200848447 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種含有二聚物殘基之不飽和聚合物，特 別係有關一種不飽和聚酯多元醇及其於聚合物（，特定言 之’應用於塗層、彈性體和熱塑性塑料之聚胺酯）中作為 構成後段上之用途 【先前技術】 聚胺酯是一種多用途材料，其可用於各種施用，例如彈 ' 性體、發泡體、塗層、接著劑、熱可塑性聚胺酯、塗層用 聚胺自旨勻散液、粉末及紡織品勻散液。聚胺酯由多元醇與 異氰酸s旨反應形成。目前用於工業的主要有兩類多元醇， 即聚醚多7L醇和聚酯多元醇，兩者都是飽和產物。不飽和 夕元醇如聚丁二烯二醇也用於聚胺酯，但是不飽和可能降 低抗紫外光能力。 ♦胺s旨一旦形成時，隨即由胺基甲酸酯官能基與水氣進 行化干反應，形成交聯材料，其根據施用領域有不同性 貝。沒些聚胺®旨有單一類型的固化位置，即胺基甲酸酯官 月匕土來胺δ日亦可能沒有反應性，意指他們在施用之後不 需要（濕）固化。 靶用領域包括層壓用聚胺酯熱熔接著劑、用於地板、裝200848447 IX. Description of the Invention: [Technical Field] The present invention relates to an unsaturated polymer containing a dimer residue, in particular to an unsaturated polyester polyol and its polymer (specifically, 'Used in polyurethanes for coatings, elastomers and thermoplastics' as a component on the back section [Prior Art] Polyurethane is a versatile material that can be used in various applications such as elastomers, foams, coatings. , Adhesives, thermoplastic polyurethanes, polyamines for coatings, powders and textile dispersions. Polyurethanes are formed by the reaction of a polyol with isocyanate. There are two main types of polyols currently used in the industry, namely polyether 7L alcohols and polyester polyols, both of which are saturated products. Unsaturated alcohols such as polybutadiene diols are also used in polyurethanes, but unsaturation may reduce the ability to resist ultraviolet light. ♦ Amine s is once formed, and then the urethane functional group is subjected to a dry reaction with moisture to form a crosslinked material which has different properties depending on the field of application. None of the Polyamine®s have a single type of cure position, i.e., the urethane glutamate δ day may also be non-reactive, meaning that they do not require (wet) cure after application. Target areas include laminated polyurethane hot melt adhesives for flooring and equipment
產品性能（如：童 酯粘結劑、用於汽車的聚胺酯密 層、工業塗料、木材塗料和接著劑、地 、絕緣體、彈性體鞋底、溜冰鞋輪子等。 韌性和撓性）可以例如透過選擇多元醇類 127030.doc 200848447 型及多元醇與異氰酸㈣比率，廣泛地調節。源於飽和聚 酯多元醇的聚胺酯對各種基材都有良好的粘著性，撓性比 以聚醚為主之聚胺酯低、熱氧化穩定性良好但抗水解能力 較弱。 含有羥基的（曱基）丙烯酸單體可以與乙烯基單體和丙烯 酸單體聚合/共聚合以形成中間聚合物。中間聚合物的羥 基與聚異氰酸酯反應形成具有兩個固化點的聚胺酯，即胺 基曱酸酯官能基（異氰酸酯）和甲基丙烯酸脂不飽和，其可 以分別經由與水氣和紫外光反應來固化。與只有一個固化 點的材料相比，這些材料具有不同的性質，比如濕強度提 高、粘著力提高、剪切膠粘力破壞溫度提高、塗層硬度提 高、塗層、接著劑、彈性體和發泡體的模數和韌性提高。 此外施用粘度可能下降。生成具有兩個固定點的聚胺酯的 方法缺點是在固化發生前，有游離的丙烯酸單體殘基存 在。這些單體易揮發，需要採取預防措施來安全地處理它 們。吾人已知丙烯酸單體會引起對皮膚、眼睛、鼻咽喉和 呼吸道的刺激。 【發明内容】 吾人已發現一種不飽和聚酯多元醇及其在廣泛的聚合物 應用上之用途，其減少或基本上克服上述至少一個問題。 因此’本發明提供了 一種包含至少2個經基且經值為1 1 至225 mgKOH/g之不飽和聚酯多元醇，本發明包括至少一 種二魏酸和至少一種多元醇的反應產物，其中酸和多元醇 中至少一者包括二聚脂肪酸及/或二聚脂二醇。 127030.doc 200848447 本發明又提供製備一種羥值為11至225 mgK〇H/g的不飽 和聚醋多元醇之方法，其包括由至少一種二羧酸和至少一 種多元醇以1:1 ·〇1至5·〇的莫耳比反應，其中酸和多元醇中 至y 種包括二聚脂肪酸及/或二聚脂二醇。 本發明又包括一種聚胺酯，其由⑴聚異氰酸酯、（ii)不 飽和聚酯多元醇，與（可視需要選用）（iii)增鏈劑反應獲 得’其中聚醋多元醇至少有兩個羥基，且羥值為丨丨至225 mgKOH /g，其包括至少一種二羧酸和至少一種多元醇的 反應產物，其中酸和多元醇中至少有一種包括二聚脂肪酸 及/或二聚脂二醇。 本發明又提供以如本文所定義不飽和聚酯多元醇作為用 於形成聚胺酯之構成嵌段上之用途，其中聚胺酯形態為發 泡體、彈性體、塗層、接著劑、用於塗層或接著劑的勾散 液或熱可塑性材料。 本發明又提供-種聚合物，其包括⑴一個烯煙系不飽和 基團，（u) —個能夠在水之存在下反應的基團，（iii)二聚脂 肪酸及/或一聚脂二醇的反應產物。 本發明又提供—種共聚_，其包括-個硬鏈段和-個軟 鏈段，其中軟鏈段包括本文所定義的不飽和聚s旨多元醇。 本發明另外又提供一種聚酯醯胺共聚物，其包括至少一 個包括至少-個醯胺鍵的硬鏈段和至少—個包括本文所定 義的不飽和聚酯多元醇的軟鍵段。 不飽和聚醋多元醇包括-種不飽和二羧酸及/或多元醇 的反應錢’其最好包料—個碳雙鍵。^鮮二叛酸 127030.doc 200848447 較佳，宜自馬來酸、富馬酸、衣康酸及其酯和酐所組成群 中至少選擇一種；最好是馬來酸、富馬酸及其酸酐。特別 佳的是馬來酸酐。 根據本發明不飽和聚酯多元醇包括至少一種二聚脂肪酸 及/或'一 t月曰-一酵及/或其同等物的反應產物。 二聚脂肪酸一詞係可相關技藝習知，指單不飽和脂肪酸 或多不飽和脂肪酸及/或其酯的二聚產物。較佳的二聚脂 肪酸為含0：1()至Cw碳原子的二聚物，含Cl2至c24個碳原子 的更佳’特定言之，Cm至CM個碳原子，尤其是Cl8個碳原 子的烧基鏈。適當的二聚脂肪酸包括油酸、亞油酸、亞麻 酸、棕櫚油酸和反油酸的二聚產物。也可使用由天然油脂 (例如：葵花油、大豆油、橄欖油、菜籽油、棉子油和松 油）水解獲得之不飽和脂肪酸混合物的二聚產物。也可以 使用經例如使用鎳催化劑氫化的二聚脂肪酸。 除了二聚脂肪酸外，二聚合作用通常產生不同數量的寡 脂肪酸（所谓的π二聚物”），並存在單體脂肪酸（所謂的，， 單體）或其酯殘基。單體的數量可以透過例如蒸顧法來減 少。適當的二聚脂肪酸具有大於6〇 wt%的二聚酸含量，大 於75 wt%較佳，90至99.5 wt%之範圍更佳，特定言之92至 99 wt%，尤指95至98 Wt%。三聚物含量宜低於4〇 wt%， 0.01至25 wt°/〇之範圍較佳，0 05至15 wt%更佳，特定言之 0.1至5 wt%，尤指1至4 wt%。單體含量最好低於1〇 wt%， 〇·〇1至5 wt%之範圍更佳，特別是，尤其是 0.05至0·4 wt%。上述所有重量百分比數值都以三聚物、二 127030.doc 200848447 聚物和單體的總含量為基準計。 二聚脂二醇可以透過相應的二聚脂肪酸氫化來生產。適 當的二聚脂二醇的二聚二醇含量大於6〇 wt%，大於乃wt% 較佳，90至99.5 wt%之範圍更佳，特定言之93至99 wt%， . 尤指94至98 wt%。三聚物含量宜低於4〇 wt%，〇·〇1至25 wt%之範圍較佳，〇·〇5至15 wt%更佳，特定言之〇·ι至5 wt% ’尤指〇·5至3 wt%。單體含量最好低於10 wt%，〇」至 5 wt%之範圍更佳，特別是〇·3至4 wt%，尤其是（^至^ k ’ wt%。上述所有重量百分比數值都以三聚物、二聚物和單 體的總含量為基準計。 如果在根據本發明不飽和聚酯多元醇中不存在二聚脂二 醇（亦即使用二聚脂肪酸時），則使用除了二聚脂二醇以外 之至少一種多元醇。除了二聚脂二醇，還可以使用其他的 多元醇。 至少一種其他的多元醇宜具有小於4〇〇的分子量，小於 y 3〇〇較佳，小於200更佳，特定言之48至16〇，尤指“至 120。至少一種其他的多元醇最好選自由季戊四醇、甘 油、二羥甲基丙烷、乙二醇、二甘醇、-丙二醇、丨，3_ •丙二醇、二丙二醇、丁二醇、1，6-己二醇、新戊二 醇、3-曱基戊二醇、1‘雙（經曱基）環己烷、Μ-環己烷_ 二甲醇所組成之群中。特別佳的其他多元醇為二醇類， 如··乙二醇、二甘醇、丨，2-丙二醇、1，3-丙二醇、二丙二 醇、1，4-丁二醇、己二醇、新戊二醇、3_甲基戊二醇、 1，4-一（羥甲基）¾己烷、丨，4_環己烷_二甲醇及其混合物。 127030.doc -10- 200848447 特別佳為乙二醇、二甘醇、1，2-丙二醇、丙二醇、二 丙二醇、丨〆-丁二醇、1，6-己二醇及其混合物。 可採用本文所述二聚脂肪酸和不飽和二羧酸以外之二元 魏酸生產根據本發明不飽和聚酯多元醇。較佳為脂肪族二 羧酸，合適的飽和酸類選自：己二酸、戊二酸、丁二酸、 庚二酸、辛二酸、壬二酸、癸二酸、庚烷二羧酸、辛烷二 緩酸、壬焼二魏酸、癸烧一緩酸、十一院二魏酸、十二燒 一幾酸與其更高碳同系物及其混合物。特別佳的其他二敌 酸包括己二酸、癸二酸、壬二酸及其混合物。 根據本發明不飽和聚酯多元醇的兩端最好用羥基封端。 因此，多元醇的莫耳數隶好多於二叛酸。不飽和聚酯多元 醇宜由二羧酸與多元醇（以二醇較佳）形成，起始物的莫耳 比率為1:1.001至5.0，1:1_〇1至4.0較佳，1:1.2至30更佳， 特別是1:1.4至2.0，尤其是1:1.5至1.7。 不飽和聚酯多元醇宜具有500至10,000的數量平均分子 罝，600至8,000較佳，800至6,000更佳，特別是9〇〇至 5,000，尤其是 ι，〇〇〇 至 4,〇〇〇。 不飽和聚醋多元醇最好包括平均少於88個酯鍵，介於i 至45個更佳，特別是2至25個，尤其是3至15個。此外，聚 醋最好平均包括（1)1至15個二聚物殘基，1至1〇個更佳，特 別疋2至6個’尤其是2至5個；及/或（ϋ)少於44個碳雙鍵，j 至26個更佳’特別是2至20個，尤其是3至10個。 不飽和聚酯多元醇最好具有丨4至190 mgKOH/g範圍内的 羥值，20至14〇 mgK〇H/g更佳，特別是3〇至 127030.doc 200848447 mgKOH/g’尤其是35至12〇 mgK〇H/g。此外，聚酯的酸值 最好小於3.0，小於！.5較佳，小於丨3更佳，特別是小於1〇 mgKOH/g，及/或含水率小於，小於〇·5%更佳，特別是 小於0.2%，尤其是小於〇. 1〇/。。 在室溫下（25°C )之不飽和聚酯多元醇可以是液體或一種 (半）結晶固體，最好為液體。 當不飽和聚醋多元醇為一種液體時，25t時的動態枯度 最好介於4,000至100,000，6,〇〇〇至8〇5〇〇〇更佳，特別是 8,000至 70,000，尤其是 10,〇〇〇至65,〇〇〇。 §不飽和♦ S曰多元醇為固體時，炼點最好至少為* 〇。〇， 45至80°C更佳，特別是50至70°C，尤其是55至65Ό。 較佳的不飽和聚酯多元醇源於不飽和二羧酸和二聚脂二 醇的反應。二羧酸宜為馬來酸酐，其含量之重量百分比最 好為1至15 wt%，6.5至13 Wt%更佳，特別是8sU _% ; 二聚脂二醇，例如PripolTM 2〇33 (Uni^ma公司生產），之 δ里重里百分比隶好為85至99 wt%，87至93.5 wt%更佳， 特別是89至92 wt%。 另一種較佳的不飽和聚酯多元醇源於不飽和二緩酸、二 聚脂肪酸和多元醇的反應。二羧酸最好為馬來酸酐，其含 里重里百分比隶好為1至45 wt°/〇之範圍内，1〇至35 wt〇/。更 佳’特別是10至25 wt% ;二聚脂肪酸，例如ρΗρ〇ιΤΜ l〇〇6(Uniqema公司生產）之含量重量百分比最好為5至85 wt。/。