JPS59115327A - Thermoplastic polyester of excellent adhesiveness - Google Patents

Abstract

PURPOSE:The titled polymer excellent in adhesion to a gas-barrier resin, a variety of polymers, and metals, comprising a polyester unit to which both an Al atom and a monocarboxylic acid are attached. CONSTITUTION:A thermoplastic polyester comprising a structural unit (A) of formula I , wherein R1 is a bivalent group derived by removing the carboxyl groups from terephthalic, isophthalic, orthophthalic, or a 4-10C straight-chain aliphatic dicarboxylic acid; D is a bivalent group derived by removing the hydroxyl group from a 2-6C aliphatic diol or a 6-8C alicyclic diol; m and n are each 0 or 1, and m+n=1, a unit (B) of formula II, and a unit (C) of formula III(wherein R2 is a monovalent group derived by removing the carboxyl group from a 6-30C aliphatic or alicyclic monocarboxylic or a 7-20C aromatic monocarboxylic acid), wherein the molar ratio, A/B, is 1,000:1-100:5; the molar ratio, B/C, is 4:1-1:10, and the limiting viscosity is at least 0.5dl/g. This Al- containing polyester shows excellent adhesion not only to a gas barrier resin but also to a carboxylic acid (anhydride)modified polyolefin or a metal.

Description

[Detailed description of the invention] The present invention relates to polyester with excellent adhesive properties.

More specifically, the present invention relates to a novel polyester in which an Ae element and a monocarboxylic acid are bonded.

Polyethylene terephthalate (hereinafter abbreviated as PET)
Polyester, represented by , has excellent mechanical properties,
Due to its transparency, heat resistance, electrical properties, etc., demand is increasing not only for fibers and films, but also for food containers and food packaging films.

By the way, when polyester is used as a food container or food packaging film, it itself has a certain degree of gas barrier property and is preferable for food preservation, but depending on the food to be filled or enclosed, There is a demand for improved gas barrier properties. In order to improve gas barrier properties, attempts have been made to produce containers and films with multilayer structures in which gas barrier resins such as ethylene-vinyl alcohol copolymers and polyvinylidene chloride are laminated onto polyester. However, the adhesion between the polyester and the above-mentioned gas barrier resin was extremely poor, and delamination easily occurred, making it unsuitable for practical use.

Therefore, the current situation is that there is a strong demand for improvement in adhesive properties in producing such multilayer molded products.

The present inventors investigated various modifications of polyester for the purpose of improving the adhesion between gas barrier resin and polyester. As a result, the inventors discovered that an aluminum-containing polyester obtained by adding a special aluminum organometallic compound during the polymerization of polyester. The inventors have discovered that this object can be achieved, and have arrived at the present invention. In addition, the polyester of the present invention not only has excellent adhesion to gas barrier resins, but also has high adhesion to polyolefins modified with carboxylic acid or its anhydride and ethylene-vinyl acetate copolymers. It was also discovered that it has excellent adhesion to metals.

That is, the present invention provides a structural unit (in the formula, R1 represents a divalent group obtained by removing the carboxyl group of terephthalic acid, isophthalic acid, orthophthalic acid, or a straight aliphatic dicarboxylic acid having 4 to 10 carbon atoms, and D represents a carbon Represents a divalent group obtained by removing the hydroxyl group from an aliphatic diol having 2 to 6 carbon atoms or an alicyclic diol having 6 to 8 carbon atoms.
, n is 0 or 1, and is a number that satisfies m + n = 1. ) / (Company) -Alx ([[) -0-C-R2 1 (wherein R2 is an aliphatic or alicyclic monocarboxylic acid having 6 to 60 carbon atoms or an aromatic monocarboxylic acid having 7 to 20 carbon atoms) represents a monovalent group from which the carboxyl group has been removed), and the molar ratio of (1):(2) is 1000:1.
~100:5, and the molar ratio of ■:aI[) is ~4:1
It is a thermoplastic polyester having a ratio of 1:10 and an intrinsic viscosity of 0.5 d6/7 or more.

