JPH09151308A - Polyester resin composition - Google Patents
Polyester resin compositionInfo
- Publication number
- JPH09151308A JPH09151308A JP10343696A JP10343696A JPH09151308A JP H09151308 A JPH09151308 A JP H09151308A JP 10343696 A JP10343696 A JP 10343696A JP 10343696 A JP10343696 A JP 10343696A JP H09151308 A JPH09151308 A JP H09151308A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- polyester resin
- molding
- resin composition
- crystallization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエステル樹脂
組成物に関するものであり、詳しくは、連続成形性およ
び透明性を損なうことなく結晶化速度を制御したポリエ
ステル樹脂組成物であって、特に、ボトル成形に有用な
ポリエステル樹脂組成物に関するものである。TECHNICAL FIELD The present invention relates to a polyester resin composition, and more particularly to a polyester resin composition having a controlled crystallization rate without impairing continuous moldability and transparency, and particularly, a bottle resin composition. The present invention relates to a polyester resin composition useful for molding.
【０００２】[0002]
【従来の技術】ポリエチレンテレフタレート（以下「Ｐ
ＥＴ」という。）は、機械的強度、化学的安定性、透明
性、衛生性、ガスバリヤー性などに優れており、また、
軽量かつ安価であるため、各種のシート及び容器とし
て、幅広く包装材料に使用され、特に、炭酸飲料、果汁
飲料、液体調味料、食用油、酒、ワイン用などの容器と
しての伸びが著しい。この様なＰＥＴは、例えば、ボト
ルの場合、射出成形機で中空成形体用のプリフォームを
成形し、このプリフォームを所定形状の金型内で延伸ブ
ローする。2. Description of the Related Art Polyethylene terephthalate (hereinafter referred to as "P
ET ”. ) Is excellent in mechanical strength, chemical stability, transparency, hygiene, gas barrier property, etc.
Since it is lightweight and inexpensive, it is widely used as a variety of sheets and containers for packaging materials, and in particular, it is remarkably expanding as a container for carbonated drinks, fruit juice drinks, liquid seasonings, edible oil, liquor, wine and the like. In the case of such a PET, for example, in the case of a bottle, a preform for a hollow molded body is molded by an injection molding machine, and the preform is stretch-blown in a mold having a predetermined shape.
【０００３】また、果汁飲料などの様に熱充填を必要と
する内溶液の場合は、一般的に、プリフォーム又は成形
されたボトルの口栓部を熱処理して結晶化する（特開昭
５５−７９２３７号公報、特開昭５８−１１０２２１号
公報）。In the case of an internal solution that requires hot filling, such as a fruit juice beverage, the preform or molded bottle is generally heat-treated to crystallize it (JP-A-55). -79237, JP-A-58-110221).
【０００４】上記の様な公知の方法、すなわち、口栓部
や肩部を熱処理して耐熱性を向上させる方法において
は、結晶化処理の時間や温度が生産性に大きく影響する
ため、低温でかつ短時間で処理出来る、結晶化速度の速
いポリエステル樹脂が要求される。一方、胴部について
は、充填物の色調を悪化させない様に、斯かる熱処理を
行った後でも白化しないことが要求されている。従っ
て、口栓部と胴部では相反する特性が必要である。In the known method as described above, that is, in the method of heat-treating the spout and the shoulder to improve the heat resistance, the crystallization time and temperature have a great influence on the productivity. A polyester resin having a high crystallization rate and capable of being processed in a short time is required. On the other hand, the body portion is required not to be whitened even after such heat treatment so as not to deteriorate the color tone of the filler. Therefore, the spout and the body need to have opposite properties.
【０００５】しかしながら、透明性に優れたポリエステ
ル樹脂は、通常、結晶化が遅いため、成形物の透明性や
強度を犠牲にし、樹脂の極限粘度を低下させることで結
晶化速度を改良するか、または、生産性を犠牲にし、高
温かつ長時間の熱処理を行う必要がある。However, a polyester resin having excellent transparency usually has a slow crystallization, so that the transparency and strength of the molded product are sacrificed and the intrinsic viscosity of the resin is lowered to improve the crystallization rate. Alternatively, it is necessary to sacrifice productivity and perform heat treatment at high temperature for a long time.
【０００６】これに対し、特公平５−７６９７４号公報
には、ポリエステル樹脂に０．０５〜５００ｐｐｍのポ
リエチレンを均一に混合することにより、透明性を損な
うことなく結晶化速度を改善する方法が提案されてい
る。On the other hand, Japanese Patent Publication No. 5-76974 proposes a method of improving the crystallization rate without impairing the transparency by uniformly mixing 0.05 to 500 ppm of polyethylene with a polyester resin. Has been done.
【０００７】しかしながら、本発明者らの検討結果によ
れば、上記範囲でポリエチレンを添加した場合、ボトル
成形品の透明性は良好であるものの、口栓部および肩部
に熱処理を施すと、僅かではあるが白化傾向が見られ、
結晶性と透明性の両方の物性を同時に満足させることは
困難である。However, according to the results of studies by the present inventors, when polyethylene is added in the above range, the transparency of the bottle molded product is good, but when the heat treatment is applied to the plug portion and the shoulder portion, it is slightly However, there is a whitening tendency,
It is difficult to satisfy both physical properties of crystallinity and transparency at the same time.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記実情に
鑑みなされたものであり、その目的は、連続成形性に優
れ、しかも、成形物またはその前駆体であるプリフォー
ムを熱処理して耐熱性を付与する際に、透明性を損なう
ことなく結晶化速度のみを制御することが出来るポリエ
ステル樹脂組成物を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to obtain a molded article or a precursor thereof, which is heat-treated by heat treatment. It is an object of the present invention to provide a polyester resin composition capable of controlling only the crystallization rate without impairing transparency when imparting properties.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために鋭意検討した結果、驚くべき事に、
特定のポリエステル樹脂を使用するならば、特公平５−
７６９７４号公報記載発明では効果が見られなかった極
微量のポリエチレンを配合することにより、ボトル製造
時の必須要件である透明性と結晶化速度という相反する
特性を同時に満足でき、更に、連続成形性の改良された
ポリエステル樹脂組成物が得られることを見い出し、本
発明に到達した。Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventors have surprisingly found that
If you use a specific polyester resin,
In the invention described in Japanese Patent No. 76974, by blending a very small amount of polyethylene, which is not effective, it is possible to simultaneously satisfy the contradictory characteristics of transparency and crystallization rate, which are indispensable requirements at the time of bottle production. It has been found that an improved polyester resin composition can be obtained and the present invention has been completed.
【００１０】すなわち、本発明の要旨は、エチレンテレ
フタレート単位を主体とし、ジエチレングリコール単位
の割合が全ジオール単位中１．０〜２．５モル％であり
且つ環状三量体の含有量が０．５重量％以下であるポリ
エステル樹脂に０．１〜４５ｐｐｂのポリエチレンを配
合して成ることを特徴とするポリエステル樹脂組成物に
存する。That is, the gist of the present invention is mainly ethylene terephthalate units, the proportion of diethylene glycol units is 1.0 to 2.5 mol% in the total diol units, and the content of cyclic trimer is 0.5. A polyester resin composition is characterized by comprising 0.1 to 45 ppb of polyethylene mixed with a polyester resin of not more than wt%.
