JP2003063541A - 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 consists of an intermediate layer of resin composite (A) layer comprising saponified substance of ethylene-vinyl acetate copolymer (A1), saponified substance of olefin-carboxylic acid vinyl ester copolymer (A2) and olefin-unsaturated carboxylic acid copolymer (A3), 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 structure of such a container,
In addition to the polyolefin resin layer and the intermediate EVOH layer, two additional adhesive resin layers are required, so equipment investment such as an extruder and a multilayer die becomes expensive, and the adhesive resin as a raw material is also expensive. Therefore, it is economically disadvantageous to produce. Therefore, 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,
A resin composition (A) layer containing (A1), a saponified product of an olefin-carboxylic acid vinyl ester copolymer (A2) and an olefin-unsaturated carboxylic acid copolymer (A3) is used as an intermediate layer, The present invention has been completed by finding that a squeezed multilayer container having a polyolefin resin (B) layer on both sides meets the above-mentioned object.

[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 saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer used in the resin composition (A) together with the EVOH (A1) is a carboxylic acid vinyl ester (general Formula CH ₂
═CH—OCOR, R is a linear or branched alkyl group having 0 to 20 carbon atoms), and the carboxylic acid vinyl ester component of the polymer is (partially)
It is a saponified product that is saponified to form a hydroxyl group.

Examples of the olefin in the copolymer include ethylene, propylene, butylene, styrene, etc. Among them, ethylene is most preferably used. As the carboxylic acid vinyl ester in the copolymer, R in the above general formula is a linear or branched alkyl group having 0 to 20 carbon atoms, and examples thereof include vinyl formate, vinyl acetate and propionic acid. Examples thereof include vinyl, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate, and of these, vinyl acetate is most preferably used.

The olefin content in the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer is 40
~ 99 mol% (more preferably 50-98 mol%, especially 70
~ 97 mol%) is preferably used. When the olefin content is less than 40 mol%, the thermal stability of the resin composition (A) tends to decrease, and conversely, when it exceeds 99 mol%, The squeezed multilayer container to be used is not preferable because the interlayer adhesion, squeeze property and regrind property may be insufficient.

The saponification degree of the carboxylic acid vinyl ester component of the saponification product (A2) of the olefin-carboxylic acid vinyl ester copolymer is 20 to 99.9 mol% (further 40%).
.About.99.9 mol%, particularly 70 to 99.9 mol%, especially 96 to 99.9 mol%) are preferably used,
If the saponification degree is out of the above range, the resulting squeezed-out multilayer container may have insufficient appearance, interlayer adhesion, squeeze property, etc., which is not preferable. The melt flow rate (MFR) of the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer (measured at 190 ° C. and a load of 2160 g) is 0.5 to 100 g / 10 minutes (further 1 to 50).
g / 10 min, especially 2-30 g / 10 min) is EVOH
It is preferable because it has excellent compatibility with (A1) and the effects of the present invention can be more remarkably exhibited. The saponified product of the olefin-carboxylic acid vinyl ester copolymer used in the present invention (A
2) As long as the above conditions are satisfied,
It can be preferably used, and particularly has an ethylene content of 70 to 9
It is preferable to use a partially saponified ethylene-vinyl acetate copolymer having 7 mol% and a saponification degree of the vinyl acetate component of 20 to 99.9 mol%.

As the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer, EVO is further included.
In order to improve the compatibility with H (A1), it may be a modified product containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride 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.

In the present invention, as the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer, two or more kinds of olefin-carboxylic acid vinyl ester copolymers having different kinds, structures, compositions, molecular weights (MFR) and the like are used. The saponified product (A2) can also be used together.

Further, together with the above EVOH (A1) and the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer, the olefin-unsaturated carboxylic acid copolymer (A3) used in the resin composition (A). Is a polymer obtained by copolymerizing an unsaturated carboxylic acid with an olefin as a main component, and may be a so-called ionomer in which the carboxylic acid component is (partially) neutralized with 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 (A3) 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 (A3) 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 (A3) (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. .

