JP2000313095A - Multi-layer bottle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layer bottle excellent in heat resistance and gas- barrier properties. SOLUTION: A multi-layer bottle has a barrel part comprising the layers of a thermoplastic polyester A and the layer of at least one thermoplastic resin B selected from the group consisting of a thermoplastic polyamide, polyvinylidene chloride, and a vinylidene chloride-vinyl chloride copolymer, and in the barrel part, the layers of the polyester A contact the layer of the resin B to form the laminated structure of A-layer/B-layer/A-layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a multi-layer bottle, and more particularly, to a multi-layer bottle having excellent gas barrier properties.

[0002]

BACKGROUND OF THE INVENTION Multilayer bottles are known per se. The following techniques are known for multilayer bottles. JP-A-1-26
No. 940 describes a multilayer hollow molded article composed of polyethylene terephthalate and ethylene naphthalate. JP-A-4-310719 discloses a multilayer container comprising a thermoplastic polyester containing 1 mol% or more and less than 80 mol% of ethylene naphthalate units as repeating units and a polyolefin containing 70 mol% or more of propylene units. ing. Japanese Patent Application Laid-Open No. Hei 4-223134 describes a flexible bottle having a two-layer structure in which a body portion is formed by laminating polyester and polyamide and having a thickness of 20 to 150 μm.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a multilayer bottle having excellent heat resistance and gas barrier properties.

[0004]

That is, the present invention relates to: 1) a layer of a thermoplastic polyester (A), comprising a thermoplastic polyamide, polyvinylidene chloride and vinylidene chloride /
A body comprising at least one layer of a thermoplastic resin (B) selected from the group consisting of vinyl chloride copolymers, wherein the layer of the thermoplastic polyester (A) comprises a layer of the thermoplastic resin (B). A) a multilayer bottle having a laminated structure in the order of A layer / B layer / A layer in contact with a layer of the thermoplastic polyester (A); and a thermoplastic polyamide, polyvinylidene chloride and vinylidene chloride. /
A body comprising at least one layer of a thermoplastic resin (B) selected from the group consisting of vinyl chloride copolymers, wherein the layer of the thermoplastic polyester (A) comprises a layer of the thermoplastic resin (B). Is a multilayer bottle having a laminated structure in the order of layer A / layer B / layer A / layer B / layer A in contact with the layer A. Hereinafter, the present invention will be described in detail.

[Multilayer Bottle] A multilayer bottle has a body and a mouth. In this specification, layer A means a layer of thermoplastic polyester (A), and layer B means a layer of thermoplastic resin (B).

[0006] In the body of the multilayer bottle, the layer of thermoplastic polyester (A) is in contact with the layer of thermoplastic resin (B), and has a laminated structure in the order of A layer / B layer / A layer. Constitute. If the body of the multilayer bottle does not have this laminated structure, the thermoplastic resin (B) comes into contact with the contents or the outside air, and the heat resistance, chemical resistance, flavor and the like of the bottle are insufficient.

[0007] The three-layered structure of layer A / layer B / layer A may form the body of the bottle without any other layers, and further contact layer A to form layer B and layer B. The layer A may be brought into contact with the layer to form a laminated structure of five layers in the order of layer A / layer B / layer A / layer B / layer A. When the body of the multilayer bottle has the laminated structure of the five layers, the gas barrier property is further improved.

The mouth of the multilayer bottle is preferably made of thermoplastic polyester (A) in order to obtain high heat resistance. However, in order to obtain uniform stretchability of the trunk, it is preferable that the thermoplastic resin (B) is sufficiently introduced into the trunk, and for that purpose, a small amount of the thermoplastic resin (B) is mixed into the mouth. Is also good.

[Layer of thermoplastic polyester (A)] The layer of thermoplastic polyester (A) is made of thermoplastic polyester (A). The thermoplastic polyester (A) contains ethylene-2,6-naphthalenedicarboxylate unit as a repeating unit in an amount of preferably 10% by weight or more, more preferably 8% by weight, based on the total thermoplastic polyester (A).
Contains 5% by weight or more. If the content of the ethylene-2,6-naphthalenedicarboxylate unit is less than this, heat resistance, moisture resistance, chemical resistance, and ultraviolet barrier properties are inferior and are not preferable.

