JP2002200725A - Biodegradable resin laminate, container and container cover - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate having excellent biodegradability, oxygen absorbability, gas barrier properties and transparency, perfume and taste retentivity of a content, preservability of the content, a container and a container cover. SOLUTION: The resin laminate comprises a saturated polyester resin having a hydroxyalkanoate unit as a main body as a resin component. The laminate comprises at least one resin layer having oxygen absorbability and at least one resin layer having gas barrier coating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable resin laminate, a container and a container lid made of the resin laminate, and more particularly, to a resin composition comprising a saturated polyester resin mainly composed of hydroxyalkanoate units. The present invention also relates to a resin laminate having both oxygen absorption and gas barrier properties, and a container and a container lid made of the resin laminate.

[0002]

2. Description of the Related Art Conventionally, metal cans, glass bottles, various plastic containers and the like have been used as packaging containers.
Deterioration of contents and reduction in flavor due to oxygen remaining in the container and oxygen permeating the container wall have become problems.

[0003] In particular, in a metal can or a glass bottle, oxygen permeation through the container wall is zero, and only oxygen remaining in the container is a problem, whereas in a plastic container, oxygen permeation through the container wall is zero. It occurs in orders that cannot be ignored and poses a problem in the preservability of the contents.

In order to prevent this, in a plastic container, the container wall has a multilayer structure, and at least one of the layers is made of an oxygen-permeable resin such as an ethylene-vinyl alcohol copolymer. I have.

[0005] An oxygen absorber has been used for a long time to remove oxygen in a container. An example of applying the oxygen absorber to the container wall is disclosed in Japanese Patent Publication No. 62-1824. According to the above, a layer formed by mixing a deoxygenating agent mainly composed of a reducing substance such as iron powder with an oxygen-permeable resin and a layer having an oxygen gas barrier property are laminated to form a multilayer structure for packaging. Is described.

On the other hand, as an ideal solution for plastic waste, degradable plastics that disappear in the natural environment are attracting attention.
It is desired to provide a container having excellent preservability of the contents.

[0007]

Among biodegradable plastics, among biodegradable plastics, bacteria and fungi are degraded by the action of enzymes released outside the body. By adding a transition metal catalyst, oxygen absorption is reduced. Although it is known that it can be obtained, it has a problem that when it is applied to a container, the oxygen absorption rate to the contents is insufficient because of its low gas barrier property.

The oxygen-absorbing resin composition containing a transition metal-based catalyst has the advantage that it can be applied to packaging containers that are substantially transparent, but the oxygen absorption rate is still insufficient. Moreover, there is still a problem in the balance that the oxygen in the container or the oxygen permeating through the container wall is effectively absorbed and the mechanical properties required for the container are sufficiently maintained during the storage of the container. I have.

Accordingly, an object of the present invention is to have biodegradability, excellent oxygen absorption, gas barrier properties, and transparency, and excellent flavor retention of contents and preservation of contents. To provide a resin laminate, a container, and a container lid.

[0010]

According to the present invention, there is provided a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, wherein at least one resin layer having oxygen absorbability is provided. A resin laminate comprising at least one gas barrier coating is provided. In the resin laminate of the present invention, 1. The oxygen-absorbing resin layer is composed of a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. 2. the gas barrier coating is an inorganic vapor-deposited coating; It is preferable to have a biodegradable resin layer containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component on the inner surface side. Further, according to the present invention, there is provided a container or a container lid made of the above resin laminate.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, comprising at least one oxygen-absorbing resin layer and a gas barrier coating. It is an important feature that it comprises at least one layer. That is, in the laminate of the present invention, when molded into a container or the like, the residual oxygen and the like in the container are absorbed by the resin layer having an oxygen-absorbing property, and the gas barrier coating allows transmission of oxygen and the like from the outside. Can be effectively prevented, and a container or the like excellent in preservation of the contents can be provided. Moreover, since the resin component of the laminate is made of a saturated polyester resin mainly composed of hydroxyalkanoate units, the container made of such a laminate also has biodegradability.

