JPH0555558B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesive made of polyester to which aluminum atoms and monocarboxylic acid residues are bonded. Due to its excellent mechanical properties, transparency, heat resistance, electrical properties, etc., polyester, represented by polyethylene terephthalate, is in increasing demand not only as fibers and films, but also as films for beverage and food containers and food packaging. ing. By the way, when polyester is used as beverage/food containers or food packaging films, it itself has a certain degree of gas barrier property and is preferable for preserving foods and beverages. Further improvements in gas barrier properties are required for certain foods and beverages. Therefore, attempts have been made to create containers and films with multilayer structures in which polyester is laminated with resins (especially ethylene-vinyl alcohol copolymers) with even better gas barrier properties. For example, JP-A-56-77144 and JP-A-57-128516 disclose hollow containers in which polyester and ethylene-vinyl alcohol copolymer are laminated. However, since the adhesiveness between polyester and ethylene-vinyl alcohol copolymer is poor, and no adhesive is used to bond the two, these hollow containers easily separate between the layers. Furthermore, in JP-A-53-108162, a polyester layer and an ethylene-vinyl alcohol copolymer layer are bonded together using a blend of polyester and ethylene-vinyl alcohol copolymer, which are the materials of both layers. A laminated hollow container has been disclosed, published in Japanese Unexamined Patent Application Publication No. 1983
Japanese Patent No. 117653 discloses a laminated hollow container in which polyester and a normal ethylene-vinyl alcohol copolymer are bonded together using an ethylene-vinyl alcohol copolymer having a high ethylene content.
However, even with these adhesives, the adhesion performance between the layers was low, so these hollow containers were not suitable for practical use. In particular, the problem was that the adhesive strength between the adhesive and the polyester layer was low. Therefore, an adhesive that can firmly bond polyester and ethylene-vinyl alcohol copolymer,
The development of an improved polyester for substrates that can adhere to polyolefin adhesives containing carboxyl groups, which are known to adhere well to ethylene-vinyl alcohol copolymers, has led to the development of polyesters for base materials that can be bonded to polyolefin adhesives containing carboxyl groups, which are known to adhere well to ethylene-vinyl alcohol copolymers. It is strongly required in manufacturing laminated molded products with polymers. The object of the present invention is to resist adhesives made of polyester, which have excellent adhesive properties. The object of the present invention is a polyester having the following structure: the structural units are of the following formulas (), (), () and () () () (-O)―― _o D(-O)―― _o () () (In the formula, R ₁ is 2 which is obtained by removing the carboxyl group from one or more dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid, osophthalic acid, and straight chain aliphatic dicarboxylic acids having 4 to 10 carbon atoms.)
_R2 represents one or more monocarboxylic acids selected from the group consisting of aliphatic or alicyclic monocarboxylic acids having 6 to 30 carbon atoms and aromatic monocarboxylic acids having 7 to 20 carbon atoms. Represents a monovalent group obtained by removing the carboxyl group from an acid, and D has 2 to 2 carbon atoms.
It represents a divalent group obtained by removing the hydroxyl group from one or more diols selected from the group consisting of 10 aliphatic diols and alicyclic diols having 6 to 8 carbon atoms. Moreover, m, n, p ₁ , p ₂ , p ₃ and q are each 0
or 1, and each constituent unit is () and (),
() and (), () and (), () and (),
Combined between () and between () and (),
Such a bond represents that only one oxygen atom is involved. ), and the molar ratio of ():() is substantially 1:
1, and the molar ratio of ():() is 1000:1 ~
100:5, and the molar ratio of ():() is 4:1 to
1:10, intrinsic viscosity
This can be achieved by obtaining a thermoplastic polyester having a 0.5 dl/g or more. The thermoplastic polyester of the present invention mainly comprises:
It consists of a polyester chain in which structural units () and () are alternately bonded. Such a polyester chain is branched by introducing a structural unit () into a part thereof, and the structural unit () is combined with () and () to control the degree of chaining and branching. There is. Furthermore, the thermoplastic polyester of the present invention includes those having a small amount of polyvalent organic compound units in addition to the above-mentioned structural units, but in this case, if necessary, more may be added. () may be included. Hereinafter, the thermoplastic polyester of the present invention will be explained in detail. The main structural units of the polyester of the present invention are () and (). The units represented by formula () include terephthalic acid, isophthalic acid, orthophthalic acid, succinic acid, adivic acid, azelaic acid,
It is a unit derived from one or more dicarboxylic acids selected from the group consisting of straight chain aliphatic dicarboxylic acids having 4 to 10 carbon atoms such as sebacic acid. In addition, ethylene glycol represented by the formula (),
Trimethylene glycol, 1,4-butanediol, pentamethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, tri- Derived from one or more diols selected from the group consisting of aliphatic diols having 2 to 10 carbon atoms such as ethylene glycol and cycloaliphatic diols having 6 to 8 carbon atoms such as dichlorohexane diol and cyclohexanedimethanol. It is a unit of Such main structural units () and () must be present in the polyester of the present invention in a molar ratio of ():() of substantially 1:1, thereby ensuring that both units are present in the polyester of the present invention. combined by a bond

A polyester chain having repeating units of the formula is formed. Such polyester chains are the main part constituting the polyester of the present invention, and are therefore important in imparting the same excellent physical properties (such as mechanical strength) to the polyester of the present invention as conventional polyesters. Therefore, by selecting the dicarboxylic acid unit () and the diol unit (), it is possible to provide the polyester of the present invention with physical properties depending on its purpose and use. As described below, when the polyester of the present invention is used as an adhesive, it is preferable that the glass transition temperature of the polyester of the present invention is 30°C or lower. It can be obtained by increasing the content of units derived from acids and/or units derived from long chain diols having 4 or more carbon atoms in the diol units (). Further, when the polyester of the present invention is used as a base material for a laminate, it is preferable that the glass transition temperature is higher than 30°C and/or if it is crystalline, the melting point is 120°C or higher. In such a polyester, for example, 70 mol% or more of the dicarboxylic acid units () are terephthalic acid units, the remaining 0 to 30 mol% are isophthalic acid units, and 70 mol% or more of the diol units () are ethylene units. A unit consisting of glycol or 1,4-butanediol, in which the remaining 0 to 30 mol% is ethylene glycol (when the main component is not ethylene glycol), 1,4-butanediol (when the main component is not 1,4-butane (if not a diol), 1,
The unit is preferably made of 4-cyclohexanedimethanol or diethylene glycol, but is not limited thereto. Aluminum in the units () constituting the polyester of the present invention is a trivalent metal element, and at least one of the bonds of the aluminum atom is connected to a dicarboxylic acid unit () or a diol unit () via an oxygen atom. Combine each

