JPH06228425A - Polyester resin composition and packing material using the same - Google Patents

Abstract

PURPOSE:To obtain a composition useful as packing material, etc., having excellent moldability, processability, mechanical characteristics, heat resistance, etc., comprising specific two polyesters and a polycarbonate. CONSTITUTION:The composition comprises (A) a polyester having a dicarboxylic acid component composed of (i) 40-100mol% terephthalic acid, (ii) 0-60mol% aromatic dicarboxylic acid except the component (i) and (iii) a dicarboxylic acid component containing 0-20mol% aliphatic or alicyclic dicarboxylic acid and a glycol component composed of (iv) 40-100mol% ethylene glycol and (v) 60-0mol% aliphatic or alicyclic glycol except the component (iv), (B) a polyester having a dicarboxylic acid component composed of 40-100mol% of the component (i), 0-60mol% of the component (ii) and 0-20mol% of the component (iii) and a glycol component composed of 0-90mol% of the component (iv) and (vi) 10-100mol% 1,4-cyclohexanedimethanol and (C) a polycarbonate in the weight ratio of the component B to the components B+C of 0.01-0.5 and >=50 pts.wt. of the component C based on 100 pts.wt. of total of the components A to the component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding processability, mechanical properties, heat adhesion, a polyester resin composition having excellent heat resistance capable of withstanding retort sterilization, and a packaging material using the same. The composition of the present invention, especially foods, pharmaceuticals,
It is suitable for use as a packaging material for packaging cosmetics and the like, and has very little adsorption of medicinal components, aroma components, etc. possessed by the above-mentioned packaged article, and transferring the odor of the packaging material itself to the article. It is used as a packaging material that can be stored in good condition without heat treatment (retort treatment) for sterilizing the contents.

[0002]

2. Description of the Related Art Conventionally, as a packaging material (including a film, a sheet, a container, etc.) for various foods, beverages, pharmaceuticals, cosmetics, etc., it is lightweight and easy to manufacture. Various plastic bottles, sheets, bags, etc. are used. Further, a laminate obtained by laminating a plastic sheet and a cardboard is preferably used for so-called paper packs of milk, soft drink, alcoholic beverages, soy sauce and the like. As plastics used for these, polyethylene, polypropylene, ethylene-vinyl acetate copolymer and the like are used. However, such a resin
There is a drawback in that the aroma and quality of the packaged item is deteriorated because the aroma component of the packaged item is absorbed or diffused. Further, it has a drawback that the odor of the resin itself is transferred to the packaged article. In addition, as a sealant material having heat resistance that can withstand retort sterilization, etc.,
Among the above olefin polymers, polypropylene having a relatively high melting point is used. Polypropylene is
Although it has excellent heat sealability and heat resistance, the drawbacks and the like shown by the above-mentioned olefin-based polymer have not been solved.

Other heat resistant materials include polyethylene terephthalate (hereinafter abbreviated as PET) that has been stretched and heat set. Since the PET-based packaging material is hygienic and has excellent mechanical properties, the contents can be sufficiently protected. Moreover, since it is difficult to adsorb the aroma component of food, the scent of the contents can be maintained. However, since it is stretched and heat-fixed, it has a drawback that the heat-sealing property is poor, and it cannot be used as a packaging material (sealant material) for retort foods or general foods under the present circumstances. On the other hand, unstretched amorphous copolyesters generally have a glass transition temperature of at most 70 to 80 ° C and have good heat sealability, but at a retort treatment temperature (usually about 121 minutes at 121 ° C for about 30 minutes). Has the drawback of not being able to withstand enough.

