TW552266B - Method for preparing saturated polyester with excellent mechanical properties - Google Patents

Abstract

Disclosed is a method for preparing saturated polyester used in various molded products, such as films, synthetic fibers, vessels and housings. In particular, the method improves mechanical properties, including tensile strength or impact resistance, of saturated polyester. In DMT method or TPA method, the saturated polyester is synthesized through transesterification or esterification and polycondensation, in which metal compounds, such as metal acetate compounds, metal metal hydroxides, and metal oxides, are added in the larger amounts upon synthesis, and thus crystalline internal grains are formed, thereby improving the mechanical properties. As such, the metal compound can be used alone or in combination with a phosphorous-based compound.

Description

552266 _案號 90118405_年月日_魅_ 五、發明說明（1) 發明背景 【發明領域】 本發明係關於一種製備飽和聚酯之方法，此飽和聚酯 通常用在薄膜、合成纖維及各種模造產品中。更具體地說 ，本發明是關於一種藉由在聚酯之聚合鏈内形成内部細粒 而改善聚酯之機械性質之方法。 【先前技術】 一般而言，習知的飽和聚酯通常為具有酯類鍵結之熱 塑性直鏈聚合物，如聚乙烯酞酸鹽（PET)，聚丁烯對酞 酸鹽（PBT)等等，皆具有絕佳的因次穩定性，周圍穩定 性和去表面能力，以及透明度和良好的外觀，使其被廣泛 地應用在模造產品（包括合成纖維，薄膜，容器或外罩） 中 〇 然而，此類飽和聚酯與其他工程用塑膠比較之下，卻 因高熔點和結晶性而苦於具有較低之衝擊抵抗性和抗張強 度之問題。 一般來說，就改善合成樹脂之機械性質的方法而論， 有一種塑造一填充料或強化物質之方法，其對於改善合成 基礎樹脂之融化射出或注入時的機械性質很重要。V旦此方 法卻具有填充料或強化物質較基礎樹脂貴之缺點，導致包 括各種程序花費的製備成本變得較高。 . 此外，製備飽和聚酯時，已知可在合成反應期間使用 金屬化合物作為觸媒，或者，在樹脂製備之後或合成樹脂 時的融化射出步驟時使用金屬化合物或金屬細粒，以改善552266 _Case No. 90118405_Year Month_Charm_ V. Description of the invention (1) Background of the invention [Field of the invention] The present invention relates to a method for preparing saturated polyester, which is usually used in films, synthetic fibers and various In molded products. More specifically, the present invention relates to a method for improving the mechanical properties of a polyester by forming internal fine particles within a polymer's polymer chain. [Prior art] In general, the conventional saturated polyesters are usually thermoplastic linear polymers with ester linkages, such as polyethylene phthalate (PET), polybutylene terephthalate (PBT), etc. All have excellent dimensional stability, peripheral stability and surface removal ability, as well as transparency and good appearance, which makes them widely used in molded products (including synthetic fibers, films, containers or covers). However, Compared with other engineering plastics, this type of saturated polyester suffers from low impact resistance and tensile strength due to its high melting point and crystallinity. In general, in terms of a method for improving the mechanical properties of synthetic resins, there is a method for molding a filler or a reinforcing material, which is important for improving the mechanical properties of a synthetic base resin when it is melted and injected. However, this method has the disadvantage that the filler or reinforcing material is more expensive than the base resin, resulting in higher preparation costs including various procedures. In addition, when preparing saturated polyesters, it is known that a metal compound can be used as a catalyst during a synthetic reaction, or a metal compound or metal fine particles can be used after the resin preparation or during the melting injection step during the synthetic resin to improve

