^01765 A6 ________B_6_ 五、發明説明（） 本發明傜有_ 一種用於光電攝影、靜電印刷及其相似 之靜電荷影像及潛磁像顯像之做為色粉之聚酯樹脂。 在形成光電攝影、靜電荷印刷之及其相似之圖像中， 一方法為將記錄之圖像在靜電紀錄材料表面上轉換為一潛 電圖像，如靜電圖或電導圖像，此潛圖像顯像並以帶電荷 色粉形成，且將在此靜電記錄材料表面上形成之色粉圖像 聚合移轉並固定在紙上或一記錄膜上。此圖像形成方法之 優點在於複製操作可在一高速下進行，在記錄材料表面之 圖安定性為良好，且使用之裝置可非常簡單的製備。依此 ，圖像形成方法可廣泛的使用於影印機、雷射印表機及其 類似範圍中。 ' 例如，以光電攝影之圖像形成，滾軸表面由光導光感 材料形成進行一電荷處理，由暴於由原販反射之射線的光 形成之靜電潛圖像可由色粉形成，所得之色粉圖像轉移至 一紙或其相似物上，且轉移色粉圖像在熱壓下固定在紙上 經濟部中央標準局貝工消费合作社印製 至於色粉之結合樹脂，使用苯乙烯/丙烯樹脂、一聚 酯樹脂、一環氧樹脂及其相似物，但近來注意到聚酯樹脂 做為結合劑樹脂具有良好固定性質，可得良好圆像，且具 有良好抗增塑劑性，此增塑劑傅統用於於聚氯乙烯及其他 樹脂。 如色粉需要之重要性質，必需提及固定性質及非偏離 性質。提供具宵良好固定性質及非偏離性質之色粉的方法 ，已建議使用三官能或多官能單而提供一交聯結構至-- 一 3_ 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公婕) 經濟部中央標準局貝工消费合作社印製 ^01765__ 五、發明説明（） 結合劑樹脂中。具有交聯結構之色粉的聚酯樹脂一般例示 掲露於美國專利Re. 3 1,07 2之說明書中。 具有交聯結構之聚酯樹脂不可避免由交聯反應製備。 . 此交聯反應不同於一般線聚酯樹脂之聚縮合反應在於交聯 反應快速進行，且迅速形成膠。依此，反應的控制是非常 簌重的問題。在美國專利第4 , 84 9 , 4 9 5 Q號之說明書中， 本發明之發明人建議交聯聚酯製備方法，其中該交聯反應 在低於150托耳之高真空下進行，真空程度由交聯反應開 始點逐漸降低，因此可控制交聯反應之進行。雖然如此， 已發現當製備方法在工業量生産時，膠化作用之控制有時 依單體之組合變為相當困難。亦即，已發現在工業製備交 聯聚酯中，膠化作用控制之難易主要砍單體之組合。 本發明主要為基於解決前述問題所進行之研究，因而 發現若三價或四價單體（稱為交聯劑）及具有低聚化反應性 之芳香族或環脂族二醇成分，至少其中一羥基為二级羥基 ，使用一特定固定比例，可安定地製備具有交聯結構之聚 酯樹脂。本發明為基於此一發現：， 因此，本發明之主要目為提供一用於色粉之聚酯，其 可穩定的製備而未有快速交聯反應之産生。 依本發明為提供一用於色粉之具有交聯結構之聚酯樹 脂，其衍生自（a)至少由下列組成之組群中選出之一成分 :三鹼基及四鹼基羧酸成分及三氫及四氫醇成分；（b)芳 香族或璟脂族二醇成分，至少其中之一羥蕋為二级羥基； (c)合宜之其他二醇成分·，及（d)二羧S自成分；其中成分（a (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度逍用中Η國家樣準(CNS)甲4規格(210X297公龙) -4- 經濟部中央標準局貝工消費合作社印製 ^01765 A 6 ___BJ_ 五、發明説明（） )單元及成分（b)簞元之含量滿足下式之要求： (8 m + 2 Ο n ) a — ( 8 0 m + 8 η ) < b < (8m + 20n) a — (1 2m+30n) 其中m表示由成分（a)衍生之單元的三鹸基羧酸成分及三 氪基酵成分單元之某耳分數，η表示由成分（a)衍生之單 元的四鹼基羧酸成分及四氫基醇成分單元之莫耳分數，m 及η之總數等於1,且a及b分別表示羧酸成分總量之成 分（a)單元及成分（b)單元之莫耳分數。 用於本發明之三鹼基或四鹼基羧酸成分並未恃別限制 。例如，逑及偏苯六甲酸、甲苯一三羧酸、環己烷-三羧 酸、2, 5, 7 —萘—三耧酸、1', 2, 4— 丁烷—三羧酸、1 ，2, 5 —己烷—三羧酸、1, 3 —二羧酸一2 -甲基一2—亞 甲基-羧基丙烷、四（亞甲基一羧基）甲烷、1, 2，7, 8 -辛烷-四羧酸及苯四甲酸、及其等之酐與低级烷酯。此 多元鹼羧酸成分可單獨使用或其等至少二成分之混合物， 形式。 用於本發明之三羥或四羥醇成分並非持別制。例如可 為甘油、1, 1, 1—三羥甲基乙烷、1, 1, 1—三羥甲基丙 烷、1, 1, 1 一三羥甲基丁烷、五赤藻糖醇、1, 1, 2, 2 —四羥甲基乙烷及1, 1, 3, 3—四羥甲基丙烷。此些多元 羥成可單獨使用或其等至少二成分之混合物形式。 用於本發明之二羧酸成分並未恃別限制。例如可為對 苯二甲酸、異酞酸、酞酸、順丁烯二酸、延胡索酸、中康 酸、甲順丁烯二酸、依康酸、環己烷一二羧酸、丁二酸、 (請先W讀背面之注意事項再填寫本頁)^ 01765 A6 ________B_6_ V. Description of the invention () The invention has _ a polyester resin used as toner for photoelectric photography, electrostatic printing and similar electrostatic charge image and latent magnetic image development. In the formation of photoelectric photography, electrostatic charge printing and similar images, one method is to convert the recorded image on the surface of the electrostatic recording material into a latent electric image, such as an electrostatic image or a conductive image, this latent image The image is developed and formed with charged toner, and the toner image formed on the surface of the electrostatic recording material is polymerized and transferred and fixed on paper or a recording film. The advantage of this image forming method is that the copying operation can be performed at a high speed, the image stability on the surface of the recording material is good, and the device used can be prepared very simply. Accordingly, the image forming method can be widely used in photocopiers, laser printers, and the like. 'For example, the image is formed by photoelectric photography, and the surface of the roller is formed by a photoconductive material for a charge process. The electrostatic latent image formed by the light exposed to the rays reflected by the original dealer can be formed by toner, and the resulting color The powder image is transferred to a piece of paper or the like, and the transferred toner image is fixed on the paper under hot pressing. Printed by the Pongong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy. , A polyester resin, an epoxy resin and the like, but recently noticed that polyester resin as a binder resin has good fixing properties, can get a good round image, and has good plasticizer resistance, this plasticizer Agent Fu is used for PVC and other resins. If the toner requires important properties, it is necessary to mention fixed properties and non-deviation properties. To provide toners with good fixing properties and non-deviation properties, it