In general, foods, the above-mentioned pharmaceuticals, cosmetics and the like have odorous components. For example, soft drinks such as orange juice are D-limonene, decanal and the like, and confectionery is methylsulfate. Rate, vanillin, etc., soy sauce and sauce, 3-methylthiol propyl alcohol, eugenol, etc.
-Menthol and the like, and cosmetics and soaps contain fragrances such as benzaldehyde, citral and zeranyl acetate. Therefore, a resin that does not adsorb or desorb the odorous components as described above is desired as a packaging material application or a sealant application. By further improving the resin to have heat resistance (tolerant to retort treatment), its application can be dramatically expanded.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art. The object is to endure molding processability, mechanical properties, heat adhesiveness, retort sterilization, etc. Another object of the present invention is to provide a polyester resin composition having excellent heat resistance which can be suitably used for packaging materials such as foods, pharmaceuticals and cosmetics. Another object of the present invention is to provide a packaging material which is extremely unlikely to adsorb medicinal components, aroma components, etc. possessed by an article intended for packaging, and which does not transfer the odor of itself to the article. Especially. Still another object of the present invention is to provide a packaging material obtained by processing the above resin composition into a film or forming a laminated body in which the films are laminated.

[0006]

[Means for Solving the Problems] In order to solve the above problems, the present inventors have earnestly studied, studied, and made efforts to finally complete the present invention. That is, the present invention is a polyester resin composition containing polyester (A), polyester (B) and polycarbonate (C), wherein the polyester (A) is 40 to 1 terephthalic acid.
00 mol%, aromatic dicarboxylic acids other than terephthalic acid 0
~ 60 mol% and 0 aliphatic or alicyclic dicarboxylic acids
Obtained from a dicarboxylic acid component containing 20 to 20 mol% of ethylene glycol and a glycol component containing 40 to 100 mol% of ethylene glycol and 60 to 0 mol% of an aliphatic or alicyclic glycol other than ethylene glycol, and the polyester (B).
Is a dicarboxylic acid component containing 40 to 100 mol% of terephthalic acid, 0 to 60 mol% of an aromatic dicarboxylic acid other than terephthalic acid, and 0 to 20 mol% of an aliphatic or alicyclic dicarboxylic acid, and 0 to 90 mol of ethylene glycol. % And 1,
A polyester obtained from a glycol component containing 10 to 100 mol% of 4-cyclohexanedimethanol, wherein the total of the components (A), (B) and (C) is 100.
When expressed as parts by weight, the weight ratio of the component (B) to the total of the components (B) and (C) is 0.01 to 0.5, and the content of the component (C) is 50 parts by weight or more. And a packaging material containing the same.

The polyester (A) contained in the composition of the present invention is 40 to 100 mol% terephthalic acid, preferably 55 to 100 mol%, and 0 to 60 mol% aromatic dicarboxylic acid other than terephthalic acid, preferably 0-45 mol%,
And 0 to 20 mol% of aliphatic or alicyclic dicarboxylic acid,
A dicarboxylic acid component preferably containing 0 to 10 mol%,
40 to 100 mol% of ethylene glycol, preferably 5
It is obtained from a glycol component containing 0 to 100 mol%, and 60 to 0 mol%, preferably 50 to 0 mol% of an aliphatic or alicyclic glycol other than ethylene glycol.
In the above dicarboxylic acid component, when the proportion of terephthalic acid is less than 40 mol% and the proportion of aromatic dicarboxylic acid other than terephthalic acid is more than 60 mol%, the moldability of the resin composition is lowered, and It is not preferable because the mechanical properties and heat resistance of the molded product (film etc.) to be obtained are lowered. When the proportion of the aliphatic and alicyclic dicarboxylic acids exceeds 20 mol%, the surface hardness, strength physical properties, and heat resistance of the obtained molded product deteriorate. On the other hand, in the glycol component, the proportion of ethylene glycol is less than 40 mol% and the proportion of aliphatic or alicyclic glycol other than ethylene glycol is 60 mol%.
If it exceeds, the molding processability of the obtained resin composition will deteriorate, and if the appearance of the obtained molded product is impaired, the mechanical properties will also deteriorate, which is not preferable.

Specific examples of the dicarboxylic acid component constituting the polyester (A) contained in the resin composition of the present invention include terephthalic acid, orthophthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid and biphenyldicarboxylic acid. Aromatic dicarboxylic acid other than terephthalic acid,
Aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and dimer acid,
And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, and terephthalic acid and isophthalic acid are particularly preferable. Specific examples of the glycol component constituting the polyester (A) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 3-methyl. Aliphatic glycols other than ethylene glycol such as -1,5-pentanediol and neopentyl glycol, and 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and 2,2-bis Examples thereof include alicyclic glycols such as (4′-β-hydroxyethoxyphenyl) propane, and ethylene glycol is particularly preferable.

