572929 玖_明_明 (發明)說明應麵：翻所屬之技術領域、先前技術、內容、實施方式及圖式簡單酬 【發明所屬之技術領域】 本發明係關於一種聚對苯二甲酸乙二酯(PET)共聚酯之配方，尤指得用 於產製10公升以上甚至達5加侖容積聚酯瓶之共聚酯配方，以及用此聚對 本一甲酸乙一酯(PET)共聚酯配方所製作之重量達到6〇〇公克以上，厚度大 於7.0公厘之瓶胚，和內容積高於1〇公升以上之容器者。 【先前技術】 隨著大眾普遍對飮用水質的重視，目前許多公共場所或辦公處所經常 採用5加侖容器盛裝蒸餾水供人員飮用。因此，大包裝飮用水的市場(Bulk water market)乃逐漸1增力口。 目前此類大型的裝水容器，主要以聚氯乙烯(PVC)材質或聚碳酸酯(PC) 材質所製成，其中PVC材質容器，因爲不具有環保價値，已逐漸被取代。 而PC容器雖具有優越的品質，但原料成本卻相對較高。 而廣泛用來製作包裝碳酸飮料、礦泉水或茶飮料瓶子的PET共聚酯， 其組成份通常含有基於共聚酯之0至3mole%的間位苯二甲酸，或含有基於共 聚酯之1.5至4.0mole%的二乙二醇，在射出拉伸吹瓶的加工過程中，由於具 有易於結晶的特性’故適用於生產瓶胚厚度約3〜4mm，重量最高約僅100至 120公克，和內容積小於5公升的瓶子；尤其此類共聚酯被加工製作厚度約 達7公厘以上、重量達600公克以上的瓶胚時，會發生結晶白化的現象。而 瓶胚有結晶白化發生，將造成後續之吹瓶步驟無法穩定吹製瓶子；此外， 倘若爲避免瓶胚有結晶白化現象，而將瓶胚冷卻時間延長，又會導致產量 5 572929 下降而不具有經濟價値。 爲解決以上之問題，美國第6,309,718B1專利揭露一種共聚酯配方，可 用來加工製作重量200公克以上，內容積達數加侖的瓶子。該共聚酯的組成 份係含有4至10旲耳％之環己院二甲醇，或含有6至17莫耳。/。之間位苯二甲酸 ，或者由以上兩種化合物混合組成之共聚酯；而且，該共聚酯的組成份， 也可再加入雙竣酸化合物例如2,6-萘二竣酸其含量最多爲5〇莫耳％，該共聚 酯之固有黏度介於0.75至0.85公合（dl) /公克 【內容】 本發明係在揭露一種聚對苯二甲酸乙二酯(PET)共聚酯之配方，得用來 製作瓶胚厚度達7公分以上，重量達600公克以上，內容積大於10公升的聚 酯瓶。 本發明所揭露之聚對苯二甲酸乙二酯(PET)共聚酯配方，其主要成分爲 聚對苯二甲酸乙二酯(PET)樹脂，而組成分含有乂莫耳％間位苯二甲酸(IPA) ，丫莫耳％之二乙二醇(DEG)及Z莫耳％之2,6-萘二羧酸；其中X，Y，Z符合以下 條件： 2.5^Χ^6.0, 2·5$Υ$5·0， 0£Ζ£5.0; 及該共聚酯的固有黏度介於〇·75至〇·85公合（dl) /公克。 本發明所揭露之聚對苯二甲酸乙二酯(PET)共聚酯配方’可用工業界f 知之射出拉伸吹瓶法製出大內容積的聚酯瓶；其方法係將本發明所揭露之 6 572929 聚對苯二甲酸乙二酯(PET)共聚酯，以射出機製成透明的瓶胚後，再以近紅 外光燈管，將瓶胚加熱至高於玻璃轉移溫度後，進一步將瓶胚吹脹成瓶子 〇 由本發明所揭露之聚對苯二甲酸乙二酯(PET)共聚酯配方所製成的大 內容積瓶子，具有良好的透明度，強度足夠盛裝超過10公升以上甚至達5 加侖的水，在搬運過程中不會發生瓶子破裂的問題，並可回收瓶子淸洗後 再使用多次；再者，本發明之共聚酯具有比聚碳酸酯更具成本低廉的優勢 〇 發明之詳細說明 本發明係揭露一種共聚酯之配方，其組成分主要含有聚對苯二甲酸乙二 酯(PET)樹脂，和含有基於共聚酯之义莫耳％間位苯二甲酸(IPA)，Y莫耳％ 之二乙二醇(DEG)及Z莫耳％之2,6-萘二羧酸淇中X，Y，Z符合以下條件： 2.5^X^6.0， 2.5^Y^5.0， 0^Ζ^5.0， 間位苯二甲酸係於熔融反應製程中加入，而二乙二醇除在熔融反應自身發 生外，需再額外加入二乙二醇，使之達到欲添加之目標含量。 本發明之聚對苯二甲酸乙二酯(PET)共聚酯，係以聚酯工業界所熟知之 熔融聚合反應製備而得’其方法係於純對苯二甲酸(PTA)、乙二醇的反應漿 體(Slurry)中，加入基於最終共聚酯之2.5至6.0莫耳％的間位苯二甲酸，並額 外加入二乙二醇，使得額外加入之二乙二醇與製程中自發生成之二乙二醇 7 572929 的總和，爲基於最終共聚酯之2.5至5.0莫耳％，另外再加入2,6-萘二殘酸’ 其含量不高於最終共聚酯之5.0莫耳％ ;於250至260°C的反應溫度進行酯化 反應，當酯化反應結束前加入觸媒、熱安定劑、色料及其他添加劑如抗氧 化劑、光安定劑或滑劑等；再於265至275°C的反應溫度及真空環境下進行 預聚合反應，再於275至285的反應溫度，真空度ltorr下進行聚縮合反應 ，當聚合體之固有黏度(Intrinsic viscosity)至少達到OMdl/g後，將聚合體經過 卸料冷卻並切成圓柱型之聚酯原粒。 由以上熔融聚合反應得到之聚酯原粒，再經過固相聚合反應提昇酯粒 之固有黏度至0.75至0.85dl/g ;此固相聚合反應可以用連續式製程，先經過 結晶、乾燥再預熱至205〜220°C後，進入固相聚合槽進行提昇固有黏度，固 相聚合槽中藉著連續通氮氣將反應發生之乙二醇或水移除。 由此所得之共聚酯再經過乾燥後，可以利用射出機製成重量600公克以 上，厚度7公厘以上，長度36公分之瓶胚 ;瓶胚重量較好爲介於600至_公克，瓶胚厚度較好爲介於7·5〜9.5公厘， 瓶胚長度較好爲介於36至42公分，射出週期爲90至130秒。本發明之共聚酯 製成上述瓶胚，其透明度良好，未發生結晶白化的現象。 本發明進一步利用微差掃描分析儀(DSC)分析本發明之共聚酯，其檢驗 步驟爲取下約3毫克(3mg)固相聚合後之共聚酯，先升溫至3〇〇°C，將共聚酯 熔融後維持5分鐘，經過急冷至室溫後，再以每分鐘2(rc的昇溫速率使聚合 體經歷玻璃轉移溫度區、結晶溫度區及熔點溫度區；其中結晶溫度區之波 峰(peak)所圍成之面積代表結晶的放熱量，本發明之共聚酯其具有之共同點 8 572929 ’爲此Ιριηη放熱的面積均小於10焦耳/公克，更好爲小於6焦耳/公克；此數 値遠小於用於生產一般常見較小內容積聚酯瓶之共聚酯的結晶放熱量，通 常一般共聚酯的結晶放熱量都高於15焦耳/公克以上，甚至高於25焦耳/公克 。因此，本發明之共聚酯藉由添加常見之共聚合改質劑，能夠抑制結晶速 率和能夠在短加工週期內生產既透明又厚重的瓶胚。 本發明之瓶胚再以工業界所熟知的拉伸吹瓶法，進一步製成內容積大 於10至20公升的容器，該製法係以近紅外光加熱使瓶胚的溫度達到玻璃轉 移溫度以上，最好在高於玻璃轉移溫度20至40°C時進行拉伸吹瓶。由本發 明之共聚酯配分所製成的大內容積容器，具有良好的透明度及強度，並可 供多次回收淸洗後再使用，故環保價値極高。 【實施方式】 以下之實施例係爲說明本發明之效果，但並非以此限制本發明。 實施例1 取79.54公斤純對本—^甲酸(PTA) ’ 4_755公斤間位苯二甲酸(ιρΑ)，1.38 公斤二乙二醇(DEG)及37.78公斤之乙二醇(EG)，予以攪泮形成均勻的漿體 後，加熱此獎體至260°C進行酯化反應，酯化壓力維持丨.5至2.0Kg/cm2，當 酯化率達到95%以上，加入14公克磷酸，45公克醋酸鍊及100公克醋酸鈷， 予以升溫至27(TC進行預聚合反應，反應壓力控制於760〜20toIT，經過丨小時 反應後，將溫度再提昇至280°C，真空度降至ltorr以下，進行聚縮合反應直 至固有黏度達到0.60dl/g，予以經過模頭擠壓冷卻切成圓柱型聚酯原粒。