A carboxylate bond of the formula [Formula] and an alkoxide bond of -O-D-O-Al are formed. In addition, as described later, some aluminum atoms are Al-O-Al or

Dicarboxylic acid unit () or diol unit () via alumina bond such as [Formula]
join to

【formula】

【formula】

[expression] or

[Formula], etc.). In addition, the aluminum atom also has a bond with a monocarboxylic acid unit () as described later. Also, regarding the molar ratio of () and (), the molar ratio of ():() is 1000:
It is necessary that the ratio be in the range of 1 to 100:5.
When () is less than this range, there is almost no effect of improving adhesion, and conversely, when it is more than this range, the polymer may gel during polymerization, or a large amount is added to prevent gelation. This is not preferred because the chain-terminating effect of monocarboxylic acids lowers the molecular weight achieved. The units () constituting the polyester of the present invention are one or more selected from the group consisting of aliphatic or alicyclic monocarboxylic acids having 6 to 30 carbon atoms and aromatic monocarboxylic acids having 7 to 20 carbon atoms. is a monovalent group derived from a monocarboxylic acid. Examples of such monocarboxylic acids 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. In addition to linear saturated acids such as acid, melisic acid, unsaturated acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, etc.
Also included are those having substituents such as 12-hydroxystearic acid and 2-ethylhexanoic acid. Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid, cyclopentanecarboxylic acid, and 2-decalincarboxylic acid. Also,
Examples of aliphatic monocarboxylic acids include benzoic acid, phenylacetic acid, diphenylacetic acid, β-naphthoic acid, anthracene-2-carboxylic acid, p-oxybenzoic acid, p-ethylbenzoic acid, and 1-chloroanthraquinone-2-carboxylic acid. etc. can be mentioned. Among these, linear saturated aliphatic monocarboxylic acid, benzoic acid and p-oxybenzoic acid are preferred, and benzoic acid is particularly preferred. (), which is a monovalent group derived from these monocarboxylic acids, is bonded to () through an ester bond.

[Formula]) or carboxylate () and combine (

[formula]). Further, it is necessary that the molar ratio of ():() for () is in the range of 4:1 to 1:10.
If () is less than this range, the branching effect of () is significant, and the melt fluidity of the polyester is significantly impaired, but the polyester gels during polymerization, making polymerization impossible and making it impossible to obtain a practical polymer. Conversely, when the amount of () is greater than the above range, the chain termination effect of () is significant, making it difficult to obtain a polyester with a high degree of polymerization. The polyester of the present invention has phenol/1,
1,2,2 tetrachloroethane mixed solvent (1:1
Intrinsic viscosity (weight ratio) measured at 30℃
viscosity) of 0.5 dl/g or more, preferably 0.6 dl/g
g or more. If the intrinsic viscosity is less than 0.5 dl/g, a polyester with sufficient mechanical strength cannot be obtained. Furthermore, when the polyester of the present invention is laminated by coextrusion with a thermoplastic resin such as an ethylene-vinyl alcohol copolymer, the intrinsic viscosity is 0.7 dl/g or more in terms of melt flowability.
Furthermore, it is preferably 0.8 dl/g or more.
There is no particular limit on the upper limit, but 2.0dl/
If it is more than 100 g, it becomes difficult to polymerize. As mentioned above, the polyester of the present invention consists of the structural units (), (), () and (), but if the amount is small, a part of the dicarboxylic acid unit () and/or diol unit () (preferably 10 mol% or less) can be replaced with other dicarboxylic acid units or diol units. Such dicarboxylic acid units include oxalic acid, hexahydroterephthalic acid, 5-sodium sulfoisophthalic acid, chlorterephthalic acid, bromiterephthalic acid, dichloroterephthalic acid, dibromoterephthalic acid, bromiisophthalic acid, naphthalene dicarboxylic acid. (each isomer), chlornaphthalene dicarboxylic acid,
Examples include units derived from dicarboxylic acids selected from bromonaphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and the like. Diol units include polyethylene glycol, polytetramethylene glycol, neopentyl glycol, 1,4-bis(β-hydroxyethoxy)benzene, 2,2-bis(p-β-hydroxyethoxyphenyl)propane, bis( Examples include units derived from diols selected from p-β-hydroxyethoxyphenyl) sulfone and the like. As mentioned above, when the polyester of the present invention is laminated by coextrusion with a thermoplastic resin such as an ethylene-vinyl alcohol copolymer, it is preferable that the intrinsic viscosity is 0.7 dl/g or more. It can be obtained by polymerizing polyester by allowing a sufficient polymerization time or by adding a polyvalent organic compound containing a total of 3 to 4 hydroxyl groups and/or carboxyl groups in the molecule in an amount within a specific range. The latter method is effective in cases where the degree of polymerization of the polyester cannot be sufficiently increased simply by increasing the polymerization time, or in cases where the polyester polymerization time cannot be increased too much due to thermal decomposition. In addition, in the polyester of the present invention, the average particle diameter is 50 to 450 Å.
By adding silica which can be mixed with water or alcohols in any proportion, it may be possible to prevent clouding due to the progress of crystallization of such polyesters at room temperature. The above-mentioned silica is usually dispersed in water or alcohol to form a sol, and is available as colloidal silica (for example, SNOWTEX 20L, manufactured by Nissan Chemical Industries, Ltd.). Such silica is contained in the polyester of the present invention in an amount of 0.1 to 5% by weight as a solid content.
It is preferable to contain (more preferably 0.2 to 1% by weight). Next, the method for producing polyester of the present invention will be described. The polyester of the present invention is produced by combining a dicarboxylic acid that provides the structural unit () with a diol that provides the structural unit () or an ester-forming derivative that can provide these units in the presence of the aluminum compound below or with the aluminum compound and the structural unit. It can be produced by polymerization in the presence of a monocarboxylic acid or its ester, which is a raw material for (). [Here, R ₅ represents a monovalent group excluding the hydroxyl group of an aliphatic, alicyclic, or monocyclic aromatic alcohol, and is preferably a lower alkyl group such as a propyl group or a butyl group. R ₆ is the above-mentioned R ₂ or a monovalent group excluding the carboxyl group of an aliphatic monocarboxylic acid having 1 to 5 carbon atoms (which may be substituted with a hydroxyl group, etc.), or R ₂ COOH or a monovalent group having 1 to 5 carbon atoms. 5 represents a monovalent group excluding the free carboxyl group of dicarboxylic acid monoesters or dicarboxylic acid monoalkali metal salts which are derivatives of aliphatic monocarboxylic acids, preferably a phenyl group,
A p-hydroxyphenyl group or a straight-chain alkyl group having 5 to 17 carbon atoms, more preferably a phenyl group. In addition, R ₇ is a methyl group or a phenyl group,
R ₈ represents a methyl group, a phenyl group, or a monovalent group obtained by removing the proton of the hydroxyl group of an aliphatic alcohol. Furthermore, j, j, and k indicate the average value of each group bonded to the aluminum atom, i+j+k=3, and 0≦i≦2, 0≦j≦
3, 0≦k≦3. ] As such an aluminum compound, those having the above structure can be used, but in particular, approximately
Al[O-CH( _CH3 ) ₂ ](