Formula (I) which is the main structural unit of the polyester of the present invention
The unit represented by is a dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, and straight aliphatic dicarboxylic acids having 4 to 10 carbon atoms such as succinic acid, adipic acid, azelaic acid, and sebacic acid. and aliphatic diols having 2 to 2 carbon atoms such as ethylene glycol, trimethylene glycol, 1.4-7 tanediol, pentamethylene glycol, 1.6-hexanediol, diethylene glycol, triethylene glycol, cyclohexanediol, cyclohexane dimeta It is an ester unit obtained by condensation with a diol selected from the group consisting of alicyclic diols having 6 to 8 carbon atoms such as tools. The dicarboxylic acid and diol components may each be composed of a single component, or may be composed of two or more types of components.

The unit (a) constituting the polyester of the present invention is an aluminum atom. Aluminum is a trivalent metal element and has three bonds, at least one of which is (
It is combined with I). In other words, (I) and (2) are combined in this case. And the molar ratio of (I):QL) is 1
It is necessary that the ratio be in the range of 000:1 to 100:5. If (6) is less than this range, the effect of improving adhesion will hardly be exhibited, and if it is more than this range, the polymer may gel during polymerization, or a large amount of additives may be added to prevent gelation. This is not preferable because the chain-terminating effect of carboxylic acid may lower the achieved molecular weight.

The unit (T) constituting the polyester of the present invention has 6 carbon atoms.
It is a monovalent group derived from a monocarboxylic acid selected from the group consisting of aliphatic or alicyclic monocarboxylic acids having 60 to 60 carbon atoms and aromatic monocarboxylic acids having 7 to 20 carbon atoms. Examples of such monocarboxylic acid binders include the following. Aliphatic monocarboxylic acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nondecylic acid, and arahin. It includes not only linear saturated acids such as acids, but also unsaturated acids such as oleic acid, linoleic acid, lylunic acid, and arachidonic acid, and those having substituents such as 12-hydroxystearic acid and 2-ethylhexanoic acid. Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid,
- Decalin carboxylic acid can be mentioned. Further, as the aromatic monocarboxylic acid, benzoic acid can be used. Among these, direct saturated aliphatic monocarboxylic acids,
Benzoic acid and P-oxybenzoic acid are preferred. (n[) is a monovalent group derived from these monocarboxylic acids.
is bound to (I) through an ester bond or to (6) through a carboxylate bond.

In order to improve adhesiveness, the polyester of the present invention needs to contain a predetermined amount of (I) as described above, but since (2) acts as a branching agent, (
If it consists only of 6), the fluidity of the polyester will be significantly impaired, or it will gel during polymerization, making it impossible to polymerize, making it impossible to obtain a practical polymer.

In order to prevent such a phenomenon and to make the polyester have favorable fluidity and mechanical properties, the molar ratio of (6) decoy is in the range of 4:1 to 1:10 in the polyester of the present invention. It is necessary. If (2) is less than this range, the fluidity of the polyester cannot be maintained well, and if it is more than this range, it becomes difficult to polymerize polyester with a high degree of polymerization.

The polyester of the present invention has an intrinsic viscosity of 0.5 dφ or more, preferably 0.6 del, as measured at 30° C. in a mixed solvent of phenol/tetrachloroethane (1:1 weight ratio).
It is more than t. If the intrinsic viscosity is less than 0.5 d□, a polyester having sufficient mechanical strength cannot be obtained. There is no particular limit on the upper limit, but 2. Od//
? Polymerization becomes difficult if the above substances are used.

The polyester of the present invention has the structural unit (1) as described above.
, (9) and @), but if it is a small amount, a part (preferably 10 mol% or less) of the dicarboxylic acid component and/or diol component of the structural unit (I) may be added to other dicarboxylic acids, diols or It can be replaced with polyhydric carboxylic acid or polyhydric alcohol. Such dicarboxylic acids for modification include oxalic acid, hexahydroterephthalic acid, 5-sodium sulfoisophthalic acid, chlorterephthalic acid, bremthyrephthalic acid, dichloroterephthalic acid,
Examples include dibromoterephthalic acid, bromoisophthalic acid, naphthalene dicarboxylic acid (each isomer), chlornaphthalene dicarboxylic acid, boomnaphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, and diphenyl-4,4'-dicarboxylic acid. .

Diols include polyethylene glycol, polytetramethylene glycol, neopentyl glycol,
1.4-bis(β-hydroxyethoxy)benzene, 2
．． 2'bis(P-β-hydroxyethoxyphenyl)propane, bis(P-β-hydroxyethoxyphenyl)
Sulfone etc. can be applied.

