成物，其中異氰酸酯之存在量為胺基 及醇基之莫耳量之約60%或60%以上。 在一較佳具體實例中，胺基及羥基官能聚酯包含以下 化合物之一或其混合物： 胺基及羥基官能聚酯（式I )。 本發明之另一較佳具體實例包含以上胺基及羥基官能 聚醋與任何以下市售組分的摻合物： 1) 羥基官能聚酯； 2) 經基官能丙稀酸聚合物； 201247728 3) 其他羥基官能聚合物； 4) 聚天冬胺酸酯。 在一較佳具體實例中，胺基及羥基官能聚酯具有式I 之通式結構：II - 〇 - c - CH = CH - The weight percentage (% by weight) of nitrogen is from 0.01% to 9.0%, and the percentage by weight of hydroxyl groups (% OH) is from 0 to 1%. While prior art techniques used aspartate to make coatings, other improvements in the properties of balance curing speeds in combination with adhesion, adhesion, and durability are still challenging. SUMMARY OF THE INVENTION In a first embodiment, the present invention is directed to an amine group and a hydroxy-functional polyester wherein the amine functional group is a secondary amine in the form of an aspartate, and wherein the amine group and the hydroxy function The polyester has: (a) a molecular weight (Mn) of at least about 500; (b) an acid value of about 5 or less; (c) a warp value of about 30 or more; (d) an amine of about 30 or more; (e) The hydroxyl group is a hindered primary hydroxyl group and/or a secondary hydroxyl group. Preferably, the amine amine and hydroxyl functional molecules of the polyester have: (Ο at least one secondary amine cap in the form of aspartate; (g) and/or at least one hydroxyl; 201247728 (h) 1.8 per molecule or In the second embodiment of the present invention, the present invention relates to a low molecular weight amine group and a hydroxy functional polyester which are unsaturated esters and a single stage. The amines have an average of at least one and a maximum of 8% of the fumarate or maleate units. The amine functionality is from 8 to 1.8 groups per molecule. It is in the form of a secondary amine in the form of aspartate. The minimum value of the hydroxyl functionality is 1 hydroxyl group per molecule and the maximum is 2 hydroxyl groups per molecule. The number average molecular weight of the amine group and the base functional polyester is 204 to 1 〇, 〇〇〇, and more preferably from 482 to 5,000. The amine group and the hydroxy-functional polyester contain 〇"wt0/〇 to 7% by weight of nitrogen in the form of a secondary amine in the form of aspartate. And 〇.1〇/〇 to 10%—hydroxyl and/or secondary hydroxyl. Preferably, the H group is a secondary hydroxyl group and/or The primary hydroxyl group is hindered. The maximum acid value of the amine group and the hydroxy functional polyester is 2 and preferably less than 1. Further, the present invention relates to a curable composition comprising the amine group and a hydroxy functional polyester and polyisocyanuric acid, Wherein the isocyanate is present in an amount of about 60% or more by moles of the amine group and the alcohol group. In a preferred embodiment, the amine group and the hydroxy-functional polyester comprise one or a mixture of the following compounds: And a hydroxy-functional polyester (Formula I). Another preferred embodiment of the invention comprises a blend of the above amine groups and hydroxy-functional polyesters with any of the following commercially available components: 1) hydroxy-functional polyester; 2) Base functional acrylic polymer; 201247728 3) Other hydroxy functional polymers; 4) Polyaspartate. In a preferred embodiment, the amine and hydroxy functional polyesters have the general structure of Formula I:

其中：R=單價烷基、芳基及/或芳烷基；Wherein: R = monovalent alkyl, aryl and / or aralkyl;

Rf自多元醇移除OH基團後獲得之具有1至6之原子 價之殘基；a residue having an valence of from 1 to 6 obtained after Rf is removed from the polyol by the OH group;

Rz=自多元醇移除OH基團後獲得之具有2至6之原子 價之殘基； R3 =二價飽和及/或不飽和烷基及/或芳基； E=H或具有1至1 8個碳原子之醯基； X1、X2=具有0至5之相等或不同值的整數，但χΐ與 X2之總和為至少1 ; y、ζ=具有0或1之值的整數； ρ=具有0至4之值的整數； g=e及/或具有以下結構之殘基：Rz = residue having a valence of 2 to 6 obtained after removal of the OH group from the polyol; R3 = divalent saturated and/or unsaturated alkyl and/or aryl; E = H or having 1 to 1醯 of 8 carbon atoms; X1, X2 = integers having equal or different values from 0 to 5, but the sum of χΐ and X2 is at least 1; y, ζ = an integer having a value of 0 or 1; An integer from 0 to 4; g=e and/or a residue having the following structure:

8 S 2012477288 S 201247728

(〇Ε)χ η=具有1至10之值的整數。 在以上具體實例中，式〖中之胺基及經基官能聚醋之數 量平均分子量較佳為約500或高於500及約5,000或低於 5，000。此外，胺基及羥基官能化合物之聚合度分佈性為約 4或低於4，及約1.2或高於1.2。 此外，在一具體實例中，在式I中，胺基及羥基官能聚 酯之羥值為約40或高於40及約300或低於300。 在另一具體實例中，在式I中，胺基及羥基官能聚酯之 胺值為約40或高於40及約300或低於300。 在又一具體實例中，在式I中’胺基及羥基官能聚酯之 平均總官能度為約1·8或1.8以上及約1〇或10以下。 在一更佳具體實例中，胺基及羥基官能聚酯之通式結 構示於式II中。(〇Ε) χ η = an integer having a value of 1 to 10. In the above specific examples, the number average molecular weight of the amine group and the trans-functional polyester in the formula is preferably about 500 or more and about 5,000 or less than 5,000. Further, the degree of polymerization of the amine group and the hydroxy functional compound is about 4 or less, and about 1.2 or more than 1.2. Further, in one embodiment, in Formula I, the hydroxy value of the amine group and the hydroxy-functional polyester is about 40 or higher and about 300 or lower. In another embodiment, in Formula I, the amine and hydroxy functional polyesters have an amine value of about 40 or greater than 40 and about 300 or less than 300. In yet another embodiment, the average total functionality of the 'amino and hydroxy functional polyesters in Formula I is about 1.8 or more and about 1 or less. In a more preferred embodiment, the general structure of the amine and hydroxy functional polyesters is shown in Formula II.

式II 基團； /、中尺單饧烧基、务基及/或芳烧基，且可含有〇Η 201247728a group of formula II; /, a medium-sized monoterpene group, a sulfhydryl group, and/or an aryl group, and may contain 〇Η 201247728

Ri與R·2可相似或不同，且各自為自多元醇移除〇H基 團後所獲得之具有1至6之原子價的殘基，且x=具有〇至 6之值的整數，且η具有1至1.8之值。 在本發明之又一較佳具體實例中，藉由包含製備包含 順丁稀·一酸醋不飽和度及反丁稀二酸醋不飽和度中之至少 一者之不飽和羥基官能聚酯的方法來製備胺基·及羥基官能 聚醋’且在該方法中藉由假邁克爾加成反應（pSeud〇 Michael addition reaction )使該順丁烯二酸酯不飽和度及反丁烯二 酸醋不飽和度與脂族或芳族胺化合物反應來製備天冬胺酸 酉旨。 假邁克爾加成反應在本文中定義為作為邁克爾加成供 體之一級胺與作為邁克爾加成受體之不飽和聚酯雙鍵加 成。 在本發明之又一較佳具體實例中，由以下各物製備包 含如下重量份（pbw )之以下組分的塗料組合物： (a) 本發明之胺基多元醇（1至go pbw); (b) 聚異亂酸醋化合物（1至65pbw); (c )其他黏合劑組分（〇至6〇 pbw ); (d )著色劑（〇至4〇 pbw ); (e )添加劑（〇至1〇 pbw); (f) 催化劑（0至1 pbw); (g) 溶劑（0 至 30pbw); 其中組分a至f總共為1〇〇。 在基於以上之另一具體實例中，組分（c )存在量為i 201247728 至60 pbw，且其中組分（c)包含以下中之一或多者： i.羥基官能丙稀酸聚合物、羥基官能聚酯、羥基官能活 性稀釋劑、經基官能聚驗、經基官能聚碳酸醋或經基官能 聚胺基曱酸酯； 11·無官能聚合物或官能基當量為約5〇〇〇或高於5000 之低官能聚合物；及 m·除化合物（a )以外之天冬胺酸酯官能化合物。 在其他具體實例中，組分（c)存在量為5至50 pbw， 及/或包含羥基官能丙烯酸聚合物，及/或包含除化合物（a) 以外之天冬胺酸酯官能化合物。此外，在另一具體實例中， 所存在之組分（g)相對於組分（ a)至（f)為約1〇 pbw或 10 pbw以下。本發明之新穎胺基及羥基官能聚酯看似極其 適用作黏合劑用於與聚異氰酸酯交聯，以產生具有良好可 撓性、耐久性、耐化學性及低V〇c之快速固化聚（脲/胺基 甲酸酯）混合塗料。先前技術中沒有一個教示所定義之具有 天冬胺酸醋與羥基官能基之聚酯之製備，該等聚酯適用於 製備呈包含天冬胺酸酯及羥基官能基與聚異氰酸酯硬化劑 之塗料組成物形式之聚（脲/胺基甲酸酯）混合塗料。 【實施方式】 下文描述本發明之某些具體實例，該等具體實例僅以 實例方式且參考圖式提供。 本發明係關於胺基及羥基官能聚酯，其中該胺為呈天 冬胺酸醋形式之二級胺，且其中該胺基及羥基官能化合物 具有（a)至少約5〇〇之分子量（Mn)、（ b)約5或5以下 201247728 之酸值、（c)約30或30以上之跑赶n , ,.值及（d)約30或30以 上之胺值、以及低於1·8之胺官能度。 胺基及經基官能分子較佳具有平均至少約 胺酸醋形式之二級胺基及至少約i個經基，均驗 及羥基官能度為每分子至少約丨8 $ t β 卞岣t胺基 或 1.8 以上。 胺基及羥基官能聚酯之數量平均 卞9刀子I為約500或高 於500，較佳為約600或高於60〇。右 在一較佳具體實例中， 胺基及羥基官能聚酯之數量平均分子 刀于里為2〇4至10,000， 且更佳為482至5_。一般而言’數量平均分子量（施） 為約5，_或低於5,〇〇〇,較佳為約3,〇〇〇或低於3 〇〇〇，且 甚至更佳為約12〇〇或低於1200。數量平均分子量可例如在 5〇〇至3_或600至5000範圍内。分子量表示為道_ (Dahon)，且藉由GPC在THF中相對於聚苯乙歸標準物量 測分子量及聚合度分佈性；改適管柱來量測適當分子量。 胺基及羥基官能聚酯之聚合度分佈性較佳為約4或低 於4,更佳為，約2.5或低於2·5β 一般而言，聚合度分佈性 將為約1.2或高於1.2 ^較低聚合度分佈性之優勢在於改良 黏度以便需要較少有機溶劑。 胺基及羥基官能聚酯之酸值一般為約5或5以下，且 甚至更佳為約3或3以下，例如為0至3。 胺基及羥基官能聚酯一般具有約30或高於3〇之經 值’較佳為約40或高於40〇 —般而言’羥值將為約3〇〇或 低於300，較佳為約200或低於200，且最佳為約15〇或低 於1 50。高羥值可能由於過高交聯密度而導致脆性。約3〇Ri and R·2 may be similar or different, and each is a residue having a valence of 1 to 6 obtained after removing the 〇H group from the polyol, and x=an integer having a value of 〇 to 6, and η has a value of from 1 to 1.8. In still another preferred embodiment of the present invention, the method comprises the step of preparing an unsaturated hydroxy-functional polyester comprising at least one of cis-butyl sulphate unsaturation and anti-succinic sulphate unsaturation. Method for preparing an amine group and a hydroxy-functional polyester vinegar' and in the method, the maleic acid ester unsaturation and the fumaric acid vinegar are not obtained by a pseudo-Michael addition reaction (pSeud〇Michael addition reaction) The degree of saturation is reacted with an aliphatic or aromatic amine compound to prepare aspartate. The pseudo-Michael addition reaction is defined herein as a double bond addition of a primary amine as a Michael addition donor to an unsaturated polyester as a Michael addition acceptor. In still another preferred embodiment of the present invention, a coating composition comprising the following components in the following parts by weight (pbw) is prepared from: (a) an amine-based polyol of the present invention (1 to go pbw); (b) Polyisophoric acid vinegar compound (1 to 65 pbw); (c) Other binder components (〇 to 6〇pbw); (d) Colorant (〇 to 4〇pbw); (e) Additive (〇) To (1) pbw); (f) catalyst (0 to 1 pbw); (g) solvent (0 to 30 pbw); wherein components a to f are 1 Å in total. In another embodiment based on the above, component (c) is present in an amount from i 201247728 to 60 pbw, and wherein component (c) comprises one or more of the following: i. a hydroxy-functional acrylic polymer, Hydroxyl-functional polyester, hydroxy-functional reactive diluent, trans-functionalized, trans-functionalized polycarbonate or trans-functional polyamine phthalate; 11. Non-functional polymer or functional equivalent of about 5 〇〇〇 Or a low-functionality polymer of more than 5,000; and m. an aspartate functional compound other than the compound (a). In other embodiments, component (c) is present in an amount from 5 to 50 pbw, and/or comprises a hydroxy-functional acrylic polymer, and/or comprises an aspartate functional compound other than compound (a). Further, in another embodiment, the component (g) present is about 1 〇 pbw or less than 10 pbw with respect to the components (a) to (f). The novel amine and hydroxy functional polyesters of the present invention appear to be extremely useful as binders for crosslinking with polyisocyanates to produce fast curing poly(s) with good flexibility, durability, chemical resistance, and low V〇c ( Urea/urethane) mixed coating. None of the prior art teaches the preparation of a polyester having an aspartic acid vinegar and a hydroxy functional group, which is suitable for use in the preparation of a coating comprising an aspartic acid ester and a hydroxy functional group and a polyisocyanate hardener. A poly(urea/urethane) mixed coating in the form of a composition. [Embodiment] Some specific examples of the invention are described below, which are provided by way of example only and with reference to the drawings. The present invention relates to an amine group and a hydroxy functional polyester, wherein the amine is a secondary amine in the form of aspartic acid vinegar, and wherein the amine group and the hydroxy functional compound have (a) a molecular weight of at least about 5 Å (Mn) ), (b) an acid value of about 5 or less 201247728, (c) a runaway n of about 30 or more, and a value of (d) an amine of about 30 or more, and less than 1.8. Amine functionality. Preferably, the amine group and the transfunctional molecule have a secondary amine group having an average of at least about the acid vinegar form and at least about one mesogenic group, and the hydroxyl functionality is at least about $8 $ t β 卞岣t amine per molecule. Base or above 1.8. The number of amine and hydroxy functional polyesters is on average 卞9 K I is about 500 or higher than 500, preferably about 600 or higher. Right In a preferred embodiment, the number average molecular weight of the amine and hydroxy functional polyesters is from 2 to 4, and more preferably from 482 to 5%. Generally, the number average molecular weight (applied) is about 5, _ or less than 5, 〇〇〇, preferably about 3, 〇〇〇 or less than 3 〇〇〇, and even more preferably about 12 〇〇. Or less than 1200. The number average molecular weight can be, for example, in the range of 5 Å to 3 Å or 600 to 5,000. The molecular weight is expressed as Dao, and the molecular weight and degree of polymerization are measured by GPC in THF relative to the polystyrene standard; the column is adapted to measure the appropriate molecular weight. The degree of polymerization of the amine group and the hydroxy functional polyester is preferably about 4 or less, more preferably about 2.5 or less than 2. 5 β. Generally, the degree of polymerization distribution will be about 1.2 or higher. The advantage of lower degree of polymerization distribution is the improved viscosity to require less organic solvent. The acid value of the amine group and the hydroxy functional polyester is generally about 5 or less, and even more preferably about 3 or less, for example, 0 to 3. The amine and hydroxy functional polyesters generally have a menstrual value of about 30 or greater than 3 Å, preferably about 40 or greater than 40 Å. Typically, the hydroxy value will be about 3 Torr or less, preferably. It is about 200 or less, and most preferably about 15 〇 or less than 150. High hydroxyl values may result in brittleness due to excessively high crosslink density. About 3〇

