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經濟部中央標準局員工消費合作社印製 五、發明説明（1 ) 本發明係有關於一種聚酯型乳化劑，特別是有關於 —種具有多種親水基，低voc(揮發性有機化合物），高 分子量，可作為乳化聚合之聚酯型乳化劑及製法。 既有之乳化劑，其分子量均在丨000以下，應用於乳 化合成，因其低分子量之因素，易遷移至表面，而影響 接著性造成接著物體之剝離，或影響與顏料或添加劑之 相容’造成滲色之不良影響。 既有之含親水基之聚酯，若僅含磺酸鹽基，其親水 性太好，因此使用時易有粘手及耐水性不好之缺點。例 如美國專利ΝΟ·3,779,993，5,294,650及日本公開公報 JP-01-058092所合成之水分散性聚酯僅含磺酸基，雖可 分散於水中，但成膜後吸水性高，耐水性差’光澤不好。 另一方面，既有之僅含多官能羧酸基之聚酯，例如 美國專利Ν〇·4,943,612，使用時需加入大量的中和劑如 胺等鹼類化合物才可分散於水中，加工時中和劑揮發後 會造成環境污染，且分子量低，機械安定性差，使用為 乳化劑時使用量高，影響物性。 歐洲專利Ν0.050266號揭示了 一種同時含有磺醆鹽 基及羧酸基之聚酯，但由於酸價偏低（9_14 mg Κ〇Η/幻’ 故使用時需加入共溶劑幫助溶於水而供作塗料之用，也 不適於應用為乳化劑。 有鑑於以上習知技術之缺點，本發明之目的乃在提 供一種具有多種親水基、低VOC，高分子量，可作為乳 化聚合之乳化劑的聚酯。 3 本紙張尺度適用中國國家標率（CNS ) Α4規格（21〇Χ 297公釐} _ "" ----- (會先聞讀背面之注意事項再填寫本頁) 、?τ 1 ϋ 2&Fh6 修i£ A7 B7 五、發明説明（2 ) 本發明人等發現於聚酯中同時導入適當比例之磺酸鹽基 及多官能羧酸基並控制重量平均分子量在2000-20000，酸價 在5-80mg KOH/g丄〇Hn丨、於2mg KOH/^可達成上述目 的。此乃因爲多官能羧酸基可提供作爲交聯之反應基，使製 得之聚酯提高耐水性及機械強度及高韌性，而另一方面磺酸 基提供親水性，具有良好之水分散性，因而使用此乳化劑所 合成之乳液具有良好之合成安定性，合成乳膠粒徑小，改善 使用低分子量多幾酸基此方面之缺點又能達到低胺中和，低 v〇c之效果。 _ 本發明之聚酯具有下列之構造： HOC-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (1) The present invention relates to a polyester emulsifier, and in particular to a kind of emulsifier with a variety of hydrophilic groups, low voc (volatile organic compounds), high Molecular weight, can be used as a polyester emulsifier for emulsion polymerization and its preparation method. Existing emulsifiers, whose molecular weights are all below 1,000, are used in emulsification synthesis. Due to their low molecular weight, they are easy to migrate to the surface, which affects the adhesion and causes the peeling of the bonding object, or affects the compatibility with pigments or additives. 'Cause adverse effects of bleeding. Existing hydrophilic group-containing polyesters, if only containing sulfonate groups, are too hydrophilic, so they tend to have the disadvantages of sticky hands and poor water resistance when used. For example, the water-dispersible polyester synthesized in U.S. Patent Nos. 3,779,993, 5,294,650 and Japanese Publication Gazette JP-01-058092 contains only sulfonic acid groups. Although it can be dispersed in water, it has high water absorption after film formation and poor water resistance. it is good. On the other hand, existing polyesters containing only polyfunctional carboxylic acid groups, such as U.S. Patent No. 4,943,612, need to be added with a large amount of neutralizing agents such as amines to disperse in water during processing. The volatilizer will cause environmental pollution, and has a low molecular weight and poor mechanical stability. When used as an emulsifier, the amount used is high, which affects physical properties. European Patent No. 0.050266 discloses a polyester containing both a sulfonium salt group and a carboxylic acid group, but since the acid value is relatively low (9_14 mg Κ〇Η / 幻 '), a co-solvent needs to be added to help dissolve in water. It is not suitable for use as an emulsifier for coatings. In view of the disadvantages of the above-mentioned conventional technologies, the object of the present invention is to provide an emulsifier for emulsification polymerization with various hydrophilic groups, low VOC and high molecular weight. Polyester. 