JPH07109340A - Polyethylene naphthalenedicarboxylate composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in heat stability, hue and transparency and useful as a packaging material such as a bottle or a sheet by mixing a specified composition of catalysts and a specified ammonium compound therein. CONSTITUTION:This composition is prepared by blending an ammonium compound of the formula [R1 to R4 are each H, a (substituted) alkyl, a (substituted) cycloalkyl or a (substituted) aryl, provided that a rind may be formed from R3 and R4; A is an anion residue] with a polyester synthesized from (A) naphthalene dicarboxylic acid as the main acid component, (B) ethylene glycol as the main glycol component, etc., and containing a catalyst composed of (C) an Mg compound, (D) a Ca compound, (E) a P compound, (F) a Ge compound and (G) an Sb compound in a ratio satisfying 2.6<=C+D<=4.1, 1.3g<=C/D<=6.0, 1.0<=E/(C+D)<=1.5 and 1.0<=F or G<=3.0 on mole base based on A=10g. The amount of the blended ammonium compound us 0.04 to 0.4mol based on A=10<6>g.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene naphthalate composition, and more specifically, it has excellent heat stability, excellent hue and transparency, and is useful as a packaging material for bottles, sheets and the like. It relates to a carboxylate (hereinafter abbreviated as PEN) composition.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION PEN
Is superior to polyethylene terephthalate (hereinafter abbreviated as PET) in basic physical properties such as heat resistance, gas barrier properties, and strength, and is expected to be useful as a packaging material mainly for sheets and bottles. And 2,
Three proposals are also made.

In general, a packaging material having a good hue and transparency is strongly desired. PEN is basically P
Although a catalyst system similar to that of ET can be used, when a titanium compound is used as a catalyst, the coloration during polymerization is severe and the hue deteriorates. Therefore, a catalyst other than the titanium compound should be used. However, other than that, PEN has a large whitening at the time of molding as compared with PET, and there is a problem in transparency. After that, as a result of investigating the cause of hindering the transparency, what was mainly used as a catalyst and what formed a polymer component and a compound became a precipitate, which was present inside the polymer and / or the surface layer, and thus the optical It was presumed that the transparency was impaired due to the dynamic scattering. On the other hand, it has been proposed to limit the specific catalyst species, amount and ratio as a means for reducing the formation of precipitates due to this catalyst or the like, and the transparency of PEN for this catalyst system was certainly improved. However, it is not completely satisfactory in terms of hue and thermal stability. The reason for this is to suppress the formation of precipitates,
The addition amount of the phosphorus compound used to deactivate the transesterification catalyst is less than the equimolar amount, and since the catalytic action is not completely deactivated, when molding the polymer,
The decomposition rate becomes large.

In view of the above situation, the present inventors have made earnest studies, and as a result, in a test in which the species, amount and ratio of a specific catalyst are changed and added, the amount of the phosphorus compound is at least compared with the amount of the transesterification catalyst. The inventors have found that a polyethylene naphthalate composition having good thermal stability and excellent hue and transparency can be obtained by adding an equimolar amount and further blending a specific ammonium compound, and arrived at the present invention.

[0005]

That is, the present invention is a polyester containing naphthalenedicarboxylic acid as a main acid component and ethylene glycol as a main glycol component, and a magnesium compound, a calcium compound, a phosphorus compound, a germanium compound as a catalyst. And / or the antimony compound is represented by the following formulas (1) to (4) or (1) to
The ammonium compound represented by the chemical formula I is contained in an amount of 10 ⁶ g.
It is a polyethylene naphthalate composition characterized in that 0.04 to 0.4 mol is added per one.

[0006]

## EQU2 ## 2.6 mol ≦ (Mg + Ca) ≦ 4.1 mol (1) 1.3 ≦ (Mg / Ca) ≦ 6.0 (2) 1.0 ≦ P / (Mg + Ca) ≦ 1.5 ( 3) 0.4 mol ≤ Ge ≤ 3.0 mol (4) 0.4 mol ≤ Sb ≤ 3.0 mol (5) (Each metal element in the above formula represents the number of mols per 10 ⁶ g of the acid component. Show.)

[0007]

[Chemical 2]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group and substituted derivatives thereof, and R ₃ and R ₄ form a ring. Further, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, and A represents an anion residue.) The present invention will be described in detail below.

The term "mainly" as used herein means that it exceeds 70 mol%, and preferably exceeds 80 mol%. Therefore, less than 30 mol% of other components may be included as a copolymer or mixture.

In the present invention, "naphthalenedicarboxylic acid" means, for example, 2,6-naphthalenedicarboxylic acid,
The main target is 2,7-naphthalenedicarboxylic acid and its ester-forming derivatives, but some of them (30 mol%
Other than dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and other dicarboxylic acids; terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid Alicyclic dicarboxylic acids such as hexahydroterephthalic acid, decalin dicarboxylic acid and tereralin dicarboxylic acid; oxy acids such as glycolic acid and p-oxybenzoic acid may be substituted. Examples of the ester-forming derivative of the acid component include lower alkyl ester, phenyl ester, acid anhydride and the like.