S 12 201247728 .或$於30之羥值對於獲得具有良好性質之穩定塗層具有重 要思義。應瞭解，胺值表示為K〇H重量（毫克），其鹼度 等於1公克化合物中所存在之NH。羥值亦表示為κ〇Η毫 克數其將中和由θΗ_官能化合物與乙酸酐反應所釋放之乙 酸0 胺基及羥基官能聚酯一般具有約30或高於30之胺 值，較佳為約40或高於4〇之胺值。一般而言，胺值將為 約300或低於3〇〇 ’較佳為約2〇〇或低於2〇〇。胺值最佳為 50至150。胺基官能基為天冬胺酸酯型官能基。 胺基及羥基官能聚酯較佳具有約18或18以上之平均 官能度’較佳為約2.0或2.0以上 且更佳為約2.5或2.5 以上且甚至更佳為約3或3以上。一般而言，平均官能 度將為約10《1〇以下’較佳為約5或5以下。官能度可 在例如2至5或2至1 〇範圍内。 羥基當量較佳為約2500或低於25〇〇，且更佳為約2〇〇〇 或低於2000。一般而言，羥基當量將為約3〇〇或高於3〇〇， 較佳為約400或高於4〇〇，且更佳為約5〇〇或高於5⑻。當 量可為例如400至2000。 胺當量較佳為約2000或低於2〇〇〇β 一般而言，胺當量 將為約15〇0或低於1500,較佳為約麵或低於贈，且 更佳為約600或低於600。胺當量較佳將為約15〇或高於 150,較佳為約200或高於2〇〇β當量可能為例如^❹至1〇〇〇 或 200 至 1500 。 其中使該等羥基及 可用標準方式量測總羥值及胺值，S 12 201247728 . or a hydroxyl value of 30 is important for obtaining a stable coating with good properties. It will be appreciated that the amine value is expressed as K 〇 H weight (mg) and its alkalinity is equal to 1 gram of NH present in the compound. The hydroxyl number is also expressed as the κ 〇Η mg number which neutralizes the acetic acid 0 amine group and the hydroxy functional polyester released by the reaction of the θ Η _ functional compound with acetic anhydride, generally having an amine value of about 30 or higher, preferably Amine value of about 40 or higher. In general, the amine value will be about 300 or less than 3 Å', preferably about 2 Torr or less. The amine value is preferably from 50 to 150. The amino functional group is an aspartate type functional group. The amine and hydroxy functional polyesters preferably have an average functionality of about 18 or greater and are preferably about 2.0 or greater and more preferably about 2.5 or greater and even more preferably about 3 or greater. In general, the average functionality will be about 10 "1" or less, preferably about 5 or less. The functionality can range, for example, from 2 to 5 or 2 to 1 Torr. The hydroxyl equivalent is preferably about 2,500 or less, and more preferably about 2, or less than 2,000. In general, the hydroxyl equivalent will be about 3 Torr or higher than 3 Torr, preferably about 400 or higher than 4 Torr, and more preferably about 5 Torr or higher than 5 (8). The amount can be, for example, 400 to 2000. Preferably, the amine equivalent weight is about 2000 or less than 2 〇〇〇. Generally, the amine equivalent weight will be about 15 〇 0 or less, preferably about 5% or less, and more preferably about 600 or less. At 600. The amine equivalent weight will preferably be about 15 Torr or higher, preferably about 200 or higher than 2 〇〇β equivalent, such as from ❹ to 1 〇〇〇 or from 200 to 1500. Wherein the hydroxyl groups and the total hydroxyl value and the amine value can be measured in a standard manner,

13 201247728 胺基與過量乙酸酐反應，且用KOH反滴定所得自由乙酸基 以評定1公克樣品中之羥基及胺基之總毫莫耳量。亦可藉 由用0_1 N鹽酸滴定（ASTM D2572-91 )來評定胺值，且此 後反算成mg KOH。可藉由自總胺及羥值中減去胺值來計算 羥值之理論莫耳量。 可用多種方法製造胺基及羥基官能聚酯。 在用於製備基於聚酯之胺基及羥基官能化合物的較佳 方法中’製備（用一或多個合成步驟）不飽和經基官能聚 S旨’該聚酯包含順丁烯二酸酯或反丁烯二酸酯不飽和度β 使用順丁烯二酸酯及/或反丁烯二酸酯不飽和度藉由添加脂 族或芳族一級胺化合物來製備天冬胺酸酯。 此外’本發明係關於包含該胺基及羥基官能聚酯及聚 異氰酸酯之可固化組成物，其中異氰酸酯之存在量為該胺 基及醇基（異氰酸酯活性基團）之莫耳量之約6〇%或6〇〇/〇 以上。 異氣酸醋之量較佳為胺基及醇基之莫耳量之約7〇%或 70〇/。以上，且甚至更佳為約8〇%或8〇%以上。一般而言該 量為約140%或140%以下，較佳為11〇%或u〇%以下。最 佳量約為異氰酸酯及異氰酸酯活性基團之相同量。 塗料組成物至少含有本發明之胺基及羥基官能組分及 異氰酸酯化合物。然而，可存在若干其他組分，諸如（a ) 其他黏合劑組分、（b )無活性稀釋劑、（c )著色劑、（d )催 化劑、流動劑及其他常用添加劑。 其他黏合劑組分可為其他聚合物、活性稀釋劑及無活13 201247728 The amine group was reacted with an excess of acetic anhydride, and the resulting free acetate group was back-titrated with KOH to evaluate the total millimolar amount of the hydroxyl group and the amine group in the 1 gram sample. The amine value can also be assessed by titration with 0_1 N hydrochloric acid (ASTM D2572-91) and thereafter backcalculated to mg KOH. The theoretical amount of hydroxyl number can be calculated by subtracting the amine value from the total amine and hydroxyl value. Amino and hydroxy functional polyesters can be made in a variety of ways. In a preferred process for the preparation of polyester-based amine and hydroxy functional compounds, 'preparation (with one or more synthetic steps) of unsaturated trans-functionalized poly(S) polyesters containing maleic acid esters or Fumarate Unsaturation β The aspartate is prepared by the addition of an aliphatic or aromatic primary amine compound using maleic acid ester and/or fumarate unsaturation. Further, the present invention relates to a curable composition comprising the amine group and a hydroxy-functional polyester and a polyisocyanate, wherein the isocyanate is present in an amount of about 6 Torr of the amine group and the alcohol group (isocyanate reactive group). % or 6〇〇/〇 or more. The amount of the isogastric acid vinegar is preferably about 7 % or 70 Å of the molar amount of the amine group and the alcohol group. The above, and even more preferably, is about 8% or more. Generally, the amount is about 140% or less, preferably 11% or less. The optimum amount is about the same amount of isocyanate and isocyanate reactive groups. The coating composition contains at least the amine group and the hydroxy functional component of the present invention and an isocyanate compound. However, several other components may be present such as (a) other binder components, (b) inactive diluents, (c) colorants, (d) catalysts, flow agents, and other conventional additives. Other binder components can be other polymers, reactive diluents and inactive

S 201247728 性聚合物，其中引入後幾種化合物將導致形成互穿網路 (IPN )。其他適合黏合劑聚合添加劑包含聚§旨多元醇、聚 丙烯酸多元醇、聚醚多元醇及其類似物。除本發明所述者 以外之但例如先前技術中所述者的天冬胺酸酯官能組分可 與本發明之胺基及羥基官能化合物混合使用。 關於無活性稀釋劑（或溶劑），可使用習知有機溶劑。 塗料組成物可調配成具有相對較低量之溶劑及/或其他揮發 性有機化合物（V0C)的高含固量塗料。一般而言，v〇c 之量為總塗料組成物之約20重量份（pbw)或20 pbw以下， 較佳為約l〇pbw或i〇pbw以下，且更隹為約5补你或5pbw 以下。 關於著色劑，可使用較佳呈顏料分散液形式之習知顏 料、增效劑及染料，其甲顏料經.穩定以供分散於有機塗料 組成物中。適合顏料包括有機及無機顏料。無機顏料包括 二氧化鈦、氧化鐵、氧化辞、其他金屬氧化物及碳黑。有 機顏料包括狄菁藍及醜菁綠顏料、茈、η比洛、芳基化物、 陰丹士林（indanthrone )、洋紅及喹吖啶酮紅及許多其他顏 料。彩色顏料可選自HERBST等人，Industrial 〇—心 〜心价，pr〇ducti〇n，Pr〇perties，Applicati〇ns;第 3 版， Wiley-VCH，2004, ISBN 35273〇5769 所揭示之彩色顏料。適 « h效劑包括妷酸鈣、滑石、硫酸鋇、水合矽酸鋁（葉蠟 石）、偏矽酸鈣（矽灰石）、高嶺黏土及其他填料。 適合添加劑包含催化劑[諸如錫化合物]搖變減黏 膠、消泡劑、顏料分散劑、流動劑、增效劑、脫水劑（如 15 201247728 分子篩）及其類似物。 塗料組成物一般包含如下重量份（pbw)之以* u)本發明之胺基多元醇（1至8〇pbw);下級分 (b)聚異氰酸酯化合物（i至65 pbw (Ο其他黏合劑組分（〇至60 pbw); (d)著色劑（0至40 pbw); (Ο添加劑（0至10 pbw); (Ο催化劑（0至1 pbw); (g)溶劑（0 至 30 pbw); 其中組分a至f總共為1〇〇。 在一更佳具體實例中，組分（c)存在量 較佳為4。至60 一 I為1至6。—， 在一更佳具體實例中·，本發明提供—種高^量塗料 組成物，其中所存在之組分（g)相對於 刀、a)至(f) 為約10 pbw或1〇 pbw以下。 一般而言，胺基及羥基官能聚酯中之在〇H基團周圍具 有最小位阻之羥基與位阻〇H基團相比更快地與異氰酸醋 反應以形成胺基曱酸酯鍵聯。因而，一級羥基比二級經基 快地與NC〇反應，且比三級羥基甚至快得多地與NCO反 應。在一較佳具體實例中，聚酯包含二級羥基及/或位阻一 級經基作為活性基團以便與異氰酸酯反應。位阻一級羥基 為如以下結構中所示在2-位具有取代基（X!、X2 )的羥基：S 201247728 A polymer in which several compounds are introduced will result in the formation of an interpenetrating network (IPN). Other suitable binder polymerization additives include polyhydric alcohols, polyacrylic polyols, polyether polyols, and the like. An aspartate functional component other than those described in the present invention, such as those described in the prior art, can be used in admixture with the amine and hydroxy functional compounds of the present invention. As the inactive diluent (or solvent), a conventional organic solvent can be used. The coating composition can be formulated as a high solids coating having a relatively low amount of solvent and/or other volatile organic compound (VOC). In general, the amount of v〇c is about 20 parts by weight (pbw) or less than 20 pbw of the total coating composition, preferably about 1 〇pbw or less 〇pbw, and more preferably about 5 or 5 pbw. the following. As the coloring agent, a conventional pigment, a synergist and a dye which are preferably in the form of a pigment dispersion liquid, which is stabilized for dispersion in the organic coating composition can be used. Suitable pigments include organic and inorganic pigments. Inorganic pigments include titanium dioxide, iron oxide, oxidized words, other metal oxides, and carbon black. Organic pigments include delphidine blue and ugly green pigments, anthraquinone, etapirol, aryl compounds, indanthrone, magenta and quinacridone red, and many other pigments. The color pigments may be selected from the color pigments disclosed by HERBST et al., Industrial 〇-heart ~ heart price, pr〇ducti〇n, Pr〇perties, Applicati〇ns; 3rd edition, Wiley-VCH, 2004, ISBN 35273〇5769. . Suitable agents include calcium citrate, talc, barium sulfate, hydrated aluminum citrate (paride), calcium metasilicate (silver), kaolin clay and other fillers. Suitable additives include catalysts such as tin compounds, shake-down viscosifiers, defoamers, pigment dispersants, flow agents, synergists, dehydrating agents (e.g., 15 201247728 molecular sieves), and the like. The coating composition generally comprises the following parts by weight (pbw) of *u) the amine-based polyol of the invention (1 to 8 〇pbw); the lower fraction (b) of the polyisocyanate compound (i to 65 pbw (Ο other binder group) (d to 60 pbw); (d) colorant (0 to 40 pbw); (Ο additive (0 to 10 pbw); (Ο catalyst (0 to 1 pbw); (g) solvent (0 to 30 pbw) Wherein components a to f are 1 in total. In a more preferred embodiment, component (c) is preferably present in an amount of from 4. to 60 to 1 in an amount of from 1 to 6. In a preferred embodiment The present invention provides a high-quality coating composition in which the component (g) present is about 10 pbw or less than 1 〇pbw with respect to the knives, a) to (f). In general, an amine group And the hydroxyl group having the least steric hindrance around the hydrazine H group in the hydroxy-functional polyester reacts faster with the isocyanate to form an amino phthalate linkage than the sterically hindered H group. Thus, The hydroxyl group reacts with the NC oxime faster than the secondary thiol group and reacts with the NCO much faster than the tertiary hydroxyl group. In a preferred embodiment, the polyester comprises a secondary hydroxyl group and/or a hindered primary thiol group. Active group The ester is reacted with an isocyanate hindered hydroxyl as shown in the following structure having a substituent group at the 2-position (X, X2!) Hydroxyl group:

16 S 20124772816 S 201247728

經基官能聚醋較佳將具有至少約丨〇〇之數量平均分子 里。典型數量平均分子量將在約1〇〇至約1〇,〇〇〇範圍内， 且尤其為100至約3,000。為了控制最終雙組分塗料之適用 哥命且因而控制黏度增加速率，在實施本發明時較佳利用 具有一級及/或二級且甚至具有三級羥基官能基之羥基官能 聚酯。羥基位阻愈大，固化速率將愈慢。 代表性經基官能聚酯包括以下所述者： 經基官能聚醋為藉由此項技術中所熟知之縮聚反應技 術製備的聚酿^代表性縮聚反應包括在包括或不包括乾性 油、半乾性油或非乾性油脂肪酸的情況下藉由多元醇與聚 缓酸或酸酐之縮合來製得之聚酯。藉由調節醇及酸之化學 S十量同時維持經基過量，可容易地製造羥基官能聚酯以提 供廣泛範圍之所要分子量、不飽和度含量及效能特徵。 聚醋多元醇係衍生自一或多種芳族及/或脂族聚羧酸、 其酸肝及一或多種脂族及/或芳族多元醇。羧酸包括飽和及 不飽和聚羧酸及其衍生物，諸如順丁烯二酸、反丁烯二酸、 丁二酸、己二酸、壬二酸、二環戊二烯二羧酸、六氮鄰苯 二曱酸酐、曱基六氫鄰笨二曱酸酐、諸如鄰笨二曱酸、間 笨二曱酸、對苯二曱酸等之芳族聚缓酸。亦可使用諸如順 丁烯二酸酐、鄰苯二曱酸酐、偏苯三酸酐或甲基納迪克酸 酐（Nadic Methyl Anhydride;甲基雙環[2.2.]庚浠-2,3-二·甲The base functional polyester will preferably have a number average molecular weight of at least about 丨〇〇. A typical number average molecular weight will range from about 1 Torr to about 1 Torr, and especially from 100 to about 3,000. In order to control the useful life of the final two-component coating and thus control the rate of viscosity increase, it is preferred to utilize a hydroxy-functional polyester having primary and/or secondary and even tertiary functional groups in the practice of the invention. The greater the hydroxyl block resistance, the slower the cure rate will be. Representative trans-functional polyesters include those described below: The base-functional polyester is a polycondensation reaction prepared by a polycondensation reaction technique well known in the art, including or without a drying oil, half A polyester obtained by condensation of a polyol with a poly-acid or an acid anhydride in the case of a dry oil or a non-drying oil fatty acid. The hydroxy-functional polyester can be readily fabricated by adjusting the chemical and alcoholic acid S and maintaining the radical excess to provide a wide range of desired molecular weights, unsaturation levels, and performance characteristics. Polyvinyl alcohols are derived from one or more aromatic and/or aliphatic polycarboxylic acids, their acid livers and one or more aliphatic and/or aromatic polyols. Carboxylic acids include saturated and unsaturated polycarboxylic acids and derivatives thereof, such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, dicyclopentadiene dicarboxylic acid, six Nitrophthalic anhydride, mercaptohexahydro-dodecanoic anhydride, aromatic polyacids such as o-didecanoic acid, m-dicarboxylic acid, terephthalic acid, and the like. It is also possible to use, for example, maleic anhydride, phthalic anhydride, trimellitic anhydride or methyl nadic acid anhydride (Nadic Methyl Anhydride; methylbicyclo[2.2.]glycan-2,3-di.

17 201247728 酸針異構物之商標名）之酸酐。 可在化學計量過量下與羧酸反應以產生羥基官能聚醋 的代表性飽和及不飽和多元醇包括二醇，諸如乙二醇、二 丙一醇、2,2,4-三甲基-1，3-戊二醇、新戊二醇、1，2_丙二醇、 1，4-丁二醇、丨，3_丁二醇、2,3 丁二醇、丨，5-戊二醇、^-己 一醇、2,2-二甲基- l，3_丙二醇、ι，4-環己烧二曱醇、12-環 己烷二甲醇、1>3_環己烷二曱醇、丨，心雙（2_羥基乙氧基）環己 烷、丙二醇、丁二醇、戊二醇、己二醇、癸二醇、二乙二 醇一乙一醇、四乙一醇、降冰片二醇（norbornylene glycol)、ι4_苯二甲醇、苯二乙醇、2,4二甲基·2_伸乙 基己烷-1，3-二醇、2-伸丁基_1，4-二醇；及多元醇，諸如三羥 甲基乙烷'三羥甲基丙烷、三羥甲基己烷、三羥乙基丙烷、 1，2,4-丁三醇、甘油、季戊四醇、二季戊四醇等。 典型地，多元醇與聚羧酸之反應係在約12(rc至約 22〇C下在存在或不存在諸如氧化二丁錫之酯化催化劑的情 況下進行。 此外’羥基官能聚酯可藉由用環氧化物及/或聚環氧化 物替代一些或所有上述多元醇來製備，其中酸及酸酐可打 開環氧乙烧環以形成相應酯及經基。代表性聚環氧化物包 括藉由通常在鹼性條件下縮合多元醇或多元酚與諸如表氣 醇之表齒代醇而製備者。一些此等縮合產物分別可以名稱 EP0N 或 DER 購自 Hexion Specialty Chemicals 或 Dow17 201247728 Acidic needle isomers under the trade name of the acid anhydride. Representative saturated and unsaturated polyols which can be reacted with a carboxylic acid in a stoichiometric excess to produce a hydroxy functional polyester include glycols such as ethylene glycol, dipropanol, 2,2,4-trimethyl-1 , 3-pentanediol, neopentyl glycol, 1,2-propylene glycol, 1,4-butanediol, hydrazine, 3-butanediol, 2,3 butanediol, hydrazine, 5-pentanediol, ^ -hexanol, 2,2-dimethyl-l,3-propanediol, iota, cyclohexanol, 12-cyclohexanedimethanol, 1> 3_cyclohexanedimethanol, hydrazine , bis(2-hydroxyethoxy)cyclohexane, propylene glycol, butanediol, pentanediol, hexanediol, decanediol, diethylene glycol monoethyl alcohol, tetraethylene glycol, norbornene diol ( Norbornylene glycol), ι4_benzene dimethanol, phenylenediethanol, 2,4 dimethyl 2, ethyl hexane-1,3-diol, 2-butyl 1,4-1,4-diol; Polyols such as trimethylolethane 'trimethylolpropane, trimethylolhexane, trishydroxyethylpropane, 1,2,4-butanetriol, glycerin, pentaerythritol, dipentaerythritol, and the like. Typically, the reaction of the polyol with the polycarboxylic acid is carried out at about 12 (rc to about 22 ° C in the presence or absence of an esterification catalyst such as dibutyltin oxide. Further, the 'hydroxy functional polyester can be used Epoxides and/or polyepoxides are prepared in place of some or all of the above polyols, wherein the acid and anhydride can open the epoxidised ring to form the corresponding ester and mesogenic groups. Representative polyepoxides are included by Prepared under basic conditions to condense polyols or polyhydric phenols with epidentate alcohols such as surface alcohols. Some of these condensation products are available from Hexion Specialty Chemicals or Dow under the name EP0N or DER, respectively.

Chemical公司，且美國專利第2,592,56〇號、第2,582,985 號及第2,694,694號代表性地教示製備方法，所有該等專利The production process, all of which are representatively taught by the company of U.S. Patent Nos. 2,592,56, 2,582,985 and 2,694,694.

18 S 201247728 -均以全文引用的方式併入本文t。 若在製備羥基官能聚酯期間使用環氧化合物，則環脂 族環氧化物為較佳環氧化物。代表性較佳環脂族環氧化物 之市售實例包括3,4-環氧基環己烷甲酸3,4_環氧基環己基 罗酉曰（例如「來自Dow Chemical之ERL-4221」）；己二酸雙 (「3，心環氧基環己基f酯）（例如來自d〇w 丨之 ERX 4299」），3,4-環氧基-6-甲基環己烧甲酸3,4_環氧基 -「6_甲基環己基甲醋（例如來自D〇w Chemicai之 ERL 4201」），己二酸雙（3,4_環氧基_6_甲基環己基甲酯） ^列如來自D0wChemical之「erl_4289」）；雙（2,3 —環氧基 %戊基）醚（例如來自D〇w Chemica丨之「ERL 〇4〇〇」）；二 氧化戍婦（例如來自Dow Chemical之「ERL-4269」）； 2_(3，心環氧基環己基_5，5_螺_3，4_環氧基）環己烷間二噁烷 (=如來自D0wChemical之「ERL_4234」）。其他市售環脂 族t氧化物可購自Ciba_Geigy公司，諸如環氧當量為約I” 之環脂族二縮水甘油S旨環氧樹脂CY 192。代表性環脂族環 氧匕物之製造敎示於多個專利中，包括美國專利第 M84,4G8號、第3,027,3 57號及第3,247，144號，所有專利 係以全文引用的方式併入本文中。 — >可此適用於實施本發明之其他聚環氧化物包括脂族及 “聚％氧化物’諸如藉由脂族多元醇或多元酚與表鹵代 1貞製備者。其他適用環氧化物包括衍生自諸如丙稀酸 油S旨或甲基丙烯酸縮水甘油S旨之烯系不飽和環氧基 S月b單體與諸如下文所列出之其他可共聚單體組合的環氧 19 201247728 油及丙烯酸聚合物。 形成尤其較佳羥基官能聚酯之 、 (預縮合）聚酯之羥基與增鏈劑、較 ▲方法包3藉由使 聚氧化丙稀或己㈣、戊内_及4諸如聚氧化乙稀' ®日之聚燒麵或内酷沒 應來使經基官能聚酯進行增鏈反應。 一 可使用單羧酸製備羥基官能窄 Λ ^ 聚酯以控制分子量、官能 度及其他特徵性質。單羧酸可為脂 q如碩、環脂族、芳族 混合物。單叛S"交佳含有6至18個碳原子，最佳含有 14個碳原子，諸如辛酸、2·乙基己酸' 異壬酸、癸酸、十 二烷酸、苯曱酸、六氫苯甲酸及其混合物。 可使用單經基化合物實施本發明以控制分子量、官能 度及其他特徵性質。適合單官能酿 平^此醇之貫例包括具有4至18 個碳原子之醇，諸如2-乙基丁醇、戊醇、己醇、十二烷醇、 環己醇及三甲基環己醇。 可使用Μ官能酸替《一些及/或所有上$酸及多元 醇。可使用之典型經基酸包括二經甲基丙酸、經基特戍酸 及經基硬脂酸。 在本發明之一更佳具體實例中，由一級胺與羥基官能 不飽和聚酯在至801範圍内之溫度下的加成反應來製 備胺基及羥基官能聚酯。由多元醇與含有順丁烯二酸酐及/ 或反丁稀二酸之多元羧酸之聚縮合或者順丁烯二酸單烷基 醋與環氧化合物之加成反應來製備羥基官能不飽和聚酯。 在羥基官能聚酯中，羥基與羧酸基團之比率始終高於1 : J， 且其可在1 · 1:1至3 :1範圍内。18 S 201247728 - each incorporated herein by reference in its entirety. If an epoxy compound is used during the preparation of the hydroxy-functional polyester, the cycloaliphatic epoxide is a preferred epoxide. Commercially available examples of representative preferred cycloaliphatic epoxides include 3,4-epoxycyclohexane ruthenium 3,4-epoxycyclohexanecarboxylate (e.g. "ERL-4221 from Dow Chemical"). ; adipic acid bis ("3, epi-epoxycyclohexyl f ester" (eg ERX 4299 from d〇w 」)), 3,4-epoxy-6-methylcyclohexane carboxylic acid 3,4 _Epoxy-"6-methylcyclohexylmethine (eg ERL 4201 from D〇w Chemicai)), bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate ^ Columns such as "erl_4289" from D0wChemical; bis(2,3-epoxy%pentyl)ether (eg "ERL 〇4〇〇" from D〇w Chemica丨); oxidized widows (eg from Dow) Chemical "ERL-4269"); 2_(3,epoxycyclohexyl_5,5-spiro-3,4-epoxy)cyclohexanedioxane (= as "ERL_4234" from D0wChemical ). Other commercially available cycloaliphatic t-oxides are commercially available from Ciba_Geigy, Inc., such as cycloaliphatic diglycidyl s epoxide CY 192 having an epoxy equivalent of about 1". Manufacture of representative cycloaliphatic epoxy oximes It is shown in a number of patents, including U.S. Patent Nos. M84, 4G8, 3, 027, 3, 57, and 3, 247, 144, all of which are incorporated herein by reference in their entirety. Other polyepoxides of the invention include aliphatic and "poly% oxides" such as those prepared by aliphatic or polyhydric phenols and epihalohydrazides. Other suitable epoxides include those derived from an ethylenically unsaturated epoxy S-b monomer such as acrylic acid oil or glycidyl methacrylate, in combination with other copolymerizable monomers such as those listed below. Epoxy 19 201247728 Oil and acrylic polymer. Forming a particularly preferred hydroxy-functional polyester, a hydroxyl group of a (precondensed) polyester and a chain extender, and a method of coating 3 by using polyoxypropylene or hexamethylene, pentane _ and 4 such as polyethylene oxide ® Day's poly-fired noodles or internal cooling should not be used to carry out the chain extension reaction of the trans-functional polyester. A hydroxy-functional narrow Λ ^ polyester can be prepared using a monocarboxylic acid to control molecular weight, functionality, and other characteristic properties. The monocarboxylic acid can be a lipid such as a master, a cycloaliphatic or an aromatic mixture. Single-rebel S" has a 6 to 18 carbon atoms, preferably 14 carbon atoms, such as octanoic acid, ethyl 2-hexanoic acid, isophthalic acid, decanoic acid, dodecanoic acid, benzoic acid, hexahydrogen Benzoic acid and mixtures thereof. The invention can be practiced using mono-based compounds to control molecular weight, functionality, and other characteristic properties. Suitable examples of monofunctional styrene include alcohols having 4 to 18 carbon atoms, such as 2-ethylbutanol, pentanol, hexanol, dodecanol, cyclohexanol, and trimethylcyclohexane. alcohol. Some and/or all of the above acids and polyols can be replaced with hydrazine functional acids. Typical transbasic acids which can be used include di-methylpropionic acid, thioterpene acid and stearic acid. In a more preferred embodiment of the invention, the amine and hydroxy functional polyesters are prepared by an addition reaction of a primary amine with a hydroxy functional unsaturated polyester at a temperature in the range of up to 801. Preparation of hydroxy-functional unsaturated polycondensation by polycondensation of a polyhydric alcohol with a polycarboxylic acid containing maleic anhydride and/or a reversed dicarboxylic acid or addition reaction of a maleic acid monoalkyl vinegar with an epoxy compound ester. In the hydroxy-functional polyester, the ratio of hydroxyl groups to carboxylic acid groups is always higher than 1: J, and it may range from 1 1:1 to 3:1.