3 This paper size applies to China National Standards (CNS) Α4 specifications (21〇 × 297 mm) _ " " ----- (will read the precautions on the back before filling this page), ? τ 1 ϋ 2 & Fh6 i A7 B7 V. Description of the invention (2) The inventors found that the appropriate amount of sulfonate group and polyfunctional carboxylic acid group were introduced into the polyester and the weight average molecular weight was controlled to 2000 -20000, the acid value is 5-80mg KOH / g 丄 OHn 丨, the above purpose can be achieved at 2mg KOH / ^. This is because the polyfunctional carboxylic acid group can provide a reactive group for crosslinking, making the polyester Improve water resistance and mechanical strength and high toughness, while sulfonic acid groups provide It is water-based and has good water dispersibility. Therefore, the emulsion synthesized by using this emulsifier has good synthetic stability, small particle size of synthetic latex, improvement of the disadvantages of using low molecular weight polyacid groups, and low amine neutralization. , Low voc effect. _ The polyester of the present invention has the following structure: HOC-
Kj-C-f-O-R^O-C-R^c i^pOH G G G (式—） 經濟部中央標準局貝工消費合作社印製 其中G可爲Q (磺酸鹽基S〇3M，M爲鹼金屬或鹼土金 屬）’ 〇2(羧酸基COOH)或(¾氫原子Η)，並jl其中民及反2爲 2〜12個碳之亞烴基(alkylene)或芳香環基，式一中組成份佔之 莫耳百分率G!(S〇3M)爲對全部聚酯莫耳數之3〜25mole%， G2(CCX)印爲對全部聚酯莫耳數之5〜25mole%，GXH)爲對全 部聚酯莫耳數之50〜92mole %。 上述本發明之聚酯乃利用含羧酸基之化合物及含磺酸鹽 基之化合物與一般二元酸及二元醇經酯化，再聚合而合成。 4 (修正頁） 1880325A.doc.Kj-CfOR ^ OCR ^ ci ^ pOH GGG (Equation —) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs where G can be Q (sulfonate S03M, M is an alkali metal or alkaline earth metal) '〇2 (Carboxylic acid group COOH) or (¾ hydrogen atom Η), and jl in which min and trans 2 are alkylene groups or aromatic ring groups of 2 to 12 carbons, the mole percentage G of the components in formula 1 is G! (S〇3M) is 3 ~ 25mole% for all polyester moles, G2 (CCX) is printed as 5 ~ 25mole% for all polyester moles, GXH) is 50 for all polyester moles ~ 92mole%. The polyester of the present invention described above is synthesized by esterifying and then polymerizing a compound containing a carboxylic acid group and a compound containing a sulfonate group with a general dibasic acid and a diol. 4 (revision page) 1880325A.doc.
I.^衣------ir-------A (請先閱讀背面之注意事項再填寫本頁J 46297 6 A7 B7 經濟部中央標準局員工消費合作社印裝 五、發明説明（3) 依照本發明，所使用之含羧酸基之化合物，其結構 為Ra-COOH，其中Ra可為含二元酸（diacid)，二元醇（diol) 或酸酐（anhydride)之破氫化合物，其中Ra為4至12個碳 之亞煙基（alkylene group)或芳香環基（aromatic group)。例 如苯偏三酸 if (trimellitic anhydride，TMA)，苯偏三酸 (trimellitic acid) ’ 二經曱基丙酸（dimethylol propionic acid)、苯均三酸（trimesicacid)、苯均四酸酐（pyromellitic anhydride)、苯均四酸二酐（pyromellitic dianhydride)、 3,3’，4,4|苯醯苯二酸針（3,3'，4,4^6112〇卩11611〇]16(1丨&1111)^]：丨(16) 等。 依照本發明所使用之含磺酸鹽基之化合物，其結構 如下Rb-S03M，其中Rb為含二元酸（diacid)、二元醇（diol) 或酸酐之碳氫化合物部分，碳數可為4至12，可含有芳 香環基（aromatic group)。Μ為驗金屬離子或驗土金屬離 子如Li+，Na+，K+，Mg+2，Ca+2。例如5·磺酸間苯二 甲酸鈉鹽（SSIPA，Sodium Salt of Sulfoisophthalate)，5-磺酸間笨二甲酸二曱酯鈉鹽（SSIPM，Sodium Salt of Dimethyl 5-Sulfoisophthalate)，績酸 2,6-务二甲酸鈉鹽 (Sodium Salt of Sulfo-2,6-naphthalene dicarboxyl)，績酸 丁二酸納鹽（Sodium Salt of Sulfo-Succinate，Sodium Sulfosuccinic acid)，績酸乙二醇納鹽（Sodium Salt of Sulfo-ethy lene glycol)，或確酸丁二醇納鹽（Sodium Salt of butylene diol)等及其混合物。 