[0010] Ethylene of the thermoplastic polyester (A)
The 2,6-naphthalenedicarboxylate unit may be present as a unit formed by a copolymer component, or may be present as a unit constituting another polymer used as a polymer mixture (blend).

The thermoplastic polyester (A) may be a copolymer polyester comprising an ethylene terephthalate unit and an ethylene-2,6-naphthalenedicarboxylate unit.

[0012] The thermoplastic polyester (A) may be a mixture of polyethylene terephthalate and polyethylene 2,6-naphthalenedicarboxylate.

The thermoplastic polyester (A) preferably contains at least one compound selected from the group consisting of benzotriazole compounds, triazine compounds, benzophenone compounds, cyanoacrylate compounds and benzoxazine compounds. It is a thermoplastic polyester composition.

As the benzotriazole compound, 2
-(2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl)
Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2)
-Yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazole-2)
-Yl) 4,6-bis (1,1-dimethylethyl) phenol, 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl-4-methyl) phenol , 2- (2H-benzotriazole-
2-yl) -4,6-bis (1,1-dimethylpropyl) phenol, 2,2′-methylenebis [6- (2H
-Benzotriazol-2-yl) -4- (1,1,
3,3-tetramethylbutyl) phenol, 2- (2H
-Benzotriazol-2-yl) -6-dodecyl-4
-Methylphenol, among which 2- (2H
-Benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl)-
4,6-bis (1-methyl-1-phenylethyl) phenol is preferably used.

As triazine compounds, 2- (4,4
6-diphenyl-1,3,5-triazin-2-yl)
-5- (hexyloxy) phenol, 2- [4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 1,5,8,12-tetrakis [4,6-bis (N
-Butyl-N-1,2,2,6,6-pentamethyl-4
-Piperidylamino) -1,3,5-triazine-2-
Yl] -1,5,8,12-tetraazododecane, among which 2- (4,6-diphenyl-1,3,3
5-triazin-2-yl) -5- (hexyloxy)
Phenol is preferably used.

As the benzophenone-based compound, 2-hydroxy-4-methoxy-5-sulfobenzophenone,
2-hydroxy-4-n-octoxybenzophenone,
2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone are exemplified.

As the cyanoacrylate compound, 2
-Ethylhexyl-2-cyano-3,3'-diphenyl acrylate and 2-ethyl-2-cyano-3,3'-diphenyl acrylate.

As the benzoxazine-based compound, 2-
p-methoxyphenyl (3,1-benzoxazine-4
-One), 2-α-naphthyl (3,1-benzoxazin-4-one), 2-β-naphthyl (3,1-benzoxazin-4-one), 2-p-phthalimidophenyl (3,1 -Benzoxazin-4-one), 2,2'-
Bis (3,1-benzoxazin-4-one), 2,
2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene)
Bis (3,1-benzoxazin-4-one), 2,
2 ′-(2,6- or 1,5-naphthalene) bis (3,
1-benzoxazin-4-one) and 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene, among which 2,2′-bis (3
1-benzoxazin-4-one), 2,2'-p-phenylenebis (3,1-benzoxazin-4-one)
Is preferably used.

The thermoplastic polyester (A) is at least one pigment selected from the group consisting of oxide pigments, ferrocyanide pigments, silicate pigments, phosphate pigments, carbon black, condensed polycyclic pigments and phthalocyanine pigments. And a thermoplastic polyester composition containing

Examples of the oxide pigments include titanium dioxide, ferric oxide (bengara), chromium oxide, cobalt blue (cobalt oxide / aluminum oxide composite oxide pigment), zinc oxide (zinc white), and lead tetroxide ( Lead red), cuprous oxide (cuprous oxide), and titanium nickel yellow. As the ferrocyanide pigment, navy blue can be exemplified. Manganese violet can be exemplified as the phosphate pigment. An example of the condensed polycyclic pigment is an anthraquinone pigment. Examples of the phthalocyanine pigment include phthalocyanine blue, metal-free phthalocyanine, phthalocyanine green, and fast sky blue. Examples of the silicate pigment include ultramarine blue, talc, and white carbon. Examples of the white carbon include silicic anhydride, hydrous silicic acid, hydrous magnesium silicate, hydrous calcium silicate, and hydrous aluminum silicate.