The polyester (B) included in the present invention is
40-100 mol% terephthalic acid, preferably 55-1
00 mol%, aromatic dicarboxylic acids other than terephthalic acid 0
To 60 mol%, preferably 0 to 45 mol%, and a dicarboxylic acid component containing 0 to 20 mol%, preferably 0 to 10 mol% of an aliphatic or alicyclic dicarboxylic acid, and 0 to 90 mol% of ethylene glycol, Preferably 0-80 mol%,
And 1,4-cyclohexanedimethanol 10 to 10
It is obtained from a glycol component containing 0 mol%, preferably 20 to 100 mol%. In the dicarboxylic acid component constituting the polyester (B), when the proportion of terephthalic acid is less than 40 mol% and the proportion of aromatic dicarboxylic acid other than terephthalic acid is more than 60 mol%, the polyester (A) is as much as However, it is not preferable because the moldability of the resin composition is deteriorated, and the heat resistance and strength physical properties of the resulting molded product are deteriorated.

As the dicarboxylic acid component of the polyester (B), the same dicarboxylic acid component as the dicarboxylic acid component of the polyester (A) can be used. Preferably, terephthalic acid and isophthalic acid are used. As the glycol component, ethylene glycol and 1,4-cyclohexanedimethanol are used.

The polyester (B) has the functions of improving the compatibility between the polyester (A) and the polycarbonate described below and adjusting the heat resistance of the polycarbonate (capable of withstanding retort sterilization). The action is
1,4 contained in the glycol component of polyester (B)
-Derived from the interaction between the monomer component of cyclohexanedimethanol and the bisphenol component of polycarbonate. Therefore, in the glycol component of the polyester (B), when the ratio of 1,4-cyclohexanedimethanol is less than 10 mol%, the compatibility of the polyester (B) and the polycarbonate decreases, and the resin composition of the present invention Molding processability, mechanical properties and the like are deteriorated, which is not preferable.

In order to further improve the compatibility of the polyester (B) with the polycarbonate (C) of the resin composition of the present invention and the polyester (B), the mechanical properties and molding processability of the molded article are improved. , Polyester (B)
A modified polyester obtained by graft-polymerizing an unsaturated dicarboxylic acid or an anhydride thereof may be used. Examples of the unsaturated dicarboxylic acid used as the modifying agent for the modified polyester include maleic acid, fumaric acid, itaconic acid and the like. It is also possible to use acrylic acid, crotonic acid or the like together with these dicarboxylic acids. Further, anhydrides of these unsaturated dicarboxylic acids may be used. Maleic anhydride is preferably used. As a modification method, for example, the unsaturated dicarboxylic acid or its anhydride is added to the unmodified polyester (B) at a ratio of 5 to 60 mol, preferably 10 to 50 mol, per 10 ⁶ g of the unmodified polyester, and It is obtained by graft polymerization by the method. This graft polymerization is carried out in a solvent such as 1,4-dioxane or in a molten state. For graft polymerization,
An organic peroxide is used as a catalyst, and examples of the organic peroxide include dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide and the like. Further, when the resin composition containing the polyester (A), the polyester (B) and the polycarbonate (C) is melt-kneaded, the unsaturated dicarboxylic acid and the organic peroxide are simultaneously charged, and the grafting reaction is performed at the time of melting and kneading. Done,
It is also possible to produce modified polyesters. The modified polyester thus obtained has a function of further improving the compatibility between the polyester (A) and the polycarbonate described below.