依照本發明，所使用之二元酸或其衍生物，例如對 5 ------I---表-----I訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Ad規格（210X297公釐） 46297 6 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（4 ) 苯二曱酸（terephthalic acid)，間苯二甲酸（isophthalic acid)，己二酸（adipic acid)、丁二酸（succinic acid)，十二 院基二酸（dodecane dicarboxylic acid)，等此類之化合物 或其混合物。 依照本發明，所使用之二元醇例如乙二醇（ethylene glycol)，丙二醇（propylene glycol)，二乙二醇（diethylene glycol) 5 1，4-環己二醇（1，4-cyclohexanediol)，2,2-二曱 基丙二醇（neopentyl glycol)， 1,4-環己二曱醇（1,4- cyclohexane dimethanol) ， 聚乙稀 鍵二醇 （Polyethylene ether glycol)等。 本發明之聚酯之製造方法分為酯化及聚合之階段， 而酯化之方法可將含羧酸基之化合物（Ra-COOH)，含磺 酸鹽基之化合物（Rb-S03M)，二元酸及二元醇在反應中一 齊加入反應槽中進行酯化後聚合。亦可先加入含磺酸鹽 基之化合物，二元酸及二元醇進行S旨化，再聚合，而後 再加入含羧酸基之化合物再酯化。此外，亦可於酯化階 段時先加入一部份之含羧酸基化合物，而於聚合階段再 將剩餘之含羧酸基化合物加入。 詳而言之，例如，先將含叛酸基之化合物，含績酸 基之化合物，二羧酸及二元醇一齊加入反應槽中於165-250 °C進行酯化或酯交換。至酯化轉化率至90%以上再以 低真空方式（<15 torr)將多餘之二元醇等化合物抽出。接 著進行聚合反應，聚合溫度在240 °C〜290 °C之間並在10 torr以下之真空度進行聚合反應合成IV20.1 d〖/g之聚 (請先閲讀背面之注意事項再填寫本頁} 訂 -1 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0 X 297公釐） 經濟部中央橾準局負工消費合作杜印製 48297 6 A7 _______B7_ 五、發明説明（5 ) m ° 另外，亦可先將二元酸（diacid)，二元醇（diol)及含續 酸鹽基化合物加入反應槽中進行酯化反應，酯化溫度在 165°C~25 0 °C間進行酯化或酯交換，接著進行聚合反應， 聚合溫度在240 °C〜290 °C間，並且在10 torr以下之真空 度進行聚合反應，合成IVkO.l df/g之含確酸鹽基之聚 酯，再降溫至180 °C〜210°C間將含羧酸基之化合物加入 進行酯化或酯交換化合物，如此即可合成IV20.1 d《/g之 聚酯型乳化劑。 依照本發明，含磺酸鹽基之化合物之添加量為對二 元酸之3-25 mol%，較好為5-25mol%，最好為5-15mol% ; 對二元醇之添加量為3〜25mol%。 依照本發明，含羧酸基之化合物之添加量為對二元 酸之 5-25mol%。 依照本發明’在酯化反應（或酯交換反應時）所使用之 二元醇對二元酸之比例為1.05:1至ι〇.〇:ι ;最好是ι.1:1 至 6.0:1 。 以下藉由實施例進一步說明本發明，但本發明之範 圍並不限定於以下之實施例而是由所附之申請專利範圍 來界定。 實施例1 在具備有攪拌器、蒸餾管、溫度計、加料口、氮氣 通入口之四口反應瓶内放入間苯二甲酸（IPA，isophthalic 7 本紙張尺度剌中病"家縣（CNS ) Α4· ( 21Gx297公着) -----;-----木------IT------·\ (I先聞讀背面之注意事項再填寫本頁) 46297 6 A7 B7 經濟部中央標準局—工消費合作社印聚 五、發明説明（6) acid)，5-磺酸間笨二甲酸二甲酯鈉鹽（SSIPM)’ 丁二酸 (SA, succinic acid)，二乙二酸（DEG)，2,2-二甲基丙二醇 (NPG)和催化劑（如表1)。慢慢攪拌並升溫至165 t以上 開始酯化反應’待反應出水率達95%以上，約2hr後再升 高溫度’並慢慢降低壓力，使聚合溫度在275。(： '真空 度5 torr約聚合lhr後再降低溫度，並以氮氣破真空，待 /皿度降到210 C時’再加入苯偏三酸針（trimellitic anhydride)，再反應1.5hr後，即可得到高分子型乳化劑。 實施例2 在實施例1的反應裝置中，加入己二酸（AA，adipic acid) ’ 5-績酸間笨二甲酸納鹽（ssiPA)，二乙二醇 (DEG)，1，4環己二醇（CHDM)和催化劑（如表2)。在165 °C以上開始進行酯化反應約1.5hr後，升高溫度，並慢慢 降低壓力’使聚合溫度在250 °C，真空度約8 ton·，聚合 1 5hr後，降低溫度’並以n2破真空，待溫度降至185 °C 時加入笨偏三酸酐（trimellitic anhydride)再反應1.5hr後 即可得到南分子型乳化劑。 實施例3 在實施例1的反應裝置中，加入間苯二甲酸（ipA)， 5-磺酸間苯二甲酸二曱酯鈉鹽（SSIP]vf)，丁二酸（SA， succinic acid) ’ 二乙二醇（DEG)， 2,2-二甲基丙二醇 (NPG)’部份之苯偏三酸酐（trimellitic anhydride)和催化 劑（如表在165 °C以上進行酯化反應，待反應出水率 8 (請先閱讀背面之注意事項再填寫本頁) 訂 文！ 本紙張尺度適用中國國家標準（CNS ) A4规格（2丨0><297公釐） 46297 6 A7 B7五、發明説明（7) 達95%以上，約2hr後，再升高溫度並降低壓力，使聚合 溫度在250 °C真空度2torr，約聚合lhr後再降低溫度至 200 °C並以N2破真空，再加入其餘之苯偏三酸酐 (trimellitic anhydride)待反應約lhr後即可得高分子型乳 化劑。 實施例4 在實施例1中的反應裝置中，加入間苯二甲酸 (IPA)， 5-磺酸間苯二曱酸鈉鹽（SSIPA)，丁二酸（SA， succinic acid)，二乙醇（DEG)，2，2-二甲基丙二醇（NPG) 和催化劑（如表4)慢慢攪拌並升溫至1 65 °C以上開始酯化 反應，待反應約12hr後再加入苯偏三酸酐（TMA)再反應 1.5hr，即可得高分子型乳化劑。 實施例5 如實施例1中之反應裝置及組成，將2,2-二甲基丙二 醇（NPG，neopentyl glycol)改為乙二醇（EG) ’其餘與實施1 中相同（如表5)。所得之高分子型乳化劑之性質如表5所 示。 L---------,4------ΐτ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 46 297 6 A7 B7 五、發明说明（8 ) 表1.