【００１１】[0011]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において、ＰＥＴとは、全構成繰り返し単位に対
するテレフタル酸およびエチレングリコールから成るオ
キシエチレンオキシテレフタロイル単位（以下「ＥＴ単
位」という。）の比率が８０当量％以上であるポリエチ
レンテレフタレートを言い、本発明におけるＰＥＴは、
ＥＴ単位以外の構成繰り返し単位を２０当量％未満の範
囲で含んでいてもよい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, PET means polyethylene terephthalate in which the ratio of oxyethylene oxyterephthaloyl units (hereinafter referred to as “ET units”) composed of terephthalic acid and ethylene glycol to all the constitutional repeating units is 80 equivalent% or more, PET in the present invention is
Constituent repeating units other than ET units may be contained in a range of less than 20 equivalent%.
【００１２】本発明におけるＰＥＴは、テレフタル酸ま
たはその低級アルキルエステルとエチレングリコールと
を主たる原料として製造されるが、前述の通り、他の酸
成分および／または他のグリコール成分を併せて原料と
して用いてもよい。The PET in the present invention is produced by using terephthalic acid or its lower alkyl ester and ethylene glycol as main raw materials. As mentioned above, other acid components and / or other glycol components are used as raw materials in combination. May be.
【００１３】テレフタル酸以外の酸成分としては、フタ
ル酸、イソフタル酸、ナフタレンジカルボン酸、４，
４’−ジフェニルスルホンジカルボン酸、４，４’−ビ
フェニルジカルボン酸、１，４−シクロヘキサンジカル
ボン酸、１，３−フェニレンジオキシジ酢酸およびこれ
らの構造異性体、マロン酸、コハク酸、アジピン酸など
のジカルボン酸およびその誘導体、ｐ−ヒドロキシ安息
香酸、グリコール酸などのオキシ酸またはその誘導体が
挙げられる。Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,
4'-diphenylsulfone dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-phenylenedioxydiacetic acid and their structural isomers, malonic acid, succinic acid, adipic acid, etc. Dicarboxylic acids and derivatives thereof, oxy acids such as p-hydroxybenzoic acid and glycolic acid, or derivatives thereof.
【００１４】また、エチレングリコール以外のジオール
成分としては、１，２−プロパンジオール、１，３−プ
ロパンジオール、１，４−ブタンジオール、ペンタメチ
レングリコール、ヘキサメチレングリコール、ネオペン
チルグリコール等の脂肪族グリコール、シクロヘキサン
ジメタノール等の脂環式グリコール、ビスフェノール
Ａ、ビスフェノールＳ等の芳香族ジヒドロキシ化合物誘
導体などを挙げられる。Examples of diol components other than ethylene glycol include aliphatic compounds such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol and neopentyl glycol. Examples thereof include alicyclic glycols such as glycol and cyclohexanedimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.
【００１５】上記の様なテレフタル酸またはそのエステ
ル形成性誘導体とエチレングリコールとを含む原料は、
エステル化触媒またはエステル交換触媒の存在下のエス
テル化反応またはエステル交換反応により、ビス（β−
ヒドロキシエチル）テレフタレート及び／又はそのオリ
ゴマーを形成させ、その後、重縮合触媒および安定剤の
存在下で高温減圧下に溶融重縮合を行ってポリマーとさ
れる。A raw material containing terephthalic acid or an ester-forming derivative thereof and ethylene glycol as described above is
By the esterification reaction or the transesterification reaction in the presence of the esterification catalyst or the transesterification catalyst, bis (β-
Hydroxyethyl) terephthalate and / or its oligomer is formed, and then melt polycondensation is performed under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer to obtain a polymer.
【００１６】エステル化触媒は、テレフタル酸がエステ
ル化反応の自己触媒となるため、特に使用する必要はな
い。また、エステル化反応は、エステル化触媒と後述す
る重縮合触媒の共存下に実施することも可能であり、ま
た、少量の無機酸などの存在下に実施することが出来
る。エステル交換触媒としては、ナトリウム、リチウム
等のアルカリ金属塩、マグネシウム、カルシウム等のア
ルカリ土類金属塩、亜鉛、マンガン等の金属化合物が好
ましく使用されるが、透明性の観点からマンガン化合物
が特に好ましい。It is not necessary to use an esterification catalyst because terephthalic acid serves as an autocatalyst for the esterification reaction. Further, the esterification reaction can be carried out in the coexistence of an esterification catalyst and a polycondensation catalyst described later, or can be carried out in the presence of a small amount of an inorganic acid or the like. As the transesterification catalyst, alkali metal salts such as sodium and lithium, alkaline earth metal salts such as magnesium and calcium, metal compounds such as zinc and manganese are preferably used, but manganese compounds are particularly preferable from the viewpoint of transparency. .
【００１７】重縮合触媒としては、ゲルマニウム化合
物、アンチモン化合物、チタン化合物、コバルト化合
物、錫化合物などの反応系に可溶な化合物が単独または
組み合わせて使用される。重縮合触媒としては、色調お
よび透明性などの観点から二酸化ゲルマニウムが特に好
ましい。As the polycondensation catalyst, compounds soluble in the reaction system such as germanium compounds, antimony compounds, titanium compounds, cobalt compounds and tin compounds are used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferable from the viewpoint of color tone and transparency.
【００１８】安定剤としては、トリメチルホスフェー
ト、トリエチルホスフェート、トリフェニルホスフェー
ト等のリン酸エステル類、トリフェニルホスファイト、
トリスドデシルホスファイト等の亜リン酸エステル類、
メチルアシッドホスフェート、ジブチルホスフェート、
モノブチルホスフェート酸性リン酸エステル、リン酸、
亜リン酸、次亜リン酸、ポリリン酸などのリン化合物が
好ましい。Examples of the stabilizer include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triphenyl phosphite,
Phosphites such as trisdodecyl phosphite,
Methyl acid phosphate, dibutyl phosphate,
Monobutyl phosphate acidic phosphate, phosphoric acid,
Phosphorus compounds such as phosphorous acid, hypophosphorous acid and polyphosphoric acid are preferred.
【００１９】上記の触媒の使用割合は、全重合原料中、
触媒中の金属の重量として、通常５〜２０００ｐｐｍ、
好ましくは１０〜５００ｐｐｍの範囲とされ、安定剤の
使用割合は、全重合原料中、安定剤中のリン原子の重量
として、通常１０〜１０００ｐｐｍ、好ましくは２０〜
２００ｐｐｍの範囲とされる。触媒および安定剤の供給
は、原料スラリー調製時の他、エステル化反応またはエ
ステル交換反応の任意の段階において行うことが出来
る。更に、重縮合反応工程の初期に供給することも出来
る。The proportion of the above catalyst used is such that
Usually 5 to 2000 ppm by weight of metal in the catalyst,
It is preferably in the range of 10 to 500 ppm, and the proportion of the stabilizer used is generally 10 to 1000 ppm, preferably 20 to 100 ppm, as the weight of phosphorus atoms in the stabilizer in all the polymerization raw materials.
It is in the range of 200 ppm. The catalyst and the stabilizer can be supplied at any stage of the esterification reaction or the transesterification reaction, in addition to the preparation of the raw material slurry. Further, it can be supplied at the beginning of the polycondensation reaction step.
