JPH11106622A - Flexible polyester resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in flexibility, transparency and resistance to volatility by kneading polyethylene terephthalate with an aliphatic polyester and a crystallization inhibitor in a molten state to cause transesterification. SOLUTION: This composition is obtained by compounding (A) 100 pts.wt. of polyethylene terephthalate with (B) 10-100 pts.wt. of an aliphatic polyester (e.g. polyethylene sebacate) preferably having a number-average molecular weight of 25,000-30,000 and (C) a crystallization inhibitor [e.g. 1,3-bis(2- hydroxyethoxy)benzene], which is contained in a quantity of 0.1-15 pts.wt. based on 100 pts.wt. of a sum quantity of the component A and the component B, at preferably 250-300 deg.C to cause partial or whole transesterification.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible polyester resin composition and its use.
The present invention relates to a polyester resin composition excellent in flexibility, transparency, volatility, and the like and excellent in moldability, and a film, a sheet, and the like made of the composition.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polyethylene terephthalate is
Because it has excellent mechanical properties, chemical resistance, gas barrier properties, fragrance retention, etc., and generates little toxic gas even when incinerated,
In recent years, it has been used in large quantities as a container (PET bottle) for filling beverages such as juice, soft drinks, and carbonated drinks. However, since polyethylene terephthalate has poor flexibility, its use is limited, and it can be used only for magnetic tapes and some food packaging for sheets and films.

As a method of imparting flexibility to polyethylene terephthalate, a method of copolymerizing dodecanedicarboxylic acid, azelaic acid, dimer acid or the like as a soft segment in order to improve the flexibility of polyethylene terephthalate itself, polytetramethylene A method of preparing a polyester-polyether block copolymer using a soft segment as glycol has been proposed. Further, a method of adding flexibility to polyethylene terephthalate by adding a resin modifier such as an aromatic ester compound, an aromatic ether compound, an ethylene-vinyl acetate copolymer, an olefin elastomer, or an ionomer resin has also been proposed. However, the obtained polyethylene terephthalate has insufficient transparency, moldability, heat resistance, and volatility.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have melt-kneaded polyethylene terephthalate, an aliphatic polyester, and a crystallization inhibitor such as an aromatic diol ethylene oxide adduct. ,
It has been found that a composition partially or wholly transesterified has high transparency and excellent flexibility, and has completed the present invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flexible polyester resin composition having excellent flexibility, transparency and volatility, and its use.

[0006]

SUMMARY OF THE INVENTION The flexible polyester resin composition according to the present invention comprises (A) polyethylene terephthalate and (B)
The aliphatic polyester and the (C) crystallization inhibitor are mixed in an amount of 10 to 100 with respect to (A) 100 parts by weight.
(A) and (B) in a ratio of 100 parts by weight.
It is characterized by being obtained by melt-kneading at a ratio of 0.1 to 15 parts by weight of (C) to parts by weight and transesterifying a part or all of (A) and (B). .

In the present invention, the proportion of the aliphatic polyester (B) is preferably 40 to 100 parts by weight based on 100 parts by weight of the component (A). The flexible polyester resin composition according to the present invention has a flexural modulus of 1200M.
It is preferably Pa or less.

The (B) aliphatic polyester includes:
A polyester obtained from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic glycol having 2 to 13 carbon atoms and having a number average molecular weight in the range of 2,500 to 30,000, is preferred. , (I) a polyester obtained from sebacic acid and propylene glycol, (i)
Examples include i) a polyester obtained from adipic acid and propylene glycol, and (iii) a polyester obtained from adipic acid and ethylene glycol.

In the present invention, the (C) crystallization inhibiting component is preferably an aromatic diol ethylene oxide adduct, particularly a compound represented by any of the following formulas (I) to (III): Preferably, there is.

[0010]

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(Wherein m and n may be the same or different from each other and are integers from 1 to 5, and R ¹ to R ⁸ may be the same or different from each other, and include a hydrogen atom, a boron atom or a methyl group, X is a direct _{bond, -O -, - CH 2 -} , - S -, - SO 2 -,

[0012]

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[0013]

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(In the formula, m and n may be the same or different from each other, and are each an integer of 1 to 5.)

[0015]

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(In the formula, m and n may be the same or different and are each an integer of 1 to 5.) Among the crystallization inhibiting components, bisphenol fluorene hydroxyethyl ether, 2,6- At least one selected from the group consisting of bis (2-hydroxyethoxy) naphthalene, 1,3-bis (2-hydroxyethoxy) benzene and 4,4 ′-(1-phenylethylidene) bis (2-hydroxyethoxyphenol) Are particularly preferred.