Furthermore, examples of polyhydric carboxylic acids include trimellitic acid, trimesic acid, and pyromellitic acid, and examples of polyhydric alcohols include glycerin, trimethylolpropane, pentaerythritol, hexanetriol-1,2,6,
Trimethylolethane, trimethylolhexane, trimethylolbenzene-1,3,5, tripropyrrolbenzene-1,3,5, tributyolbenzene-1,3
, 5 etc. are available. Furthermore, dimethylolpropionic acid and the like can also be used.

The polyester of the present invention is produced by combining dicarboxylic acids and diols, which are the raw materials for the structural unit (I), or their ester-forming derivatives, in the presence of the organoaluminum compounds listed below, or with the aluminum compounds, which are the raw materials for the structural unit (g). It can be produced by polymerization in the presence of a carboxylic acid or its ester.

(Here, R represents a monovalent group excluding the hydroxyl group of an aliphatic, alicyclic or aromatic alcohol. Melon represents the above-mentioned R2 or an aliphatic monocarboxylic acid having 1 to 5 carbon atoms excluding the carboxyl group. represents a monovalent group other than the carboxyl group of dicarboxylic acid monoesters or dicarboxylic acid monoalkali metal salts.R represents a methyl group, a phenyl group, a methyl group, a phenyl group, or a monovalent group excluding the carboxyl group. Represents a monovalent group excluding the proton of the hydroxyl group of an aliphatic alcohol.Furthermore, i and j indicate the average value of each group bonded to the M atom, and i+j+ =
3, and 0≦i≦2.0≦j≦6.0≦ and ≦6.

) The above aluminum compound can be used after the esterification reaction between the dicarboxylic acid and the diol has progressed and the carboxyl group content in the reaction system has become a trace amount, or after the transesterification reaction between the dicarboxylic acid ester and the diol is almost completed. It is preferable to add it to the reaction system at a temperature of 230°C or lower. In particular, the above-mentioned aluminum compound may deactivate a commonly used transesterification catalyst, so it is preferably added after the transesterification reaction is completed. It is preferable to add it by dissolving it in a diol. The above aluminum compound can be produced by various methods well known to those skilled in the art, examples of which are shown in Examples. When a monocarboxylic acid or its ester is used together with the aluminum compound, it is appropriate to add it to the reaction system at the time of charging the raw materials or before the esterification or transesterification reaction. When a transesterification reaction is employed, it may be carried out immediately after the transesterification reaction.

For the esterification reaction between a dicarboxylic acid and a diol or the transesterification reaction between a dicarboxylic acid ester and a diol, and the subsequent polymerization reaction, conditions normally employed for polymerization of polyester can be employed.

That is, an esterification reaction between a dicarboxylic acid and a diol or a transesterification reaction between a dialkyl ester of a dicarboxylic acid and a diol is carried out at a temperature of 180 to 2!10'C in the presence or absence of a catalyst, and then antimony Polymerization is carried out using a compound such as , titanium or germanium as a catalyst at a temperature of 260 to 300C under a pressure of 1 mmJ and 1 g or less.

When the above-mentioned sita aluminum compound is added to the reaction system, it reacts with the dicarboxylic acid or diol component and bonds with the alcohol 130 corresponding to these groups.
ft or β-diketone or ketoMn<cocnzc
ol is desorbed and transferred into the distillate. In addition, the R4C0〇- group is niha when ru matches the ru of the formula
It remains bonded to g in the polyester, and the remaining residue undergoes an exchange reaction with the dicarboxylic acid, is eliminated, and is bonded to the end of the polyester molecule. When the group is a monocarboxylic acid having 5 or less carbon atoms from which the carboxyl group has been removed, most of the monocarboxylic acid or its alkyl ester migrates into the distillate. In this way, M is bonded to the center of the polyester molecule or to the end of the molecule chain. M
Since most of the added amount is bonded to the polyester, the amount of the above-mentioned aluminum compound added is suitably in the range of 0.1 to 5 moles per 100 moles of dicarboxylic acid. In addition, the monocarboxylic acid serving as the raw material for the structural unit (g) is such that the total amount of the 12000-group in the aluminum compound and the monocarboxylic acid or its ester is 0 based on the number of moles of M. It is preferable to add it in an amount of .25 to 10 mol.

It was confirmed from the facts described below that the polyester of the present invention can be obtained by the method described above.