has been suggested to use tri-functional or multi-functional monomers to provide a cross-linked structure to-1 3_ This paper scale is free to use China National Standard (CNS) A 4 specifications (210x297 Gongjie) Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 01765__ V. Description of the invention () In the binder resin. The polyester resin with a toner having a cross-linked structure is generally exemplified in the specification of US Patent Re. 3 1,07 2. The polyester resin with a cross-linked structure is inevitably prepared by the cross-linking reaction. . This cross-linking reaction is different from the general polycondensation reaction of linear polyester resin in that the cross-linking reaction proceeds quickly and quickly forms a glue. Accordingly, the control of the reaction is a very serious problem. In the specification of U.S. Patent No. 4, 84 9, 4 9 5 Q, the inventor of the present invention suggests a preparation method of cross-linked polyester, in which the cross-linking reaction is performed under a high vacuum of less than 150 Torr, the degree of vacuum The starting point of the cross-linking reaction gradually decreases, so the progress of the cross-linking reaction can be controlled. Nevertheless, it has been found that when the production method is produced in industrial quantities, the control of gelation sometimes becomes quite difficult depending on the combination of monomers. That is, it has been found that in the industrial preparation of crosslinked polyesters, the difficulty of controlling gelation is mainly due to the combination of monomers. The present invention is mainly based on research conducted to solve the aforementioned problems, and it has been found that if trivalent or tetravalent monomers (called crosslinking agents) and aromatic or cycloaliphatic diol components having oligomerization reactivity, at least One hydroxyl group is a secondary hydroxyl group, and a specific fixed ratio can be used to stably prepare a polyester resin having a cross-linked structure. The present invention is based on this finding: Therefore, the main object of the present invention is to provide a polyester for toners which can be stably prepared without rapid cross-linking reaction. According to the present invention, there is provided a polyester resin having a cross-linked structure for toner, which is derived from (a) at least one component selected from the group consisting of three base and four base carboxylic acid components and Trihydro and tetrahydro alcohol components; (b) Aromatic or Jing aliphatic diol components, at least one of which is a secondary hydroxyl group; (c) Suitable other diol components, and (d) Dicarboxy S Self-composition; among them (a (please read the precautions on the back before filling in this page) This paper is used in Chinese National Standards (CNS) A 4 specifications (210X297 male dragon) -4- Central Ministry of Economic Affairs Printed by the Industrial and Consumer Cooperative ^ 01765 A 6 ___BJ_ V. Description of the invention ()) Units and components (b) The content of the scion element meets the requirements of the following formula: (8 m + 2 Ο n) a — (8 0 m + 8 η ) < b < (8m + 20n) a — (1 2m + 30n) where m represents the fraction of the ear of the unit of the tri-chrysyl carboxylic acid and the unit of the tri-krypton-based enzyme derived from the component (a), η Represents the molar fraction of the four base carboxylic acid component and the tetrahydroalcohol component unit derived from the component (a), the total number of m and η is equal to 1, and a and b represent carboxyl groups, respectively Component to the total of components (a) mole fraction of the component unit, and (b) of the unit. The three-base or four-base carboxylic acid component used in the present invention is not particularly limited. For example, benzene and trimellitic acid, toluene-tricarboxylic acid, cyclohexane-tricarboxylic acid, 2, 5, 7-naphthalene-tricarboxylic acid, 1 ', 2, 4-butane-tricarboxylic acid, 1 , 2,5-hexane-tricarboxylic acid, 1,3-dicarboxylic acid 2-methyl-2-methylene-carboxypropane, tetrakis (methylene-carboxy) methane, 1, 2,7, 