1247766 農號88122_ 五、發明說明（1) 【發明領域】 •水解ΐϊ:月ΐ有關於聚醋組成物，且特別是有關於-種耐 Κ解水S日組成物與其製造方法。 【發明背景】 延伸類樹脂如今已被廣泛地應用在各種高度分子配向 ?2 = DO(orlented articles)的製造’例如單絲、纖維 理性質ί製品等。這類樹脂與Ϊ製品通f具有良好的物 解性不#’、、而’大部分的聚酯在高溫潮濕的環境下的耐水 =ί:在此種條件τ，聚醋極易受其殘存末端酸基之 催化而水解，造成物理性質的劣化。 由於這種對濕氣敏感的特性大幅限制了聚酯在產業上 1應用，目此，為了擴展其應用領域，實有上 問題謀求改善之道。 女Τ耵上江 【先前技藝】 既有技術以低分子型封鎖劑來封鎖聚酯殘存之末端基 ，以提昇其耐水解性，但由於低分子封鎖劑之耐熱性差: 易分解且易揮發，故封鎖效率差，通常需要添加過量之封 鎖劑以彌補高溫封鎖劑在反應時之揮發損失；舉例而古， 日本專利公報特開昭5 7-49620係以M〇no〜〇 a 二’ PET末端基封鎖劑；特公昭61_3997 3、61〜4853 1 48532等係以m〇no-oxazoline為封鎖劑；特開昭53_ 1 1 2796 及特公昭63- 1 0 73 1係以mo no-epoxy作為封鎖巧。1247766 Agricultural No. 88122_ V. INSTRUCTION DESCRIPTION (1) [Field of the Invention] • Hydrolyzed hydrazine: The ceramium has a composition for a vinegar, and particularly relates to a composition for preventing hydrazine hydration and a method for producing the same. BACKGROUND OF THE INVENTION Extended-type resins are now widely used in the manufacture of various highly molecular alignments, such as monofilaments, fibrous properties, and the like. This kind of resin has good decomposability with the bismuth product, and 'the majority of the polyester is resistant to water in a high temperature and humid environment. ί: In this condition τ, the vinegar is extremely susceptible to its residual Hydrolysis by catalysis of the terminal acid group causes deterioration of physical properties. Because of this moisture-sensitive property, the application of polyester in the industry has been greatly limited. Therefore, in order to expand its application field, there are problems to improve. Nvwa Shangjiang [former skill] The existing technology uses a low molecular type blocking agent to block the residual terminal group of the polyester to improve its hydrolysis resistance, but the low molecular blocker has poor heat resistance: easy to decompose and volatile, Therefore, the blocking efficiency is poor, and it is usually necessary to add an excessive amount of blocking agent to compensate for the volatilization loss of the high-temperature blocking agent during the reaction; for example, the Japanese Patent Publication No. 5 7-49620 is based on M〇no~〇a II' PET end. Base blocking agent; special public Zhao 61_3997 3, 61~4853 1 48532, etc. with m〇no-oxazoline as a blocking agent; special opening 53_ 1 1 2796 and special public Zhao 63- 1 0 73 1 with mo no-epoxy as a blockade Skillful.