之範圍内，10到75 wt%更佳，特別是3〇至65〜％;多 兀醇宜為1，3-丙二醇，其含量重量百分比最好為 127030.doc -12 - 200848447Product properties (eg, children's ester binders, polyurethane seals for automotive applications, industrial coatings, wood coatings and adhesives, flooring, insulators, elastomeric soles, skate wheels, etc. Toughness and flexibility) can be selected, for example, through Polyols 127030.doc Type 200848447 and polyols are widely adjusted in ratio to isocyanate (iv). Polyurethanes derived from saturated polyester polyols have good adhesion to a variety of substrates, are less flexible than polyether-based polyurethanes, have good thermal oxidation stability, but are less resistant to hydrolysis. The hydroxyl group-containing (fluorenyl)acrylic monomer can be polymerized/copolymerized with a vinyl monomer and an acrylic monomer to form an intermediate polymer. The hydroxyl group of the intermediate polymer reacts with the polyisocyanate to form a polyurethane having two cure points, namely an amino phthalate functional group (isocyanate) and methacrylate unsaturated, which can be cured by reaction with moisture and ultraviolet light, respectively. . These materials have different properties compared to materials with only one cure point, such as increased wet strength, increased adhesion, increased shear adhesion damage temperature, increased coating hardness, coatings, adhesives, elastomers, and hair. The modulus and toughness of the foam are improved. In addition, the application viscosity may decrease. A disadvantage of the method of forming a polyurethane having two fixed points is that free acrylic monomer residues are present before curing occurs. These monomers are volatile and require precautions to safely handle them. It is known that acrylic monomers cause irritation to the skin, eyes, nose, throat and respiratory tract. SUMMARY OF THE INVENTION We have discovered an unsaturated polyester polyol and its use in a wide range of polymer applications that reduce or substantially overcome at least one of the above problems. Thus, the present invention provides an unsaturated polyester polyol comprising at least 2 mercapto groups and having a value of from 1 1 to 225 mg KOH/g, the invention comprising a reaction product of at least one diweiling acid and at least one polyol, wherein At least one of the acid and the polyol includes a dimer fatty acid and/or a dimer diol. 127030.doc 200848447 The invention further provides a process for the preparation of an unsaturated polyhydric polyol having a hydroxyl number of from 11 to 225 mg K〇H/g, comprising 1:1 · 由 from at least one dicarboxylic acid and at least one polyol A molar ratio of 1 to 5·〇, wherein the acid and the polyol to y include a dimer fatty acid and/or a dimer diol. The invention further comprises a polyurethane which is obtained by reacting (1) a polyisocyanate, (ii) an unsaturated polyester polyol, (optional) (iii) a chain extender to obtain 'in which the polyglycol polyol has at least two hydroxyl groups, and The hydroxyl number is from 丨丨 to 225 mgKOH/g, which comprises the reaction product of at least one dicarboxylic acid and at least one polyol, wherein at least one of the acid and the polyol comprises a dimerized fatty acid and/or a dimer diol. The invention further provides the use of an unsaturated polyester polyol as defined herein as a constituent block for forming a polyurethane, wherein the polyurethane form is a foam, an elastomer, a coating, an adhesive, a coating or A hooking liquid or a thermoplastic material of the subsequent agent. The present invention further provides a polymer comprising (1) an olefinic unsaturated group, (u) a group capable of reacting in the presence of water, (iii) a dimerized fatty acid and/or a polyester II. The reaction product of an alcohol. The invention further provides a copolymerization comprising - a hard segment and a soft segment, wherein the soft segment comprises an unsaturated poly s-defined polyol as defined herein. The invention further provides a polyester guanamine copolymer comprising at least one hard segment comprising at least one guanamine linkage and at least one soft bond segment comprising an unsaturated polyester polyol as defined herein. Unsaturated polyglycol polyols include the reaction of an unsaturated dicarboxylic acid and/or a polyol, which is preferably a carbon-bond. ^鲜二叛酸127030.doc 200848447 Preferably, at least one selected from the group consisting of maleic acid, fumaric acid, itaconic acid and its esters and anhydrides; preferably maleic acid, fumaric acid and Anhydride. Particularly preferred is maleic anhydride. The unsaturated polyester polyol according to the invention comprises the reaction product of at least one dimerized fatty acid and/or <RTIgt; The term dimerized fatty acid is art-relevant and refers to a dimerization product of a monounsaturated fatty acid or a polyunsaturated fatty acid and/or an ester thereof. Preferred dimer fatty acids are dimers containing from 0:1 () to Cw carbon atoms, more preferably from Cl2 to c24 carbon atoms, specifically from Cm to CM carbon atoms, especially Cl8 carbon atoms Burning base chain. Suitable dimerized fatty acids include dimerization products of oleic acid, linoleic acid, linolenic acid, palmitoleic acid and elaidic acid. It is also possible to use a dimerization product of an unsaturated fatty acid mixture obtained by hydrolysis of natural oils such as sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and pine oil. It is also possible to use dimerized fatty acids which are hydrogenated, for example, using a nickel catalyst. In addition to dimerized fatty acids, dimerization usually produces different amounts of oligo-fatty acids (so-called π dimers), and there are monomeric fatty acids (so-called, monomers) or their ester residues. The number of monomers can be Reduced by, for example, steaming. Suitable dimer fatty acids have a dimer acid content greater than 6 〇 wt%, preferably greater than 75 wt%, more preferably in the range of 90 to 99.5 wt%, specifically 92 to 99 wt% , especially 95 to 98 Wt%. The content of the trimer is preferably less than 4% by weight, the range of 0.01 to 25 wt ° / 〇 is better, and the ratio of 0 05 to 15 wt% is more preferable, specifically 0.1 to 5 wt%. In particular, it is 1 to 4 wt%. The monomer content is preferably less than 1% by weight, and the range of 〇·〇1 to 5 wt% is more preferable, especially, especially 0.05 to 0.4% by weight. The percentage values are based on the total content of terpolymer, 127030.doc 200848447 polymer and monomer. Dimer diol can be produced by hydrogenation of the corresponding dimerized fatty acid. The polyglycol content is more than 6 〇 wt%, more preferably than wt%, more preferably 90 to 99.5 wt%, specifically 93 to 99 wt%, especially 94 to 98. Wt%. The content of the trimer is preferably less than 4% by weight, the range of 〇·〇1 to 25 wt% is better, and the range of 〇·〇5 to 15 wt% is better, specifically 〇·ι to 5 wt% ' Especially 〇·5 to 3 wt%. The monomer content is preferably less than 10 wt%, and the range of 〇" to 5 wt% is more preferable, especially 〇·3 to 4 wt%, especially (^ to ^ k ' Wt%. All of the above weight percentage values are