In order to improve the flow characteristics of the resin composition of the present invention, trifunctional or higher polycarboxylic acid may be copolymerized with each of the polyester (A) and the polyester (B). Examples of the polycarboxylic acid include trimellitic acid, pyromellitic acid, trimesic acid, and anhydrides of these compounds. The trifunctional or higher polycarboxylic acid is copolymerized in an amount of 5 mol% or less, preferably 0.5 to 3 mol%, based on the total dicarboxylic acid components of the polyester (A) and the polyester (B). When the content of the trifunctional or higher polycarboxylic acid exceeds 5 mol%, the moldability of the obtained resin composition deteriorates, which is not preferable. Similarly, in order to improve the flow characteristics of the resin composition of the present invention, a trifunctional or higher functional polyol may be copolymerized with each of the polyester (A) and the polyester (B). Examples of the polyol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. This 3
The functional or higher polyol is copolymerized in an amount of 5 mol% or less, preferably 0.5 to 3 mol%, based on all the glycol components of the polyester (A) and the polyester (B). The content of trifunctional or higher polyol is 5 mol%
If it exceeds the range, the resin composition obtained will have poor moldability, which is not preferable.

The reduced viscosity of the polyester (A) and the polyester (B) contained in the resin composition of the present invention is preferably 0.6 or more. When the reduced viscosity is less than 0.6,
It may not be possible to impart desired mechanical properties, particularly strength physical properties, to the obtained molded product, which is not preferable. The reduced viscosity referred to here is a value measured at 30 ° C. using a phenol-tetrachloroethane mixed solvent (60/40 V / V).

The polycarbonate (C) contained in the resin composition of the present invention is a polycarbonate resin containing dihydroxyphenylalkane or diphenol as a raw material, and is a copolymer composed of a combination of the respective raw materials. Good. There is no limitation on the method for producing the polycarbonate (C), and the polycarbonate (C) can be obtained by adopting a known method such as a transesterification method or a phosgene method. Weight average molecular weight of the obtained polycarbonate (measured by light scattering method)
Is preferably 10,000 to 100,000, more preferably 20,000 to 80,000. If the weight average molecular weight of the polycarbonate is less than 10,000, the strength properties of the obtained molded article are slightly deteriorated, and conversely 100,0.
When it exceeds 00, the flow characteristics of the obtained resin composition are slightly deteriorated, and as a result, the moldability is deteriorated, which is not preferable.

In the polycarbonate (C), the polycarbonate (C) may have a branched structure in order to improve the flow characteristics of the resin composition of the present invention. In the case of forming a branched structure, a small amount, preferably about 0.05 to 3.0 mol% of a trifunctional or more polyfunctional compound, particularly a compound having three or more phenolic hydroxy groups is cocondensed by a known method. It can be obtained by Examples of the compound having 3 or more phenolic hydroxy groups include chloroglucinol, 4,6
-Dimethyl-2,4,6-tri (4-hydroxyphenyl) hept-2-ene, 4,6-dimethyl-2,4,6
-Tri (4-hydroxyphenyl) heptane, 1,3
5-tri (4-hydroxyphenyl) benzene and the like. If the content of the above trifunctional or higher polyfunctional compound exceeds 5 mol%, the moldability of the obtained resin composition deteriorates, which is not preferable.

The thermoplastic polyester resin composition of the present invention has (B) relative to the total of (B) and (C) components, when the total of (A), (B) and (C) components is 100 parts by weight. The weight ratio of the components is 0.01 to 0.5, preferably 0.01 to 0.3, and the component (C) is 50 parts by weight or more, preferably 50 to 90 parts by weight, particularly preferably 5 parts by weight.
0 to 85 parts by weight. However, polyester (A) is 1
The polyester (B) is contained in a proportion of 0 to 50 parts by weight.
The content of is preferably 0.5 to 40 parts by weight. When the weight ratio of the component (B) to the total of the components (B) and (C) is less than 0.01, it becomes difficult to improve the compatibility between the polyester (A) and the polycarbonate, and the obtained molding is obtained. The toughness of the product is insufficient, and the poor heat-sealing property of polycarbonate is directly reflected in the molded product, which is not preferable. Conversely, if it exceeds 0.5,
Since the excellent heat resistance of the polycarbonate (C) is too low in the polyester (B), the heat resistance of the obtained molded article is lowered, which is not preferable.