【００２０】エステル化反応またはエステル交換反応時
の反応温度は、通常２４０〜２８０℃であり、反応圧力
は通常１〜３ｋｇ／ｃｍ2 Ｇである。また、重縮合反応
時の反応温度は、通常２５０〜３００℃であり、反応圧
力は通常５００〜０．１ｍｍＨｇである。この様なエス
テル化またはエステル交換反応および重縮合反応は、１
段階で行なっても、複数段階に分けて行なってもよい。
この様にして得られるポリエステルは、極限粘度が通常
０．４５〜０．７０ｄｌ／ｇであり、常法によりチップ
化される。ポリエステルチップの平均粒径は、通常２．
０〜５．５ｍｍ、好ましくは２．２〜４．０ｍｍの範囲
とされる。The reaction temperature during the esterification reaction or transesterification reaction is usually 240 to 280 ° C., and the reaction pressure is usually 1 to 3 kg / cm 2 G. The reaction temperature during the polycondensation reaction is usually 250 to 300 ° C., and the reaction pressure is usually 500 to 0.1 mmHg. Such esterification or transesterification reaction and polycondensation reaction are
It may be carried out in stages or in a plurality of stages.
The polyester thus obtained has an intrinsic viscosity of usually 0.45 to 0.70 dl / g, and is formed into chips by a conventional method. The average particle size of polyester chips is usually 2.
The range is 0 to 5.5 mm, preferably 2.2 to 4.0 mm.
【００２１】次に、上記の様に溶融重縮合により得られ
たポリマーは、通常、固相重合に供される。固相重合に
供されるポリマーチップは、予め、固相重合を行う温度
より低い温度に加熱して予備結晶化を行った後、固相重
合に供してもよい。この様な予備結晶化は、（ａ）乾燥
状態のポリマーチップを、通常１２０〜２００℃、好ま
しくは１３０〜１８０℃の温度で１分間〜４時間加熱す
る方法、（ｂ）乾燥状態のポリマーチップを、水蒸気ま
たは水蒸気含有不活性ガス雰囲気下、通常１２０〜２０
０℃の温度で１分間以上加熱する方法、（ｃ）水、水蒸
気または水蒸気含有不活性ガス雰囲気下で吸湿させ調湿
したポリマーチップを、通常１２０〜２００℃の温度で
１分間以上加熱する方法などによって行うことが出来
る。Next, the polymer obtained by melt polycondensation as described above is usually subjected to solid phase polymerization. The polymer chip to be subjected to the solid phase polymerization may be heated to a temperature lower than the temperature at which the solid phase polymerization is performed in advance to carry out the pre-crystallization, and then subjected to the solid phase polymerization. Such pre-crystallization is carried out by (a) heating the dried polymer chips at a temperature of usually 120 to 200 ° C., preferably 130 to 180 ° C. for 1 minute to 4 hours, and (b) dried polymer chips. In an atmosphere of water vapor or water vapor-containing inert gas, usually 120 to 20
Method of heating at a temperature of 0 ° C. for 1 minute or more, (c) Method of heating a polymer chip, which has been conditioned by moisture absorption under an atmosphere of water, steam or a steam-containing inert gas, at a temperature of 120 to 200 ° C. for 1 minute or more. It can be done by etc.
【００２２】ポリマーチップの調湿は、その含水率が通
常１００〜１００００ｐｐｍ、好ましくは１０００〜５
０００ｐｐｍの範囲となる様に実施される。調湿したポ
リマーチップを結晶化や固相重合に供することにより、
ＰＥＴに含まれるアセトアルデヒドや微量含まれる不純
物の量を一層低減化することが可能である。The moisture content of the polymer chips is usually 100 to 10000 ppm, preferably 1000 to 5 for moisture control.
It is carried out so that the range is 000 ppm. By subjecting the conditioned polymer chips to crystallization and solid-state polymerization,
It is possible to further reduce the amounts of acetaldehyde contained in PET and impurities contained in a trace amount.
【００２３】固相重合工程は、少なくとも１段から成
り、通常１９０〜２３０℃、好ましくは１９５〜２２５
℃の重合温度、通常１ｋｇ／ｃｍ2 Ｇ〜１０ｍｍＨｇ、
好ましくは０．５ｋｇ／ｃｍ2 Ｇ〜１００ｍｍＨｇの重
合圧力の条件下、窒素、アルゴン、二酸化炭素などの不
活性ガス流通下で実施される。固相重合時間は、温度が
高いほど短時間でよいが、通常１〜５０時間、好ましく
は５〜３０時間、更に好ましくは１０〜２５時間であ
る。固相重合により得られたポリマーの極限粘度は、通
常０．７２〜０．８５ｄｌ／ｇの範囲である。The solid phase polymerization step comprises at least one step, and is usually 190 to 230 ° C., preferably 195 to 225.
Polymerization temperature of ℃, usually 1kg / cm 2 G ~ 10mmHg,
It is preferably carried out under a polymerization pressure of 0.5 kg / cm 2 G to 100 mmHg under a flow of an inert gas such as nitrogen, argon or carbon dioxide. The solid phase polymerization time may be shorter as the temperature is higher, but is usually 1 to 50 hours, preferably 5 to 30 hours, and more preferably 10 to 25 hours. The intrinsic viscosity of the polymer obtained by solid phase polymerization is usually in the range of 0.72 to 0.85 dl / g.
【００２４】本発明においては、上記方法により、最終
的に得られるポリエステル樹脂を構成するジエチレング
リコール単位（以下「ＤＥＧ」と略称する。）の含有量
およびポリエステル樹脂中の環状三量体（以下「ＣＴ」
と略称する。）の含有量が特定の範囲内にあることを必
須とする。斯かる条件を満足することにより、本発明の
目的とする、連続成形性に優れ且つ透明性を損なうこと
なく結晶化速度を制御し、特にボトル用として好適なポ
リエステル樹脂組成物を得ることが出来る。In the present invention, the content of diethylene glycol units (hereinafter abbreviated as "DEG") constituting the polyester resin finally obtained by the above method and the cyclic trimer in the polyester resin (hereinafter "CT") "
Is abbreviated. It is essential that the content of) be within a specific range. By satisfying such conditions, it is possible to obtain a polyester resin composition, which is an object of the present invention, is excellent in continuous moldability and controls the crystallization rate without impairing transparency, and is particularly suitable for bottles. .
【００２５】本発明において、最終的に得られるポリエ
ステル樹脂を構成するＤＥＧ量は、ポリエステルを構成
する全ジオール単位に対し、１．０〜２．５モル％、好
ましくは１．２〜２．２モル％である。ＤＥＧ量が少な
過ぎる場合は、成形後のボトルの胴部の透明性が悪化す
る、また、多過ぎる場合は、耐熱性が低下し、更に、結
晶化促進効果が小さくなる。In the present invention, the amount of DEG constituting the polyester resin finally obtained is 1.0 to 2.5 mol%, preferably 1.2 to 2.2, based on all the diol units constituting the polyester. Mol%. When the DEG amount is too small, the transparency of the body of the bottle after molding is deteriorated, and when it is too large, the heat resistance is lowered and the crystallization promoting effect is further reduced.
【００２６】上記範囲内にＤＥＧ量を調節する方法とし
ては、ジエチレングリコールを重合原料として使用する
他、主原料として使用するエチレングリコールからジエ
チレングリコールが一部副生するため、反応条件、添加
剤などを適宜選択することによってその副生成量を調節
する方法が挙げられる。As a method for adjusting the DEG amount within the above range, in addition to using diethylene glycol as a raw material for polymerization, since diethylene glycol is partially by-produced from ethylene glycol used as a main raw material, reaction conditions, additives and the like are appropriately used. A method of adjusting the amount of the by-product by selecting it can be mentioned.