第5頁 552266 _案號 90Π8405 五、發明說明（2) 年 月 曰 修正 聚酯纖維的發火抵抗性和質地。 就這點而言，美國專利編號第4，3 0 7，1 5 2號和第 4，3 7 1，4 8 5號是關於藉由將金屬化合物加入聚酯樹脂並紡 織以改善聚酯纖維之抗火性和保水性的技術。此外，美國 專利編號第4，5 4 5，9 4 9號揭示一種使用金屬化合物作為酯 基交換作用之觸媒來改善纺織操作並提昇反應。 在如上所述的傳統技術中，係使用少量金屬化合物作 為觸媒來提昇聚酯的合成反應。然而，當使用大量的金屬 化合物時，飽和聚酯會包含作為外部細粒的金屬化合物細 粒（約1 -1 0/z m)，使得金屬化合物無法改善飽和聚酯的 機械性質，甚至降低了其性質。 發明概述 所以，本發明之一目的為克服上述先前技術中所遇到 之問題，而提供一種改善飽和聚酯之機械性質的新穎方法 ，其藉由在飽和聚酯樹脂合成時添加具有離子基的金屬化 合物，使金屬離子分散於聚酯之聚合鏈中或與其反應，而 產生内部結晶細粒。 貫施例之詳細說明 本發明製備飽和聚酯之方法特色係在於當藉由酯基交 換作用（或酯化）及聚合濃縮來製備飽和聚酯時，所使用 的金屬化合物重量含量比例為1 - 1 0% 在本發明中，係使用芳香族二魏酸或酯類衍生物及乙 烯乙二醇作為主要的起始物質，且可進一步包含其他第三 成分。芳香族二羧酸可選自異酞酸，對苯二甲酸，2，6 -萘Page 5 552266 _ Case No. 90Π8405 V. Description of the invention (2) Month, month, and date Correction The fire resistance and texture of polyester fiber. In this regard, U.S. Patent Nos. 4,3,07,152 and 4,3,7,4,85 are related to improving polyester fibers by adding metal compounds to polyester resins and spinning Fire resistance and water retention technology. In addition, U.S. Patent No. 4,5 4 5,9 4 9 discloses the use of a metal compound as a transesterification catalyst to improve textile operations and response. In the conventional technique as described above, a small amount of a metal compound is used as a catalyst to promote the synthesis reaction of polyester. However, when a large amount of a metal compound is used, the saturated polyester contains metal compound fine particles (approximately 1 -1 0 / zm) as external fine particles, so that the metal compound cannot improve the mechanical properties of the saturated polyester, or even reduce its nature. SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to overcome the problems encountered in the foregoing prior art, and to provide a novel method for improving the mechanical properties of saturated polyester by adding an ionic group during the synthesis of a saturated polyester resin. A metal compound disperses or reacts metal ions in the polymer chain of the polyester to produce internal crystalline fine particles. The detailed description of the examples is that the method for preparing saturated polyester of the present invention is characterized in that when the saturated polyester is prepared by transesterification (or esterification) and polymerization and concentration, the weight ratio of the metal compound used is 1- 10% In the present invention, an aromatic diferulic acid or an ester derivative and ethylene glycol are used as the main starting materials, and other third components may be further included. The aromatic dicarboxylic acid may be selected from isophthalic acid, terephthalic acid, 2,6-naphthalene

議Ιι國 I：Country I I:

11 第6頁 552266 _案號90118405_年月日_Ifi_ 五、發明說明（3) 二羧酸，酞酸，己二酸，癸二酸所組成的基團，或其混合 物。例如乙二醇成分可以乙烯乙二醇來製造。此外，丙烯 乙二醇，丁二醇，1，4 -環己二曱醇，新戊基乙二醇等皆可 少量使用。 需要的話，本發明所合成的飽和聚酯可進一步包含添 加劑，如熱穩定劑，抗阻塞劑，抗氧化劑，抗靜電劑，以 及紫外光吸收劑。11 Page 6 552266 _Case No. 90118405_Year_Ifi_ V. Description of the invention (3) Group consisting of dicarboxylic acid, phthalic acid, adipic acid, sebacic acid, or a mixture thereof. For example, the ethylene glycol component can be produced from ethylene glycol. In addition, propylene glycol, butylene glycol, 1,4-cyclohexanediol, neopentyl glycol, etc. can be used in small amounts. If necessary, the saturated polyester synthesized in the present invention may further contain additives such as a heat stabilizer, an anti-blocking agent, an antioxidant, an antistatic agent, and an ultraviolet light absorber.

