JPH0671825A - Laminated body for packaging - Google Patents

Abstract

PURPOSE:To obtain a laminate for packaging having prominent biodegradability as well as the combination of a yield point strength and rigidity by a method wherein a saturated polyester resin layer and an ethylene vinylalcohol copolymer layer are laminated through a resin bonding agent layer. CONSTITUTION:The laminate is constituted of a first layer, containing saturated polyester resin having the principal body of hydroxy alkanoate unit, a resin bonding agent layer and a second layer containing ethylene-vinylalcohol copolymer containing 10-60mol% of ethylene unit. The laminate 1 is constituted of a biodegradable saturated polyester resin layer 2, an ethylene-vinylalcohol copolymer layer 3 and a resin bonding agent layer 4 interposed between both layers. The saturated polyester resin layer 2 is preferable to be positioned at the outer surface of a vessel while the ethylene-vinylalcohol copolymer layer 3 is preferable to be positioned at the inner surface of the vessel.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a packaging laminate having biodegradability and improved mechanical properties, and more particularly to a packaging laminate comprising a saturated polyester and an ethylene-vinyl alcohol copolymer. Regarding a laminate.

[0002]

2. Description of the Related Art In recent years, the amount of solid waste discharged by cities has become huge, and the capacity of waste disposal is approaching its limit. Plastic is always pointed out as one of the causes of this solid waste.

As an ideal solution for plastic waste, degradable plastics that disappear in the natural environment have been attracting attention. Degradable plastics include photodegradable plastics in which the molecular chain of the polymer is cleaved by ultraviolet rays, and biodegradable plastics that are destroyed by the action of enzymes released by bacteria and fungi outside the body.

However, in the case of photodegradable plastics, the effect of burying in the soil cannot be expected, and there is also a fear of environmental pollution due to decomposition products, so that great expectations are placed on biodegradable plastics.

Conventional biodegradable plastics include polyhydroxybutyrate (PHA), 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3H).
Random copolymers with V) are known.

A resin composition in which a biodegradable plastic such as polycaprolactone (PCL) is blended with another resin is already known, for example, JP-A-4-139248.
The publication describes a biodegradable resin composition comprising 5 to 99% by weight of an ethylene-vinyl alcohol copolymer and 95 to 1% by weight of an aliphatic polyester.

[0007]

Known biodegradable plastics are stable in the air, and decompose in soil in which bacteria are active and in water, and the decomposition products are carbon dioxide gas. Although it has the advantage of being water, it still has problems that must be solved when applied to packaging, which is the main use of plastics.

That is, all of the biodegradable saturated polyesters have problems in mechanical properties, such as β-type ones such as PCL have small elongation and are brittle, and ω-type ones such as PCL have low yield strength. It has a defect in mechanical strength, and in order to maintain the strength of the container when filling a heavy internal material, the thickness of the container must be made considerably larger than that of the conventional one. There is a problem that the cost increases.

In order to solve this problem, it is conceivable to laminate the biodegradable saturated polyester with other plastics. However, plastics having high strength are generally low in biodegradability, and the intended purpose cannot be achieved. become.

The present inventors have succeeded in laminating a saturated polyester having biodegradability and an ethylene-vinyl alcohol copolymer, and this laminate has excellent biodegradability as a whole and is excellent. It has been found that it has a combination of yield point strength and tenacity (toughness).

That is, an object of the present invention is to combine a saturated polyester and an ethylene-vinyl alcohol copolymer, which has an excellent biodegradability as a whole, and an excellent yield point strength and tenacious property (toughness). To provide a packaging laminate having

[0012]

According to the present invention,
(A) A first layer containing a saturated polyester resin mainly containing hydroxyalkanoate units, (B) a resin adhesive layer, and (C) ethylene-vinyl alcohol containing 10 to 60 mol% of ethylene units. A packaging laminate is provided comprising a second layer comprising a copolymer.

Also according to the present invention, (A) a first surface layer containing a saturated polyester resin mainly composed of hydroxyalkanoate units, and (B) a resin adhesive layer,
(C) an intermediate layer containing an ethylene-vinyl alcohol copolymer containing 10 to 60 mol% of ethylene, and (D)
A packaging laminate comprising a resin adhesive layer and a second surface layer containing a saturated polyester resin mainly composed of (E) hydroxyalkanoate units.