8-Octane-tetracarboxylic acid and pyromellitic acid, and their anhydrides and lower alkyl esters. This polybasic alkali carboxylic acid component can be used alone or as a mixture of at least two components. The trihydric or tetrahydric alcohol components used in the present invention are not separately prepared. For example, it can be glycerin, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane, 1, 1, 1-trimethylolbutane, pentaerythritol, 1 , 1, 2, 2-tetramethylolethane and 1, 1, 3, 3-tetramethylolpropane. These polyhydric hydroxyl groups can be used alone or as a mixture of at least two components. The dicarboxylic acid component used in the present invention is not particularly limited. For example, terephthalic acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid, mesaconic acid, maleic acid, itaconic acid, cyclohexane dicarboxylic acid, succinic acid, (Please read the notes on the back before filling this page)
X 裝. 訂· -線· 本紙張尺度逍用中國國家櫺準(CNS)甲4規格(210X297公*) -5- 經濟部中央標毕局貝工消費合作社印製 i,〇1765 A6 ___B_6_ 五、發明説明（） 己二酸、癸二酸、丙二酸及戊二酸、及其等之酐與低级烷 酯。此些二羧酸成可單獨使用或其等至少二成分之混合物 形式。 用於本發明之芳香族或琛脂族二醇成分，其中一羥基 為二级羥基，並未特別制。例如可為聚亞氣丙基（k) 一 2 ,2—雙（4 一羥基苯基）丙烷（k表示亞氣丙基單元之莫耳 數）、環己烷二醇、簠化雙酚A、氫化雙酚F及氫化雙酚 S。此些二醇成可單獨使用或其等至少二成分之混合物形 式。 用於本發明之其他二醇成分並非待別制。例如可為乙 二醇、1, 2 —丙院二酵、1，3 —丙院二醇、1, 4 —丙院二 醇、1, 3—丁烷二醇、1, 2-丁烷二醇、二甘醇、三甘醇 、四共醇、1, 6_己烷二酵、新戊二醇、環己烷二甲醇及 多亞氣乙基（1)— 2, 2—雙（4-羥基苯基）丙烷（1表示亞 氣乙基單元莫耳數）。此些二醇成可單獨使用或其等至少 二成分之混合物形式。 本發明之最重要特戡為單元（a)三價或四價多元羧酸 成及/或三氫或四氫多元氫醇成分，及單元（b)芳香族或 環脂族二醇成分，至少一羥基為二级羥基，的含量滿足前 述式（I)表示之要求。 若成分（b)單元的量少於式（I)定義的範圍，則交聯反 應速率太高且難以停止交聯反應。若成分（b)單元的量超 過式（I)定義的範圍，則交聯反應速率太低且難以到逹交 聯點。其他二醇成分（C)(合宜成分）及二羧酸成分（D)的量 (請先閲讀背面之注意事項再填窝本頁) 裝* 訂· 線· 本紙張尺度逍用中國爾家標準(CNS)甲4規格(210X297公 -6- ^01765 A 6 B6 經濟部中央標準局员工消費合作社印製 五、發明説明（） 適當依定義於前述式（I)之成分（a)及（b)的量選擇之。 較佳地，本發明聚酯樹脂之玻璃轉化溫度（Tg)在50 至75°C之間。若Tg低於5(TC,則色粉之封阻抗力容易降低 ，而若Tg超過75°C,則色粉之固定性質通常變為不良。 較佳地，本發明之樹脂的酸值不大於15 rag— KOH/g 。若酸值超過15 mg— KOH/g,色粉抗濕性變為不良。 本發明之聚酯樹脂可由適用於一般聚酯樹脂生産之傳 統方法製備。例如首先進行酯化或酯交換反應並持續之直 至水或低级醇之蒸餾作用止。在此反應中，可依需要使用 一已知之交換催化劑。然後聚縮合反應在低於15 G托耳真 空下進行，當反應混合物達至預期之交聯程度時终止反應 。在此反應中可依需要使用已知聚縮合催化劑。 在本説明書中，“交聯點”意指在聚縮合反應中反應 混合物黏度急速增加的點，“具有交聯結構之樹脂”意指 已達交聯點之樹脂。 本發明參考下列實施例更詳盡描述，但非用以限制本 發明。 在實施例中，聚酯樹脂之酸值藉將樣品溶於苄基醇中 ，並以Κ0Η滴定溶液而測定，而玻璃轉化溫度Tg以在5。C/ min溫度升高速率進行測定時，使用一位差掃描計熱器所 得之基準線與在T g附近熱吸收曲線之正切線交叉點而得。 實施例1 在具有蒸餾管及2升容量之高壓爐中餵入如表1中所 示之配方，對苯二甲酸、異酸、偏苯六甲酸酊、乙二醇 (請先閲讀背面之注意事項再蜞寫本頁) -裝. 訂· 線· 本紙張尺度逍用中困國家標準(CNS)甲4規格(210X297公龙） voltes A 6 B6 五、發明説明（) 、聚氣亞丙基一 +(2, 3)— 2, 2—雙（4 一羥基苯基）丙烷及 新戊二醇（總重為1 kg),加入酸成分之500 ppm(重量）之 三氣化銻，並進行酯化反應。由反應停止形成水蒸餾的點 時，酯化反應完成。在此點，攪拌轉矩為0.3 kg_CB 100 rpn。然後在24 0°C内部溫度下於3托真空進行聚縮合反應 ,反應混合物之黏度開始增加，且當轉矩達3.0 kg— cm時 ,真空狀態以加入氪氣消除至大氣壓之壓力。持續攪拌同 時維持内部溫度在240° C,雖然攪拌持绩進行30分鐘，轉 矩保持3,0 U- cm。亦卽在本實施例樹脂中，交聯反應未 激烈進行但可在所需交聯度時停止。所得樹脂之組合、Tg 及酸值列於表1中。 ' (請先閲讀背面之注意事項再填寫本頁) 裝· 訂. 線- 經濟部中央標準局貝工消費合作社印製 本紙張尺度逍用中8國家標準(CNS)甲4規格(210x297公货) A 6 B6 五、發明説明（） 表1 餵入量 樹脂中量 酸成分 偏苯六甲酸酐（莫耳份） 11 11 對苯二甲酸（莫耳份） 89 89 異酞酸 （莫耳份） 1〇 1〇 醇成分 ΒΡΡ0；1 (莫耳份） 55 55 乙二醇 （莫耳份） 5 0 4 2 新戊二醇 （莫耳份）· 2 5 2 0 m 1 η 〇 a 1 〇 b 50 樹脂之物理性質 Tg (°C) 63 酸值 （rag-KOH/g) 5 (請先閲讀背面之注意事項再填寫本頁) 裝- 線- 經濟部中央標準局A工消費合作社印製 註聚氯亞丙基一（2, 3)— 2, 2 —雙（4 一羥基苯基）丙 烷（相同於此後表2、4、6及8 ) 實施例2至5 本紙張尺度逍用中國國家標準（CNS)甲4規格(210x297公婕) —9一 經濟部中央標準局貝工消費合作社印製 A6 _B6 五、發明説明（） 表2 實施例 2 3 4 5 餵入 樹脂 餵入 樹脂 餵入 樹脂 餵入 樹脂 酸成分 量 中量 量 中量 量 中量 量 中漏 偏苯六甲酸酐（莫耳份） 10 10 14 14 — — — — 苯四甲酸酐 (莫耳份） — — — — 3 3 5 5 對苯二甲酸 (莫耳份） 90 90 70 70 60 60 90 90 異酞酸 (莫耳份） — — 10 10 37 37 5 5 己二酸 (莫耳份） — — 6 6 — — — — 醇成分 ΒΡΡ0 (莫耳份） 15 15 45 45 10 10 25 25 氫化雙酚A (莫耳份） 15 15 5 5 — — — — 乙二醇 (莫耳份） 90 70 60 54 125 116 65 59 二甘醇 (莫耳份） — — — — 5 4 — — ΒΡΕ0"1 20 20 10 10 — — 25 25 m 1 1 0 0 η 0 0 1 1 a 10 14 3 5 b • 30 50 10 25 樹脂之物理性質 Tg (°C) 58 65 51 61 酸值 (nig-K0H/g) 3 14 5 12 註-1:聚氣亞乙基一（2, 3) — 2, 2_雙（4 —羥基苯基）丙烷（相同於此後表10) (請先閲讀背面之注意事項再填寫本頁) 裝· 訂_ 本紙張尺度逍用中國國家標準（CNS)甲4規格(210x297公龙） -10- A 6 B6 經濟部中央標毕局貝工消費合作社印製 五、發明説明（） 依表2所示乏餵入配方，反應以實施例1所述之相同 方式進行。所得之結果示於表2及3中。在實施例2至5 中，每一交聯反應可被停止。 表3 實施例2 在壓力回至大氣壓後轉矩在超過5分鐘 内增加至3.5 kg- cm,但轉矩在此量保 持30分鐘 實施例3 在壓力回至大氣壓後，轉矩在3.0 kg — cm保持30分- 實施例4 相同實施例3 實施例5 在壓力回至大氣壓後轉矩在超過10分鐘 内增加至3. 8 kg - cm,然後轉矩保持此 值 實施例6至8 依表4所示之餺入配方，反應以實施例1所述之相同 方式進行，除了以200 ppm量（為酸成分之重量）之醋酸鉛 及4 Q Q ppm量（為酸成分之重量）之二丁基氧化錫做為催化 劑。所得之結果示於表4及5中。在實施例6至8中，毎 一交聯反應可被停止。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂. 線. 