Products using such a flexible polyester resin composition include, for example, sheets, films, retort containers, cups, lids for cups, wallpapers, a layer (such as a heat seal layer) comprising the composition and a substrate. There are a packaging material comprising a laminate with a layer (resin, metal foil, etc.), a metal can and a paper pack having an inner wall coated with the composition, a laminated plywood and a laminated steel sheet having a surface layer comprising the composition.

[0018]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the flexible polyester composition according to the present invention will be specifically described. The flexible polyester resin composition according to the present invention comprises (A) polyethylene terephthalate, (B) an aliphatic polyester,
It is obtained by melt-kneading (C) a crystallization inhibitor. First, each of these components will be described.

(A) Polyethylene Terephthalate (A) Polyethylene terephthalate used in the present invention is an aromatic dicarboxylic acid containing terephthalic acid or an ester derivative thereof (eg, lower alkyl ester, phenyl ester, etc.), ethylene glycol or an ester thereof. And diols containing derivatives.

(A) Polyethylene terephthalate may contain 15 mol% or less of a structural unit derived from an aromatic dicarboxylic acid other than terephthalic acid or an ester derivative thereof if necessary (100 mol of all the structural units derived from an aromatic dicarboxylic acid may be used). %). Specifically as an aromatic dicarboxylic acid other than terephthalic acid or an ester derivative thereof, isophthalic acid, phthalic acid,
Examples include naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, and the like, and ester derivatives thereof.

The polyethylene terephthalate (A) may have, if necessary, 15 mol% or less of structural units derived from a diol other than ethylene glycol or its ester derivative (100 mol% of all structural units derived from diol). They may be contained in proportions. Specific examples of diols other than ethylene glycol or ester derivatives thereof include diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol (propylene glycol), butanediol,
Pentanediol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as polyethylene glycol, alicyclic glycols such as cyclohexane dimethanol, bisphenols, aromatic diols such as hydroquinones,
And their ester derivatives.

Further, (A) polyethylene terephthalate may contain a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane or pentaerythritol, if necessary. , For example, 2 mol%
It may be contained in the following amount (the total of the constituent units derived from the aromatic dicarboxylic acid and the constituent units derived from the diol is 100 mol%).

Such (A) polyethylene terephthalate is substantially linear, which is confirmed by the fact that the polyethylene terephthalate dissolves in o-chlorophenol.

(A) Polyethylene terephthalate has an intrinsic viscosity (IV) measured at 25 ° C. in a 1: 1 (weight ratio) mixed solvent of phenol and tetrachloroethane which is usually 0.3 to 1.5 dl /. g, preferably 0.5 to 1.2
It is desirably in the range of dl / g.

The polyethylene terephthalate (A) used in the present invention is produced from the above-mentioned aromatic dicarboxylic acid and diol by a conventionally known production method. In the present invention, as the polyethylene terephthalate (A), “raw material polyethylene terephthalate” which is usually commercially available in the form of pellets is used, but if necessary, “recovered polyethylene terephthalate” may be used. Further, "raw polyethylene terephthalate" and "recovered polyethylene terephthalate" may be mixed and used at an arbitrary ratio.

In the present specification, “raw polyethylene terephthalate” refers to a molded product such as a bottle or a preform which is usually produced in the form of pellets from a dicarboxylic acid and a diol and which is passed through a molding machine in a heated and molten state. Polyethylene terephthalate which has no history of molding.
The term "recovered polyethylene terephthalate" refers to polyethylene terephthalate obtained by pelletizing polyethylene terephthalate obtained by passing such a raw material polyethylene terephthalate through a molding machine at least once in a heated and molten state. The process of “passing the raw material polyethylene terephthalate through a molding machine in a heated and melted state” is performed by heating and melting a pellet (chip) made of the raw material polyethylene terephthalate and forming it into a desired shape such as a preform or a bottle.

(B) Aliphatic Polyester The (B) aliphatic polyester used in the present invention is a polyester having no aromatic ring in the main chain, for example, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms or an ester thereof. It is obtained from a derivative and an aliphatic glycol having 2 to 13 carbon atoms or an ester derivative thereof and / or an alicyclic glycol having 4 to 13 carbon atoms or an ester derivative thereof.

Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms and ester derivatives thereof include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and the like. And ester derivatives of
(B) The aliphatic polyester may have, if necessary, 15 mol% or less of structural units derived from an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid or an ester derivative thereof (100 mol% of all structural units derived from dicarboxylic acid).
).