[Formula]) Those represented by ₂ are preferred. The aluminum compound mentioned above can be heated at a temperature after the esterification reaction between the dicarboxylic acid and the diol has progressed and the carboxyl group content in the reaction system has become extremely small, or after the transesterification reaction between the dicarboxylic acid diester and the diol has been almost completed. is 180~
It is preferably added to the reaction system under conditions of 300°C (more preferably 180 to 250°C). 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 or dispersing it in a diol. Note that the above aluminum compound can be produced by various methods well known to those skilled in the art, one example of which is shown in Examples. When using a monocarboxylic acid or an ester thereof to provide the structural unit () 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 diester and a diol, and the subsequent polymerization reaction, conditions used for ordinary polyester polymerization can be employed. That is, the esterification reaction between a dicarboxylic acid and a diol or the transesterification reaction between a dialkyl ester of a dicarboxylic acid and a diol is carried out at a temperature of 180 to 230°C in the absence or presence of a catalyst such as zinc, calcium, or manganese. Then, polymerization is carried out using a compound such as antimony, titanium, germanium, etc. as a catalyst at a temperature of 260 to 300°C under a pressure of 1 mmHg or less. Note that at this time, a phosphoric acid compound may be added as a heat stabilizer. In addition, when adding silica to prevent clouding of polyester, when preparing dicarboxylic acid or its ester and diol as raw materials,
It is preferable to add a mixture of colloidal silica and diol (preferably one containing no water). The above-mentioned aluminum compound is added to the reaction system and at the same time R ₅ -O- group and

[Formula] Most of the group parts react and bond with dicarboxylic acid or diol components, and the alcohol R ₅ OH or β-diketone or keto acid ester R ₈ COCH ₂ COR ₇ corresponding to these groups is eliminated and distilled. Transfers during exudation. Well, when R ₆ matches R ₂ in formula (), some of the R ₆ COO− groups remain bonded to Al in the polyester, and the rest undergoes an exchange reaction with the dicarboxylic acid. It is detached and attached to the end of the polyester molecule. When R ₆ is a group obtained by removing the carboxyl group from a monocarboxylic acid having 5 or less carbon atoms, most of the monocarboxylic acid or its alkyl ester migrates into the distillate. In this way, Al is bonded to the polyester molecular chain or to the end of the molecular chain, either directly through an alkoxide bond or a carboxylate bond, or indirectly through an alumina bond therebetween. As described above, most of the added amount of Al bonds with the polyester, so the amount of the aluminum compound added is smaller than that of the dicarboxylic acid.
A suitable range is 0.1 to 5 moles per 100 moles. In addition, the monocarboxylic acid that is the raw material for the structural unit () is such that the total amount of the R ₂ COO− group in the aluminum compound and the monocarboxylic acid (R ₂ COOH) or its ester added separately is Al
It is preferable to add 0.25 to 10 times the mole amount based on the number of moles of . Furthermore, when adding a polyvalent organic compound giving polyvalent organic compound units () to (), most of these are introduced into the polyester, so the amount of the polyvalent organic compound added is 100% of the dicarboxylic acid. It is preferably within 1 mole. Also, accordingly,
When monocarboxylic acid (R ₂ COOH) or its ester is additionally added, the amount added is preferably within 15 times the number of moles of the polyvalent organic compound. It was confirmed from the following facts that the polyester of the present invention can be obtained by the method described above. (1) R ₅ -O- group of aluminum compound and