在以上述起始物質來合成飽和聚酯時，即可加入金屬 化合物。此類金屬化合物在反應時可為金屬離子形式，以 金屬醋酸鹽化合物為例，如醋酸鋰，醋酸鈉，醋酸鉀，醋 酸鈣，醋酸錳，醋酸鎂，醋酸鋅，以及醋酸銻；金屬氫氧 化物，如氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化鈣、氫 氧化錳、氳氧化辞、氬氧化鎂；金屬氧化物，如氧化銻、 氧化鍺、氧化鈦。金屬化合物可單獨使用或與其他化合物 混合。 理想上，金屬氧化物的使用量為金屬重量含量的1 -1 0 % ，更理想地說為1. 5 - 3. 0% 。若使用量之重量比例少於1 % ，則會形成内部細粒但機械性質並不會改善。換言之，When the saturated polyester is synthesized from the above starting materials, a metal compound can be added. Such metal compounds can be in the form of metal ions during the reaction. Metal acetate compounds are used as examples, such as lithium acetate, sodium acetate, potassium acetate, calcium acetate, manganese acetate, magnesium acetate, zinc acetate, and antimony acetate; metal hydroxide Materials, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, manganese hydroxide, rhenium oxide, argon magnesium oxide; metal oxides, such as antimony oxide, germanium oxide, and titanium oxide. The metal compound may be used alone or mixed with other compounds. Ideally, the metal oxide is used in an amount of 1 to 10% by weight of the metal, more preferably 1.5 to 3.0%. If the weight ratio of the used amount is less than 1%, internal fine particles will be formed but the mechanical properties will not be improved. In other words,

若重量比例超過1 0% ，則處理性會較差且無法良好地正常 反應，而性質的穩定性亦會降低。 此外，當添加金屬化合物時，含礎化合物，包括礎酸 ，TMP (三甲基磷酸鹽），TEP (三乙基磷酸鹽），以及 TPP (三苯基填酸鹽），皆可添加在一起。在此類情況中 ，含鱗化合物對於改善樹脂顏色以及藉由在樹脂中形成具If the weight ratio exceeds 10%, the handleability will be poor and the normal reaction will not be good, and the stability of the properties will be reduced. In addition, when metal compounds are added, basic compounds including basic acids, TMP (trimethyl phosphate), TEP (triethyl phosphate), and TPP (triphenyl salt) can be added together. . In such cases, scale-containing compounds are useful for improving resin color and by forming