In the present invention, the oxygen-absorbing resin layer comprises
It is desirable that the resin composition comprises a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. That is, in a resin composition in which an organic transition metal salt is contained in a saturated polyester resin mainly composed of hydroxyalkanoate units, the tertiary carbon or α-methylene moiety of the saturated polyester resin mainly composed of hydroxyalkanoate units composed of transition metal is used. Generation of radicals by abstraction of hydrogen atoms of
It is considered that oxygen absorption is generated through each elementary reaction of generation of a peroxy radical by addition of an oxygen molecule to this radical and abstraction of a hydrogen atom by the peroxy radical.

However, under the coexistence of a transition metal which does not cause deterioration of the resin under normal conditions, there is an induction period in the generation of the above radicals and addition of oxygen, and it is considered that these elementary reactions are not necessarily carried out effectively. Can be In the present invention, the unsaturated polyester is further contained in a resin composition containing a saturated polyester resin mainly composed of hydroxyalkanoate units and an organic transition metal salt, so that the elementary reaction is effectively performed, and oxygen is added. It increases the absorption capacity.
That is, in the unsaturated hydrocarbon used in the present invention, the hydrogen atom can be easily extracted at the position of the carbon atom adjacent to the carbon-carbon double bond, whereby a radical is generated and the elementary reaction is rapidly performed. In addition, it is performed effectively, and the oxygen absorbing ability can be increased.

(Saturated polyester resin mainly composed of hydroxyalkanoate units) As the saturated polyester resin mainly composed of hydroxyalkanoate units used as a resin component of the resin laminate, a polyhydroxy resin conventionally known as a biodegradable plastic is used. Butyrate (PH
B), a random copolymer of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV),
Poly (ε-caprolactone) (PCL), polybutylene succinate (PBS), polybutylene succinate
Aliphatic polyesters such as adipate (PBAS) and polylactic acid (PLLA) can be suitably used alone or in combination of two or more.

Polylactic acid (hereinafter sometimes referred to as PLLA) which can be particularly preferably used in the present invention is represented by the following formula (1)

Embedded image Is an aliphatic polyester that is industrially mass-produced, easily available, and environmentally friendly. It is decomposed by water and carbon dioxide by natural microorganisms, and is a complete recycling system type resin. Has also attracted attention. The glass transition point (Tg) is also about 58 ° C., which is close to the Tg of polyethylene terephthalate.

The saturated polyester resin mainly comprising hydroxyalkanoate units used in the present invention is, of course, not limited to, but 10,000 to 300,000, particularly 20
It preferably has a weight average molecular weight in the range of 000 to 200,000. The density is 1.20 to 1.26 g / cm
³ , melting point 165 to 200 ° C, melt flow rate (AS
(TMD1238, 190 ° C.) 2-20 g / 10 min.

(Organic Transition Metal Salt) As the transition metal,
Particularly preferred are Group VIII metal components of the periodic table such as iron, cobalt, and nickel.Others are Group I metals such as copper and silver; and Group IV metals such as tin, titanium and zirconium; and vanadium and the like.
Examples of the metal component include Group V metals such as Group V and chromium and Group VII such as manganese. Among these metal components, the cobalt component has a high oxygen absorption rate and is particularly suitable for the purpose of the present invention. Examples of the organic acid salt include carboxylate, sulfonate, phosphonate and the like,
Carboxylates are suitable for the purposes of the present invention, examples of which include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid,
Hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margarine Acid, stearic acid, arachidic acid, lindelic acid,
Transition metal salts such as tsunic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, sulfamic acid, naphthenic acid and the like can be mentioned.

(Unsaturated Hydrocarbon) The unsaturated hydrocarbon is not limited to this, but may have 1 to 10 carbon atoms.
Can be suitably used, for example, ethylene,
Propylene, 1-butene, 4-methyl-1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-tetradecene, 1-pentadecene, 1
-Hexadecene, 1-heptadecene, 1-nonadecene,
Α-olefins such as 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene; conjugated dienes such as isoprene and butadiene; 1,4-hexadiene and 3-methyl- 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Methyl-1,4-hexadiene, 4,5-dimethyl-
Chain non-conjugated dienes such as 1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2- Norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene,
Cyclic non-conjugated dienes such as dicyclopentadiene; 2,3-
Trienes such as diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, chloroprene and the like can be mentioned. These unsaturated hydrocarbons can be used alone or in combination of two or more, or in the form of a polymer or copolymer thereof.