[Layer of thermoplastic resin (B)] The layer of thermoplastic resin (B) is made of thermoplastic resin (B). The thermoplastic resin (B) is at least one thermoplastic resin selected from the group consisting of thermoplastic polyamide, polyvinylidene chloride, and vinylidene chloride / vinyl copolymer. If the thermoplastic resin (B) is one of these resins, the gas barrier property of the bottle is greatly improved, and if the thermoplastic resin (B) is any other resin, the gas barrier property of the bottle is insufficient.

[0022] The thermoplastic resin (B) is preferably a thermoplastic polyamide. As a thermoplastic polyamide, m-
Diamine selected from xylylenediamine, bis (p-aminocyclohexyl) methane, tetramethylenediamine, hexamethylenediamine, 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and adipic acid; Sebacic acid,
Dodecane diacid salt, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, succinic acid, azelaic acid, polyamide comprising a polyamide consisting of a dicarboxylic acid selected from cyclohexanedicarboxylic acid and the like, and ε-caprolactam and ε-aminocapron Examples of the polyamide include an acid polyamide, a polyamide composed of ω-aminoundecanoic acid, and a polyamide composed of ω-laurolactam and ω-aminododecanoic acid. By using thermoplastic polyamide, the heat resistance and gas barrier properties of the bottle are improved. The thermoplastic polyamide is particularly preferably a polyamide composed of m-xylylenediamine. In particular, by using a polyamide made of m-xylylenediamine, gas barrier properties can be improved, and there is little change with time.

The average thickness of the body of the multilayer bottle of the present invention is preferably 0.15 to 1 mm, and more preferably 0.25 to 0.7 mm. If it is less than 0.15 mm, the strength and barrier properties of the bottle are undesirably reduced. On the other hand, if it exceeds 1 mm, the basis weight of the whole bottle increases, and the cost increases, which is not preferable.

The thickness of the layer of the thermoplastic resin (B) is preferably 1 to 20%, more preferably 3 to 1%, based on the total thickness.
5%.

The draw ratio of the multilayer bottle is preferably 10
１５０150 times, more preferably 20-100 times.
The stretching ratio referred to here is a value obtained by dividing the internal volume (ml) of the bottle by the internal volume (ml) of the preform. However,
The volume does not include the mouth.

If the stretching ratio is less than 10, the orientation of the bottle is insufficient and the barrier property cannot be exhibited, and if it exceeds 150 times, the rate of breakage at the time of stretching increases, and the productivity decreases, which is not preferable.

[0027]

Embodiments will be described below with reference to embodiments. The characteristics in the examples were measured by the following methods.

(1) Evaluation of heat resistance A bottle sample was filled with hot water of 80 ° C.,
After 5 minutes of rectification, it was cooled with running water. The volume shrinkage before and after was measured.

(2) Evaluation of Gas Barrier Property Purified water (ion-exchanged water) was filled to 90% of the volume (below the screw portion of the bottle), and nitrogen bubbling was performed in a nitrogen atmosphere for 10 minutes to dissolve the gas at the initial stage. The oxygen value was measured. After replacing the upper air with nitrogen, sealed with silicone rubber in standard condition (2
(3 ° C., humidity 50%). After 96 hours, the stopper was opened under a nitrogen atmosphere, and the dissolved oxygen was measured. For dissolved oxygen meter, YS
Company I Model5000 diaphragm polarograph was used.

(3) Production of thermoplastic polyester A thermoplastic polyester was produced by the method of the following Reference Example.

REFERENCE EXAMPLE 1 100 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester and 70 parts by weight of ethylene glycol were used as a transesterification catalyst with cobalt acetate, calcium acetate, and magnesium acetate. The ester exchange reaction was carried out while heating and raising the temperature to 250 ° C., and when methanol was almost completely distilled off, germanium acetate was added as a polymerization catalyst, and then trimethyl phosphate was added as a stabilizer. The exchange reaction was terminated. Next, the reaction product was subjected to a polycondensation reaction under high temperature and high vacuum to obtain a prepolymer having an intrinsic viscosity of 0.50 (a mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol at 25 ° C.). This prepolymer is made into a strand type chip, and further subjected to solid phase polymerization under heating and vacuum to obtain a solid phase polymerization having an intrinsic viscosity (a mixed solvent of 2 parts by weight of trichlorophenol and 3 parts by weight of phenol at 35 ° C.) of 0.65. A thermoplastic polyester as a polymer was obtained.