曰 ⑽1M990__年月日_修正 五、發明說明（2) 【發明概述】 、 本發明的主要目的就是為解決上述問題而提供一種耐 欠解聚S旨組成物。 八 為達上述目的，本發明係選用耐高溫且不易揮發之高 分子型封鎖劑來封鎖聚酯殘存之末端基，以提昇聚酯之耐 火解性’擴展其產業應用領域。 力 本發明之耐水解聚酯組成物，包括由下列成分經炫融 °熱封鎖反應而成··聚酯，·以及（β)以聚酯為重量基準 〇·〇5 5重里百分比之高分子型末端基封鎖劑，其末端具 有擇自··環氧基或胺基之官能基。 本發明更包括此種耐水解聚酯組成之製造方法，其包 上二2 =驟· 2)提供一具有末端酸基之聚酯；以及（b)將 以^平=與士同分子型封鎖劑經加熱熔融進行封鎖反應， =酸基封鎖，其中上述高分有 ¥目· ％氧基或胺基之官能基。 【發明詳述】 本發明所使用之樹脂包括久 、薄臈、模製品的熱塑性聚醋，為單絲、：維 元醇所反應而成之㈣旨。*香族么=方^二S酸與二 二甲酸、間苯二甲酸、萘系二元70 -文=實例包括：對苯 醇可為含碳數2〜1〇之烷：二醇，：實述之混合。二元 二醇、二乙二醇、丙丄其m括：乙二醉、丁 己燒雙二醇、2-乙基-2_ 丁基d 3：=基I，3-丙二醉、環 。 ， 丙一醇、或前述之混合 1247766 _案號88122990_生 月 日 修正__— 五、發明說明（3) 在本發明中適當的聚醋例如有：聚對苯二甲酸乙稀酉旨 (PET)、聚對苯二甲酸丁烯酯（PBT)、聚萘酸乙二酯（PEN) 、PET之共聚物、PBT之共聚物或其熱塑性彈性體團塊共聚 物、PEN之共聚物等，其中又以PET較佳。 上述之聚酯與共聚酯可依傳統之聚酯反應加以製造， 通常可由二元酸及二元醇直接酯化及聚縮合反應而得，或 是由其酯類單體進行酯交換反應及聚縮合反應而得。舉例 而言，PET可由乙二醇與對苯二甲酸直接酯化及聚縮合反 應而得，或者，亦可由乙二醇與對苯二甲酸二甲酯進行酉旨 交換反應及聚縮合反應而得。本發明所使用之聚酯其本性 黏度（I· V·)最好在〇· 55〜1· 5之間。 、 本發明用來改善聚酯之耐水性所添加之封鎖劑為一種 高分子型封鎖劑，其具有擇自：環氧基或胺基之官能基。 高分子型封鎖劑的實例包括：乙稀—甲基丙烯酸環氧丙"醋 (ethylene glycidyl methacrylate ;EGMA)共聚體、環氧 化乙烯-丙烯酸乙酯共聚物、環氧化笨乙烯—丁二烯—苯 <乙 烯團塊共聚物、胺化聚乙烯共聚物等，本發明所選用之高 分子。型封鎖劑，其熱解重量分析（TGA)之耐熱分解溫度^ 4 0 0 C，具有耐高溫不易揮發之特性。 本發明之高分子型封鎖劑的重量平均分子量約在 5,000〜30 0,〇〇〇，其中又以10,0〇〇〜1〇〇 〇〇〇較佳，”而習知 所使用之封鎖劑其重量平均分子量一般僅有數十到數百而 本發明之高分子型封鎖劑的添加量係以聚酯曰 (10) 1M990__年月日日_Amendment 5, Invention Description (2) [Outline of the Invention] The main object of the present invention is to provide a composition for refractory S-dissolving to solve the above problems. VIII In order to achieve the above object, the present invention selects a high-temperature and non-volatile high-molecular blocking agent to block the residual terminal groups of the polyester to enhance the fire resistance of the polyester to expand its industrial application field. The hydrolysis-resistant polyester composition of the present invention comprises a polymer which is subjected to a heat-blocking reaction by the following components, a polyester, and a (β) polymer based on a weight ratio of 〇·〇5 5 by weight of the polyester. A terminal group-blocking agent having a functional group selected from an epoxy group or an amine group at its terminal. The present invention further comprises a method for producing such a hydrolysis-resistant polyester composition, which comprises a 2 2 = a 2) polyester which provides a terminal acid group; and (b) is blocked with a genotype The agent is heated and melted to block the reaction, and the acid group is blocked, wherein the above-mentioned high score has a functional group of a methyl group or an amine group. DETAILED DESCRIPTION OF THE INVENTION The resin used in the present invention comprises a thermoplastic, long-lasting, thin-twisted, molded product, which is obtained by reacting a monofilament or a valence alcohol (IV). *香族么=方^2 S acid and dicarboxylic acid, isophthalic acid, naphthalene binary 70 - text = examples include: p-phenyl alcohol can be a carbon number 2 ~ 1 〇 alkane: diol,: A mixture of facts. Diethylene glycol, diethylene glycol, and propylene glycol include: ethylene dihydrogen, dibutyl bis-diol, 2-ethyl-2-butyl butyl d 3:= group I, 3-propanol, ring. , propanol, or a mixture of the foregoing 1247766 _ case number 88122990_ 生月日修正__- V. Description of the invention (3) In the present invention, suitable polyacetate is, for example, polyethylene terephthalate ( PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolymer of PET, copolymer of PBT or thermoplastic elastomer agglomerate