based on the total content of trimer, dimer and monomer. If dimerdiol is not present in the unsaturated polyester polyol according to the invention (ie use In the case of a dimerized fatty acid, at least one polyol other than the dimer diol is used. In addition to the dimer diol, other polyols may be used. At least one other polyol preferably has a molecular weight of less than 4 Å. Preferably, less than y 3 , is preferred, less than 200 is more preferred, specifically 48 to 16 Å, especially "to 120. At least one other polyol is preferably selected from the group consisting of pentaerythritol, glycerol, dimethylolpropane, and ethylene. Alcohol, diethylene glycol, -propylene glycol, hydrazine, 3_ • propylene glycol, dipropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, 3-mercapto a group of alcohol, 1' bis(fluorenyl)cyclohexane, hydrazine-cyclohexane-dimethanol. Particularly preferred other polyols are glycols such as ethylene glycol, diethylene glycol,丨, 2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, hexanediol, neopentyl glycol, 3-methylpentanediol, 1,4-mono(hydroxymethyl) 3⁄4 hexane, hydrazine, 4_cyclohexane-dimethanol and mixtures thereof. 127030.doc -10- 200848447 Particularly preferred are ethylene glycol, diethylene glycol, 1,2-propanediol, propylene glycol, dipropylene glycol, hydrazine- Butylene glycol, 1,6-hexanediol, and mixtures thereof. The unsaturated polyester polyols according to the present invention can be produced using the dimerized fatty acids described herein and the dibasic acids other than the unsaturated dicarboxylic acids. Preferably, it is an aliphatic dicarboxylic acid, and a suitable saturated acid is selected from the group consisting of adipic acid, glutaric acid, succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptane dicarboxylic acid, Octane bis-acid, bismuth diteric acid, simmering acid, sputum, diteric acid, twelfth sulphuric acid and its higher carbon homologues and mixtures thereof. Other preferred diacids include adipic acid, sebacic acid, sebacic acid and mixtures thereof. Both ends of the unsaturated polyester polyol according to the present invention are preferably terminated with a hydroxyl group. Therefore, the molar number of the polyol is better than the two. The unsaturated polyester polyol is preferably formed from a dicarboxylic acid and a polyhydric alcohol (preferably a diol), and the molar ratio of the starting material is from 1:1.01 to 5.0, preferably from 1:1:1 to 4.0, 1: More preferably from 1.2 to 30, especially from 1:1.4 to 2.0, especially from 1:1.5 to 1.7. The unsaturated polyester polyol preferably has a number average molecular weight of from 500 to 10,000, preferably from 600 to 8,000, more preferably from 800 to 6,000, particularly from 9 to 5,000, especially from ι to 4 to 4, 〇〇〇 . The unsaturated polyglycol polyol preferably comprises an average of less than 88 ester linkages, more preferably from i to 45, especially from 2 to 25, especially from 3 to 15. Further, the polyacetate preferably comprises on average (1) 1 to 15 dimer residues, more preferably 1 to 1 ,, especially 疋 2 to 6 'especially 2 to 5; and/or (ϋ) less For 44 carbon double bonds, j to 26 are better 'especially 2 to 20, especially 3 to 10. The unsaturated polyester polyol preferably has a hydroxyl value in the range of from 4 to 190 mgKOH/g, more preferably from 20 to 14 mgK〇H/g, especially from 3 to 127030.doc 200848447 mgKOH/g' especially 35 Up to 12〇mgK〇H/g. In addition, the acid value of the polyester is preferably less than 3.0, less than! Preferably, it is less than 丨3, particularly less than 1 〇 mgKOH/g, and/or the water content is less than 〇·5%, more preferably less than 0.2%, especially less than 〇.1〇/. . The unsaturated polyester polyol at room temperature (25 ° C) may be a liquid or a (semi)crystalline solid, preferably a liquid. When the unsaturated polyglycol polyol is a liquid, the dynamic dryness at 25t is preferably from 4,000 to 100,000, preferably from 〇〇〇 to 8〇5, especially from 8,000 to 70,000, especially 10 , 〇〇〇 to 65, 〇〇〇. § Unsaturated ♦ When the S 曰 polyol is a solid, the refining point is preferably at least * 〇. 〇, 45 to 80 ° C is more preferable, especially 50 to 70 ° C, especially 55 to 65 Ό. Preferred unsaturated polyester polyols result from the reaction of an unsaturated dicarboxylic acid and a dimer diol. The dicarboxylic acid is preferably maleic anhydride, preferably in an amount of from 1 to 15% by weight, more preferably from 6.5 to 13 Wt%, especially 8 sU _%; dimer diol, such as PripolTM 2〇33 (Uni ^ma company produces), the δ liter percentage is preferably 85 to 99 wt%, 87 to 93.5 wt% is better, especially 89 to 92 wt%. Another preferred unsaturated polyester polyol results from the reaction of an unsaturated dibasic acid, a dimerized fatty acid, and a polyol. The dicarboxylic acid is preferably maleic anhydride, and the percentage of the weight of the dicarboxylic acid is in the range of from 1 to 45 wt ° / ,, from 1 35 to 35 wt 〇 /. More preferably, it is particularly 10 to 25 wt%; the dimerized fatty acid, for example, ρΗρ〇ιΤΜ l〇〇6 (manufactured by Uniqema Co., Ltd.) is preferably contained in an amount of 5 to 85 wt%. /. In the range, 10 to 75 wt% is more preferable, especially 3 to 65 to %; the polyterpene alcohol is preferably 1,3-propanediol, and the content by weight is preferably 127030.doc -12 - 200848447
Wt%，10至5〇Wt%更佳，特別是15至30wt%。 另一種較佳不飽和聚酯多元醇源於不飽和二羧酸、二聚 月曰一醇和多70醇的反應。二羧酸最好為馬來酸酐，其含量 重里百分比最好為1至45 wt%之範圍内，1〇至4〇 wt%更 仫，特別是20至30 wt%;二聚脂二醇，例如Prip〇iTM 2〇33 (Uniqema公司生產），之含量重量百分比最好為5至85 之範圍内’ 10到75 wt%更佳，特別是25至60 wt% ;多元醇 宜為1，3-丙二醇，其含量重量百分比最好為1至55 wt%之範 圍内’ 10至50 wt%更佳，特別是15至45 wt〇/〇 ; 除了含不飽和或含二聚物之物質以外，使用其他二緩酸 和多元醇可使如羥值、分子量和不飽和度等性質彼此獨立 地變化。 例如羥值1 00的不飽和聚酯可源於（i) 7.2%的馬來酸酐 (MA)、21.4%的丙二醇（PG)和71.4%的二聚脂肪酸 (DFA)(最好為 Prip〇lTM 1〇〇6) ; (ii) 11% MA、23.5% PG和 65·5°/〇 DFA;(iii) 10.4% ΜΑ、32.6% PG、28.5% 己二酸和 28.5% DFA;(iv) 8% ΜΑ、32% PG、30% 己二酸和 30% DFA;(v) 46% ΜΑ、27% PG 和 27% 二聚脂二醇（DFD) (最好為 PripolTM 2033) ; (vi) 46% ΜΑ、38% PG 和 16% DFD 〇 此外，羥值為35 mgKOH/g的不飽和聚酯可源自於⑴ 7.5% ΜΑ、17.9% PG和 74·6% DFA ; (ii) 11·6% ΜΑ、20.4% ?0和68%0卩八;（^〇8-6%1^八、29.1%?〇、31.1%己二酸 和 31.2% DFA;(iv) 10.9% ΜΑ、29.9% PG、 29.6% 己二酸 127030.doc -13- 200848447 55% DFD;及（vi) 和 29.6% DFA;(V) 26% MA、19% PG 和 48% ΜΑ、37% PG和 15% DFD。 根據本發明聚胺酯可透過 钦異亂酸酯、本文所定義之不 飽和聚酯多元醇和可視雷Iμ μ 吁τ』祝而要璉用的增鏈劑反應來獲得。例 如水δ旨可以是一種塗層或用於淨思斗、括— 土曰4用於塗層或接著劑的勻散液、 一種彈性體、一種埶可领柯从 > ,,..ηη 裡…』塑性物，例如橡膠或接著劑，或一 種發泡體。