Further, the "glycol component" is intended mainly for ethylene glycol, but a part (less than 30 mol%) of it is used for other glycols such as tetramethylene glycol, propylene glycol, 1,3-butanediol, neo. Aliphatic diols such as pentyl glycol; alicyclic diols such as cyclohexanedimethanol and tricyclodecane dimethylol; bisphenol A, bisphenol S, bishydroxyethoxybisphenol A, tetrabromobisphenol A, etc. Good. Also, like ordinary polyesters, heat stabilizers such as phosphorus, antioxidants such as hindered phenols, UV absorbers such as benzotriazole, hydroxybenzophenone and cyanoacrylate, pigments such as titanium oxide, carbon black and terazol blue. , Dyes, nucleating agents such as talc, crystallization accelerators such as higher fatty acid salts,
It does not matter even if a release agent is added.

In the present invention, a trifunctional or higher polycarboxylic acid or polyhydroxy compound, such as trimellitic acid, is used in an amount in a substantially linear range, for example, an amount of 2 mol% or less based on the total acid component. And a copolymer of pentaerythritol and the like are also included.

In the present invention, for example, in the case of the transesterification method, it is soluble in the lower alkyl ester of naphthalenedicarboxylic acid and usually ethylene glycol in the reaction system in a total amount of 2.6 to 4.1 mol with respect to the acid component. Then, a magnesium compound and a calcium compound are added as a transesterification reaction catalyst (hereinafter, mole means the number of moles per 10 ⁶ g of the acid component). When the total addition amount of the calcium compound and the magnesium compound with respect to the acid component as the transesterification catalyst exceeds 5.1 mol, a whitening phenomenon is observed at the time of molding due to the influence of precipitated particles due to the catalyst residue, and transparency is deteriorated. Absent. On the other hand, if it is less than 2.6 mol, not only the transesterification reaction becomes insufficient, but also the subsequent polymerization reaction is slow, which is not preferable. Further, the molar ratio of the addition amount of the magnesium compound to the above-mentioned calcium compound is 1.3 to
The range is 6.0. Particularly preferably, it is in the range of 1.4 to 4.0. Even if the molar ratio exceeds 6.0, or conversely less than 1.3, due to the influence of the catalyst residue, a whitening phenomenon is observed when molded and the transparency is impaired. Further, a phosphorus compound is added to deactivate the transesterification reaction catalyst, but the phosphorus compound addition amount (molar ratio) is 1.0 to 1.5 with respect to the total addition amount of the calcium compound and the magnesium compound. Must be in the range. More preferably, it is in the range of 1.1 to 1.3. If this molar ratio is less than 1.0, the transesterification catalyst will not be completely deactivated, the thermal stability will be poor, and the polymer will be colored due to the effect, and the physical properties during molding will deteriorate. vice versa,
If it exceeds 1.5, the thermal stability is poor and it is not preferable.

Further, for the purpose of suppressing the precipitation of precipitated particles and / or making the particles finely dispersed by the transesterification catalyst, it is necessary to add an ammonium compound represented by the following chemical formula I.

[0015]

[Chemical 3]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group and a substituted derivative thereof, and R ₃ and R ₄ form a ring. Further, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different, wherein A represents an anion residue.)

Specific examples of the ammonium compound include quaternary ammonium salts such as hydroxytetramethylammonium, hydroxytetraethylammonium, hydroxytetrabutylammonium and tetraethylammonium chloride; tertiary ammonium salts such as hydroxytrimethylammonium. Etc .; secondary ammonium salts such as hydroxydimethylammonium; primary ammonium salts such as hydroxymethylammonium; ammonium salts such as hydroxyammonium and ammonium chloride. The above ammonium compounds may be used alone or in combination of two or more.

The amount of the ammonium compound compounded is 0.04 to 0.4 mol per 10 ⁶ of the acid component. A preferred range is 0.07 to 0.2 mol. When it is less than 0.04, the effect of deposition printing of catalyst particles and / or fine dispersion is small and the transparency is not so good. On the other hand, when it exceeds 0.4, there is a problem that the effect is not particularly enhanced and, conversely, the polymerization reactivity is deteriorated. Also, as a polymerization reaction catalyst,
A germanium or antimony compound is added, and the addition amount is in the range of 1.0 to 3.0 mol. If it is less than 1.0 mol, the polymerization reactivity will be poor and the productivity will be poor, which is substantially undesirable. On the other hand, if the amount exceeds 3.0 mols, the thermal stability will be poor and the physical properties during molding and / or the hue will deteriorate.

The calcium compound and magnesium compound used in the present invention are not particularly limited, and oxides, chlorides, carbonates, carboxylates and the like can be used. However, acetate salts, that is, calcium acetate and magnesium acetate, are particularly preferable.

Examples of phosphorus compounds include trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate and the like. Preferred is trimethyl phosphate.

Further, the germanium compound includes germanium dioxide, and the antimony compound includes antimony acetate and antimony trioxide, which are preferable examples.