【００２７】上記の添加剤としては、例えば、トリエチ
ルアミン、トリ−ｎ−ブチルアミン、ベンジルジメチル
アミン等の第３級アミン、水酸化テトラエチルアンモニ
ウム、水酸化テトラブチルアンモニウム、水酸化トリメ
チルベンジルアンモニウム等の水酸化第４級アンモニウ
ム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、酢
酸ナトリウム等の塩基性化合物が挙げられる。これらの
少量添加により、ＤＥＧの生成を抑制することが出来
る。一方、硫酸などの無機酸、安息香酸などの有機酸を
重合原料中に少量添加すれば、ＤＥＧの生成が促進し、
その含有量を増加させることも出来る。ＤＥＧの生成量
をコントロールする上記の添加剤は、必要に応じ、通
常、全重合原料の０．００１〜１０重量％、好ましく
は、０．００５〜１重量％の範囲で使用される。Examples of the above-mentioned additives include tertiary amines such as triethylamine, tri-n-butylamine and benzyldimethylamine, and hydroxides such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Basic compounds such as quaternary ammonium, lithium carbonate, sodium carbonate, potassium carbonate and sodium acetate can be mentioned. The addition of a small amount of these can suppress the generation of DEG. On the other hand, when a small amount of an inorganic acid such as sulfuric acid or an organic acid such as benzoic acid is added to the polymerization raw material, generation of DEG is promoted,
The content can also be increased. The above-mentioned additive for controlling the amount of DEG produced is used, if necessary, in the range of usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, based on the whole polymerization raw material.
【００２８】また、最終的に得られるポリエステル樹脂
中のＣＴ含有量は、０．５重量％以下、好ましくは０．
４５重量％以下、更に好ましくは０．４重量％以下、最
も好ましくは０．３５重量％以下である。０．５重量％
を超える場合は、金型などの汚染が顕著に認められ、し
かも、成形体の胴部が白化し易くなる。ＣＴ量は、固相
重合温度を高くし、更に、重合時間を長くすることによ
り、低減することが可能である。The CT content in the finally obtained polyester resin is 0.5% by weight or less, preferably 0.
It is 45% by weight or less, more preferably 0.4% by weight or less, and most preferably 0.35% by weight or less. 0.5% by weight
If it exceeds, the contamination of the mold and the like is noticeable, and the body of the molded body is liable to be whitened. The CT amount can be reduced by increasing the solid phase polymerization temperature and further increasing the polymerization time.
【００２９】更に、ＣＴの低減効果を高めるため、固相
重合に供される溶融重縮合後のポリマー中の末端カルボ
キシル基の濃度は、１０〜３０ｅｑ／トンの範囲にする
ことが好ましく、１５〜２５ｅｑ／トンの範囲にするこ
とが特に好ましい。末端カルボキシル基の濃度が上記範
囲に満たない場合は、固相重合性が悪くて極限粘度を大
きくするのに長時間を要することがあり、一方、上記範
囲を超える場合は、固相重合に供した場合のＣＴ等のオ
リゴマーの低減効果が少ないことがある。Further, in order to enhance the effect of reducing CT, the concentration of terminal carboxyl groups in the polymer after melt polycondensation used for solid phase polymerization is preferably in the range of 10 to 30 eq / ton. A range of 25 eq / ton is particularly preferred. If the concentration of the terminal carboxyl group is less than the above range, the solid phase polymerizability may be poor and it may take a long time to increase the intrinsic viscosity. In that case, the effect of reducing oligomers such as CT may be small.
【００３０】本発明は、上記の様な特定のポリエステル
樹脂にポリエチレンを配合することを特徴とする。ポリ
エチレン（以下「ＰＥ」と略記する。）の種類として
は、特に限定されず、高密度ポリエチレン、低密度ポリ
エチレン、線状低密度ポリエチレン等の何れであっても
よい。The present invention is characterized in that polyethylene is blended with the specific polyester resin as described above. The type of polyethylene (hereinafter abbreviated as “PE”) is not particularly limited, and may be any of high density polyethylene, low density polyethylene, linear low density polyethylene and the like.
【００３１】上記の様な特定のポリエステル樹脂を使用
する結果、ＰＥは、極めて微量の配合量でその効果を十
分に発揮することが出来る。ＰＥの具体的な配合量は、
０．１〜４５ｐｐｂ、好ましくは１．０ｐｐｂ〜４０ｐ
ｐｂの範囲とされる。配合量が０．１ｐｐｂ未満の場合
は、結晶化促進効果が不充分であり、４５ｐｐｂを超え
る場合は、結晶化促進効果が大き過ぎ、口栓部の結晶化
およびボトルの熱処理時に肩部および胴部が白濁して透
明性が損なわれる。As a result of using the specific polyester resin as described above, PE can sufficiently exert its effect even in an extremely small amount. The specific blending amount of PE is
0.1-45 ppb, preferably 1.0 ppb-40 p
It is set in the range of pb. When the compounding amount is less than 0.1 ppb, the crystallization promoting effect is insufficient, and when the compounding amount exceeds 45 ppb, the crystallization promoting effect is too large and the shoulder part and the body are not crystallized during the crystallization of the mouth part and the heat treatment of the bottle. The part becomes cloudy and the transparency is impaired.
【００３２】ポリエステル樹脂にＰＥを配合する方法
は、ポリエステル製造工程中での添加、製造後のポリエ
ステルとのドライブレンド等、均一に混合し得る限り如
何なる方法でもよいが、ポリエステル製造工程中、具体
的には、原料スラリー調製時、エステル化反応またはエ
ステル交換反応の任意の段階および重縮合反応工程の初
期の何れかの時点で添加することが好ましい。The method of blending PE with the polyester resin may be any method as long as it can be uniformly mixed, such as addition in the polyester production step, dry blending with the polyester after production, etc. In addition, it is preferable to add it at any stage of preparing the raw material slurry, at any stage of the esterification reaction or transesterification reaction, and at the initial stage of the polycondensation reaction process.
【００３３】また、本発明のポリエステル樹脂組成物
は、２８０℃の成形温度で射出成形して得られた成形品
について示差走査熱量計にて測定した際の昇温時の結晶
化温度（以下「ＴC1」と略称する。）が、１５５℃〜１
７２℃であることが好ましく、１６０〜１７０℃である
ことが特に好ましい。ＴC1が上記範囲未満の場合は、成
形して得られたボトルの口栓部の結晶化およびボトルの
熱処理の際、肩部や胴部が白化して透明性を損なうこと
がある。一方、ＴC1が上記範囲を超える場合は、結晶化
速度の充分な改良効果が得難い。上記のＴC1の条件を満
足することにより、成形品の結晶性および透明性の両方
の物性を同時に充分満足することが出来る。The polyester resin composition of the present invention has a crystallization temperature (hereinafter referred to as "crystallization temperature" at the time of temperature rise when measured by a differential scanning calorimeter with respect to a molded product obtained by injection molding at a molding temperature of 280 ° C. Abbreviated as "T C1 ").
The temperature is preferably 72 ° C, and particularly preferably 160 to 170 ° C. When T C1 is less than the above range, the shoulder portion or the body portion may be whitened and the transparency may be impaired during the crystallization of the bottle cap obtained by molding and the heat treatment of the bottle. On the other hand, when T C1 exceeds the above range, it is difficult to obtain a sufficient effect of improving the crystallization rate. By satisfying the above-mentioned condition of T C1 , it is possible to satisfy both the crystallinity and the transparency of the molded product at the same time.
