JP2000141571A5

JP2000141571A5 -

Info

Publication number: JP2000141571A5
Application number: JP1998322210A
Authority: JP
Filing date: 1998-11-12
Publication date: 2005-08-11
Anticipated expiration: 2018-11-12

Description

ＰＥＮは基本的にＰＥＴと同様な触媒で反応させることによって得ることができ、ナフタレンジカルボン酸エステル形成性誘導体とエチレングリコールまたはそのエステル形成性誘導体とをエステル化触媒の存在下でエステル交換反応をさせた後、重合触媒として、二酸化ゲルマニウムまたは三酸化アンチモンを用いて重縮合し、次いで固相重合して得る事が出来る。又、射出成形機などの成形機にＰＥＮを供給してプリフォームを成形し、このプリフォームを延伸ブロー成形しボトル化される。 PEN can be obtained by reacting with a catalyst similar to PET basically, and a transesterification reaction of a naphthalenedicarboxylic acid ester-forming derivative and ethylene glycol or an ester-forming derivative thereof is carried out in the presence of an esterification catalyst. After that, it can be obtained by transesterification using germanium dioxide or antimony trioxide as a polymerization catalyst, and then solid-phase polymerization. Further, PEN is supplied to a molding machine such as an injection molding machine to form a preform, and this preform is stretch blow molded to be bottled.

【０００６】
【課題を解決するための手段】
即ち、本発明は、最内層、中間層及び最外層からなる多層ボトルであり、最内層及び最外層を形成するポリエステル（Ａ）と中間層を形成するポリエステル（Ｂ）が各々ナフタレンジカルボン酸単位を主たる酸成分とし、エチレングリコール単位を主たるグリコール成分とするポリエステルからなり、かつ、式（１）及び（２）の条件を満たす多層ボトルである。
０．８５≧ＩＶ（Ａ）≧０．４０かつ０．８５≧ＩＶ（Ｂ）≧０．４０
・・・（１）
Ｔｇ（Ａ）≧１００℃ かつＴｇ（Ｂ）≧１００℃・・・（２）
（但し、Ｔｇ（Ａ）はポリエステル（Ａ）のガラス転位温度、Ｔｇ（Ｂ）はポリエステル（Ｂ）のガラス転位温度、ＩＶ（Ａ）はポリエステル（Ａ）の固有粘度、ＩＶ（Ｂ）はポリエステル（Ｂ）の固有粘度である。） 0006
[Means for solving problems]
That is, the present invention is a multi-layer bottle composed of an innermost layer, an intermediate layer and an outermost layer, and the polyester (A) forming the innermost layer and the outermost layer and the polyester (B) forming the intermediate layer each contain a naphthalene dicarboxylic acid unit. It is a multi-layer bottle made of polyester having an ethylene glycol unit as a main glycol component as a main acid component and satisfying the conditions of the formulas (1) and (2).
0.85 ≧ IV (A) ≧ 0.40 and 0.85 ≧ IV (B) ≧ 0.40
... (1)
Tg (A) ≥100 ° C and Tg (B) ≥100 ° C ... (2)
(However, Tg (A) is the glass transition temperature of polyester (A), Tg (B) is the glass transition temperature of polyester (B), IV (A) is the intrinsic viscosity of polyester (A), and IV (B) is polyester. (B) is the intrinsic viscosity.)