20 S 201247728 一般而έ ’ 一級胺與順丁烯二酸酯或反丁烯二酸酯反 應產生對NCO具有不同活性度之天冬胺酸酯基。胺之氮原 子周圍的位阻愈高，則對NC〇之活性愈慢，且反之亦然。 適用於本發明之一級胺包括但不限於分子中具有丨至 30個奴原子之各種烷基胺、芳基胺或芳烷基胺。烷基胺之 特定實例包括甲胺、乙胺、丙胺及異丙胺、丁胺、異丁胺 及第二丁胺、1，3_二甲基丁胺及3,3二甲基丁胺、戊胺、異 戊胺、第三戊胺及新戊胺、己胺異構物、環己胺、2曱基環 己胺異構物、4-甲基環己胺異構物、環庚胺、庚胺異構物、 辛胺異構物、壬胺、十二烷胺、十八烷胺、環己基甲胺、α_ 甲基環己烧甲胺。芳基胺之實例包括苯胺、甲苯胺異構物、 苯胺、二甲基苯胺異構物、乙基苯胺異構物、丙基苯胺及 異丙基苯胺異構物、2,6_:乙基苯胺及各種經取代之苯胺。 芳烷基胺之實例包括笨甲胺、α_曱基苯甲胺、α乙基苯曱 胺、4，α-二▼基苯甲胺、苯乙胺、烷基苯乙胺異構物及4_ 苯基丁胺。適用於本發明之其他胺為胺基多元醇，諸如 胺基羥基丙烷異構物、2_胺基_2_甲基]，3_丙二醇、2_胺基-2_ 乙基-1，3-丙二醇、2_胺基_2_羥甲基_〖，3_丙二醇；及胺基酸 之烷基酯，諸如甘胺酸、丙胺酸、***酸、白胺酸、異 白胺酸、天冬胺酸、麩胺酸及纈胺酸之甲基、乙基、丙基 及丁基酯。 本發明之塗料組成物包含（視情況經封端之）異氰酸 醋官能交聯劑。此等化合物係基於熟習此項技術者已知的 常見異氰酸酯官能化合物。塗料組成物更佳包含具有至少20 S 201247728 In general έ 'Primary amines react with maleic acid esters or fumarates to produce aspartate groups having different activities for NCO. The higher the steric hindrance around the nitrogen atom of the amine, the slower the activity against NC〇 and vice versa. Suitable amines for use in the present invention include, but are not limited to, various alkylamines, arylamines or aralkylamines having from 丨 to 30 slave atoms in the molecule. Specific examples of alkylamines include methylamine, ethylamine, propylamine and isopropylamine, butylamine, isobutylamine and second butylamine, 1,3-dimethylbutylamine and 3,3 dimethylbutylamine, pentane Amine, isoamylamine, third pentylamine and neopentylamine, hexylamine isomer, cyclohexylamine, 2-nonylcyclohexylamine isomer, 4-methylcyclohexylamine isomer, cycloheptylamine, Heptylamine isomer, octylamine isomer, decylamine, dodecylamine, octadecylamine, cyclohexylmethylamine, α-methylcyclohexylmethylamine. Examples of the arylamine include aniline, toluidine isomer, aniline, dimethylaniline isomer, ethylaniline isomer, propylaniline and isopropylaniline isomer, 2,6-:ethylaniline And various substituted anilines. Examples of the aralkylamine include stupylmethylamine, α-mercaptobenzylamine, α-ethylbenzamine, 4,α-diheptylbenzylamine, phenethylamine, alkylphenylethylamine isomer and 4_ Phenylbutylamine. Other amines suitable for use in the present invention are amine based polyols such as amino hydroxypropane isomers, 2-amino-2-methyl], 3-propylene glycol, 2-amino-2_ethyl-1,3- Propylene glycol, 2-amino-2 hydroxymethyl _, 3 propylene glycol; and alkyl ester of amino acid, such as glycine, alanine, phenylalanine, leucine, isoleucine, aspartic Methyl, ethyl, propyl and butyl esters of aminic acid, glutamic acid and valine. The coating composition of the present invention comprises (optionally blocked) an isocyanate-functional crosslinker. These compounds are based on common isocyanate functional compounds known to those skilled in the art. Better coating composition comprising at least

21 201247728 兩個異氰酸酿基之交聯劑。包含至少兩個異氰酸酯基之化 合物之實例為脂族、脂環族及芳族異氰酸酯，諸如二異氰 酸伸己醋、二異氰酸2,4,4-三曱基伸己酯、二聚物酸二異氰 酸酿（諸如購自Henkel之DDI® 1410)、二異氰酸1，2-伸環 己醋、二異氰酸1，4-伸環己酯、二異氰酸4,4，-二伸環己酯 甲燒、二異氰酸3，3·-二甲基-4，4·-二伸環己酯甲烷、降冰片 燒二異氰酸酯、二異氰酸間伸苯酯及二異氰酸對伸苯酯、 I3-雙（異氰酸酯甲基）苯及1，4-雙（異氰酸酯甲基）苯、丨，5_ 一甲基-2,4-雙（異氰酸酯曱基）苯、2，4-甲苯二異氰酸酯及 2,6-甲苯二異氰酸酯、2,4,6-曱苯三異氰酸酯、二異氰酸 α，α’α’，α’_四曱基鄰伸二甲苯酯、二異氰酸α，α，α，，α，_四甲基間 一甲笨酯及二異氰酸α，α，αι，αι_四曱基對伸二曱苯酯、二 異氰酸4,4'-二伸苯g旨曱烷、二異氰酸4,4，_二伸苯醋、萘 一異氰酸酯、異佛爾酮二異氰酸酯、二異氰酸4_異氰酸基 基1，8-伸辛酯、關於製備以上羥基官能胺基甲酸酯所述 之異氡酸酯，及上述聚異氰酸酯之混合物。 .其他（視情況經封端之）異氰酸酯化合物係基於発s21 201247728 Two crosslinkers of isocyanate. Examples of compounds comprising at least two isocyanate groups are aliphatic, cycloaliphatic and aromatic isocyanates, such as diisocyanate hexanoic acid, diisocyanato 2,4,4-trimethylhexyl hexyl ester, dimers Acid diisocyanate (such as DDI® 1410 from Henkel), diisocyanate diisocyanate, 1,4-cyclohexyl diisocyanate, diisocyanate 4,4 ,-dicyclohexylesterate, diisocyanate 3,3·-dimethyl-4,4·-dicyclohexyl methane, norbornene diisocyanate, diisocyanate and phenyl ester Diphenyl isocyanate, I3-bis(isocyanatemethyl)benzene and 1,4-bis(isocyanatemethyl)benzene, anthracene, 5-monomethyl-2,4-bis(isocyanate) benzene, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, 2,4,6-nonylbenzene triisocyanate, diisocyanate α,α'α',α'_tetradecyl ortho-xylylene ester, two Isocyanic acid α,α,α,,α,_tetramethyl m-methyl ester and diisocyanate α,α,αι,αι_tetradecyl p-diphenyl phenyl ester, diisocyanate 4,4 '-Diexene benzene g decane, diisocyanate 4,4, _ bis benzene vinegar, naphthalene monoisocyanate Ester, isophorone diisocyanate, diisocyanate 4-isocyanato 1,8-octyl ester, isophthalic acid ester as described for the preparation of the above hydroxy-functional urethane, and the above polyisocyanate a mixture. Other (as appropriate) isocyanate compounds are based on 発s

、氛峻酯之加合物、以 ‘物、1分子三羥甲基丙烷與3分子異佛 1合物、1分子季戊四醇與4分子曱苯二 以商標名 Desmodur®N3390 獲自 Bayer S； 22 201247728 之二異氰酸伸己酯之異氰尿酸酯、以商標名Desmodur® N3400獲自Bayer的二異氰酸伸己酯之脲二酮環及異氰尿酸 酉曰之混合物、以商標名Desm〇dur@ Ls 21〇1獲自Bayer之 二異氰酸伸己酯之脲基甲酸酯、及以商標名Vestanat@ T1890獲自Evonik之異佛爾酮二異氰酸酯之異氰尿酸酯。 此外，適合使用異氰酸酯官能單體之（共）聚合物，諸如 異氰酸α，α’-二曱基-間異丙烯基苯甲酯。最後，如習此相關 技藝之人士已知，上述異氰酸酯及其加合物可至少部分地 以封端異氰酸酯之形式存在。 為了將聚異氰酸酯封端，原則上可能採用可用於聚異 氰酸酯封端且具有足夠低之解封溫度的任何封端劑。此種 封端劑對習此相關技藝之人士為熟知的且本文不需進一步 -兒明。可⑬採用含有經第—封端劑封端之異氰酸醋基與經 第二封端劑封端之異氰酸酯基兩者的封端聚異氰酸酯之混 合物。參考WO 98/40442,該案係以全文引用的式併入本文 中0 本文中所弓丨用之所有專利申請案及專利均係以引用的 方式併入本文中。 將藉由以下非限制性實施例進—步說明本發明： 實施例： Α)製備胺基聚醋多元醇 1.2個 只施例1為製備每分子平均具有〗2 贿基團之聚醋之實施例。 ㈣及 實施例1-Α :製備不飽和聚酯多元醇, an ester of an ester of ester, a substance, one molecule of trimethylolpropane and three molecules of isophora, one molecule of pentaerythritol and four molecules of phthalic acid were obtained from Bayer S under the trade name Desmodur® N3390; 201247728 bis isocyanurate isocyanurate, a mixture of uretdione ring and guanidinium isocyanurate obtained from Bayer under the trade name Desmodur® N3400 from hexamethylene diisocyanate, under the trade name Desm〇dur@ Ls 21〇1 is obtained from Bayer's allophanate of dihexyl hexanoate and the isocyanurate of isophorone diisocyanate available under the trade name Vestanat@ T1890 from Evonik. Further, a (co)polymer of an isocyanate functional monomer such as α,α'-didecyl-m-isopropenylbenzyl isocyanate is suitably used. Finally, it is known to those skilled in the art that the above isocyanates and their adducts can be present, at least in part, in the form of blocked isocyanates. In order to cap the polyisocyanate, it is in principle possible to use any blocking agent which can be used for polyisocyanate end-capping and which has a sufficiently low deblocking temperature. Such endcapping agents are well known to those skilled in the art and need not be further described herein. A mixture of blocked polyisocyanates containing both isocyanate groups blocked with a first blocking agent and isocyanate groups blocked with a second blocking agent can be used. Reference is made to WO 98/40442, which is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in the the the the the the the the the the the The invention will be further illustrated by the following non-limiting examples: EXAMPLES: Α) Preparation of Amino Polyvinyl Polyol 1.2 Only Example 1 is the preparation of a polyester having an average of 2 brittle groups per molecule. example. (4) and Example 1-Α: Preparation of unsaturated polyester polyol