[0014]

The packaging laminate of the present invention is characterized in that a saturated polyester resin layer mainly containing hydroxyalkanoate units and an ethylene-vinyl alcohol copolymer layer are laminated via a resin adhesive layer. . The saturated polyester resin layer is an essential component for imparting biodegradability to the packaging material. In the present invention, an ethylene-vinyl alcohol copolymer layer is laminated on this.

The ethylene-vinyl alcohol copolymer is
It is well known as a plastic packaging material having an excellent gas barrier property against oxygen and the like, but in the present invention, this ethylene-vinyl alcohol copolymer is used to enhance the yield strength and rigidity of the laminate.

In general, additivity may be established between the mechanical properties of the entire laminate and the mechanical properties of the constituent layers. In the case of the laminate of the present invention, it was found that this additivity holds for the yield strength. That is, the yield strength of the laminate is σ obs, the yield strength of the ethylene-vinyl alcohol copolymer is σ EVOH, and the yield strength of the saturated polyester resin layer is σ SAP, and the thickness ratio of the ethylene-vinyl alcohol copolymer in the laminate is Is λ,

[Formula 1] σobs = λσEVOH + (1−λ) σSAP holds. Thus, according to the present invention, the yield strength can be remarkably improved by laminating the ethylene-vinyl alcohol copolymer on the saturated polyester resin mainly containing the hydroxyalkanoate unit.

According to the present invention, the above-mentioned lamination provides an unexpected synergistic effect on the tenacity (toughness) of the laminate. See Table 1 and FIG. 1 below. That is,
Both the saturated polyester resin (FIG. 1B) and the ethylene-vinyl alcohol copolymer (FIG. 1A) exhibit approximately the same level of elongation at yield, but the laminate of the present invention (FIG. 1C) has the highest of these resins. The upper yield point elongation is 10% or more, especially 20 to 40% larger than the upper yield point elongation.
Since the upper yield point elongation is closely related to the tenacity (toughness) of the plastic, in the laminate of the present invention, the tenacity of the laminate is synergistically beyond the range predicted from each constituent resin layer. The fact that (toughness) is improving becomes clear. Further, the ethylene-vinyl alcohol copolymer,
When a strain exceeding the upper yield point elongation is given, there is a drawback that the stress is rapidly reduced and the fracture occurs (Fig. 1A). However, in the laminate of the present invention, when the strain exceeding the upper yield point elongation is given. Even so, the stress is maintained at a high level, and the structure is resistant to breakage.

In this packaging laminate, since the saturated polyester resin is present on at least one of the inner and outer surfaces, the saturated polyester resin on the surface is decomposed by bacteria, and the ethylene-vinyl alcohol copolymer layer adjacent thereto is also present. Since the decomposition of water is promoted by the absorption of water and the ethylene-vinyl alcohol copolymer itself is decomposed and eluted, there is an excellent effect that the disintegration of the packaging container is significantly accelerated.

Further, ethylene having an excellent gas barrier property
The presence of the vinyl alcohol copolymer in the packaging laminate provides excellent gas barrier properties against oxygen gas, aroma components and the like. Moreover, in the packaging laminate provided with the saturated polyester resin layer on the inner and outer surface layers, the water resistance when used as a container is improved, and as a result that the moisture absorption of the ethylene-vinyl alcohol copolymer is suppressed, the gas due to moisture absorption The advantage that the reduction in barrier property is suppressed is also obtained.

Since the saturated polyester resin and the ethylene-vinyl alcohol copolymer used in the present invention do not have thermal adhesiveness, they can be laminated and integrated by interposing a resin adhesive between them. . The biodegradable saturated polyester resin has a low melting point of 40 to 180 ° C. and a decomposition temperature of about 170 ° C. or higher, which is close to the molding temperature of general resins, so that it is one of the difficult things to laminate. In the invention, since the resin adhesive layer to be used acts as a heat blocking layer for both resins in contact therewith, lamination can be easily performed while suppressing thermal decomposition of the saturated polyester resin.

In the packaging laminate of the present invention, (A) a saturated polyester resin layer mainly containing a hydroxyalkanoate unit and (B) an ethylene-vinyl alcohol copolymer layer, A: B = 200: 1 to It is also important to contain it in a thickness ratio of 2: 1, especially 80: 1 to 4: 1. That is, outside the above range, the tenacity (toughness) of the laminate cannot be synergistically improved, and when the thickness of the saturated polyester resin layer is smaller than this range, the biodegradability decreases, while the ethylene- If the thickness of the vinyl alcohol copolymer is less than this range, the yield strength is lowered to such an extent that it is not suitable for containers.