Examples of the aliphatic glycol having 2 to 13 carbon atoms include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-propanediol, tetramethylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, Examples of the alicyclic glycol having 4 to 13 carbon atoms include cyclohexanediol, cyclohexane dimethylol, and 2,2-bis (4-hydroxycyclohexyl) methane.

The aliphatic polyester (B) used in the present invention includes, for example, polyethylene adipate, polyethylene sebacate, polytetramethylene dodecane, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, etc. And an aliphatic copolyester obtained from two or more kinds of aliphatic dicarboxylic acids and one kind of glycol selected from aliphatic glycols and alicyclic glycols, one kind of aliphatic dicarboxylic acids, and aliphatic glycols and alicyclics Aliphatic polyesters obtained from two or more glycols selected from aliphatic glycols, fats obtained from two or more aliphatic dicarboxylic acids, and two or more glycols selected from aliphatic glycols and alicyclic glycols Group copolyester and the like.

As the aliphatic polyester (B) used in the present invention, at least one aliphatic dicarboxylic acid selected from adipic acid and sebacic acid and at least one aliphatic dicarboxylic acid selected from ethylene glycol, propylene glycol and tetramethylene glycol And aliphatic polyesters obtained from (i) a polyester obtained from sebacic acid and propylene glycol; (ii) a polyester obtained from adipic acid and propylene glycol; (iii) adipic acid; Polyesters obtained from ethylene glycol are preferred.

The aliphatic polyester (B) used in the present invention is produced by a conventionally known production method. The number average molecular weight of the aliphatic polyester is from 2,500 to 30,0.
00, preferably in the range of 5,000 to 20,000. Aliphatic polyester having a molecular weight of 3
If it exceeds 000, the transparency of the flexible polyester resin composition may decrease.

(C) Crystallization Inhibiting Component The crystallization inhibiting component includes, for example, an aromatic diol ethylene oxide adduct.

Examples of the aromatic diol ethylene oxide adduct include diol ethylene oxide adducts such as a benzene ring, a naphthalene ring, bisphenol and 2,2-diphenolpropane. Specifically, the following general formulas (I) to (I) Compounds represented by any of (III) are mentioned.

[0035]

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In the formula, m and n may be the same or different and are each an integer of 1 to 5, preferably 1 to 3. R ¹ to R ⁸ may be the same or different and represent a hydrogen atom, a boron atom or a methyl group.

X is a direct bond, -O-, -CH ₂ -,-
S -, - SO ₂ -,

[0038]

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[0039]

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In the formula, m and n may be the same or different, and are each an integer of 1 to 5, preferably 1 to 3.

[0041]

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In the formula, m and n may be the same or different and are each an integer of 1 to 5, preferably 1 to 3. As a crystallization inhibitor, 2,2-bis [4-
(2-hydroxyethoxy) phenol] propane, 4,4-
Compounds represented by the general formula (I) such as (1-phenylethylidene) bis (2-hydroxyethoxyphenol) and bisphenol fluorenedihydroxyethyl ether; and general compounds such as 1,3-bis (2-hydroxyethoxy) benzene A compound represented by the formula (II); the above-mentioned general formula (III) such as 2,6-bis (2-hydroxyethoxy) naphthalene
And the isomers thereof are preferred.

These (C) crystallization inhibiting components can be used alone or in combination of two or more. If the amount of the (C) crystallization inhibitor exceeds 15 parts by weight, the flexibility of the resin composition may be impaired.

When a crystallization inhibitor such as an aromatic diol ethylene oxide adduct is added to the polyester resin composition, the melting point of the composition is lowered, and the transparency and flexibility are improved. In addition, it is possible to suppress a change with time of the elastic modulus and the transparency of the flexible polyester resin composition.

Flexible Polyester Resin Composition The flexible polyester resin composition according to the present invention comprises, for example, (A) polyethylene terephthalate, (B) an aliphatic polyester, and (C) a crystallization-inhibiting component. 10) to 100 parts by weight, preferably 40 to 100 parts by weight, of (B) based on 100 parts by weight, and the amount of (C) is 0.1 to 100 parts by weight of the total of (A) and (B). It can be produced by melt-kneading at a ratio of 1 to 15 parts by weight, preferably 0.5 to 5 parts by weight. The melt-kneading temperature is usually from 250 to 300C, preferably from 270 to 290C.

