JPH09176464A - Gas barrier container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier container being transparent and excellent in gas barrier properties and being in the form of a bottle, a cup or another shaping. SOLUTION: A bottle having gas barrier properties and made from a transparent polyester/polycarbonate composition, more particularly a bottle or a container made from a transparent polyester/polycarbonate composition prepared by melt-kneading a polycarbonate and a polyester in the presence of a transesterification catalyst and/or a proton acid and having gas barrier properties and mechanical strengths is provided. The transparent polyester/ polycarbonate composition used is a composition having a single glass transition point and a single-phase morphology.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to foods and drinks, pharmaceuticals,
The present invention relates to a container having a gas barrier property, which is used as a material for packaging various other articles. The containers mentioned here include containers of various shapes such as a bottle (bottle shape), a cylinder shape, a cup shape, a box shape, an ellipse shape, and a polygonal shape, and the size, the depth, the presence / absence of a lid, and the opening It is not affected by the shape.

[0002]

2. Description of the Related Art Polyethylene terephthalate (hereinafter PE
T) is excellent in mechanical strength, chemical stability, transparency, hygiene, and aroma retention, and is lightweight and inexpensive, so it is widely used as various sheets and containers for packaging materials. In particular, the growth as a container for carbonated drinks, fruit juice drinks, liquid seasonings, edible oils, liquors and wine is remarkable.

Such a PET is, for example, a bottle-shaped container,
That is, in the case of a bottle, a preform for a hollow molded body is molded by an injection molding machine, and this preform is stretch-blown in a mold having a predetermined shape.

When the transparent PET bottle molded in this manner is subjected to a heat treatment for the purpose of sterilization or the like, crystallization progresses and it becomes cloudy, and the transparency cannot be maintained. Further, when the crystallization further progresses, there is a problem that the shape cannot be maintained due to shrinkage due to the crystallization.

Also, it is difficult to use a large bottle due to its insufficient impact strength.

On the other hand, polycarbonate is excellent in transparency, hygiene, mechanical strength, especially impact strength, and is used for various purposes. It is also suitable as a large container because it has higher heat resistance than transparent PET, has no turbidity or dimensional change even after sterilization, and has excellent impact strength.

Further, it has a high fragrance retaining property, and for example, polycarbonate is exclusively used for a curry roux container.

[0008] However, food applications having a low gas barrier property, such as a large-sized water bottle container, which have a low gas barrier property and are averse to oxygen, have a problem in terms of storability of the internal solution.

There has been a demand for transparent bottles and containers having both the excellent mechanical and chemical properties of these resins and having a good gas barrier property.

In order to improve these problems, a composition obtained by ordinary kneading, for example, kneading of polycarbonate and polyester such as polyethylene terephthalate or polybutylene terephthalate with an extruder or the like is a polyethylene terephthalate or polybutylene terephthalate. Transparency is lost by the addition of.

This is because polycarbonate is essentially incompatible with polyesters such as polyethylene terephthalate and polybutylene terephthalate, so that independent phases are formed and the polyester phase is crystallized, so that the transparency is improved. Is thought to be lost. Thus, it was difficult to obtain a transparent composition only by ordinary kneading.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above problems of the prior art by using PET.
By providing a bottle and a container using a transparent polyester / polycarbonate composition which has higher heat resistance and transparency than that of polycarbonate, has better gas barrier properties and moldability than polycarbonate, and is also excellent in mechanical strength. is there

[0013]

Means for Solving the Problems As a result of earnest research, the present inventors have found that when kneading polyester and polycarbonate,
By using a transparent bottle and container using a transparent polyester / polycarbonate composition obtained by adding a transesterification catalyst and / or a protonic acid, etc., the gas barrier property is higher than that of polycarbonate, and sterilization treatment etc. It was found that a transparent container without whitening or dimensional change can be obtained even by performing high temperature treatment.

Such a transparent polyester / polycarbonate composition can be produced by a method of transesterifying a polyester oligomer and a polycarbonate oligomer in a reaction layer (see JP-A-1-236235) or a terminal hydroxyl group (phenol) of a polycarbonate. (A hydroxyl group) concentration is increased to shorten the reaction time (see Japanese Patent Application Laid-Open No. 3-203956) or a method for adding a transesterification reaction catalyst to enable transparentization in a short time in an extruder (this application) It can be obtained by Japanese Patent Application No. 7-108321 and Japanese Patent Application No. 7-108322. Among these production methods, an extruder with a catalyst added is used from the viewpoint of production simplicity and economy. The method is preferred.

The container produced from the transparent polyester / polycarbonate composition produced by the above-mentioned production method can obtain a composition having an arbitrary glass transition temperature by changing the polyester / polycarbonate composition ratio.

The transparent polyester / polycarbonate composition preferably has a single glass transition point and a single morphology (transmission electron microscope observation).

For example, those having a relatively low progress of transesterification reaction are transparent at the initial stage when formed into a film or the like, but by stretching or heat treatment (a temperature near the glass transition point or higher). It can be crystallized, and in that case, it can be used as an indicator utilizing the whitening phenomenon due to crystallization while improving chemical resistance and gas barrier properties. On the other hand, there are problems such as opacity and dimensional change due to crystallization.

On the other hand, a transparent polyester / polycarbonate composition in which the transesterification reaction has proceeded sufficiently is
The transparency can be maintained even after a heat treatment (heat treatment) at a temperature near the glass transition temperature or higher. Regarding the retention of transparency, the difference in haze (%) between the initial stage of a molded article and that after heat treatment is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and most preferably 1 or less. . For example, there is a feature that the transparency can be maintained even when a high temperature treatment such as a sterilization treatment used for food use or medical use is performed. Further, there is no problem of becoming opaque during the molding process or when the molded product is used under heating. Also,
By adjusting the composition ratio, there is a feature that even if the food is reheated by a microwave oven or the like, there is no deformation or cloudiness, and a container with good visibility can be manufactured.