高分子型乳化劑之組成及性質 樣品1 樣品2 樣品 3 樣品4 重量(g)莫耳％ 重量(g) 莫耳％ 重量(g)莫耳％ 重量(g) 莫耳％ IPA 136.6 82.3 109.6 66 117.5 70.8 117.5 70.8 SSIPM 26.4 8.9 59.2 20 26.4 8.9 44.4 15 SA - 10 8.5 13.6 11.5 10.9 9.2 DEG 127.2 120 127.2 120 127.2 120 90.7 60 NPG 62.4 60 62.4 60 62.4 60 62.48 60 ΊΜΑ 16.9 8.8 10.6 5.5 16.9 8.8 9.6 5 Ti2+ 0.094 - 0,1 - 0.1 0.06 - IV 0.28 0,3 0.43 0.3 AN 39 52.8 46.8 28 表2.高分子型乳化劑之組成及性質 _樣品5_ 樣品6 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 重量(g) 莫耳％ 重量(g) 莫耳0/〇 AA 121.2 83 112.4 77 SSIPA 24.1 9 8.04 3 DEG 127.2 120 127.2 120 CHDM 86.58 60 86.5 60 TMA 15.4 8 38.4 20 Ti2+ 0,15 - 0.15 - IV 0.36 0.12 AN 42 76 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 462976 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明（9) 表3.高分子型乳化劑之組成及性質 樣品 7 樣品 8 重量(g) 莫耳％ 重量(g) 莫耳％ ΙΡΑ 117.5 70.8 103.7 62.5 SSIPM 14.8 5 44.3 15 SA 13.6 11.5 13.6 11.5 DEG 127.2 120 127.2 120 NPG 62.4 60 62.4 60 ΤΜΑ(第i階段） 9.6 5 5.8 3 TMA(第2階段） 14.8 7.7 15.4 8 Ti2+ 0.16 0.16 - IV 0.32 0.24 AN 21 25 表4.高分子型乳化劑之組成及性質 樣品 9 樣品 10 重量(g) 莫耳％ 重量(g) 莫耳％ IPA 115.0 69.3 107.9 65 SSIPA 15.3 5.7 40.2 15 SA 15.3 13 9.44 8 TMA 23.0 12 23.0 12 DEG 53 50 66.8 63 NPG 62.4 60 41.6 40 Ti2+ 0.16 - 0.06 - IV 0.17 0.16 AN 51 53 11 f— I--- n - - i -- - - I (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 462976 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（ίο) 表5.高分子型乳化劑之組成及性質 樣品11 樣品12 樣品13 重量(g) 莫耳％ 重量(g)莫耳％ 重量(g). 莫耳％ IPA 113.7 68.5 113.7 68.5 113.7 68.5 SSIPM 29.6 10 29.6 10 29,6 10 SA 13.6 11.5 13.6 11.5 13.6 11.5 TMA 19.2 10 19.2 10 19.2 10 DEG 137.8 130 74.2 70 53 50 EG - _ 49,6 80 NPG - 62.4 60 _ Ti2+ 0.90 - 0.9 - 0.9 IV 0.34 0.25 0.3 AN 47 42 43 應用例1 分別以表 1中樣品3 ;、樣品 4 所合成之產物 Eastman Chemical Co_，aqhs為乳化劑和甲基丙烯酸甲 酯（MMA)，丙烯酸丁酯（BA)，在7〇〜8〇χ：間進行乳化聚 合，待4.5心後，將所得產物做各種性質之測試，如結塊 量、機械安定性、粒徑、粘度等測試，所得測試之值為 ---—--------^1 - - —r - ir ·請先閲读背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 46297 6 五、發明説明（11 ) 表 編號 6 樣品14 樣品15 樣品16 高分子型乳化劑種類 樣品3 樣品4 AQ55S 單體種類 MMA/BA MMA/BA MMA/BA 結塊量C%) 0.13 0.14 0.04 粒徑（rnn丨 132 118 117 枯度（cps) 11.2 8.2 7 固成份 40.3 45 39.5 乳液成膜性 好 好 好 可交聯性 好 好 不佳 膜耐水性 好 好 不佳 由表6可知分別以本發明之高分子型乳化劑I. ^ 衣 ------ ir ------- A (Please read the notes on the back before filling in this page J 46297 6 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (3) According to the present invention, the carboxylic acid group-containing compound used has a structure of Ra-COOH, where Ra may be dihydrogen containing diacid, diol, or anhydride. Compounds in which Ra is an alkylene group or aromatic group of 4 to 12 carbons, such as trimellitic anhydride (TMA), trimellitic acid Via dimethylol propionic acid, trimesicacid, pyromellitic anhydride, pyromellitic dianhydride, 3,3 ', 4,4 | benzene Phthalic acid needle (3,3 ', 4,4 ^ 6112〇 卩 11611〇] 16 (1 丨 & 1111) ^]: 丨 (16), etc. Compounds containing sulfonate groups used in accordance with the present invention Its structure is as follows Rb-S03M, where Rb is a hydrocarbon part containing diacid, diol or anhydride, and the carbon number can be 4 to 12, but There is an aromatic ring group. M is a metal ion or a metal ion such as Li +, Na +, K +, Mg + 2, Ca + 2. For example, sodium sulfonic acid isophthalate (SSIPA, Sodium Salt of Sulfoisophthalate), Sodium Salt of Dimethyl 5-Sulfoisophthalate (SSIPM), Sodium Salt of Sulfo-2,6-naphthalene dicarboxyl ), Sodium Salt of Sulfo-Succinate (Sodium