[0022]

Preferred Embodiment of the Invention

(Laminate Structure) In FIG. 2 showing a cross-sectional structure of an example of the packaging laminate of the present invention, this laminate 1 comprises a biodegradable saturated polyester resin layer 2, an ethylene-vinyl alcohol copolymer layer 3 and both. It is composed of a resin adhesive layer 4 interposed therebetween. The saturated polyester resin layer 2 is the outer surface of the container,
The ethylene-vinyl alcohol copolymer layer 3 is preferably located on the inner surface of the container, and this packaging container is useful for containing oily contents, organic solvent-containing contents, and the like.

In FIG. 3, which shows the cross-sectional structure of another example of the packaging laminate of the present invention, this laminate 1 comprises a biodegradable saturated polyester resin outer layer 2a, a resin adhesive layer 4a, and an ethylene-vinyl alcohol copolymer weight. Combined intermediate layer 3 and resin adhesive layer 4
b and the symmetry 5 of the biodegradable saturated polyester resin inner layer 2b
Made of layered structure. This container has excellent storability of contents and biodegradability.

(Saturated Polyester Resin) As the saturated polyester resin, any biodegradable saturated polyester resin mainly containing a hydroxyalkanoate unit is used. The saturated polyester resin should have at least a molecular weight capable of forming a film, and generally its number average molecular weight is in the range of 5 × 10 ^{4 to} 12 × 10 ⁴ , particularly 6 × 10 ^{4 to} 11 × 10 ^4. Is good. Examples of suitable saturated polyester resins are poly-β-hydroxyalkanoates, or aliphatic polylactones to poly-ω-hydroxyalkanoates or copolymers thereof.

The poly-β-hydroxyalkanoate has the following formula:

[Chemical 1] In the formula, R is a linear or branched alkyl group, for example, a repeating unit represented by: 3-hydroxybutyrate [R = -CH3, 3HB], 3-hydroxyvalerate [R = -CH2 CH3 3HV], 3-hydroxycaproate [R =-(CH2) 2 CH3], 3-hydroxyheptanoate [R =-(CH2) 3 CH3], 3-
Hydroxy octanoate [R =-(CH2) 4 CH3
], 3-hydroxynonanoate [R =-(CH2) 5
CH3], 3-hydroxydecanoate [R =-(C
H2) 6CH3] and the like.

Suitable resins of this type are 3-hydroxybutyrate and other 3-hydroxyalkanoates,
Particularly, it is a copolymer obtained by copolymerizing with 3-hydroxyvalerate, and is a copolymer containing these in a weight ratio of 95: 5 to 85:15, particularly 92: 8 to 88:12.

The aliphatic polylactone or poly-ω-hydroxyalkanoate has the following formula:

[Chemical 2] In the formula, R is a linear or branched alkylene group, and a repeating unit represented by, for example, γ-butyrolactone, δ-
1 of repeating units such as valerolactone and ε-caprolactone
Examples thereof include polymers of one kind or two or more kinds.

Suitable examples of this type of resin are polycaprolactone or copolymers of caprolactone with other lactones.

In the present invention, it is also possible to use a copolymer comprising a repeating unit of "Chemical formula 1" and a repeating unit of "Chemical formula 2". A suitable example of this copolymer is a copolymer of 3-hydroxybutyrate and γ-butyrolactone or ε-caprolactone. Also, a blend of two or more of the above may be used.

(Ethylene-vinyl alcohol copolymer)
In the present invention, the saturated polyester resin is combined with an ethylene-vinyl alcohol copolymer. The copolymer preferably has an ethylene content of 10 to 60 mol%, particularly 20 to 50 mol%, and a saponification degree of 95% or more, particularly 98% or more. As the ethylene content in the copolymer decreases, that is, as the vinyl alcohol content increases, the yield point strength increases, but on the contrary, the upper yield point elongation decreases, and the brittleness increases, particularly at low temperatures. It is convenient for the purpose of the present invention to use the ethylene-vinyl alcohol copolymer in the above range.

In this ethylene-vinyl alcohol copolymer, even if there are ethylene segments in which ethylene units are bonded to each other, the molecular weight of the segment is preferably 500 or less from the viewpoint of biodegradability. On the other hand, it is preferable that there are also segments in which vinyl alcohol units are bonded to each other. Multiple vinyl alcohol,
In particular, it is said that one secondary hydroxyl group becomes a keto group and decomposes rapidly in a segment in which three are bonded.