As described above, since the bottle and the container using the transparent polyester / polycarbonate according to the present invention have a higher gas barrier property than polycarbonate, they can be used as a material for foods, drinks, pharmaceuticals, medical products and other various articles. It is suitable.

Further, since the melt viscosity is higher than that of polyethylene terephthalate used for ordinary bottles, the blow moldability is good and direct blow molding is possible.

The transparent polyester / polycarbonate composition used in the present invention is, for example, C) transesterification catalyst and / or D) protonic acid and / or its derivative when kneading A) polycarbonate and B) polyester. Or by adding C) a transesterification catalyst, D) a protonic acid and / or its derivative, and E) a compound having a hydroxyl group.

The component A) polycarbonate is an aromatic homopolycarbonate or copolycarbonate produced by reacting an aromatic dihydroxy compound with a carbonate precursor.

Further, the polycarbonate of the present invention may be branched. Such branched polycarbonates are obtained by reacting polyfunctional aromatic compounds with aromatic dihydroxy compounds and carbonate precursors. Representative examples of polyfunctional aromatic compounds used to make branched polycarbonates are found in US Pat. No. 3,028,385.
No. 3,334,154, 4,001,124, 4,131,576.

Polycarbonate resins generally have the following formula (Formula 1):

(-O-A-O-C (= O)-) (Chemical formula 1)

It is characterized as having a repeating structural unit represented by the formula (A is a divalent residue of an aromatic dihydroxy compound). The aromatic dihydroxy compound used is a mononuclear or polynuclear aromatic compound containing two hydroxy groups as functional groups, each of which is directly bonded to a carbon atom of the aromatic nucleus. The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used.

As an example, the following equation (Formula 2):

[0028]

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(In the formula, Ra and Rb are each independently a halogen atom (eg chlorine, bromine, fluorine, iodine))
Alternatively, it is a monovalent hydrocarbon group, and X is-(Rc-) C.
(-Rd)-, -C (= Re)-, -O-, -S-, -S
O- or -SO2-, Rc and Rd each independently represent a hydrogen atom or a monovalent hydrocarbon group, and Re
Is a divalent hydrocarbon group, n and n ′ are each independently an integer of 0 to 4, and d is 0 or 1).

Specifically, bis (4hydroxyphenyl) methane, 1,1 bis (4hydroxyphenyl) ethane, 1,2 bis (4hydroxyphenyl) ethane, bis (4hydroxyphenyl) phenylmethane, bis (4 Hydroxyphenyl) diphenylmethane, 2,2bis (4
Hydroxyphenyl) propane (so-called bisphenol A), 2,2 bis (4 hydroxyphenyl) butane,
2,2 bis (4 hydroxyphenyl) octane, bis (3,5 dimethyl-4-hydroxyphenyl) methane, 1,
1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,2-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3 , 5Dimethyl-4-hydroxyphenyl) propane, 2,2bis (3,5dimethyl-4)
Hydroxyphenyl) butane, bis (3,5dimethyl-4)
Hydroxyphenyl) phenylmethane, bis (3,5dimethyl-4-hydroxyphenyl) diphenylmethane, 1,
1-bis (4hydroxy-t-butylphenyl) propane, bis (3,5dichloro-4hydroxyphenyl) methane, 2,2bis (3,5dichloro-4hydroxyphenyl) propane, bis (3,5dibromo-4hydroxy) Phenyl) methane, 2,2-bis (3bromo-4-hydroxyphenyl) propane, dihydroxyarylalkanes such as 2,2bis (3,5dibromo-4-hydroxyphenyl) propane, 1,1-bis (4hydroxyphenyl) cyclo Bis (hydroxyaryl) cycloalkanes such as pentane, 1,1 bis (4hydroxyphenyl) cyclohexane, bis (4hydroxyphenyl) sulfone, bis (3,5dimethyl-4hydroxyphenyl) sulfone, bis (3,5dibromo) Dihydroxy aryl sulfo such as -4-hydroxyphenyl) sulfone , Bis (4hydroxyphenyl) ether, bis (3,5dimethyl-4-hydroxyphenyl) ether, dihydroxyarylethers such as bis (3,5dibromo-4hydroxyphenyl) ether, bis (4hydroxyphenyl) sulfide, Bis (3,5dimethyl-4-hydroxyphenyl) sulfide, bis (3,5dibromo-4hydroxyphenyl)
Dihydroxyaryl sulfides such as sulfides,
Examples thereof include dihydroxyaryl ketones such as 4,4′dihydroxybenzophenone, sulfoxides such as bis (4hydroxyphenyl) sulfoxide, and 4,4′-biphenol. Among these, in particular,
2,2-bis (4-hydroxyphenyl) propane is preferably used.