Sulfosuccinic acid), Sodium Salt of Sulfo-ethy lene glycol, or Sodium Sodium Glycol Sodium Salt (Sodium Salt of butylene diol), etc. and mixtures thereof. According to the present invention, the dibasic acid or its derivative is used, for example, order 5 ------ I --- Table ----- I (Please read first Note on the back, please fill out this page again) This paper size applies Chinese National Standards (CNS) Ad specifications (210X297 mm) 46297 6 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Benzodiazepine Acid (terephthalic acid), isophthalic acid (adiphthalic acid) adipic acid), succinic acid (succinic acid), twelve homes acid group (dodecane dicarboxylic acid), and the like of such compounds or mixtures thereof. According to the present invention, the glycols used are, for example, ethylene glycol, propylene glycol, diethylene glycol 5 1,4-cyclohexanediol, 2,2-Diopentyl glycol, 1,4-cyclohexane dimethanol, Polyethylene ether glycol, etc. The manufacturing method of the polyester of the present invention is divided into the stages of esterification and polymerization, and the method of esterification can be a compound containing a carboxylic acid group (Ra-COOH) and a compound containing a sulfonate group (Rb-S03M). The monobasic acid and diol are added to the reaction tank together during the reaction to carry out the esterification and polymerization. It is also possible to first add a compound containing a sulfonate group, a dibasic acid and a diol for S polymerization, and then polymerize, and then add a compound containing a carboxylic acid group and then esterify. In addition, it is also possible to add a part of the carboxylic acid group-containing compound at the esterification stage, and then add the remaining carboxylic acid group-containing compound at the polymerization stage. In detail, for example, firstly, a compound containing an acid group, a compound containing a chromic acid group, a dicarboxylic acid and a glycol are all added to a reaction tank at a temperature of 165-250 ° C for esterification or transesterification. After the esterification conversion rate reaches 90% or more, the excess glycol and other compounds are extracted in a low vacuum (<15 torr). The polymerization reaction is then carried out. The polymerization temperature is between 240 ° C ~ 290 ° C and the vacuum is below 10 torr to synthesize IV20.1 d [/ g polymer (please read the precautions on the back before filling this page) } Order-1 This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) Printed by the Central Government Standards Bureau, Ministry of Economic Affairs, Consumer Cooperation Du printed 48297 6 A7 _______B7_ V. Description of the invention (5) m ° In addition, you can also add diacid, dihydric alcohol (diol) and a compound containing a continuous acid salt to the reaction tank to perform the esterification reaction. The esterification temperature is between 165 ° C ~ 25 0 ° C. Esterification or transesterification, followed by polymerization reaction, the polymerization temperature is between 240 ° C ~ 290 ° C, and the polymerization reaction is carried out at a vacuum degree below 10 torr, to synthesize IVkO.l df / g polyester