copolymer, copolymer of PEN, etc. Among them, PET is preferred. The above polyester and copolyester can be produced by the reaction of a conventional polyester, usually obtained by direct esterification and polycondensation of a dibasic acid and a glycol, or by transesterification of an ester monomer thereof. It is obtained by polycondensation reaction. For example, PET can be obtained by direct esterification and polycondensation of ethylene glycol with terephthalic acid, or by ethylene glycol and dimethyl terephthalate for exchange reaction and polycondensation reaction. . The polyester used in the present invention preferably has a viscosity (I·V·) of between 〇 55 and 1.5. The blocking agent added to improve the water resistance of the polyester of the present invention is a polymer type blocking agent having a functional group selected from an epoxy group or an amine group. Examples of polymeric blocking agents include: ethylene glycol methacrylate (EGMA) interpolymer, epoxidized ethylene-ethyl acrylate copolymer, epoxidized stupid ethylene-butadiene- Benzene <ethylene agglomerate copolymer, aminated polyethylene copolymer, etc., a polymer selected for use in the present invention. The type of blocking agent, its thermal decomposition temperature (TGA) has a heat-resistant decomposition temperature of 4,000 C, and has the characteristics of high temperature resistance and low volatilization. The polymer type blocking agent of the present invention has a weight average molecular weight of about 5,000 to 30 Å, preferably 10,0 Å to 1 Torr, and the blocking agent is conventionally used. The weight average molecular weight is generally only tens to hundreds and the addition amount of the polymer type blocking agent of the present invention is polyester.
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1247766 _案號 881229901247766 _ case number 88122990
五、發明說明（4) f發明之聚酯組成物除了上述主要成分之外，尚可添 加其、匕習知的添加劑如，熱安定劑、抗氧化劑、光安定 潤⑺W]、著色劑（如染料、顏料）、各種填充劑、 *、結晶劑等。 d 一在本發明之製程中，係將上述之高分子型封鎖劑與 經水5 το畢的聚酯一起混煉進行封鎖反應，以將聚酯之 端酸基封鎖。混煉的方法可依照習知技藝十既有各種的方 式達成 般而S ，可在一封閉系統中以熔融混煉達成， 例如可利用單螺桿或多螺桿押出機、Banbury密煉機、 = = = 1捏合機，在足夠的高溫下將兩者進行熔融混煉封 鎖反應即可。亦可於聚酯之聚縮合反應結束時，再通入 氣及攪拌下加入封鎖劑以進行熔融態之封鎖反應。根據本 發明，混煉及封鎖反應的溫度約在265〜2 ‘ 之間較佳。混煉的時間約在。.5~5分 尤：； 〜3分鐘之間較佳。 < 间兀以1 上述混煉封鎖反應物可經由押出機造 加於押出機反應後製成各種形式之成或=接； 聚r ϋ過一 I^ ί、 域應用。聚酯單絲可將熔融的 Λ °早、、糸孔模押出、冷卻、延伸而得。聚醋镳维可 將溶融抽絲法，將心的聚s旨透過—多孔噴絲^日義維叮 = plnr|eret)抽出、冷卻、然後再會合成 :以利用熔融押出的方式製出各種單軸或雙唯軸二'膜 ::零件、聚酯容器則可利用各種模製法製 出Λ 製、押出模製、中空吹塑押出模製等。 射出模V. INSTRUCTION DESCRIPTION OF THE INVENTION (4) The polyester composition of the f invention may be added with conventional additives such as thermal stabilizers, antioxidants, chlorhexidine (7) W], and colorants in addition to the above main components. Dyes, pigments, various fillers, *, crystallizers, and the like. d. In the process of the present invention, the above-mentioned polymer type blocking agent is kneaded together with a water of 5 Torr to carry out a blocking reaction to block the terminal acid groups of the polyester. The method of mixing can be achieved in a variety of ways according to the conventional art, and can be achieved by melt-kneading in a closed system, for example, a single-screw or multi-screw extruder, a Banbury mixer, == = 1 kneading machine, at a sufficient high temperature, the two can be melt-kneaded to block the reaction. At the end of the polycondensation reaction of the polyester, a blocking agent may