Besides the above, as the aromatic dihydroxy compound, the following general formula (Formula 3):

[0032]

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(Here, each Rf independently has 1 to 1 carbon atoms.
It is 10 hydrocarbon groups or a halogen compound or a halogen atom, and m is an integer of 0 to 4. For example, resorcinol, and 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-tert-butylresorcinol,
3-phenylresorcinol, 3-cumylresorcinol, 2,3,
Substituted resorcinols such as 4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3 -T-butylhydroquinone, 3
-Phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,
5,6-tetra-t-butylhydroquinone, 2,3,5,6
-Substituted fluoroquinone such as tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, and the following formula (Formula 4):

[0034]

Embedded image

2,2,2 ', 2'-tetrahydro-3 represented by
3,3 ′, 3′-Tetramethyl-1,1′-spirobis (1H-indene) -7,7 ′ diol can also be used.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

Known methods can be used for producing the polycarbonate, for example, a method of synthesizing the polycarbonate by subjecting an aromatic dihydroxy compound and a carbonate precursor (for example, a carbonic acid diester) to a transesterification reaction in a molten state; And a method of reacting an aromatic dihydroxy compound with a carbonate precursor (for example, phosgene) (especially an interfacial method).

Regarding the manufacturing method of these, for example, JP-A-2-75723, JP-A-2-124934, US Pat.
001,184, 4,238,569, 4,238,597, 4,474,9
No. 99 specification and the like. Regarding the carbonic acid diester, the catalyst and the like used in the above method, those described in JP-A-2-75723 and JP-A-2-124934 can be preferably used.

Examples of such carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate. , Dicyclohexyl carbonate and the like, but are not limited thereto. Preferably, diphenyl carbonate is used.

Preferred catalysts are Lewis acid catalysts, basic compound catalysts, etc., such as those disclosed by the applicant of the present invention, which are described in JP-A-4-17.
The compound proposed in Japanese Patent No. 5368 can be used.

Examples of the carbonate precursor used in the method (1) include carbonyl halide, diaryl carbonate and bishaloformate, and any of them may be used. Examples of the carbonyl halide include carbonyl bromide, carbonyl chloride (so-called phosgene), and a mixture thereof. Examples of the aryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate and the like. Also, as the bishaloformate,
For example, bischloroformate of an aromatic dihydroxy compound such as 2,2 bis (4hydroxyphenyl) propane (so-called bisphenol A) and hydroquinone or bisbromoformate; bischloroformate of glycols such as ethylene glycol or bis Examples include bromoformate. While all of the above carbonate precursors are useful, carbonyl chloride (so-called phosgene) is preferred.

In producing a polycarbonate, it is also possible to use a polyfunctional compound having three or more functional groups in one molecule together with an aromatic dihydroxy compound and a carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or carboxyl are preferable, and compounds having three phenolic hydroxyl groups are particularly preferable.

Preferred specific examples of such compounds include 1,1,1-tris (4-hydroxyphenyl) ethane,
2,2 ', 2 "-tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α', α'-tris (4-
Hydroxyphenyl) -1,4-diethylbenzene, α,
α ', α "tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2, 1,3,5-tri (4-hydroxyphenyl) benzene, 2,2-bis- (4,4- (4,4′-dihydroxyphenyl) -cyclohexyl) -propane, trimetic acid,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

More preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene or the like.

The polyfunctional compound is preferably 0.03 mol or less, more preferably 0.001 to 0.02 mol, particularly preferably 0.01 to 0.02 mol, based on 1 mol of the aromatic dihydroxy compound. It can be molar.

The polycarbonate having a hydroxyl group at the terminal can be obtained by the following method.

That is, the amount of terminal hydroxyl groups of the polycarbonate can be easily adjusted by changing the molar ratio of the dihydric phenol as a raw material and the carbonic acid diester when producing the polycarbonate in the case of melt polymerization.

For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester, the terminal group of the polycarbonate is a phenolic residue derived from bisphenol A and a phenyl group derived from diphenyl carbonate.
When the molar ratio of bisphenol A is increased, the equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) in the produced polycarbonate increases.

Further, in addition to the above-mentioned method of producing by reacting a dihydric phenol with a carbonate precursor, the polycarbonate having a phenolic hydroxyl group terminal can be easily obtained by decomposing (for example, hydrolyzing) the polycarbonate. .

As a decomposition method, there is a method of kneading polycarbonate and a compound having a hydroxyl group or a carboxyl group and / or water in a melt-kneading apparatus such as an extruder.

In this case, it is preferable to add a catalyst, and the component C) in the present invention is effective as such a catalyst.

Here, the compound having a hydroxyl group may be any compound having an alcoholic or phenolic hydroxyl group, in which the position of the hydroxyl group may be anywhere in the compound.
For example, the compound having one hydroxyl group is an aliphatic genus having 1 to 30 carbon atoms, an alicyclic genus, an aromatic genus, and a combination thereof, such as ethanol, butanol, octanol, stearyl alcohol, cyclohexanol, and methylcyclohexanol. , Octylcyclohexanol, phenol, naphthol, cresol, xylenol, t-butylphenol, dioctylphenol and stearylphenol.

As the compound having two or more hydroxyl groups,
In addition to the examples of the diol and the compound having 3 or more hydroxyl groups mentioned above and below as the constituent components of the component A) and the component B), glycerol, pentaerythritol and the like can be mentioned. In a compound having two or more hydroxyl groups, a part of the hydroxyl groups may be an ester.

Further, a polycarbonate oligomer having a phenolic hydroxyl group at a terminal and a molecular weight of 5000 or less, which is obtained by using a dihydric or trihydric phenol and a carbonyl precursor, for example, diphenyl carbonate and bisphenol A, or a phenolic compound using dicarboxylic acid and bisphenol A, is used. A polyester oligomer having a hydroxyl group at the terminal and a molecular weight of 5000 or less, and a molecular weight of 500 having a hydroxyl group at the terminal using an aliphatic or alicyclic diol and a dicarboxylic acid
And 0 or less polyester oligomers.

Of these, aromatic diols such as bisphenol A and polycarbonate oligomers are preferred.