〔polymerization〕

Attach a nitrogen gas introduction tube, stirrer, and cooling tube to a 300ml three-necked flask, and add dimethyl terephthalate.
Add 100 g of ethylene glycol, 68 g of ethylene glycol, and 40 mg of zinc acetate, heat to 200°C under a nitrogen gas stream, and react for 3 hours to perform transesterification. Subsequently, 25μ of tributyl phosphate and 40mg of antimony trioxide were added at 200°C, 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, to the contents of the flask. After dissolving the aluminum compound solution, the temperature of the oil bath was raised to 260°C, and the pressure was gradually reduced to 280°C, and polymerization was carried out for 90 minutes under a reduced pressure of 0.1 mmHg to obtain a pale green polymer. The resulting polyester is transparent in the molten state and has an intrinsic viscosity ([η])
was 0.71 dl/g. Also, the glass transition temperature is 74
℃, and the melting point was 252℃. Precisely weigh 1 g of the obtained polyester into a crucible,
Several drops of concentrated sulfuric acid were added, and the mixture was heated and decomposed on an electric stove for 5 hours. The obtained solid material is further heated in an electric furnace for 500~
Heating to 700°C for 1 hour gave a white residue. This was dissolved in 1N hydrochloric acid to make a 10.0 ml solution, and aluminum atoms were determined by atomic absorption spectroscopy. As a result, the content of aluminum atoms in the polyester was 700 ppm. This value almost matches the theoretical content (730 ppm) calculated from the amount added. The NMR spectrum of the obtained polyester is shown in FIG. Absorption of the methylene proton of caprylic acid at 0.90 ppm and the phenyl proton of p-oxybenzoic acid are observed at 6.65 ppm. 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 almost matched the amount charged. FIG. 2 shows the FT-IR spectrum of the obtained polyester. Weak absorption is observed at 1600 cm ^-1 and 590 cm ^-1 , but this absorption is not observed at all in the spectrum of polyethylene terephthalate shown in Figure 3. As explained in the text, the absorption at 1600 cm ^-1 is based on aluminum carboxylate, and the absorption at 590 cm ^-1 is based on aluminum alcoholate and alumina bonds. Example 2 A nitrogen gas introduction tube, a stirrer, and a cooling tube were attached to a 300ml three-necked flask, and dimethyl terephthalate was added.
100 g of ethylene glycol, 68 g of ethylene glycol, 0.88 g of methyl benzoate, and 40 mg of zinc acetate were added, heated to 200° C. under a stream of nitrogen gas, and reacted for 3 hours to perform a transesterification reaction. Subsequently, tributyl phosphate
Add 25μ and 40mg of antimony trioxide, add aluminum acetylacetonate to 0.50mol per 100mol of dimethyl terephthalate and dissolve, then raise the temperature of the oil bath to 260℃ and gradually reduce the pressure to 280℃. °C and under a reduced pressure of 0.1 mmHg
Polymerization was continued for 90 minutes to obtain a pale yellow polymer. The obtained polyester was transparent in a molten state, and [η] was 0.70 dl/g. Further, its glass transition temperature was 78°C and melting point was 253°C. The aluminum atom content in polyester was determined by the same method as in Example 1.
It was 660ppm (theoretical amount is 700ppm). The FT-IR spectrum of the obtained polyester is shown in FIG. Absorption of aluminum carboxylate is observed at 1600 cm ^-1 and absorption of aluminum alcoholate and alumina bond is observed at 590 cm ^-1 . In addition, as a result of NMR spectrum analysis of the distillate distilled after the transesterification reaction of this polyester until the end of the polymerization, absorption derived from acetylacetone was observed, and as a result of quantitative analysis, it was found that the added aluminum acetylacetonate An amount approximately corresponding to that of acetylacetone was detected. The above shows that aluminum acetylacetonate releases acetylacetone during the polymerization process and changes into aluminum carboxylate, alcoholate, and aluminum oxide with other aluminum atoms. Example 3 [Preparation of aluminum compound] While passing nitrogen gas through the flying device in Example 1,
100 ml of hexylene glycol was taken, 0.10 mol of aluminum isopropoxide powder was added thereto, and the mixture was stirred. Next, 0.05 mol of caprylic acid and 0.15 mol of p-oxybenzoic acid were added, and the mixture was placed in an oil bath with stirring and heated to 100°C. The reaction was maintained at this temperature 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 a solution of an aluminum compound. [Polymerization] In the same manner as in Example 1, a transesterification reaction of dimethyl terephthalate and ethylene glycol was carried out, and 25μ of tributyl phosphate and antimony trioxide were added.
Add 40mg of the above aluminum compound solution to dimethyl terephthalate in terms of aluminum atoms.
Add aluminum in an amount of 0.52 mol to 100 mol, raise the temperature to 260°C, raise the temperature to 280°C while gradually reducing the pressure, and further reduce the pressure to 0.1 mmHg and polymerize for 90 minutes. I proceeded. The obtained polyester was pale yellow and transparent in the molten state, and contained no insoluble matter. [η] of the polyester was 0.76 dl/g. Additionally, the glass transition temperature of this polyester is 75℃, and the melting point is 251℃.
The aluminum atom content in the polyester was 680 ppm (theoretical value was 730 ppm). Example 4 A nitrogen gas introduction tube, a stirrer, and a cooling tube were attached to a 300ml three-necked flask, and dimethyl terephthalate 70 was added to the flask.
g, 30 g of dimethyl isophthalate, 68 g of ethylene glycol, and 40 mg of zinc acetate were added, and the transesterification reaction was carried out at 200° C. for 3 hours under a nitrogen gas stream.
Tributyl phosphate 25μ, antimony trioxide 40mg
was added, and the aluminum compound solution prepared in Example 1 was added so that the amount of aluminum added was 0.52 mol in terms of aluminum atoms, per 100 mol of the total of dimethyl terephthalate and dimethyl isophthalate. Polymerization was carried out in the same manner. The obtained polymer was a pale yellow-green transparent glassy polymer. The glass transition temperature by DSC was about 65°C, and the melting point could not be measured due to its amorphous nature. Also, this polyester [η] is 0.72
dl/g, and the aluminum atom content in the polyester was 670 ppm (theoretical value was 730 ppm). Example 5 A 300ml round bottom flask with a nitrogen gas introduction tube, a stirrer,
Attach the cooling pipe, dimethyl terephrate 97g, methyl benzoate 0.85g, ethylene glycol 57.4
g, 1,4-cyclohexanedimethanol 25.2
g, add 40 mg of zinc acetate, and add 200 mg of zinc acetate under a nitrogen gas stream.
The mixture was heated to ℃ and the transesterification reaction proceeded for 3 hours.
Tributyl phosphate 25μ, antimony trioxide 40
mg, 1.0g aluminum acetylacetonate
In addition, the temperature was raised to 260°C, the pressure was reduced to 280°C, the pressure was further reduced to approximately 0.1 mmHg, and polymerization was proceeded for 90 minutes. The resulting polymer was a pale green glassy polymer that was transparent in the molten state. Moreover, [η] of this polyester was 0.68 dl/g. The glass transition temperature measured by DSC was 78°C, and the melting point could not be measured because it was amorphous. In addition, the aluminum atom content in polyester is
It was 740ppm (theoretical value 810ppm). Example 6 Into the same polymerization apparatus as in Example 1, 100 g of dimethyl terephthalate, 100 g of 1,4-butanediol, and an n-hexa solution of tetrabutyl titanate were added so that the amount of tetrabutyl titanate was 40 mg.
Transesterification reactions were carried out at 180°C for 1 hour, at 200°C for 1 hour, and at 220°C for 1 hour. 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 260°C, the pressure was gradually reduced to 270°C, and the pressure was further reduced. The polymerization was carried out for 90 minutes at a pressure of about 0.1 mmHg. The obtained polyester was a pale yellow crystalline polyester, and due to its high crystallinity, the glass transition temperature could not be measured, and the melting point was 221°C. Such polyester is transparent in the molten state, and [η] is 0.73 dl/
It was hot at g. Further, the aluminum atom content in the polyester was 230 ppm (theoretical value 250 ppm). Example 7 64.0 g of bis-β-hydroxyethyl terephthalate, 25.0 g of succinic anhydride, 15.5 g of ethylene glycol, and 14.9 g of diethylene glycol were placed in the reaction apparatus described in Example 1, and heated at 200°C under a nitrogen gas stream.
The temperature was raised to 215°C and the reaction was carried out for 1 hour.The temperature was raised to 215°C and the reaction was carried out for 1 hour. Add 25μ of tributyl phosphate and 36mg of antimony trioxide, add the aluminum compound solution used in Example 1 so that aluminum atoms are 0.50mol per 100mol of dicarboxylic acid component, and heat to 260°C while reducing pressure. 275℃,
Polymerization was carried out for 90 minutes under reduced pressure of about 0.1 mmHg. The resulting polyester was a hard, rubbery, transparent, pale yellow polymer at room temperature, with a glass transition temperature of 27° C., and its melting point could not be measured due to its amorphous nature. In addition, this polyester [η] is 0.64 dl/g, and the aluminum atom content in the polyester is
It was 720ppm (theoretical value 770ppm). Example 8 In a polymerization apparatus similar to Example 1, 64 g of bis-β-hydroxyethyl terephthalate and 36.5 g of adipic acid were added.
g, 15.5 g of ethylene glycol, and 14.9 g of diethylene glycol were added, and the esterification reaction was proceeded at 200° C. for 5 hours under a nitrogen gas stream. Add 25μ of tributyl phosphate and 36mg of antimony trioxide, add the aluminum compound solution used in Example 1 so that the number of moles of aluminum atoms is 0.5 moles per 100 moles of the dicarboxylic acid component, and raise the temperature to 260 ° C. The temperature was reduced to 280°C, and polymerization was carried out for 1 hour under a vacuum of about 0.1 mmHg. The obtained polyester was orange-colored, hard rubber-like, and transparent in the molten state. The glass transition temperature of this polyester was -5°C, and its melting point could not be measured due to its amorphous nature. Moreover, [η]=0.59 dl/g. Further, the aluminum atom content in the polyester was 690 ppm (theoretical value 710 ppm). In addition,
The FT-IR spectrum of such polyester is
As shown in the figure. Example 9 [Preparation of aluminum compound] Aluminum isopropoxide in 1 flask
30.6g (0.15mol) n-hexane (150ml used)
I made a solution. A solution of 36.6 g (0.30 mol) of benzoic acid in isopropyl alcohol (148 ml) was added dropwise to this at 20°C under nitrogen gas over 20 minutes, and at the same temperature
After stirring for a minute, the aluminum compound precipitate formed was separated. The obtained white powder was vacuum dried at 50 to 60°C for 4 hours. The yield was 45.6g. [Polymerization] In the same reaction apparatus as used in Example 1, a first
Dicarboxylic acid dimethyl ester (CH ₃ OOC−R ₁ −COOCH ₃ ) and diols (HO
-D-OH) was added in a molar ratio of 0.5:1.1, and the transesterification reaction and excess diol removal were carried out in the manner shown in Example 1. Next, 0.6% by weight based on the theoretical yield of polyester (0.4 to 0.7 mol% based on the dicarboxylic acid component) of the above aluminum compound was added to a small amount of diol [ethylene glycol in Examples 9(a) to (e), In Examples 9(f) to (i), a polymerization reaction was carried out according to the method shown in Example 1 in the presence of a polymerization catalyst shown in Table 1 by adding a dispersion in 1,4-butanediol]. (However, in Example 9(i), the polymerization temperature was 260°C and the polymerization time was 120 minutes). Table 1 shows the intrinsic viscosity and aluminum atom content of the polyester thus obtained. Note that all polyesters were transparent in the molten state.