Wt%, 10 to 5 〇 Wt% is more preferable, particularly 15 to 30% by weight. Another preferred unsaturated polyester polyol results from the reaction of an unsaturated dicarboxylic acid, a dimercaptol alcohol, and a polyhydric alcohol. The dicarboxylic acid is preferably maleic anhydride, and the content thereof is preferably in the range of from 1 to 45 wt%, from 1 to 4 wt%, more particularly from 20 to 30 wt%; dimerdiol, For example, Prip〇iTM 2〇33 (manufactured by Uniqema), the content by weight is preferably in the range of 5 to 85, preferably 10 to 75 wt%, particularly 25 to 60 wt%; and the polyol is preferably 1,3. - propylene glycol, preferably in a range of from 1 to 55% by weight, more preferably from 10 to 50% by weight, particularly preferably from 15 to 45% by weight; in addition to substances containing an unsaturated or dimer-containing substance, The use of other diacids and polyols allows properties such as hydroxyl number, molecular weight and unsaturation to vary independently of one another. For example, an unsaturated polyester having a hydroxyl number of 100 may be derived from (i) 7.2% maleic anhydride (MA), 21.4% propylene glycol (PG), and 71.4% dimer fatty acid (DFA) (preferably Prip〇lTM). 1〇〇6) ; (ii) 11% MA, 23.5% PG and 65·5°/〇DFA; (iii) 10.4% ΜΑ, 32.6% PG, 28.5% adipic acid and 28.5% DFA; (iv) 8 % ΜΑ, 32% PG, 30% adipic acid and 30% DFA; (v) 46% ΜΑ, 27% PG and 27% dimer diol (DFD) (preferably PripolTM 2033); (vi) 46 % ΜΑ, 38% PG and 16% DFD 〇 In addition, unsaturated polyesters with a hydroxyl value of 35 mg KOH/g can be derived from (1) 7.5% ΜΑ, 17.9% PG and 74.6% DFA; (ii) 11·6 %ΜΑ, 20.4%?0 and 68%0卩8; (^〇8-6%1^8, 29.1%?〇, 31.1% adipic acid and 31.2% DFA; (iv) 10.9% ΜΑ, 29.9% PG 29.6% adipic acid 127030.doc -13- 200848447 55% DFD; and (vi) and 29.6% DFA; (V) 26% MA, 19% PG and 48% bismuth, 37% PG and 15% DFD. The polyurethane of the present invention can be obtained by reacting a chaotic acid ester, an unsaturated polyester polyol as defined herein, and a chain extender which can be used as a visual ray. For example, water δ can be a coating. For the net thinking, including - the soil layer 4 is used for the coating or the dispersion of the dispersion, an elastomer, a kind of 埶, 柯 柯 & 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 』 Agent, or a foam.
聚異氛酸醋最好至少是一種官能度至少為2的異氰酸 醋’且可以是-種脂肪族異氰酸醋，％ :六亞甲基^.二 異氰酸酯，但更佳的是芳香族異氰酸酯，如：伸甲苯基二 異氰酸酯（TDI)、鄰-伸苯基二異氰酸酯、對-伸苯基二異氰 酸醋、苯二甲基二異氰酸醋、4,4，_二苯甲院二異氰酸醋 (MDI)、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯 (IPDI)、3,3，-二曱基_4,4，-伸聯苯基二異氣酸酉旨、3,3，_二甲 基-4,4 - 一苯基甲烷二異氰酸醋、3,3，-二氣_4,4，_伸聯苯基 二異氰酸酯、1，5—萘二異氰酸酯或及其經修飾化合物， 如：經脲酮亞胺修飾之化合物。聚異氰酸醋單體能單獨使 用或作為混合物使用。較佳實施例中，使用（經修識 之）4,4’-二苯甲烷二異氰酸酯（Mm)、伸曱苯基二異氰酸酯 (TDI)及/或異佛爾酮二異氰酸酯（IpDI)。 在本發明一項實施例中，由至少一種上述聚異氰酸酯與 至少一種上述不飽和聚酯多元醇反應形成一種預聚物。混 合在一起反應形成預聚物之聚異氰酸酯與不飽和聚酯起始 物之莫耳比率最好為20至80% : 20至80%之範圍内，35至 127030.doc -14- 200848447 75/0.25至65%更佳，特別是45至鳩·川至训，尤其是^ 至70%.30至45%。聚異氛酸酿之莫耳用量最好超過聚醋的 土胃團莫耳3里，以獲得包含以異氰酸酯封端的預聚物 足里的未反應*異氰酸g旨之反應混合物；因此後來再加 ' $曰鏈」此引起形成聚胺酯的反應，不需要再添加聚 異氰酸酯。 預聚物反應混合物的異氰酸g旨含量範圍最好為。至15% 的 NCO，〇.1 至 8%爭 /土 仏’特別是〇·5至4%，尤其是1.5至 * 1 3.5% 〇 &其他的單體，如：丙烯酸或丙烯酸S旨可以併入聚胺酉旨預 來物中，/或該預聚物可以與其他聚合物（如丙稀酸混 合。 預♦物可以用於例如：製造聚胺酯勻散液、熱可塑性聚 胺酯和聚胺酯發泡體。 :於製造聚胺酯勻散液時，在分散到水中之前或之後之 C，予:來物可能需要增鏈。如果不用增鏈劑，不飽和聚酯多元 醇之莫耳用置要倡獗異氰酸醋莫耳用量，以獲得以經基封 ❿之聚合物’產生非反應性聚胺酯。預聚物反應混合物的 一氰馱自曰含里範圍最好為〇至6%的Nc〇，〇 2至5%更佳， ’ 寺别疋0.5至4/〇 ’尤其是2至3.5%。用於非反應性聚胺醋句 散液之異氰酸酯含量最好為0〇/〇。 本文所述聚胺自旨句散液可以與其他聚合㈣散液混合， J汝·與水乙酸乙烯酯、聚乙酸乙烯酯-乙烯或聚丙烯酸 龍勻散液混合。 127〇3〇.d〇c •15· 200848447 用於熱可塑性聚胺酯時，用於混合在一起反應形成預聚 物之聚異氰酸酯與不飽和聚酯多元醇起始物之莫耳比率最 好為20至80% : 20至80%之範圍内，25至65%:35至75%更 佳，特別是30至55%:45至70%，尤其是30至50%:50至 70% 〇 預聚物可以增鏈。熱可塑性聚胺酯的起始物可以在最終 產品的模具中反應。此時，由可視需要選用的增鏈劑反應 進入聚胺酯。聚酯的莫耳用量最好超過或幾乎相當於聚異 氰酸酯的NCO莫耳含量，幾乎沒有異氰酸酯活性基團可進 行濕固化。 用於聚胺酯發泡體時，水通常包括在反應混合物中以促 進氣泡形成，氣泡的成因是水與異氰酸酯反應生成二氧化 碳氣體。彈性發泡體通常使用2至3%的水。硬質發泡體則 使較少水，但可以加入其他起泡劑。用於混合在_起反應 形成預聚物之聚異氰酸g旨與不飽和聚自旨多元醇起始物之莫 耳比率最好為20至80%比20至80%之範圍内，25至65%·35 至75%更佳，特別是30至55%:45至70%，尤其是3〇至 45%:5 5至70%。可調整聚異氰酸酯與聚酯的比率，以便於 調配物中的水與聚異氰酸酯反應，剩下足量的異氰酸酿活 性基團與聚酯反應。在與調配物中的水反應而減少nc〇數 量後，聚醋的莫耳數最好超過或幾乎相當於聚異氰酸酿的 NCO莫耳含量，幾乎沒有剩下異氰酸酯活性基團可 、、蟁 固化。 订、"、，、 可用於形成根據本發明聚胺酯之增鏈劑組分宜包括具有 2個或2個以上活性氫基的低分子化合物，例如多元醇有 如：乙二醇、二甘醇、丙二醇、丨，扣丁二醇、丨，5_戊二 127030.doc -16- 200848447 醇、甲基戊二醇、1，6-己二醇、新戊二醇、三羥甲基丙 烷、對苯二酚醚烷氧基化物、間苯二酚醚烷氧基化物、丙 三醇、季戊四醇、雙甘油、葡萄糖和14:3,6雙脫水己糖 醇，如·雙脫水甘路醇、異山梨糖醇和二脫水艾杜糖醇 (isoidide);脂肪族多元胺，如：乙二胺、六甲基二胺和異 氟爾酮二胺；芳族多元胺，如：亞甲基雙（2_氣苯胺）、亞 甲基雙（二丙苯胺）、二乙基曱苯二胺、丙二醇二_對_胺基Preferably, the polyisocyanuric acid vinegar is at least one isocyanate vinegar having a functionality of at least 2 and may be an aliphatic isocyanate vinegar, %: hexamethylene^.diisocyanate, but more preferably aromatic Isocyanates, such as: tolyl diisocyanate (TDI), o-phenylene diisocyanate, p-phenylene diisocyanate, benzodimethylisocyanate, 4,4, benzene A hospital diisocyanate (MDI), hexamethylene diisocyanate, isophorone diisocyanate (IPDI), 3,3,-dimercapto-4,4,-strandyl diisoxamic acid酉, 3,3,_Dimethyl-4,4-phenylene methane diisocyanate, 3,3,-digas _4,4,_Exbiphenyl diisocyanate, 1,5- Naphthalene diisocyanate or a modified compound thereof, such as a compound modified with uretonimine. The polyisocyanate monomer can be used alone or as a mixture. In a preferred embodiment, (modified) 4,4'-diphenylmethane diisocyanate (Mm), phenylene diisocyanate (TDI) and/or isophorone diisocyanate (IpDI) are used. In one embodiment of the invention, at least one of the above polyisocyanates is reacted with at least one of the above unsaturated polyester polyols to form a prepolymer. The molar ratio of the polyisocyanate and the unsaturated polyester starting material which are mixed together to form the prepolymer is preferably from 20 to 80%: from 20 to 80%, from 35 to 127030.doc -14 to 200848447 75/ 0.25 to 65% is better, especially 45 to 鸠·chuan to training, especially ^ to 70%. 30 to 45%. The polyiso-acidic acid is preferably used in an amount of more than the vinegar of the vinegar to obtain a reaction mixture containing the unreacted *isocyanate g of the isocyanate-terminated prepolymer; therefore Adding a '$曰 chain" causes a reaction to form a polyurethane, and no additional polyisocyanate is required. The isocyanate g content of the prepolymer reaction mixture preferably ranges. Up to 15% of NCO, 〇.1 to 8% contend / bandit 'especially 〇·5 to 4%, especially 1.5 to * 1 3.5% 〇& other monomers, such as: acrylic or acrylic S Incorporating into the polyamine precursor, and/or the prepolymer can be mixed with other polymers such as acrylic acid. The pre-form can be used, for example, to manufacture polyurethane dispersion, thermoplastic polyurethane and polyurethane foam. In the production of polyurethane homogenate, before or after dispersing into water, C: The material may need to be chain extended. If the chain extender is not used, the use of unsaturated polyester polyols is advocated. The amount of isocyanate used to obtain the non-reactive polyurethane of the base-blocked polymer. The prepolymer of the prepolymer reaction mixture has a range of from 〇 to 6% of Nc〇. 