As the compound having a carboxyl group,
2 to 2 carbon atoms such as acetic acid, butyric acid, stearic acid and benzoic acid
There may be mentioned 30 aliphatic, alicyclic and aromatic monocarboxylic acids. Examples of the compound having two or more carboxyl groups include the dibasic acids, citric acid, malic acid and the like, which are listed below as the constituent components of the component A) and the component B).

Other degradable compounds include nucleophilic compounds such as amines, dibasic acid or higher acids and salts.

The amount of the compound having a hydroxyl group or water and the compound having a nucleophilic property is such that the polycarbonate 10
0.001 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 0 parts by weight.
01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight,
It is more preferably 0.05 to 2 parts by weight, and particularly preferably 0.05 to 1 parts by weight for maintaining the physical properties of the polycarbonate.

The ratio of the terminal hydroxyl groups is preferably the equivalent ratio (I) :( II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) of 5:95 to 100: 0, more preferably 10. : 90 to 100: 0 is preferable.

By using such a polycarbonate having a hydroxyl group at the terminal, the transparency after melt-kneading with the polyester is further improved as compared with the polycarbonate having no hydroxyl group.

The polyester (component B)) is a polyester of a diol (or an ester-forming derivative thereof) and a dicarboxylic acid (or an ester-forming derivative thereof), and the diol component and the dicarboxylic acid component are each the following compounds alone. They may be used or may be used in combination.

Further, a compound having a hydroxyl group and a carboxylic acid group in one molecule such as lactone may be combined.

As the diol component, ethylene glycol, propylene 1,2-glycol, propylene 1,3-glycol, 1,4-butanediol, 2,3-butanediol,
Hexane 1,6-diol, octane 1,8-diol, neopentyl glycol, decane 1,10-diol, diethylene glycol, triethylene glycol, etc., having 2 carbon atoms
The aliphatic diols of 15 to 15 can be mentioned. Preferred aliphatic diols are ethylene glycol, 1,4-butanediol.

Further, 1,2-cyclohexanediol and 1,4-
Cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These alicyclic diols can be used in either the cis or trans configuration, or as a mixture of both. A preferred cycloaliphatic diol is 1,4-cyclohexanedimethanol.

Furthermore, aromatic dihydric phenols such as resorcin, hydroquinone and naphthalene diol, polyethylene glycol having a molecular weight of 400 to 6000, polyglycols such as polypropylene glycol and polytetramethylene glycol, bisphenol A and bisphenol B.
Examples thereof include bisphenols described in JP-A No. 3-203956.

As the dicarboxylic acid component, isophthalic acid, terephthalic acid, orthophthalic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 1,2-di (4-carboxyphenyl) ethane, adipic acid, Examples thereof include aliphatic and alicyclic dicarboxylic acids such as succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and cyclohexanedicarboxylic acid.

As the component B), these diols and dicarboxylic acids may be used alone, or two or more kinds of diols or dicarboxylic acids may be used in combination. The obtained polyesters may be used alone or in combination.

The catalyst used for producing the polyester may be a conventional catalyst, for example, an antimony compound, a titanium compound, a tin compound or a germanium compound, but the amount of the catalyst to be added is preferably. A catalyst that does not have volatility, such as an antimony compound, a titanium compound, or a tin compound, that can reduce the amount is preferable.

Further, in a polyester obtained by polymerizing a carboxylic acid ester and a diol, the more hydroxyl group terminals derived from the diol, the more transparent the kneaded composition with the polycarbonate according to the present method becomes.

The polyester (component B)) is a polyester of a diol (or an ester-forming derivative thereof) and a dicarboxylic acid (or an ester-forming derivative thereof), and the diol component and the dicarboxylic acid component are the following compounds each alone. They may be used or may be used in combination. Further, a compound having a hydroxyl group and a carboxylic acid group in one molecule such as lactone may be combined.

As the diol component, ethylene glycol, propylene 1,2-glycol, propylene 1,3-glycol, 1,4-butanediol, 2,3-butanediol,
Hexane 1,6-diol, octane 1,8-diol, neopentyl glycol, decane 1,10-diol, diethylene glycol, triethylene glycol, etc., having 2 carbon atoms
The aliphatic diols of 15 to 15 can be mentioned. Preferred aliphatic diols are ethylene glycol, 1,4-butanediol.

Further, 1,2-cyclohexanediol, 1,4-cyclohexanediol,
Cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These alicyclic diols can be used in either the cis or trans configuration, or as a mixture of both. A preferred cycloaliphatic diol is 1,4-cyclohexanedimethanol.

Further, aromatic dihydric phenols such as resorcin, hydroquinone and naphthalene diol, polyethylene glycol having a molecular weight of 400 to 6000, polyglycols such as polypropylene glycol and polytetramethylene glycol, bisphenol A and bisphenol B.
Examples thereof include bisphenols described in JP-A No. 3-203956.

As the dicarboxylic acid component, isophthalic acid, terephthalic acid, orthophthalic acid, 2,2′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 1,2-di (4-carboxyphenyl) ethane, adipic acid, Examples thereof include aliphatic and alicyclic dicarboxylic acids such as succinic acid, oxalic acid, malonic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and cyclohexanedicarboxylic acid.

As the component B), these diols and dicarboxylic acids may be used alone, or two or more diols or dicarboxylic acids may be used in combination. The obtained polyesters may be used alone or in combination.

The catalyst used for producing the polyester may be any ordinary catalyst such as antimony compound, titanium compound, tin compound or germanium compound.