552266 案號 90118405 年 月 曰 修正 五、發明說明（4) 有金屬離子之鹽類以改善機械性質是很重要的。此類含磷 化合物的添加量會被控制，其是根據金屬離子的化學計量 比例而定，理想上所添加的重量比例為0 . 0 5 - 5 . 0% ，其係 以構的含量為基準。 如上所述，當聚酯合成時加入金屬化合物或者金屬化 合物和含磷化合物之混合物，則添加程序及添加時間在本 發明中並不限制。然而，在DMT (二曱基對酞酸鹽）方法 中，同時添加大量化合物會因快速反應而造成液流，而阻 礙整個反應系統。所以，緩慢添加上述化合物是較佳的。 此外，酯化作用進行了 7 0%或更多之後，是添加化合物的 較佳時機。如此的話，抵抗液流的穩定性會變高。 TPA (對苯二曱酸）方法之添加程序及時間並不受限 制，這是因為液流發生的危險性較低之故。但，酯化作用 進行至9 0%或更多時，是添加化合物的較佳時機。快速添 加溶解於EG中的金屬化合物會使得反應溫度猛然下降，而 造成反應速率降低之問題。因此，理想上化合物應緩慢地 添加（超過2 0分鐘或更多）。 在酯基交換作用或聚合期間加入金屬化合物及含磷化 合物會在BHT (雙-礙-羥基乙烯對酞酸鹽）-曱基形式或 Β Η T -甲基-填。在Β Η T内所產生的細粒是以某種形式（内部 細粒）存在，這種形式是由聚合鏈和極小或直徑為埃之金 屬離子反應所形成的形式。此類ΒΗΤ包含強健的結晶細 粒。内部細粒依ΒΗΤ的聚合程度而有不同的尺寸。高聚合 程度的ΒΗΤ會導致所產生的内部細粒數量及尺寸增加。552266 Case No. 90118405 Amendment V. Description of the invention (4) It is important to improve the mechanical properties of salts with metal ions. The amount of such phosphorus-containing compounds will be controlled, which is determined according to the stoichiometric ratio of metal ions. Ideally, the weight ratio is 0.05 to 5.0%, which is based on the content of the structure. . As described above, when a metal compound or a mixture of a metal compound and a phosphorus-containing compound is added during polyester synthesis, the addition procedure and time are not limited in the present invention. However, in the DMT (difluorenyl terephthalate) method, the simultaneous addition of a large amount of compounds can cause liquid flow due to rapid reactions, which hinders the entire reaction system. Therefore, it is preferable to slowly add the above compounds. In addition, after 70% or more of the esterification, it is a better time to add the compound. In this way, the stability against liquid flow becomes high. The procedure and time for adding TPA (terephthalic acid) is not limited, because the danger of liquid flow is low. However, when the esterification proceeds to 90% or more, it is a better time to add the compound. The rapid addition of metal compounds dissolved in EG will cause the reaction temperature to drop sharply, which will cause the problem of reduced reaction rate. Therefore, ideally the compound should be added slowly (over 20 minutes or more). The addition of metal compounds and phosphorus-containing compounds during transesterification or polymerization can result in a BHT (bis-blocker-hydroxyethylene terephthalate) -fluorenyl form or a BΗT-methyl-filler. The fine particles produced in B Η T exist in a form (internal fine particles), which is a form formed by the reaction of polymerized chains and metal ions with extremely small or angstrom diameters. These BHTs contain robust crystalline fine particles. The internal fine particles have different sizes depending on the degree of polymerization of BHT. A high degree of polymerization of BHT results in an increase in the number and size of internal fine particles produced.

第8頁 552266 -^^.^90118405 修正 曰 五、發明說明（5) 此外，合凰几人， 入％ 5 士 a I a物可以固體形式來添加，但以金屬化 八®此豹六p ;早m中之形式是較佳的，如E G，藉使 ,,,a, , RR 子化且付到均勻尺寸的内部細粒。 在纟兄明本發明的间性 「j寸，耩由苓考特定範例可得到進一步的 ^ ^ ~別指定，否則這些範例在此僅供說明而非 作為限制。 範例一 ^卜，1〇〇_重里單位的對苯二曱酸（了？人）和45重量單位之 力…反應器，並勸熱，使得反應 ，㈣增至23〇°C。接著，酯基交換作用4小時以製 加入1 3 5重量單位融化的EG且使反應器溫度維 、 ，此E G具有8 · 0%重量比例的醋酸鈣。當反應5| 藉由攪拌被加熱時，溫度會從22(rc增至24(rc，這期ϋ 含有EG及TPA( EG對ΤΡΑ的莫耳比為115)之143重量單位 的漿料以超過2小時的時間加入其中，且維 其進-步反應。之後，加入U3重量單位之三在氧 應壓力會在40分鐘期間降至κ 0托爾。使溫 鐘的時間從24扣增至_，並執行聚合濃縮^ ^Page 8 552266-^^. ^ 90118405 Amendments to the fifth and description of the invention (5) In addition, a few people in Hehuang, 5% a Shi a I a thing can be added in solid form, but with metallized eight this leopard six p ; The form in early m is better, such as EG, if ,,, a,, RR is protonated and paid to the inner fine particles of uniform size. In Xiong Ming's understanding of the present invention, the "j inch", the specific examples of Lingyu can be further specified. Otherwise, these examples are for illustration only and not for limitation. Example 1 ^ 卜 ， １０〇 _The unit of terephthalic acid (by? Man) and the force of 45 units of weight ... reactor, and persuaded the heat to make the reaction increase to 23 ° C. Then, the transesterification was performed for 4 hours to add 1 3 5 weight units of melted EG and the reactor temperature dimension, this EG has a ratio of 8. 0% by weight of calcium acetate. When the reaction 5 | is heated by stirring, the temperature will increase from 22 (rc to 24 ( rc, this period ϋ slurry containing 143 weight units of EG and TPA (the molar ratio of EG to TPA is 115) was added to it for more than 2 hours, and it was further reacted. Then, U3 weight units were added The third is that the oxygen stress will drop to κ 0 Torr in 40 minutes. The time of the temperature clock is increased from 24 to _, and the polymerization is concentrated ^ ^