For the melt-kneading, any known method may be used. However, in a polymerization apparatus equipped with a double helical stirring blade capable of stirring under reduced pressure, water, alcohol, glycol, and the like by-produced at a pressure of 133.3 Pa or less. It is preferable to employ a method of melt-kneading while depressurizing and distilling out of the system, or a method of melt-kneading using a single-screw or twin-screw extruder. When melt kneading is performed using an extruder, a flexible polyester resin composition can be manufactured with higher productivity.

(A) polyethylene terephthalate,
When melt-kneaded with the (B) aliphatic polyester and the (C) crystallization-inhibiting component, a part or all of the components (A) and (B) undergo transesterification, and therefore have excellent flexibility and volatility resistance. A flexible polyester resin composition is obtained. Further, the composition is excellent in transparency.

The flexible polyester resin composition according to the present invention has a flexural modulus of press sheet of 1200 MPa or less, preferably 40 to 10 MPa, as measured by a method described later.
It is desirable to be in the range of 00 MPa. Simply melt-kneading (A) polyethylene terephthalate and (B) aliphatic polyester does not provide a composition having the above-mentioned elastic modulus, and transesterification is carried out in part or all of (A) and (B). The composition having the elastic modulus as described above is obtained by the occurrence of

In the flexible polyester resin composition according to the present invention, the haze value of the press sheet measured by the method described below is 60% or less, preferably 30% or less, more preferably 20% or less. desirable.

In producing the flexible polyester resin composition, a catalyst generally used in producing polyester may be used. This catalyst includes lithium, sodium, potassium, cesium, magnesium,
Metals such as calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, cadmium, manganese, and the like, and their organometallic compounds, organic acid salts, metal alkoxides,
And metal oxides. Particularly preferred catalysts are calcium acetate, dibutyltin oxide, tetrabutyl titanate, germanium dioxide, and antimony trioxide. These catalysts can be used alone or in combination of two or more.

In order to improve the thermal stability during melt-kneading,
Various stabilizers such as a hindered phenol-based antioxidant and a phosphorus-based stabilizer may be used. The addition amount of these stabilizers is preferably 0.05 to 5% by weight.

Examples of hindered phenolic antioxidants include triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3 -(3,5-dibutyl-
4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,5-t-butyl- 4-hydroxy-benzylphosphonate-diethyl ester, tris- (3,
5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-4-methylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane, N, N'-hexamethylenebis (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamamide), octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane and the like.

Examples of the phosphorus-based stabilizer include tris (nonylphenyl) phosphite, triisooctyl phosphite, triisodecyl phosphite, triphenyl phosphite, diphenyl isodecyl phosphite,
Phosphite compounds such as phenylisodecyl phosphite, diisooctyl phenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol-di-phosphite, dioctyl pentaerythritol-di- Phosphite, diisodecylpentaerythritol-di-phosphite, bis (2,4-
And pentaerythritol-di-phosphite compounds such as (di-t-butylphenyl) pentaerythritol.

The flexible polyester resin composition according to the present invention can be used for applications requiring flexibility, heat sealability, fragrance retention, volatilization resistance, etc., for example, a single- or multi-layer food packaging material, coating agent, It can be widely used for building materials. It is also used as a resin modifier in addition to other resins.

As a single-layer packaging material, films, sheets, bag-in-boxes, retort containers, food trays,
Examples include egg packs, hollow containers such as cups, lids for hollow containers, and pipe-shaped containers. The film thickness is usually 5
150 μm, and the thickness of the sheet is usually 150 to 300
μm. Such packaging materials are tasteless and odorless,
Low adsorption and permeation of flavor components, excellent fragrance retention, and excellent volatility resistance. The single-layer packaging material can be manufactured by a conventionally known method.

Examples of the multilayer packaging material include a film, a sheet, a bag-in-box, a retort container, a food tray, and a laminate of two or more layers including a layer made of a flexible polyester resin composition and a base material layer. Examples include egg packs, hollow containers such as cups, lids for hollow containers, and pipe-shaped containers. Here, examples of the material used for the base layer include synthetic resins such as polyethylene, polypropylene, and polyamide, and metal foils such as aluminum foil. When used as a multilayer packaging material, it is preferable that the layer made of the flexible polyester resin composition is the inner layer. Further, the layer made of the flexible polyester resin composition may be a heat seal layer. Such a packaging material has little adsorption and permeation of flavor components, is excellent in fragrance retention, and is excellent in volatility resistance. When the layer made of the flexible polyester resin composition is a heat seal layer, a plastic odor does not occur at the time of heat sealing, and the flavor of the food is not spoiled. The thickness of the multilayer packaging material is usually 150 to 300
μm, and the thickness of each layer is usually 5 to 150 μm.
The multilayer packaging material can be manufactured by a conventionally known method.