Further, in a polyester obtained by polymerizing a carboxylic acid ester and a diol, the more hydroxyl group terminals derived from the diol, the more transparent the kneaded composition with the polycarbonate according to the present method becomes.

Polyesters, preferably polyesters of alkyldicarboxylic acids and aromatic diols and polyesters of aromatic dicarboxylic acids and alkylene glycols, specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate,
Poly (1,4-cyclohexane dimethanol terephthalate), poly (1,4-cyclohexane dimethanol terephthalate-co-isophthalate), poly (1,4-butylene terephthalate-co-isophthalate), poly (ethylene-co- 1,4-
Cyclohexanedimethanol terephthalate) and the like.

When kneading, the weight composition ratio of polycarbonate (component A)) and polyester (component B)) is
A / B is 99/1 to 1/99, preferably 95/5 to 2
0/80, more preferably 90/10 to 30/70,
It is particularly preferably 80/20 to 40/60, and most preferably 70/30 to 50/50.

Preferably, the intrinsic viscosity IV (methylene chloride, 25 ° C.) of polycarbonate is 0.3 to 1.0.
dl / g, more preferably 0.35 to 0.8 dl / g, and particularly preferably 0.4 to 0.7 dl / g is good.
V (tetrachloroethane / phenol = 2/1, 30
C) is 0.3 to 2.0 dl / g, more preferably 0.5 to
1.7 dl / g, particularly preferably 0.6 to 1.4 dl / g. When the IV value is lower than the above value, the mechanical strength of the kneading composition decreases, and when the IV value is higher, the moldability decreases.

As the transesterification reaction catalyst (component C), a catalyst known as a transesterification catalyst can be used. For example, Lewis acid catalysts include tin compounds such as dibutyltin oxide, tin oxalate, tin acetate, tin oxide, dibutyltin dimethoxide, and butyltin hydroxide oxide, and titanium compounds such as tetrabutoxy titanium, tetraphenoxy titanium, titanium oxide, and titanium oxalate. , Antimony trioxide, antimony compounds such as antimony tartrate oxide, zinc compounds such as zinc acetate, zinc stearate, zinc acetylacetone, triphenoxyboron, borate compounds such as zinc borate, germanium oxide, germanium compounds such as germanium ethoxide, Manganese acetate,
Cobalt acetate etc. can be mentioned.

Examples of the basic catalyst include organic basic compounds, alkalis, alkaline earth metals and the like.

As the organic base compound, a nitrogen-containing basic compound, for example, an ammonium hydroxide having an alkyl or aryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and tetraphenylammonium hydroxide. And salts of the above-mentioned ammonium with an acid weaker than PKa4.

Further, as nitrogen-containing basic compounds other than the above, trimethylamine, triethylamine, trioctylamine, triphenylamine, dibenzylmethylamine and the like NR3 (wherein R is methyl, ethyl, phenyl, benzyl, toluyl) Such as alkyl and aryl groups having 1 to 25 carbon atoms), secondary and primary amines represented by NHR2 and NH2R (wherein R is the same as above), And pyridine, methylpyridine, methoxypyridine, quinoline, imidazole, ammonia and the like.

Furthermore, tetraalkyl or tetraarylphosphonium hydroxide such as tetrabutylphosphonium hydroxide can be mentioned.

As the alkali or alkaline earth metal compounds, for example, as inorganic compounds, hydroxides and hydrides of alkali metals such as sodium, potassium, lithium and cesium and alkaline earth metals such as calcium, magnesium and barium. , Amides, carbonates, phosphates,
A borate etc. can be mentioned.

Further, examples of salts with organic acids include carboxylates, salts with phenolic hydroxyl groups, and salts with alcoholic hydroxyl groups.

Further, compounds with acetylacetone, crown ether and the like can be mentioned.

The transesterification catalyst (component C)) is preferably 0.0001 to 1 part by weight, more preferably 0, in the case of a Lewis acid catalyst, based on 100 parts by weight of components A) and B) in total. 0.0005 to 0.5 parts by weight, more preferably 0.001 to 0.1 parts by weight, and particularly preferably 0.00.
It is in the range of 005 to 0.05 parts by weight. Further, in the case of a basic catalyst, preferably 0.00001 to 0.1 part by weight, more preferably 0.00005 to 0.05 part by weight, further preferably 0.0001 to 0.01 part by weight,
Particularly preferably, it is in the range of 0.0005 to 0.005 parts by weight.

Further, the Lewis acid catalyst and the basic catalyst may be used at the same time, and in this case, the amount of the catalyst used can be reduced as compared with the case where each is used alone.

If the amount of the catalyst is less than the above range, the effect of addition does not appear, and if it is more than the above range, the molecular weight decreases during kneading and the physical properties deteriorate.

As the protic acid and / or its derivative (component D)), any acid is effective as long as it is a protic acid. Examples of the derivative include a compound that exhibits acidity during granulation due to heat or a reaction with a resin, such as an ester of sulfonic acid, an ammonium salt of a strong acid, or a metal salt.

Further, when the acid is a dibasic acid or more, it may be a partial esterified compound or a partial metal salt. These acidic compounds may be used alone or in a mixture.