【００３４】ところで、本発明においては、前述した様
に、ポリエステルの製造中または製造後にＰＥを添加す
るが、ＰＥの添加によってポリエステルのＴC1が低下す
る。従って、ポリエステル製造後にＰＥを添加する場合
は、ＴC1の上記の条件を満足させるため、ＰＥ添加前の
ＴC1が１５５℃以上のポリエステルを使用する必要があ
る。また、ＰＥの添加量が過剰である場合は、ポリエス
テル樹脂のＴC1が低下し過ぎ、ＴC1が上記の条件を外れ
ることがある。By the way, in the present invention, as described above, PE is added during or after the production of the polyester, but the addition of PE lowers the T C1 of the polyester. Therefore, when adding PE after polyester production, in order to satisfy the above conditions of T C1, it is necessary to PE before the addition T C1 uses 155 ° C. or more polyesters. Further, when the amount of PE added is excessive, T C1 of the polyester resin may be too low, and T C1 may deviate from the above conditions.
【００３５】本発明のポリエステル樹脂組成物は、一般
的に使用される溶融成形法を採用してボトルに成形する
ことが出来る。具体的には、例えば、射出成形または押
出成形で一旦パリソンを成形し、そのまま又は口栓部お
よび底部を加工後、再加熱し、ホットパリソン法または
コールドパリソン法などの延伸ブロー成形法を適用す
る。この場合の成形温度（具体的には試験機のシリンダ
ー各部およびノズルの温度）は、通常２６０〜３００
℃、延伸温度は、通常７０〜１２０℃である。延伸倍率
は、通常、縦方向に１．５〜３．５倍、円周方向に２〜
５倍の範囲である。The polyester resin composition of the present invention can be molded into a bottle by using a generally used melt molding method. Specifically, for example, a parison is once molded by injection molding or extrusion molding, and as it is or after processing the plug portion and the bottom portion, it is reheated, and a stretch blow molding method such as a hot parison method or a cold parison method is applied. . The molding temperature in this case (specifically, the temperature of each part of the cylinder of the tester and the nozzle) is usually 260 to 300.
The stretching temperature is usually 70 to 120 ° C. The draw ratio is usually 1.5 to 3.5 times in the machine direction and 2 to 2 in the circumferential direction.
It is a range of 5 times.
【００３６】得られたボトルは、そのまま使用できる
が、特に、果汁飲料、ウーロン茶などの様に熱充填を必
要とする内溶液の場合は、一般に、ブロー金型内で熱固
定し、更に耐熱性を付与して使用される。熱固定は、通
常、圧空などによる緊張下、１００〜２００℃で数秒〜
数分間行われる。The obtained bottle can be used as it is, but in the case of an internal solution that requires heat filling, such as fruit juice drinks and oolong tea, it is generally heat-set in a blow mold to further improve heat resistance. Is used. The heat setting is usually performed at 100 to 200 ° C for several seconds under tension such as compressed air.
It will take a few minutes.
【００３７】[0037]
【実施例】以下、実施例により、本発明を更に詳細に説
明するが、本発明はその要旨を超えない限り、以下の実
施例に限定されるものではない。なお、本実施例で使用
した種々の測定方法を以下に示す。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Various measuring methods used in this example are shown below.
【００３８】（１）極限粘度（以下「ＩＶ」という。） フェノール／テトラクロロエタン（重量比１／１）の混
合溶媒中３０℃で測定した。(1) Intrinsic viscosity (hereinafter referred to as "IV") It was measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).
【００３９】（２）ヘーズ シリンダー各部およびノズルヘッドの温度を２８０℃、
スクリュー回転数を２００ｒｐｍ、射出時間を６０秒、
金型冷却水温度を１０℃に設定した射出成形機（名機製
作所（株）製「Ｍ−７０Ａ」）で得られた段付き成形板
の、厚み４ｍｍ及び５ｍｍの部分をヘーズメーター（日
本電色（株）社製「ＮＤＨ−３００Ａ」）で測定した。(2) Haze The temperature of each part of the cylinder and the nozzle head is set to 280 ° C.
Screw rotation speed is 200 rpm, injection time is 60 seconds,
The haze meter (Nippon Denki Co., Ltd.) was used to measure the thicknesses of 4 mm and 5 mm of the stepped molding plate obtained with an injection molding machine (“M-70A” manufactured by Meiki Seisakusho Co., Ltd.) in which the mold cooling water temperature was set to 10 ° C. "NDH-300A" manufactured by Color Co., Ltd.).
【００４０】（３）結晶化温度 示差走査熱量計（セイコー電子（株）社製「ＤＳＣ２２
０Ｃ」）を使用し、サンプルとして段付き成形板の厚み
５ｍｍの部分を使用した。室温から２８５℃までの２０
℃／分の速度で昇温している途中で観察される結晶化ピ
ークのトップ温度を昇温結晶化温度（ＴC1）とした。更
に昇温を続け２８５℃に達した時点から３分間保持した
後、１０℃／分の速度で降温した。この時に観察される
結晶化ピークのトップ温度を冷結晶化温度（ＴC2）とし
た。(3) Crystallization temperature Differential scanning calorimeter (“DSC22” manufactured by Seiko Denshi KK)
0C ") was used, and a portion of the stepped molding plate having a thickness of 5 mm was used as a sample. 20 from room temperature to 285 ° C
The top temperature of the crystallization peak observed while the temperature was rising at a rate of ° C / min was defined as the temperature rising crystallization temperature (T C1 ). The temperature was further raised, and after the temperature reached 285 ° C., the temperature was maintained for 3 minutes, and then the temperature was decreased at a rate of 10 ° C./min. The top temperature of the crystallization peak observed at this time was defined as the cold crystallization temperature (T C2 ).
【００４１】（４）ボトルの透明性 シリンダー各部およびノズルヘッドの温度を２８０℃、
スクリュー回転数を１００ｒｐｍ、射出時間を１０秒、
金型冷却水温度を１０℃に設定した射出成形機（東芝
（株）社製「ＩＳ−６０Ｂ」）でプリフォームを成形
し、次いで、予熱炉温度を９０℃、ブロー圧力を２０ｋ
ｇ／ｃｍ2 、成形サイクルを１０秒に設定した延伸ブロ
ー成形機で成形し、胴部平均肉圧３００μｍ、内容積１
リットルの瓶とし、目視により透明性を判断した。(4) Transparency of bottle The temperature of each part of the cylinder and the nozzle head is 280 ° C.
Screw rotation speed 100 rpm, injection time 10 seconds,
A preform is molded with an injection molding machine (“IS-60B” manufactured by Toshiba Corporation) in which the mold cooling water temperature is set to 10 ° C., and then the preheating furnace temperature is 90 ° C. and the blow pressure is 20 k.
Molded by a stretch blow molding machine with g / cm 2 and a molding cycle set to 10 seconds, the average body pressure of the body was 300 μm, and the internal volume was 1
A liter bottle was prepared, and the transparency was visually judged.
【００４２】（５）環状３量体量（以下「ＣＴ量」とい
う。） ＰＥＴ試料２００ｍｇをクロロホルム／ヘキサフルオロ
イソプロパノール（容量比３／２）混液２ｍｌに溶解
し、更に、クロロホルム２０ｍｌを加えて希釈した。こ
れにメタノール１０ｍｌを加えて試料を再析出させ、次
いで、濾過して濾液を得た。当該濾液を乾固後、残渣を
ジメチルホルムアミド２５ｍｌに溶解した液について液
体クロマトグラフで分析定量した。(5) Cyclic trimer amount (hereinafter referred to as "CT amount") 200 mg of a PET sample was dissolved in 2 ml of a chloroform / hexafluoroisopropanol (volume ratio 3/2) mixed solution, and 20 ml of chloroform was further added to dilute it. did. 10 ml of methanol was added to this to reprecipitate a sample, and then filtered to obtain a filtrate. After the filtrate was dried and solidified, a liquid obtained by dissolving the residue in 25 ml of dimethylformamide was analyzed and quantified by liquid chromatography.