分 析此聚酯原粒之IPA含量爲基於共聚酯之5·5莫耳。/。，DEG含量爲基於共聚酯 9 572929 之2.5莫耳％。 再將此聚酯原粒進一步放入一雙椎型的旋轉真空聚合槽，於200至22〇 t的溫度，真空度爲ltorr以下的環境中，進行固相聚合反應，將聚酯粒之 固有黏度提昇至〇.80dl/g。 以Perkin Elmer公司之微差掃描分析儀(DSC)分析該固相聚合後之共聚 酯，先以快速升溫至3〇(TC使之完全熔解後，經過急速冷卻後再以20°C/分鐘 的昇溫速率加熱此聚酯，該聚酯之結晶放熱量爲4.5焦耳/公克。 將此固相聚合後之共聚酯，利用射出機於275至280°C的熔融溫度射出 製成重量685公克，瓶胚之瓶身位置的厚度介於8·5至9.0公厘，瓶胚之長度 爲410公厘；該共聚酯所得的瓶胚透明度良好，無結晶白化現象。 將由此製得的瓶胚，進一步放入拉伸吹瓶機中，於瓶胚溫度110°C時吹 製成爲內容積爲5加侖之容器，其拉伸吹製過程穩定，且容器之透明度及 強度均良好。 實施例2 同實施例1之做法，但合成之共聚酯的組成份中含有1?八4.5莫耳％， DEG 2.5莫耳％，固相聚合後之固有黏度0.81dl/g。 以DSC分析，結晶放熱量爲6.8焦耳/公克。 以射出機製得之瓶胚，其透明度良好，無結晶白化現象；該瓶胚再 伸吹瓶可穩定製成5加侖的瓶子，透明度及強度良好。 實施例3 同實施例1之做法，但合成之共聚酯的組成份中含有1?八2.5莫耳％， 572929 DEG 2.5莫耳％及2,6·萘二羧酸5·0莫耳％，經固相聚合後之固有黏度〇J8dl/g 〇572929 明 _ 明 _ 明 (Invention) Explanation should be made in the following technical fields, prior art, content, embodiments, and simple drawings [Technical Field to which the Invention belongs] The present invention relates to a polyethylene terephthalate Esters (PET) copolyester formulations, especially copolyester formulations that can be used to produce polyester bottles of more than 10 liters and even up to 5 gallons in volume, and the use of this polyethylene terephthalate (PET) copolyester formulation Bottle preforms with a weight of more than 600 grams and a thickness of more than 7.0 mm, and containers with a content of more than 10 liters. [Previous Technology] With the general public's emphasis on the quality of radon water, many public places or office premises often use 5 gallon containers for distilled water. Therefore, the bulk water market is gradually increasing. At present, such large water containers are mainly made of polyvinyl chloride (PVC) or polycarbonate (PC). Among them, PVC containers have gradually been replaced because they do not have environmental protection prices. Although the PC container has superior quality, the cost of raw materials is relatively high. PET copolyesters, which are widely used to make carbonated bottles, mineral water or tea bottles, usually contain 0 to 3 mole% of isophthalic acid based on copolyester, or 1.5% based on copolyester. To 4.0mole% of diethylene glycol, which is easy to crystallize during the process of injection stretch blow molding, so it is suitable for producing preforms with a thickness of about 3 ~ 4mm and a weight of only about 100 to 120 grams, and Bottles with an internal volume of less than 5 liters; especially when such copolyesters are processed to produce preforms with a thickness of more than 7 mm and a weight of 600 grams or more, crystal whitening occurs. Crystal whitening of the preform will cause the bottle to be blown steadily in the subsequent blowing step. In addition, if the preform cooling time is extended to avoid the crystal whitening of the bottle preform, the yield will be reduced by 5 572929 without Has economic value. To solve the above problems, U.S. Patent No. 6,309,718B1 discloses a copolyester formula that can be used to process bottles with a weight of more than 200 grams and a volume of several gallons. The composition of the copolyester is 4 to 10 mole% of cyclohexane