As the protic acid, various acids can be mentioned. For example, phenol, phenols such as cresol and xylenol, phenols having electron-withdrawing groups as substituents such as 2,4 dinitrophenol and 2,4,6 trinitrophenol, formic acid, methoxyacetic acid, acetic acid, butyric acid, citric acid , Carboxylic acids such as malic acid, trifluoroacetic acid, trichloroacetic acid, 1,1-difluoropropionic acid, monochloroacetic acid, dichloroacetic acid, monofluoroacetic acid, carboxylic acids having an electron-withdrawing group at the α-position such as nitroacetic acid and cyanoacetic acid, Aromatic carboxylic acids having an electron-withdrawing group as a substituent, such as m-nitrobenzoic acid, 2,4 dinitrobenzoic acid and 2,4,6 trinitrobenzoic acid, oxalic acid, 2-carboxypropionic acid, malonic acid, succinic acid, Dicarboxylic acids such as fumaric acid and maleic acid, phthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as terephthalic acid and 1,3-naphthalenedicaric acid, boric acid, hydrobromic acid, nitric acid, iodic acid, perchloric acid, periodic acid, inorganic acids such as bromic acid and sulfuric acid, benzenesulfonic acid , P-toluenesulfonic acid, naphthalenesulfonic acid, sulfonic acids such as methylsulfonic acid and fluorosulfonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid,
Examples thereof include phosphoric acids such as metaphosphoric acid and polyphosphoric acid.

Examples of the ester derivative include methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, butyl p-toluene sulfonate, phenyl p-toluene sulfonate, benzyl p-toluene sulfonate, butyl naphthalene sulfonate. And sulfonic acid esters such as butyl methyl sulfonate, phosphoric acid mono (2,4 ditertiary butylphenyl), phosphoric acid di (2,4 ditertiary butylphenyl), phosphorous acid monophenyl,
Examples thereof include mono- and diesters such as dimethyl phosphate, di (2,4 dimethylphenyl) phosphate and diethyl phosphite, and dimethyl sulfate.

Further, as the metal salt derivative, for example,
Monosodium carbonate, monosodium phosphate, disodium phosphate, sodium acid pyrophosphate, monopotassium phosphate,
Examples include dilithium phosphate, magnesium phosphate, monosodium phosphite, disodium phosphite, monopotassium phosphite, dilithium phosphite, calcium phosphite, monosodium oxalate, monopotassium phthalate, monosodium borate and monopotassium sulfate. I can.

The acid component (component D)) is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, and more preferably 100 parts by weight of the components A) and B). 0.005-0.1 parts by weight, particularly preferably 0.1.
It is preferable to use 01 to 0.1 parts by weight.

If the addition amount of component D) is less than 0.0001 parts by weight, the effect of addition is not exhibited, and if it is more than 1 part by weight, the resin component is adversely affected during granulation and molding, and the mechanical strength decreases. Not preferable.

If the compound having a hydroxyl group (component E) is a compound having water or an alcoholic or phenolic hydroxyl group, the position of the hydroxyl group in the compound may be anywhere.

The compound having one hydroxyl group is an aliphatic genus having 1 to 30 carbon atoms, an alicyclic genus, an aromatic genus and a combination thereof, such as ethanol, butanol,
Octanol, stearyl alcohol, cyclohexanol, methylcyclohexanol, octylcyclohexanol, benzyl alcohol, phenol, naphthol, cresol, xylenol, t-butylphenol, stearylphenol and the like can be mentioned.

As the compound having two or more hydroxyl groups,
In addition to the examples of the diol and the compound having three or more hydroxyl groups as the constituents of the components A) and B), glycerol, pentaerythritol and the like can be mentioned.

Further, in the compound having two or more hydroxyl groups, part of the hydroxyl groups may be an ester.

Furthermore, the above-mentioned dihydric or trihydric phenol and a carbonyl precursor, for example, phosgene or diphenyl carbonate, having a hydroxyl group-terminated polycarbonate oligomer having a molecular weight of 5000 or less, or having a phenolic hydroxyl group using a dicarboxylic acid at the terminal are used. A polyester oligomer having a molecular weight of 5,000 or less, and a molecular weight of 500 having a hydroxyl group at the terminal using a diol and a dicarboxylic acid
The polyester oligomer of 0 or less can be mentioned.

Of the compounds having a hydroxyl group mentioned above, aromatic diols such as bisphenol A and polycarbonate oligomers are preferable. These compounds having a hydroxyl group may be used alone or in combination of two or more.

The amount of the compound having a hydroxyl group (component E) added is 0.001 to 10 parts by weight based on 100 parts by weight of the resin,
Preferably 0.002 to 1 part by weight, more preferably 0.002.
005-0.1 parts by weight are blended. If it is less than 0.001 parts by weight, the addition effect does not appear, and if it is more than 10 parts by weight, mechanical strength is lowered due to a decrease in molecular weight and bleeding out from a molded product is not preferable. .

The kneading of the above-mentioned mixture may be carried out by a kneader, a single-screw or twin-screw extruder, a vertical or horizontal reaction tank having a stirring function, a mixer, an apparatus having a melt-kneading function such as a roll. For example, any device may be used regardless of the shape of the device. Above all, it is preferable to use a single-screw or twin-screw extruder from the viewpoints of simplicity of production and economy.

Further, all the components may be kneaded at the same time when kneading, but it is preferable to knead each component excluding the protonic acid and then add the kneading with the protic acid, or kneading each component excluding the protic acid. A method of adding a protonic acid component by a method such as medium and side feed is preferable.

Suitable examples of the molding method include a method using a film and a sheet, injection molding, blow molding, extrusion molding, compression molding and the like, but any method may be used.

The film or sheet may be molded by any method such as an inflation method, a calendar method, a T-die method, a casting method, a cutting method, an emulsion method and a hot pressing method. Further, the film or sheet may or may not be stretched. Further, for forming the film or sheet, any forming method such as vacuum forming and compression forming may be used.