containing acid salt group Then, the temperature is lowered to 180 ° C ~ 210 ° C, and a compound containing a carboxylic acid group is added for esterification or transesterification, so that a polyester emulsifier of IV20.1 d / g can be synthesized. According to the present invention, The sulfonate group-containing compound is added in an amount of 3-25 mol% to the dibasic acid, preferably 5-25 mol%, preferably 5-15 mol%; the amount added to the diol is 3 to 25 mol%. According to the present invention, the amount of the carboxylic acid group-containing compound is 5-25 mol% to the dibasic acid. According to the invention, the ratio of the glycol to the diacid used in the esterification reaction (or transesterification reaction) is 1.05: 1 to ι〇.〇: ι; preferably ι.1: 1 to 6.0: 1. Hereinafter, the present invention will be further explained by examples, but the scope of the present invention is not limited to the following examples, but is defined by the scope of the attached patent application. Example 1 A stirrer, a distillation tube, a thermometer, and a feed are provided. Isophthalic acid (IPA, isophthalic 7 paper scales) " Home County (CNS) Α4 · (21Gx297) -----;- --- Wood ------ IT ------ · \ (I read and read the notes on the back before filling in this page) 46297 6 A7 B7 Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives Description of the Invention (6) acid), dimethyl 5-sulfonic acid sodium dimethyl dicarboxylate (SSIPM) 'succinic acid (SA, succinic acid), diethylene glycol (DEG), 2,2-dimethyl Propylene glycol (NPG) Catalyst (as shown in Table 1). Stir slowly and raise the temperature to above 165 t to start the esterification reaction. 'The water yield of the reaction should reach 95% or more, and then increase the temperature after about 2 hours' and slowly reduce the pressure to bring the polymerization temperature to 275. (: 'The degree of vacuum is 5 torr, then reduce the temperature after polymerization for about 1 hour, and then break the vacuum with nitrogen until the plate temperature drops to 210 C.' Then add trimellitic anhydride and react for another 1.5 hours, that is, A polymer-type emulsifier can be obtained. Example 2 In the reaction device of Example 1, adipic acid (AA, adipic acid) '5-dicarboxylic acid sodium salt (ssiPA), diethylene glycol (DEG), and 1,4-cyclohexane were added. Diols (CHDM) and catalysts (see Table 2). After starting the esterification reaction above 165 ° C for about 1.5 hours, increase the temperature and slowly reduce the pressure to bring the polymerization temperature to 250 ° C and the degree of vacuum to about 8 ton. After 15 hours of polymerization, reduce the temperature and then After n2 breaks the vacuum, when the temperature drops to 185 ° C, add trimellitic anhydride and react for 1.5hr to obtain the south molecular emulsifier. Example 3 In the reaction apparatus of Example 1, isophthalic acid (ipA), disulfonic acid isophthalate sodium salt (SSIP) vf), and succinic acid (SA, succinic acid) were added. Diethylene glycol (DEG), 2,2-dimethylpropanediol (NPG) 'part of trimellitic anhydride and catalyst (such as the table above 165 ° C for esterification reaction, the reaction water