〇 2 to 5% is better, 'Temple 疋 0.5 to 4 〇 尤其' is especially 2 to 3.5%. The isocyanate content for the non-reactive polyamine vinegar dispersion is preferably 0 〇 / 〇. Polyamine can be mixed with other polymeric (four) dispersions, J汝· with water vinyl acetate, polyvinyl acetate-ethylene or poly Acrylic Longyun Dispersion Mixing 127〇3〇.d〇c •15· 200848447 For thermoplastic polyurethanes, the polyisocyanate and unsaturated polyester polyol starting materials used to react together to form a prepolymer The molar ratio is preferably from 20 to 80%: from 20 to 80%, from 25 to 65%: from 35 to 75%, especially from 30 to 55%: from 45 to 70%, especially from 30 to 50%: 50 to 70% of the ruthenium prepolymer can be chain extended. The starting material of the thermoplastic polyurethane can be reacted in the mold of the final product. At this time, the chain extender which can be optionally used is reacted into the polyurethane. The molar amount of the polyester is the most It is better or almost equivalent to the NCO molar content of polyisocyanate, and almost no isocyanate reactive groups can be moisture-cured. When used in polyurethane foams, water is usually included in the reaction mixture to promote bubble formation, and the cause of bubbles is water. It reacts with isocyanate to form carbon dioxide gas. The elastic foam usually uses 2 to 3% of water. The rigid foam makes less water, but other foaming agents can be added for mixing to form a prepolymer. Polyisocyanate g and unsaturated The molar ratio of the polyhydric alcohol starting material is preferably in the range of 20 to 80% to 20 to 80%, more preferably 25 to 65%·35 to 75%, particularly 30 to 55%: 45 to 70. %, especially 3〇 to 45%: 5 5 to 70%. The ratio of polyisocyanate to polyester can be adjusted to facilitate the reaction of water in the formulation with the polyisocyanate, leaving a sufficient amount of isocyanate-reactive groups Reacts with the polyester. After reacting with the water in the formulation to reduce the amount of nc〇, the molar number of the vinegar preferably exceeds or almost corresponds to the NCO molar content of the polyisocyanate, and almost no isocyanate activity remains. The group can be cured. The composition of the chain extender which can be used to form the polyurethane according to the present invention preferably comprises a low molecular compound having two or more active hydrogen groups, such as a glycol such as ethylene glycol or diethylene glycol. Propylene glycol, hydrazine, butane diol, hydrazine, 5_ pentane 127030.doc -16- 200848447 alcohol, methyl pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, pair Dihydroxybenzene ether alkoxylate, resorcinol ether alkoxylate, glycerol, pentaerythritol, diglycerin, glucose and 14:3,6 dianhydrohexitol, such as · dianhydroglycol, different Sorbitol and diced iodide; aliphatic polyamines such as ethylenediamine, hexamethyldiamine and isophorone diamine; aromatic polyamines such as methylene bis (2) _ gas aniline), methylene bis(dipropylaniline), diethyl phenylenediamine, propylene glycol di-p-amino group
苯甲酸；燒醇胺類，如：二乙醇胺、三乙醇胺和二異丙醇 胺；及聚氧伸烧基胺類。 本發明一項實施例中，不飽和聚酯多元醇可以與增鏈劑 一起加入反應以形成聚胺酯。所用的不飽和聚酯多元醇可 以與用於形成預聚合物的不飽和聚酯多元醇相同或不同。 相對於不飽和聚酯多元醇，增鏈劑的用量最好為〇至8〇 wt%之範圍内，〇至50 wt%更佳，特別是〇至3〇 ，尤其 是0至1 5 wt%，用量取決於各應用所需的性質。 本文所述的不飽和聚酯多元醇之用途意指其具有兩個固 化點，以加強根據本發明聚胺酯的性能。例如聚胺酯塗層 可以具有改善的硬度、耐久性和抗刮力、耐熱性和耐溶劑 性及/或良好的加工性能。聚胺酯彈性體可以具有改善的 耐熱性和耐溶劑性。 根據本發明不飽和聚酯多元醇也可以用作形成聚胺酯以 外之聚合物的構成嵌段，其也含有能夠在水分存在下反應 的基團，例如·烧氧矽烷基。不飽和聚酯多元醇可例如： /、種烧氧石夕烧反應以形成具有兩個固化點（即濕固化和 127030.doc -17- 200848447 紫外線固化）的聚羥基矽烷聚合物。在一個實施例中，不 飽和聚酯多元醇形成的聚合物可以同時包括烷氧矽烷和胺 基曱酸酯兩個基團。 不飽和聚酯多元醇可以用作形成其他聚合物（如：聚酯 共聚物和聚酯醯胺共聚物）的構成嵌段。 因此，本發明的另一個實施例是一種共聚酯，最好為嵌 段共聚物’其包括一個硬鏈段和一個軟鏈段，其中軟鏈段 含有本文所定義的不飽和聚酯多元醇。 共聚酯硬鏈段的組成可在很大範圍内變化。硬鏈段最好 為芳族聚醋。用於形成硬鏈段的合適芳族二羧酸及/或其 醋衍生物包括對苯二甲酸、間苯二甲酸、萘二甲酸、聯苯 二羧酸或其混合物。以對苯二甲酸及/或其酯衍生物特別 佳。硬鏈段最好由超過50 m〇1%W芳族二羧酸及/或其酯衍 生物形成，超過70 mol%更佳，特別是超過90 mol%，尤其 是超過95 mol%至1〇〇 mol%。其餘（補足1〇〇 m〇1%)之二羧 酸（如果有的話）最好由脂肪族二羧酸，如：己二酸、癸二 酸或環己烷二羧酸組成。 用於形成硬鏈段的合適二醇或乙二醇包括脂肪族二醇， 如：乙二醇、1，3-丙二醇、M-丁二醇、1，6_己二醇、新 戊二醇、丙二醇、丁二醇和環己烷二甲醇，或芳族二醇， 如：2,2-雙（4-羥苯基）丙烷。硬鏈段最好由超過5〇 ， 較佳地超過70 mol%，特別是超過9〇 m〇1%，尤其是超過 95瓜〇1%至100瓜〇1%的脂肪族乙二醇，最好是乙二醇及/或 1，4-丁二醇形成。 127030.doc -18· 200848447 酿、聚對苯二曱酸伸乙基酯、聚萘曱酸伸乙基酯或其混合 物，尤其是聚對苯二甲酸伸丁基酯。 硬鏈段的數量平均分子量較佳地為1，000至3〇,〇〇〇，更佳 地為2,000至15,000，特別是2,500至1〇,〇〇〇，尤其是3,000 至 5,000 〇 硬鏈段的熔點（Tm)較佳地為200至280°C，更佳地為210 至270°C，特別是215至255t，尤其是220至23(TC。Benzoic acid; alkanolamines such as diethanolamine, triethanolamine and diisopropanolamine; and polyoxyalkylene amines. In one embodiment of the invention, the unsaturated polyester polyol can be added to the reaction with a chain extender to form a polyurethane. The unsaturated polyester polyol used may be the same as or different from the unsaturated polyester polyol used to form the prepolymer. The chain extender is preferably used in an amount of from 〇 to 8% by weight, more preferably from 50% by weight, particularly 〇 to 3 Å, especially from 0 to 5% by weight, based on the unsaturated polyester polyol. The amount depends on the properties required for each application. The use of the unsaturated polyester polyols described herein means that it has two cure points to enhance the properties of the polyurethanes according to the present invention. For example, the polyurethane coating may have improved hardness, durability and scratch resistance, heat resistance and solvent resistance, and/or good processability. The polyurethane elastomer may have improved heat resistance and solvent resistance. The unsaturated polyester polyol according to the present invention can also be used as a constituent block of a polymer other than the polyurethane, which also contains a group capable of reacting in the presence of moisture, for example, a pyrithione group. The unsaturated polyester polyol can be, for example, a perovskite reaction to form a polyhydroxydecane polymer having two cure points (i.e., moisture cure and 127030.doc -17-200848447 UV cure). In one embodiment, the polymer formed from the unsaturated polyester polyol may include both alkoxysilane and amino phthalate groups. The unsaturated polyester polyol can be used as a constituent block for forming other polymers such as a polyester copolymer and a polyester decylamine copolymer. Accordingly, another