Various additives may be added within the range not impairing the gist of the present invention. As an additive, for example, in the case of a stabilizer, Irgafos168 (trademark: manufactured by Ciba-Geigy), Chelex L
(Trademark: Sakai Chemical Industry Co., Ltd.), 3P2S (Trademark: Ihara Chemical Industry Co., Ltd.), Mark 329K (Trademark: Asahi Denka Kogyo Co., Ltd.)
Mark P (same as above), Weston 618 (Trademark: Sanko Chemical Co., Ltd.)
Phosphorus, such as BHT (trade name: Takeda Pharmaceutical Co., Ltd.), Ion
ox100 (trademark: Shell Chemical Co.), Age Rite Superlite
(Trademark: Vander bilt), Santonox R (Trademark: Monsanto), Antioxidant ZKF (Trademark: Bayer), Irganox 10
Cyasorb UV-5411, hindered phenolic compounds such as 76 (trademark: manufactured by Ciba Geigy), HYoechst VPOSPI (trademark: manufactured by Hoechst), Irganox 1010 (trademark: manufactured by Ciba Geigy)
(Trademark: ACC), Cyasorb UV-531 (Trademark: ACC), Ti
nuvin 326 (trademark: manufactured by Ciba Geigy), Tinuvin 320
(Same as above), Tinuvin 234 (Same as above), Tinuvin 120 (Same as above), Uvi
Examples thereof include ultraviolet absorbers such as nul D49 (trademark: manufactured by GAF) such as triazole type and other stabilizers such as epoxy type, thiol type and metal salt type.

Specific examples of the above-mentioned epoxy stabilizers include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allylglycidyl ether,
There are 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate and the like. Commercially, Celoxide 2021P (trademark: manufactured by Daicel Chemical Industries, Ltd.), Adeka Sizer O-180A (trademark: Asahi Denka Kogyo) Co., Ltd.) and the like.

Examples of the flame retardant include TPP, resorcinol polyphosphate, bisphenol-A polyphosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) and other phosphoric acid ester-based and halogen-based compounds such as brominated BPA, brominated BPA polycarbonate and oligomers thereof. Inorganic flame retardants and flame retardant aids such as antimony trioxide, magnesium hydroxide, calcium hydroxide and the like can be mentioned.

Further, calcium phosphate as a slip modifier,
Examples thereof include inorganic compounds such as calcium carbonate, talc and silica, and organic particulate compounds obtained by granulating crosslinked polyester, crosslinked polyamide, crosslinked polymethylmethacrylate and the like.

As the releasing agent, glycerin monostearate, distearate, tristearate, pentaerythritol tetrastearate, etc. are used in the alkyl ester type, and TSF437 (trade name: manufactured by Toshiba Silicon Co., Ltd.) in the silicon type. Etc. can be mentioned.
In addition, a coloring agent, a fibrous reinforcing agent or the like may be added.

[0114]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. Resin : A-1 PC LEXAN (trademark: manufactured by Nippon GE Plastics Co., Ltd.) Terminal hydroxyl group ratio 35%, intrinsic viscosity at 25 ° C in methylene chloride is 0.5 dl / g A-2 PC LEXAN (trademark: same as above) Terminal hydroxyl ratio 0% In methylene chloride, the intrinsic viscosity at 25 ° C is 0.5 dl / g B-1 PBT VALOX (trademark: same as before) MI (250 ° C, 2.09mmφ, 2.16kg) = 20g / 10min B-2 PET Mitui PET J025 (Trademark: Mitsui Petrochemical Industry Co., Ltd.)

[0115]Kneading : The sample was kneaded with a 30φ mm twin-screw extruder. Kneading conditions Cylinder temperature 270 ℃, screw rotation speed 150rpminjection molding : A test plate was prepared from the dried sample using a PS60 injection molding machine manufactured by Nissei Plastic Industry Co., Ltd. Molding conditions Cylinder temperature 270 ℃, Mold temperature 80 ℃Film molding : The sample was previously dried (90 ° C., reduced pressure, 8 hours) and formed into a film using a Thermoplastics 30 Φmm uniaxial T-die film forming machine. Molding conditions Cylinder temperature 280 ℃, Die temperature 270 ℃ Roll temperature 80-130 ℃Vacuum forming A film having a size of 300 μm was prepared, and molding was performed at a residual heat temperature of 390 ° C. for a time of 9 seconds to 17 seconds using a mold having an 85 mm square and a depth of 30 mm. The evaluation was performed by transparency. Evaluation ○ The molded product retains transparency. × The molded product is not transparent and opaque.Heat treatment test : The following test plates were aged and evaluated by the haze before and after. Test piece An injection-molded test piece; 5 cm square × thickness 3 mm was used. Equipment Tabai's Perfect Oven GPHH, 150 ℃, 1hrHue (YI) The x, y, z values were measured using an ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd., and an injection-molded plate (thickness: 3 mm) was measured by a transmission method to obtain yellowness (YI).Haze, light transmittance A haze and light transmittance of an injection-molded plate (thickness: 3 mm) were measured using NDH-200 manufactured by Nippon Denshoku Industries Co., Ltd.Glass transition temperature (Tg) : Using RDX (Dynamic Viscoelasticity Measuring Device) of Rheometrics Co., Ltd., measure injection molded plate (3.2mm thickness) at temperature rising rate of 3 ° C / min, frequency of 6.28rad / sec and strain of 0.1%. did. Differential scanning calorimeter (DSC) : Measured under the following temperature conditions using SSC5200 manufactured by Seiko Instruments Inc. Measurement conditions Room temperature → 300 ° C. (80 ° C./min) Hold for 2 minutes 300 ° C. → 20 ° C. (20 ° C./min) Hold for 2 minutes 20 ° C. → 300 ° C. (20 ° C./min)

Examples 1 to 13 and Comparative Examples 1 to 8 Polycarbonates having different rates of phenolic hydroxyl groups at all terminals (components A [a-1] and A [a-2]: manufactured by Nippon GE Plastics Co., Ltd.) , Polyester (component B [b-1] PBT: manufactured by Nippon GE Plastics Co., Ltd., and component B [b-2] PE
T: manufactured by Mitsui Petrochemical Co., Ltd., an ester exchange catalyst (component C: reagent), an acidic component (component D: reagent), and
A diol component (component E: bisphenol-A; manufactured by Nippon GE Plastics Co., Ltd.) was blended in the composition shown in Table 1 and kneaded with an extruder to form pellets.