Polycarbonate (C) has the effects of delaying the crystallization of polyester (A) and lowering its crystallinity. Therefore, the impact resistance of the polyester (A) is improved. It also has the effect of imparting heat resistance and toughness to the obtained molded product. Therefore, when the content of the polycarbonate is less than 50 parts by weight, the crystallization of the polyester (A) cannot be delayed and the crystallinity of the polyester (A) becomes high, and as a result, the molded article obtained by using the composition can be obtained. The impact resistance becomes low. Further, it is not preferable because the impact resistance inherent in polycarbonate cannot be expressed and the heat resistance is lowered. On the other hand, when it exceeds 90 parts, the heat resistance of the obtained molded product is good, but the moldability of the resin composition is deteriorated and the heat seal property is deteriorated, which is not preferable.

The resin composition of the present invention may contain the following resins singly or in combination as long as the physical properties thereof are not impaired. For example, thermoplastic resin such as styrene resin, acrylic resin, fluorine resin, polyamide resin, polyarylate resin, polysulfone, polyolefin (for example, ethylene-vinyl acetate copolymer, polyester elastomer, various ionomers) and phenol resin, melamine resin Thermosetting resins such as unsaturated polyester and silicone resin.

The resin composition of the present invention may further contain various additives in order to improve other properties, as long as the physical properties are not impaired. For example, a nucleating agent may be contained for the purpose of increasing the crystallinity of the resin and improving the productivity at the time of molding, and the material of the nucleating agent is an inorganic substance (for example, alkaline earth metal such as calcium carbonate and magnesium carbonate). Alkaline earth metal sulfates such as carbonates, calcium sulfate, metal oxides such as titanium oxide, aluminum oxide and zinc oxide,
Talc, graphite, aluminum silicate, clay, etc., metal salts of organic acids (eg stearate, benzoate, salicylate, tartrate, montanate, terephthalate, etc.) and α-olefins and α, β -Ionic copolymers composed of unsaturated carboxylic acid salts and the like.

In order to impart flame retardancy to the composition of the present invention, a flame retardant and a flame retardant aid may be contained. Examples of the flame retardant include decabromobiphenyl ether, octabromobiphenyl ether, hexabromobiphenyl ether, halogenated polycarbonate oligomer (for example, polycarbonate oligomer produced from brominated bisphenol A as a raw material), halogenated epoxy compound,
And halogen-containing compounds such as halogenated polystyrene oligomers (eg tribromostyrene oligomer), phosphorus compounds and phosphorus-nitrogen compounds such as phosphonamide. Further, examples of the flame retardant aid include antimony trioxide and the like. Further, in order to improve the heat resistance of the composition of the present invention, an antioxidant such as a hindered phenol compound and a sulfur compound or a heat stabilizer such as a phosphorus compound may be contained. Examples of the hindered phenol compound include pentaerythrityl-tetrakis [3- (3 ', 5'-di-t-butyl-4'-hydroxydiphenyl) propionate], octadecyl-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-butylidene-bis (2-t-butyl-5-methylphenol) and the like can be mentioned. Examples of sulfur compounds include 4,4′-
Thiobis (2-t-butyl-5-methylphenol), MARK AO-23 (manufactured by Adeka Argus)
And MARK AO-412S (manufactured by Adeka Argus Co., Ltd.) and the like. Examples of phosphorus compounds include phosphoric acid, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, and other phosphoric acid esters, trimethyl phosphite, and phosphorous acid. Phosphorous acid esters such as triethyl, triphenyl phosphite, phosphonic acid, phenyl phosphonic acid, phenyl phosphonic acid, phenyl phosphonic acid and its derivatives, phosphinic acid, phenyl phosphinic acid, dimethyl phosphinic acid, etc. And the derivatives thereof. Of these, particularly preferred are (phosphite) esters such as trimethyl phosphate, triphenyl (phosphite), and the like.
These phosphorus compounds can be used alone or in combination of two or more kinds.