(1) R30- group and R, C0 in aluminum compound
The amount of CH=C-0- groups and the amount of C0Cf (2CO) detected in the distillate almost match.

(2) As a result of trace analysis using a 400 MHz ultra-high resolution NMR spectrum, R2COO- groups are present in the polyester, and the amount thereof is the total amount of 1.000- groups and monocarboxylic acid or its ester in the added aluminum compound. matches.

(3) Fluorescence X-ray analysis shows that M atoms are present in the polyester in an amount almost equal to the amount added.

(4) As a result of FT-IR spectrum analysis of polyester, new absorptions are observed at 1600Ci1 and 590i' that are not observed in ordinary polyesters. The former absorption is for example Analytical C! Hemistry, Vol. 24, p. 655 (1952), the absorption of aluminum carboxylic acid salts;
d and Re1ated Vibrations”
.

This is the absorption of metal alkoxides as shown by Edward Armold (I:Indon).

From the above results, the aluminum compound described above undergoes chemical changes during the polymerization reaction process, and forms an alkoxide bond with a diol component, a carboxylate bond with a dicarboxylic acid component, and a monocarboxylic acid component represented by formula (2). It is thought that it was converted into an aluminum compound having a carboxylate bond and incorporated into the center or end of the polyester molecule.

As mentioned above, the polyester of the present invention is made of a gas barrier resin such as an ethylene-vinyl alcohol copolymer or polyvinylidene chloride, a polyolefin modified with a carboxylic acid or its anhydride, an ethylene-vinyl acetate copolymer, and a metal. It has excellent adhesive properties, and of course it also has excellent adhesive properties with polyester, so it is extremely useful as a constituent material for various laminates or as an adhesive.1. Examples of laminates: If indicated, the polyester of the present invention/cass barrier resin, the polyester of the present invention/carboxylic acid or its anhydride-modified polyolefin, or the ethylene-vinyl acetate copolymer/gas barrier
polyester, conventional polyester/polyester of the present invention/
Combinations of gas barrier resins, polyester/aluminum foil, tach sheet/polyolefin, etc. of the present invention can be mentioned. These laminates can take various shapes such as films, sheets, hollow bodies, or by molding them into compacts, trays, and potnos.
It has excellent gas barrier properties, making it extremely useful for food packaging and storage.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to such embodiments.

In addition, the melting point of the crystalline polyester in the examples is
(Differential scanning calorimeter). That is, 5 of the quenched film
The peak temperature of the crystal melting peak when mf was heated from room temperature at 20 c/min was defined as the melting point.

In addition, the glass transition temperature of non-grade polyester is the same (D
Obtained from SC. The temperature increase rate is 20°C/min.

Below 17. ) Miroku Example 1 [Preparation of aluminum compound] 600 m1 equipped with nitrogen gas introduction pipe, stirrer, and cooling pipe
100 ml of hexylene glycol was placed in a round bottom flask while nitrogen gas was passed through it, and 0.10 mol of awominium inoproboxide powder was added thereto at room temperature, followed by stirring. Next, 0.05 mol of caprylic acid and 0.15 mol of P-oxybenzoic acid were added, and the mixture was heated to 100°C by placing it in an oil bath while stirring. Bring to this temperature and continue the reaction for 15 minutes. after that,
Add 0.10 mol of acetylacetone and heat to 1 at 100°C.
The reaction was continued for 5 minutes to prepare an aluminum compound.

As a result of measuring the infrared absorption spectrum of this reaction solution, 1
A slight absorption of unreacted carboxylic acid is observed in 700cm, but the absorption of carboxylic acid aluminum salt in 1600cm and the absorption of acetylacetone complex salt in 1540i appear strongly, indicating that the alcoholade bond is a carboxylic acid salt and acetylacetone complex. This shows that the bond has changed to a complex salt bond.

〔polymerization〕

A nitrogen gas introduction tube, a stirrer, and a cooling tube were attached to a 300-sized three-ring flask, and 100 g of dimethyl terephthalate, 68 y of ethylene glycol, and 40 mg of zinc acetate were added, and the mixture was heated to 200°C under a stream of nitrogen gas for 6 hours. The mixture is reacted to perform a transesterification reaction. Subsequently, 200℃
Add tributyl phosphate to 25 μl 13 liters antimony 4
0 rng was added, and the above aluminum compound solution was added in an amount of 0.52 mol per 100 mol of dimethyl terephthalate in terms of aluminum atoms. After dissolving the aluminum compound solution in the contents of the flask, the temperature of the oil bath was lowered. The temperature was raised to 2600C, and the pressure was gradually reduced to 280C.
The polymerization was carried out for 90 minutes under a reduced pressure of 0.1 rranHf to obtain a pale green polymer. The intrinsic viscosity ([η]) of the obtained polyester was 0.71 dl/fl. Moreover, the melting point was 252°C.