(Oxygen-absorbing layer) In the resin laminate of the present invention, the organic transition metal salt is contained in an amount of from 10 to 8,000 ppm, particularly from 50 to 5,000 ppm, based on a saturated polyester resin mainly containing hydroxyalkanoate units as a metal.
Is preferably contained in an amount of Further, in the present invention, the unsaturated hydrocarbon is used in an amount of 0.5 to 20 per saturated polyester resin mainly composed of hydroxyalkanoate units.
It is preferably contained in an amount of from 1 to 5% by weight.

In the resin laminate of the present invention, there is no particular limitation on the blending of each of the above components, and the above two or three components may be separately blended, or two of the above three components may be blended in advance. Then, this and the remaining components may be blended. As an example of the method of this compounding, a method in which a saturated polyester resin mainly containing a hydroxyalkanoate unit and an unsaturated hydrocarbon are preliminarily mixed, and an organic transition metal salt is added thereto, or a method mainly including a hydroxyalkanoate unit Pre-blend saturated polyester resin and organic transition metal salt,
There may be mentioned a method of blending an unsaturated hydrocarbon with the mixture.

Various methods can be used for blending the organic transition metal salt with the saturated polyester resin mainly composed of hydroxyalkanoate units. For example, it is also possible to simply blend the organic transition metal salt with the resin by a dry method. Although it is possible, since the organic transition metal salt is in a smaller amount than the saturated polyester resin mainly composed of hydroxyalkanoate units, the organic transition metal salt is dissolved in an organic solvent in order to homogenize the blend, and this solution is used. And a powdery or granular resin, and if necessary, drying the mixture under an inert atmosphere. Examples of the solvent for dissolving the organic transition metal salt include alcohol solvents such as methanol, ethanol and butanol; ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran and dioxane; ketone solvents such as methyl ethyl ketone and cyclohexanone; -A hydrocarbon solvent such as hexane and cyclohexane can be used, and it is generally preferable to use a concentration such that the concentration of the organic transition metal salt is 5 to 90% by weight.

The mixing of the saturated polyester resin mainly composed of hydroxyalkanoate units with the organic transition metal salt and the subsequent storage are performed in a non-oxidizing atmosphere so as to prevent the oxidation of the composition at the previous stage. Is good. For this purpose, mixing or drying under reduced pressure or in a nitrogen stream is preferred. This mixing and drying can be carried out at an earlier stage of the molding process by using an extruder or an injection machine equipped with a vent type or a dryer. In this case, special consideration is given to the preservation of the resin containing the organic transition metal salt. Is achieved. Alternatively, an oxygen-absorbing resin composition can be prepared by preparing a masterbatch of a resin containing a relatively high concentration of an organic transition metal salt and dry-blending the masterbatch with an unblended resin. The resin composition used in the present invention is preferably dried at a temperature of 40 to 160 ° C., which is a general drying condition, under a reduced pressure of 0.5 to 2 mmHg for 2 to 24 hours, and then used for molding described below.

The oxygen-absorbing layer in the laminate of the present invention is not generally required, but may optionally contain a known activator. Suitable examples of activators include, but are not limited to, polyethylene glycol,
Hydroxyl and / or carboxyl group-containing polymers such as polypropylene glycol, ethylene vinyl alcohol copolymer, ethylene / methacrylic acid copolymer, and various ionomers. These hydroxyl and / or carboxyl group-containing polymers can be blended in an amount of 30 parts by weight or less, particularly 0.01 to 10 parts by weight, per 100 parts by weight of the saturated polyester resin mainly composed of hydroxyalkanoate units. In the oxygen-absorbing resin composition used in the present invention,
Known resins such as fillers, colorants, heat stabilizers, weather stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants such as metal soaps and waxes, modifying resins and rubbers, etc. The compounding agent can be compounded according to a formulation known per se.

(Gas Barrier Coating) The gas barrier coating in the resin laminate of the present invention may be, for example, a resin obtained by coating a saturated polyester resin film mainly composed of a hydroxyalkanoate unit as a resin component with epoxyamine, or SiOx. And an inorganic vapor-deposited film obtained by evaporating a ceramic or carbon, or a metal-inorganic vapor-deposited film obtained by evaporating a metal such as aluminum. Preferably, it is an inorganic vapor-deposited film.