23 201247728 將裝備冷凝器、攪拌器、加熱包、加料漏斗、連接至 溫度控制之熱電偶及用二〒苯底塗之迪安-斯達克分離器 (Dean-St ark trap )的四頸反應燒瓶中裝入44.34份（以重 量計）新戊二醇（NPG)、5.02份三羥甲基丙烷（TMP)、18.95 份己二酸（AdA)、17.78 份順丁烯二酸酐（MAn)、24.64 份異壬酸（iNA)、0.14份磷酸三苯酯及0.035份Fascat 9100 (獲自Arkema公司之丁基錫酸催化劑），且在〇5 SCFH(標 準立方呎/小時）（0.014 m3^)氮氣流下加熱至195。〇至 200°C。在165°C下，水開始共沸蒸餾。使反應溫度逐漸增 加至200°C，並維持在該溫度直至酸值小於2 ^所收集之共 沸水為10_7份。將迪安-斯達克分離器排空，並且用氮氣淨 化反應混合物以移除大部分揮發性物質。將不飽和聚醋多 元醇（UPPO)冷卻至150°C並過濾。 所獲得之UPPO具有96.45%非揮發性物質（藉由以 NCO/OU 1:1混合樹脂與nco且在13(rc下加熱1小時來量 測）；酸值為1.2 5 ;羥值為1 〇 3 ;數量平均分子量（)為 1013 ;重量平均分子量（Mw )為1900 ;且聚合度分佈性為 1.87。 貫施例1-B :製備胺基聚醋多元醇（appo ) 將如實施例1-A所裝備之四頸反應燒瓶中裝入82·2份 實施例1-A之UPPO ’並加熱至4(TC。經由加料漏斗經1 小時逐滴添加α-曱基苯甲胺（17.8份），同時將溫度維持在 5 0 C或5 〇 C以下。在5 01：下繼續加熱隔夜。過.渡所獲得之 所得淡黃色黏性液體。所得樹脂具有97.2%非揮發性物質 201247728 (NVM) ’黏度為8000 mpa.s ;數量平均分子量（Mn)為 1070;重量平均分子量（Mw)為195〇;且聚合度分佈性為 1:82。羥基當量為658 ( OH值=85)，且胺當量為669 (胺值 = 84)，且總官能基之平均當量為332。藉由用〇.丨N鹽酸滴 定胺（ASTM方法D25 72-91 )來測定胺值。藉由用乙酸酐 使羥基.與胺基乙醯化且接著用K〇H滴定乙酸來測定總羥基 加胺值。接著，藉由自總胺加羥值減去胺值來確定羥值。 實施例2 : 實施例2為製備每分子平均具有丨個羥基及4個NH基 團之聚酯的實施例。 實施例2-A :製備不飽和聚酯多元醇 此實施例使用實施例1-A之程序。因而，由45 25份新 戊二醇（NPG)、5.69份三羥曱基丙烷（TMp )、37 35份順 v 丁烯二酸酐（MAn)、20.95份異壬酸、〇 14份磷酸三苯酯 及0.05伤Fascat9100，獲得不飽和聚酯多元醇（uppQ )。 此UPPO具有99%非揮發性物質（藉由以nc〇/〇h 1:1混合 樹脂與NCO且在130°C下加熱1小時來量測）；酸值為丨〇 ; 經值為125，數量平均分子量（Μη)為1150;重量平均分 子量（Mw)為1800 ;且聚合度分佈性為i 6。 實施例2-B :製備胺基聚酯多元醇（APPO ) 此實施例使用實施例1-B之程序。因而，由69· 1份實 施例2-A之UPPO及30.9份α-甲基苯甲胺獲得黏性黃色胺 基聚酯多元醇（八？？0)樹脂。八？？〇具有99.75%非揮發性 物質（NVM)含量’黏度為435 mPa.s; Μη為1200 ; Mw 25 201247728 為1900 ;且聚合度分佈性為ι·6 ^此appo之羥基當量為 1452’胺當量為380，且總官能基之平均當量為3〇1。 實施例3 : 實施例3為製備每分子平均具有1個羥基及2個nh基 團之聚酯的實施例。 實施例3-A :製備不飽和聚酯多元醇 此貫施例使用實施例1 - A之程序。因而，由44.1 7份新 戊二醇（NPG)、5.02份三羥甲基丙烷（TMp)、u 46份己 二酸（AdA)、25.00份順丁烯二酸酐（MAn)、24 55份異壬 I、0.14伤鱗酸二苯酯及〇.〇5份pascat 9丨⑼獲得黏性upp〇 樹脂。將不飽和聚酯多元醇（υρρ〇)冷卻至15〇。〇並過濾。 所得UPPO具有99%非揮發性物質；酸值為j 〇 ;羥值 為125 ;數量平均分子量（Mn)為1177 ;重量平均分子量. (Mw)為2800;經基當量為732;不飽和當量為如。 貫施例3 -B .製備胺基聚酯多元醇（Appo ) 此實施例使用實施例之程序。因而’由1〇〇份實 施例3-A t UPPO及19.1份α_甲基苯甲胺獲得黏性黃色胺 基聚S日多it醇（ΑΡΡΟ )樹脂。過遽所獲得之所得淡黃色黏 性液體。所得樹脂具有97·6%非揮發性物質（nvm); Μη 為n〇o;Mw為2950;經基當量為938;胺當量為5〇2 •且 平均當量為327。 實施例4 此實施例顯示所使用之一級胺之位阻對+異氛酸醋之 APPO之固化速度或膠凝時間的影響。23 201247728 A four-neck reaction equipped with a condenser, a stirrer, a heating pack, an addition funnel, a thermocouple connected to a temperature control, and a Dean-Stark trap with a diphenylbenzene primer The flask was charged with 44.34 parts by weight of neopentyl glycol (NPG), 5.02 parts of trimethylolpropane (TMP), 18.95 parts of adipic acid (AdA), 17.78 parts of maleic anhydride (MAn), 24.64 parts of isophthalic acid (iNA), 0.14 parts of triphenyl phosphate and 0.035 parts of Fascat 9100 (a butyl stannic acid catalyst from Arkema) and under a nitrogen flow of 〇5 SCFH (standard cubic 呎/hr) (0.014 m3^) Heat to 195. 〇 to 200 ° C. At 165 ° C, water begins azeotropic distillation. The reaction temperature was gradually increased to 200 ° C and maintained at this temperature until the acid value was less than 2 ^ and the azeotropic water collected was 10-7 parts. The Dean-Stark separator was vented and the reaction mixture was purged with nitrogen to remove most of the volatiles. The unsaturated polyacetal polyol (UPPO) was cooled to 150 ° C and filtered. The obtained UPPO had 96.45% non-volatile matter (measured by mixing NCO/OU 1:1 with nco and heating at 13 (rc for 1 hour); acid value was 1.2 5; hydroxyl value was 1 〇 3; the number average molecular weight () is 1013; the weight average molecular weight (Mw) is 1900; and the degree of polymerization distribution is 1.87. Example 1-B: Preparation of an amine-based polyglycol polyol (appo) as in Example 1- A four-necked reaction flask equipped with A was charged with 82. 2 parts of UPPO' of Example 1-A and heated to 4 (TC. A-mercaptobenzylamine (17.8 parts) was added dropwise via an addition funnel over 1 hour. At the same time, maintain the temperature below 50 ° C or below 5 ° C. Continue heating at 5 01: overnight. Obtain the resulting pale yellow viscous liquid. The resulting resin has 97.2% non-volatiles 201247728 (NVM) 'The viscosity is 8000 mpa.s; the number average molecular weight (Mn) is 1070; the weight average molecular weight (Mw) is 195 〇; and the degree of polymerization distribution is 1:82. The hydroxyl equivalent is 658 (OH value = 85), and the amine The equivalent weight is 669 (amine value = 84) and the average equivalent weight of the total functional groups is 332. The amine is determined by titration of amine with 〇.丨N hydrochloric acid (ASTM method D25 72-91) The total hydroxyl addition value was determined by deuteration of the hydroxyl group with aminoacetic acid and then titration of acetic acid with K. H. Next, the hydroxyl value was determined by subtracting the amine value from the total amine plus hydroxyl value. Example 2: Example 2 is an example of preparing a polyester having an average of one hydroxyl group and four NH groups per molecule. Example 2-A: Preparation of unsaturated polyester polyol This example uses Example 1- Procedure of A. Thus, from 45 25 parts of neopentyl glycol (NPG), 5.69 parts of trishydroxyhydropropane (TMp), 37 35 parts of cis-v-butenedioic anhydride (MAn), 20.95 parts of isononanoic acid, 〇14 Part of triphenyl phosphate and 0.05 wound Fascat 9100, obtained unsaturated polyester polyol (uppQ). This UPPO has 99% non-volatile matter (by nc〇 / 〇h 1:1 mixed resin with NCO and at 130 ° The temperature was measured by heating for 1 hour; the acid value was 丨〇; the pass value was 125, the number average molecular weight (?n) was 1150; the weight average molecular weight (Mw) was 1800; and the degree of polymerization distribution was i6. 2-B: Preparation of Amino Polyol Polyol (APPO) This example uses the procedure of Example 1-B. Thus, from 69. 1 part of UPPO and 30.9 of Example 2-A Α-methylbenzylamine obtained viscous yellow amine-based polyester polyol (octa?? 0) resin. Octa fluorene has 99.75% non-volatile matter (NVM) content 'viscosity of 435 mPa.s; Μη is 1200 ; Mw 25 201247728 is 1900 ; and the degree of polymerization distribution is ι·6 ^ The hydroxyl equivalent of this appo is 1452' amine equivalent is 380, and the average equivalent weight of the total functional group is 3〇1. Example 3: Example 3 is an example of preparing a polyester having an average of 1 hydroxyl group and 2 nh groups per molecule. Example 3-A: Preparation of Unsaturated Polyester Polyol This procedure was carried out using the procedure of Example 1-A. Thus, from 44.1 7 parts of neopentyl glycol (NPG), 5.02 parts of trimethylolpropane (TMp), u 46 parts of adipic acid (AdA), 25.00 parts of maleic anhydride (MAn), 24 55 parts different壬I, 0.14 diphenyl phthalate and 〇. 5 parts pascat 9 丨 (9) to obtain viscous upp 〇 resin. The unsaturated polyester polyol (υρρ〇) was cooled to 15 Torr. 〇 and filter. The obtained UPPO has 99% nonvolatile matter; the acid value is j 〇; the hydroxyl value is 125; the number average molecular weight (Mn) is 1177; the weight average molecular weight (Mw) is 2800; the base equivalent is 732; the unsaturated equivalent is Such as. Example 3 - B. Preparation of Amino Polyol Polyol (Appo) This example uses the procedure of the examples. Thus, a viscous yellow amine poly S-day poly-alcohol (ΑΡΡΟ) resin was obtained from 1 part of Example 3-A UPPOPO and 19.1 parts of α-methylbenzylamine. The resulting pale yellow viscous liquid obtained after sputum. The obtained resin had 97.6% nonvolatile matter (nvm); Μη was n〇o; Mw was 2950; base equivalent was 938; amine equivalent was 5〇2 • and the average equivalent was 327. EXAMPLE 4 This example shows the effect of the steric hindrance of the mono-amine used on the cure speed or gel time of the APPO of the oleic acid vinegar.

26 S 201247728 使用專莫耳;g;之2 -曱基環己胺替代以_曱基苯甲胺再現 貫施例3 B。因而，由7 7 · 6份實施例3 - A之不飽和聚醋及 22.4份2-甲基環己胺獲得黏性淡黃色液體，其Mn為1180; M.w為2780;經基當直為943;胺當量為5〇6;且平均當量 為 329。 實施例5 : 此實施例顯示所使用之羥基之位阻對含異氰酸酯之 ΑΡΡΟ之固化速度或膠凝時間的影響。 此處使用實施例3 Α之程序製備受阻不飽和聚酯多元 醇。因而，由52_6份2,2,4-三甲基-u-戊二醇、4·26份主 經甲基丙烷、9_7份己二酸、21 _2份順丁烯二酸酐、20.8份 異壬酸及0.2份磷酸三苯酯獲得酸值為7.8的不飽和聚酯多 元醇。添加柯赫酸縮水甘油酯（3份）以消耗殘餘酸，且在 125 C下加熱反應6小時。如實施例3-Β中所述，用α-曱基 本甲胺（25.4份）處理所得不飽和聚g旨多元醇（1〇〇份）。 所传胺基聚醋多元醇之Μη為1280; Mw為2880;經基當 S為‘905，胺當置為597，且平均當量為359。 B)胺基及經基官能聚g旨之塗料效能： 由根據本發明製備之樹脂製得白漆（實施例6至12 )， 且製造比較實施例A及B之類似油漆。使用以下一般程序 來製備該等白漆。 製備白漆之一般程序：26 S 201247728 The use of monomole; g; 2 - decylcyclohexylamine instead of _mercaptobenzylamine Reproduces Example 3 B. Thus, from 7 7 · 6 parts of the unsaturated polyester of Example 3-A and 22.4 parts of 2-methylcyclohexylamine, a viscous pale yellow liquid having an Mn of 1180; Mw of 2780; The amine equivalent is 5〇6; and the average equivalent weight is 329. Example 5: This example shows the effect of the steric hindrance of the hydroxyl groups used on the cure rate or gel time of the isocyanate-containing oxime. The hindered unsaturated polyester polyol was prepared using the procedure of Example 3 herein. Thus, from 52-6 parts of 2,2,4-trimethyl-u-pentanediol, 4.26 parts of main methyl propane, 9-7 parts of adipic acid, 21 _2 parts of maleic anhydride, 20.8 parts of isoindole The acid and 0.2 parts of triphenyl phosphate gave an unsaturated polyester polyol having an acid value of 7.8. Glucin (3 parts) was added to consume residual acid, and the reaction was heated at 125 C for 6 hours. The resulting unsaturated polyglycol polyol (1 part) was treated with α-mercaptomethylamine (25.4 parts) as described in Example 3 -. The amine-based polyglycol polyol has a Μη of 1280; Mw is 2880; the base is S 905, the amine is set to 597, and the average equivalent weight is 359. B) Coating performance of amine groups and base functional groups: White paints (Examples 6 to 12) were prepared from resins prepared according to the present invention, and similar paints of Comparative Examples A and B were produced. The white paint was prepared using the following general procedure. General procedure for preparing white paint:

向高速考爾斯混合器（Cowles mixer )中添加以下成分： 19.5份實施例3-B之APP〇、2.〇份二曱笨、0.47份MPA a 27 201247728 4020-X (得自 Elementis之防沉劑）、1.24份曱基戊基酮 (MAK)及 1.41 份 Disperbyk 163 (得自 BYK-Chemie 之顏 料分散劑），且在低速下混合5分鐘。緩慢篩入二氧化鈦 (46.8份，得自DuPont之R7〇6 )同時混合。添加甲基戊 基酮（1.24份），且在高速下分散漿液15分鐘或直至獲得 6.5至7之亥格曼細度（Hegman grind )。再添加實施例3-B 之樹脂（9.76 份）、Byk 077 ( 0.47 份）、Byk 306 ( 〇.〇9 份） 及甲基異丁酮（4.3 1份）。在低速下將Ti02研磨基質再混合 20至30分鐘’且添加16.67份Desmodur N-3390 (得自 Bayer ) 〇The following ingredients were added to a high speed Cowles mixer: 19.5 parts of the APP of Example 3-B, 2. part of the two, and 0.47 parts of MPA a 27 201247728 4020-X (from Elementis) The precipitant), 1.24 parts of decyl amyl ketone (MAK) and 1.41 parts of Disperbyk 163 (pigment dispersant from BYK-Chemie) were mixed for 5 minutes at low speed. Titanium dioxide (46.8 parts, R7〇6 from DuPont) was slowly sieved while mixing. Methyl amyl ketone (1.24 parts) was added, and the slurry was dispersed at a high speed for 15 minutes or until a Hegman grind of 6.5 to 7 was obtained. Further, the resin of Example 3-B (9.76 parts), Byk 077 (0.47 parts), Byk 306 (〇.〇9 parts) and methyl isobutyl ketone (4.3 parts) were further added. The Ti02 grinding matrix was mixed for a further 20 to 30 minutes at low speed' and 16.67 parts of Desmodur N-3390 (from Bayer) were added.

比較實施例A及B 根據上述一般油漆程序製造比較實施例A及B，使用 DesmophenNH-1520 (得自Baye〇作為比較實施例A之黏 合劑且使用丙烯酸多元醇27-1316 ( 2.2% OH ;得自Nuplex Resins )作為比較實施例b之黏合劑。 實施例6至10 : APPO之塗料效能 如以上一般程序中所述，由實施例丨_B、實施例2 B及 實施例3-B、實施例4及實施例5之樹脂製造白漆，且進行 各種試驗。根據表1中所列出之試驗方法及儀器進行表2 中所列出之各種試驗。使用新製備之油漆量測克雷布黏度 (Krebviscosity)及膠凝時間。對於後一試驗，將約i〇〇g 新活化之白漆置於紙杯中，且將Shy〇dugelTime(i〇〇型， 由Paul N. Gardner公司製造）之[形軸浸入油漆中並開始 旋轉。繼續旋轉直至油漆膠凝且軸已停止。軸自由旋轉所Comparative Examples A and B Comparative Examples A and B were made according to the above general paint procedure, using Desmophen NH-1520 (available from Baye® as the binder of Comparative Example A and using acrylic polyol 27-1316 (2.2% OH; From Nuplex Resins) as the binder of Comparative Example b. Examples 6 to 10: Coating performance of APPO as described in the general procedure above, from Example 丨B, Example 2 B and Example 3-B, The white paints of the resins of Examples 4 and 5 were subjected to various tests. The various tests listed in Table 2 were carried out according to the test methods and instruments listed in Table 1. The freshly prepared paint was used to measure Kreb. Krebviscosity and gel time. For the latter test, approximately i〇〇g of newly activated white paint was placed in a paper cup, and Shy〇dugelTime (i〇〇 type, manufactured by Paul N. Gardner) was used. [The shaft is immersed in the paint and begins to rotate. Continue to rotate until the paint gels and the shaft has stopped. The shaft is free to rotate.