Further, in order to improve the melt viscosity stability and the hydrolysis resistance of the composition of the present invention, various epoxy compounds may be contained. Specifically as an epoxy compound,
Bisphenol A type epoxy compound obtained by reacting bisphenol A and epichlorohydrin, aliphatic glycidyl ether formed by reaction of various glycols and glycerol with epichlorohydrin, novolak type epoxy compound obtained from novolak resin and epochlorohydrin, alicyclic group An alicyclic compound type epoxy compound obtained from the compound is preferably used. Particularly preferred epoxy compounds include diglycidyl ethers of bisphenol A type epoxy compounds and low molecular weight polyethylene glycols, and diglycidyl esters of aromatic dicarboxylic acids.

Examples of additives other than the above include ultraviolet absorbers, colorants, lubricants, antistatic agents, foaming agents, fillers and reinforcing agents. When the above fillers, reinforcing agents, etc. are added to the resin composition of the present invention, a silane coupling agent or the like may be contained in order to improve the adhesiveness between these additives and the resin.

The composition of the present invention comprises the above polyester (A), polyester (B) and polycarbonate (C).
Further, various additives are mixed as necessary to obtain the resin composition of the present invention, and a known method can be adopted for mixing these components. For example, all blending ingredients are blended at the same time with a blender such as a blender or a kneader or an extruder, a method of homogenizing, a part of the blending ingredients are mixed with the above blender, and the remaining ingredients are mixed, A method of homogenizing is included. Most commonly, the previously dry blended composition is melt-kneaded in a further heated extruder and extruded into a wire, then cut to the desired length and granulated to form pellets. As a further alternative, during the preparation of the polyester (A), before the polycondensation reaction, after the polycondensation reaction, or during the polycondensation reaction, the polyester (B), the polycarbonate (C) and, if necessary, other components are added. A method of adding and mixing can also be adopted.

A packaging material is prepared by the usual method using the resin composition of the present invention, and the method is not particularly limited. For example, the components of the above composition are mixed, melted and kneaded, or the pellets obtained by previously melting and kneading the components are melted and molded by an appropriate method. For example, a film or sheet can be obtained by melting sufficiently dried pellets and performing extrusion molding. Alternatively, the bottle is manufactured by performing injection molding. The film or sheet may be coated on a base material used as a protective layer or a decorative layer to form a laminate. Examples of the substrate include synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, nylon and poval, metal foils such as aluminum foil, and paper. The above-mentioned laminate is, for example, a method of directly extruding a resin composition on a base material to form a resin layer, forming the resin composition in a film shape in advance, and then pasting it on the base material using a known adhesive. And the like.

Of the packaging materials of the present invention, the above-mentioned film or sheet is usually used by being colored and used as a packaging film, a packaging sheet, or a bag. The bottle is suitably used as a container for various beverages, liquid medicines, cosmetics and the like. The above laminated body is milk,
It is suitable for applications such as so-called paper packs for juice and alcoholic beverages.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, all parts are parts by weight,
Each physical property value was measured by the following methods. Film formability: It was evaluated by visual observation in three grades of ◯, Δ and ×. (◯: thickness and width are uniform, Δ: edge is slightly wavy, width is not uniform, x: cannot be pulled at all) ・ Tensile strength and tensile elongation: JIS Z 170
It measured based on 2. Peeling adhesive strength: A film having a thickness of 50 μm adjusted according to the present invention is cut into a size of 5 cm × 10 cm. Separately, a polyester film having a thickness of 25 μ (E-5000, manufactured by Toyobo Co., Ltd.) was cut into the same size, and this was laminated on the above film and bent in half, and one end in the longitudinal direction was 1 cm wide × Heat seal over a length of 5 cm.
Heat sealing is performed at a pressure of 2 kgf / cm ² and 150 ° C. for 5
Went for a second. The T-type peeling adhesive strength of the obtained film was measured at 25 ° C. using a tensile tester (Tensilon RTM-100, manufactured by Toyo Baldwin Co., Ltd.). The pulling speed at this time was 300 mm / min. -Retort resistance: A film having a thickness of 50 µm adjusted according to the present invention was cut into a size of 10 cm x 10 cm, and each sample was heat-treated in a retort container at 121 ° C for 30 minutes. The degree of whitening and the degree of deformation of each film after the treatment were visually evaluated for ⊚, ○, Δ, and × (the degree of whitening and deformation was large in the order of ⊚ → ○ → Δ → ×).