本紙張尺度逍用中BB家樣準（CNS)甲4規格(210X297公釐） 0176b A6 B6 五、發明説明（ 表4 6 7 8 餵入 樹脂 餵入 樹脂 餵入 樹I 量 中量 量 中量 量 中1 50 50 100 100 90 90 50 50 一 一 5 5 (請先閲讀背面之注意事項再填寫本頁) 實施例 酸成分 對苯二甲酸（莫耳份） 異酞酸 （莫耳份） 環己烷一二羧酸（莫耳份） 醇成分 五赤藻糖醇（莫耳份） 三羥甲基丙烷（莫耳份） — — — — 15 15 BPPO (莫耳份） 40 40 65 65 60 6C 氫化雙酚A (莫耳份） — — 10 10 10 C 環己二醇 (莫耳份） 10 7 一 — — — 乙二醇 (莫耳份） 71 54 30 18 45 4C 三甘醇 (莫耳份） — — 10 10 — — 經濟部中央標準局員工消費合作社印製 m 0 0 1 η 1 1 0 a 4 6 15 b 47 75 69 樹脂之物理性質 Tg (°C) 64 67 71 酸值 （rag—KOH/g) 2 5 6 本紙張尺度逍用中Η B家標準（CNS)甲4規格(210x297公龙） -12- ^01tC5 A6 __B_6_ 五、發明説明（） 表5 實施例6 在壓力回至大氣壓後轉矩在3.0 kg— cm 保持30分鐘 實施例7 在壓力回至大氣壓後轉矩在超過10分鐘 内增加至3.5 kg— cm,然後轉矩保持此 值 實施例5 在壓力回至大氣壓後轉矩在3.0 kg— cm 保持30分鐘 比較實施例1至3 ' 除了起始物質之餵入量如表6所示，反應以實施例1 所述之相同方式進行。在比較實施例1中，反應未達交聯 點。在比較實施例2至3中，交聯反應不能被停止。 (請先閲讀背面之注意事項再填寫本頁) 裝. 訂- 線. 經濟部中央標準局貝工消費合作社印製 本紙張尺度逍用中國困家標準(CNS)甲4規格(210x297公龙）-13- 五、發明説明（ 表6 A6 B6 3 經濟部中央標準局貝工消費合作社印製 比較實施例 2 餵入 樹脂 餵人 樹脂 酸成分 量 中量 量 中量 偏苯六甲酸酐（莫耳份） 6 6 19 19 苯四甲酸酐 (莫耳份） — — — — 對苯二甲酸 (奠耳份） 85 85 51 51 異酞酸 (莫耳份） 9 9 30 30 己二酸 (莫耳份） — — — — 醇成分 ΒΡΡ0 (莫耳份） 45 45 65 65 氫化雙酚A (莫耳份） 5 4 5 5 乙二醇 (莫耳份） 70 56 40 35 1, 4一 丁二醇（莫耳份） 10 8 一 — m 1 1 π 0 0 a 6 19 b 50 70 樹脂之物理性質 Tg (°C) — 61 酸值 (mg- KOH/ g) 24 入 餵 量 樹中 8 ο 7 8 ο 7 2 2 2 2 5 2 5 2 ο 0 18 5 2 3 4 4 1 (請先閲讀背面之注意事項再填寫本頁) 裝- 本紙張尺度逍用中國S家標準（CNS)甲4規格(210x297公釐) -14- A 6 B6 五、發明説明（） 表7 比較實施例1 聚縮合作用進行10小時，但反應混合 %物黏度並未增加 比較實施例2 在壓力回至大氣壓後，轉矩在超過10 分鐘内增加至7.0 kg— cm,且黏度增 加，停止攪拌，並由反應容器中移出 樹脂 比較實施例3 在轉矩增加至1.0 kg— cm後，卽使壓 力回至大氣壓且停止攪拌，黏度快速 升高且反k並未停止，樹脂黏度太高 而由反應容器中回收樹脂變為困難 比較實施例4至6 除了起始物質之餵入量如表8所示，反應以實施例4 所述之相同方式進行。結果顯示於表8及9。在比較實施 例4中，反應未達交聯點。在比較實施例6，交聯反應不 能被停止。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 -15 — 本紙張尺度逍用中國國家標準(CNS)甲4規格(210x297公货) 01765 A6 B6 五、發明説明（） 表8 經濟部中央標準局貝工消費合作社印製 實施例 4 5 6 餵入 樹脂 餵入 樹脂 餵入 樹辟 酸成分 量 中量 量 中童 量 中售 對苯二甲酸 (莫耳份） 60 60 50 50 60 60 異酞酸 (莫耳份） 40 40 50 50 40 40 醇成分 五赤藻糖醇 (莫耳份） 2 2 5 5 — — 三羥甲基丙烷（莫耳份） — — — — 13 13 ΒΡΡ0 (莫耳份） 25 25 90 90 15 15 氫化雙酚A (莫耳份） 5 5 — — — — 乙二醇 (莫耳份） 70 53 25 13 77 69 三甘醇 (莫耳份） 18 18 — — — — 新戊二醇 (莫耳份） — 一 — — 10 8 ΓΤΊ 0 0 1 η 1 1 0 a 2 5 13 b 30 90 15 樹脂之物理性質 Tg (°C) —— — 57 酸值 (mg- KOH/ g) (請先閲讀背面之注意事項再填寫本頁)X pack. Order · -Line · The size of this paper is easy to use China National Standards (CNS) A 4 specifications (210X297 g *) -5- Printed by the Beigong Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs i, 〇1765 A6 ___B_6_ 5 Description of the invention () Adipic acid, sebacic acid, malonic acid and glutaric acid, and their anhydrides and lower alkyl esters. These dicarboxylic acids may be used alone or as a mixture of at least two components. The aromatic or aliphatic aliphatic diol component used in the present invention, wherein one hydroxyl group is a secondary hydroxyl group, is not specially prepared. For example, it can be poly (propylene) (k) -2,2-bis (4-hydroxyphenyl) propane (k represents the number of moles of the propylene unit), cyclohexanediol, bisphenol A , Hydrogenated bisphenol F and hydrogenated bisphenol S. These diols can be used alone or as a mixture of at least two components. The other diol components used in the present invention are not to be prepared separately. For example, it can be ethylene glycol, 1, 2-propanol diol, 1,3-propanol diol, 1, 4-propanol diol, 1, 3-butanediol, 1, 2-butane diol Alcohol, diethylene glycol, triethylene glycol, tetracoholol, 1, 6_ hexane two fermentation, neopentyl glycol, cyclohexane dimethanol and polynitroethylene (1)-2, 2-bis (4 -Hydroxyphenyl) propane (1 represents the number of moles of ethylene subunits). These diols can be used alone or as a mixture of at least two components. The most important features of the present invention are unit (a) trivalent or tetravalent polycarboxylic acid component and / or trihydro or tetrahydropolyhydric alcohol component, and unit (b) aromatic or cycloaliphatic diol component, at least The one hydroxyl group is a secondary hydroxyl group, and the content thereof satisfies the requirements represented by the aforementioned formula (I). If the amount of the component (b) unit is less than the range defined by formula (I), the crosslinking reaction rate is too high and it is difficult to stop the crosslinking reaction. If the amount of the component (b) unit exceeds the range