dimethanol, or 6 to 17 moles. /. Meta-phthalic acid, or a copolyester composed of a mixture of the above two compounds; moreover, a component of the copolyester can also be added with a di-junic acid compound such as 2,6-naphthalenedi-junic acid, which has the highest content It is 50 mol%. The inherent viscosity of the copolyester is between 0.75 and 0.85 liters (dl) per gram. [Content] The present invention is to disclose a polyethylene terephthalate (PET) copolyester. The formula can be used to make polyester bottles with a preform thickness of more than 7 cm, a weight of more than 600 grams, and an internal volume of more than 10 liters. The polyethylene terephthalate (PET) copolyester formulation disclosed in the present invention is mainly composed of polyethylene terephthalate (PET) resin, and the composition contains mol% of meta-phenylene. Formic acid (IPA), mol% of diethylene glycol (DEG), and Zmol% of 2,6-naphthalene dicarboxylic acid; X, Y, Z meet the following conditions: 2.5 ^ × ^ 6.0, 2 · 5 $ Υ $ 5.0, 0 £ Z £ 5.0; and the inherent viscosity of the copolyester is between 0.75 and 0.85 gram (dl) / gram. The polyethylene terephthalate (PET) copolyester formulation disclosed in the present invention can be made into a polyester bottle with a large internal volume by the injection stretch blow-blow method known in the industry; the method is based on the method disclosed in the present invention. 6 572929 Polyethylene terephthalate (PET) copolyester, made into a transparent preform with an injection machine, and then using a near-infrared light tube to heat the preform above the glass transition temperature, and then further preform the preform Inflated into a bottle. Large internal volume bottle made of the polyethylene terephthalate (PET) copolyester formula disclosed in the present invention. It has good transparency and strength enough to hold more than 10 liters and even up to 5 gallons. Water, the problem of bottle breakage does not occur during the transportation process, and the bottle can be recycled and reused after washing and washing. Furthermore, the copolyester of the present invention has the advantage of lower cost than polycarbonate. DETAILED DESCRIPTION The present invention discloses a formulation of a copolyester, the composition of which mainly contains polyethylene terephthalate (PET) resin, and contains co-polyester-based isomol% isophthalic acid (IPA). , Y mole% diethylene glycol (DEG) Z mole% of 2,6-naphthalenedicarboxylic acid in X, Y, Z meets the following conditions: 2.5 ^ X ^ 6.0, 2.5 ^ Y ^ 5.0, 0 ^ Z ^ 5.0, m-phthalic acid in the melt It is added in the reaction process, and in addition to the occurrence of the melting reaction itself, diethylene glycol needs to be additionally added to achieve the target content to be added. The polyethylene terephthalate (PET) copolyester of the present invention is prepared by melt polymerization reaction which is well known in the polyester industry. The method is based on pure terephthalic acid (PTA) and ethylene glycol. In the reaction slurry (Slurry), 2.5 to 6.0 mol% of isophthalic acid based on the final