Examples 1 to 15 and Comparative Examples 1 to 9 The components of polyester (A) shown in Table 1 were used, and the components were subjected to transesterification reaction, and then polycondensed at 260 ° C. under high vacuum to obtain polyesters. (A) was obtained. Next, each component of the polyester (B) shown in Table 1 was used, and the polyester (B) was prepared in the same manner as above. Examples of the polycarbonate include Examples 1 to 9, 12 to 15 and Comparative Examples 1 to 1.
6, 8 to 9 used Iupilon S-2000 (weight average molecular weight 2.5 × 10 ⁴ , Mitsubishi Gas Chemical Co., Inc., glass transition temperature = about 150 ° C.), and Examples 10 and 11 and Comparative Example 7 were used. "APEC HT KU 1-9350" (copolycarbonate resin, manufactured by Bayer) was used.

Next, the above polyester (A), polyester (B), and polycarbonate (C) were charged into a twin-screw extruder (manufactured by Ikegai Co., Ltd.) at a ratio shown in Table 1, and 250
C. and 280.degree. C. (in the case of Examples 10 and 11 and Comparative Example 7) were melt-kneaded, and this was extruded from a nozzle and pelletized. The obtained chips were vacuum dried at 70 ° C. for 20 hours. The dried chips are placed in a film forming machine with an inner diameter of 40 mm (manufactured by Nikko Co., Ltd.) to form a film and have a thickness of 50 μm.
I got a film of. The results are shown in Table 2.

[0030]

[Table 1] In Table 1, the numerical value of each polyester item is mol%,
And the blending rate of polyester (A), polyester (B), and polycarbonate shows a weight ratio. IV
Indicates reduced viscosity. TPA is terephthalic acid, IPA is isophthalic acid, EG is ethylene glycol and CHDM
Indicates 1,4-cyclohexanedimethanol. The reduced viscosity is a value measured at 30 ° C. in a phenol-tetrachloroethane mixed solvent (60/40 V / V).

[0031]

[Table 2]

[0032]

As is clear from Table 2, the composition of the present invention is excellent in molding processability, mechanical properties, thermal adhesiveness and retort resistance (heat resistance), and therefore, the polyester resin composition of the present invention. The packaging material using the product is extremely unlikely to adsorb medicinal components, aroma components, etc. possessed by the packaged product, does not transfer the odor possessed by the packaging product to the product, and sterilizes the contents. Heat treatment (retort treatment)
It is possible to store the article in good condition. Therefore, the packaging material of the present invention can be suitably used as a packaging material for packaging foods, pharmaceuticals, cosmetics and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08G 63/199 NNC 7107-4J

Claims (2)

[Claims] 1. A polyester resin composition containing a polyester (A), a polyester (B) and a polycarbonate (C), wherein the polyester (A) comprises:
40-100 mol% of terephthalic acid, 0-60 mol% of an aromatic dicarboxylic acid other than terephthalic acid, and a dicarboxylic acid component containing 0-20 mol% of an aliphatic or alicyclic dicarboxylic acid, and 40-100 mol% of ethylene glycol And a glycol component containing 60 to 0 mol% of an aliphatic or alicyclic glycol other than ethylene glycol, wherein the polyester (B) contains 40 to 100 mol% of terephthalic acid and an aromatic dicarboxylic acid other than terephthalic acid. ~ 60
A dicarboxylic acid component containing mol% and 0 to 20 mol% of an aliphatic or alicyclic dicarboxylic acid;
A polyester obtained from a glycol component containing ˜90 mol% and 1,4-cyclohexanedimethanol 10 to 100 mol%, wherein the total of the components (A), (B) and (C) is 100 parts by weight. Then, the weight ratio of the component (B) to the total of the components (B) and (C) was 0.
A polyester resin composition having a content of 01 to 0.5 and containing (C) component in an amount of 50 parts by weight or more. 2. A packaging material containing the polyester resin composition according to claim 1.