The NMR spectrum of the obtained polyester is shown in FIG. Absorption of the methylene proton of caprylic acid is observed at 0.90 PFn, and the phenyl proton of P-oxybenzoic acid is observed at 6.65 PFl. Although the amount of caprylic acid present in the polymer determined from this spectrum was slightly smaller than the value calculated from the amount charged, the amount of P-oxybenzoic acid present was consistent with the amount charged.

FIG. 2 shows the FT-IR spectrum of the polyester obtained. Weak absorption is observed at j6DIJ> and 590crn, but this absorption is not observed at all in the spectrum of polyethylene terephthalate shown in FIG. These absorptions, as explained in the text,
The absorption at m is an absorption based on carboxylic acid aluminum salt, and the absorption at 59 [] cm' is an absorption based on aluminum alcoholade.

Example 2 A 500 ml three-loaf flask was equipped with a nitrogen gas introduction tube, a stirrer,
Attach the cooling pipe and add 100 g of dimethyl terephthalate, 68 g of ethylene glycol, and 8.77 g of methyl benzene.
g, 40 rng of zinc acetate, and 2
The transesterification reaction is carried out by heating to 00°C and reacting for 3 hours. Subsequently, 25 μl of tributyl phosphate and 40 mg of antimony trioxide were added, and aluminum acetylacetonate was added to 0.50 mol per 100 mol of dimethyl terephthalate to dissolve it, and the temperature of the oil bath was increased to 260'. Raise the temperature to Q and gradually reduce the pressure to 280
The polymerization was carried out for 90 minutes under a reduced pressure of 0.1 mIn to obtain a pale yellow polymer. of the obtained polyester [
ηJ was 7°dJ/fl. Moreover, its melting point was 253°C.

The FT-IR spectrum of the obtained polyester is shown in Figure @4. Iin of carvone [1 fluminiram] is observed at 16ooCm1, and absorption of aluminum alcoholade is observed at 5907.

In addition, as a result of analyzing the distillate distilled from the transesterification reaction of this polyester to the polymerization path Y using NM spectroscopy, absorption derived from acetylacetone was observed.
As a result of the quantitative analysis, an amount almost corresponding to the amount of acetylacetone in the added aluminum acetylacetonate was detected. The above shows that aluminum acetylacetonate released acetylacetone during the polymerization process, and was converted into an alj = +7 L carboxylate and an alcoholate.

Example 3 [Preparation of aluminum compound] While passing nitrogen gas through the apparatus described in Example 1.

To 100 ml of hexylene glycol, add 0.10 mol of aluminum isopropoxide powder and stir. Next, 0.05 mol of caprylic acid and 0.15 mol of P-oxybenzoic acid were added, and without stirring, the mixture was placed in an oil bath and heated to 100°C.
The temperature rises to Keep at this temperature and allow to react for 15 minutes.

Next, 0.10 mol of ethyl acetoacetate was added and the reaction was continued at 100°C for 15 minutes to prepare an aluminum compound. [Polymerization] In the same manner as in Example 1, transesterification of dimethyl terephthalate and 1-toethylene glycol was carried out. 25 μl of tributyl phosphate and 40 mg of antimony trioxide were added, and the above aluminum compound solution was added so that the amount of aluminum added was 0.52 mol per 100 mol of dimethyl terephthalate in terms of aluminum atoms.
Raise the temperature to 0°C and gradually reduce the pressure to 280°C.
The temperature was raised to 0.1 m Hp and the pressure was further reduced.
Polymerization was continued for 90 minutes. The obtained polyester was pale yellow and contained no insoluble matter. Polyester Jl
/'s [η] was 0.76 dJ/V. Moreover, the melting point of this polyester was 251°C.