embodiment of the present invention is a copolyester, preferably a block copolymer comprising a hard segment and a soft segment, wherein the soft segment comprises an unsaturated polyester polyol as defined herein. . The composition of the copolyester hard segments can vary over a wide range. The hard segment is preferably an aromatic polyester. Suitable aromatic dicarboxylic acids and/or vinegar derivatives thereof for forming the hard segments include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid or mixtures thereof. Terephthalic acid and/or its ester derivatives are particularly preferred. The hard segment is preferably formed from more than 50 m〇1% W of the aromatic dicarboxylic acid and/or its ester derivative, more preferably more than 70 mol%, especially more than 90 mol%, especially more than 95 mol% to 1〇 〇mol%. The remainder (complementing 1 〇〇 m 〇 1%) of the dicarboxylic acid, if any, preferably consists of an aliphatic dicarboxylic acid such as adipic acid, sebacic acid or cyclohexane dicarboxylic acid. Suitable diols or glycols for forming hard segments include aliphatic diols such as ethylene glycol, 1,3-propanediol, M-butylene glycol, 1,6-hexanediol, neopentyl glycol. , propylene glycol, butanediol and cyclohexane dimethanol, or an aromatic diol such as 2,2-bis(4-hydroxyphenyl)propane. Preferably, the hard segment is more than 5 Å, preferably more than 70 mol%, especially more than 9 〇m 〇 1%, especially more than 95 〇 1% to 100 〇 1% of aliphatic glycol, most It is good to form ethylene glycol and/or 1,4-butanediol. 127030.doc -18· 200848447 Stuffed, polyethylene terephthalate ethyl ester, polynaphthoic acid ethyl ester or mixtures thereof, especially polybutylene terephthalate. The number average molecular weight of the hard segment is preferably 1,000 to 3 Å, 〇〇〇, more preferably 2,000 to 15,000, particularly 2,500 to 1 〇, 〇〇〇, especially 3,000 to 5,000 〇 hard segments The melting point (Tm) is preferably from 200 to 280 ° C, more preferably from 210 to 270 ° C, especially from 215 to 255 t, especially from 220 to 23 (TC).
按重量百分比，共聚酯中之硬鏈段與軟鏈段比率較佳地 為1至20:1，更佳地為2至15··1，特別是3至1〇:1，尤其是4至 6:1。 共聚S旨的數量平均分子量較佳地為5,〇〇〇至ι〇〇,〇〇〇之範 圍内，更佳地為15,000至80,0〇〇，特別是25,〇〇〇至60,000， 尤其是 30,000 至 40,000。 共聚醋的熔點（Tm)較佳地為2〇〇至28〇t：i範圍内，更佳 地為210至265它，特別是215至245°C，尤其是220至225 t ;且/或共聚酯的玻璃態化溫度（丁§)為-8〇至_4〇r之範圍 内，更佳地是-70至-45°C，特別是_65至_5(rc，尤其是_6〇 至-55°C。 本文所述共聚酯可以用於許多應用領域，其中通常使用 熱可塑性彈性體，例如軸承和封條、帶子、絲和風箱、 盤繞軟管、強化外殼、電纜、電器開關及各類汽車部件。 另一個實施例是一種共聚酯醯胺，較佳地為嵌段共聚 物’、包括至沙一個含有至少一個醯胺鍵的硬鏈段和至少 一個含有本文所定義不飽和聚酯多元醇的軟鏈段。 127030.doc -19- 200848447 根據本發明共聚酯醯胺的硬鏈段包括至少一個，最好2 至3 5個，更佳地3至20個，特別是4至15個，尤其是5至10 個醯胺鍵。因此，硬鏈段較佳地為醯胺募聚醯胺或聚醯胺 (以下稱聚醯胺）。 共聚酯硬鏈段的組成可在很大範圍内變化。聚醯胺通常 由二羧酸與二元胺的縮合反應產生。 常用於形成聚醯胺之二羧酸有兩大類，即二聚脂肪酸和 非二聚脂肪酸。 本文描述了適合的二聚脂肪酸。適合的非二聚脂肪酸可 以是脂肪族或芳族，包括二羧酸及酯，其烷基酯較佳，最 好為末端羧基有2至20個碳原子、更佳地6至12個原子之碳 鏈之線形二羧酸，如：己二酸、庚二酸、辛二酸、壬二 酸、癸二酸、庚烷二羧酸、辛烷二羧酸、壬烷二羧酸、癸 烷二羧酸、十一烷二羧酸、十二烷二羧酸及其更高碳同系 物。 聚醯胺硬鏈段最好由二聚脂肪酸與非二聚脂肪酸形成，依 據一羧酸總重量計算，其較佳比率為〇至1〇〇%:〇至1〇〇%，更 佳地為50至1 〇〇%··〇至5〇%，特別是⑽至丨〇〇%:〇至2〇%。 適合的二元胺包括上述二羧酸之胺同等物，但通常以鏈 車乂短物質較佳，特別是彼等含有2至7個碳原子的物質。較 佳二元胺為如··乙二胺、丙二胺、嗣甲基二胺、五亞甲基 :胺、六亞甲基二胺及二聚脂二胺（源於二聚脂肪酸）。適 :的芳無—7C胺包括源於苯、甲苯及其他經取代的芳族物 貝如· 2,6-伸甲笨基二胺、4,4-二苯基甲烷二胺和 127030.doc -20- 200848447 f基二胺。其他適合的二元胺包括含有一至兩個第二胺基 的一元胺及雜環二元胺，如：旅°秦。也可以使用分支之二 元胺，如·· 3-甲基戊烷二胺。 聚醯胺也可以是不飽和的。例如，聚酿胺可以由不飽和 一魏酸形成，該二羧酸較佳地從馬來酸、富馬酸、衣康酸 及其醋和酸酐所組成群中至少選擇一種；最好是馬來酸、 富馬酸及其酸酐。特別佳的是馬來酸酐。 不飽和聚醯胺較佳地含有二聚脂肪酸及/或二聚脂二元 胺。可以產生視同與本文所述不飽和聚酯多元醇等效之不 飽和聚醯胺，其中多元胺（以二元胺較佳）可用於代替多元 醇。在與不飽和聚酯多元醇反應形成共聚酯醯胺之前，可 以單獨產生含有不飽和聚醯胺的二聚物。含有不飽和聚醯 胺的二聚物也可單獨用於與其他物質（例如：本文所述之 I異氰酸酯）反應形成聚合物，如：也兼具濕固化及紫外 線固化點之聚脲。 用於形成聚醯胺鏈段的二羧酸與二元胺起始物的比率較 佳地為1.0至5.0:1之範圍内，更佳地為1〇5至3〇:1，特別 疋1·1至2.0:1，尤其是12至14:1。聚醯胺的兩端較佳地由 羧基封端，特別是由本文所述二聚脂肪酸封端。 硬鏈段宜為一個嵌段，其數量平均分子量為5⑽至 15,〇〇〇之範圍内較佳，更佳地為“⑽至1〇,〇〇〇，特別是 1，500 至 6,〇〇〇，尤其是 2,〇〇〇 至 4〇〇〇。 硬鏈段的軟化點較佳地為6〇s2〇(rc之範圍内，65至丨5〇 C更佳，特別是70至i2yc，尤其是乃至丨⑼它。 127030.doc -21 - 200848447 按重量計算，共聚酯醯胺中之硬鏈段與軟鏈段比率較佳 地為1至2 5 :1之範圍内，更佳地為4至:丨，特別是6至 1 5 :1，尤其是8至1 〇: 1。 共聚酯醯胺的數量平均分子量較佳地為5,〇〇〇至8〇,〇〇〇之 範圍内’更佳地為10,000至50,000，特別是13,〇〇〇至 30,000，尤其是 15,〇〇〇 至 20,〇〇〇。 共聚醋醯胺的軟化點較佳地為6〇-2〇(rc之範圍内，更佳 地為65-15(TC，特別是7〇i12rc，尤其是乃至丨⑻它。及/ 或共聚酯醯胺的玻璃態化溫度（Tg)介於-6〇至〇它之範圍 内，更佳地是-50至-HTC，特別是_4〇s_2〇r，尤其是_35 至 25°C。 【實施方式】 本發明由以下非限定的實例說明。 在此說明書中，使用了以下試驗方法。 (i)用凝膠滲透色譜法測定（數量平均）分子量。 (π)羥值疋義為相當於1克樣本中羥基含量之氫氧化鉀毫 克數，且係由乙醯化後水解過量乙酸酐後測定。隨後以氫 氧化鉀之乙醇溶液滴定所形成的乙酸。 (in)酸值定義為中和丨克樣本中的游離脂肪酸所需氫氧化 鉀的耄克數，可以使用標準氫氧化鉀溶液直接滴定來測 量 ° (iv) 異氰酸酯（NC〇)值定義為樣品中的異氰酸酯重量百 分比，透過與過量的二丁胺反應並用鹽酸反滴定來測定。 (v) 動怨枯度使用布氏（Brookfield)流速計在25°C測定。 127030.doc -22- 200848447 method)進行 (Vi)含水率係依據卡爾·菲氏法（Kari_Fisehef 滴定來分析。 (vii)玻璃態化溫度（Tg)用# 、g;用差不掃描量熱法（DSC)用The ratio of hard segment to soft segment in the copolyester is preferably from 1 to 20:1, more preferably from 2 to 15·1, especially from 3 to 1 :1, especially 4, by weight. Until 6:1. The number average molecular weight of the copolymerization S is preferably from 5, 〇〇〇 to ι〇〇, within the range of 〇〇〇, more preferably from 15,000 to 80,0 Å, especially from 25, 〇〇〇 to 60,000, Especially 30,000 to 40,000. The melting point (Tm) of the copolymerized vinegar is preferably in the range of from 2 Å to 28 〇t:i, more preferably from 210 to 265, especially from 215 to 245 ° C, especially from 220 to 225 t; and/or The glass transition temperature of the copolyester (D) is in the range of -8 〇 to _4 〇r, more preferably -70 to -45 ° C, especially _65 to _5 (rc, especially _ 6〇 to -55°C. The copolyesters described herein can be used in many applications where thermoplastic elastomers such as bearings and seals, tapes, wires and bellows, coiled hoses, reinforced casings, cables, electrical appliances are commonly used. Switch and various types of automotive parts. Another embodiment is a copolyester guanamine, preferably a block copolymer', comprising to a sand having at least one guanamine bond, and at least one of which is defined herein. a soft segment of an unsaturated polyester polyol. 