【table】

〔polymerization〕

Using the same polymerization apparatus as in Example 1, 100 g of dimethyl terephthalate, 68 g of ethylene glycol,
40 mg of zinc acetate was added, and a transesterification reaction was carried out at 200°C for 3 hours under a nitrogen gas stream. Next, add 25μ of tributyl phosphate and 40mg of antimony trioxide, and add the above aluminum compound solution to 100 moles of dimethyl terephthalate.
Add it to 0.52 mol and raise the temperature to 260℃,
The temperature was set to 280°C while reducing the pressure, and the polymerization proceeded for 90 minutes under a reduced pressure of about 0.1 mmHg. The polymer began to wrap around the stirring rod after 60 minutes of polymerization time, and stirring was difficult in the latter stages of polymerization. The obtained polyester was pale yellow in color 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, 50 ml of hexylene glycol was added to
-0.01 mol of oxybenzoic acid was dissolved, 0.05 mol of aluminum isopropoxide was added, and the mixture was heated to 100°C to react. In this way, a transparent aluminum compound solution was obtained. [Polymerization] Instead of the aluminum compound solution of Comparative Example 1,
The aluminum compound solution obtained above was added in an amount of 0.52 mol of aluminum to 100 mol of dimethyl terephthalate, and polymerization was proceeded in the same manner as in Comparative Example 1. 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 Comparative Example 1, xylene 50
ml and 0.05 mol of aluminum isopropoxide were added and heated to 100°C to dissolve. Next, 0.05 mol of acetylacetone was added and reacted for 15 minutes to obtain a light brown transparent aluminum compound solution. [Polymerization] Instead of the aluminum compound in Comparative Example 1, the aluminum compound solution obtained above was added so that the amount of aluminum was 0.2 mol per 100 mol of dimethyl terephthalate, and polymerization was carried out in the same manner as in Comparative Example 1. Polymerization time was 90 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 ml of xylene
and 0.05 mol of aluminum isopropoxide were added and dissolved at room temperature. Then acetylacetone
0.05 mol was added, the temperature was raised to 50°C, and the mixture was stirred for 30 minutes.
Next, 0.10 mol of acetic acid was added and the mixture was reacted at 50°C for 30 minutes, and then the temperature was raised to 120°C to distill off isopropyl alcohol to obtain a solution of an aluminum compound. [Polymerization] Instead of the aluminum compound of Comparative Example 1, the aluminum compound solution obtained here was used in an amount of 0.52 mol of aluminum per 100 mol of dimethyl terephthalate.
The polymerization was carried out in the same manner as in Comparative Example 1. At 60 minutes of polymerization time, a phenomenon in which the polymer was wrapped around the stirring rod occurred significantly, and the polymerization was stopped. The resulting polyester was pale yellow and contained insoluble gel particles. Comparative Example 5 In Example 11, the transesterification reaction and polymerization were carried out in the same manner as in Example 11 except that 6.0 mol% of the aluminum compound was used based on the total amount of diester dicarboxylate. During polymerization, the product did not flow and gelled. . Comparative Example 6 Polymerization was attempted after transesterification in the same manner as in Example 2 except that 6.0 g of methyl benzoate was used. 280℃, under reduced pressure of 0.1mmHg
Polymerization proceeded for 120 minutes. The obtained polyester had [η] of 0.42 dl/g and was brittle. Example 12 The polyester obtained in Examples 7 and 8 was molded to a thickness of about 100μ at 180°C on a biaxially stretched polyethylene terephthalate film (thickness 100μ), and then ethylene-vinyl A 100 μ thick film of alcohol copolymer (ethylene content: 30 mol %) was placed on it, melt-pressed at 180° C. for 2 minutes (pressure: 10 Kg/cm ² ), and rapidly cooled to produce a three-layer film. A specimen with a width of 15 mm was cut from this film, and a T-peel test was conducted at room temperature using a tensile tester at a tensile speed of 200 mm/min. Furthermore, as a control example, the T-peel strength of a three-layer film with an intermediate layer made of polyester to which no aluminum compound was added was also measured. These results are shown in Table 2.