Example 4 300m/! Attach a nitrogen gas inlet tube, a stirrer, and a cooling tube to a three-hole flask, and add 70 g of dimethyl terephthalate.
Dimethyl isophthalate 509. ethylene glycol 6
8f, add 40 mg of zinc acetate, under nitrogen gas flow, 20
The transesterification reaction was allowed to proceed at 0°C for 3 hours. Add 25 μl of tributyl phosphate and 40 mg of antimony trioxide, and add the aluminum compound solution prepared in Example 1 so that the amount of aluminum added is in terms of aluminum atoms, per 100 moles of the sum of dimethyl terephthalate and dimethyl isophthalate. , 0.52 mol, Example 1
Polymerization was carried out in the same manner. The obtained polymer was a pale yellow-green transparent glassy polymer. Glass transition temperature measurement by DEC showed that 1°C was approximately 65°C. Moreover, [η] of this polyester was 72 dll'9.

Example 5 A 300ml round bottom flask with a nitrogen gas inlet tube and a stirrer.

Install the cooling pipe and add 97 da of dimethyl terephthalate.

Methyl benzoate 8.50p, ethylene glyco-A57.
47; 1,1.4-cyclohexane dimetatool 25.
2 g of zinc acetate and 40 rng of zinc acetate were added thereto, and the mixture was heated to 2006 C under a nitrogen gas stream to proceed with the transesterification reaction for 3 hours. Tributyl phosphate 25 μl, antimony trioxide 40
Hg, aluminum acetylacetonate 1.0ji
1, the temperature was raised to 260°C, the pressure was reduced to 2800C, the pressure was further reduced to about 0.1 rran H9,
Polymerization was allowed to proceed for 90 minutes. The obtained polymer was a pale green glassy polymer, and [η] was 0.68 dl/9. The glass transition temperature determined by DSC measurement was 78°C.

Example 6 Dimethyl terephthalate 1 was added to the same polymerization apparatus as in Example 1.
00y, 100 g of 1,4-butanediol and an n-hexane solution of tetrabutyl titanate were added so that the amount of tetrabutyl titanate was 40 μ, and transesterification was carried out at 180°C for 1 hour, 200°C for 1 hour, and 220°C for 1 hour. The reaction was carried out. Next, the aluminum compound solution used in Example 1 was added so that the amount of aluminum added was 0.2 mol per 100 mol of dimethyl terephthalate.
The temperature was raised to 0°C, and the pressure was gradually reduced to 270°C, and the pressure was further reduced to about 0.1 mm119, and polymerization proceeded for 90 minutes.

The obtained polyester is a pale yellow crystalline polyester.
The melting point was 221°C. In addition, [η] was 0.76 l.

Example 7 Into the reactor described in Example 1, bis-β-hydroxyethyl terephtasy) 64. Of, succinic anhydride 2
5. Q. Add 15.5 g of ethylene glycol and 14.9 p of diethylene glycol, raise the temperature to 200°C under a nitrogen gas stream, and react for 1 hour. Raise the temperature to 215°C, and allow to react for 1 hour. 25 lli of tributyl phosphate and 36 m2 of antimony trioxide were added, and the aluminum compound solution used in Example 1 was added so that the aluminum atoms were 0.50 mol per 100 mol of the dicarboxylic acid component.
The temperature was raised to 60℃, the pressure was reduced to 275℃, and 0.1m1
Polymerization was carried out for 90 minutes under reduced pressure of about 111 IIg. The obtained polyester was a hard rubber-like transparent light yellow polymer at room temperature, and [η]=0.64 dVi.

Example 8 In a polymerization apparatus similar to that of Example 1, 64'/bis-β-hydroxyethyl terephtasy, 56.5 g of adipic acid,
Add 15.5 p of ethylene glycol and 14.9 y of diethylene glycol, and proceed with the esterification reaction at 200° C. for 5 hours under a nitrogen gas stream. tributyl phosphate 25a,
Antimony trioxide 66 ~ was added, and the aluminum compound solution used in Example 1 was added so that the number of aluminum atoms was 0.5 moles per 100 moles of the dicarboxylic acid component, and the temperature was raised to 260 ° C. and the pressure was reduced. and 280℃,
Polymerization was carried out for 1 hour under a vacuum of about 0.1 mm119. The obtained polyester was orange in color and hard rubber-like. [η]=o, 59d6/r.

Example 9 Dimethyl terephthalate 4 was added to the polymerization apparatus used in Example 1.
B, 59. Dimethyl sebacate 57.69. Methyl benzoate B, 779. Ethylene glycol 49.1p.