be added by stirring and stirring to carry out a blocking reaction in a molten state. According to the present invention, the temperature of the kneading and blocking reaction is preferably between about 265 and 2 ‘. The time of mixing is about. .5~5 points Especially:; Between ~3 minutes is better. < Between 1 and 1 of the above-mentioned kneading block reaction reactants can be added to the extruder by an extruder to produce various forms or = connection; poly r ϋ I I 、, domain application. The polyester monofilament can be obtained by extruding molten Λ °, boring, cooling, and stretching. The polyacetal oxime can be melted and sifted, and the heart is collected by the porous squirting method, the porous spinning wire, the Japanese yoghurt = plnr|eret, extracted, cooled, and then synthesized: by using a melt extrusion method to produce various Single-axis or double-only shaft two-film:: Parts and polyester containers can be molded by various molding methods, extrusion molding, hollow blow molding, and the like. Injection mode
土由本發明之聚酯戶斤製成之成品比起習知技藝具有較 1247766 案號 88122990 五、發明說明（5) 佳的耐水解性，此點已經由成型品在沸水中本性黏度 (I · V ·)的下降程度得到證實。 為讓本發明之上述和其他目的、特徵、和優點能更明 ”、、員易it ’下文特舉出較佳實施例作詳細說明如下： 【實施例】將I· V·為〇· 6之PET預聚物經130 真空乾燥6小時後， 再與。經預先乾燥處理之封鎖劑乾混後，餵入丨5及 〇 C之雙軸押出機中進行南溫封鎖反應押出，所得之财 水解封鎖化g旨粒再分析其I · V ·如下表所示。 ___表 一____—1實，例2賞，例例4比較例 Λ 曰 修正 PET 孖鎖劑 130°C水煮15小 時前之I.V. 0.60 0.60 0.54 0.60 0.58 0.57 0.58 0.35 ^環氡化乙烯-丙烯鲅乙酯共聚物 聚丁物二缔-笨乙缔面塊共Μ pft m實施例可看卜經過高分子封鎖劑封鎖後之 PET ’其130 C水煮15小時後之本性黏度（ι.ν)下降很少， 其本性黏度則下降約-半，證明本發明之 取Θ日具有較佳之耐水解性。 阳定：ii發明已以較佳實施例揭露如上，然其並非用以 ίΓΓ:任何熟習此技藝者，在不脫離本發明之精神 和把圍内’當可作各種之更動與潤錦，因The finished product made of the polyester stalk of the present invention has a better hydrolysis resistance than the conventional technique than the conventional technique of 1247766, No. 88122990. 5. The point has been the inherent viscosity of the molded product in boiling water (I · The degree of decline in V ·) was confirmed. The above and other objects, features and advantages of the present invention will become more apparent. The PET prepolymer is dried under vacuum for 130 hours for 6 hours, and then dry-mixed with a pre-drying blocker, and then fed into a biaxial extruder of 丨5 and 〇C for the south temperature blockade reaction, and the resulting wealth is obtained. Hydrolysis blockade g particle analysis and its I · V · as shown in the following table. ___ Table 1 ____ 1 actual, example 2 reward, example 4 comparative example 曰 曰 modified PET 孖 lock agent 130 ° C boiled 15 IV 0.60 0.60 0.54 0.60 0.58 0.57 0.58 0.35 ^ 氡 氡 乙烯 - - - - - - - - - Μ Μ ft ft ft ft ft ft ft ft ft ft ft After PET's 130 C boiled for 15 hours, the intrinsic viscosity (ι.ν) decreased little, and its intrinsic viscosity decreased by about -half, which proved that the ingestion day of the present invention has better hydrolysis resistance. Ii invention has been disclosed above in the preferred embodiment, but it is not used to: Anyone familiar with the art, not to take off From the spirit of the present invention and the use of the inside,
第9頁 1247766 案號 88122990 Λ_η 曰 修正 五、發明說明（6) 範圍當視後附之申請專利範圍所界定者為準 lai 第10頁 1247766 _案號 88122990_年月日_修正 圖式簡單說明Page 9 1247766 Case No. 88122990 Λ_η 曰 Amendment V. Description of invention (6) Scope is subject to the definition of the scope of the patent application lai. Page 10 1247766 _ Case No. 88122990_年月日日_Revision
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