REFERENCE EXAMPLE 2 93 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 5.4 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol were prepared by using cobalt acetate and manganese acetate as transesterification catalysts. The produced methanol is distilled out of the system and 250
The ester exchange reaction was carried out while heating to ℃ C, and at the stage when methanol was almost completely distilled off, antimony trioxide was added as a polymerization catalyst, and orthophosphoric acid was subsequently added as a stabilizer to terminate the transesterification reaction. Was. Then
The reaction product was subjected to a polycondensation reaction under high temperature and high vacuum to obtain a prepolymer having an intrinsic viscosity of 0.50 (mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol, 25 ° C.). After making this prepolymer into a strand type chip, it is further subjected to solid phase polymerization under heating and vacuum to obtain an intrinsic viscosity (a mixed solvent of 2 parts by weight of trichlorophenol and 3 parts by weight of phenol,
(35 ° C.) A thermoplastic polyester, which is a solid-state polymerized polymer of 0.70, was obtained.

Reference Example 3 The polymer obtained in Reference Example 2 and polyethylene terephthalate (TR858, manufactured by Teijin Limited)
0 (IV = 0.83, hereinafter sometimes abbreviated as PET) at a ratio of 85 to 15 parts by weight to obtain a thermoplastic polyester as a blend polymer.

Reference Example 4 10 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 71.7 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol
Using cobalt acetate and manganese acetate as transesterification catalysts, methanol as a by-product was distilled off to the outside of the system.
The transesterification reaction was carried out while heating to 0 ° C., and at the stage when methanol was almost completely distilled off, antimony trioxide was added as a polymerization catalyst, and then orthophosphoric acid was added as a stabilizer to terminate the transesterification reaction. I was sorry. Next, the reaction product was subjected to a polycondensation reaction under high temperature and high vacuum to obtain a prepolymer having an intrinsic viscosity of 0.57 (a mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol at 25 ° C.). This prepolymer is made into a strand type chip, and further subjected to solid phase polymerization under heating and vacuum to obtain a solid phase polymerization having an intrinsic viscosity of 0.83 (a mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol at 25 ° C.). A thermoplastic polyester as a polymer was obtained.

Reference Examples 5 and 6 88 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 9.6 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol were used, and cobalt acetate and manganese acetate were used as transesterification catalysts. The methanol by-produced was distilled out of the system and transesterified while heating to 250 ° C.,
At the stage when methanol was almost completely distilled off, antimony trioxide was added as a polymerization catalyst, and then trimethyl phosphate was added as a stabilizer, thereby terminating the transesterification reaction. Next, the reaction product was subjected to a polycondensation reaction under high temperature and high vacuum to obtain a prepolymer having an intrinsic viscosity of 0.44 (mixed solvent of 2 parts by weight of tetrachloroethane and 3 parts by weight of phenol at 25 ° C.). After making this prepolymer into a strand type chip, it is further treated under heating and vacuum to obtain a polymer (C) having an intrinsic viscosity of 0.45 (a mixed solvent of 2 parts by weight of trichlorophenol and 3 parts by weight of phenol at 35 ° C.). Obtained.

Polymer (C) and PET (manufactured by Teijin Limited)
TR8580 (IV = 0.83)) was melt-kneaded at the following ratio to obtain a thermoplastic polyester as a blend polymer. Polymer (Reference Example 5): Polymer (C) / PET = 30
/ 70 (parts by weight) Polymer (Reference Example 6): Polymer (C) / PET = 50
/ 50 (parts by weight)

Example 1 Injection molding was performed so that the thermoplastic polyester (A) obtained in Reference Example 1 was in the skin layer and the thermoplastic resin (B) shown in the following table was in the core layer.
ml of preform was obtained. A / B / A, A / B / A /
The repetition of B / A was performed by changing the injection timing.
Subsequently, the preform was reheated and oriented blown to form a bottle. The preform was molded by a two-color molding machine manufactured by Nissei Plastic Industry (cylinder setting 295).
° C, screw rotation speed 100 rpm, molding cycle 45
sec), the average body thickness of the preform is 4 mm,
The weight was about 32 g. The bottle is KRUPP CORPOPL
Molded with AST's LB01, the bottle capacity is about 0.5L
(Liter), the average trunk thickness was 370 to 400 μm, and the average thickness of the B layer was 3 to 6% of the total thickness (trunk). The resulting bottle was evaluated. The results are shown in Tables 2 and 3.

