JP2003063543A - Squeezing-out multi-layer container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a squeezing-out multi-layer container that is excellent in outer appearance, and in gas barrier, interlaminar bonding, squeezing, and re-grinding properties. SOLUTION: The squeezing-out multi-layer container is characteristically composed of a resin composite (A) layer as an intermediate layer that comprises saponified substance of ethylene-vinyl acetate copolymer (A1), olefin-unsaturated carboxylic acid copolymer (A2), and polyolefin resin (A3), with the content ratio of (A2) and (A3), namely, A2/A3 being 50/50 to 99/1 (weight ratio), with layers of polyolefin resin (B) being disposed on both sides thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a squeezed multi-layer container using a resin composition of an ethylene-vinyl acetate copolymer saponified product (hereinafter abbreviated as EVOH), and more particularly to appearance properties, gas barrier properties, and interlayer properties. The present invention relates to a squeezed multilayer container excellent in adhesiveness, squeeze property and regrind property.

[0002]

EVOH is excellent in transparency, gas barrier property, aroma retaining property, solvent resistance, oil resistance and the like, and by utilizing such characteristics, food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, pesticides, etc. It is used for various packaging materials such as packaging materials.

A typical example is a squeeze multi-layer container containing a viscous viscous food such as mayonnaise or ketchup, which is typically EVOH.
As a middle layer, and a polyolefin resin such as polyethylene is laminated on both outer layers. As a specific example, JP-A-60-125667 discloses low-density polyethylene as inner and outer layers and a middle layer. Is EVOH, and an adhesive resin layer containing acid-modified linear low-density polyethylene is arranged between the layers, and there is a disclosure of a multilayer plastic container.

However, in the construction of such a container, in addition to the two polyolefin resin layers inside and outside and the intermediate EVOH layer, two more adhesive resin layers are required, so that capital investment such as an extruder and a multilayer die is required. Is expensive, and the adhesive resin as a raw material is also expensive, which is economically disadvantageous in production. It goes without saying that it would be economically advantageous if the container can be constituted only by the polyolefin resin layer and the EVOH layer without the adhesive resin layer. However, since the polyolefin resin and EVOH have a poor chemical affinity, the interlayer adhesiveness between the two becomes insufficient unless an adhesive resin layer is provided, and delamination occurs during shipping and use of the container, resulting in commercial value. However, there is a problem that

As a countermeasure, it is considered that EVOH is blended with another resin to improve the interlayer adhesion, and conventionally, various blended products have been studied. For example, a method using a composition obtained by blending EVOH with an ionomer or an ethylene-vinyl acetate copolymer (JP-A-49-35482), a composition obtained by blending EVOH with nylon and a polyethylene copolymer containing a metal ion are used. Method used (Japanese Patent Laid-Open No. 49-10735)
No. 1), and a method using a composition obtained by blending EVOH with a polyolefin and a carbonyl group-containing thermoplastic polymer (JP-A-52-116387 and JP-A-54-4).
9285, JP-A-55-156579),
A method of using a composition in which an ethylene-α-olefin copolymer, a graft modified polymer, and a saponified ethylene-vinyl acetate copolymer having a high ethylene content are blended with EVOH (JP-A-54-53089), EVOH A method of using a composition obtained by blending a saponified product of an ethylene-vinyl acetate copolymer having a high ethylene content with polyvinyl alcohol (JP-A-54-156082), a composition obtained by blending two kinds of polyvinyl alcohol with EVOH. Has been proposed (JP-A-56-75856).

[0006]

However, when the present inventor examined the blended products described in each of the above-mentioned publications in detail, JP-A-55-156579 and JP-A-52-116387, JP-A-54-49285, JP-A-54-53089, JP-A-49-1
In the blends disclosed in JP-A-07351 and JP-A-49-35482, the squeezed multilayer container obtained may have poor appearance such as transparency and transparency, or may have insufficient gas barrier properties depending on the ratio of the layer constitution. In addition, the interlayer adhesion and squeezeability of the obtained squeezed multilayer container cannot be said to be sufficient.
Even with the blends disclosed in JP-A No. 2 and JP-A-56-75856, it is sometimes difficult to obtain a squeezed multilayer container having good appearance because of its poor long-run melt moldability and regrindability, and thus it is transparent. Appearance such as transparency and transparency,
A squeezed multilayer container having excellent gas barrier properties, interlayer adhesion, squeeze properties, and regrind properties is desired.

[0007]

In view of such circumstances, the present inventor has studied in detail the EVOH blend used in the squeezed multilayer container, and as a result,
(A1), olefin-unsaturated carboxylic acid copolymer (A2)
And a polyolefin resin (A3), and the content ratio (A2 / A3) of (A2) and (A3) is 50 / 50-9.
It has been found that a squeezed multilayer container having a resin composition (A) layer of 9/1 (weight ratio) as an intermediate layer and a polyolefin resin (B) layer on both sides thereof meets the above-mentioned object. The present invention has been completed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The EVOH (A1) used in the present invention is not particularly limited, but has an ethylene content of 10 to 70.
Mol% (further 20-60 mol%, especially 25-50
Mol%), a saponification degree of 90 mol% or more (further 95 mol% or more, particularly 99 mol% or more) is used.
When the ethylene content is less than 10 mol%, the gas barrier property and appearance of the squeezed-out multilayer container at high humidity are deteriorated.
When it exceeds mol%, sufficient gas barrier properties of the squeezed-out multi-layer container cannot be obtained, and when the saponification degree is less than 90 mol%, the gas barrier properties and moisture resistance of the squeezed-out multi-layered container are deteriorated, which is not preferable.

Further, the intrinsic viscosity of the EVOH (A1) (30% in a mixed solvent of 85% by weight of phenol and 15% by weight of water,
Measured at 0.6 ° C.) is 0.6 to 1.5 dl / g (further more than 0.
7-1.3 dl / g, especially 0.8-1.2 dl / g)
Is preferable, and the viscosity is less than 0.6 dl / g or 1.5.
Exceeding dl / g is not preferable because the extrusion moldability may become unstable.

Further, the melt flow rate (MFR) of the EVOH (A1) (measured at 210 ° C. and a load of 2160 g)
Is 0.5 to 100 g / 10 minutes (further 1 to 50 g /
10 minutes, particularly 3 to 35 g / 10 minutes) is preferable, and when the melt flow rate is smaller than the above range, the inside of the extruder is in a high torque state during molding, which makes extrusion process difficult, and more than the above range. If it is too large, the accuracy of the thickness of the resin composition (A) layer of the obtained squeezed multilayer container is reduced, which is not preferable.

The EVOH is obtained by saponification of (A1) an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer is obtained by any known polymerization method such as solution polymerization, suspension polymerization, It may be produced by emulsion polymerization or the like, and saponification of an ethylene-vinyl acetate copolymer may be carried out by a known method.