[0117]

[Table 1] Blending ratio of Examples and Comparative Examples In the table, StCOONa: sodium stearate, BPA: bisphenol-A, Na ₂ H ₂ P ₂ O ₇ : sodium acid pyrophosphate are shown.

Then injection molding and film (thickness 1
00 and 300 μm) molding was performed. Physical properties of the obtained molded product are shown in Tables 2 and 3.

Incidentally, after dyeing with ruthenium oxide (RuO ₄ ) using a transmission electron microscope, Examples 2, 4, 5 and
7, 9, 10, 12, 13 and Comparative Examples 4, 5, 6,
Morphology of 7 and 8 was observed. As a result, Example 2
No phase-separated structure was confirmed in 4, 5, 7, 9, 10, 12, and 13, and the phase was a single phase. On the other hand, Comparative Examples 4, 5, 6,
In 7 and 8, a phase-separated structure was confirmed.

In the comparative examples, completely separated phase structures of polycarbonate and polyester (PET in comparative example 4, PBT in comparative examples 5, 6, 7, and 8) were observed. Furthermore, the phase-separated structure was not observed even after the test piece of Example 7 was heat-treated at 150 ° C. for 1 hour.

The glass transition temperatures were 152 ° C. and 106 ° C. in Examples 4 and 13, respectively, but in Comparative Example 4, polycarbonate and polyethylene terephthalate were adjusted to 158 ° C. and 83 ° C., and Comparative Example 7 was used. At 135 ℃
At 62 ° C. and 62 ° C., two glass transition temperatures due to the respective components of polycarbonate and polybutylene terephthalate were observed, and similar to the observation with a transmission electron microscope, a single phase without a phase separation structure was observed in the examples, and a phase was observed in the comparative examples. It has been shown to be a separate structure.

Further, in the measurement using a differential scanning calorimeter (DSC), the peaks of crystallization and melting point due to polyester did not appear in Examples 2, 7 and 10, but
In Comparative Examples 2 and 5, a melting point peak appeared at around 220 ° C.

[0123]

[Table 2] Physical property table (1) Table Note * 1 Vacuum formability int is initial. Anneal at 150 ° C for 1 hr (1 hour). A slight turbidity was recognized in the evaluation Δ. * 2 Light transmittance is small and reference value

[0109]

[Table 3] Table Note: * 1 Elmendorf tear test (according to JIS Z1702). * 2 Test speed: 200 mm / min, Young's modulus is 50 mm / min (according to JIS K6781). * 3 Gas permeability coefficient: The lower the value, the higher the barrier property. Measurement film thickness 0.1 mm, area 50 cm ² Oxygen permeability coefficient (cc mm / m ² 24 hr atm) Measurement temperature 23 ° C, humidity 0% RH Water vapor permeability coefficient (g mm / m ² day) Measurement temperature 40 ℃, humidity 90% RH

[0110]

[Table 4] Table Note: * 1 The maximum temperature at which the seal part is completely peeled without breaking and its peel strength. * 2 The minimum temperature at which the peel strength of the seal is almost constant and the peel strength. However, the seal part broke, not peeled.

As is clear from the examples, the molded articles using the blended composition kneaded based on the exemplification of the present invention have high transparency (above light transmittance and haze values) and a simple glass transition temperature. The morphology was a single phase. Further, even after the heat treatment, the haze did not increase and the transparency was maintained.

Further, the gas barrier property, the tear strength, etc. are improved while maintaining the transparency.

[0117]

EFFECTS OF THE INVENTION As described above, high temperature sterilization treatment is particularly required as a bottle-shaped container for foods, medical products, etc., that is, a container suitable for a wide range of shapes, dimensions, applications, etc. Suitable for use, the above food,
It is expected to be applied to a wide range of applications including medical applications.

Claims (7)

[Claims] 1. A container formed from a transparent polyester / polycarbonate composition. 2. A container using a transparent polyester / polycarbonate composition having a single glass transition point and a single morphology morphology. 3. A container using the transparent polyester / polycarbonate composition according to claim 1, which is formed by melt-kneading polycarbonate and polyester. 4. A container using the transparent polyester / polycarbonate composition according to claim 1, wherein a transesterification catalyst and an acid are added during melt-kneading of the polycarbonate and the polyester. 5. A container using the transparent polyester / polycarbonate composition according to claim 1, wherein the weight composition ratio of polyester / polycarbonate is 99/1 to 1/99. 6. A container using the transparent polyester / polycarbonate composition according to any one of claims 1 to 5, wherein the polyester is a polyester selected from polyethylene terephthalate and polybutylene terephthalate, and is a single type or a combination of two types. . 7. A transparent polyester / polycarbonate composition according to any one of claims 1 to 6, wherein the polycarbonate has a phenolic hydroxyl group at the terminal, and the proportion of the polycarbonate is 5% or more of all terminals. Used container.