127030.doc -19- 200848447 The hard segment of the copolyester guanamine according to the invention comprises at least one, preferably 2 to 3 5, more preferably 3 to 20, In particular, 4 to 15, especially 5 to 10, amidoxime bonds. Therefore, the hard segment is preferably a guanamine polycondensed guanamine or polyamine (hereinafter referred to as polyamine) The composition of the copolyester hard segment can vary over a wide range. Polydecylamine is usually produced by the condensation reaction of a dicarboxylic acid with a diamine. The dicarboxylic acids commonly used to form polyamines have two major classes, namely, dimerization. Fatty acids and non-dimerized fatty acids. Suitable dimer fatty acids are described herein. Suitable non-dimerized fatty acids may be aliphatic or aromatic, including dicarboxylic acids and esters, preferably alkyl esters, preferably terminal carboxyl groups. a linear dicarboxylic acid having 2 to 20 carbon atoms, more preferably 6 to 12 carbon chains, such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, heptane dicarboxylate Acid, octane dicarboxylic acid, decane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid and higher carbon homologs. Polyurethane hard segment is preferably composed of The dimerized fatty acid is formed with the non-dimerized fatty acid, and the preferred ratio is from 〇 to 1% by weight, from 〇 to 1% by weight, more preferably from 50 to 1% by weight, based on the total weight of the monocarboxylic acid. Up to 5%, especially (10) to 丨〇〇%: 〇 to 〇%. Suitable diamines include the amine equivalents of the above dicarboxylic acids, but usually are short in chain rutting Preferably, especially those having 2 to 7 carbon atoms. Preferred diamines are such as ethylenediamine, propylenediamine, decylmethylamine, pentamethylene:amine, and hexa Methyl diamine and dimer aliphatic diamine (derived from dimerized fatty acids). Suitable: aryl-free 7C amines include benzene, toluene and other substituted aromatics such as bei 2,6-extension Diamine, 4,4-diphenylmethanediamine and 127030.doc -20- 200848447 f-diamine. Other suitable diamines include monoamines and heterocyclics containing one to two second amine groups. Amines, such as: brigade. It is also possible to use branched diamines such as 3-methylpentanediamine. Polyamides can also be unsaturated. For example, the polystyrene may be formed from an unsaturated mono-dicarboxylic acid, preferably at least one selected from the group consisting of maleic acid, fumaric acid, itaconic acid, and vinegar and anhydride; preferably a horse Acid, fumaric acid and its anhydride. Particularly preferred is maleic anhydride. The unsaturated polyamine preferably contains a dimerized fatty acid and/or a dimerized diamine. Unsaturated polyamines which are equivalent to the unsaturated polyester polyols described herein can be produced, with polyamines (preferably diamines) being used in place of the polyols. The dimer containing the unsaturated polyamine can be produced separately before it is reacted with the unsaturated polyester polyol to form the copolyester decylamine. Dimers containing unsaturated polyamines can also be used alone to react with other materials (e.g., I isocyanates described herein) to form polymers, such as polyureas which also have moisture cure and UV cure points. The ratio of the dicarboxylic acid to the diamine starting material used to form the polyamine segment is preferably in the range of 1.0 to 5.0:1, more preferably 1〇5 to 3〇:1, especially 疋1 • 1 to 2.0:1, especially 12 to 14:1. Both ends of the polyamine are preferably capped with a carboxyl group, particularly by a dimerized fatty acid as described herein. The hard segment is preferably a block having a number average molecular weight of 5 (10) to 15 and preferably in the range of 〇〇〇, more preferably "(10) to 1 〇, 〇〇〇, especially 1,500 to 6, 〇 〇〇, especially 2, 〇〇〇 to 4 〇〇〇. The softening point of the hard segment is preferably 6 〇 s2 〇 (in the range of rc, 65 to 丨 5 〇 C is better, especially 70 to i2 yc , especially even 丨 (9) it. 127030.doc -21 - 200848447 The ratio of hard segment to soft segment in the copolyester guanamine is preferably in the range of 1 to 2 5:1 by weight, more preferably The ground is 4 to: 丨, especially 6 to 15:1, especially 8 to 1 〇: 1. The number average molecular weight of the copolyester guanamine is preferably 5, 〇〇〇 to 8 〇, 〇〇〇 Within the range of 'more preferably 10,000 to 50,000, especially 13, 〇〇〇 to 30,000, especially 15, 〇〇〇 to 20, 〇〇〇. The softening point of the copolymerized acetamide is preferably 6 〇 - 2 〇 (in the range of rc, more preferably 65-15 (TC, especially 7〇i12rc, especially even 丨 (8) it. And / or copolyester decylamine glass transition temperature (Tg) between - 6〇 to its range, more preferably -50 to -HTC, especially Further, it is _4 〇 s_2 〇 r, especially _35 to 25 ° C. [Embodiment] The present invention is illustrated by the following non-limiting examples. In this specification, the following test methods are used. (i) Gel penetration Chromatographic determination of (quantitative average) molecular weight. (π) Hydroxyl value is defined as the number of milligrams of potassium hydroxide equivalent to the hydroxyl content of 1 gram of sample, and is determined by hydrolysis of excess acetic anhydride after acetylation. The acetic acid solution is titrated by potassium in ethanol. (in) The acid value is defined as the number of grams of potassium hydroxide required to neutralize the free fatty acids in the sample. It can be directly titrated using standard potassium hydroxide solution to measure ° (iv The isocyanate (NC〇) value is defined as the weight percent of isocyanate in the sample, determined by reaction with excess dibutylamine and back titration with hydrochloric acid. (v) Dynamic stagnation using a Brookfield flow meter at 25 ° C 127030.doc -22- 200848447 method) The (Vi) water content is analyzed according to the Karl Fischer method (Kari_Fisehef titration. (vii) The glass transition temperature (Tg) is #, g; Thermal method (DSC)
MettlerDSC30以2(TC/分鐘的掃描速率測量。 (vHi)由試驗小組決定施用聚㈣句散液之紡織品的手感 或觸感’分為1至5級，1代表軟，3代表中等軟，5代表 硬0 ⑽施用於橡膠之聚胺醋句散液的枯著力按照刪53151 來測定1著力以0至5分級，_表無㈣力損失，5代表 超過65%的粘著力損失。 實例 實例1 2310.2克二聚脂二醇（Prip〇1TM 2〇33( Uniyma& 司產）) 和300克馬來酸酐（默克公司（Merck)生產）加入玻璃反應器 中並逐漸升溫至225 C。水在加熱過程中經由蒸鶴除去。 在約一小時後’使用〇·〇〇5糾〇/0的2〇 wt〇/。四丁醇鈦（丁bt)溶 液催化。在225°C持續反應至酸值小於1() mgKOH/g為止。 不飽和聚醋多元醇產物表現出以下性質： (數量平均）分子量 0.57 mgKOH/g 56 mgKOH/g 0.01% 27,800 mPa.s 酸值 羥值 含水率 2 5 °C下的動態粘度 實例2 127030.doc -23- 200848447 按照實例1的步驟（但不使用催化劑），由2426 1古- •兄二聚脂 二醇（Pi*ipolTM 203 3)和186.6克馬來酸酐（默克公司 生產）在 225 °C下一起反應。不飽和聚酯多元醇產物表現出 阳U下性 質： (數量平均）分子量 974 酸值 1.19 mgKOH/g 羥值 114 mgKOH/g 含水率 0.01%The Mettler DSC30 was measured at a scan rate of 2 (TC/min. (vHi). The feel of the textile or the tactile sensation of the textile applied to the poly (four) sentence dispersion was determined by the test group to be 1 to 5, with 1 being soft and 3 being moderately soft, 5 Representative hard 0 (10) The dryness of the polyamine vinegar spray applied to the rubber is determined according to the deletion of 53151. The force is graded from 0 to 5, the _ table has no (four) force loss, and the 5 represents the adhesion loss of more than 65%. 