Further, in the present invention, a copolymerizable monomer may be copolymerized within a range that does not impair the effects of the present invention. Examples of such a monomer include propylene, 1-butene,
Olefins such as isobutene, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid and (anhydrous) itaconic acid, or salts thereof, or mono- or dialkyl having 1 to 18 carbon atoms Ester, acrylamide, C1-C18 N-alkyl acrylamide, N, N-dimethyl acrylamide, 2
-Acrylamidopropanesulfonic acid or salts thereof,
Acrylamide such as acrylamide propyl dimethyl amine or its acid salt or its quaternary salt, methacrylamide, N-alkyl methacrylamide having 1 to 18 carbon atoms, N, N-dimethyl methacrylamide, 2-methacrylamide propane sulfonic acid or the like Methacrylamides such as salts, methacrylamidopropyldimethylamine or its acid salts or quaternary salts thereof, N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide and N-vinylacetamide, acrylonitrile,
Vinyl cyanides such as methacrylonitrile, carbon number 1 to
18 vinyl ethers such as alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkoxy alkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halides such as vinyl bromide, vinylsilanes such as trimethoxyvinylsilane, acetic acid Allyl, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and the like can be mentioned. Further, within the range that does not impair the gist of the present invention,
It may be post-modified such as urethanated, acetalized, cyanoethylated, etc.

It is also possible to use two or more different EVOHs as the EVOH (A1), in which case the ethylene content is 5 mol% or more (further 5 to 25 mol%, particularly 8 to 20 mol%). Mol%) and / or the saponification degree is 1 mol% or more (further 1 to 15 mol%, especially 2).
EVOH which is different and / or has a MFR ratio of 2 or more (more preferably 3 to 20, especially 4 to 15).
By using the blended product of, while maintaining the gas barrier property, further flexibility, interlayer adhesion, squeeze property,
It is useful because it improves blow moldability. The method for producing two or more different EVOHs (blends) is not particularly limited. For example, a method of mixing each paste of EVA before saponification and then saponification, a mixture of alcohols of each EVOH after saponification or water and alcohol. Method of mixing solutions, each EVO
Examples of the method include a method in which H is mixed and then melt-kneaded.

The olefin-unsaturated carboxylic acid copolymer (A2) used in the resin composition (A) together with the above EVOH (A1) is a copolymer obtained by copolymerizing an unsaturated carboxylic acid with olefin as the main component. It may be a so-called ionomer in which the carboxylic acid component is (partially) neutralized by a metal ion. Examples of the olefin in the copolymer include ethylene, propylene, butylene, styrene and the like, among which ethylene is most preferably used.

Examples of the unsaturated carboxylic acid in the olefin-unsaturated carboxylic acid copolymer (A2) include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, and fumaric acid. Ethylenically unsaturated dicarboxylic acids such as itaconic acid, maleic acid, monomethyl maleate, monoethyl maleate, and maleic anhydride, and anhydrides thereof, half esters, and the like, among which acrylic acid or methacrylic acid is most preferably used .

The content of unsaturated carboxylic acid in the copolymer (A2) is preferably 1 to 30% by weight (further 2 to 25% by weight, particularly 3 to 20% by weight). If the unsaturated carboxylic acid content is less than 1% by weight, the resulting squeezed multilayer container may have insufficient appearance, interlayer adhesion, squeeze property, and the like. The thermal stability of the product (A) tends to decrease, which is not preferable.

The melt flow rate (MFR) of the copolymer (A2) (190 ° C., load 2160 g) is 0.5 to
100 g / 10 min (further, 1 to 50 g / 10 min, particularly 2 to 25 g / 10 min) is preferable because it has excellent compatibility with EVOH (A1) and the effect of the present invention can be more significantly exhibited. .

The copolymer (A2) may be an olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer in which an unsaturated carboxylic acid ester is copolymerized,
Examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, fumaric acid monomethyl ester,
Examples include fumaric acid monoethyl ester, of which methyl acrylate and ethyl acrylate are most preferably used.

The copolymer (A2) is EVOH.
In order to further improve the compatibility with (A1), it may be a modified product containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof by an addition reaction or a graft reaction. As the unsaturated carboxylic acid or its anhydride, for example, ethylenic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid, maleic acid. Examples thereof include ethylenically unsaturated dicarboxylic acids such as monomethyl, monoethyl maleate and maleic anhydride, and anhydrides and half esters thereof. Among them, maleic anhydride is preferably used because of its excellent effect.

Further, as the ionomer (A2) of the copolymer, the carboxylic acid component of the above-mentioned olefin-unsaturated carboxylic acid copolymer is (partially) neutralized with a metal ion. , Specifically zinc,
Examples thereof include sodium, potassium, magnesium, calcium, barium, lithium and the like, among which zinc, sodium and potassium are most preferably used. The degree of neutralization of the carboxylic acid component with a metal ion is preferably 5 to 100% (further 10 to 90%, particularly 30 to 70%).

Melt flow rate (MFR) of the copolymer ionomer (A2) (210 ° C., load 2160 g)
Is 0.5 to 100 g / 10 minutes (further 1 to 50 g / 1
0 minutes, especially 1.5-25g / 10 minutes), EVOH
It is preferable because it has excellent compatibility with (A1) and the effects of the present invention can be more remarkably exhibited.

In the present invention, as the olefin-unsaturated carboxylic acid copolymer (A2), two or more kinds of olefin-unsaturated carboxylic acid copolymer (A2) having different kinds, structures, compositions, molecular weights (MFR) and the like are used. Can also be used together.

The polyolefin resin (A3) used in the resin composition (A) together with the above EVOH (A1) and the saponified product (A2) of an olefin-carboxylic acid vinyl ester copolymer is a linear low-molecular-weight resin. Density polyethylene (LLDPE), low density polyethylene (LDPE), ultra low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-propylene ( (Block or random) copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, polypropylene (PP), propylene-α-olefin (C4-20 α-olefin) copolymer , Polybutene, polypentene, polymethylpentene, etc. Homo- or copolymer, or a modified product containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to a homo- or copolymer of these olefins by an addition reaction or a graft reaction, etc. Examples of the polyolefin resin in the broad sense of, the appearance of the obtained squeezed multilayer container, interlayer adhesion,
Containing linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ultra-low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), or their carboxyl groups in terms of excellent squeeze property The modified product is preferably used.

Examples of the unsaturated carboxylic acid or its anhydride chemically bonded to the polyolefin resin (A3) include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, , Fumaric acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monoethyl maleate, ethylenically unsaturated dicarboxylic acids such as maleic anhydride and anhydrides thereof, half esters and the like, among them, excellent in its effect. From this point, maleic anhydride is preferably used.
At this time, the amount of unsaturated carboxylic acid or its anhydride contained in the polyolefin resin (A3) is 0.001 to
It is preferably 3% by weight, more preferably 0.01 to 1% by weight, particularly preferably 0.03 to 0.5% by weight.
If the amount of modification in the modified product is small, the effect of improving the compatibility with EVOH (A1) is poor, and if it is large, a cross-linking reaction may occur and the thermal stability of the resin composition (A) may deteriorate. Not preferable.

In the present invention, the polyolefin resin (A
As 3), two or more kinds of polyolefin resins (A3) having different kinds, structures, compositions, molecular weights (MFR) and the like can be used together.

The resin composition (A) used in the present invention contains the above-mentioned (A1) to (A3), but in the present invention, it contains (A2) and (A3). Weight ratio (A2 /
A3) 50/50 to 99/1 (further 60/40 to 9)
7/3, especially 70/30 to 95/5) is important, and when the weight ratio is smaller than 50/50, poor appearance such as transparency and transparency of the squeezed multilayer container occurs. On the contrary, when it is larger than 99/1, the interlayer adhesion and squeeze property of the squeezed-out multilayer container are deteriorated and the object of the present invention cannot be achieved.