defined by formula (I), the crosslinking reaction rate is too low and it is difficult to reach the crosslinking point. The amount of other diol component (C) (convenient component) and dicarboxylic acid component (D) (please read the precautions on the back before filling the nest page) Pack * Order · Thread · The paper size is in accordance with Chinese standard (CNS) A4 specifications (210X297 Gong-6- ^ 01765 A 6 B6 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description () Appropriately according to the components (a) and (b) defined in the aforementioned formula (I) ) Is selected. Preferably, the glass transition temperature (Tg) of the polyester resin of the present invention is between 50 and 75 ° C. If the Tg is lower than 5 (TC, the sealing resistance of the toner is likely to decrease, and If the Tg exceeds 75 ° C, the fixing properties of the toner usually become poor. Preferably, the acid value of the resin of the present invention is not greater than 15 rag—KOH / g. If the acid value exceeds 15 mg—KOH / g, the color The powder's moisture resistance becomes poor. The polyester resin of the present invention can be prepared by a conventional method suitable for general polyester resin production. For example, the esterification or transesterification reaction is first carried out and continued until the distillation of water or lower alcohol is stopped. In this reaction, a known exchange catalyst can be used as required. Then the polycondensation reaction is below 15 G Torr It is carried out in air, and the reaction is terminated when the reaction mixture reaches the expected degree of crosslinking. In this reaction, a known polycondensation catalyst can be used as needed. In this specification, "crosslinking point" means in the polycondensation reaction The point where the viscosity of the reaction mixture increases rapidly, "resin with a cross-linked structure" means a resin that has reached the cross-linked point. The present invention is described in more detail with reference to the following examples, but is not intended to limit the present invention. In the examples, polymer The acid value of the ester resin is determined by dissolving the sample in benzyl alcohol and titrating the solution with KOH, and the glass transition temperature Tg is measured at a temperature increase rate of 5. C / min using a differential scanning calorimeter. The reference line obtained by the device and the tangent line of the heat absorption curve near T g are obtained at the intersection point. Example 1 The formula shown in Table 1 was fed into a high-pressure furnace with a distillation tube and a capacity of 2 liters. Formic acid, isoacid, trimellitic acid tincture, ethylene glycol (please read the precautions on the back before writing this page)-Pack. Order · Thread · This paper standard is used in the national standard (CNS) A 4 specifications (210X297 male dragon) voltes A 6 B6 Description (), Polypropylene mono- (2, 3) — 2, 2-bis (4-hydroxyphenyl) propane and neopentyl glycol (total weight 1 kg), add 500 ppm of acid component (Weight) No. 3 vaporizes antimony and performs esterification reaction. When the point where the reaction stops forming water distillation, the esterification reaction is completed. At this point, the stirring torque is 0.3 kg_CB 100 rpn. Then within 24 0 ° C The polycondensation reaction is carried out under vacuum at 3 Torr under temperature, and the viscosity of the reaction mixture begins to increase, and when the torque reaches 3.0 kg-cm, the vacuum state is eliminated by adding krypton gas to atmospheric pressure. Continue to stir while maintaining the internal temperature at 240 ° C, although the stirring was performed for 30 minutes and the torque was maintained at 3,0 U-cm. Also in the resin of this example, the cross-linking reaction does not proceed vigorously but can be stopped when the desired cross-linking degree is reached. The combination of resins obtained, Tg and acid value are shown in Table 1. '(Please read the precautions on the back before filling in this page) Binding · Order. Thread-Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Beigong