Further, the copolymer (A3) may be an olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester copolymer obtained by copolymerizing an unsaturated carboxylic acid ester. Examples of the acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, fumaric acid monomethyl ester, fumaric acid monoethyl ester. Among these, methyl acrylate and ethyl acrylate are most preferably used.

Further, as the ionomer (A3) of the copolymer, the carboxylic acid component of the above-mentioned olefin-unsaturated carboxylic acid copolymer is (partially) neutralized with a metal ion. Specific examples thereof include zinc, 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 metal ions is 5 to 100% (further 1
0 to 90%, particularly 30 to 70%) is preferable.

Melt flow rate (MFR) of the copolymer ionomer (A3) (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 (A3), two or more kinds of olefin-unsaturated carboxylic acid copolymer (A3) having different kinds, structures, compositions, molecular weights (MFR) and the like are used. Can also be used together.

(A1) in the above resin composition (A),
Although the content ratio of (A2) and (A3) is not particularly limited,
Content ratio of total amount of (A2) and (A3) to (A1) (A1
/ A2 + A3) is 50/50 to 99/1 (further 60 /)
40 to 97/3, particularly 70/30 to 95/5), and when the weight ratio is less than 50/50, the gas barrier property of the squeezed-out multi-layer container and the appearance such as transparency and transparency are insufficient. On the contrary, when it is larger than 99/1, the interlayer adhesion, squeeze property, and regrind property of the squeezed-out multilayer container may be insufficient, which is not preferable.

Further, the content weight ratio (A2 / A3) of (A2) and (A3) is 50/50 to 99/1 (further 60/4).
0-97 / 3, especially 70 / 30-95 / 5) is preferable, and when the weight ratio is less than 50/50, the squeezed-out multi-layer container may have insufficient appearance such as transparency and transparency. On the contrary, when it is larger than 99/1, the interlayer adhesion and squeeze 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, and it is sufficient that (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.

In the present invention, the water content is 1 to 60% by weight.
When EVOH (A1), saponified product of olefin-carboxylic acid vinyl ester copolymer (A2) and olefin-unsaturated carboxylic acid copolymer (A3) are melt-kneaded,
It is particularly preferable because it is possible to obtain a resin composition (A) which is excellent in the mixing properties of (A1) with (A2) and (A3) and has excellent quality with reduced thermal coloring and thermal deterioration. It is particularly preferable to use an excellent EVOH (A1) pelletized water-containing material in terms of easy handling. Hereinafter, such a method will be described, but the present invention is not limited thereto.

No particular limitation is imposed on obtaining EVOH (A1) pellets having a water content of 1 to 60% by weight.
During the step of producing VOH (A1), that is, in the step of extruding a solution of EVOH (A1) into a coagulating solution in a strand form to coagulate it, and then cutting it into pellets and then washing with water, EVOH ( A1) The water content of the pellet is 1 to
60% by weight (further 1 to 45% by weight, especially 1 to 30%
% By weight). If the water content is less than 1% by weight, the effects of the blending method (mixing property, suppression of heat deterioration and coloration, production efficiency, etc.) cannot be sufficiently exhibited, and if it exceeds 60% by weight, melting occurs. During the kneading, the resin and water are partially separated from each other, which makes the melt kneading unstable, which is not preferable.

The EVOH before melt-kneading referred to here
The water content of (A1) is measured and calculated by the following method.

[Measurement Method of Moisture Content] EVOH (A1) was weighed by an electronic balance (W1: unit g), put in a hot air oven type dryer maintained at 150 ° C., and dried for 5 hours, and then further. The weight after allowing to cool in a desiccator for 30 minutes is similarly weighed (W2: unit g) and calculated from the following equation (1). Moisture content (%) = {(W1-W2) / W1} × 100 (1)

The method for obtaining such hydrous EVOH (A1) (pellets) will be described in detail below. EVOH (A1) used in the present invention is obtained by saponifying an ethylene-vinyl acetate copolymer as described above, and the saponification reaction is carried out in the presence of an alkali catalyst. As the catalyst, a conventionally known catalyst used for the saponification reaction of polyvinyl acetate and ethylene-vinyl acetate copolymer with an alkali catalyst can be used as it is. Specifically, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, sodium methylate, alkali metal alcoholates such as potassium t-butoxide, 1,8-diazabicyclo [5,4,10]. A cobasic amine represented by undecene-7 (DBU), an alkali metal carbonate, an alkali metal hydrogencarbonate and the like can be mentioned, but sodium hydroxide is preferably used from the viewpoint of easy handling, catalyst cost and the like.