yield 8 (Please read the precautions on the back before filling this page) Article! This paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 0 > < 297 mm) 46297 6 A7 B7 V. Description of the invention (7 ) When the temperature reaches 95% or higher, increase the temperature and decrease the pressure after about 2 hours, so that the polymerization temperature is at 250 ° C and the vacuum degree is 2torr. After about 1 hour, lower the temperature to 200 ° C and break the vacuum with N2, then add the rest After the trimellitic anhydride is reacted for about 1 hour, a polymer-type emulsifier can be obtained. Example 4 In the reaction device in Example 1, isophthalic acid (IPA) and 5-sulfonic acid m-benzene were added. Sodium succinate (SSIPA), succinic acid (SA), diethanol (DEG), 2,2-dimethylpropane The alcohol (NPG) and catalyst (as shown in Table 4) are slowly stirred and warmed to above 1 65 ° C to start the esterification reaction. After the reaction is about 12 hours, add trimellitic anhydride (TMA) and then react for 1.5 hours. Molecular emulsifier. Example 5 As in the reaction device and composition in Example 1, 2,2-dimethylpropylene glycol (NPG, neopentyl glycol) was changed to ethylene glycol (EG). The rest is the same as in Example 1 ( (Table 5). The properties of the obtained polymer-type emulsifier are shown in Table 5. L ---------, 4 ------ ΐτ (Please read the precautions on the back before filling in this Page) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 46 297 6 A7 B7 V. Description of the invention (8) Table 1. Composition and properties Sample 1 Sample 2 Sample 3 Sample 4 Weight (g) Molar% Weight (g) Molar% Weight (g) Molar% Weight (g) Molar% IPA 136.6 82.3 109.6 66 117.5 70.8 117.5 70.8 SSIPM 26.4 8.9 59.2 20 26.4 8.9 44.4 15 SA-10 8.5 13.6 11.5 10.9 9.2 DEG 127.2 120 127.2 120 127.2 120 90.7 60 NPG 62.4 60 62.4 60 62.4 60 62.48 60 ΊΜΑ 16.9 8.8 10.6 5.5 16.9 8.8 9.6 5 Ti2 + 0.094-0,1-0.1 0.06-IV 0.28 0,3 0.43 0.3 AN 39 52.8 46.8 28 Table 2. Composition and properties of polymer emulsifiers _Sample 5_ Sample 6 (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Weight (g) Molar% Weight (g) Molar 0 / 〇AA 121.2 83 112.4 77 SSIPA 24.1 9 8.04 3 DEG 127.2 120 127.2 120 CHDM 86.58 60 86.5 60 TMA 15.4 8 38.4 20 Ti2 + 0,15-0.15-IV 0.36 0.12 AN 42 76 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) 462976 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Table 3. Composition and properties of polymer emulsifiers Sample 7 Sample 8 Weight (g) Molar% Weight (g) Molar % IPA 117.5 70.8 103.7 62.5 SSIPM 14.8 5 44.3 15 SA 13.6 11.5 13.6 11.5 DEG 127.2 120 127.2 120 NPG 62.4 60 62.4 60 TMA (Phase i) 9.6 5 5.8 3 TMA (Phase 2) 14.8 7.7 15.4 8 Ti 2+ 0.16 0.16-IV 0.32 0.24 AN 21 25 Table 4. Composition and properties of polymer emulsifier Sample 9 Sample 10 Weight (g) Molar% Weight (g) Molar% IPA 115.0 69.3 107.9 65 SSIPA 15.3 5.7 40.2 15 SA 15.3 13 9.44 8 TMA 23.0 12 23.0 12 DEG 53 50 66.8 63 NPG 62.4 60 41.6 40 Ti2 + 0.16-0.06-IV 0.17 0.16 AN 51 53 11 f— I --- n--i---I (Please Please read the notes on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 462976 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Composition