Further, in the resin composition (A), (A
The content ratio of 1), (A2) and (A3) is not particularly limited, but the content ratio (A1 / A2 + A3) of the total amount of (A2) and (A3) to (A1) is 50/50 to 99/1 ( Further 60
/ 40 to 97/3, particularly 70/30 to 95/5) (weight ratio), and when such weight ratio is smaller than 50/50, gas barrier properties and transparency of the squeezed multilayer container
The external appearance such as transparency may be insufficient, and conversely 9
When it is larger than 9/1, the interlayer adhesion, squeeze property, and regrind property of the squeezed-out multilayer container may be insufficient, which is not preferable.

In blending the above (A1), (A2) and (A3), there is no particular limitation, and a known method such as a method of melt kneading each resin or a method of mixing in a solution state is adopted. The method of melt-kneading is industrially advantageous.

The melt-kneading is not particularly limited, as long as (A1), (A2) and (A3) are sufficiently melt-kneaded, and a known method can be adopted. For example, a known kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, a plastomill can be used, and usually melted at 100 to 300 ° C (further 150 to 280 ° C) for about 1 minute to 1 hour. It is preferable to knead, industrially it is advantageous to use an extruder such as a single-screw extruder or a twin-screw extruder, and if necessary, a vent suction device, a gear pump device, a screen device, etc. should be provided. Is also preferable. In particular, in order to remove water and by-products (pyrolysis low molecular weight substances, etc.), one or more vent holes are provided in the extruder to suck under reduced pressure, and to prevent oxygen from mixing into the extruder. By continuously supplying an inert gas such as nitrogen into the hopper, it is possible to obtain a resin composition (A) with excellent quality in which thermal coloring and thermal deterioration are reduced. In the melt-kneading, 1) solid (A
1), (A2) and (A3) are mixed together and melt-kneaded, 2) (A1) in the molten state is solid (A2) and (A2)
Method of charging 3) and melting and kneading, 3) in the molten state (A2)
Method of adding solid (A1) and (A3) to melt kneading, 4) Method of adding solid (A1) and (A2) to melt (A3) and melt kneading, 5) A method in which solid (A3) is added to molten (A1) and (A2) and melt-kneaded,
6) A method in which solid (A2) is added to melted (A1) and (A3) and melt-kneaded, 7) Molten (A2) and (A3)
Examples thereof include a method of adding solid (A1) to and melt-kneading, and 8) a method of mixing (A1), (A2) and (A3) in a molten state and melt-kneading.

Thus, the resin composition (A) is obtained. In the present invention, however, the resin composition (A) may also contain an acid component or a metal salt thereof. ) Color tone, thermal stability, long-run moldability,
Appearance of the obtained squeezed multilayer container, interlayer adhesion, heat stretch moldability, regrindability and the like are preferable in terms of improvement, and such acid components include acetic acid, propionic acid, butyric acid,
Examples thereof include organic acids such as lauric acid, stearic acid, oleic acid, and behenic acid, and inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, boric acid, and phosphoric acid. Metal salts include sodium salts, potassium salts, and calcium salts of the above acids. Examples thereof include alkali metal such as magnesium salt and zinc salt, metal salt such as alkaline earth metal and transition metal, and acetic acid, phosphoric acid, boric acid and alkali metal salt thereof, and alkaline earth metal salt are particularly effective. It is preferably used from the viewpoint.

The content of such acetic acid is 5 to 1000 ppm (more preferably 10 to 5) with respect to the resin composition (A).
00 ppm, particularly 20 to 300 ppm) is preferable, and if the content is less than 5 ppm, the content effect may not be sufficiently obtained, and conversely, if it exceeds 1000 ppm, the appearance of the squeezed multilayer container obtained is deteriorated. Or odor may be observed, which is not preferable.

The content of such phosphoric acid is 5 to 1000 ppm in terms of phosphoric acid radical based on the resin composition (A).
(Further 10-500ppm, especially 20-300p
pm), and the content is 5 ppm
If it is less than 100 ppm, the effect of the content may not be sufficiently obtained. On the contrary, if it exceeds 1000 ppm, the appearance of the squeezed multilayer container obtained may be deteriorated, which is not preferable.

The content of such boric acid is 10 to 10,000 ppm in terms of boron based on the resin composition (A).
(Further 20-5000 ppm, especially 50-200
0 ppm) is preferable, and the content is 10
If it is less than ppm, the effect of the content may not be sufficiently obtained, and conversely, if it exceeds 10,000 ppm, the appearance of the squeezed multilayer container may deteriorate, which is not preferable.

The content of the metal salt is 5 to 1000 ppm (more preferably 10 to 500 ppm, particularly 20 to 300 pp) in terms of metal based on the resin composition (A).
m) is preferable, and if the content is less than 5 ppm, the content effect may not be sufficiently obtained, and conversely, if it exceeds 1000 ppm, the appearance of the squeezed multilayer container obtained may be unfavorable. When the resin composition (A) contains two or more kinds of alkali metal and / or alkaline earth metal salts, the total amount thereof is preferably within the above range.

The method of incorporating the acid component and its metal salt in the resin composition (A) is not particularly limited, and E
VOH (A1) may be contained in the
It is contained in the unsaturated carboxylic acid copolymer (A2) or in advance in the polyolefin resin (A3), EVOH (A1) and olefin-unsaturated carboxylic acid copolymer (A2) and polyolefin It is contained at the same time when the resin (A3) is blended, or it is contained in the resin composition (A) after blending the EVOH (A1), the olefin-unsaturated carboxylic acid copolymer (A2) and the polyolefin resin (A3). Or a combination of these methods. In order to obtain the effect more markedly, EVOH is previously prepared.
The method of making it contained in (A1) is preferable from the viewpoint of excellent dispersibility of the acid component and its metal salt.

As a method of preliminarily containing EVOH (A1), a) EVOH (A) having a water content of 20 to 80% by weight is used.
In addition to the method in which the porous precipitate of 1) is brought into contact with an aqueous solution of an acid component or its metal salt to contain the acid component or its metal salt and then dried, a) a uniform solution of EVOH (A1) (water) (/ Alcohol solution, etc.) containing an acid component or a metal salt thereof, extruded into a coagulating solution in a strand shape, and then cutting the obtained strand to form pellets, and further drying treatment, c) EVOH ( A1) and the acid component or its metal salt are mixed together and then melt-kneaded with an extruder, etc. d) The alkali (sodium hydroxide, water) used in the saponification step during the production of EVOH (A1) (Eg, potassium oxide) with an acid component such as acetic acid, and adjusting the amount of residual acid component such as acetic acid and by-produced alkali metal salts such as sodium acetate and potassium acetate by washing with water. Can be mentioned . In order to obtain the effect more remarkably, a) which has excellent dispersibility of the acid component and its metal salt,
The method a) or d) is preferable, and the method a) or d) described above is particularly preferable in view of the industrial viewpoint.