The coating agent is used as a coating agent for an inner wall of a metal can, a coating agent for an inner wall of a paper pack, or the like. Metal cans and paper packs having an inner wall coated with a flexible polyester resin composition have less adsorption and permeation of flavor components, and are excellent in fragrance retention. Metal cans and paper packs having an inner wall coated with a flexible polyester resin composition can be manufactured by a conventionally known method.

Examples of the building material include a wallpaper made of a flexible polyester resin composition, a laminated plywood having a surface layer made of the flexible polyester resin composition, and a laminated steel sheet. Wallpaper made of the flexible polyester resin composition is free from bleed-out of the plasticizer and generation of volatile components, and is excellent in preserving the indoor environment. Further, the laminated plywood and the laminated steel sheet do not bleed out or generate volatile components of the plasticizer. The laminated plywood and the laminated steel sheet can be manufactured by a conventionally known method.

The packaging materials and building materials made of the flexible polyester resin composition according to the present invention do not generate toxic gas during incineration, and thus do not cause environmental pollution problems.

[0060]

Industrial Applicability The flexible polyester resin composition according to the present invention is excellent in flexibility and volatility as well as excellent in transparency, and is suitable as a packaging material, a coating agent and a building material.

[0061]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the measurement of various characteristics and the molding of the sheet were performed as follows. (1) Intrinsic viscosity (IV) 1: 1 (weight ratio) of phenol and tetrachloroethane
A 0.5 g / dl sample solution is prepared using the mixed solvent,
The intrinsic viscosity (IV) was calculated from the solution viscosity measured at 25 ° C.

(2) Melting point (Tm) The melting point (Tm) was determined using a differential scanning calorimeter (manufactured by Seiko Instruments Inc.). The dried sample was placed under a nitrogen stream at 270 ° C. × 5
Hold for 1 minute and then use liquid nitrogen at -150 ° C
And held for 10 minutes. This sample was heated at a rate of 10 ° C./min, and the crystal melting temperature was measured.

(3) Press Sheet Forming Method The dried sample was subjected to a press forming machine at a forming temperature of 280 ° C.
A quenched press sheet was prepared by heating and melting in a spacer shape of 100 mm × 100 mm × 1.5 mm and immediately transferring to a press forming machine at 0 ° C. for forming.

(4) Bending test 1.27 cm in width and 6.3 in length cut from a press sheet
Using a tensile tester model 4501 manufactured by Instron, a 5 cm strip-shaped test piece was measured at 23 ° C. and a crosshead speed of 5 mm / min.

(5) Transparency (Haze Value) The dried sample was molded at a molding temperature of 280 ° C. by a press molding machine.
Then, a quenched press sheet having a shape of 30 mm × 30 mm × 0.5 mm was molded by using the method described above, and the transparency (haze value; diffuse reflectance of white light) of the molded product was measured.

(6) Tensile Strength and Elongation Using an Instron Digital Control Universal Material Testing Machine Model 4501, the test piece shape was measured according to JIS K7113-2, a tensile speed of 30 mm / min, and a room temperature of 23 ° C.

(7) Number average molecular weight The number average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC) under the following conditions is shown.

Column: PLgel 5μ MIXD-C 7.5 × 30
2 mm 0 mm (manufactured by Polymer Laboratories) Mobile phase: chloroform (for high performance liquid chromatography, manufactured by Kanto Kagaku) Flow rate: 1.0 ml / min Sample concentration: 0.5% chloroform solution (8) d-limonene adsorption test The dried sample was heated and melted in a molding machine at a molding temperature of 28 ° C. in a spacer shape of 30 mm × 30 mm × 0.5 mm, immediately transferred to a press molding machine at 0 ° C., and subjected to pressure molding to form a quenched press sheet. After measuring the weight of this press sheet, it was immersed in a 100% solution of d-limonene, which is an aroma component, stored in a constant temperature room at 23 ° C., taken out after a predetermined time, wiped the surface with a bleached cotton cloth, and immediately weighed. It was measured. From the weight change of the press sheet before and after d-limonene immersion, the amount of d-limonene adsorbed on the press sheet was calculated and shown as% by weight. (9) Heat seal test The dried sample was molded at a molding temperature of 280 ° C by a press molding machine.
Was heated and melted in a 140 mm × 140 mm × 0.1 mm spacer shape, immediately transferred to a press forming machine at 0 ° C. and pressed to form a quenched press sheet. After leaving this press sheet in a room at 23 ° C. and a relative humidity of 50% for one week, cut out to a width of 20 mm, sandwiched between two pieces of 50 μm soft aluminum, and sandwiched a bar of 100 μm Teflon sheets on both sides. The temperature was changed to 170 ° C, 190 ° C, and 220 ° C under the conditions of a pressure of 0.2 MPa and a heating time of 5 seconds with a sealer, and heat sealing was performed. Next, the width of the heat-sealed portion is 15
mm so as to obtain a T-shaped peel strength measurement sample. The T-peel strength was measured in an indoor environment at 23 ° C. and a relative humidity of 50% using a tensile tester under the conditions of a distance between chucks of 50 mm and a tensile speed of 100 mm / min.