copolyester is added, and diethylene glycol is additionally added, so that the additional diethylene glycol is self-generating in the process. The sum of the two ethylene glycol 7 572929 is 2.5 to 5.0 mol% based on the final copolyester, and 2,6-naphthalene diresidual acid is added. Its content is not higher than 5.0 mol% of the final copolyester. ; Perform the esterification reaction at a reaction temperature of 250 to 260 ° C. Before the end of the esterification reaction, add a catalyst, a heat stabilizer, a colorant and other additives such as an antioxidant, a light stabilizer or a lubricant; and then at 265 to 275. The pre-polymerization reaction is carried out under a reaction temperature of ° C and a vacuum environment, and then the polycondensation reaction is carried out at a reaction temperature of 275 to 285 under a vacuum degree of ltorr. When the intrinsic viscosity of the polymer reaches at least OMdl / g, The polymer is cooled by discharging and cut into cylindrical polyester pellets. The original polyester granules obtained from the above melt polymerization reaction are then used to increase the inherent viscosity of the ester granules to 0.75 to 0.85 dl / g through solid-phase polymerization. This solid-phase polymerization reaction can be carried out by a continuous process, followed by crystallization, drying, and then After heating to 205 ~ 220 ° C, it enters the solid-phase polymerization tank to increase the inherent viscosity. The solid-phase polymerization tank removes the ethylene glycol or water from the reaction by continuously passing nitrogen gas. After the copolyester thus obtained is dried, it can be made into preforms having a weight of 600 g or more, a thickness of 7 mm or more, and a length of 36 cm by using an injection machine; the weight of the preform is preferably between 600 and _g. The embryo thickness is preferably between 7.5 and 9.5 mm, the length of the preform is preferably between 36 and 42 cm, and the injection cycle is between 90 and 130 seconds. The copolyester of the present invention is made into the above-mentioned preform, which has good transparency and does not cause whitening of crystals. The present invention further uses a differential scanning analyzer (DSC) to analyze the copolyester of the present invention. The inspection step is to remove about 3 milligrams (3mg) of the copolyester after solid-phase polymerization, and first raise the temperature to 300 ° C. The copolyester is melted and maintained for 5 minutes. After being rapidly cooled to room temperature, the polymer is subjected to a glass transition temperature region, a crystallization temperature region, and a melting point temperature region at a heating rate of 2 ° C per minute. The area enclosed by (peak) represents the exothermic heat of crystals. The copolyesters of the present invention have in common 8 572929 'for this purpose, the areas exothermic by Iριηη are all less than 10 Joules / gram, more preferably less than 6 Joules / gram; This number is much smaller than the crystalline exothermic heat of the copolyester used to produce the common smaller