The ethylene-vinyl alcohol copolymer should have a molecular weight sufficient to form a film, and it is measured at a temperature of 30 ° C. in a mixed solvent of 85% by weight of phenol and 15% by weight of water. , The intrinsic viscosity (IV)
It is preferably in the range of 0.07 to 0.17 dl / g.

(Resin Adhesive) In the present invention, the resin adhesive may be any thermoplastic or thermosetting resin adhesive as long as it can bond the saturated polyester resin and the ethylene-vinyl alcohol copolymer. Agents are used.
Examples of resin adhesives include urethane adhesives, epoxy adhesives, acid-modified olefin resin adhesives, copolyamide adhesives, copolyester adhesives, and the like.

Resin adhesives which are convenient for the purpose of the present invention include polyester-urethane adhesives and polyester-epoxy-urethane adhesives. As the polyester-urethane adhesive, an isocyanate-terminated polyester urethane obtained by reacting a hydroxyl group-terminated polyester with a diisocyanate is crosslinked with a crosslinking agent or a curing agent such as a polyhydric alcohol, a polyhydric alcohol, a polycarboxylic acid and A hydroxyl group-terminated polyester urethane obtained by reacting diisocyanate is crosslinked using diisocyanate as a crosslinking agent. The latter is particularly suitable.

Polyhydric carboxylic acids constituting the polyester include succinic acid, adipic acid, sebacic acid, decanecarboxylic acid and the like, and polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, glycerin, neopentane glycol, Erythritol, sorbitol, mannitol and the like are used. Examples of the diisocyanate include xylylene diisocyanate, tolylene diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate.

The polyester-epoxy-urethane adhesive comprises a composition containing a hydroxyl-terminated polyester, an epoxy resin and a diisocyanate crosslinking agent,
As the polyvalent carboxylic acid, polyhydric alcohol or diisocyanate that constitutes the hydroxyl group-terminated polyester, those exemplified above are used. An epoxy resin obtained by reacting bisphenol A and epichlorohydrin is used as the epoxy resin.

(Production of Laminate) The production of a laminate can be carried out by a lamination method such as dry lamination, sandwich lamination, extrusion coating, multi-layer coextrusion, multi-layer injection. In the multi-layer simultaneous extrusion, after melt-kneading with an extruder corresponding to each resin layer, it is extruded into a predetermined shape through a multi-layer multiple die such as a T-die and a circular die. Further, after melt-kneading with an injection machine corresponding to each resin layer, co-injection or sequential injection into an injection mold is performed to manufacture a multilayer container or a preform for the container. In any of these lamination methods,
A resin adhesive such as a coat or extrusion is interposed between the saturated polyester resin layer and the ethylene-vinyl alcohol copolymer layer.

The molded product may be in the form of a film, a sheet, a parison or pipe for forming a bottle or a tube, a preform for forming a bottle or a tube, or the like. Parison,
The formation of a bottle from a pipe or a preform is easily performed by pinching off an extrudate with a pair of split molds and blowing a fluid into the interior. Further, a stretched blow bottle or the like can be obtained by cooling the pipe or the preform, heating it to a stretching temperature, stretching it in the axial direction, and blow-stretching it in the circumferential direction by fluid pressure.

Further, the film or sheet is vacuum formed,
A cup-shaped, tray-shaped, or other packaging container can be obtained by applying means such as pressure molding, bulging molding, and plug assist molding.

Further, in the case of a multi-layer film, the multi-layer film may be laminated or folded in a bag shape and the periphery thereof may be heat-sealed to form a bag-shaped container.

[0041]

EXAMPLES Next, the method of the present invention will be described with reference to examples. Polycaprolactone H-7 manufactured by Daicel Chemical Industries, Ltd. was used as the saturated polyester (poly-ω-hydroxyalkanoate), and Eval G manufactured by Kuraray Co., Ltd. was used as the ethylene vinyl alcohol copolymer. As the adhesive, a polyester-urethane adhesive (AD-506-R-40 manufactured by Toyo Morton Co., Ltd. and curing agent AD-RT-1 manufactured by the same) was used. In addition, as a saturated polyester (poly-β-hydroxyalkanoate)
A laminate was manufactured in the same manner by using ICI Biopol (hydroxystyrate containing 10 mol% of hydroxyvalerate, hydroxyvalerate copolymer).