In this example, the following were used as (A) polyethylene terephthalate, (B) an aliphatic polyester, and (C) a crystallization inhibitor. Polyethylene terephthalate (A-1) is obtained from terephthalic acid and ethylene glycol, and has an intrinsic viscosity (IV) of 0.79 in a 1: 1 (weight ratio) mixed solvent of phenol and tetrachloroethane measured at 25 ° C.
dl / g polyethylene terephthalate.

A 10 equipped with a cooling pipe for removing distillate from the aliphatic polyester (B-1) reaction
In a 00 ml four-necked kolben, add dimethyl adipate 34
8.0 g, 365.0 g of propylene glycol and 0.245 g of manganese acetate (0.05 mol% based on the acid)
While stirring under a nitrogen stream, to 220 ° C.
The esterification reaction was carried out by raising the temperature over time, and the reaction rate was 97
% Of the esterification reaction was obtained. 500 g of the obtained esterification reaction product, 0.240 g of antimony acetate (0.042 mol% based on the acid) and 2.5 g of Irganox 1010 ^™ (manufactured by Ciba-Geigy) were placed in a polymerization vessel equipped with a double spiral type stirring blade. After replacing with nitrogen, the number of rotations was 4.2 s ^-1 under reduced pressure.
The temperature was raised to 235 ° C. over 3.5 hours while stirring at
Further, while maintaining 235 ° C., the mixture was maintained for 4 hours while distilling off propylene glycol by-produced under a reduced pressure of 133.3 Pa, and the number average molecular weight obtained by condensation polymerization was 5,030.
Aliphatic polyester.

A 10 equipped with a cooling pipe for removing distillate from the aliphatic polyester (B-2) reaction
Add dimethyl adipate 450.
0 g, ethylene glycol 384.8 g and manganese acetate 0.317 g (0.05 mol% based on the acid) were charged, and the mixture was heated to 220 ° C. over 8 hours while stirring under a nitrogen stream to carry out an esterification reaction. An esterification reaction product having a conversion of 95.4% was obtained. Obtained esterification reaction product 5
50 g, 0.052 g of germanium dioxide (0.021 mol% based on the acid) and 2.75 g of Irganox 1010 ^™ (manufactured by Ciba Geigy) were placed in a polymerization vessel equipped with a double helix-type stirring blade, and after purging with nitrogen, the pressure was reduced. 4.2s rotation speed below
^The temperature was raised to 235 ° C. over 3.5 hours while stirring at ⁻¹ , and further maintained at 235 ° C. under reduced pressure of 133.3 Pa for 4 hours while distilling off by-produced ethylene glycol to reduce the temperature. Number average molecular weight obtained by polymerization is 5,5
70 aliphatic polyesters.

Polysizer P-202 ^™ (Dainippon Ink Chemicals)
An aliphatic polyester having a number average molecular weight of 18,600 and obtained from sebacic acid and propylene glycol.

Polysizer W-4000 ^™ (Dainippon Ink Chemicals)
Industry Co., Ltd.) having a viscosity of 15,000~30,000mPa · s,
Adipic acid-based polyester plasticizer.

[0075]

Example 1 Polyethylene Terephthalate (A-1) 26
8 g, 132 g of Polysizer P-202 ^{™, 5} g of bisphenol full orange hydroxyethyl ether (manufactured by Nippon Steel Chemical Co., Ltd.), 2.0 g of Irganox 1010 ^™ (manufactured by Ciba Geigy) and 0.043 of germanium dioxide
g was placed in a 500 ml polymerization vessel equipped with a double spiral stirrer, and after purging with nitrogen, the temperature was raised to 180 ° C. and 13.3 P
a was kept under reduced pressure for 3 hours. Then 1 to 280 ° C
The temperature was raised over a period of time, and the number of rotations was 4 under a reduced pressure of 39.9 Pa.
Stirred at 2s ^-1 for 2 hours. Various physical properties of the obtained flexible polyester resin composition were measured.