internal volume polyester bottles. Generally, the crystalline exothermic heat of the general copolyester is higher than 15 joules / gram, and even higher than 25 joules / G. Therefore, the copolyester of the present invention can suppress the crystallization rate and can produce both transparent and heavy preforms in a short processing period by adding common co-polymerization modifiers. Well-known stretch The bottle method is further made into a container with an internal volume greater than 10 to 20 liters. The method is to use near-infrared light to heat the preform to a temperature above the glass transition temperature, and preferably to pull it at a temperature of 20 to 40 ° C above the glass transition temperature. Stretch blow bottle. The large internal volume container made of the copolyester composition of the present invention has good transparency and strength, and can be used after repeated recycling and washing, so the environmental protection price is extremely high. [Embodiment] The following The example is to illustrate the effect of the present invention, but not to limit the present invention. Example 1 Take 79.54 kg of pure p-formic acid (PTA) '4_755 kg of metaphthalic acid (ιρΑ), 1.38 kg of diethylene glycol After the alcohol (DEG) and 37.78 kg of ethylene glycol (EG) are stirred to form a uniform slurry, the prize body is heated to 260 ° C for esterification reaction, and the esterification pressure is maintained. 1.5 to 2.0 Kg / cm2 When the esterification rate reached 95% or more, 14 grams of phosphoric acid, 45 grams of acetate chain and 100 grams of cobalt acetate were added, and the temperature was raised to 27 ° C for prepolymerization. The reaction pressure was controlled at 760 to 20 to IT. Raise the temperature to 280 ° C again , The vacuum degree drops below ltorr, and the polycondensation reaction is performed until the intrinsic viscosity reaches 0.60 dl / g, which is then extruded and cooled through a die to cut into cylindrical polyester raw pellets. The analysis of the IPA content of this polyester raw pellet is based on copolymerization 5.5 moles of ester. DEG content is 2.5 mole% based on copolyester 9 572929. The polyester pellets are further placed in a two-vertebral rotary vacuum polymerization tank at 200 to 22 At a temperature of 0 ° C and a vacuum of less than ltorr, solid-phase polymerization was carried out to increase the inherent viscosity of the polyester pellets to 0.80 dl / g. This was analyzed by a Perkin Elmer's differential scanning analyzer (DSC). After solid phase polymerization, the copolyester is first rapidly heated to 30 ° C to completely dissolve it, and then rapidly cooled, and then the polyester is heated at a heating rate of 20 ° C / min. It is 4.5 joules / g. This solid-phase polymerized copolyester was injected at a melting temperature of 275 to 280 ° C using an injection machine to produce a weight of 685 grams. The thickness of the bottle body at the position of the preform was between 8.5 and 9.0 mm. The length is 410 mm; the preform obtained from the copolyester has good transparency and no crystal whitening