In the present invention, an olefin-unsaturated carboxylic acid copolymer (including ionomer) (A2) is further used.
In order to improve the compatibility between OH and EVOH (A1), it is also possible to add a polyamide resin (A4) as the fourth component,
This is preferable in that the olefin-unsaturated carboxylic acid copolymer (A2) in EVOH (A1) has a good dispersion state and the effect of the present invention can be more remarkably expressed. As such a polyamide resin (A4), Polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecane amide (nylon 11), polylauryllactam (nylon 12), polyethylenediamine adipamide (Nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 6)
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2), polyoctamethylene adipamide (nylon 8
6), polydecamethylene adipamide (nylon 10
8), caprolactam / lauryllactam copolymer (nylon 6/12), caprolactam / ω-aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), Lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/6
6), ethylenediamine adipamide / hexamethylene diammonium adipate copolymer (nylon 26/6
6), caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 66/610), ethylene ammonium adipate / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer (nylon 6 / 66/610), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / terephthalamide copolymer or polyamide resins modified with aromatic amines such as methylenebenzylamine and metaxylenediamine. And metaxylylene diammonium adipate and the like, and one or more of these are used. Further, among these, the melting point is 240 ° C. or less, particularly the melting point is 11 or less. To 230 ° C. of the polyamide resin is preferably from the viewpoint of excellent balance of miscibility improvement and thermal stability, specifically polycapramide (nylon 6), polylauryllactam (nylon 12), caprolactam /
Lauryl lactam copolymer (nylon 6/12), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66) and the like are preferably used.

In incorporating such a polyamide resin (A4), EVOH (A1), olefin-unsaturated carboxylic acid copolymer (A2) and polyolefin resin (A
Add at the same time during mixing such as melt kneading in 3), or use EV beforehand.
It may be mixed with OH (A1) or the olefin-unsaturated carboxylic acid copolymer (A2) by melt-kneading or the like.
The content of the polyamide resin (A4) is not particularly limited, but is 1 to 100 parts by weight (further 5 to 80 parts by weight, relative to 100 parts by weight of the olefin-unsaturated carboxylic acid copolymer (A2), In particular, it is preferably 10 to 50 parts by weight). When the content is less than 1 part by weight, the effect of improving compatibility is poor, and conversely, when the content is more than 100 parts by weight, the heat of the resin composition (A) is reduced. Stability may be deteriorated, which is not preferable.

Further, in the present invention, such a resin composition (A) may be used in the range that does not impair the object of the present invention.
Saturated aliphatic amide (eg stearic acid amide etc.), unsaturated fatty acid amide (eg oleic acid amide etc.), bis fatty acid amide (eg ethylene bisstearic acid amide etc.), higher fatty acid metal salt (eg calcium stearate, magnesium stearate, Zinc stearate, etc., low molecular weight polyolefin (for example, molecular weight 500-
Lubricants such as low molecular weight polyethylene of about 10,000 or low molecular weight polypropylene, etc., inorganic salts (eg hydrotalcite etc.), plasticizers (eg aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol etc.), Oxygen absorber [For example, as an inorganic oxygen absorber, reduced iron powder, further water-absorbing substances and electrolytes, aluminum powder, potassium sulfite, titanium oxide photocatalyst, etc. , Ascorbic acid, its fatty acid esters and metal salts,
Hydroquinone, gallic acid, polyhydric phenols such as hydroxyl group-containing phenol aldehyde resin, bis-salicylaldehyde-imine cobalt, tetraethylene pentamine cobalt, cobalt-Schiff base complex, porphyrins,
Macrocyclic polyamine complexes, coordination complexes of nitrogen-containing compounds such as polyethyleneimine-cobalt complexes with transition metals, terpene compounds, reactants of amino acids and hydroxyl group-containing reducing substances, triphenylmethyl compounds, etc. As a system oxygen absorber, a coordination bond between a nitrogen-containing resin and a transition metal (eg, a combination of MXD nylon and cobalt), a blend of a tertiary hydrogen-containing resin and a transition metal (eg, a combination of polypropylene and cobalt) , A blend of a carbon-carbon unsaturated bond-containing resin and a transition metal (eg, a combination of polybutadiene and cobalt), a photooxidatively degradable resin (eg: polyketone), an anthraquinone polymer (eg: polyvinyl anthraquinone), and the like, Photoinitiators (such as benzophenone), peroxide scavengers (such as commercially available antioxidants) and deodorants (active agents) Such as those obtained by adding coal or the like), heat stabilizers, light stabilizers, such as antioxidants (e.g., Ciba Specialty Chemicals "IRGANOX1098"),
UV absorbers, colorants, adhesives, antistatic agents, surfactants, antibacterial agents, antiblocking agents (such as talc particles), slip agents (such as amorphous silica), inorganic fillers (such as silicon oxide, dioxide) Titanium, clay, talc, bentonite, water-swelling phyllosilicate, etc.), other resin (for example, polyester resin, etc.) and the like may be blended.

The polyolefin resin (B) laminated with the above resin composition (A) includes linear low density polyethylene (LLDPE) and low density polyethylene (LDP).
E), ultra low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDP)
E), ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer (EA)
A), ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer (EMAA), ethylene-methacrylic acid ester copolymer, polypropylene (P
P), propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, olefin homopolymer or copolymer such as polybutene, polypentene, polymethylpentene, or homopolymer or copolymer of these olefins. Examples include polyolefin resins in a broad sense such as those that are graft-modified with unsaturated carboxylic acids or their esters, but the appearance (transparency, surface gloss, etc.), interlayer adhesion, and squeezeability of the resulting squeezed multilayer container are In terms of excellence,
Linear low density polyethylene (LLDPE), low density polyethylene (LDPE), ethylene-propylene (block or random) copolymer, polypropylene (PP),
A propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer is preferable, and particularly, the melt flow rate (MFR) (measured at 190 ° C. and a load of 2160 g) is 0.1 to 2 g / 10 minutes (further, 0.2-1.5g / 1
0 minutes, especially 0.3 to 1 g / 10 minutes) with a density of 0.9
20 to 0.930 g / cm ³ (further 0.920 to
0.925 g / cm ³ ) low density polyethylene (LDP)
E) is most preferably used.

Further, in the present invention, it is also possible to use a blend of two or more kinds of polyolefin resins (B) having different kinds of resins and physical properties (density, MFR, molecular weight distribution, etc.). Further, the above-mentioned various additives, fillers, modifiers, other resins and the like may be added to the polyolefin resin (B) within a range that does not impair the object of the present invention.

The squeezed multilayer container of the present invention comprises the above-mentioned resin composition (A) layer as an intermediate layer and a polyolefin resin (B) layer on both sides thereof. Will be described.

In producing the squeezed multilayer container of the present invention, the resin composition (A) is used as an intermediate layer and a polyolefin resin (B) is laminated on both sides of the resin composition (A) to form a multi-layer parison (a hollow tubular pre-blow before blowing). After making a molded product), place the parison in the mold and blow it into the mold by blowing fluid pressure such as air and water, and mold it into a hollow container such as a bottle or tube (blow molding). ).