[0076]

Example 2 In Example 1, 2,6-bis (2-
A flexible polyester composition was produced in the same manner as in Example 1 except that (hydroxyethoxy) naphthalene (own product) was used. Various physical properties of the obtained flexible polyester resin composition were measured.

[0077]

Example 3 In Example 1, 1,3-bis (2-
A flexible polyester composition was produced in the same manner as in Example 1 except that (hydroxyethoxy) benzene (manufactured by the company) was used. Various physical properties of the obtained flexible polyester resin composition were measured.

[0078]

Comparative Example 1 Polyethylene Terephthalate (A-1) 26
8 g, 132 g of Polysizer P-202 ^™ , 2.0 g of Irganox 1010 ^™ (manufactured by Ciba Geigy) and 0.043 g of germanium dioxide were placed in a 500 ml polymerization vessel equipped with a double helix-type stirring blade, replaced with nitrogen, and then cooled to 180 ° C. The temperature was raised and maintained under a reduced pressure of 13.3 Pa for 3 hours. Then, the temperature was raised to 280 ° C. over 1 hour, and the mixture was stirred under a reduced pressure of 39.9 Pa at a rotation speed of 4.2 s ⁻¹ for 2 hours. Various physical properties of the obtained polyester resin composition were measured.

[0079]

Example 4 In Example 1, the amount of polyethylene terephthalate (A-1) used was changed to 300 g, and Polysizer P-
202 ^TM except that the amount was 100g of Example 1
A flexible polyester resin composition was produced in the same manner as described above. Various physical properties of the obtained flexible polyester resin composition were measured.

[0080]

Example 5 The procedure of Example 4 was repeated except that 2,6-bis (2-hydroxyethoxy) naphthalene (manufactured by the company) was used instead of bisphenol fluorene hydroxyethyl ether. A hydrophilic polyester resin composition was produced. Various physical properties of the obtained flexible polyester resin composition were measured.

[0081]

Example 6 The procedure of Example 4 was repeated, except that 1,3-bis (2-hydroxyethoxy) benzene (manufactured by the company) was used instead of bisphenol fluorene hydroxyethyl ether. A hydrophilic polyester resin composition was produced. Various physical properties of the obtained flexible polyester resin composition were measured.

[0082]

Comparative Example 2 The amount of polyethylene terephthalate (A-1) used in Comparative Example 1 was changed to 300 g, and Polysizer P-
Except that the was 100g amount of 202 ^TM manufactured flexibility polyester resin composition in the same manner as in Example 1.
Various physical properties of the obtained polyester resin composition were measured.

[0083]

EXAMPLE 7 Instead of Polycizer P-202 ^TM in Example 1, except for using an aliphatic polyester (B-1) in the same manner as in Example 1 to produce a flexible polyester resin composition. Various physical properties of the obtained polyester resin composition were measured.

[0084]

[Comparative Example 3] instead of Polycizer P-202 ^TM in Comparative Example 1 was produced a flexible polyester resin composition in the same manner as in Comparative Example 1 except for using an aliphatic polyester (B-1). Various physical properties of the obtained polyester resin composition were measured.

[0085]

Instead of Polycizer P-202 ^TM in Example 8 Example 1, to produce a flexible polyester resin composition in the same manner in Example 1 except for using an aliphatic polyester (B-2). Various physical properties of the obtained flexible polyester resin composition were measured.

[0086]

Instead of Polycizer P-202 ^TM in Example 9 Example 1, using the aliphatic polyester (B-2), and in place of the bisphenol fluorene dihydroxy ethyl ether, 2,6-bis (2-hydroxyethoxy ) A flexible polyester resin composition was produced in the same manner as in Example 1 except that naphthalene (own product) was used. Various physical properties of the obtained flexible polyester resin composition were measured.

[0087]

Instead of Polycizer P-202 ^TM in Comparative Example 4 Comparative Example 1 was produced a flexible polyester resin composition in the same manner as in Example 1 except for using an aliphatic polyester (B-2). Various physical properties of the obtained polyester resin composition were measured.

[0088]

Comparative Example 5 Melt flow rate: 3.7 g / 10 min, density: 0.923 g / cm ³ , endothermic peak temperature: 110 ° C.
Molding temperature 160 ° C using low density polyethylene
After forming a quenched press sheet having a shape of 30 mm x 30 mm x 0.5 mm by using and measuring the weight. The adsorption test of d-limonene was evaluated. In addition, 140m at a molding temperature of 180 ° C
A quenched press sheet having a shape of mx 140 mm x 0.1 mm was formed, and the heat sea strength was evaluated.