生聚酯（I ) 。 U Τ I 範例二 完成如範例一所述之程序，但將含有8. 〇%重量比例 之1 3 5重量單位的EG改為醋酸鈣而產生聚酯（ ’。 將1 00重量單位的TPA和45重量單位的EG加入反應器，Raw polyester (I). U T I Example 2 completes the procedure as described in Example 1, but changes EG containing 8.0% by weight to 35 units of EG to calcium acetate to produce polyester ('. TPA and unit of 100 units by weight 45 weight units of EG were added to the reactor,

第9頁 552266 月 案號 90118405 五、發明說明（6) 並攪拌加熱，使反應溫度從1 9 〇t增至2 3 〇°C。 , ^ 交換作用4小時以製備BHT，然後加入22. 4二，後’，5 和EG的混合物’其包含3. 0%重量比例的磷酸里二，,::夂 1 35重量單位融化的EG且使反應器溫度維持在，σ ^有8. 0% ί量比例的醋酸！弓。當反應器藉被 時’溫度會從22 0°C增至24(TC，這期間將含有“及τρΑ、、、 C EG對TPΑ的莫耳比為1· 15)之143重詈嚴你仏时 2小¥的k間加入其中’且維持在2 4扣下使其進一步反應 tt、時。之後，加入〇.03重量單位之三氧化銻且反應壓〜 力會在40分鐘期間降至1.0托爾。使溫度以超過5〇分鐘的 時間從240°C增至2 8 5X：，並執行聚合濃縮3小時而產生聚 酯（瓜）。 範例四 以相同於範例三之程序來執行，但具有3·⑽重量比 例之磷酸與EG的混合物之添加量改為6 · 9重量單位，且將 1 3 5重$單位融化E G所含有的8 · 0%重量比例醋酸鋰改為醋 酸鈣以得到聚酯（IV )。 比較範例一Page 9 552266 June No. 90118405 V. Description of the invention (6) Stirring and heating to increase the reaction temperature from 190 t to 230 ° C. ^ Exchange for 4 hours to prepare BHT, and then add 22. 4 two, after the 'mixture of 5 and EG' which contains 3.0% by weight of phosphoric acid lysine, :: 夂 1 35 weight units of melted EG And the reactor temperature was maintained at σ ^ with 8. 0% ί amount of acetic acid! bow. When the reactor is borrowed, the temperature will increase from 22 0 ° C to 24 (TC, during which the molar ratio of τρΑ ,,, C EG to TPΑ is 1.15). Add k 'between 2 hours and k' and keep it under 24 to make it react further. After that, add 0.03 weight unit of antimony trioxide and the reaction pressure will drop to 1.0 in 40 minutes. Thor. The temperature was increased from 240 ° C to 2 8 5X: over 50 minutes, and the polymerization was concentrated for 3 hours to produce polyester (melon). Example 4 was performed using the same procedure as Example 3, but The addition amount of a mixture of phosphoric acid and EG having a weight ratio of 3 · ⑽ was changed to 6.9 weight units, and 8.5% by weight of EG was used to melt the 8.0% by weight lithium acetate contained in calcium acetate into calcium acetate to obtain Polyester (IV). Comparative example one