Consumer Cooperative, this paper standard is used in the 8 National Standard (CNS) A 4 specifications (210x297 public goods ) A 6 B6 V. Description of the invention () Table 1 The amount of acid component trimellitic anhydride (mol parts) in the resin fed 11 11 Terephthalic acid (mol parts) 89 89 Isophthalic acid (mol parts) 1〇1〇 alcohol component BPP0; 1 (mol parts) 55 55 ethylene glycol (mol parts) 5 0 4 2 neopentyl glycol (mol parts) · 2 5 2 0 m 1 η 〇a 1 〇b 50 Physical properties of resin Tg (° C) 63 Acid value (rag-KOH / g) 5 (Please read the precautions on the back before filling out this page) Packing-Line-Printed by the Ministry of Economic Affairs Central Standards Bureau A Industrial and Consumer Cooperative Printed Note Polychloropropylene mono (2, 3)-2, 2-bis (4 monohydroxyphenyl) propane (same as in Tables 2, 4, 6 and 8 hereafter) Examples 2 to 5 This paper size is used in China Standard (CNS) A4 specifications (210x297 gongjie) — 9 A6 _B6 printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Invention description () Table 2 Example 2 3 4 5 Feeding resin feeding resin feeding resin feeding resin acid content of the medium amount of medium amount of medium amount of medium amount of trimellitic anhydride (mol parts) 10 10 14 14 — — — — pyromellitic anhydride (mol Parts) — — — 3 3 5 5 terephthalic acid (mol parts) 90 90 70 70 60 60 90 90 isophthalic acid (mol parts) — — 10 10 37 37 5 5 adipic acid (mol parts) ) — 6 6 — — — — Alcohol component BPP0 (mole parts) 15 15 45 45 10 10 25 25 Hydrogenated bisphenol A (mole parts) 15 15 5 5 — — — Ethylene glycol (mole parts) 90 70 60 54 125 116 65 59 Diethylene glycol (moles) — — — — 5 4 — — BPE0 " 1 20 20 10 10 — — 25 25 m 1 1 0 0 η 0 0 1 1 a 10 14 3 5 b • 30 50 10 25 Physical properties of resin Tg (° C) 58 65 51 61 Acid value (nig-K0H / g) 3 14 5 12 Note-1: Polyethylene ethylene one (2, 3) — 2, 2_bis (4-hydroxyphenyl) propane (same as in Table 10 hereafter) (Please read the note on the back first Please fill in this page again for details) Binding · Order _ This paper scale is printed in Chinese National Standard (CNS) A4 specifications (210x297 male dragon) -10- A 6 B6 Printed by Beigong Consumer Cooperative of Central Bureau of Economy, Ministry of Economy V. Inventions Explanation () According to the feed formula shown in Table 2, the reaction was carried out in the same manner as described in Example 1. The results obtained are shown in Tables 2 and 3. In Examples 2 to 5, each crosslinking reaction can be stopped. Table 3 Example 2 After the pressure returns to atmospheric pressure, the torque increases to 3.5 kg-cm in more than 5 minutes, but the torque is maintained at this amount for 30 minutes. Example 3 After the pressure returns to atmospheric pressure, the torque is 3.0 kg — cm is maintained for 30 minutes-Example 4 is the same as Example 3 Example 5 The torque increases to 3.8 kg-cm in more than 10 minutes after the pressure is returned to atmospheric pressure, and then the torque is maintained at this value Examples 6 to 8 according to the table The formula shown in 4 is added, and the reaction is carried out in the same manner as described in Example 1, except that lead acetate in an amount of 200 ppm (weight of the acid component) and dibutyl in an amount of 4 QQ ppm (weight of the acid component) Tin oxide is used as a catalyst. The results obtained are shown in Tables 4 and 5. In Examples 6 to 8, each crosslinking reaction can be stopped. (Please read the precautions on the back before filling in this page) Binding · Order. Line. This paper size is easy to use in the BB home sample standard (CNS) A 4 specifications (210X297 mm) 0176b A6 B6 V. Invention description (Table 4 6 7 8 Resin feeding Resin feeding tree I Amount of medium amount Amount of medium amount 1 50 50 100 100 90 90 50 50 1 1 5 5 (please read the precautions on the back before filling this page) Example acid Ingredients Terephthalic acid (mole part) Isophthalic acid (mole part) Cyclohexane dicarboxylic acid (mole part) Alcohol component Pentaerythritol (mole part) Trimethylolpropane (mole part) Parts) — 15 — 15 15 BPPO (mole parts) 40 40 65 65 60 6C Hydrogenated