32.6y of diethylene glycol and 40m9 of zinc acetate are added, heated to 200°C under a nitrogen gas stream, and transesterified for 3 hours. Next, tributyl phosphate 25J, antimony trioxide 40m9. 1.0.9 of aluminum acetylacetonate) was added, and the temperature was raised to 260°C. The pressure was gradually reduced to 275° C., and polymerization proceeded for 120 minutes while reducing the pressure to about 0.1 mmHy.

The obtained polyester is translucent, soft rubber-like,
It was pale green in color. [η) -0.56 dll/f.

Comparative example 1 [Preparation of aluminum compound] 200mI! A nitrogen gas inlet tube and a stirrer to the round bottom flask.

Attach a cooling pipe, add 50 rnl of hexylene glycol, add 10 g of powdered aluminum isopropoxide, and raise the temperature to 120°C to distill off the impropatol and dissolve the aluminum isopropoxide.

〔polymerization〕

Using the same polymerization apparatus as in Example 1, 100 g of dimethyl terephthalate and 6 Bf/ethylene glycol were added.

Add 40 m7 of zinc acetate and carry out transesterification reaction at 200°C for 6 hours under a nitrogen gas stream to obtain 2 tributyl phosphate.
5 J and 40 μm of antimony trioxide were added, and the above-mentioned aluminum compound solution was added in an amount of 0.52 mol of aluminum per 100 mol of dimethyl terephthalate.
Polymerization proceeded for 90 minutes under reduced pressure of about 0.1 mmH9.

The polymer began to wrap around the stirrer after 60 minutes of polymerization time, and stirring was difficult in the latter stage of polymerization. The obtained polyester was pale yellow and contained a large amount of particulate insoluble gel.

Comparative Example 2 [Preparation of aluminum compound] Using the reaction apparatus used for preparing the aluminum compound in Comparative Example 1, 0.01 mol of P-oxybenzoic acid was dissolved in 50 ml of hexylene glycol, and 0.05 mol of aluminum isopropoxide was dissolved. mol was added and heated to 100°C to react. The resulting clear solution was used for the next polymerization.

〔polymerization〕

Instead of the aluminum compound solution of Comparative Example 1, the aluminum compound solution obtained above was added so that aluminum was 0.52 mol per 100 mol of dimethyl terephthalate, and polymerization was carried out in the same manner as in Comparative Example 1. advanced.

After 60 minutes of polymerization, conspicuous wrapping began to occur, making stirring difficult. The obtained polyester was pale yellow and contained a large amount of large insoluble gel.

Comparative Example 3 [Preparation of aluminum compound] Using the same reaction apparatus as in Comparative Example 1, take 5゜i of xylene, add 0.05 mol of aluminum isopropoxide,
Heat to 100°C to dissolve. Next, 0.05 mol of acetylacetone was added and reacted for 15 minutes to obtain a light brown transparent solution.

〔polymerization〕

In place of the aluminum compound of Comparative Example 1, the aluminum compound solution obtained above was added to dimethyl terephthalate 100%.
Aluminum was added in an amount of 0.2 moles per mole, and polymerization was proceeded in the same manner as in Comparative Example 1. Polymerization time is 9
It is 0 minutes. Again, a wrapping phenomenon was observed in the late stage of polymerization.

The obtained polyester was pale yellow and contained insoluble gel-like particles.

Comparative Example 4 [Preparation of aluminum compound] Using the same reaction apparatus as Comparative Example 1, 50 k of xylene was taken,
Add 0.05 mol of aluminum isopropoxide and dissolve at room temperature. Next, 0.05 mol of acetylacetone was added, the temperature was raised to 50°C, and the mixture was stirred for 30 minutes. Next, 0.1 acetic acid
After adding 0 mol and reacting at 50℃ for 60 minutes, 120℃
Improbanol was removed by distillation.

〔polymerization〕

Instead of the aluminum compound of Comparative Example 1, the aluminum compound bath solution obtained here was used as dimethyl terephthalate 10
Aluminum was added in an amount of 0.52 mol per 0 mol, and polymerization was proceeded in the same manner as in Comparative Example 1. At 60 minutes of polymerization time, a remarkable phenomenon of polymer wrapping around the stirring rod occurred.
Polymerization was stopped. The resulting polyester was pale yellow and contained insoluble gel particles.