[0089]

Comparative Example 6 Hytrel 5526 ^™ (a block copolymer of polybutylene terephthalate and polyether, manufactured by Du Pont-Toray Co., Ltd., intrinsic viscosity = 1.433dl /
Various physical properties of g) were measured. The press sheet produced from this block copolymer by the above method was opaque.

[0090]

Comparative Example 7 Various physical properties of polyethylene terephthalate (A-1) were measured. Tables 1 to 3 show the above results.
Are shown together. Table 1 shows that the flexible polyester resin composition containing the (C) crystallization-inhibiting component is excellent in transparency and flexibility.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI C08K 5/36 B65D 1/00 A

Claims (21)

[Claims] (A) polyethylene terephthalate,
(B) an aliphatic polyester and (C) a crystallization-inhibiting component, wherein (B) is 10 to 10 parts by weight of (A).
(C) is melt-kneaded at a ratio of 0.1 to 15 parts by weight with respect to 100 parts by weight of the total of (A) and (B) at a ratio of 100 parts by weight. A) a flexible polyester resin composition obtained by subjecting part or all of the above) to a transesterification reaction. 2. The flexible polyester resin composition according to claim 1, wherein the proportion of the aliphatic polyester (B) is 40 to 100 parts by weight based on 100 parts by weight of the component (A). 3. The flexible polyester resin composition according to claim 1, which has a flexural modulus of 1200 MPa or less. 4. The (B) aliphatic polyester is composed of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and 2 carbon atoms.
The flexible polyester composition according to any one of claims 1 to 3, which is obtained from an aliphatic glycol of from 1 to 13, and has a number average molecular weight in the range of 2,500 to 30,000. 5. The flexible polyester composition according to claim 4, wherein (B) the aliphatic polyester is at least one selected from the following (i) to (iii): (i) sebacic acid and propylene (Ii) Polyester obtained from adipic acid and propylene glycol (iii) Polyester obtained from adipic acid and ethylene glycol 6. The flexible polyester resin composition according to claim 1, wherein the (C) crystallization inhibitor is an aromatic diol ethylene oxide adduct. 7. The flexible polyester resin composition according to claim 6, wherein the aromatic diol ethylene oxide adduct is represented by any one of the following general formulas (I) to (III): (In the formula, m and n may be the same or different from each other and may be an integer of 1 to 5, R ¹ to R ⁸ may be the same or different from each other, and may be a hydrogen atom, a boron atom or a methyl group. X is a direct bond, -O-,-
CH ₂ —, —S—, —SO ₂ —, Embedded image (In the formula, m and n may be the same or different, and are each an integer of 1 to 5.) (In the formula, m and n may be the same or different, and are each an integer of 1 to 5.) 8. The aromatic diol ethylene oxide adduct comprises bisphenol full orange hydroxyethyl ether, 2,6-bis (2-hydroxyethoxy) naphthalene, 1,3-bis (2-hydroxyethoxy) benzene and 4,4 The flexible polyester resin composition according to claim 6, which is at least one compound selected from the group consisting of '-(1-phenylethylidene) bis (2-hydroxyethoxyphenol). 9. A sheet comprising the flexible polyester resin composition according to claim 1. 10. A film comprising the flexible polyester resin composition according to claim 1. A retort container comprising the flexible polyester resin composition according to any one of claims 1 to 8. 12. A cup comprising the flexible polyester resin composition according to any one of claims 1 to 8. 13. A lid for a cup, comprising the flexible polyester resin composition according to claim 1. Description: 14. A packaging material comprising a laminate of a layer made of the flexible polyester resin composition according to claim 1 and a base material layer. 15. The packaging material according to claim 14, wherein the layer made of the flexible polyester resin composition is a heat seal layer. 16. The method according to claim 1, wherein the base material layer is a metal foil layer.
16. The packaging material according to 4 or 15. 17. A metal can having an inner wall coated with the flexible polyester resin composition according to claim 1. Description: 18. A paper pack comprising an inner wall coated with the flexible polyester resin composition according to any one of claims 1 to 8. A wallpaper comprising the flexible polyester resin composition according to any one of claims 1 to 8. 20. A laminated plywood laminated with the flexible polyester resin composition according to any one of claims 1 to 8. 21. A laminated steel sheet laminated with the flexible polyester resin composition according to any one of claims 1 to 8.