S 28 201247728 需之時間稱為膠凝時間。用到刀將油漆下引於Bonderite B-1000板上以獲得2至2.5密耳乾膜厚度，且立即將濕板 置於Gardner乾燥時間記錄器下。乾燥後在控制溫度及濕度 (分別為72°F及50% RH )下進行光澤、硬度、抗衝擊性及 錐形心軸撓度試驗。 表1 :各種塗料試驗所使用之設備及ASTM方法 試驗 儀器 ASTM方法編號 黏度 BYK Gardner KU1+型 Stormer D-562 20°/60° 光澤 BYK-Gardner4430 型光澤計 D-523 乾燥時間 Gardco DT-5020型乾燥計時器 D-5895 抗衝擊性 Gardner衝擊試驗機 D-2794 伸長率 Gardner錐形心軸 D-522 Koenig擺硬度 BYK-Gardner Koenig 擺式試驗機 D-5895 實施例8至1 2之各種試驗之塗料結果示於表2中。 3 201247728 表2 : ^ f施例6至1 0之塗料資料 實施例6 實施例7 實施例8 實施例9 實施例10 樹脂類型 實施例1B 實施例2B 實施例3B 實施例4 實施例5 漆黏度（KU) 88 97 89 80 78 光澤 20°/60° 87/93 93/97 89/95 85/93 89/95 VOC (g/1) 218 218 218 227 227 乾燥時間 觸乾 18分鐘 8分鐘 16分鐘 15分鐘 16分鐘 不黏 54分鐘 12分鐘 34分鐘 1小時14分鐘 1小時10分鐘 乾硬 1小時20分鐘 22分鐘 46分鐘 2小時36分鐘 3小時08分鐘 乾透 2小時44分鐘 38分鐘 1小時20分鐘 4小時14分鐘 5小時10分鐘 KPH硬度 1天 10 47 14 33 22 7天 18 86 39 49 42 抗衝擊性 7天 (正向/反向） P寸-碎 (inch. lb.) 160/160 40/20 145/140 160/150 110/110 伸長率（錐形心轴） 7天 無影響 無影響 無影響 無影響 無影響 膠凝時間 1小時6分鐘 16分鐘 41分鐘 4小時5分鐘 4小時35分鐘 實施例11至12及比較實施例A及B : 為測試本發明與先前技術相比之優勢，實施例9之白 漆與比較實施例A或B在50/50重量％摻合比下的摻合物分 別產生實施例12及13。實施例14為由實施例4之AAPO 製造的油漆。實施例14與比較實施例A之油漆摻合物提供 實施例1 5。實施例12至1 5及比較實施例A及B之塗料測 試資料示於表3中。 30S 28 201247728 The time required is called the gel time. The paint was applied to a Bonderite B-1000 plate with a knife to obtain a dry film thickness of 2 to 2.5 mils, and the wet plate was immediately placed under a Gardner drying time recorder. After drying, the gloss, hardness, impact resistance and conical mandrel deflection test were carried out under controlled temperature and humidity (72 °F and 50% RH, respectively). Table 1: Equipment used in various coating tests and ASTM method Test equipment ASTM method No. Viscosity BYK Gardner KU1+ type Stormer D-562 20°/60° Glossy BYK-Gardner 4430 type gloss meter D-523 Drying time Gardco DT-5020 type drying Timer D-5895 Impact Resistance Gardner Impact Tester D-2794 Elongation Gardner Conical Mandrel D-522 Koenig Pendulum Hardness BYK-Gardner Koenig Pendulum Tester D-5895 Paints of the various tests of Examples 8 to 12 The results are shown in Table 2. 3 201247728 Table 2: ^ f Coating Materials of Examples 6 to 10 Example 6 Example 7 Example 8 Example 9 Example 10 Resin Type Example 1B Example 2B Example 3B Example 4 Example 5 Paint Viscosity (KU) 88 97 89 80 78 Gloss 20°/60° 87/93 93/97 89/95 85/93 89/95 VOC (g/1) 218 218 218 227 227 Drying time 18 minutes, 8 minutes, 16 minutes 15 minutes 16 minutes not sticky 54 minutes 12 minutes 34 minutes 1 hour 14 minutes 1 hour 10 minutes dry hard 1 hour 20 minutes 22 minutes 46 minutes 2 hours 36 minutes 3 hours 08 minutes dry 2 hours 44 minutes 38 minutes 1 hour 20 minutes 4 hours 14 minutes 5 hours 10 minutes KPH hardness 1 day 10 47 14 33 22 7 days 18 86 39 49 42 Impact resistance 7 days (forward / reverse) P inch - broken (inch. lb.) 160/160 40 /20 145/140 160/150 110/110 Elongation (conical mandrel) 7 days no effect no effect no effect no effect no effect gel time 1 hour 6 minutes 16 minutes 41 minutes 4 hours 5 minutes 4 hours 35 minutes Examples 11 to 12 and Comparative Examples A and B: To test the superiority of the present invention compared to the prior art , White paint Example 9 and Comparison Example A or B respectively in the blend ratio to produce a 50/50 wt% blend of Example 12 and 13. Example 14 is a paint made from AAPO of Example 4. The paint blend of Example 14 and Comparative Example A was provided as Example 15. The paint test materials of Examples 12 to 15 and Comparative Examples A and B are shown in Table 3. 30

S 201247728 表3 :實施例11至12及比較實施例A及B之塗料資料」 實施例 編號 11 12 比較實施例A 比較實施例B 樹脂類型 實施例3與 NH-1520 之 50/50%摻合物 實施例3與 27-1316 之 50/50 摻合物 NH-1520* 天冬胺酸酯 27-1316* 丙烯酸多元醇 油漆黏度 74KU 92 KU 64 KU 72 KTI 光澤 20760° 88/93 89/94 87/93 89/95 V〇C,g/l 197 226 215 —--- 333 乾燥時間 ------ 觸乾 16分鐘 18分鐘 1小時 30分鐘 ------- 3〇分鐘 不黏. 1小時 32分鐘 2小時4 〇分鐘 2小時 45分錄 乾硬 1小時 40分鐘 1小時 5小時 50分鐘 13小時 30分鐘 乾透 2小時 0分鐘 2小時 15分鐘 10小時 --- >24小時 KPH硬度 _ 1天 81 14 149 ----- 14 7天 129 37 176 54 我衝擊性 7天 (正向/反向） 叶-碎 45/20 120/135 10/0 ~--- 130/130 伸長率(錐形心軸） '~'~~ 7天 無影響 無影響 完全分層 無影響 膠凝時間 2小時 24分鐘 1小時 47分鐘 11小時 8分鐘 >24小時 *比較實施例A=NH-1520,得自Bayer之聚天冬胺酸醋樹脂 **比較實施例B=27-m6,得自Nuplex Resins之丙烯酸多元醇(2·2% OH) 1--·— — ---- 表1及表2之結果明確顯示，含有本發明樹脂之塗料 與比較實驗A及B中所示之基於先前技術之塗料相比具有 更短乾燥時間、更高抗衝擊性及更佳伸長率或可撓性。 31 201247728 實施例8、11、12及比較實施例A及B之白漆之QUV 313加速風化示於圖丨中，該圖顯示若干胺基及羥基官能化 合物在若干實施例中所述之白漆中的2〇。保光性。 QUV為由Q_Lab公司製造之儀器的名稱。QUV試驗箱 使用螢光燈提供以紫外線波長為主之辕射光譜。藉由強制 冷凝提供水分’且藉由加熱器控制溫度。可能提及之測試 參考方法為 ASTM D4329、ASTM D4587。 圖中之結果明確顯示基於本發明之塗料與先前技術之 塗料相比之優良对久性。此外，其顯示根據本發明製造之 油漆可改良習知丙烯酸胺基曱酸酿塗料之耐久性（實施例 12)。 c)以下㈣你m明低分子量胺基及㈣官能聚醋之特 定特徵： 實施例1 3-A :製備順丁烯二酸單丁醋 將裝備冷凝器、攪拌器、加熱包、加料漏斗、連接至 溫度控制之熱電偶及用二曱苯底塗之迪安_斯達克分離器的 四頸反應燒瓶中裝入57.0份（以重量計）順丁烯二酸酐及 43.0份（以重量計）丨-丁醇，並在〇 5 SCFH (標準立方呎/ 小時）（0.0 14 m h )氮氣流下加熱至5〇〇c^藉由傅裏葉變 換紅外光譜（FT-ΠΙ)監測反應進展。在此溫度下進行反應 直至1 776及185 1 cm 1處之酸酐吸收消失。將所獲得之順 丁烯二酸單丁酯儲存在玻璃反應器中。過濾不飽和順丁烯 二酸單丁酯並儲存。其具有1〇〇%非揮發性物質；酸值為 326;不飽和當量為172;數量平均分子量（Mn)為262‘；S 201247728 Table 3: Coating Materials of Examples 11 to 12 and Comparative Examples A and B" Example No. 11 12 Comparative Example A Comparative Example B Resin Type 50/50% blending of Example 3 with NH-1520 Example 3 with a 50/50 blend of 27-1316 NH-1520* Aspartate 27-1316* Acrylic polyol Paint Viscosity 74KU 92 KU 64 KU 72 KTI Gloss 20760° 88/93 89/94 87 /93 89/95 V〇C,g/l 197 226 215 —--- 333 Drying time ------ Drying 16 minutes 18 minutes 1 hour 30 minutes ------- 3 minutes not sticky 1 hour 32 minutes 2 hours 4 minutes 2 hours 45 minutes dry hard 1 hour 40 minutes 1 hour 5 hours 50 minutes 13 hours 30 minutes dry 2 hours 0 minutes 2 hours 15 minutes 10 hours --- > 24 hours KPH hardness _ 1 day 81 14 149 ----- 14 7 days 129 37 176 54 I am 7 days of impact (forward / reverse) Leaf - broken 45/20 120/135 10/0 ~--- 130/ 130 Elongation (conical mandrel) '~'~~ 7 days no effect no effect complete delamination no effect gel time 2 hours 24 minutes 1 hour 47 minutes 11 hours 8 minutes>2 4 hours*Comparative Example A = NH-1520, polyaspartic acid vinegar resin from Bayer ** Comparative Example B = 27-m6, acrylic polyol (2·2% OH) from Nuplex Resins 1 --·—— The results of Tables 1 and 2 clearly show that the coating containing the resin of the present invention has a shorter drying time and higher than the prior art coatings shown in Comparative Experiments A and B. Impact resistance and better elongation or flexibility. 31 201247728 The QUV 313 accelerated weathering of the white lacquers of Examples 8, 11, 12 and Comparative Examples A and B is shown in the figure, which shows the white paint of several amine and hydroxy functional compounds in several embodiments. 2 in the middle. Light retention. QUV is the name of the instrument manufactured by Q_Lab. QUV test chamber Fluorescent lamps are used to provide a spectroscopy spectrum based on ultraviolet wavelengths. The moisture is supplied by forced condensation and the temperature is controlled by the heater. Tests that may be mentioned Reference methods are ASTM D4329, ASTM D4587. The results in the figures clearly show the superior durability of the coatings according to the invention compared to prior art coatings. Furthermore, it shows that the paint made according to the present invention can improve the durability of the conventional acrylamide-based enamel coating (Example 12). c) The following (4) specific characteristics of the low molecular weight amine group and the (iv) functional polyester: Example 1 3-A: Preparation of maleic acid monobutyl vinegar will be equipped with a condenser, a stirrer, a heating pack, an addition funnel, 57.0 parts by weight of maleic anhydride and 43.0 parts by weight to a temperature controlled thermocouple and a four-neck reaction flask using a diterpene benzene-coated Dean_Stark separator丨-butanol was heated to 5 〇〇c under a nitrogen flow of 〇5 SCFH (standard cubic 呎/hr) (0.0 14 mh). The progress of the reaction was monitored by Fourier transform infrared spectroscopy (FT-ΠΙ). The reaction was carried out at this temperature until the absorption of the anhydride at 1 776 and 185 1 cm 1 disappeared. The obtained monobutyl maleate was stored in a glass reactor. The unsaturated monobutyl maleate was filtered and stored. It has 1% by weight of non-volatile matter; acid value is 326; unsaturated equivalent is 172; number average molecular weight (Mn) is 262';

S 32 201247728 . 重量平均分子量（Mw)為271 ;且聚合度分佈性為丨〇3 β 實施例1 3-Β :製備1 〇〇 % NVM不飽和聚酯多元醇 將如實施例13-A中所裝備之四頸反應燒瓶中裝入57 份（以重量計）2,2-二甲基辛酸環氧乙烷_2_基曱醋 (Cardura-Ε-ΙΟ)。添加N，N-二甲基苯曱胺（i g)作為催化 劑。經2小時緩慢添加順丁烯二酸單丁酯（43重量份，實 施例13-A)。添加後，在0·5 SCFH(標準立方呎/小時）（〇 〇14 )氮氣流下將反應加熱至i25〇c，並維持在此溫度下直 至酸值小於2。不向反應中添加溶劑。過濾不飽和聚酯多元 醇並儲存。所獲得之不飽和聚酯多元醇具有i 〇〇%非揮發性 物吳（藉由以NCO/OH 1:1混合樹脂與NCO且在1 30°C下加 熱1小時來量測）；酸值為1.6 ;羥值為140 ;不飽和當量為 400 ;數量平均分子量（Mn)為469 ;重量平均分子量（Mw) 為565:;且聚合度分佈性為12。 實施例1 3-C :製備胺基聚酯多元醇-將如實施例13-A所裝備之四頸反應燒瓶中裝入84 6份 實施例1 3-B。經由加料漏斗經1小時逐滴添加第二丁胺 (15.4份）’同時將溫度維持在5〇。〇或5〇。〇以下。在5〇<>c下 繼續加熱隔夜。過濾所獲得之所得淡黃色黏性液體並在室 溫下儲存6週。所得樹脂具有1〇〇%非揮發性物質（NVM ); 黏度為1100 mPa.s ;數量平均分子量（Μη)為524 ;重量 平均分子量（Mw)為654 ;且聚合度分佈性為1>25。羥基 當量為467 ( OH值=120)，且胺當量為474 (胺值= 118)， 且總官能基之平均當量為470.5。藉由用0.1 N鹽酸滴定胺 33 201247728 (ASTM方法D2572_91)來測定胺值。藉由用乙酸酐使羥基 與胺基乙醯化且接著用K〇H滴定乙酸來測定總羥基加胺 值。接著，藉由自總胺加羥值減去胺值來確定羥值。 實施例U-A:製備l〇〇%NVM不飽和聚酯多元醇 將裝備冷凝器 '攪拌器、加熱包、加料漏斗、連接至 溫度控制之熱電偶及用二甲苯底塗之迪安_斯達克分離器的 四頸反應燒瓶中裝人51.6份（以重量計）己二酸雙（3,4_環 氧基環己基甲醋）（ERL 4299;購自Dow —之工業 品）。添加N，N-二曱基苯曱胺（1 g)作為催化劑 '經2小 時緩慢添加順丁烯二酸單丁酯（48 4重量份，實施例卜幻。 添加後，在0.5 SCFH (標準立方吸/小時）（〇 〇14 “.，）氮 氣流下將反應力σ熱至1 2 5。〇，並堆桩Aώ： 士 . ^亚维得在邊溫度下直至酸值小 於2。不向反應令添加溶劑。過遽不飽和聚酯多元醇並儲S 32 201247728 . Weight average molecular weight (Mw) is 271 ; and degree of polymerization distribution is 丨〇 3 β Example 1 3-Β : Preparation of 1 〇〇 % NVM unsaturated polyester polyol will be as in Example 13-A The four-necked reaction flask was equipped with 57 parts by weight of 2,2-dimethyloctanoic acid ethylene oxide _2 ketone vinegar (Cardura-Ε-ΙΟ). N,N-dimethylbenzamide (i g) was added as a catalyst. Maleic acid monobutyl ester (43 parts by weight, Example 13-A) was slowly added over 2 hours. After the addition, the reaction was heated to i25 〇c under a nitrogen flow of 0·5 SCFH (standard cubic 呎/hr) (〇 〇 14 ) and maintained at this temperature until the acid value was less than 2. No solvent was added to the reaction. The unsaturated polyester polyol is filtered and stored. The obtained unsaturated polyester polyol has i 〇〇 % nonvolatiles Wu (measured by mixing NCO/OH 1:1 with NCO and heating at 1 30 ° C for 1 hour); acid value It is 1.6; the hydroxyl value is 140; the unsaturated equivalent is 400; the number average molecular weight (Mn) is 469; the weight average molecular weight (Mw) is 565:; and the degree of polymerization distribution is 12. Example 1 3-C: Preparation of Amino Polyol Polyol - A four-neck reaction flask equipped as in Example 13-A was charged with 84 6 parts of Example 1-B. The second butylamine (15.4 parts) was added dropwise via an addition funnel over 1 hour while maintaining the temperature at 5 Torr. 〇 or 5〇. 〇The following. Continue heating overnight at 5 〇 <>c. The resulting pale yellow viscous liquid was filtered and stored at room temperature for 6 weeks. The obtained resin had 1% by weight of nonvolatile matter (NVM); viscosity was 1100 mPa·s; number average molecular weight (?n) was 524; weight average molecular weight (Mw) was 654; and degree of polymerization distribution was 1 > The hydroxyl equivalent was 467 (OH value = 120) and the amine equivalent was 474 (amine value = 118), and the average equivalent weight of the total functional group was 470.5. The amine value was determined by titrating the amine 33 201247728 (ASTM method D2572_91) with 0.1 N hydrochloric acid. The total hydroxyaddition value was determined by decylating a hydroxyl group with an amino group with acetic anhydride and then titrating acetic acid with K〇H. Next, the hydroxyl value is determined by subtracting the amine value from the total amine plus hydroxyl value. Example UA: Preparation of a 10% NVM Unsaturated Polyester Polyol will be equipped with a condenser 'mixer, heating pack, addition funnel, thermocouple connected to temperature control, and Dean _Stark coated with xylene A four-neck reaction flask of the separator was charged with 51.6 parts by weight of bis(3,4-epoxycyclohexyl acetal) adipate (ERL 4299; industrial product available from Dow). N,N-dimercaptobenzamide (1 g) was added as a catalyst'. The maleic acid monobutyl ester was slowly added over 2 hours (48 4 parts by weight, Example PZ. After addition, at 0.5 SCFH (standard Cubic suction / hour) (〇〇14 ".,) The reaction force σ is heated to 1 2 5 under a nitrogen stream. 〇, and pile A ώ: 士. ^ 亚维得 at the edge temperature until the acid value is less than 2. The reaction is added with a solvent. The unsaturated polyester polyol is stored and stored.