The blow molding method is also not particularly limited, and the extrusion direct blow molding method (double head type, die moving type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison type blow method. Molding method, injection blow molding method, biaxial stretch blow molding method (extrusion cold parison biaxial stretch blow molding, injection cold parison biaxial stretch blow molding, injection molding in-line biaxial stretch blow molding, etc.) and the like, The extrusion direct blow molding method is most preferable from the viewpoint that the effects of the present invention can be exhibited most. Further, it is also preferable to further heat-treat the hollow container obtained by blow molding, because improvement in delamination resistance and gas barrier property can be recognized. Heat treatment temperature is 10
The heat treatment time is 0 to 240 ° C. and is 1 second or more.

Further, regarding the tubular squeezed multilayer container, a laminated sheet having the above-mentioned constitution is produced by coextrusion molding or the like, and the laminated sheets are laminated and joined to form a tubular shape, and one end of the tubular body portion is formed. By attaching a screw-shaped extrusion port formed by injection molding of a thermoplastic resin and a conical shoulder continuous with this to the part, and by closing the other end of the tubular body by fusion or the like. It is also possible to produce.

Thus, a squeezed multilayer container is obtained. In the present invention, however, in the thickness direction of the multilayer container, all the resin composition (A) layers are 50 to 98% (more preferably 60%) from the inside to the outside. ~ 95%, especially 6
0 to 90%), and when the resin composition (A) layer is out of this range or when the layer is partially outside this range, the obtained squeezed multilayer container Interlayer adhesion and squeeze may become insufficient. When the resin composition (A) layer is composed of two or more layers, it is preferable that all the resin composition (A) layers are within the above range.

The layer structure of such a squeezed-out multi-layer container is b / a / b, where a is a layer composed of the resin composition (A) and b is a layer composed of the polyolefin resin (B).
Not only the layer structure of b / a / b / a, b / a / b / a
/ B, b / a / b / a / b / a, b / a / b / a / b /
Any combination such as a / b is possible, and further,
When R is a regrind layer composed of a mixture of at least the resin composition (A) and the polyolefin resin (B), b / R / a / b, R / b / a / b, b / R / a / R
/ B, b / a / R / a / b, b / R / a / R / a / R /
b, b / R / a / b / a / R / b, etc. are also possible.

Particularly in blow molding, when producing such a multilayer container, a large amount of scraps, unnecessary portions at the ends, and defective products are usually produced, which is industrially involved. In terms of economy, it is necessary to recycle the composition (scrap composition) consisting of scraps generated at the time of molding, and it is preferable to use again as one of one or more layers of the multilayer container by melt molding as a regrind layer. The most preferable layer structure of the squeezed-out multilayer container is b / R / a / b, b / R / a / R / b, b
/ A / R / a / b and the like.

Generally, polyolefin resin (B) and E
When VOH and recycle are used as the regrind layer, the phase separation foreign matter (eye resin), which is considered to be due to the difference in melt viscosity between them and the incompatibility, is mixed into the regrind layer,
Although there may be some inconveniences such as delamination between the regrind layer and the adjacent layer and deterioration of mechanical properties such as impact resistance of the regrind layer, the resin composition (A) of the present invention may be used. When used, the problems of the regrind layer are reduced, and a squeezed multilayer container with good quality can be obtained, which is preferable.

In the squeezed-out multilayer container of the present invention, an adhesive resin is not necessary between the layers, probably because the resin composition (A) is excellent in affinity and adhesiveness with the polyolefin resin (B). To the extent that the object of the invention is not impaired,
It is also possible to provide an adhesive resin layer composed of a modified olefin-based polymer containing a carboxyl group chemically bonded to an unsaturated carboxylic acid or an anhydride thereof by an addition reaction or a graft reaction, and further, if necessary. Accordingly, a resin layer other than the resin composition (A) and the polyolefin resin (B) can be provided.

The thickness of each layer of the squeezed multilayer container of the present invention thus obtained cannot be generally determined depending on the layer structure, the container form, the use of the container, the required physical properties, etc.
The layer is selected from the range of 1 to 200 μm (further 3 to 50 μm) and the layer b is selected from the range of 10 to 1000 μm (further 30 to 500 μm). If the layer a is less than 1 μm, the gas barrier property is insufficient, and its thickness control becomes unstable. On the contrary, if it exceeds 200 μm, the squeeze property is poor and it is not economically preferable, and if the layer b is less than 10 μm, the rigidity is insufficient. On the contrary, if it exceeds 1000 μm, the weight becomes large, the squeeze property is deteriorated, and it is not economical and not preferable.

Furthermore, the thickness of all layers of the squeezed-out multilayer container of the present invention cannot be generally stated depending on the layer structure, the container form, the use of the container, the required physical properties, etc., but it is usually 50 to 2000.
It is selected from the range of about μm (further, 150 to 600 μm). If the total layer thickness is less than 50 μm, the rigidity is insufficient,
On the other hand, if it exceeds 2000 μm, the weight becomes large, the squeeze property is deteriorated, and it is not economical and not preferable.

The ratio of the thickness of the resin composition (A) layer to the thickness of all the layers of the squeezed multilayer container of the present invention is not particularly limited, but the thickness of the resin composition (A) layer is 1 to 20 of the total layer thickness. % (Further 1.5 to 15%, especially 2-1)
0%) is preferable, and if the thickness ratio is less than 1%, the gas barrier property of the squeezed-out multilayer container obtained may be poor, and conversely, if it exceeds 20%, the interlayer adhesion and squeeze property of the squeezed-out multilayer container obtained. However, the regrindability may be insufficient, which is not preferable.

The squeezed multilayer container consisting of bottles, tubes and the like obtained as described above is used for general foods, seasonings,
Fermented foods, oil and fat foods, beverages, cosmetics, pharmaceuticals, detergents, cosmetics, industrial chemicals, pesticides, fuels, and various containers are useful. Specifically, mayonnaise, ketchup, sauce,
Viscous liquid or pasty foods such as miso, lard, jam, chocolate, butter, margarine, jelly, yogurt, wasabi, mustard, ginger, garlic, toothpaste, shampoo, rinse, conditioner, hair dye, and seasoning It is useful for foods, spices, beverages, cosmetics, pharmaceuticals, etc., and is particularly useful as a squeezed multilayer container (squeeze bottle) whose content is at least one selected from mayonnaise, ketchup and sauce.

[0056]

EXAMPLES The present invention will be specifically described below with reference to examples.

In the examples, "part" and "%" are based on weight unless otherwise specified. For the measurement of the acetic acid content in EVOH (A1) and resin composition (A), see EV
OH (A1) and the resin composition (A) were extracted with hot water at 95 ° C. for 3 hours, and the acetic acid in the extract was neutralized and titrated with an aqueous sodium hydroxide solution. Further, regarding the measurement of the boric acid content in the EVOH (A1) and the resin composition (A), the EVOH (A1) and the resin composition (A) are alkali-melted and the boron is quantified by the ICP emission spectrometry. I went by. Furthermore, for the measurement of alkali (earth) metal content, EVOH (A1) and resin composition (A) are ashed, dissolved in hydrochloric acid aqueous solution, and alkali (earth) metal is quantified by atomic absorption spectrometry. It was done by doing.