bisphenol A (mole parts) — — 10 10 10 C Cyclohexanediol (mole parts) 10 7 — — Ethylene glycol (moles) 71 54 30 18 45 4C Triethylene glycol (moles) — — 10 10 — — Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs m 0 0 1 η 1 1 0 a 4 6 15 b 47 75 69 Physical properties of the resin Tg (° C) 64 67 71 Acid value (rag—KOH / g) 2 5 6 This paper is used in the middle of the family standard (CNS) A 4 Grid (210x297 male dragon) -12- ^ 01tC5 A6 __B_6_ V. Description of the invention () Table 5 Example 6 Torque at 3.0 kg-cm after pressure returned to atmospheric pressure for 30 minutes Example 7 Example 7 After pressure returned to atmospheric pressure The torque increases to 3.5 kg-cm in more than 10 minutes, and then the torque is maintained at this value. Example 5 After the pressure is returned to atmospheric pressure, the torque is maintained at 3.0 kg-cm for 30 minutes. Comparative Examples 1 to 3 'Except for the starting material The feeding amount is shown in Table 6, and the reaction was carried out in the same manner as described in Example 1. In Comparative Example 1, the reaction did not reach the crosslinking point. In Comparative Examples 2 to 3, the crosslinking reaction could not be stopped (Please read the precautions on the back before filling in this page). Binding. Thread. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper scale is free to use the China Sleepy Family Standard (CNS) Grade 4 (210x297 male dragon) ) -13- V. Description of the invention (Table 6 A6 B6 3 Comparative example printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 2 Feeding the resin and feeding the resin The amount of resin acid content is moderate to moderate amount of trimellitic anhydride (mole Servings) 6 6 19 19 Pyromellitic anhydride (mole Parts) — — — — terephthalic acid (molar part) 85 85 51 51 isophthalic acid (mole part) 9 9 30 30 adipic acid (mole part) — — — alcohol component BPP0 (mole part ) 45 45 65 65 Hydrogenated bisphenol A (mole parts) 5 4 5 5 Ethylene glycol (mole parts) 70 56 40 35 1, 4-butanediol (mole parts) 10 8 mono — m 1 1 π 0 0 a 6 19 b 50 70 Physical properties of the resin Tg (° C) — 61 Acid value (mg-KOH / g) 24 Enter the feeding tree 8 ο 7 8 ο 7 2 2 2 2 5 2 5 2 ο 0 18 5 2 3 4 4 1 (please read the precautions on the back before filling in this page) Packing-This paper scale uses Chinese S family standard (CNS) A4 specifications (210x297 mm) -14- A 6 B6 5. Description of the invention () Table 7 Comparative Example 1 Polycondensation was carried out for 10 hours, but the viscosity of the reaction mixture% did not increase. Comparative Example 2 After the pressure was returned to atmospheric pressure, the torque increased to 7.0 kg-cm in more than 10 minutes , And the viscosity increases, the stirring is stopped, and the resin is removed from the reaction vessel. Comparative Example 3 After the torque is increased to 1.0 kg-cm, the pressure is returned to atmospheric pressure And the stirring was stopped, the viscosity increased rapidly and the reaction did not stop. The resin viscosity was too high and it was difficult to recover the resin from the reaction vessel. Comparative Examples 4 to 6 Except for the feed amount of the starting material, as shown in Table 8, the reaction This was carried out in the same manner as described in Example 4. The results are shown in Tables 8 and 9. In Comparative Example 4, the reaction did not reach the cross-linking point. In Comparative Example 6, the cross-linking reaction cannot be stopped. (Please read the precautions on the back and then fill out this page) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -15 — This paper scale uses the Chinese National Standard (CNS) A 4 specifications (210x297 public goods) 01765 A6 B6 V Description of the invention () Table 8 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 4 5 6 Feeding resin Feeding resin feeding resin The amount of acid content in the medium amount The amount of children sold in terephthalic acid (Mo Ear parts) 60 60 50 50 60 60 Isophthalic acid (mol parts) 40 40 50 50 40 40 Alcohol component Pentaerythritol (mol parts) 2 2 5 5 — Trimethylolpropane (mol parts) ) — — — — 13 13 BPP0 (mol parts) 25 25 90 90 15 15 Hydrogenated bisphenol A (mol parts) 5 5 — — — — Ethylene glycol (mol parts) 70 53 25 13 77 69 Alcohol (parts in moles) 18 18 — — — — neopentyl glycol (parts in moles) — 1 — 10 8 ΓΤΊ 0 0 1 η 1 1 0 a 2 5 13 b 30 90 15 Physical properties of the resin Tg (° C) —— — 57 acid value (mg- KOH / g) (please read the notes on the back first (Fill in this page again)