1()〇%非揮發性物質（藉由以Nc〇/〇H 1:1混合樹脂與NCO且在13〇。广丁|為1 , ·» 仕i C下加熱1小時來量測）；酸 值為1.6;羥值為158;不餉釦木县达 个铯和當量為355.4 ;數量平均分子 量（Μη)為1100 ;重量平约公 里卞β刀子$ ( Mw)為3000 ;且聚 合度分佈性為2.72。 實施例14-B:製備胺基聚輯多元醇 將如實施例13_B所奘供七 汁裝備之四頸反應燒瓶中裝入82.9份 實施例14 - B之不飽和.聚西t夕_· # -曰夕το醇。經由加料漏斗經1小時 逐滴添加第二丁胺（1 7 · 1份、m 士 伤）’同時將溫度維持在5(rc或50<t 以下。在5〇t：下繼續加埶ps山 &仪。過濾所獲得之所得淡黃色 黏性液體並在室溫下儲存 週。所得樹脂具有1 〇〇%非揮發1 () 〇% non-volatile matter (by Nc 〇 / 〇 H 1:1 mixed resin and NCO and at 13 〇. 广丁 | is 1 , ·» 仕 i C heating for 1 hour to measure); The acid value is 1.6; the hydroxyl value is 158; the 铯 当量 当量 当量 35 35 35 35 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 饷 ; The sex is 2.72. Example 14-B: Preparation of Amine-Polymer Polyol The four-neck reaction flask for the seven juices as in Example 13_B was charged with 82.9 parts of Example 14-B. Unsaturated. - 曰 τ ο 醇 alcohol. The second butylamine (1 7 · 1 part, m smear) was added dropwise via the addition funnel over 1 hour while maintaining the temperature at 5 (rc or 50 < t. Continue to add 埶ps mountain at 5 〇t: & Instrument. The obtained pale yellow viscous liquid was filtered and stored at room temperature for one week. The obtained resin had 1 〇〇% non-volatile

S 34 201247728 性物質（NVM);數量平均分子量（Mn)為ιΐ5〇;重量平 均分子量（Mw)為3100;且聚合度分佈性為2 7〇。羥基當 量為428 (OH值= 131)，且胺當量為428 5 (胺值=131)， 且總官能基之平均當量為428。藉由用〇1 N鹽酸滴定胺 (ASTM方法D2572-91 )來測定胺值。藉由用乙酸肝使經基 與胺基乙醯化且接著用K0H滴定乙酸來測定總羥基加胺 值。接著，藉由自總胺加羥值減去胺值來確定羥值。 實施例1 5 : 實施例15為製備每分子平均具有19個羥基及1個1^1} 基團之聚酯的實施例。 實施例1 5 - A :製備不飽和聚酯多元醇 將裝備冷凝器、授拌器、加熱包、加料漏斗、連接至 /廉度控制之熱電偶及用一甲苯底塗之迪安_斯達克分離器的 四頸反應燒瓶中裝入74.22份（以重量計）2,2,4_三甲基-込弘 戊一醇（TMPD )、25.78 份’及 0.035 份 Fascat 9100 (得自S 34 201247728 Sexual substance (NVM); the number average molecular weight (Mn) is ιΐ5〇; the weight average molecular weight (Mw) is 3100; and the degree of polymerization distribution is 27 〇. The hydroxyl group was 428 (OH value = 131) and the amine equivalent was 428 5 (amine value = 131), and the average equivalent weight of the total functional group was 428. The amine value was determined by titration of the amine with 〇1 N hydrochloric acid (ASTM method D2572-91). The total hydroxyaddition value was determined by acetylating the thiol group with the amino group and then titrating the acetic acid with K0H. Next, the hydroxyl value is determined by subtracting the amine value from the total amine plus hydroxyl value. Example 1 5: Example 15 is an example of preparing a polyester having an average of 19 hydroxyl groups and 1 1 1 group per molecule. Example 1 5 - A: Preparation of Unsaturated Polyester Polyol will be equipped with a condenser, a stirrer, a heating pack, an addition funnel, a thermocouple connected to / insufficiency control, and a Dean-stack with a toluene primer The four-neck reaction flask of the gram separator was charged with 74.22 parts by weight of 2,2,4-trimethyl-hydrazinol (TMPD), 25.78 parts' and 0.035 parts of Fascat 9100 (from

Arkema公司之丁基錫酸催化劑），且在0.5 SCFH (標準立 方呎/小時）（0.014 m3!!·1)氮氣流下加熱至195。(：至2〇(rc。 在16 5 C下，水開始共沸蒸餾。使反應溫度逐漸增加至 2 0 0 C，且維持在該溫度下直至酸值小於2。所收集之共沸 水為5.2份。將迪安-斯達克分離器排空，並且用氮氣淨化 反應混合物以移除大部分揮發性物質。將不飽和聚酯多元 醇冷卻至150°C並過濾。所獲得之樹脂具有98%非揮發性物 質（藉由以NCO/OH 1:1混合樹脂與NCO且在1 30°C下加熱 1小時來量測）；酸值為1.31 ;羥值為569.6 ;數量平均分子 Ο 201247728 量（Μη)為700;重量平均分.子量（Mw)為i〇5〇;且聚合 度分佈性為1.50。 實施例15-B :製備胺基聚酯多元醇 將如實施例1 5-A所裝備之四頸反應燒瓶中裝入83 7份 貫施例1 5 - A之不飽和聚酯多元醇。經由加料漏斗經1小時 逐滴添加第二丁胺（16.3份），同時將溫度維持在5〇。〇或5〇。〇 以下。在5 0 C下繼續加熱隔夜。過滤所獲得之所得淡黃色 黏性液體®所得樹脂具有98.3%非揮發性物質（nvm );黏 度為40000 mpa.s ;數量平均分子量（Mn)為695 ;重量平 均分子量（Mw)為1047 ;且聚合度分佈性為！ 5。羥基當 置為235 ( %〇Η=7·25 ; OH值=238 )，且胺當量為436 (%Ν=3·2 ;胺值= 129)且總官能基之平均當量為153。藉由 用〇.1 Ν鹽酸滴定胺（ASTM方法D2572_91)來測定胺值。 藉由用乙酸酐使羥基與胺基乙醯化且接著用K〇H滴定乙酸 來测定總羥基加胺值。接著，藉由自總胺加羥值減去胺值 來確定經值。 實施例1 6 : 實施例16與實施例14相同，除了所使用之一級胺為 第三丁基胺，而不是第二丁基胺。所得樹脂具有99 〇%非揮 發性物質（NVM );平均分子量（Mn )為;重量平均分 子量（Mw )為1140;且聚合度分佈性為15。羥基當量為 235 (〇h值=238 )，立胺當量為436 (胺值=129)，且總官能 基之平均當量為153。 比較實施例C :Arkema's butyl stannate catalyst) was heated to 195 under a nitrogen flow of 0.5 SCFH (standard 呎/hr) (0.014 m3!!·1). (: to 2 〇 (rc.) At 16 5 C, the water begins azeotropic distillation. The reaction temperature is gradually increased to 200 ° C and maintained at this temperature until the acid value is less than 2. The azeotropic water collected is 5.2. The Dean-Stark separator was evacuated and the reaction mixture was purged with nitrogen to remove most of the volatiles. The unsaturated polyester polyol was cooled to 150 ° C and filtered. The obtained resin had 98. % non-volatiles (measured by mixing NCO/OH 1:1 with NCO and heating at 1 30 ° C for 1 hour); acid value 1.31; hydroxyl number 569.6; number average molecular weight 201247728 (Μη) is 700; the weight average fraction (Mw) is i〇5〇; and the degree of polymerization distribution is 1.50. Example 15-B: Preparation of the amine-based polyester polyol will be as in Example 1 5-A The four-neck reaction flask was equipped with 83 7 parts of the unsaturated polyester polyol of Example 15-5. The second butylamine (16.3 parts) was added dropwise via an addition funnel over 1 hour while maintaining the temperature. At 5 〇.〇 or 5 〇. 〇 below. Continue heating at 50 ° C overnight. Filter the obtained pale yellow viscous liquid® resulting tree It has 98.3% non-volatile matter (nvm); viscosity is 40,000 mpa.s; number average molecular weight (Mn) is 695; weight average molecular weight (Mw) is 1047; and polymerization degree distribution is! 5. Hydroxyl is set to 235 (% 〇Η = 7.25; OH value = 238), and the amine equivalent was 436 (% Ν = 3. 2; amine value = 129) and the average equivalent weight of the total functional groups was 153. By using 〇.1 Ν The amine value was determined by titration of hydrochloric acid (ASTM method D2572_91). The total hydroxyl addition value was determined by decylating the hydroxyl group with the amino group with acetic anhydride and then titrating the acetic acid with K〇H. Next, by adding the total amine The hydroxyl value was subtracted from the amine value to determine the value.Example 1 6: Example 16 was identical to Example 14, except that the primary amine used was a third butylamine instead of a second butylamine. The resulting resin had 99 〇% nonvolatile matter (NVM); average molecular weight (Mn); weight average molecular weight (Mw) is 1140; and degree of polymerization distribution is 15. Hydroxyl equivalent is 235 (〇h value = 238), and the equivalent amine is 436 (amine value = 129), and the average equivalent weight of the total functional groups was 153. Comparative Example C:

S 36 201247728 . 此實施例係根據先前技術製造。因而，根據類似於上 述之程序，處理以下物質以製造不飽和聚酯：新戊二醇 (34.65份）、三羥甲基丙烷（4 4份）、異壬酸（21份）、 己二醇（17.6份）及順丁烯二酸酐（3〇 3份），獲得不飽和 聚酯多元醇，其羥基當量為323 ( %OH=5.25 )，且不飽和當 量為323，對應於每分子平均3個不飽和單元。酸值為21， 且固體％為96.65%。用2-甲基環己胺處理此不飽和聚酯， 產生胺基聚酯多元醇。所得樹脂具有97.3%非揮發性物質 (NVM );平均分子量（Μη )為1〇〇〇 ;重量平均分子量（Mw ) 為2100 ;且聚合度分佈性為2.1。羥基當量為436 (%OH=3.9 ; OH 值= 129) ’ 且胺當量為 436 (氮％ = 3.2 ;胺 值= 129)且總官能基之平均當量為218。此值對應於每分子 2·5個OH基團及2.5個NH基團。 表' 4展示由實施例1 5及實施例16以及比較實施例C 製得之白色塗料經數週之硬度發展，如藉由Kdning擺硬度 試驗機所量測。可容易地觀察到’由先前技術比較實施例C 所製得之塗料的硬度顯示硬度增加至多1至2週，接著硬 度隨時間降低。而本發明實施例15及實施例16之硬度顯 示增加直至達到最大值，接著隨時間保持恆定。 3 37 201247728 表 4 :有色塗料隨時間之硬度量測1 直 時間(天） 比較實施例C 時間(天） 實施例16 實施例15 1 48 1 52 25 4 113 2 81 76 7 126 3 90 124 14 114 7 90 180 27 90 14 87 190 43 63 21 85 194 77 88 187 表5展示實施例13、實施例1 5及實施例16之透明塗 層資料。可藉由使用各種本發明樹脂來定製諸如硬度、衝 擊性及可撓性之物理性質以達到所要程度。 表5 :實施例13、實施例15及實施例16之塗層資料 樹脂類型 實施例13 實施例15 實施例16 透明塗層固體％ 74% 75% 75% DBTDL% 0.03 0.04% 0.01% 乾燥時間 觸乾 1小時 1小時 35分鐘 不黏 3小時 2小時 2小時 乾硬 12小時 6小時 9小時 KPH硬度 1天 24 52 25 7天 35 90 180 76天 88 187 抗衝擊性 7天(正向/反向)叶-碎 160/160 85/60 45/30 伸長率(錐形心轴） 7天 無影響 無影響 無影響 膠凝時間 45小時3分鐘 45小時43分鐘 4小時27分鐘 實施例1 7及實施例1 8 :胺基及羥基官能聚酯與丙烯酸S 36 201247728 . This embodiment is made in accordance with the prior art. Thus, according to a procedure similar to the above, the following materials were processed to produce an unsaturated polyester: neopentyl glycol (34.65 parts), trimethylolpropane (4 4 parts), isodecanoic acid (21 parts), hexanediol (17.6 parts) and maleic anhydride (3〇3 parts), obtaining an unsaturated polyester polyol having a hydroxyl equivalent of 323 (%OH=5.25) and an unsaturated equivalent of 323, corresponding to an average of 3 per molecule. Unsaturated units. The acid number was 21 and the % solids was 96.65%. Treatment of this unsaturated polyester with 2-methylcyclohexylamine produces an amine-based polyester polyol. The obtained resin had 97.3% nonvolatile matter (NVM); the average molecular weight (?n) was 1 Å; the weight average molecular weight (Mw) was 2100; and the degree of polymerization distribution was 2.1. The hydroxyl equivalent weight was 436 (%OH = 3.9; OH value = 129)' and the amine equivalent was 436 (nitrogen % = 3.2; amine value = 129) and the average equivalent weight of the total functional groups was 218. This value corresponds to 2·5 OH groups per molecule and 2.5 NH groups. Table '4 shows the development of the white paints obtained in Example 15 and Example 16 and Comparative Example C over several weeks, as measured by a Kdning pendulum hardness tester. It can be easily observed that the hardness of the coating prepared by the prior art Comparative Example C shows an increase in hardness of at most 1 to 2 weeks, followed by a decrease in hardness with time. While the hardness of Examples 15 and 16 of the present invention showed an increase until the maximum value was reached, it was then kept constant over time. 3 37 201247728 Table 4: Hardness measurement of colored paint over time 1 Straight time (days) Comparative Example C Time (days) Example 16 Example 15 1 48 1 52 25 4 113 2 81 76 7 126 3 90 124 14 114 7 90 180 27 90 14 87 190 43 63 21 85 194 77 88 187 Table 5 shows the clear coating materials of Example 13, Example 15 and Example 16. The physical properties such as hardness, impact and flexibility can be tailored to achieve the desired degree by using various resins of the present invention. Table 5: Coating Information for Example 13, Example 15, and Example 16 Resin Type Example 13 Example 15 Example 16 Clearcoat Solids % 74% 75% 75% DBTDL% 0.03 0.04% 0.01% Dry Time Touch Dry 1 hour 1 hour 35 minutes Not sticky 3 hours 2 hours 2 hours Dry hard 12 hours 6 hours 9 hours KPH hardness 1 day 24 52 25 7 days 35 90 180 76 days 88 187 Impact resistance 7 days (forward/reverse) ) Leaf-crush 160/160 85/60 45/30 Elongation (conical mandrel) 7 days no effect no effect no effect gel time 45 hours 3 minutes 45 hours 43 minutes 4 hours 27 minutes Example 1 7 and implementation Example 1 8: Amine and hydroxy functional polyesters with acrylic acid