Example 1 [Preparation of Resin Composition (A)] EVOH [Ethylene content 34 mol%, Saponification Degree 99.5 mol%, MFR 3.5 g
/ 10 minutes (210 ° C, load 2160g), acetic acid content 1
00 ppm, magnesium acetate content 35 ppm (magnesium conversion), calcium acetate content 20 ppm (calcium conversion)] (A1) 80 parts and ethylene-acrylic acid copolymer [acrylic acid content 8.5%, MFR 7 g /
10 minutes (190 ° C, load 2160g)] (A2) 15 parts and maleic anhydride graft modified low density polyethylene [maleic anhydride graft modified amount 0.15%, MFR 1.0g
/ 10 minutes (190 ° C, load 2160g), density 0.92
g / cm ³ ] (A3) 5 parts were dry-blended, then fed to a twin-screw extruder equipped with a strand die, melt-kneaded under the following conditions, passed through a water tank and cooled, and then pelletized. To obtain a resin composition (A) [acetic acid content in the resin composition (A) is 80 ppm, magnesium acetate content is 28 ppm (magnesium conversion), calcium acetate content is 16 ppm (calcium conversion)]. It was However, regarding acetic acid, magnesium acetate and calcium acetate in EVOH (A1), the water / methanol solution of EVOH after the saponification step during EVOH production is extruded into a water tank in a strand shape to coagulate and cut with a cutter. The pellet-shaped porous precipitate was washed with an aqueous solution of acetic acid, and then added to an aqueous solution containing acetic acid, magnesium acetate and calcium acetate, and the mixture was stirred to be contained.

[0059] [Conditions for melt pelletization with a twin-screw extruder]   Screw inner diameter 30mm (L / D = 30)   Screw shape With a 100 mm kneading disk in the compression section   Screen mesh 90/90 mesh   Screw rotation speed 150 rpm   Vent hole Perform vacuum suction   Supply nitrogen gas in hopper to replace   Extrusion temperature C1: 190 ° C                         C2: 200 ° C                         C3: 210 ° C                         C4: 220 ° C                         C5: 220 ° C                         AD: 210 ° C                         D: 210 ° C

The resin composition (A) obtained above and low-density polyethylene [Novatech LD manufactured by Nippon Polychem Co., Ltd.
ZE41 ", MFR 0.5 g / 10 min (measured at 190 ° C., load 2160 g), density 0.922 g / cm ³ ].
Using (B), these are supplied to a co-extrusion multilayer direct blow molding machine (manufactured by Placo Co.) to form a low density polyethylene (B) layer / resin composition (A) layer / low density polyethylene (B) layer constitution. After pushing out the multi-layer parison of No. 3, sandwich it with a mold and blow air to inflate it and make it adhere to the mold,
A squeezed multi-layer container (capacity 500 cc, height 200 mm, barrel) having a structure of outer low-density polyethylene (B) layer (170 μm) / resin composition (A) layer (20 μm) / inner low-density polyethylene (B) layer (200 μm) Outside diameter 80m
A gourd-shaped multi-layer hollow bottle (m-50 mm) was obtained. Burrs and scraps generated during the molding of such a squeezed multilayer container are crushed and subjected to an extruder for a regrind layer, and similarly the outer low density polyethylene (B) layer (170 μm) / resin composition (A) layer ( 20 μm) / regrind layer (15
0 μm) / Inner low-density polyethylene (B) layer (50 μm
A squeezed multilayer container having the configuration of m) (the shape is the same as above) was obtained. The resin composition (A) layer was at a position of about 51 to 56% from the inside to the outside in the thickness direction, and the thickness of the resin composition (A) layer was 5.1% of the total layer thickness.

The conditions from the parison molding to the blow molding were as follows. [Conditions of Single-Screw Extruder of Resin Composition (A)] Screw Inner Diameter 32 mm L / D 28 Extrusion Temperature C1: 180 ° C. H: 220 ° C. C: 200 ° C. N: 220 ° C. C: 220 ° C. D: 200 ° C. C4: 220 ° C

[0062] [Conditions of low density polyethylene (B) single screw extruder]     Screw inner diameter 40 mm     L / D 28     Extrusion temperature C1: 180 ° C H: 200 ° C                         C2: 200 ° C N: 200 ° C                         C3: 200 ° C D: 200 ° C                         C4: 200 ° C

[0063] [Conditions for regrind single screw extruder]     Screw inner diameter 40 mm     L / D 28     Extrusion temperature C1: 180 ° C H: 200 ° C                         C2: 200 ° C N: 200 ° C                         C3: 200 ° C D: 200 ° C                         C4: 200 ° C

The squeezed multilayer container (bottle) thus obtained was evaluated for appearance, gas barrier property, interlayer adhesion, squeeze property and regrind property as follows.

(Appearance) The bottle obtained above was filled with 500 g of commercially available mayonnaise, and the body was visually observed and evaluated according to the following criteria. ○ ・ ・ ・ Transparency and transparency are good, the original yellow color of mayonnaise can be confirmed, and the product value is high △ ・ ・ ・ Transparency and transparency are slightly poor, and mayonnaise color is slightly whitish than it actually is Appearance and slightly inferior in commercial value × ... Poor transparency and transparency, mayonnaise color looks whitish than actual, inferior in commercial value

(Gas Barrier Property) Oxygen permeability was measured by sealing the mouth surface of the bottle obtained above with an aluminum metal plate (temperature 23 ° C., outer 50% RH using “OXTRAN10 / 50” manufactured by Modern Control Co., Ltd.). , Inside 100% RH).

(Interlayer adhesion) A strip shape (width 15 mm, length 1 from the body of the bottle obtained above in the machine direction (MD))
(50 mm) test piece is cut out, the layer interface between the low-density polyethylene (B) layer and the resin composition (A) layer is peeled off, and both ends are grasped with a chuck of Autograph (manufactured by Shimadzu Corporation) and peeled by 180 °. (T peel) test was performed to measure the interlaminar peel strength (g / 15 mm). Peeling speed is 300
The measurement was performed in an atmosphere of mm / min, a temperature of 23 ° C., and a relative humidity of 50% RH.

(Squeeze property) The bottle obtained above was filled with 500 g of mayonnaise on the market, and 20 panelists were allowed to use the mayonnaise under the circumstance that it was easy to extrude the contents. Easiness of deformation and appropriate restorability) were evaluated and evaluated according to the following criteria. ◎ ・ ・ ・ The number of people who answered that it was easy to extrude was 18 or more ○ ・ ・ ・ The number of people who answered that it was easy to extrude was 15 to 17 △ ・ ・ ・ The number of people who answered that it was easy to extrude was 10 to 14 × ・ ・ ・ Easy to extrude 9 people or less

(Regrinding property) The bottle obtained above was visually observed for the presence of light yellow eye tars (phase separation foreign matter) in the regrind layer / adjacent layer and in the regrind layer. The following criteria were evaluated. ○: No eye blemishes were found. △: Eye blemishes were found slightly. X: Eye blemishes were found to some extent.

Example 2 The layer structure of the bottle in Example 1 was as follows: outer low density polyethylene (B) layer (80 μm) / resin composition (A) layer (20 μm) / regrind layer (170 μm) / inner low density A multilayer container (bottle) was similarly squeezed out except that the polyethylene (B) layer (100 μm) was used, and the same evaluation was performed. The resin composition (A) layer is at a position of about 73 to 78% from the inside to the outside in the thickness direction,
The thickness of the resin composition (A) layer was 5.4% of the total layer thickness.