[Table] Example 13 The polyesters obtained in Examples 10 and 11(a) to (i) were heat-pressed to form a quenched film with a thickness of about 100μ, and then this was made into a quenched film with an ethylene-vinyl alcohol copolymer (ethylene content: 45 mol%) film (thickness
100μ) and polyethylene terephthalate film (thickness 100μ) and stacked, crimped at 180℃ (10Kg/cm ² ), and then heated at 280℃ under almost no load.
After fusion bonding by holding for 2 minutes, a three-layer film was produced by gently sandwiching and quenching with a cooling press. Specimens with a width of 15 mm were cut from these films and subjected to a T-peel test at a tensile rate of 20 mm/min at room temperature. Further, as a control example using the polyester of Example 11, the T-peel strength of a three-layer film using a polyester in which the aluminum compound was added in an amount of 0.05 mol % based on the dicarboxylic acid component was also measured. These results are shown in Table 3.

[Table] Aluminum atom relative to dicarboxylic acid component
Polyester containing 0.1 mol% or more is
It can be seen that it has much higher adhesive strength than those with an aluminum atom content of less than 0.1 mol%. Comparative Example 7 A polyethylene terephthalate/carboxylic acid-modified polyolefin adhesive was prepared in the same manner as in Example 13, except that various carboxylic acid-modified polyolefin adhesives shown in Table 4 were used instead of the polyester of the present invention in Example 13. A three-layer film consisting of an agent/ethylene-vinyl alcohol copolymer was prepared. The peel strength of this film was measured by the same method as in Example 13, and the results are shown in Table 4. Table 4 also lists the decomposition exotherm onset temperature (measured at a heating rate of 10° C./min) of the carboxylic acid-modified polyolefin adhesive in air using a differential thermal analyzer (DTA).

[Table] The results show that it is impossible to firmly adhere and laminate polyethylene terephthalate and ethylene-vinyl alcohol copolymer using conventional adhesives. In addition, the decomposition temperature of conventional adhesives is lower than the molding temperature of polyethylene terephthalate (approximately
(280°C), these adhesives prove difficult to stably coextrude with polyethylene terephthalate. Example 14 Dimethyl terephthalate in a 200ml three-necked flask
100g, ethylene glycol 67g, zinc acetate 40mg
was added, a stirrer, a nitrogen gas inlet tube, and a cooler were attached, and the mixture was heated to 200°C to carry out the transesterification reaction for 180 minutes. Thereafter, 49 mg of tributyl phosphate and 40 mg of antimony trioxide were added, the temperature was raised to 240°C, and the pressure was gradually reduced to distill off excess ethylene glycol. Fill the flask with nitrogen gas again, and add 0.6 g of the aluminum compound prepared in Example 9 to 5 ml of 1,4-
The dispersion in butanediol was added little by little. After the addition is complete, continue stirring at 240℃ for 10 minutes, and then stir at 280℃.
After raising the temperature to , the pressure was gradually reduced, and polymerization was allowed to proceed for 120 minutes under a reduced pressure of 0.2 mmHg. The resulting polyester was transparent and almost colorless in the molten state. Further, [η] was 0.72 dl/g, the glass transition temperature was 74°C, and the melting point was 252°C. The content of aluminum atoms in polyester is 460 ppm (theoretical value)
490ppm). Example 15 As a dicarboxylic acid component, 38.8 g of dimethyl terephthalate, 69 g of dimethyl sebacate, as a diol component, 55 g of ethylene glycol, 1,4-
Add 18 g of butanediol and 0.6 g of the aluminum compound prepared in Example 9 to 10 ml of 1,4-
Example 14 except for using it dispersed in butanediol
Transesterification reaction and polymerization in the same manner as (however,
Polymerization temperature was 270°C). The obtained polyester was pale yellow and transparent at first, but when it was left at room temperature, it began to become cloudy, indicating that some crystallization had occurred. Further, [η] was 0.82 dl/g, the glass transition temperature was -1°C, and the melting point was 104°C. The aluminum atom content in polyester is
The amount was 410ppm (theoretical value was 440ppm). Example 16 Same as Example 15 except that 56.3 g of dimethyl terephthalate, 7.8 g of dimethyl isophthalate, and 39.1 g of dimethyl sebacate were used as dicarboxylic acid components, and 59.3 g of ethylene glycol and 12.9 g of 1,4-butanediol were used as diol components. The transesterification reaction and polymerization were carried out. The obtained polyester was pale yellow and transparent, but when left at room temperature, it became cloudy, indicating that some crystallization had occurred. Further, [η] was 0.77 dl/g, the glass transition temperature was 2°C, and the melting point was 86°C. Aluminum atom content in polyester is 460ppm (theoretical value 470ppm)
It was hot. Example 17 Polyethylene terephthalate/polyester obtained in Examples 14, 15, and 16/ethylene-vinyl alcohol copolymer was prepared in the same manner as in Example 13 except that the polyester obtained in Examples 14, 15, and 16 was used. (However, the ethylene content was 30 mol%) A three-layer film was prepared and subjected to a T-peel test. In addition, the width is 15 mm and the length is longer than the three-layer membrane above.
An 80mm rectangular specimen was cut out and stretched at a stretching temperature of 90℃.
A uniaxially stretched film was prepared at a stretching rate of about 3.3 times at a stretching speed of 300%/min, and a T-peel test was conducted on this stretched film in the same manner. Table 5 shows the evaluation results of adhesive strength and stretchability.