In the present invention, the timing of adding the above-mentioned catalyst is not particularly limited. The preferable addition timing of the calcium compound and the magnesium compound is before the intrinsic viscosity of the reaction system reaches 0.2. In the transesterification method, both compounds are added before the transesterification reaction is started, and the transesterification reaction catalyst is also used. It can be used and is suitable.
In addition, both compounds may be added simultaneously or separately.

On the other hand, the ammonium compound and the phosphorus compound can be added after the transesterification reaction is substantially completed and before the intrinsic viscosity reaches 0.2. The order of addition is not particularly limited, but it is preferable to add the ammonium compound before adding the phosphorus compound.

The germanium compound or antimony compound is added 10 minutes or more after the addition of the phosphorus compound and before the intrinsic viscosity reaches 0.3. The atmosphere of the reaction system at the time of addition may be atmospheric pressure before starting the polycondensation reaction or may be under reduced pressure after starting the polycondensation reaction.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In addition, "part" in an Example means a weight part.
Further, the measurement of each characteristic value in the examples is performed by the following methods.

Intrinsic viscosity [η]: Calculated from solution viscosity measured at 35 ° C. using a phenol / tetrachloroethane (component ratio: 3/2) solvent.

Colb: Hue at 160 ° C.
After being heat-treated in a dryer for 90 minutes to crystallize, it is measured with a color machine CM-7500 type color machine.

Thermal stability: Polymer at 160 ° C. × 6 hr
After drying in a dryer, flow tester (Shimadzu CFT
-500 type) is used and evaluated by the retention rate (%) of [η] when melt-held at 320 ° C. for 30 minutes.

Solution haze: A polymer having a phenol / tetrachloroethane (component ratio: 3/2) solvent was used to prepare a solution having a concentration of 10 wt%. The solution was put into a cell having a thickness of 1 cm, and a haze meter (Nippon Denshoku Industries Co., Ltd.) was used. Model 1001
Haze is measured using DP).

Molded article haze: polymer at 160 ° C. for 7 hours
After drying for an hour, use an injection molding machine Dynamelter M-100DM manufactured by Meiki Seisakusho, and use a cylinder temperature of 300 ° C.
A 50 g preform was molded and blow-stretched to obtain a bottle having an internal volume of 1.5 liters and a body wall thickness of 0.2 mm. This straight body part is cut off and the haze is measured using a haze meter (Nippon Denshoku Industries model 1001DP).

Example 1 100 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol 6
4 parts and 0.014 parts of calcium acetate monohydrate (0.8
Mol) and 0.045 parts of magnesium acetate tetrahydrate (2.
(1 mol) as a transesterification catalyst and subjected to a transesterification reaction according to a conventional method, and then 0.012 parts (0.08 mol) of a 10% aqueous solution of hydroxytetraethylammonium (hereinafter abbreviated as EA agent) was added, and After 5 minutes, 0.045 parts (3.2 mol) of trimethyl phosphate was added to substantially terminate the transesterification reaction. Next, after adding 0.017 parts (1.6 moles) of germanium dioxide, a polycondensation reaction was carried out in a usual manner under high temperature and high vacuum, and then a strand-type chip was taken out in a large amount of running water by a usual method. Obtained. The obtained polymer had an [η] of 0.60 as a target, and the polymerization reaction at that time was 120 minutes.

Examples 2 to 6 and Comparative Examples 1 to 9 Table 1 shows the amounts and ratios of calcium acetate monohydrate, magnesium acetate tetrahydrate, trimethyl phosphate EA agent and germanium dioxide or antimony acid oxide. The procedure was basically the same as in Example 1 except that the above changes were made.

Table 1 also shows the quality of the obtained polymers and the evaluation results.

[0034]

[Table 1]

[0035]

The polyethylene naphthalate of the present invention is
It has good thermal stability, low hue and haze (that is, excellent transparency), and has high commercial value when used as a packaging material for bottles, sheets and the like.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08K 5/49 KKC C08L 67/02 KJV

Claims (2)

[Claims] 1. A polyester comprising naphthalenedicarboxylic acid as a main acid component and ethylene glycol as a main glycol component, wherein a magnesium compound, a calcium compound, a phosphorus compound, a germanium compound and / or an antimony compound is used as a catalyst (1) below. To (4) or (1) to (3) and (5), the ammonium compound represented by the following chemical formula I is added in an amount of 0.04 to 0.4 mol per 10 ⁶ g of the acid component. A polyethylene naphthalene dicarboxy chelate composition which is blended. ## EQU1 ## 2.6 mol ≦ (Mg + Ca) ≦ 4.1 mol (1) 1.3 ≦ (Mg / Ca) ≦ 6.0 (2) 1.0 ≦ P / (Mg + Ca) ≦ 1.5 ( 3) 1.0 mol ≤ Ge ≤ 3.0 mol (4) 1.0 mol ≤ Sb ≤ 3.0 mol (5) (However, each metal element in the above formula is the number of mols per 10 ⁶ g of the acid component. Is shown below.) (However, R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a substituted derivative thereof, and R ₃ and R ₄ may form a ring,
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. A represents an anion residue. ) 2. The polyethylene naphthalene dicarboxylate composition according to claim 1, which has a haze of 1.0% or less when molded into a molded product having a thickness of 0.3 mm.