Example 3 In Example 2, as the component (A1), EVOH [ethylene content 29 mol%, saponification degree 99.6 mol%, MF
R4g / 10 minutes (210 ° C., load 2160 g), boric acid content 150 ppm (boron conversion), sodium acetate content 100 ppm (sodium conversion)] were used in the same manner as in resin composition (A) [resin composition ( The boric acid content in A) was 120 ppm (boron conversion) and the sodium acetate content was 80 ppm (sodium conversion)], and a squeezed multilayer container (bottle) was prepared in the same manner, and the same evaluation was performed. However, for boric acid and sodium acetate in EVOH (A1), as in Example 1, the water / methanol solution of EVOH after the saponification step during EVOH production was extruded into a water tank in the form of strands and solidified with a cutter. The pellet-shaped porous precipitate obtained by cutting was washed with an aqueous acetic acid solution, and then added to an aqueous solution containing boric acid and sodium acetate and stirred to contain the precipitate.

Example 4 In Example 2, as the component (A2), an ionomer of ethylene-methacrylic acid copolymer [methacrylic acid content 9%, ionic species Na ⁺ , density 0.94 g / cm ³ , MFR,
1.2 g / 10 minutes (190 ° C., load 2160 g)]
As the component (A3), maleic anhydride graft-modified linear low-density polyethylene [maleic anhydride graft-modified amount 0.2%, MFR 1.9 g / 10 minutes (190 ° C., load 2
160 g) and a density of 0.92 g / cm ³ ], except that the resin composition (A) [acetic acid content in the resin composition (A) was 80 ppm and magnesium acetate content was 28 pp.
m (calculated as magnesium), calcium acetate content is 16
ppm (calcium equivalent)] was obtained, a multilayer container (bottle) was similarly squeezed out, and the same evaluation was performed.

Example 5 In Example 3, as the component (A2), an ionomer of an ethylene-methacrylic acid copolymer [methacrylic acid content 11%, ionic species Na ⁺ , density 0.95 g / cm ³ , MF
R2.8g / 10 minutes (190 ° C, load 2160g)]
As component (A3), maleic anhydride graft-modified linear low-density polyethylene [maleic anhydride graft-modified amount 0.2%, MFR 1.9 g / 10 min (190 ° C., load 2160 g), density 0.92 g / cm ³ ] was used to obtain a resin composition (A) [boric acid content in the resin composition (A) was 120 ppm (boron conversion), sodium acetate content was 80 ppm (sodium conversion)]. Similarly, a squeezed multilayer container (bottle) was produced and evaluated in the same manner.

Example 6 In Example 3, as the component (A2), an ethylene-methacrylic acid copolymer [methacrylic acid content 9%, density 0.
93 g / cm ³ , MFR 8 g / 10 min (190 ° C., load 2160 g)] as the component (A3), maleic anhydride graft modified linear low density polyethylene [maleic anhydride graft modified amount 0.2%, MFR 1. 9g / 10 minutes (190 ° C, load 2160g), density 0.92g / cm
³ ] was similarly obtained except that the resin composition (A) [the boric acid content in the resin composition (A) was 120 ppm (boron conversion) and the sodium acetate content was 80 ppm (sodium conversion)], Similarly, a multilayer container (bottle) was squeezed out and evaluated in the same manner.

Example 7 In Example 4, the bottle layer structure was as follows: outer low density polyethylene (B) layer (100 μm) / resin composition (A) layer (15 μm) / regrind layer (150 μm) / inner low density A multilayer container (bottle) was similarly squeezed out except that the polyethylene (B) layer (130 μm) was used, and the same evaluation was performed. The resin composition (A) layer is at a position of about 71 to 75% from the inside to the outside in the thickness direction,
The thickness of the resin composition (A) layer was 3.8% of the total layer thickness.

Example 8 In Example 6, the bottle layer structure was as follows: outer low density polyethylene (B) layer (50 μm) / resin composition (A) layer (8 μm) / regrind layer (80 μm) / resin composition A multilayer container (bottle) was squeezed out in the same manner except that the layer (A) (8 μm) / inner low-density polyethylene (B) layer (200 μm) was used, and the same evaluation was performed. The resin composition (A) layer is about 58 to 60% (inner layer) and about 83 to 86% from the inner side to the outer side in the thickness direction.
The total thickness of the resin composition (A) layer was 4.6% of the total layer thickness at the (outer layer) position.

Example 9 In Example 2, the blending ratio of EVOH (A1), ethylene-acrylic acid copolymer (A2) and maleic anhydride graft-modified low density polyethylene (A3) was changed to EVOH (A1) 9
0 part, 7 parts of ethylene-acrylic acid copolymer (A2), and 3 parts of maleic anhydride graft-modified low-density polyethylene (A3) were used in the same manner as in resin composition (A) [in resin composition (A) Acetic acid content of 90 ppm, magnesium acetate content of 31 ppm (calculated as magnesium), calcium acetate content of 18 ppm (calculated as calcium)]
Similarly, a multilayer container (bottle) was squeezed out and evaluated in the same manner.

Example 10 In Example 4, the blending ratio of EVOH (A1), ionomer (A2) of ethylene-methacrylic acid copolymer, and maleic anhydride graft-modified linear low-density polyethylene (A3) was changed to EVOH (A). A1) 70 parts, ethylene-methacrylic acid copolymer ionomer (A2) 23 parts, maleic anhydride graft-modified linear low-density polyethylene (A3) 7 parts in the same manner except that the resin composition (A) [ In the resin composition (A), the acetic acid content was 70 ppm, the magnesium acetate content was 24 ppm (magnesium conversion), and the calcium acetate content was 14 ppm (calcium conversion).
Similarly, a multilayer container (bottle) was squeezed out and evaluated in the same manner.

Example 11 In Example 6, the blending ratio of EVOH (A1), ethylene-methacrylic acid copolymer (A2) and maleic anhydride graft-modified linear low density polyethylene (A3) was changed to EVOH.
(A1) 85 parts, ethylene-methacrylic acid copolymer (A2)
10 parts, maleic anhydride graft modified linear low density polyethylene (A3) 5 parts in the same manner except that the resin composition (A) [the boric acid content in the resin composition (A) is 127 p
pm (boron equivalent), sodium acetate content is 85pp
m (sodium conversion)] was obtained, a multilayer container (bottle) was similarly squeezed out, and the same evaluation was performed.

Example 12 In Example 2, the polyamide resin (A4) [nylon 6/66 copolymer, density 1.1] was used as the fourth component.
2 g / cm ³ , melting point 195 ° C.], and the mixing ratio of each component is (A1) :( A2) :( A3) :( A4) = 80: 1.
The resin composition (A) [acetic acid content in the resin composition (A) is 80 ppm, sodium acetate content is 90 ppm (sodium conversion), and magnesium acetate content is 28 ppm in the same manner except that 3: 5: 2 parts are used. (Magnesium equivalent),
A calcium acetate content of 16 ppm (calculated as calcium) was obtained, and a multilayer container (bottle) was similarly squeezed out and evaluated in the same manner. However, (A2) and (A4)
As for, the above was used after being melt-mixed by a twin-screw extruder and pelletized.