and Properties of Polymeric Emulsifier Sample 11 Sample 12 Sample 13 Weight (g) Mole% Weight (g) Mole% Weight (g). Mole% IPA 113.7 68.5 113.7 68.5 113.7 68.5 SSIPM 29.6 10 29.6 10 29,6 10 SA 13.6 11.5 13.6 11.5 13.6 11.5 TMA 19.2 10 19.2 10 19.2 10 DEG 137.8 130 74.2 70 53 50 EG-_ 49,6 80 NPG-62.4 60 _ Ti2 + 0.90-0.9-0.9 IV 0.34 0.25 0.3 AN 47 42 43 should Example 1 Take Eastman Chemical Co_, aqhs as emulsifier and methyl methacrylate (MMA), butyl acrylate (BA), which are synthesized from samples 3; and 4 in Table 1, respectively: Emulsification polymerization was carried out at intervals. After 4.5 hours, the obtained product was tested for various properties, such as agglomeration, mechanical stability, particle size, viscosity and other tests. The obtained test value was ----------- -^ 1---r-ir · Please read the notes on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) A7 46297 6 V. Description of invention (11 ) Table No. 6 Sample 14 Sample 15 Sample 16 Type of polymer emulsifier Sample 3 Sample 4 AQ55S Monomer type MMA / BA MMA / BA MMA / BA Agglomeration amount C%) 0.13 0.14 0.04 Particle size (rnn 丨 132 118 117 Litter (cps) 11.2 8.2 7 Solid content 40.3 45 39.5 Emulsion film formation is good, crosslinkability is good, poor film water resistance is good, Table 6 shows that the polymer type emulsifier of the present invention is
Eastman Chemical Co.，AQ55S為乳化劑合成壓克力乳 液’所得之乳液性質相當’但分別將樣品14，15，及16乳 液應用製成積層油墨時’塗佈於經過電暈（c〇r〇na)處理的 PET膜上’將塗佈油墨後的pet膜在45°c烘箱中乾燥8 小時後’將PET膜放入i〇(TC熱水中水煮3〇分鐘，用膠 帶測試油墨對PET的接著力，以樣品η做成的油墨可達 4級’以樣品15做成的油墨可達5級，而以樣品16做成 的油墨經水焘即剝離。由此可知本發明之高分子型乳化 劑可有效提升财水煮性。 雖然本發明已以較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此項技藝者，在不脫離本發明 之精神和範圍内，當可作更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者為準。 13 表紙張尺度適用中國國家標準（CNS ) Α4規格（2丨οχ”7公釐） J----------4-------訂------*-t (请先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印裝Eastman Chemical Co., AQ55S is an emulsifier synthetic acrylic emulsion 'emulsion properties are comparable', but when samples 14, 15, and 16 emulsions were applied to make laminated inks, respectively, 'coated by corona (c0. na) on the treated PET film 'after drying the coated PET film in a 45 ° C oven for 8 hours', the PET film was placed in i0 (TC hot water and boiled for 30 minutes, and the ink pair was tested with tape The adhesion force of PET can reach 4 grades with ink made with sample η ', and 5 grades with ink made with sample 15, and the ink made with sample 16 can be peeled off with water. From this, it can be seen that the height of the present invention is high. The molecular emulsifier can effectively improve the water boiling property. Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art will not depart from the spirit and scope of the present invention. When it can be modified and retouched, the scope of protection of the present invention shall be determined by the scope of the attached patent application. 13 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 οχ ”7 mm) J ---------- 4 ------- Order ------ *-t (Please read the back first Note to fill out this page) Central Bureau of Standards, Ministry of Economic Affairs negative consumer cooperatives printing and binding work