Polycaprolactone and ethylene vinyl alcohol copolymer were formed into a single layer at a temperature of up to 190 ° C. using an extrusion molding machine. Polycaprolactone is about 72μ thick and ethylene vinyl alcohol copolymer is about 25μ thick.
Molded to a thickness of μ. Also, the adhesive is AD-506-R-4
A mixture of 0.56.5 parts, a hardening agent AD-RT-1, 2.7 parts, ethyl acetate 20.4 parts, and toluene 20.1 parts was prepared.

After the above adhesive was applied to the surface of the ethylene vinyl alcohol copolymer film, a polycaprolactone monolayer film was pressure-bonded thereto. Similarly, the above adhesive was applied to the opposite surface of the ethylene vinyl alcohol film, and the polycaprolactone monolayer film was pressure-bonded thereto.

After leaving the obtained laminated structure for 5 days at room temperature,
It was used for measuring the mechanical strength shown below. Measurement of Mechanical Strength Using a UCT-5T type Tensilon manufactured by ORIENTEC Co., Ltd., a mechanical strength was measured with a 25 kg load cell at a pulling speed of 500 mm / min. The shape of the measurement sample is ASTM D-1
Model 822 was used.

Example 1 Polycaprolactone H-7 manufactured by Daicel Chemical Industries, Ltd. was used as the poly-ω-hydroxyalkanoate for the saturated polyester, and Eval G manufactured by Kuraray Co., Ltd. was used for the ethylene vinyl alcohol copolymer. . As the adhesive, a mixture of AD-506-R-40 manufactured by Toyo Morton Co., Ltd. and curing agent AD-RT-1 manufactured by the same company was used. The layer structure of the laminated structure is such that polycaprolactone is 72 μm thick on both outer surface layers,
The above urethane-based adhesive having a thickness of 5 μm was formed on the adhesive layer, and Eval G having a thickness of 25 μm was formed on the intermediate layer.

The mechanical strength of the laminated structure is measured,
The obtained tensile stress-strain curve is shown in FIG. 1, and the yield strength and upper yield elongation (%) are shown in Table-1. From FIG. 1, an ethylene vinyl alcohol copolymer having a high elastic modulus and a high yield strength but a short flat portion and a low breaking strength, and a low elastic modulus and a high yield strength but a large elongation,
The laminated structure of polycaprolactone, which is soft and tenacious, had a higher upper yield point elongation than that of the single resins of polycaprolactone and ethylene vinyl alcohol copolymer.

From Table 1, when the upper yield point elongation of a single resin of polycaprolactone is set to 100%, this laminated structure showed an increase in elongation of about 15% or more. Therefore, by making a laminated structure using polycaprolactone and ethylene vinyl alcohol copolymer, characteristic tenacity properties not found in a single resin were imparted.

On the other hand, the yield point strength of this laminated structure was substantially in agreement with the value of the above-mentioned "Formula 1" additive equation using the yield point strength value of each single resin. Therefore, the laminated structure composed of polycaprolactone and ethylene vinyl alcohol copolymer reflected the strength of ethylene vinyl alcohol, which originally had high mechanical strength, and retained the strength property. From the above, the present laminated structure had a characteristic hard and tenacious property that cannot be obtained by each single resin.

Example 2 A laminated structure composed of saturated polyester, urethane adhesive and ethylene vinyl alcohol copolymer was prepared.
The layer structure of this laminated structure is the same as that described in Example 1. A square pouch was prepared from the laminated structure using a heat sealer so that one side had a length of 10 cm. The pouch was filled with 100 ml of distilled water at 2 ° C., and the melted and pressure-bonded injection port was dropped from 10 pieces from a height of 1.2 m, but there was no damage.

Example 3 Biopolypol (hydroxybutyrate containing 10 mol% of hydroxyvalerate, hydroxyvalerate copolymer) manufactured by ICI Co., Ltd. was used as poly-β-hydroxyalkanoate for saturated polyester, and ethylene vinyl alcohol was used. EVAL G manufactured by Kuraray Co., Ltd. was used as the copolymer. As an adhesive, AD-506- manufactured by Toyo Morton Co., Ltd.
A mixture of R-40 and the curing agent AD-RT-1 manufactured by the same company was used.

The layer structure of the laminated structure has biopol on both outer surfaces, a thickness of 50 μm, and the above urethane-based adhesive, 5 on the adhesive layer.
μ, and Evar G having a thickness of 25 μ was formed on the intermediate layer.