また本発明は、ポリエステル（Ａ）及びポリエステル（Ｂ）を、剪断速度５０〜３００ｓｅｃ^-1、温度２８０〜３３０℃で、かつ、溶融粘度比が式（３）の範囲を満足する条件で成形することを特徴とする請求項１記載の多層ボトルの製造方法を包含する。
−０．５≦ｌｏｇ（η_A／η_B）≦１．２５・・・（３）
（ただし、η_Aは最内層及び最外層を構成するポリエステル（Ａ）の溶融粘度（kg/m・sec)、η_Bは中間層を構成するポリエステル（Ｂ）の溶融粘度（kg/m・sec）を示す。） Further, in the present invention, the polyester (A) and the polyester (B) are molded under a shear rate of 50 to 300 sec ^-1 , a temperature of 280 to 330 ° C., and a melt viscosity ratio satisfying the range of the formula (3). The method for producing a multilayer bottle according to claim 1, wherein the method for producing a multilayer bottle is included.
-0.5 ≤ log (η _A / η _B ) ≤ 1.25 ... (3)
(However, η _A is the melt viscosity (kg / m · sec) of the polyester (A) constituting the innermost layer and the outermost layer, and η _B is the melt viscosity (kg / m · sec) of the polyester (B) constituting the intermediate layer. ) Is shown.)

従って、２０モル％未満の他の成分が共重合又は混合体として含有されてもよい。例えば２,６−ナフタレンジカルボン酸成分の一部（２０モル％未満）を２,７−、１,５−、１,７−その他のナフタレンジカルボン酸の異性体或はテレフタル酸或はイソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェニルスルホンジカルボン酸等のごとき他の芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸等の如き脂環族ジカルボン酸、アジピン酸、セバチン酸、アゼライン酸等の如き脂肪族ジカルボン酸、ｐ−β−ヒドロキシエトキシ安息香酸、ε−オキシカプロン酸等の如きオキシ酸等の他の二官能性カルボン酸で置き換えても良い。 Therefore, less than 20 mol% of other components may be included as a copolymer or mixture. For example, a part (less than 20 mol%) of the 2,6-naphthalenedicarboxylic acid component is 2,7-, 1,5-1,7-other isomers of the naphthalenedicarboxylic acid or terephthalic acid or isophthalic acid. naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenylether dicarboxylic acid, other aromatic dicarboxylic acids such as such as diphenyl sulfone dicarboxylic acid, hexahydroterephthalic acid, such as alicyclic dicarboxylic acids such as hexahydroisophthalic acid, adipic acid, sebacic acid, such as aliphatic dicarboxylic acids such as azelaic acid, p-beta - hydroxy ethoxy benzoic acid, epsilon - other may be replaced by a difunctional carboxylic acid such as such as oxy acids such as oxycaproic acid.

更に、エチレングリコール成分の一部を例えばトリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、ジエチレングリコール、１,１−シクロヘキサンジメタノール、１,４−シクロヘキサンジメタノール、２,２−ビス（４’−β−ヒドロキシフェニル）プロパン、ビス（４’−β−ヒドロキシエトキシフェニル）スルホン酸等の他の多官能化合物の１種以上で置換して２０モル％未満の範囲で共重合せしめたコポリマーであってもよい。 Furthermore, some of the ethylene glycol components are, for example, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, 1,1 - cyclohexanedimethanol, 1,4 - cyclohexanedimethanol, 2, Substituted with one or more of other polyfunctional compounds such as 2 - bis ( 4'-β -hydroxyphenyl) propane and bis (4' -β- hydroxyethoxyphenyl) sulfonic acid, and used in the range of less than 20 mol%. It may be a polymerized copolymer.

最内層及び最外層を形成するポリエステル（Ａ）の固有粘度は０．４０〜０．８５であることが好ましく、さらには０．６０〜０．８５であることが好ましい。０．４０を下回るとブロー成形でドローダウンによる偏肉を起こしやすく更に、強度低下があり好ましくない。また０．８５を超えると射出成形によるプリフォーム成形において流動性低下の為、ゲート白化等の外観不良を起こしやすく好ましくない。 The intrinsic viscosity of the polyester (A) forming the innermost layer and the outermost layer is preferably 0.40 to 0.85, more preferably 0.60 to 0.85. Below 0.40 further prone to uneven thickness due to drawdown in Bed low molding, there is the strength undesirably reduced. Further, if it exceeds 0.85, the fluidity is lowered in the preform molding by injection molding, so that appearance defects such as gate whitening are likely to occur, which is not preferable.