【００４３】（６）ジエチレングリコール（以下「ＤＥ
Ｇ量」という。） ＰＥＴ試料５．０ｇに４Ｎ−ＫＯＨメタノール溶液５０
ミリリットル加え、撹拌しながら加熱還流し加水分解し
た。該操作により生成したジオール体成分をガスクロマ
トグラフで定量した。(6) Diethylene glycol (hereinafter referred to as "DE
G amount ”. ) 4N-KOH methanol solution 50 to PET sample 5.0g
The mixture was added with milliliter and heated under reflux with stirring to hydrolyze. The diol component produced by this operation was quantified by gas chromatography.
【００４４】実施例１〜３ テレフタル酸１３．０ｋｇ及びエチレングリコール５．
８２ｋｇのスラリーを調製し、予め、０．３０ｋｇのビ
ス（２−ヒドロキシエチル）テレフタレートを添加して
２５０℃の温度に保持したエステル化槽に４時間かけて
順次供給した。Examples 1 to 3 terephthalic acid 13.0 kg and ethylene glycol 5.
82 kg of a slurry was prepared, and 0.30 kg of bis (2-hydroxyethyl) terephthalate was added in advance and the mixture was sequentially supplied to an esterification tank kept at a temperature of 250 ° C. over 4 hours.
【００４５】供給終了後、１時間エステル化反応を進行
させた後、半量を重縮合槽に移し、リン酸０．９１ｇ
（対ポリマー１２０ｐｐｍ）、二酸化ゲルマニウム０．
９２ｇ（対ポリマー１２０ｐｐｍ）、表１に示す量のポ
リエチレン（三菱化学製「ＵＥ３２０」）を仕込み、２
５０℃から２７８℃まで漸次昇温すると共に、常圧から
漸次減圧し、０．５ｍｍＨｇに保持した。After completion of the feeding, the esterification reaction was allowed to proceed for 1 hour, and then half of the amount was transferred to a polycondensation tank to obtain 0.91 g of phosphoric acid.
(To polymer 120 ppm), germanium dioxide 0.
92 g (120 ppm of polymer), and the amount of polyethylene (“UE320” manufactured by Mitsubishi Chemical) shown in Table 1 were charged, and 2
The temperature was gradually raised from 50 ° C. to 278 ° C., the pressure was gradually reduced from normal pressure, and the pressure was maintained at 0.5 mmHg.
【００４６】反応を３時間行った後、生成したポリマー
を重縮合槽の底部に設けた抜出口よりストランド状に抜
出して水冷した後、チップ状にカットした。次に、撹拌
結晶化機（Ｂｅｐｅｘ社式）により、上記のポリマーチ
ップ表面を１５０℃で結晶化させた後、静置固相重合塔
に移し、２０リットル／ｋｇ・ｈｒの窒素流通下、約１
４０℃で３時間乾燥後、２１０℃で２０時間固相重合
し、固相重合チップを得た。上記の固相重合チップを使
用し、射出成形機（名機製作所（株）製「Ｍ−７０
Ａ」）で段付角板状成形物を得た。この成形板の物性値
を表１に示す。After the reaction was carried out for 3 hours, the produced polymer was withdrawn in a strand form from an outlet provided at the bottom of the polycondensation tank, cooled with water, and then cut into chips. Next, after the surface of the polymer chip was crystallized at 150 ° C. by a stirring crystallization machine (Bepex company), it was transferred to a stationary solid-phase polymerization tower, and was passed under a nitrogen flow of 20 liters / kg · hr for about 1
After drying at 40 ° C. for 3 hours, solid phase polymerization was performed at 210 ° C. for 20 hours to obtain a solid phase polymerization chip. An injection molding machine ("M-70" manufactured by Meiki Seisakusho Co., Ltd.) is used by using the above solid-state polymerized chip.
A)) was used to obtain a stepped rectangular plate-shaped molded product. Table 1 shows the physical properties of this molded plate.
【００４７】また、上記の固相重合チップを使用し、射
出成形機（東芝（株）製「ＩＳ−６０Ｂ」）でプリフォ
ームを成形した。このプリフォームの口栓部を自製結晶
化機で加熱結晶化させた後、延伸ブロー成形機でブロー
成形し、胴部平均肉厚３００μｍ、内容積１リットルの
瓶とし、引続き、１５０℃に設定した金型内で圧空緊張
下、１０秒間熱固定した。このボトルの物性値を表１に
示す。A preform was molded using the above solid-state polymerized chip with an injection molding machine ("IS-60B" manufactured by Toshiba Corp.). The plug part of this preform is heated and crystallized by a self-made crystallization machine, and then blow-molded by a stretch blow molding machine to obtain a bottle having an average wall thickness of 300 μm and an internal volume of 1 liter, and subsequently set at 150 ° C. The sample was heat-set in the above-described mold under compressed air tension for 10 seconds. The physical properties of this bottle are shown in Table 1.
【００４８】また、上記の固相重合チップを使用し、１
０００本の瓶を連続成形したが、射出成形、延伸ブロー
成形、熱固定の何れの金型にも汚染は認められなかっ
た。更に、９０℃で殺菌し、８５℃まで冷却したオレン
ジ果汁液を上述の瓶に充填し、密栓後１５分間倒置した
が、口栓部、肩部および胴部などの変形や液洩れは全く
認められなかった。Also, using the above solid-state polymerization chip,
Although 000 bottles were continuously molded, no contamination was found in any of the molds of injection molding, stretch blow molding and heat setting. Furthermore, the above-mentioned bottle was filled with the orange juice liquid sterilized at 90 ° C and cooled to 85 ° C, and the bottle was capped and inverted for 15 minutes. Deformation and leakage of the mouth plug, shoulder and body were completely observed. I couldn't do it.
【００４９】また、上記の固相重合チップを使用し、シ
リンダー及びノズルの各部温度を２７５℃、スクリュー
回転数を４０ｒｐｍ、押出量を８０ｇ／分に設定した３
０ｍｍ径の押出機で肉厚３００μｍのシートを成形し
た。連続的に１０時間押出成形を継続したが、冷却ドラ
ムの汚染は殆ど認められなかった。Using the above solid-state polymerization chip, the temperature of each part of the cylinder and nozzle was 275 ° C., the screw rotation speed was 40 rpm, and the extrusion rate was 80 g / min.
A sheet having a wall thickness of 300 μm was formed with an extruder having a diameter of 0 mm. The extrusion molding was continuously continued for 10 hours, but the contamination of the cooling drum was hardly recognized.
【００５０】実施例４ 実施例２において、重縮合工程中でＰＥを添加しないこ
と以外は、実施例２と同様の条件で重縮合反応を行って
ポリマーを得た。次に、実施例２と同様にして、２１０
℃で２０時間固相重合を行って固相重合チップを得た。
当該固相重合チップに粉砕したＰＥを１０ｐｐｂドライ
ブレンドしてポリエステル樹脂組成物を得た。このチッ
プより、実施例２と同様にして、内容積１リットルの熱
固定瓶を得たが、口栓部の変形、胴部の白濁は見られず
良好であった。また、上記のポリエステル樹脂組成物で
のボトルの連続成形性、熱充填試験結果も全く問題なく
良好であった。Example 4 A polymer was obtained by carrying out a polycondensation reaction under the same conditions as in Example 2 except that PE was not added in the polycondensation step. Then, in the same manner as in Example 2, 210
Solid phase polymerization was performed at 20 ° C. for 20 hours to obtain a solid phase polymerization chip.