S 38 201247728 多元醇之摻合物： 表6展示由實施例13及實施例16與丙烯酸多元醇 27-13 16 ( 2.2% OH ;購自 Nuplex Resins 之工業品）之 50/50 摻合物（以重量計）製得之白漆的塗料性質。該等摻合物 之硬度及VOC得到顯著改良。 表6 :實施例17及實施例18之塗層資料 實施例編號 實施例17 實施例18 比較實施例B 樹脂類型 實施例13與27-1316 之50/50摻合物 實施例16與27-1316 之50/50摻合鉍 27-1316 丙烯酸多元醇 固體％ 78% 76% 76% DBTDL% 0.03 0.04% 0.001% 100g/lVOC所需之 Oxsol-100 11.8% 14.9% VOC=333 g/1 乾燥時間 觸乾 45分鐘 50分鐘 30分鐘 不黏 2小時 4小時30分鐘 2小時45分鐘 .乾硬 10小時20分鐘 18小時 13小時30分鐘 KPH硬度 .1天 19 18 14 2天 29 49 5天 43 107 7 天=54 膠凝時間 2小時17分鐘 19小時36分鐘 >24小時 因而，已參考某些上述具體實例描述本發明》除上述 改進以外，可在不背離本發明之精神及範疇的情況下對本 文所述之結構及技術進行其他改進。因此，雖然已描述特 定具體實例，但此等具體實例僅為實例而不限制本發明之 範疇。 【圖式簡單說明】 參考以下圖式即可瞭解本發明之特徵及優勢，其中：S 38 201247728 Polyol Blend: Table 6 shows a 50/50 blend of Example 13 and Example 16 with an acrylic polyol 27-13 16 (2.2% OH; available from Nuplex Resins) The coating properties of the white lacquer obtained by weight. The hardness and VOC of these blends are significantly improved. Table 6: Coating Information for Example 17 and Example 18 Example No. Example 17 Example 18 Comparative Example B Resin Types Example 13 and 50/50 Blends of 27-1316 Examples 16 and 27-1316 50/50 blended 铋27-1316 Acrylic polyol solid% 78% 76% 76% DBTDL% 0.03 0.04% 0.001% 100g/l VOC required Oxsol-100 11.8% 14.9% VOC=333 g/1 Dry time touch Dry 45 minutes 50 minutes 30 minutes non-stick 2 hours 4 hours 30 minutes 2 hours 45 minutes. Dry hard 10 hours 20 minutes 18 hours 13 hours 30 minutes KPH hardness. 1 day 19 18 14 2 days 29 49 5 days 43 107 7 days =54 gel time 2 hours 17 minutes 19 hours 36 minutes> 24 hours Thus, the present invention has been described with reference to certain specific examples described above, in addition to the above-described modifications, without departing from the spirit and scope of the invention. Other improvements are made to the structure and techniques described. Therefore, although specific examples have been described, these specific examples are only examples and are not intended to limit the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The features and advantages of the present invention can be understood by reference to the following drawings, in which:

39 201247728 圖1展示根據本發明及如若干實施例中所述之基於胺 基及羥基官能聚酯之白漆在不同QUV 313曝露時間下的 20°保光性。 【主要元件符號說明】 無39 201247728 Figure 1 shows the 20° gloss retention of an amine based and hydroxy-functional polyester based paint according to the invention and as described in several embodiments at different QUV 313 exposure times. [Main component symbol description] None

SS

Claims (1)

201247728 七、申請專利範圍. 1. 一種胺基及羥基官能聚酯，其中該胺係呈天冬胺酸醋 官能基形式，且其中該胺基及羥基官能聚酯具有： a)至少約500之分子量（Μη); b) 約5或5以下之酸值； c) 約3 0或3 0以上之經值；及 d) 約30或30以上之胺值 e )且其中該羥基為位阻一級羥基及/或二級羥基。 2.如申請專利範圍第1項之胺基及羥基官能聚酯，其中 5亥聚S旨之分子平均具有： f) 至少一個呈天冬胺酸酯形式之二級胺基； g) 及/或至少一個羥基； h)及約1.8或高於18之平均總官能度。 3.如申叫專利範圍第1項之胺基及羥基官能化合物， 中該化合物呈命护之-# y , 聚S曰夕疋醉形式’且其中該聚酯具有式i之 式結構：201247728 VII. Patent application scope. 1. An amine-based and hydroxy-functional polyester, wherein the amine is in the form of an aspartic acid functional group, and wherein the amine group and the hydroxy-functional polyester have: a) at least about 500 Molecular weight (Μη); b) an acid value of about 5 or less; c) a warp value of about 30 or more; and d) an amine value of about 30 or more e) and wherein the hydroxyl group is sterically hindered Hydroxyl and/or secondary hydroxyl groups. 2. The amine group and the hydroxy-functional polyester according to claim 1, wherein the molecules of the group have an average of: f) at least one secondary amine group in the form of aspartate; g) and / Or at least one hydroxyl group; h) and an average total functionality of about 1.8 or greater. 3. For example, the amine group and the hydroxy-functional compound of claim 1 of the patent range, wherein the compound is in the form of -# y , poly-S-intoxication form and wherein the polyester has the formula of formula i: 0 〇 NHR 其中：卜單價烷基、芳基及/或芳烷基； R ^ =自客- 具有除0H基團後獲得之殘基且其中卖 、原子價； R2=自多元醇移除0H_後獲得之殘基且其“ 41 3 201247728 具有2至6之原子價； 尺尸二價飽和及/或不飽和烷基及/或芳基； E=H或具有1至1 8個碳原子之醯基； X1、X2=具有0至5之相等或不同值的整數，且其中 X1與X2之總和為至少1 ; y、z=具有0或1之值的整數； P =具有〇至4之值的整數； G=E及/或具有以下結構之殘基：0 〇NHR wherein: monovalent alkyl, aryl and/or aralkyl; R ^ = self-custom - having residues obtained after the 0H group and having a valence; R2 = removing 0H from the polyol a residue obtained after _ and its "41 3 201247728 has a valence of 2 to 6; a divalent saturated and/or unsaturated alkyl and/or aryl group; E = H or has 1 to 18 carbon atoms X1, X2 = an integer having equal or different values from 0 to 5, and wherein the sum of X1 and X2 is at least 1; y, z = an integer having a value of 0 or 1; P = having 〇 to 4 An integer of the value; G=E and/or a residue having the following structure: n=具有1至1〇之值的整數。 4. 如申請專利範圍第1項至第3項中任一項之胺基及羥 基官能聚酯’其中該胺基及羥基官能聚酯之數量平均分子 量較佳為約500或高於500及約5,000或低於5,000。 5. 如申睛專利範圍第1項至第4項中任一項之胺基及經 基官能聚酯，其中該胺基及羥基官能化合物之聚合度分佈 性為約4或低於4及約1.2或高於1.2。 6_如申請專利範圍第丨項至第5項中任一項之胺基及羥 基官能聚酯’其中該胺基及羥基官能化合物具有約4〇或高 於40及約300或低於300之羥值。 7 ·如申凊專利範圍第1項至第6項中任一項之胺基及經 基官能聚酯，其中該胺基及羥基官能聚合物具有約4〇或高 S 42 201247728 於40及約300或低於300之胺值。 8.如申請專利範圍第1項至第7項中任一項之胺基及經 基官能聚酯，其中該胺基及羥基官能聚合物具有約1.8或 1.8以上及約1 0或1 0以下之平均總官能度。 · 9 · 一種可固化組成物，其包含如申請專利範圍第1項至 第8項中任一項之胺基及羥基官能聚酯及聚異氰酸酯，其 中该異氰酸醋之存在量為胺基及醇基之莫耳量之約60%或 60%以上。 10. —種用於製備基於胺基及羥基官能化合物之聚酯之 方法，該方法包含製備包含順丁烯二酸酯及反丁烯二酸酯 不飽和度中之至少一者的羥基官能聚酯，且其中藉由假邁 克爾加成反應（pSeud〇 Michael addition reaction )使該順丁 烯二酸酯及反丁烯二酸酯不飽和度與脂族或芳族胺化合物 反應以製備天冬胺酸酯。 11·一種塗料組成物，其包含如下重量份（pbw)之以下 組分： —項之胺基 C a)如申請專利範圍第1項至第9項中任 及羥基官能聚酯（1至80 pbw); (b)聚異氰酸酯化合物（i至65 pbw); (c )其他黏合劑組分（0至6〇 pbw ); (d) 著色劑（〇至40 pbw); (e) 添加劑（0至10 pbw); (f) 錫催化劑（0至0.1 pbw); (g) 溶劑（0 至 30 pbw); 201247728 其中組分a至f總共為100 pbw。 12 ·如申明專利範圍第11項之組成物’其中組分（c ) 存在直為1至60 pbw，且其中組分^包含以下中之一或多 者： 1_每基官能丙烯酸聚合物、羥基官能聚酯、羥基官能活 性稀釋劑、經基官能聚醚、羥基官能聚碳酸酯或羥基官能 聚胺基甲酸酯； η·無官能聚合物或官能基當量為約5〇〇〇或高於5000 之低官能聚合物；及 除化合物（a)以外之天冬胺酸酯官能化合物。 Η.如申請專利範圍第u項至第12項中任一項之組成 物某中組分（c)之存在量為5至5〇pbw。 _14·如申請專利範圍第11項至第13項中任一項之組成 物，其中組分（c)包含羥基官能丙烯酸聚合物。 S 44 201247728 形式之二級胺形式。 1 8.如申請專利範圍第1 7項之聚醋，其中該幾基官能度 為每分子1至12個經基。 19. 如申請專利範圍第17項至第a項中任一項之聚 醋’其中該胺基及羥基官能聚酯之分子量為204至10,000， 且更佳為482至5000。 20. 如申請專利範圍第I?項至第19項中任一項之聚 酯，其中該胺基及羥基官能化合物含有〇.丨重量％至7重量 %呈天冬胺酸酯基形式之二級胺形式的氮及〇丨％至丨一 級經基及/或二級經基。 21·如申請專利範圍第π項至第2〇項中任一項之聚 醋’其中該胺基及羥基官能聚酿之通式結構示於式π中： 團n = an integer having a value of 1 to 1 。. 4. The amine group and the hydroxy-functional polyester of any one of claims 1 to 3 wherein the number average molecular weight of the amine group and the hydroxy-functional polyester is preferably about 500 or more and about 500 and about 5,000 or less than 5,000. 5. The amine group and the transfunctional polyester according to any one of claims 1 to 4, wherein the degree of polymerization of the amine group and the hydroxy-functional compound is about 4 or less and about 1.2 or higher than 1.2. The amine group and the hydroxy-functional polyester of any one of the above-mentioned claims, wherein the amine group and the hydroxy-functional compound have about 4 or more and about 300 or less than 300. Hydroxyl value. The amine group and the transfunctional polyester according to any one of claims 1 to 6, wherein the amine group and the hydroxy functional polymer have about 4 Å or a high S 42 201247728 at 40 and about Amine value of 300 or less. 8. The amine group and the transfunctional polyester according to any one of claims 1 to 7, wherein the amine group and the hydroxy-functional polymer have a content of about 1.8 or more and about 10 or less. Average total functionality. A curable composition comprising the amine group and the hydroxy-functional polyester and the polyisocyanate according to any one of claims 1 to 8, wherein the isocyanate is present in an amine group And about 60% or more of the molar amount of the alcohol group. 10. A method for preparing a polyester based on an amine group and a hydroxy functional compound, the method comprising preparing a hydroxyl functional group comprising at least one of a maleate and a fumarate unsaturation An ester, and wherein the maleic acid ester and fumarate unsaturation are reacted with an aliphatic or aromatic amine compound by a pseudo-Michael addition reaction to prepare an aspartame Acid ester. 11. A coating composition comprising the following components in parts by weight (pbw): - an amine group C a) as claimed in claims 1 to 9 and a hydroxy functional polyester (1 to 80) Pbw); (b) polyisocyanate compound (i to 65 pbw); (c) other binder components (0 to 6 〇pbw); (d) colorant (〇 to 40 pbw); (e) additive (0) Up to 10 pbw); (f) Tin catalyst (0 to 0.1 pbw); (g) Solvent (0 to 30 pbw); 201247728 where components a to f total 100 pbw. 12. The composition of claim 11 wherein component (c) is present in an amount of from 1 to 60 pbw, and wherein component ^ comprises one or more of the following: 1_ per functional acrylic polymer, a hydroxy-functional polyester, a hydroxy-functional reactive diluent, a trans-functional polyether, a hydroxy-functional polycarbonate or a hydroxy-functional polyurethane; η·non-functional polymer or functional equivalent of about 5 Å or higher a low-functionality polymer of 5,000; and an aspartate functional compound other than the compound (a).组成. The composition of any one of the components of the range of items u to 12 is 5 to 5 〇pbw. The composition of any one of clauses 11 to 13, wherein component (c) comprises a hydroxy-functional acrylic polymer. S 44 201247728 Form of secondary amine form. 1 8. The polyacetate of claim 17 wherein the number of functional groups is from 1 to 12 per one molecule. 19. The vinegar of any one of clauses 17 to a wherein the molecular weight of the amine group and the hydroxy-functional polyester is from 204 to 10,000, and more preferably from 482 to 5,000. The polyester according to any one of the preceding claims, wherein the amine group and the hydroxy-functional compound contain 〇.丨% by weight to 7% by weight of the aspartate group form The nitrogen and hydrazine in the form of the amines are to the primary and/or secondary meridians. 21. The polyacetate of any one of the claims π to 2, wherein the basic structure of the amine group and the hydroxy functional polymer is shown in the formula π: 式II 其中：R=單價烷基 芳基及/或芳烧基且可含有OH基 Ri與R2可相似 團後所獲得之具有1 6之值的整數，且η 3不同’且各自為自多元醇移除OH基 至6之原子價的殘基，且x=具有〇至 具有1至1.8之值。 45 .3Wherein R: a monovalent alkylaryl group and/or an aryl group and may contain an integer having a value of 16 which is obtained after the OH group Ri and R2 are similarly grouped, and η 3 is different 'and each is a self-diversity The alcohol removes the OH group to a residue of the valence of 6, and x = has a enthalpy to a value of from 1 to 1.8. 45 .3