(Layer Structure) The resin laminate of the present invention comprises a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, and has various modes as long as it has a resin layer having an oxygen absorbing property and a gas barrier coating. However, in general, a gas barrier coating is located on the side that will be the outer surface to prevent oxygen transmission from the outside, and the oxygen-absorbing layer absorbs residual oxygen and the like inside the container or the like. Therefore, it is necessary to be located inside the gas barrier coating. In general, the oxygen-absorbing layer is preferably provided inside the outer surface of the container or the like so as not to be exposed on the outer surface of the container or the like. Since the inner surface is preferably provided outside the inner surface, the inner surface is preferably provided with a layer made of a saturated polyester resin mainly composed of hydroxyalkanoate units. When the resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units is (HP), the oxygen absorbing layer is (OAR), and the gas barrier coating is (GB), the following examples can be given. (Inner surface) HP / OAR / HP / GB (Outer surface) (Inner surface) HP / OAR / GB (Outer surface) Although the thickness of each layer varies depending on the use and the like, it generally comprises a saturated polyester resin mainly composed of hydroxyalkanoate units. The layer is between 30 and 1500 μm, especially 50
To 500 μm, and the oxygen-absorbing layer is 20 to 500 μm.
m, especially 30 to 100 μm, gas barrier coating,
0.005 to 0.5 μm, especially 0.1 to 0.4 μm
Is preferably within the range. The thickness of the entire resin laminate is 100 to 2000 μm, particularly 200 to 100 μm.
It is preferably in the range of 0 μm.

(Laminate) The method for producing the resin laminate of the present invention is not particularly limited, and the resin laminate can be produced by a method known per se as long as a laminate having the above-described layer structure is produced. However, for example, an inflation casting method, an extrusion coating method, a co-extrusion method, a sandwich lamination and the like can be adopted, and a known adhesive can be used. In addition, the resin laminate of the present invention can be formed into a multilayer preform by co-injection molding or co-extrusion molding in addition to the sheet shape described above, or can be formed into a target container shape by direct co-injection molding or the like. Is also possible.

The gas barrier film is formed by previously laminating a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, an oxygen-absorbing resin layer, and the like.
Finally, a film may be formed by vapor deposition or the like, or the film may be formed in advance by forming a film on a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, and then laminated. Further, a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, an oxygen-absorbing resin layer, and the like are preliminarily laminated and molded into a target container shape, and a gas barrier coating is formed on the outer surface side. It can also be deposited.

(Container and Container Lid) The method for producing the container of the present invention is not particularly limited, and is molded by a conventionally known production method. For example, the multilayer preform may be a blow molded article obtained by stretch blow molding, or may be a container molded into a shape such as a cup or a tray by direct co-injection molding. Further, a container obtained by heating and melting a sheet-shaped resin laminate and then performing vacuum forming, pressure forming, or plug assist forming may be used.
Further, the laminate can be formed into an arbitrary shape such as a pouch-shaped container by heat sealing the periphery. Further, the container lid can be formed into a container lid by molding the container lid shell by the above-described various molding methods, or can be a seal lid formed into a mouth shape of a container to which the laminate of the present invention is applied. it can.

[0029]

Next, the present invention will be described with reference to specific examples. The present invention is not limited to the following embodiments.

(Evaluation of Oxygen Gas Barrier Property) A prototype bottle was placed in a vacuum chamber, and after depressurizing under vacuum, high-purity nitrogen gas was introduced, and the gas phase in the bottle was replaced with nitrogen gas.
Then, it was sealed with a rubber stopper.
Stored at 0 ° C.-80% RH. After 21 days, the air in the bottle was collected using a gas tight syringe, analyzed by GC, and converted to BO2.