Example 13 In Example 3, the polyamide resin (A4) [nylon 6/12 copolymer, density 1.1] was used as the fourth component.
0 g / cm ³ , melting point 196 ° C.] and the blending ratio of each component is (A1) :( A2) :( A3) :( A4) = 80: 1.
The resin composition (A) [the boric acid content in the resin composition (A) is 120 ppm (boron conversion), and the sodium acetate content is 80 ppm (sodium conversion)] except that it is 2: 5: 3 parts. Then, a squeezed multilayer container (bottle) was prepared in the same manner and evaluated in the same manner. However, (A2)
As for (A4), those which were previously melt-mixed and pelletized by a twin-screw extruder were used.

Example 14 In Example 10, polyamide resin (A4) [copolymer of nylon 6/66, density 1.
12 g / cm ³ , melting point 195 ° C.] and the blending ratio of each component is (A1) :( A2) :( A3) :( A4) = 70: 2
The resin composition (A) [acetic acid content in the resin composition (A) is 70 ppm, magnesium acetate content is 24 ppm (magnesium conversion), calcium acetate content is 14 ppm in the same manner except that it is 0: 7: 3 parts. (Calcium equivalent)]
Then, a squeezed multilayer container (bottle) was prepared in the same manner and evaluated in the same manner. However, for (A2) and (A4), those which were melt-mixed and pelletized in advance with a twin-screw extruder were used.

Comparative Example 1 Squeeze out in the same manner as in Example 1 except that the resin composition (A) did not contain the ethylene-acrylic acid copolymer (A2) and the maleic anhydride graft-modified low density polyethylene (A3). A multilayer container (bottle) was prepared and evaluated in the same manner.

Comparative Example 2 In Example 1, the ethylene-acrylic acid copolymer (A
A multilayer container (bottle) was similarly squeezed out except that 5 parts of 2) and 15 parts of maleic anhydride graft-modified low-density polyethylene (A3) were changed, and the same evaluation was performed.

Comparative Example 3 In Example 1, the ethylene-acrylic acid copolymer (A
A multilayer container (bottle) was similarly squeezed out except that 2) was changed to 19.99 parts and the maleic anhydride graft-modified low density polyethylene (A3) was changed to 0.01 part, and the same evaluation was performed.

The evaluation results of the examples and comparative examples are summarized in Table 1.

[Table 1] Appearance Gas barrier property Delamination strength Squeeze property Removability (g / 15 mm) Example 1 ○ 0.008 53 ○ ○ 〃 2 ○ 0.007 59 ◎ ○ 〃 3 ○ 0.006 58 ◎ ○ 〃 4 ○ 0.007 52 ◎ ○ 〃 5 ○ 0.006 51 ◎ ○ 〃 6 ○ 0.006 58 ◎ ○ 〃 7 ○ 0.009 50 ◎ ○ 〃 8 ○ 0.007 61 ◎ ○ 〃 9 ○ 0.006 54 ◎ ○ 〃 10 ○ 0.009 61 ◎ ○ 〃 11 ○ 0.005 54 ◎ ○ 〃 12 ○ 0.007 61 ◎ ○ 〃 13 ○ 0.006 61 ◎ ○ 〃 14 ○ 0.009 63 ◎ ○ Comparative Example 1 △ 0.004 9 × × 〃 2 × 0.0092 22 △ △ 〃 3 ○ 0.006 38 × ○ Note) The unit of gas barrier property is cc / bottle / day / air

[0088]

The squeezed-out multi-layer container of the present invention comprises a specific resin composition layer as an intermediate layer and a polyolefin resin layer on both sides thereof, so that appearance, gas barrier property, interlayer adhesiveness and squeeze property are obtained. Excellent regrindability, various packaging applications (in addition to foods, seasonings, fermented foods, oil and fat foods, beverages, cosmetics, pharmaceuticals, detergents, cosmetics, industrial chemicals, agricultural chemicals,
It is useful as a packaging material for (fuel etc.), and specifically, mayonnaise, ketchup, miso, lard, jam, chocolate, butter, margarine, jelly, yogurt, wasabi, mustard, ginger, garlic, toothpaste, shampoo, Viscous liquid or pasty foods such as rinses, conditioners, hair dyes, seasonings, spices,
It is useful for beverages, cosmetics, pharmaceuticals and the like, and is particularly useful as a squeezed multilayer container (squeeze bottle) whose content is at least one selected from mayonnaise, ketchup and sauce.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 77/00 C08L 77/00 F term (reference) 3E065 AA01 BA14 BA17 BA25 BA30 BB01 BB03 CA02 CA09 FA01 FA04 FA11 FA15 GA02 HA02 HA03 4F100 AK03A AK03B AK03C AK06A AK06B AK06C AK46A AK62A AK62B AK62C AK63A AK66A AK66B AK66C AK68A AK69A AK70A AL05A AL06A AR00D BA03 BA04 BA06 BA07 BA10B BA10C BA15 DA01 EH20 GB16 GB23 JA06B JA06C JA13B JA13C JA20A JD03 JK06 JL16 JL16D JN01 YY00A YY00B YY00C 4J002 BB08X BB21Y BE03W BN05Y CL01Z CL03Z FD020 FD170 GG01

Claims (9)

[Claims] 1. An ethylene-vinyl acetate copolymer saponified product (A1), an olefin-unsaturated carboxylic acid copolymer (A2).
And a polyolefin resin (A3), and the content ratio (A2 / A3) of (A2) and (A3) is 50 / 50-9.
A squeezed multi-layer container comprising a resin composition (A) layer of 9/1 (weight ratio) as an intermediate layer, and polyolefin resin (B) layers disposed on both sides thereof. 2. The content ratio (A1 / A2 + A3) of the total amount of the olefin-unsaturated carboxylic acid copolymer (A2) and the polyolefin resin (A3) to the saponified ethylene-vinyl acetate copolymer (A1) is 50. It is / 50-99 / 1 (weight ratio), The squeezed multilayer container of Claim 1 characterized by the above-mentioned. 3. The olefin-unsaturated carboxylic acid copolymer (A2) is an ethylene- (meth) acrylic acid copolymer having a (meth) acrylic acid content of 1 to 30% by weight or an ionomer thereof. The squeezed multilayer container according to claim 1 or 2. 4. The unsaturated carboxylic acid or its anhydride is at least one selected from linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene and ethylene-vinyl acetate copolymer as the polyolefin resin (A3). The squeezed multilayer container according to any one of claims 1 to 3, which is a modified product containing a carboxyl group, which is obtained by chemically bonding a substance by an addition reaction or a graft reaction. 5. The polyolefin resin (B) has a melt flow rate (MFR) (measured at 190 ° C. and a load of 2160 g) of 0.1 to 2 g / 10 minutes and a density of 0.920 to.
0.930 g / cm ³ low density polyethylene (LDP
E) is a squeezed-out multilayer container according to any one of claims 1 to 4. 6. The squeezed multilayer container according to claim 1, which further comprises a resin composition (A) containing a polyamide resin (A4). 7. At least a polyolefin resin (B)
7. The squeezed-out multilayer container according to claim 1, having a laminated structure of layer / resin composition (A) layer / regrind (C) layer / polyolefin resin (B) layer. 8. The squeezed multilayer container according to claim 1, wherein the thickness of the resin composition (A) layer is 1 to 20% of the total layer thickness. 9. The squeezed multilayer container according to claim 1, wherein the content is at least one selected from mayonnaise, ketchup and sauce.