將1 0 0重量單位的對苯甲酸和4 5重量單位的乙烯乙二 醇加入反應器，並攪拌加熱，使反應溫度從1 9 Ot增至2 3 〇 C以酯化4小時。將〇 · 〇 4重量單位之三氧化綈以及〇 . 〇 1 5重 量單位之磷酸與1重量單位之乙烯乙二醇混合。反應壓力 在溫度增加範圍為2 3 0 - 2 8 5它之下會下降，然後完成聚合 濃縮作用而產生聚酯（V )。100 parts by weight of p-benzoic acid and 45 parts by weight of ethylene glycol were added to the reactor, and the mixture was heated with stirring to increase the reaction temperature from 19 Ot to 230 C for 4 hours for esterification. 0.004 weight units of osmium trioxide and 0.05 weight units of phosphoric acid were mixed with 1 weight unit of ethylene glycol. The reaction pressure decreases below the temperature increase range of 2 3 0-2 8 5 and then completes the polymerization and concentration to produce polyester (V).

第10頁 552266 案號 90118405 年 月 曰 修正 五、發明說明（7) 如下之表一顯示上述範例及比較範例所得之聚合物的物理 性質。 mPage 10 552266 Case No. 90118405 Modification 5. Invention description (7) The following Table 1 shows the physical properties of the polymers obtained from the above examples and comparative examples. m

ί Tn? 2 -coon l I AZB m IIIί Tn? 2 -coon l I AZB m III

I 4;e. 比 ，標 -4 6 03I 4; e. Ratio, standard -4 6 03

ASTM-O-34 1 N/2 5NuOH -I>- I 0 03 -Γ>- l 3 64 使上述範例1至4及比較範例一所得的聚酯於2 8 5°C的 射出模造機器中融化。在模造溫度為8 0°C下製備測試樣 本，且允許在4 0分鐘期間降至2 3°C而相對溼度為5 0% 。然 後，測量樣本的抗張強度和衝擊強度，該測量值列於如下 之表二。測量方法如下： 抗張強度（kgf/cm2) : ASTM D638 衝擊強度（kg cm/m) : ASTM D256 範例一 例二 範例三 範例四 比較範例一 j 抗張強度 1 19 0 10 70 I 10 0 1 0 6 0 1 100 m ^ 5^ m. I 3 J 1 12 ! 0 1 0 所以，根據本發明所製之具有内部結晶細粒的飽和聚 酯與傳統飽和聚酯比較之下，具有絕佳的機械性質。此外 ，本發明之聚酯與以昂貴之填充料或強化物質所製之產品 比較之下，擁有較低製備成本之優點。 本發明已藉由實例來作說明，且應了解到所使用的專 門術語僅作為說明而非限制本發明。而按照上述說明皆可ASTM-O-34 1 N / 2 5NuOH -I >-I 0 03 -Γ >-l 3 64 Melt the polyester obtained in the above Examples 1 to 4 and Comparative Example 1 in an injection molding machine at 2 8 5 ° C . Test samples were prepared at a molding temperature of 80 ° C and allowed to drop to 23 ° C with a relative humidity of 50% during 40 minutes. Then, the tensile strength and impact strength of the sample were measured. The measured values are listed in Table 2 below. The measurement methods are as follows: Tensile strength (kgf / cm2): ASTM D638 Impact strength (kg cm / m): ASTM D256 Example 1 Example 2 Example 3 Example 4 Comparison Example 1 j Tensile strength 1 19 0 10 70 I 10 0 1 0 6 0 1 100 m ^ 5 ^ m. I 3 J 1 12! 0 1 0 Therefore, compared with the traditional saturated polyester, the saturated polyester with internal crystalline fine particles prepared according to the present invention has excellent mechanical properties. nature. In addition, the polyester of the present invention has the advantage of lower manufacturing costs compared to products made with expensive fillers or reinforcing materials. The invention has been described by way of example, and it should be understood that the specific terminology used is for illustration only and not for the purpose of limiting the invention. And follow the instructions above

第11頁 552266 _案號90Π8405_年月曰 修正_ 五、發明說明（8) 對本發明作許多修正和變化。所以，應了解到在附加的申 請專利範圍内皆可實施本發明而不需特別說明。Page 11 552266 _Case No. 90Π8405_ Year Month Amendment _ V. Description of the invention (8) Many amendments and changes are made to the present invention. Therefore, it should be understood that the present invention can be implemented within the scope of the attached patent application without any special explanation.