[Table] From the results in Table 5, when the polyester of the present invention is used as an adhesive, the glass transition temperature is 30°C.
Further, when co-stretching a laminate obtained using a certain adhesive, it is preferable that the melting point of the polyester of the present invention is lower than the stretching temperature, thereby improving the stretchability. It can be seen that the peel strength after stretching can be maintained at a high value. Example 18 23.2 kg of dimethyl terephthalate, 3.2 kg of dimethyl isophthalate, 16.2 kg of dimethyl sebacate, 1,
4-butanediol 5.5Kg, ethylene glycol
After charging 25.6 kg, 49.7 g of trimethylolpropane, and 12 g of zinc acetate and completing the transesterification reaction at 200 to 235°C for 210 minutes, the liquid was sent to a polymerization tank preheated to 240°C, and 18.8 g of triphenyl phosphate was prepared. , 28 g of antimony trioxide was added, and the pressure inside the polymerization tank was gradually reduced to 20 mmHg to distill off excess glycols. Next, the tank was filled with nitrogen gas, and 1,4-
Adding 240 g of the same aluminum compound as prepared in Example 9 dispersed in butanediol 4
After stirring for 10 minutes, the temperature was raised to 260°C and the pressure was gradually reduced to 0.1 mmHg or less to proceed with polymerization. By adjusting the polymerization time within a range of up to 150 minutes, four types of polymers shown in Table 6 were obtained. These polymers were extruded into strands, pelletized using a pelletizer, and dried at 80°C for 24 hours to form pellets weighing approximately 30 kg. [η] of these four types of polyesters and the aluminum atom content in the polyesters are shown in Table 6. Among the polyesters in Table 6, [η] is 1.10dl/
The apparent melt viscosity of G (polymerization time: 150 minutes) was measured using a Koka type flow tester (manufactured by Shimadzu Corporation) at a temperature of 260°C and a shear rate.
The temperature was 3500 poise at 10 ² sec ^-1 , the glass transition temperature was 1°C, and the melting temperature was 86°C. Moreover, it was transparent in the molten state. The FT-IR of this polyester is shown in FIG. Copolymerized polyethylene terephthalate (manufactured by Eastman Chemical Company, KODAPAK) was used as an intermediate layer using the four types of polyester obtained.
9921) and ethylene-vinyl alcohol copolymer (ethylene content 45 mol%) using three extruders.
Resin temperature 180℃ (obtained above polyester),
260℃ (copolymerized polyethylene terephthalate),
230℃ (ethylene-vinyl alcohol copolymer)
The material is supplied to the same die (die temperature 250℃) and molded to a thickness of approximately 500μ by multi-manifold co-extrusion.
A three-layer laminated sheet was obtained. This laminated sheet was further stretched 2.5 times in the uniaxial direction at 90°C. The conditions of coextrusion and the T-peel strength of the sheet before and after stretching (measured by the method of Example 13) are summarized in Table 6.