When the mechanical strength of this laminated structure was measured, it was found that the laminated structure of Biopol and Eval G, which had a smaller upper yield point elongation than Eval G, had a significantly increased upper yield point elongation and break elongation. The saturated polyester, which originally had a hard and brittle property, was given a hard and tenacious property by forming a laminated structure.

[Table 1]

[0053]

According to the present invention, by laminating an ethylene-vinyl alcohol copolymer on a saturated polyester resin having a hydroxyalkanoate unit as a main component, the yield point strength, which is a drawback of the biodegradable saturated polyester resin, is obtained. Can be significantly improved. Further, according to the present invention, due to the above-mentioned lamination, the upper yield point elongation of the higher one of the saturated polyester resin and the ethylene-vinyl alcohol copolymer is 10% or more, and particularly 20 to 40%. Elongation at yield is obtained, and beyond the range predicted from each constituent resin layer, the tenacity (toughness) of the laminate is synergistically
Can be improved.

In this packaging laminate, since the saturated polyester resin is present on at least one of the inner and outer surfaces, the saturated polyester resin on the surface is decomposed by bacteria, and the ethylene-vinyl alcohol copolymer layer adjacent thereto is also present. The absorption of water promotes the decomposition, resulting in excellent biodegradability. Further, the presence of the ethylene-vinyl alcohol copolymer having an excellent gas barrier property in the packaging laminate provides an excellent gas barrier property against oxygen gas, aroma components and the like.

[Brief description of drawings]

1 is a stress-strain curve of each resin, A: stress-strain curve of ethylene-vinyl alcohol copolymer (Eval), B: biodegradable saturated polyester resin (PCL)
Is a stress-strain curve, and C is a stress-strain curve of the laminated structure.

FIG. 2 is a diagram showing a cross-sectional structure of an example of the packaging laminate of the present invention.

FIG. 3 is a view showing a cross-sectional structure of another example of the packaging laminate of the present invention.

[Explanation of Symbols] 1 is a laminate, 2, 2a and 2b are biodegradable saturated polyester resin layers, 3 is an ethylene-vinyl alcohol copolymer layer, and 4, 4a and 4b are resin adhesive layers.

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[Procedure amendment]

[Submission date] September 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

That is, all biodegradable saturated polyesters have problems in mechanical properties, such as β-type ones such as PHA have small elongation and are brittle, and ω-type ones such as PCL have low yield strength. It has a defect in mechanical strength, and in order to maintain the strength of the container when filling a heavy internal material, the thickness of the container must be made considerably larger than that of the conventional one. There is a problem that the cost increases.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

(Resin Adhesive) In the present invention, the resin adhesive may be any thermoplastic or thermosetting resin adhesive as long as it can bond the saturated polyester resin and the ethylene-vinyl alcohol copolymer. Agents are used.
Examples of resin adhesives include urethane adhesives, epoxy adhesives, copolyamide adhesives, copolyester adhesives, and the like.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

EXAMPLES Next, the method of the present invention will be described with reference to examples. Polycaprolactone H-7 manufactured by Daicel Chemical Industries, Ltd. was used as the saturated polyester (poly-ω-hydroxyalkanoate), and Eval G manufactured by Kuraray Co., Ltd. was used as the ethylene vinyl alcohol copolymer. As the adhesive, a polyester-urethane adhesive (AD-506-R-40 manufactured by Toyo Morton Co., Ltd. and curing agent AD-RT-1 manufactured by the same) was used. In addition, as a saturated polyester (poly-β-hydroxyalkanoate)
Using ICI Biopol (hydroxybutyrate containing 10 mol% hydroxyvalerate , hydroxyvalerate copolymer), a laminate was prepared in the same manner.

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Claims (3)

[Claims] 1. A first layer containing (A) a saturated polyester resin mainly composed of hydroxyalkanoate units, (B) a resin adhesive layer, and (C) 10 to 60 mol%.
And a second layer containing an ethylene-vinyl alcohol copolymer containing an ethylene unit. 2. A first surface layer containing (A) a saturated polyester resin mainly containing a hydroxyalkanoate unit, (B) a resin adhesive layer, and (C) containing 10 to 60 mol% of ethylene. An intermediate layer containing an ethylene-vinyl alcohol copolymer, and (D) a resin adhesive layer,
(E) A second surface layer containing a saturated polyester resin mainly containing a hydroxyalkanoate unit, and a packaging laminate. 3. The packaging laminate according to claim 1 or 2, wherein the saturated polyester resin layer and the ethylene-vinyl alcohol copolymer layer are present in a thickness ratio of 200: 1 to 2: 1.