(Example 1) Polylactic acid lactate of Shimadzu Corporation was used. A resin layer in which the innermost layer and the outermost layer are made of polylactic acid, and an intermediate layer is a polylactic acid resin layer in which Polyip manufactured by Idemitsu Petrochemical Co., Ltd. is melt-blended at 3% by weight, and an organic metal complex (cobalt stearate) is melt-blended at a cobalt concentration of 5000 ppm. Was used. Using two injection molding machines, 19
Under the condition of 0 ° C to 200 ° C, the layer structure from the inner layer to the outer layer is
A preform having a diameter of 28 mmφ of two types and three layers of polylactic acid layer / organic metal complex-containing polylactic acid layer / polylactic acid layer was co-injection molded. The mold temperature was 15 ° C. Next, after reheating the preform to 65 ° C to 85 ° C with an infrared heater,
The bottle was blow-molded into a 500-ml bottle having an average thickness of 300 μm. Next, using a bottle-shaped electrode and an electrode placed inside the bottle, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle is decompressed by a vacuum using a CVD vapor deposition apparatus. And a film forming pressure of 0.
1-torr, 13.56 MHz high frequency power PE-CV
A D carbon film was deposited.

Example 2 Shimadzu polylactic acid lactate was used. An organic metal complex (cobalt stearate) is added to a polylactic acid resin layer in which the innermost layer is polylactic acid and the outermost layer is a 3% by weight melt blend of Polyip manufactured by Idemitsu Petrochemical Co., Ltd.
Was melt-blended at a cobalt concentration of 5000 ppm. 190 ° C. to 2 using two injection molding machines
Under the condition of 00 ° C., the layer structure from the inner layer to the outer layer has a diameter of 28 of two kinds of two layers, a polylactic acid layer / an organic metal complex-containing polylactic acid layer.
A mmφ preform was co-injection molded. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. using an infrared heater, and then blow-molded into a 500 ml bottle having an average thickness of 300 μm. Next, using a bottle-shaped electrode and an electrode placed inside the bottle, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle is decompressed by a vacuum using a CVD vapor deposition apparatus. Then, a PE-CVD carbon film was deposited at a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz.

Example 3 Shimadzu polylactic acid lactate was used. An organic metal complex (cobalt stearate) is added to a polylactic acid resin layer in which the innermost layer is polylactic acid and the outermost layer is a 3% by weight melt blend of Polyip manufactured by Idemitsu Petrochemical Co., Ltd.
Was melt-blended at a cobalt concentration of 5000 ppm. 190 ° C. to 2 using two injection molding machines
Under the condition of 00 ° C., the layer structure from the inner layer to the outer layer has a thickness of 30% of the two layers of the polylactic acid layer / organic metal complex-containing polylactic acid layer.
A 500 ml cup having a diameter of 0 μm and a mouth outer diameter of 90 mm was co-injection molded. Next, using a cup-shaped electrode electrode, a vacuum pressure was applied between the outer layer of the cup and the outer wall of the cup using a cup-shaped electrode electrode. , High frequency power 1
A 3.56 MHz PE-CVD carbon film was deposited.

Next, an organometallic complex (cobalt stearate) was melt-blended at a cobalt concentration of 5000 ppm to a polylactic acid resin layer in which the innermost layer was made of polylactic acid and the outermost layer was melt-blended with 3% by weight of Polyip manufactured by Idemitsu Petrochemical Co., Ltd. The used resin layer was used. Using two extruders, 19
Co-extrusion was performed under the conditions of 0 ° C. to 200 ° C. to form a 100 μm-thick sheet composed of two layers, a polylactic acid layer / organic metal complex-containing polylactic acid layer, from the inner layer to the outer layer. Further, after reducing the pressure in a vacuum using a CVD deposition apparatus, a mixed gas of hexane and argon is used as a source gas on the outer layer side of the sheet.
A PE-CVD carbon film was deposited at a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz.

(Comparative Example 1) Polylactic acid lactate of Shimadzu Corporation was used. Using an injection molding machine, a preform having a diameter of 28 mmφ was injection molded under the conditions of 190 ° C to 200 ° C. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. with an infrared heater, and then formed into a 500 ml blow bottle having an average thickness of 300 μm using a mold blow molding machine.