本紙張尺度逍用中國國家標準（CNS)甲4規格(210x297公龙） 16 — ίςΟί'ϊβδ A 6 Β6 五、發明説明（） ..表9 比較實施例 聚縮合作用進行10小時，但反應混合 4及5 物黏度並未增加 比較實施例6 在轉矩增加至1. 0 kg — cm後，即使壓 力回至大氣壓且停止攪拌，黏度快速 升高且反應並未停止，樹脂黏度太高 而由反應容器中回收樹脂變為困難 實施例9及1 〇 依表1 〇所示之餵入配方，反應以實施例1所述之相同 方式進行。所得之結果示於表'1 〇及11中。在實施例9及10 中，每一交聯反應可被停止。 (請先閲讀背面之注意事項再填寫本頁) 裝· 線· 經濟部中央標準局貝工消費合作社印製 本紙張尺度逍用中S a家標準(CNS)甲4規格(210x297公煃）_17_ 五、發明説明（ 表10 A 6 B6 實施例 9 10 餵入 樹脂 餵入 樹脂 酸成分 量 中量 置 中童 偏苯六甲酸酐（莫耳份） 18 18 7 7 對苯二甲酸 (莫耳份） 72 72 53 53 異酞酸 (莫耳份） 10 10 40 40 醇成分 BPP0**1 (莫耳份） 60 60 40 40 氫化雙酚A (莫耳份） 5 5 — — 乙二醇 (莫耳份） 65 60 80 74 新戊二醇 (莫耳份） 10 10 — — (請先閲讀背面之注意事項再填寫本頁) -裝. 訂- τη 1 1 η 0 0 a 18 7 b 65 40 脂之物理性質 Tg (°C) 6 1 66 酸值 (mg- KOH/ g) 本紙張尺度逍用中國國家橾準（CNS)甲4規格(210x297公*) 經濟部中央標準局貝工消費合作社印製 18- ^01765 A6 _____B6_ 五、發明説明（） 表11 實施例9 在壓力回至大氣壓後轉矩在超過10分鐘 内增加至3.7 kg— cm,然後轉矩保持此 值3 0分鐘 實施例10 在壓力回至大氣壓後轉矩在3.0 kg- cm 保持30分鐘 由前述詳細描述可見，依本發明之用於色粉的聚酯樹 脂為一具有交聯结構之樹脂，其為具有良好固定性質及良 好未偏離性質組合者，且此聚'醋樹脂可穩定製備而無快速 交聯反應的産生。 (請先閲讀背面之注意事項再填寫本頁) 裝· 經濟部中央標準局員工消費合作社印製 本紙張尺度边用中國國家櫺準(CNS)甲4規格(210X297公《)The size of this paper is in accordance with Chinese National Standard (CNS) A4 specifications (210x297 male dragon) 16 — ίςΟί'ϊβδ A 6 Β6 V. Description of invention () .. 4 and 5 The viscosity of the substance did not increase. Comparative Example 6 After the torque was increased to 1.0 kg — cm, even if the pressure returned to atmospheric pressure and the stirring was stopped, the viscosity increased rapidly and the reaction did not stop. The resin viscosity was too high. It became difficult to recover the resin in the reaction vessel. Examples 9 and 10 were fed in the formulation shown in Table 10. The reaction was carried out in the same manner as described in Example 1. The results obtained are shown in Tables '10 and 11. In Examples 9 and 10, each crosslinking reaction can be stopped. (Please read the precautions on the back before filling in this page) Installation · Line · Printed by the Central Standards Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative Paper Standards for Saa Standard (CNS) Grade 4 (210x297 Gongxu) _17_ V. Description of the invention (Table 10 A 6 B6 Example 9 10 Feeding the resin Feeding the resin with the acid content of the medium amount of phthalic anhydride (mol parts) 18 18 7 7 Terephthalic acid (mol parts) 72 72 53 53 Isophthalic acid (mol parts) 10 10 40 40 Alcohol component BPP0 ** 1 (mol parts) 60 60 40 40 Hydrogenated bisphenol A (mol parts) 5 5 — — Ethylene glycol (mol parts) Copies) 65 60 80 74 neopentyl glycol (moles) 10 10 — — (please read the precautions on the back before filling this page)-Pack. Order-τη 1 1 η 0 0 a 18 7 b 65 40 grease Physical properties Tg (° C) 6 1 66 Acid value (mg- KOH / g) This paper scale is used in China National Standard (CNS) A 4 specifications (210x297 g *) Printed by Beigong Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs System 18- ^ 01765 A6 _____B6_ V. Description of the invention () Table 11 Example 9 Torque within 10 minutes after the pressure returns to atmospheric pressure Add it to 3.7 kg-cm, and then keep the torque at this value for 30 minutes. Example 10 After the pressure is returned to atmospheric pressure, the torque is kept at 3.0 kg-cm for 30 minutes. As can be seen from the foregoing detailed description, according to the invention, it is used for toner Polyester resin is a resin with a cross-linked structure, which is a combination of good fixing properties and good non-deviation properties, and this poly vinegar resin can be stably prepared without rapid cross-linking reaction. (Please read the back side first (Notes to fill out this page) Outfit · Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Employee Consumer Cooperatives. This paper is used for the standard of China National Standards (CNS) A 4 specifications (210X297)