PE crushed to the solid-state polymerization chip was dry blended with 10 ppb to obtain a polyester resin composition. From this chip, a heat-fixing bottle having an internal volume of 1 liter was obtained in the same manner as in Example 2, but the deformation of the mouth plug part and the cloudiness of the body part were not observed, which was good. Further, the continuous moldability of the bottle with the above polyester resin composition and the result of the hot filling test were good without any problems.
【００５１】比較例１ 実施例１において、ＰＥの添加量を０．０４ｐｐｂとし
たこと以外は、実施例１と同様の条件で重縮合反応を行
ってポリマーを得た。次に、実施例１と同様にして、２
１０℃で２０時間固相重合を行って固相重合チップを得
た。このチップより、実施例１と同様にして段付成形板
を成形した。得られた成形板の物性値を表２に示す。ま
た、上記の固相重合チップを使用し、実施例１と同様に
プリフォームを成形した。このプリフォームの口栓部を
自製結晶化しようとしたが、口栓部端面に変形が認めら
れた。Comparative Example 1 A polymer was obtained by carrying out a polycondensation reaction under the same conditions as in Example 1 except that the amount of PE added was 0.04 ppb. Next, in the same manner as in Example 1, 2
Solid phase polymerization was carried out at 10 ° C. for 20 hours to obtain a solid phase polymerization chip. From this chip, a stepped molding plate was molded in the same manner as in Example 1. Table 2 shows the physical property values of the obtained molded plate. Further, a preform was molded in the same manner as in Example 1 using the above solid-state polymerization chip. An attempt was made to self-crystallize the plug portion of this preform, but deformation was observed on the end surface of the plug portion.
【００５２】比較例２ 実施例１において、ＰＥの添加量を２００ｐｐｂとした
こと以外は、実施例１と同様の条件で重縮合反応を行い
ポリマーを得た。次に、実施例３と同様にして、２１０
℃で２０時間固相重合を行って固相重合チップを得た。
このチップより、実施例１と同様にして段付成形板を成
形した。得られた成形板の物性値を表２に示す。また、
上記の固相重合チップを使用し、実施例１と同様にプリ
フォームを成形したが、プリフォームは白化して正常な
成形が行えなかった。Comparative Example 2 A polymer was obtained by carrying out a polycondensation reaction under the same conditions as in Example 1 except that the amount of PE added was 200 ppb. Then, in the same manner as in Example 3, 210
Solid phase polymerization was performed at 20 ° C. for 20 hours to obtain a solid phase polymerization chip.
From this chip, a stepped molding plate was molded in the same manner as in Example 1. Table 2 shows the physical property values of the obtained molded plate. Also,
A preform was molded using the above solid-state polymerized chip in the same manner as in Example 1, but the preform was whitened and could not be molded normally.
【００５３】比較例３ 実施例２において、製品中のＤＥＧ量が全ジオール単位
中５モル％になる様に追添した以外は、実施例２と同様
の条件で重縮合反応を行いポリマーを得た。次に、実施
例２と同様にして、２１０℃で２０時間固相重合を行っ
て固相重合チップを得た。このチップより、実施例１と
同様にして段付成形板を成形した。得られた成形板の物
性値を表２に示す。Comparative Example 3 A polymer was obtained by carrying out a polycondensation reaction under the same conditions as in Example 2 except that the amount of DEG in the product was added in an amount of 5 mol% of all diol units in Example 2. It was Then, in the same manner as in Example 2, solid phase polymerization was carried out at 210 ° C. for 20 hours to obtain a solid phase polymerization chip. From this chip, a stepped molding plate was molded in the same manner as in Example 1. Table 2 shows the physical property values of the obtained molded plate.
【００５４】また、上記の固相重合チップより、実施例
２と同様にして内容積１リットルの熱固定瓶を得たが、
口栓部の変形、胴部の白濁は見られず良好であり、連続
成形においても金型の汚染は見られなかった。しかしな
がら、９０℃で殺菌し、８５℃まで冷却したオレンジ果
汁液を充填し、密栓後１５分間倒置したところ、肩部お
よび胴部に僅かに変形が認められた。A heat-fixing bottle having an internal volume of 1 liter was obtained from the above solid-state polymerization chip in the same manner as in Example 2.
No deformation of the spout and no clouding of the body were observed, and the mold was not contaminated during continuous molding. However, when orange juice liquid sterilized at 90 ° C. and cooled to 85 ° C. was filled, and the container was capped and inverted for 15 minutes, slight deformation was observed in the shoulder and the body.
【００５５】比較例４ 実施例２と同様の条件で重縮合反応を行いポリマーを得
た。次に、実施例２と同様にして固相重合チップを得
た。但し、固相重合の温度は２１５℃、時間は１４時間
とした。このチップより、実施例２と同様にして段付成
形板を成形した。得られた成形板の物性値を表２に示
す。また、このチップより、実施例２と同様にプリフォ
ームを成形し、実施例２と同様にして内容積１リットル
の熱固定瓶を得たが、口栓部の変形、胴部の白濁は見ら
れず良好であった。更に、９０℃で殺菌し、８５℃まで
冷却したオレンジ果汁液を充填し、密栓後１５分間倒置
したが、肩部および胴部に変形等は全く認められなかっ
た。しかしながら、上記の固相重合チップで１０００本
のボトルを連続成形したところ、金型の汚染が認められ
た。Comparative Example 4 A polymer was obtained by carrying out a polycondensation reaction under the same conditions as in Example 2. Next, a solid-state polymerization chip was obtained in the same manner as in Example 2. However, the temperature of the solid phase polymerization was 215 ° C. and the time was 14 hours. From this chip, a stepped molding plate was molded in the same manner as in Example 2. Table 2 shows the physical property values of the obtained molded plate. A preform was molded from this chip in the same manner as in Example 2, and a heat-fixed bottle having an internal volume of 1 liter was obtained in the same manner as in Example 2, but the deformation of the plug part and the cloudiness of the body part were observed. It was good not to be able to. Further, it was sterilized at 90 ° C., filled with orange juice liquid cooled to 85 ° C., sealed and inverted for 15 minutes, but no deformation or the like was observed in the shoulder and the body. However, when 1000 bottles were continuously molded with the above solid-state polymerization chip, contamination of the mold was observed.