Examples 2 to 10 and Comparative Example 1 As in Example 1, bottles were molded from the raw materials shown in Table 1 and evaluated. The resulting bottle was evaluated. The results are shown in Tables 2 and 3.

[0039]

[Table 1]

However, in Table 1, it is as follows. PA: polyamide resin (manufactured by Mitsubishi Gas Chemical, MX nylon 6001) PVDC: polyvinylidene chloride / polyvinyl chloride copolymer resin (vinylidene chloride / vinyl chloride = 80/20 parts by weight) CEi-P: manufactured by Takemoto Yushi, 2, 2'-p-phenylenebis (3,1-oxazin-4-one) TP: Tinuvin P (benzotriazole type, manufactured by Ciba-Geigy) Pigment: Pigment brwoun 6 (brown, component: iron oxide) PET: Polyethylene terephthalate (T made by Teijin Limited)
R8580 (IV = 0.83))

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

According to the present invention, a multilayer bottle having excellent heat resistance and gas barrier properties can be provided.

Continued on the front page F-term (reference) 3E033 AA01 BA13 BA17 BA18 BA21 BB05 BB08 CA07 CA16 4F100 AA37H AK15B AK15D AK16B AK16D AK41A AK41C AK41E AK46B JAKA BA16 BA05 BA05A16B10 BA05B10 JB16D JB16E JD02

Claims (11)

[Claims] 1. A thermoplastic polyester (A) layer and at least one thermoplastic resin (B) layer selected from the group consisting of thermoplastic polyamide, polyvinylidene chloride and vinylidene chloride / vinyl chloride copolymer. A layer of thermoplastic polyester (A) in contact with the layer of thermoplastic resin (B),
A multilayer bottle having a laminated structure in the order of B layer / A layer. 2. A layer comprising a thermoplastic polyester (A) and a layer comprising at least one thermoplastic resin (B) selected from the group consisting of thermoplastic polyamide, polyvinylidene chloride and vinylidene chloride / vinyl chloride copolymer. A layer of thermoplastic polyester (A) in contact with the layer of thermoplastic resin (B),
A multilayer bottle having a laminated structure in the order of layer B / layer A / layer B / layer A. 3. The multilayer bottle according to claim 1, wherein the thermoplastic polyester (A) is a thermoplastic polyester containing 10% by weight or more of an ethylene-2,6-naphthalenedicarboxylate unit as a repeating unit. . 4. The multilayer bottle according to claim 1, wherein the thermoplastic polyester (A) is a thermoplastic polyester containing at least 85% by weight of ethylene-2,6-naphthalenedicarboxylate units as repeating units. . 5. The multilayer bottle according to claim 1, which has a mouth made of thermoplastic polyester (A). 6. The multilayer bottle according to claim 1, wherein the thermoplastic polyester (A) is a copolymer polyester comprising an ethylene terephthalate unit and an ethylene-2,6-naphthalenedicarboxylate unit. 7. The multilayer bottle according to claim 1, wherein the thermoplastic polyester (A) is a mixture of polyethylene terephthalate and polyethylene-2,6-naphthalenedicarboxylate. 8. The multilayer bottle according to claim 1, wherein the thermoplastic resin (B) is a thermoplastic polyamide. 9. The multilayer bottle according to claim 8, wherein the thermoplastic polyamide is a polyamide comprising m-xylylenediamine. 10. The thermosetting polyester (A) containing at least one compound selected from the group consisting of a benzotriazole compound, a triazine compound, a benzophenone compound, a cyanoacrylate compound and a benzoxazine compound. 3. The multilayer bottle according to claim 1, which is a plastic polyester composition. 11. The thermoplastic polyester (A) is at least one selected from the group consisting of oxide pigments, ferrocyanide pigments, silicate pigments, phosphate pigments, carbon black, condensed polycyclic pigments and phthalocyanine pigments. The multilayer bottle according to claim 1 or 2, which is a thermoplastic polyester composition containing the following pigment.