Comparative Example 5 Using the aluminum compound used in Example 1, polymerization was attempted to proceed in the same manner as in Example 1 by adding the aluminum compound in an amount of 10 moles per 100 moles of dimethyl terephthalate. However, when the temperature reached 260°C and the pressure was gradually reduced, it stopped flowing and turned into a gel.

Example 10 Polyesters obtained in Examples 1 to 5 and ordinary PET ((η)) containing no aluminum compound as a comparative example
=0.70) was formed into a rapidly cooled film with a thickness of about 200μ using a hot press. In addition, sufficiently dried ethylene
A 100 μm film was prepared from a vinyl alcohol copolymer (EVAL ■E manufactured by Kuraray Co., Ltd., hereinafter abbreviated as EVAL) chip. Layer both films and heat at 180℃ for 10 minutes.
Crimp at kg/cyj, then 280 kg/cyj under almost no load.
After maintaining the two polymers at ℃ for 2 minutes to melt and bond them, they were quickly cooled by being lightly sandwiched with a cooling press to produce a multilayer sheet. A rectangular specimen with a constant width of 15 mm was cut out from this sheet, and after being left at room temperature overnight, a peel test was conducted at room temperature using an Instron universal testing machine at a tensile speed of 20 m/min. The results are shown in Table 1.

The polyesters obtained in Examples 1 to 5 have peel strength at the melt-bonded interface with the ethylene-vinyl alcohol copolymer that is 10 to 40 times higher than that of ordinary PET.

Table 1 Interlayer peel strength of polyester/EVAL bonded sheet Example 11 Using the same method for preparing the aluminum compound described in Example 1, various monocarboxylic acids shown in Table 2 were added in place of caprylic acid at 0. Various aluminum compounds were prepared using 0.5 moles of aluminum. Example 1
By the polymerization method described in Example 1o, dimethyl terephthalate was added in an amount of 0.52 mol in terms of aluminum atoms to 100 mol of dimethyl terephthalate, and the resulting polyester was then bonded with EVAL by the method described in Example 1o. It was prepared and its peel strength was measured. The results are shown in Table 2.

Table 2 Interlaminar peel strength of polyester/EVAL bonded sheet Example 12 A composite using the polyester obtained in Example 7.8.9 and a polyester polymerized with the same 7-mer composition without adding an aluminum compound for comparison. A layered film was made. That is, the above-mentioned polyester was formed on a biaxially stretched PET film (thickness 100μ) at 180°C to a thickness of about 100μ, a 100μ film of EVAL was placed on top of this, and the film was heated at 180°C for 2 minutes +! I#M crimp (pressure 5 kg/
ctj) L, quenched to produce a three-layer film. A specimen with a width of 15 mm was cut from this film and subjected to a T@ separation test at room temperature and at a tensile rate of 200.7 minutes. The results are shown in Table 6.

Table 5 T-peel strength of PET/polyester/EVAL multilayer film

[Brief explanation of the drawing]

FIG. 1 shows the NM spectrum of the polyester obtained in Example 1. Further, FIG. 2 shows the FT-11t spectrum of the polyester obtained in Example 1, FIG. 5 shows the polyethylene terephthalate, and FIG. 4 shows the FT-11t spectrum of the polyester obtained in Example 2. Patent applicant: Kuraray Co., Ltd. Agent: Ken Fuyo, patent attorney

Claims (1)

[Scope of Claims] Constituent unit (the number in the formula represents a divalent group excluding the carboxyl group of terephthalic acid, isophthalic acid, orthophthalic acid, or a straight aliphatic dicarboxylic acid having 4 to 100 carbon atoms, and D is the number of carbon atoms) 2
~ B represents a divalent group obtained by removing the hydroxyl group from the aliphatic diol or alicyclic diol having 6 to 8 carbon atoms. Also, m,
n is O or 1, and is a number that satisfies m 10n == 1. ) (2) -A/ / \ (2) -〇-C-12 1 (In the formula, R2 is an aliphatic or alicyclic monocarboxylic acid having 6 to 3 carbon atoms or an aromatic monocarboxylic acid having 7 to 2 carbon atoms) It represents a monovalent group obtained by removing the carboxyl group from an acid.), and the molar ratio of (I) + (2) is 1000:
1 to 100:5, and the no molar ratio Qi):an) is 4
:1 to 1:10 tie, intrinsic viscosity is 0.5 tie/f
Thermoplastic polyester which is above.