第12頁 552266 _案號90Π8405_年月日 修正 圖式簡單說明Page 12 552266 _Case No. 90Π8405_ Year Month Day Amendment

第13頁Page 13

Claims (1)

552266 案號90Π84δ百 六、申請專利範圍 1. 一種製備具有良之 酯基交換作用或酯化及聚合濃 加入重量比例1 - 1 0%的金屬化 而該金屬化合物是選自醋酸經 月 曰 酔：¾ ~Tltt 飽和聚酯 縮時，以 合物，以 ，醋酸鈉 的方法，其係於 金屬含量為基準 產生飽和聚酯， ，醋酸鉀，醋酸 在弓，酉香酉复I孟 ，if酸J美，酉皆酸， gf酉复#弟，氮氧4匕I里，氮 氧化鈉，氫氧化鉀，氫氧化與二__氫氧化锰，氫氧化辞_____^ 氫氧化鎂，氧化銻，氧化鍺，氧化鈦所組成的基團或上 述化合物之混合物 一種製備具有 酯基交換作用 基準之重量比 準之重量比例0 . 0 5 - 5 . 0%的含 物是選自醋酸鋰，醋酸鈉，醋 飽和聚酯 縮時，加 化合物以 填化合物 酸鉀，醋 良好機械性質之 或酯化及聚合濃 例1 - 1 0%的金屬 的方法，其係於 入以金屬含量為 及以鱗含量為基 J 而該金屬化合 酸鈣，醋酸錳， 醋酸鎮，醋酸鋅，醋酸銻，氫氧化链，氫氧化鈉 ，__氫氧 化鉀，氳氧化鈣，氫氧化錳，氫氧化鋅，氫氧化鎂，氧 化銻，氧化鍺，氧化鈦所組成的基團或上述化合物之混 合物。 3.依申請 選自磷 鹽所組 專利範圍第2項所述之方法，其中含磷化合物是 酸，三甲基磷酸鹽，三乙基磷酸鹽，三苯基磷酸 成之基圑或上述化合物之混合物。552266 Case No. 90Π84δ One hundred six, the scope of patent application 1. A method for preparing metallization with good transesterification or esterification and polymerization concentration by adding 1-10% by weight and the metal compound is selected from acetic acid. ¾ ~ Tltt Saturated polyester shrinks, using the method of compound, sodium acetate, which is based on the metal content to produce saturated polyester, potassium acetate, acetic acid in the bow, huoxiangpi complex I, Jif acid J Beauty, gallic acid, gf 酉 复 # brother, nitrogen oxide, sodium hydroxide, potassium hydroxide, hydroxide and di__manganese hydroxide, hydroxide _____ ^ magnesium hydroxide, antimony oxide, A group consisting of germanium oxide, titanium oxide, or a mixture of the above compounds. A weight ratio of 0.05 to 5.0% based on the weight ratio of a transesterification basis. The content is selected from lithium acetate and sodium acetate. When the vinegar-saturated polyester shrinks, the compound is added to fill the compound potassium acid, the good mechanical properties of vinegar, or the method of esterification and polymerization of 1-10% of the metal, which is based on the metal content and scale content For the base J and the metal compound acid , Manganese acetate, acetate acetate, zinc acetate, antimony acetate, chain hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide, manganese hydroxide, zinc hydroxide, magnesium hydroxide, antimony oxide, germanium oxide, oxidation Groups of titanium or mixtures of these compounds. 3. The method according to application 2 selected from the scope of patents of the Phosphate Group, wherein the phosphorus-containing compound is an acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate or the above compound Of a mixture. 第14頁Page 14