[Table] From this result, the intrinsic viscosity of the polyester of the present invention is 0.7 dl/
g or more, more preferably 0.8 dl/
It is preferable that it is more than g. In addition, the intrinsic viscosity
It can be seen that in the range of 0.8 dl/g or more, there is no significant difference in the coextrusion situation or the peel strength of the laminated sheet. Using polyester (A) with [η] of 1.10 dl/g, copolymerized polyethylene terephthalate (manufactured by Eastman Chemical Co., KODAPAK 9921) (B) and ethylene-vinyl alcohol copolymer (ethylene content molar %) (C) and has a structure of (B)/(A)/(C)/(A)/(B) (total thickness 1360μ), multi-manifold co-extrusion molding. It was molded using the method. The obtained sheet was a coextruded sheet with an excellent appearance, in which each layer was bonded to a substantially uniform thickness over the entire width (500 mm). Also, the T peel strength of this sheet is
1.5Kg/cm, and the peeling surface is made of the polyester (A) of the present invention and ethylene-vinyl alcohol copolymer (C).
The other bonding surfaces were firmly adhered. In addition, among the polyesters in Table 6, those with an intrinsic viscosity ([η]) of 0.93 dl/g were used in Example 13.
A five-layer sheet consisting of polyethylene terephthalate/polyester of the present invention/ethylene-vinyl alcohol copolymer (ethylene content: 45 mol %)/polyester of the present invention/polyethylene terephthalate was prepared in the same manner as above. The T-peel strength of this sheet was measured in the same manner as in Example 13 and was found to be 2.8 kg/cm. This sheet at 25℃
After being left for two months under conditions of 70% RH, the T peel strength was measured and was 2.6 kg/cm, with almost no decrease in peel strength over time. Example 19 1.24 colloidal silica (SNOWTEX 20L, manufactured by Nissan Chemical Industries, Ltd.) was added to the transesterification reaction tank of a polyester polymerization apparatus.
Dispersed in 23.09Kg of ethylene glycol,
Dimethyl terephthalate 23.92Kg, dimethyl isophthalate 2.06Kg, dimethyl adipate 12.58Kg,
10.93 kg of diethylene glycol, 33.1 g of trimethylolpropane, and 40 g of calcium acetate were charged, and the mixture was heated to 200 to 235°C for 210 minutes to complete the transesterification reaction. Such a reaction mixture
The solution was sent to a polymerization tank preheated to 240°C, 18.8 g of triphenyl phosphate and 28 g of antimony trioxide were added, and the pressure inside the polymerization tank was gradually reduced to 20 mmHg to distill off excess glycols. Next, the tank was filled with nitrogen gas, and 1,4-butanediol of 2 and 2
The same aluminum compound as prepared in Example 9 dispersed in a mixture of diethylene glycol of
After adding 240 g and stirring for 10 minutes, the temperature was raised to 260°C, and the pressure was gradually reduced to 0.1 mmHg or less, and polymerization proceeded for 150 minutes. The generated polymer is pushed up into strands and taken out into pellets using a pelletizer.
Approximately 30 kg of pellets were obtained by drying at 80°C for 24 hours. [η] of such polyester is 1.10
dl/g, glass transition temperature is 3℃, melting point is
It was 103℃. In addition, the polyester was slightly cloudy in its molten state, but this cloudiness was attributed to silica. The aluminum atom content in polyester is 450 ppm (theoretical value is
490ppm). Using the obtained polyester (A), copolymerized polyethylene terephthalate [manufactured by Eastman Chemical Company, KODAPAK 9921] (B) and ethylene-vinyl alcohol copolymer (ethylene content 30 mol%) (C) were combined. Glue it together (B)／(A)／
A five-layer tube having the configuration (C)/(A)/(B) was coextruded. One end of this tube was heat-sealed to form a bottomed parison, which was then heated to 105° C. and stretch-blow molded to obtain a five-layered hollow container. Such hollow containers have excellent mechanical strength, impact resistance, water resistance, and gas barrier properties, and are also free from delamination and have excellent transparency, making them extremely suitable as containers for beverages and the like. Example 20 In a transesterification reaction tank of a polyester polymerization equipment, 24.8 kg of dimethyl terephthalate, 1.2 kg of dimethyl isophthalate, 12.6 kg of dimethyl adipate, 25.5 kg of ethylene glycol, 4.9 kg of 1,6-hexanediol, 0.050 kg of pentaerythritol, and 33 g of calcium acetate were added. After completing the transesterification reaction at 200-235℃ for 210 minutes, benzoic acid
Add 0.090Kg and stir, then send the solution to a polymerization tank preheated to 240℃, add 16.4g of phosphoric acid (purity 85%) dissolved in a small amount of ethylene glycol, and add 16.5g of antimony trioxide. gradually reduce the pressure
Glycols were distilled off at 20 mmHg. After this,
240 g of the same aluminum compound as that produced in Example 9 was added in the same manner as in Example 18, polymerization was allowed to proceed for 150 minutes, and the resulting polyester was taken out in the form of pellets. Such polyester is [η]=
It was 1.25 dl/g and transparent in the molten state.
Further, the aluminum atom content in the polyester was 480 ppm (theoretical value 490 ppm). Example 21 63.11 g of dimethyl terephthalate, 40.30 g of dimethyl sebacate,
63.6 g of ethylene glycol, 8.85 g of 1,6-hexanediol and 0.04 g of zinc acetate were added, and the mixture was reacted at 200° C. for 3 hours under a nitrogen gas stream, and the produced methanol was distilled off. Next, trimellitic anhydride
0.17g was added and stirred for 20 minutes, and then 25mg of tributyl phosphate, 40mg of antimony trioxide, and 0.60g of the aluminum compound synthesized in Example 9 were added to a small amount of 1,
After gradually adding and dissolving the dispersion in 4-butanediol, the temperature was raised to 260°C, and polymerization was proceeded at 280°C for 90 minutes under a reduced pressure of 0.1 mmHg while gradually reducing the pressure and increasing the temperature. The obtained polyester was transparent in the molten state and had [η]=1.05 dl/g. In addition, the aluminum atom content in polyester is
It was 440ppm (theoretical value 470ppm). Example 22 Polyesters obtained in Examples 1 to 5 and ordinary polyethylene terephthalate containing no aluminum compound ([η] = 0.70 dl/
g) was formed into a quenched film with a thickness of about 200μ using a hot press. Further, from sufficiently dried carboxylic acid-modified polyethylene and carboxylic acid-modified ethylene-vinyl acetate copolymer chips, a quenched film of about 200 μm was prepared using a hot press. Layering polyester film and carboxylic acid-modified polyethylene film or carboxylic acid-modified ethylene-vinyl acetate copolymer film at 180°C for 10kg/
cm ² and then held at 280° C. for 2 minutes under almost no load to melt and bond both polymers, and then lightly sandwiched in a cooling press to rapidly cool, producing a multilayer sheet. A rectangular specimen with a width of 15 mm was cut out from this sheet, and after being left at room temperature overnight, it was pulled at a tensile speed of 20 mm at room temperature.
A T-peel test was performed at mm/min. The results are shown in Table 7.

[Table] 100μ thick quenched film made of various carboxylic acid-modified polyolefins (G) and ethylene-vinyl alcohol copolymer (ethylene content 45 mol%)
Using a 100μ thick quenched film made of (H),
A three-layer emergency film consisting of (G)/(H)/(G) was prepared in the same manner as in Example 22. Furthermore, examples
By repeating the same method as 22, such 3
A 300μ thick sheet (F) of the polyester obtained in Example 14 or polyethylene terephthalate as a control example was laminated on both sides of the layer film (F)/
A sheet consisting of three types and five layers consisting of (G)/(H)/(G)/(F) was produced. This sheet was subjected to a T-peel test in the same manner as in Example 22. The results are shown in Table 8.

【table】 [Brief explanation of the drawing]

Figure 1 is a nuclear magnetic resonance spectrum of the polyester of the present invention obtained in Example 1, and Figures 2, 4, 5 and 6 are Example 1, Example 2, and Example 2, respectively. 8 and 18 are infrared absorption spectra of the polyesters of the present invention obtained in Example 18. Moreover, FIG. 3 is an infrared absorption spectrum of polyethylene terephthalate.

Claims (1)

[Claims] 1. The structural unit is the following formula (), (), () and () () () (-O)―― _o D(-O)―― _o () () (In the formula, R ₁ is a divalent dicarboxylic acid obtained by removing the carboxyl group from one or more dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, and linear aliphatic dicarboxylic acids having 4 to 10 carbon atoms.) , and R ₂ is 1 selected from the group consisting of aliphatic or alicyclic monocarboxylic acids having 6 to 30 carbon atoms and aromatic monocarboxylic acids having 7 to 20 carbon atoms.
Represents a monovalent group obtained by removing a carboxyl group from one or more monocarboxylic acids, and D has 2 carbon atoms.
It represents a divalent group obtained by removing the hydroxyl group from one or more diols selected from the group consisting of aliphatic diols having ~10 carbon atoms and alicyclic diols having 6 to 8 carbon atoms. In addition, m, n, p ₁ , p ₂ , p ₃ , and q are each 0 or 1, and each constituent unit is () and (), () and (), () and (), () and (), between (), and between () and (), and such a bond represents that only one oxygen atom is present. ), and the molar ratio of ():() is substantially 1:
1, and the molar ratio of ():() is 1000:1 ~
100:5, and the molar ratio of ():() is 4:1 to
1:10, and 30% in phenol/1,1,2,2 tetrachloroethane mixed solvent (1:1 weight ratio)
An adhesive made of thermoplastic polyester and having an intrinsic viscosity measured at °C of 0.5 dl/g or more.