また、中間層を形成するポリエステル（Ｂ）の固有粘度は０．４０〜０．８５であることが好ましく、さらには０．４０〜０．７５であることが好ましい。０．４０を下回ると強度低下があり好ましくない。また０．８５を超えると射出成形によるプリフォーム成形において流動性低下の為、均一な中間層を形成できず好ましくない。 Further, the intrinsic viscosity of the polyester (B) forming the intermediate layer is preferably 0.40 to 0.85, more preferably 0.40 to 0.75. If it is less than 0.40, the strength is lowered, which is not preferable. Also 0. If it exceeds 85, a uniform intermediate layer cannot be formed due to a decrease in fluidity in preform molding by injection molding, which is not preferable.

最内層及び最外層と中間層の重量比は、５０：５０〜９８：２の範囲であることが好ましい。中間層の重量比が５０重量部より高い場合、アセトアルデヒドのボトル内部への拡散速度が速く、また吸着匂い物質の溶出が顕著であり好ましくない。また中間層の重量比が２重量部より低いと再利用チップ、プリフォーム、ボトルの使用量が低くコストダウン効果が低く好ましくない。
The weight ratio of the innermost layer and the outermost layer to the intermediate layer is preferably in the range of 50:50 to 98: 2. When the weight ratio of the intermediate layer is higher than 50 parts by weight, the diffusion rate of acetaldehyde into the bottle is high, and the elution of the adsorbed odorant is remarkable, which is not preferable. Further, when the weight ratio of the intermediate layer is lower than 2 parts by weight, the amount of recycled chips, preforms and bottles used is low and the cost reduction effect is low, which is not preferable.

Claims

It is a multilayer bottle consisting of an innermost layer, an intermediate layer and an outermost layer. The polyester (A) forming the innermost layer and the outermost layer and the polyester (B) forming the intermediate layer each have a naphthalenedicarboxylic acid unit as a main acid component, and ethylene. A multilayer bottle made of polyester having a glycol unit as a main glycol component and satisfying the conditions of the formulas (1) and (2).

(However, Tg (A) is the glass transition temperature of polyester (A), Tg (B) is the glass transition temperature of polyester (B), IV (A) is the intrinsic viscosity of polyester (A), and IV (B) is polyester. (Inherent viscosity of (B).)

The multilayer bottle according to claim 1, wherein a weight ratio of the innermost layer and the outermost layer to the intermediate layer is in the range of 50:50 to 98: 2.

The amount of acetaldehyde in the innermost layer and the outermost layer is 35 ppm or less, the amount of acetaldehyde in the intermediate layer is 70 ppm or less, and the amount of acetaldehyde diffusing into the bottle is 4 μg / L · day or less. Multi-layer bottle.

The multilayer bottle according to claim 1 or 2, wherein the polyester forming the intermediate layer is a reused chip.

The multilayer bottle according to claim 1 or 2, wherein the polyester forming the intermediate layer is a reuse preform and / or a reuse bottle.

The multilayer bottle according to claim 1 or 2, wherein the trunk haze is 5% or less.

The multilayer bottle according to claim 1, wherein the content of naphthalenedicarboxylic acid units in the polyester (A) is 80 mol% or more.

The polyester (A) and the polyester (B) are molded under conditions where the shear rate is 50 to 300 sec ⁻¹ , the temperature is 280 to 330 ° C., and the melt viscosity ratio satisfies the range of the formula (3). The manufacturing method of the multilayer bottle of Claim 1.
−0.5 ≦ log (η _A / η _B ) ≦ 1.25 (3)
(Where η _A is the melt viscosity (kg / m · sec) of the polyester (A) constituting the innermost layer and outermost layer, and η _B is the melt viscosity (kg / m · sec) of the polyester (B) constituting the intermediate layer. )