【００５６】[0056]
【表１】 ──────────────────────────────────── 実 施 例 １ ２ ３ ４ ＰＥ含有量(ppb) 1 10 40 10 ＤＥＧ量（モル％） 2.0 1.9 2.1 2.1 ＣＴ量（重量％） 0.38 0.41 0.39 0.42 極限粘度（ｄｌ／ｇ） 0.79 0.78 0.78 0.78 段付成形板物性 ＤＳＣ：ＴC1（℃） 164.2 162.9 163.2 163.3 ：ＴC2（℃） 176.3 176.4 175.7 175.9 ヘーズ：４ｍｍ（％） 0.6 0.5 0.5 0.6 ：５ｍｍ（％） 2.7 2.9 2.8 3.0 金型の汚染 ○ ○ ○ ○ ボトル外観 ○ ○ ○ ○ 耐熱性試験 ○ ○ ○ ○ ──────────────────────────────────── 金型の汚染・・・○：連続成形試験の前後において変化無し ×：連続成形試験後に付着物有り ボトル外観・・・○：変形、濁りが無く良好 △：透明であるが変形有り ×：結晶化時に白化有り 耐熱性試験・・・○：充填後のボトルに変形が無く良好 ×：充填後のボトルに変形有り[Table 1] ──────────────────────────────────── Actual Example 1 2 3 4 PE content (ppb) 1 10 40 10 DEG amount (mol%) 2.0 1.9 2.1 2.1 CT amount (wt%) 0.38 0.41 0.39 0.42 Intrinsic viscosity (dl / g) 0.79 0.78 0.78 0.78 Physical properties of stepped plate DSC: T C1 (° C) 164.2 162.9 163.2 163.3: T C2 (℃) 176.3 176.4 175.7 175.9 Haze: 4 mm (%) 0.6 0.5 0.5 0.6: 5 mm (%) 2.7 2.9 2.8 3.0 Mold contamination ○ ○ ○ ○ Bottle appearance ○ ○ ○ ○ Heat resistance test ○ ○ ○ ○ ──────────────────────────────────── Mold contamination ・ ・ ・ ○: Continuous No change before and after molding test ×: Adhesion after continuous molding test Bottle appearance: ○: Good with no deformation or turbidity △: Transparent but with deformation ×: Whitening during crystallization Heat resistance test ··· ○: deformation is not good × the bottle after filling: Yes deformation in the bottle after filling
【００５７】[0057]
【表２】 ──────────────────────────────────── 比 較 例 １ ２ ３ ４ ＰＥ含有量(ppb) 0.04 200 10 10 ＤＥＧ量（モル％） 1.9 2.0 5.2 2.1 ＣＴ量（重量％） 0.43 0.39 0.44 0.72 極限粘度（ｄｌ／ｇ） 0.79 0.78 0.79 0.78 段付成形板物性 ＤＳＣ：ＴC1（℃） 173.9 152.3 165.9 163.3 ：ＴC2（℃） 175.1 185.4 174.1 176.4 ヘーズ：４ｍｍ（％） 0.4 7.8 0.4 0.6 ：５ｍｍ（％） 2.7 24.4 2.2 2.9 金型の汚染 ○ ○ ○ × ボトル外観 △ × △ △ 耐熱性試験 ○ ○ × ○ ────────────────────────────────────[Table 2] ──────────────────────────────────── Comparative Example 1 2 3 4 PE content (ppb) 0.04 200 10 10 DEG amount (mol%) 1.9 2.0 5.2 2.1 CT amount (wt%) 0.43 0.39 0.44 0.72 Intrinsic viscosity (dl / g) 0.79 0.78 0.79 0.78 Stepped plate physical properties DSC: T C1 (° C) 173.9 152.3 165.9 163.3: T C2 (℃) 175.1 185.4 174.1 176.4 Haze: 4 mm (%) 0.4 7.8 0.4 0.6: 5 mm (%) 2.7 24.4 2.2 2.9 Mold contamination ○ ○ ○ × Bottle appearance △ × △ △ Heat resistance test ○ ○ × ○ ────────────────────────────────────
【００５８】[0058]
【発明の効果】以上説明した本発明によれば、連続成形
性に優れ、しかも、成形物またはその前駆体であるプリ
フォームを熱処理して耐熱性を付与する際に、透明性を
損なうことなく結晶化速度のみを制御することが出来る
ポリエステル樹脂組成物が提供され、本発明のポリエス
テル樹脂組成物は、特に、ボトル成形に有用である。EFFECTS OF THE INVENTION According to the present invention described above, the continuous moldability is excellent and the transparency is not impaired when the molded product or the preform which is its precursor is heat-treated to impart heat resistance. A polyester resin composition capable of controlling only the crystallization rate is provided, and the polyester resin composition of the present invention is particularly useful for bottle molding.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中道 一也 三重県四日市市東邦町１番地 三菱化学株 式会社四日市総合研究所内 (72)発明者 木代 修 三重県四日市市東邦町１番地 三菱化学株 式会社四日市総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuya Nakamichi No. 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Chemical Co., Ltd. (72) Inventor Osamu Kishiro No. 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Company Yokkaichi Research Institute
Claims (3)
し、ジエチレングリコール単位の割合が全ジオール単位
中１．０〜２．５モル％であり且つ環状三量体の含有量
が０．５重量％以下であるポリエステル樹脂に０．１〜
４５ｐｐｂのポリエチレンを配合して成ることを特徴と
するポリエステル樹脂組成物。1. A polyester mainly comprising ethylene terephthalate units, wherein the proportion of diethylene glycol units is 1.0 to 2.5 mol% in all diol units and the content of cyclic trimer is 0.5 wt% or less. 0.1 to resin
A polyester resin composition comprising 45 ppb of polyethylene.
れた成形品について示差走査熱量計にて測定した際の昇
温時の結晶化温度が１５５℃〜１７２℃である請求項１
に記載のポリエステル樹脂組成物。2. A crystallization temperature at the time of temperature increase of 155 ° C. to 172 ° C. when measured by a differential scanning calorimeter with respect to a molded product obtained by injection molding at a molding temperature of 280 ° C.
The polyester resin composition described in 1.
である請求項１又は２に記載のポリエステル樹脂組成
物。3. The intrinsic viscosity is 0.72 to 0.85 dl / g.
The polyester resin composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10343696A JP3427202B2 (en) | 1995-09-26 | 1996-03-29 | Polyester resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-271786 | 1995-09-26 | ||
| JP27178695 | 1995-09-26 | ||
| JP10343696A JP3427202B2 (en) | 1995-09-26 | 1996-03-29 | Polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09151308A true JPH09151308A (en) | 1997-06-10 |
| JP3427202B2 JP3427202B2 (en) | 2003-07-14 |
Family
ID=26444072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10343696A Expired - Lifetime JP3427202B2 (en) | 1995-09-26 | 1996-03-29 | Polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3427202B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018842A1 (en) * | 1998-09-30 | 2000-04-06 | Mitsui Chemicals, Inc. | Polyester resin composition and hollow molded container made therefrom |
| US6392005B1 (en) | 2001-03-19 | 2002-05-21 | Nan Ya Plastics Corporation | Manufacturing method for decreasing the cyclic oligomer content in polyester |
| JP2007177089A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Inc | Polyethylene terephthalate resin composition and blow-molded container made therefrom |
| WO2012067083A1 (en) | 2010-11-16 | 2012-05-24 | 東洋紡績株式会社 | Polyester resin |
-
1996
- 1996-03-29 JP JP10343696A patent/JP3427202B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018842A1 (en) * | 1998-09-30 | 2000-04-06 | Mitsui Chemicals, Inc. | Polyester resin composition and hollow molded container made therefrom |
| US6355319B1 (en) | 1998-09-30 | 2002-03-12 | Mitsui Chemicals Inc | Polyester resin composition and hollow molded container made therefrom |
| US6392005B1 (en) | 2001-03-19 | 2002-05-21 | Nan Ya Plastics Corporation | Manufacturing method for decreasing the cyclic oligomer content in polyester |
| JP2007177089A (en) * | 2005-12-28 | 2007-07-12 | Mitsui Chemicals Inc | Polyethylene terephthalate resin composition and blow-molded container made therefrom |
| WO2012067083A1 (en) | 2010-11-16 | 2012-05-24 | 東洋紡績株式会社 | Polyester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3427202B2 (en) | 2003-07-14 |
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