(Comparative Example 2) Polylactic acid lactate of Shimadzu Corporation was used. A resin layer in which the innermost layer and the outermost layer are made of polylactic acid, and an intermediate layer is a polylactic acid resin layer in which Polyip manufactured by Idemitsu Petrochemical Co., Ltd. is melt-blended at 3% by weight, and an organic metal complex (cobalt stearate) is melt-blended at a cobalt concentration of 5000 ppm. Was used. Using two injection molding machines, 19
Under the condition of 0 ° C to 200 ° C, the layer structure from the inner layer to the outer layer is
A preform having a diameter of 28 mmφ of two types and three layers of polylactic acid layer / organic metal complex-containing polylactic acid layer / polylactic acid layer was co-injection molded. The mold temperature was 15 ° C. Next, after reheating the preform to 65 to 85 ° C. with an infrared heater,
It was biaxially stretched and molded into a mold blow bottle having an average thickness of 300 μm having a volume of 0 ml.

(Comparative Example 3) Polylactic acid lactate of Shimadzu Corporation was used. Using an injection molding machine, a preform having a diameter of 28 mmφ was injection molded under the conditions of 190 ° C to 200 ° C. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. with an infrared heater, and then biaxially stretch-molded into a 500 ml volume blow mold bottle having an average thickness of 300 μm using a mold blow molding machine. Next, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle was evacuated using a bottle-shaped electrode and an electrode placed inside the bottle with a CVD vapor deposition apparatus. 12. The film forming pressure is 0.1 torr and the high frequency power is 13.
A 56 MHz PE-CVD carbon film was deposited.

(Comparative Example 4) Polylactic acid lactate of Shimadzu Corporation was used. Injection molding is performed using an injection molding machine under the conditions of 190 ° C to 200 ° C, and the thickness is made of only polylactic acid resin.
A 500 ml cup having a diameter of 00 μm and an outer diameter of 90 mm was formed. Next, the preform is heated to 65 ° C with an infrared heater.
After reheating to 85 ° C., using a mold blow molding machine,
It was biaxially stretched and molded into a mold blow bottle having an average thickness of 300 μm and a ml volume. Next, using a cup-shaped electrode, a vacuum pressure was applied between the cup outer layer and the cup outer wall side electrode using a cup-shaped electrode, and then a hexane / argon mixed gas was used as a raw material gas on the cup outer layer surface at a film forming pressure of 0.1 torr. High frequency power 1
A 3.56 MHz PE-CVD carbon film was deposited. Next, a 100 μm-thick sheet made of polylactic acid was extruded. Further, after reducing the pressure in a vacuum by a CVD vapor deposition apparatus, a hexane / argon mixed gas was used as a raw material gas, and a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz
E-CVD carbon film deposition was performed.

[0039]

[Table 1]

[0040]

According to the present invention, there is provided a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, wherein at least one oxygen-absorbing resin layer is provided. By including at least one gas barrier coating, it is possible to have oxygen absorption and gas barrier properties while having excellent biodegradability. In particular, the oxygen-absorbing resin layer is composed of a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon, and a gas. The fact that the barrier coating comprises an inorganic vapor-deposited coating makes it possible to have an increased oxygen absorption rate and to impart transparency. According to the container and the container lid made of the resin laminate of the present invention,
In addition to having biodegradability, it has become possible to impart excellent flavor retention and preservation of contents.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) // B32B 9/00 B32B 9/00 A F term (reference) 3E086 AB01 AD01 AD04 AD05 AD06 BA04 BA15 BA40 BB01 BB05 BB90 4F100 AA01A AA37 AH04B AK02B AK41B AK41C AL05B AR00A BA03 BA04 BA07 BA10A BA10B EH31 EH36 EH66A GB16 GB18 JC00B JD02A JD03B JM02

Claims (6)

[Claims] 1. A resin laminate containing, as a resin component, a saturated polyester resin mainly composed of hydroxyalkanoate units, comprising at least one resin layer having oxygen absorbability and at least one gas barrier coating. A resin laminate characterized by the above-mentioned. 2. An oxygen-absorbing resin layer comprising a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. The resin laminate according to claim 1, wherein: 3. The resin laminate according to claim 1, wherein the gas barrier coating is an inorganic vapor-deposited coating. 4. The resin laminate according to claim 1, further comprising a biodegradable resin layer containing, as a resin component, a saturated polyester resin mainly composed of hydroxyalkanoate units on the inner surface side. body. 5. A container comprising the resin laminate according to any one of claims 1 to 4. 6. A container lid comprising the resin laminate according to any one of claims 1 to 4.