JP2009001670A5

JP2009001670A5 -

Info

Publication number: JP2009001670A5
Application number: JP2007163893A
Authority: JP
Filing date: 2007-06-21
Publication date: 2010-07-01
Anticipated expiration: 2027-06-21

Description

前記した本発明の目的は、少なくとも脂環族ジカルボン酸成分及びスピログリコールを含む下記式（１）、（２）を満足するポリエステル樹脂を製造するに際し、エステル化反応及び／又はエステル交換反応を経て重縮合触媒の存在下で重縮合反応を行うことにより固有粘度０．６０ｄｌ／ｇ以下のポリエステル樹脂プレポリマーを生成し、該ポリエステル樹脂プレポリマーを２００℃以下の温度で固相重縮合することを特徴とするポリエステル樹脂の製造方法によって達成される。 The object of the present invention described above is to undergo an esterification reaction and / or a transesterification reaction in producing a polyester resin satisfying the following formulas (1) and (2) containing at least an alicyclic dicarboxylic acid component and spiroglycol. A polyester resin prepolymer having an intrinsic viscosity of 0.60 dl / g or less is generated by performing a polycondensation reaction in the presence of a polycondensation catalyst, and the polyester resin prepolymer is subjected to solid-phase polycondensation at a temperature of 200 ° C. or less. It is achieved by the manufacturing method of the characteristic polyester resin.

本発明のポリエステル樹脂の製造方法は、少なくとも脂環族ジカルボン酸成分及びスピログリコールを含む下記式（１）、（２）を満足するポリエステル樹脂を製造するに際し、エステル化反応及び／又はエステル交換反応を経て重縮合触媒の存在下で重縮合反応を行うことにより固有粘度０．６０ｄｌ／ｇ以下のポリエステル樹脂プレポリマーを生成し、該ポリエステル樹脂プレポリマーを２００℃以下の温度で固相重縮合を行うことを特徴とするポリエステル樹脂の製造方法である。 The production method of the polyester resin of the present invention is an esterification reaction and / or transesterification reaction in producing a polyester resin satisfying the following formulas (1) and (2) containing at least an alicyclic dicarboxylic acid component and spiroglycol. To produce a polyester resin prepolymer having an intrinsic viscosity of 0.60 dl / g or less by performing a polycondensation reaction in the presence of a polycondensation catalyst, and subjecting the polyester resin prepolymer to solid phase polycondensation at a temperature of 200 ° C. or less. It is the manufacturing method of the polyester resin characterized by performing.

本発明における脂環族ジオールとしては得られるポリエステルの色調の観点からスピログリコールが用いられる。ここでスピログリコールとは３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンを指す。 Spiroglycol is used as the alicyclic diol in the present invention from the viewpoint of the color tone of the obtained polyester. Here, spiroglycol refers to 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.

本発明において、例えばＰＥＴの場合、テレフタル酸成分（芳香環成分）をシクロヘキサンジカルボン酸等で置換するとＴｇが低下する。そこでスピログリコールなど脂環族ジオールをエチレングリコール成分に置換することでＴｇが上昇し、結果として本発明のポリエステル組成物と積層するＰＥＴと同程度のＴｇに調整することができる。Ｔｇを上昇させる効果はスピログリコール成分において顕著である。 In the present invention, for example, in the case of PET, Tg decreases when the terephthalic acid component (aromatic ring component) is substituted with cyclohexanedicarboxylic acid or the like. Therefore Tg increases the Supiroguriko Le soil alicyclic diol by replacing the ethylene glycol component, it may be adjusted to PET and comparable Tg of laminating the polyester composition of the present invention as a result. Effect of increasing the Tg is remarkable Oite spiro glycol Ingredients.

参考例１４
ＳＰＧの代わりにイソソルビド１０ｍｏｌに変更する以外は実施例１と同様にしてポリエステル樹脂プレポリマーの重合および固相重縮合を行いポリエステル樹脂を得た。さらに実施例１で重合したＰＥＴ樹脂を用い、同様の条件で積層フィルムを得た。 Reference Example 14
A polyester resin was obtained by polymerization and solid phase polycondensation of a polyester resin prepolymer in the same manner as in Example 1 except that 10 mol of isosorbide was used instead of SPG. Furthermore, using the PET resin polymerized in Example 1, a laminated film was obtained under the same conditions.

Claims

In producing a polyester resin satisfying the following formulas (1) and (2) containing at least an alicyclic dicarboxylic acid component and spiroglycol , the polyester resin undergoes esterification and / or transesterification in the presence of a polycondensation catalyst. A polyester resin prepolymer having an intrinsic viscosity of 0.60 dl / g or less is produced by performing a condensation reaction, and the polyester resin prepolymer is subjected to solid-phase polycondensation at a temperature of 200 ° C. or less. .
65 ° C. ≦ Glass transition temperature by differential scanning calorimetry ≦ 90 ° C. (1)
1.500 ≦ refractive index at sodium D line ≦ 1.570 (2)

The method for producing a polyester resin according to claim 1, wherein a titanium compound is used as the polycondensation catalyst.

Titanium compound is an alkoxy group, method for producing a polyester resin according to claim 1 or 2, characterized in that it comprises at least one substituent selected from the group consisting of acylate group Contact and hydroxyl.

The alkoxy group of the titanium compound is at least one functional group selected from the group consisting of a β-diketone functional group, a hydroxycarboxylic acid functional group, and a ketoester functional group. A method for producing a polyester resin according to item 1.

5. The polyester resin according to claim 1, wherein a trivalent phosphorus compound is added at any stage from the start of the esterification reaction and / or the transesterification reaction to the end of the polycondensation reaction. Production method.

The method for producing a polyester resin according to any one of claims 1 to 5, wherein the alicyclic dicarboxylic acid component is a cyclohexane dicarboxylic acid component and is contained in an amount of 5 to 80 mol% in all dicarboxylic acid components.

The polyester resin according to any one of claims 1 to 6, wherein the cyclohexanedicarboxylic acid component contains cis and trans isomers of a stereoisomer, and the trans isomer content is 40% or less. Production method.

Spiroglycol contains 5-80 mol% in all the diol components, The manufacturing method of the polyester resin of any one of Claims 1-7 characterized by the above-mentioned.

The method for producing a polyester resin according to any one of claims 1 to 8, wherein the molar number of aromatic rings contained in the polyester repeating unit is 4.8 mol or less in terms of 1 kg of the polyester resin.