phenomenon. The preform thus obtained was further placed in a stretch blow molding machine, and was blown into a container with a content of 5 gallons at a preform temperature of 110 ° C. The stretch blowing process was stable, and the transparency and All strengths are good. Example 2 The method of Example 1 is the same, but the composition of the synthesized copolyester contains 1.8 to 4.5 mol%, DEG to 2.5 mol%, and the inherent viscosity after solid phase polymerization is 0.81 dl / g. According to DSC analysis, the exotherm of the crystal was 6.8 Joules / gram. The preform obtained by the injection mechanism has good transparency without crystallization and whitening. The preform can be stretched and blown into a 5-gallon bottle with good transparency and strength. Example 3 The same method as in Example 1, except that the composition of the synthesized copolyester contained 1.8 to 2.5 mol%, 572929 DEG to 2.5 mol%, and 2,6 · naphthalenedicarboxylic acid to 5.0 mol%. ， Intrinsic viscosity after solid phase polymerization 〇J8dl / g 〇
C〇〇H 其中，2,6-萘二羧酸的化學結構式爲： 以DSC分析，結晶放熱量爲2.2焦耳/公克。 以射出機製得之瓶胚透明度良好，無結晶白化現象；該瓶胚再經拉伸 吹瓶可穩定製成5加侖的瓶子，透明度及強度均良好。 比較例1 同實施例1之做法，但合成之共聚酯的組成份中含有IPA2·4莫耳％ ’ DEG2.4莫耳％，固相聚合後之固有黏度0.80dl/g。 以DSC分析，結晶放熱量爲17.3焦耳/公克。 以射出機製得之瓶胚透明度不佳，出現結晶白化現象；該瓶胚於拉伸 吹瓶時再經過近紅外光燈管予以加熱後，瓶胚逐漸白化，於吹製5加侖的瓶 子，瓶子變成白霧狀且於吹製過程中容易破瓶。 比較例2 同實施例1之做法，但合成之共聚酯的組成份中含有IPA 2.4莫耳％， DEG 2.4莫耳％，而固相聚合後之固有黏度〇.84dl/g。 以DSC分析，結晶放熱量爲15.5焦耳/公克。 以射出機製得之瓶胚透明度不佳，出現結晶白化現象;該瓶胚於拉伸吹 瓶時再經過近紅外光燈管予以加熱後，瓶胚逐漸白化，於吹製5加侖的瓶 子，瓶子變成白霧狀且於吹製過程中容易破瓶。COH Among which, the chemical structural formula of 2,6-naphthalenedicarboxylic acid is: According to DSC analysis, the exothermic heat of crystallization is 2.2 Joules / gram. The preform obtained by the injection mechanism has good transparency without crystal bleaching. The preform can be stretched and blown to form a 5-gallon bottle with good transparency and strength. Comparative Example 1 The same procedure as in Example 1 was performed, except that the composition of the synthesized copolyester contained IPA2.4 mole% 'DEG2.4 mole%, and the intrinsic viscosity after solid-phase polymerization was 0.80 dl / g. According to DSC analysis, the exotherm of the crystal was 17.3 Joules / gram. The preform obtained by the injection mechanism has poor transparency and crystal bleaching. After the preform is stretched and blown by a near-infrared light tube, the preform is gradually whitened, and a 5-gallon bottle is blown. It becomes white mist and easily breaks the bottle during blowing. Comparative Example 2 The method of Example 1 was the same, but the composition of the synthesized copolyester contained 2.4 Molar IPA and 2.4 Molar DEG, and the inherent viscosity after solid phase polymerization was 0.84 dl / g. According to the DSC analysis, the crystal exotherm was 15.5 Joules / gram. The preform obtained by the injection mechanism has poor transparency and crystal bleaching phenomenon. The preform is gradually whitened after being heated by a near-infrared light tube during stretch blowing, and the 5-gallon bottle is blown. It becomes white mist and easily breaks the bottle during blowing.