2310.2 g of dimer diol (Prip〇1TM 2〇33 (produced by Uniyma & Co.)) and 300 g of maleic anhydride (manufactured by Merck) were added to the glass reactor and gradually heated to 225 C. The water was heated. In the process, it is removed by steaming crane. After about one hour, it is catalyzed by a solution of 〇·〇〇5=002〇wt〇/. titanium tetrabutoxide (but bt) solution. The reaction is continued at 225 ° C until the acid value. Less than 1 () mgKOH / g. The unsaturated polyacetate polyol product exhibits the following properties: (number average) molecular weight 0.57 mgKOH / g 56 mg KOH / g 0.01% 27,800 mPa.s acid value hydroxyl value water content 2 5 ° C Dynamic viscosity example 2 127030.doc -23- 200848447 Follow the procedure of Example 1 (but without using a catalyst) , reacted by 2426 1 Gu- • brother dipolyglycol (Pi*ipolTM 203 3) and 186.6 g maleic anhydride (manufactured by Merck) at 225 ° C. The unsaturated polyester polyol product showed a positive U Lower nature: (quantitative average) molecular weight 974 acid value 1.19 mgKOH / g hydroxyl value 114 mgKOH / g water content 0.01%
25°C下的動態粘度 6850 mPa.s 實例3 按照實例1的方法，將1718.2克二聚脂肪酸（PripolTM 1009，Uniqema生產）和625.9克丙二醇（默克公司生產）在 22 5 °C下反應。在約一小時後，在225 °C下將0.13 ml 20 wt% TBT加入反應混合物中。再過5小時後，當酸值為約 〇·4時，將壓力逐漸地降至1毫巴以餾出過量的丙二醇。當 餾出105.7克丙二醇與不飽和聚酯多元醇產物後，停止蒸 餾。不飽和聚酯多元醇冷卻至i 50°c (在完全真空下），然後 過濾。不飽和聚酯多元醇產物表現出以下性質： (數2：平均）分子量 1900 0.28 mgKOH/g 59 mgKOH/g 0.01% 343,000 mPa.s 酸值 經值 含水率 25°C下的動態粘度 實例4 127030.doc 24 - 200848447 2820 0.8 mgKOH/g 39 mgKOH/g 0.01% 63,500 mPa.s 按照實例1的步驟，將2504.8克二聚月旨二醇（PripolTM 2033)和368.2克馬來酸酐（默克公司產）在225°C下，在0.005 wt%的20 wt% TBT溶液催化下反應。不飽和聚酯多元醇產 物表現出以下性質 (數量平均）分子量 酸值 羥值 含水率 25°C下的動態粘度 實例5 按照以下組成生產聚胺酯： 重量份數比 在實例3中製備的聚酯多元醇 142 N-甲基吡咯烷酮（NMP) 35 二羥甲基丙酸（DMPA) 13.5 異佛爾酮二異氰酸酯（IPDI) 55 二月桂酸二丁錫（DBTL) 0.2 三乙基胺（TEA) 9.6 Jeffamine D230 13.4 水 350 將不飽和聚酯多元醇和85% NMP加入反應器中，反應器 配備部分冷凝器、全冷凝器、攪拌器惰性氣體滌氣機和温 度計。將混合物加熱至80-100°C，當混合物達均相時，加 入DMPA並抽真空，直到混合物再次變為均相（約1 5分 127030.doc -25- 200848447 鐘）°混合物冷卻至65°C，加入DBTL，在一小時期間内加 入1PDI。加料完畢後，提高溫度至70-751。持續反應直 至獲得恒定的NCO值。（約2.5%)。將溫度下降至65°C，在 1 0分鐘期間内添加TEA和剩餘的1 5% NMP。繼續攪拌15分 鐘。生成的預聚合物加入25°C的水中，在此溫度下攪拌3〇 刀姜里°在15分鐘期間内加入Jeffamine D230，將溫度保持 在30°C下，並持續攪拌2小時。生成的聚胺酯分散樹脂產 物之pH值約8，含有約35 wt%不揮發物，4.5 wt%揮發物。 實例6 這是不按照本發明的對照實例。 除了改用以飽和二聚脂肪酸為主的聚酯多元醇來代替不 飽和聚S旨多元醇外，其餘皆按照實例5生產聚胺酯勻散 液。飽和聚醋多元醇的分子量為2〇〇〇 g/m〇1，由50/50重量 比的己二酸和二聚脂肪酸（Prip〇1TM，uniqema生產）及1，6-己二醇形成。 實例7 按照本文所述試驗步驟，測試實例5和6中生產的聚胺酯 句散液於纺織品上的手感和對橡膠的粘著力。結果如表1 所示 表1 實例號 纺織品手感 ----- 對橡膠的粘著力 5 ___ 2 1-2 6(對照） 5 5 127030.doc -26- 200848447 根據本發明聚胺酯勻散液在紡織品上的手感較柔軟，在 橡膠上粘著力提高。 上述實例說明已改善根據本發明不飽和聚酯多元醇和聚 胺酯之性能。 127030.doc -27-Dynamic viscosity at 25 ° C 6850 mPa.s Example 3 According to the method of Example 1, 1718.2 g of a dimer fatty acid (PripolTM 1009, manufactured by Uniqema) and 625.9 g of propylene glycol (manufactured by Merck & Co.) were reacted at 22 5 °C. After about one hour, 0.13 ml of 20 wt% TBT was added to the reaction mixture at 225 °C. After another 5 hours, when the acid value was about 〇·4, the pressure was gradually lowered to 1 mbar to distill off the excess propylene glycol. After 105.7 g of propylene glycol and the unsaturated polyester polyol product were distilled off, the distillation was stopped. The unsaturated polyester polyol was cooled to i 50 ° C (under full vacuum) and then filtered. The unsaturated polyester polyol product exhibited the following properties: (Number 2: average) Molecular weight 1900 0.28 mgKOH/g 59 mgKOH/g 0.01% 343,000 mPa.s Acid value Permeability Dynamic viscosity at 25 ° C Example 4 127030 .doc 24 - 200848447 2820 0.8 mgKOH/g 39 mgKOH/g 0.01% 63,500 mPa.s According to the procedure of Example 1, 2504.8 g of dimerized diol (PripolTM 2033) and 368.2 g of maleic anhydride (manufactured by Merck & Co.) The reaction was catalyzed by 0.005 wt% of a 20 wt% TBT solution at 225 °C. The unsaturated polyester polyol product exhibited the following properties (number average) molecular weight acid value hydroxyl value moisture content dynamic viscosity at 25 ° C Example 5 Production of polyurethane according to the following composition: Part by weight of polyester polyol prepared in Example 3. Alcohol 142 N-methylpyrrolidone (NMP) 35 Dimethylolpropionic acid (DMPA) 13.5 Isophorone diisocyanate (IPDI) 55 Dibutyltin dilaurate (DBTL) 0.2 Triethylamine (TEA) 9.6 Jeffamine D230 13.4 Water 350 An unsaturated polyester polyol and 85% NMP were charged to the reactor. The reactor was equipped with a partial condenser, a full condenser, a stirrer inert gas scrubber and a thermometer. The mixture is heated to 80-100 ° C. When the mixture reaches a homogeneous phase, DMPA is added and vacuumed until the mixture becomes homogeneous again (about 15 minutes 127030.doc -25-200848447). The mixture is cooled to 65°. C, join DBTL, add 1PDI within one hour. After the addition is completed, increase the temperature to 70-751. The reaction is continued until a constant NCO value is obtained. (about 2.5%). The temperature was lowered to 65 ° C and TEA and the remaining 1 5% NMP were added over a period of 10 minutes. Continue to stir for 15 minutes. The resulting prepolymer was added to water at 25 ° C, and stirred at this temperature for 3 liters of ginger. The Jeffamine D230 was added over a period of 15 minutes, the temperature was maintained at 30 ° C, and stirring was continued for 2 hours. The resulting polyurethane resin dispersion product had a pH of about 8, containing about 35 wt% nonvolatiles, and 4.5 wt% volatiles. Example 6 This is a comparative example not according to the present invention. In addition to the use of a saturated dimerized fatty acid-based polyester polyol instead of the unsaturated poly-S-polyol, the polyurethane ester dispersion was produced according to Example 5. The saturated polyester polyol has a molecular weight of 2 〇〇〇 g/m 〇 1, and is formed by 50/50 by weight of adipic acid and dimer fatty acid (Prip 〇 1 TM, manufactured by uniqema) and 1,6-hexanediol. Example 7 The feel of the polyurethane foam produced in Examples 5 and 6 on the textile and the adhesion to the rubber were tested in accordance with the test procedures described herein. The results are shown in Table 1. Table 1 Example No. Textile Handle---- Adhesion to Rubber 5 ___ 2 1-2 6 (Control) 5 5 127030.doc -26- 200848447 According to the present invention, the polyurethane dispersion is The hand on the textile is softer and the adhesion on the rubber is increased. The above examples illustrate the improved properties of unsaturated polyester polyols and polyurethanes in accordance with the present invention. 127030.doc -27-