The amount of the catalyst used varies depending on the required saponification degree, reaction temperature and the like, but is used in an amount of 0.05 equivalent or less, preferably 0.03 equivalent, based on the residual acetic acid groups in the ethylene-vinyl acetate copolymer. It is the following. It is also possible to use an acid catalyst such as hydrochloric acid or sulfuric acid instead of the alkali catalyst.

In the saponification, the above ethylene-vinyl acetate copolymer is dissolved in alcohol or an alcohol-containing medium to a concentration of about 20 to 60% by weight, and an alkali catalyst or an acid catalyst is added. 40-1
The reaction is carried out at a temperature of 40 ° C. If the EVOH (A1) after the reaction is not deposited at the solution temperature, the E
The concentration of VOH (A1) is not particularly limited, but it is usually 10 to 55% by weight, preferably 15 to 50% by weight.

Next, the alcohol solution of EVOH (A1) obtained above may be used as it is, but preferably, water is added directly, or the EVOH (A1) solution is appropriately concentrated or diluted and then water is added. To prepare a solution for strand production. In the case of the aqueous solution, the mixing weight ratio of water / alcohol is in the range of 80/20 to 5/95, and the content A (% by weight) of alcohol is 2.55E-40.75 ≦ A.
≤2.55E-15.75 (where E is EV
It is preferable that the ethylene content (mol%) of OH (A1) is satisfied from the viewpoint of the stability of the solution, and the amount of EVOH (A1) contained in the solution is 20 to 55% by weight ( Further, 25 to 50% by weight) is preferable from the viewpoint of stability of the subsequent coagulation work.

Next, the EVOH (A1) solution obtained above is extruded in a strand form and pelletized. At this point, saturated aliphatic amide (eg stearic acid amide etc.) and 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, etc.), low molecular weight polyolefin (eg, low molecular weight polyethylene having a molecular weight of about 500 to 10,000, or low molecular weight). Lubricant such as polypropylene)
Inorganic acids (eg phosphoric acid, boric acid etc.), organic acids (eg acetic acid, stearic acid etc.), inorganic salts (eg phosphoric acid alkali metal / alkaline earth metal salts, hydrotalcite etc.), organic acid salts (eg Alkali metal and alkaline earth metal salts of acetic acid), plasticizers (eg ethylene glycol,
Aliphatic polyhydric alcohols such as glycerin and hexanediol), antioxidants (eg IRGANOX 1098 manufactured by Ciba Specialty Chemicals), UV absorbers, colorants, antibacterial agents, antiblocking agents (eg talc particles), slip agents (For example, amorphous silica fine particles and the like), inorganic filler (for example, silicon oxide, titanium dioxide, clay, talc, bentonite, water-swelling phyllosilicate, etc.) may be blended.

As the coagulating liquid to be precipitated, water or a water / alcohol mixed solvent, aromatic hydrocarbons such as benzene, ketones such as acetone and methyl ethyl ketone, ethers such as dipropyl ether, methyl acetate, ethyl acetate and propionic acid. Organic acid esters such as methyl are used,
Water or a water / alcohol mixed solvent is preferable from the viewpoint of easy handling. As the alcohol, alcohols such as methanol, ethanol and propanol are used, but methanol is preferably used industrially.

The weight ratio of the coagulating liquid in the coagulating liquid and the strand of EVOH (A1) (coagulating liquid / strand of EVOH (A1)) is preferably 50 to 10,000, more preferably 100 to 1,000. . By setting the weight ratio within this range, it becomes possible to obtain EVOH (A1) pellets having a uniform size distribution.

Further, 1 to 1 of carboxylic acid is added to the coagulating liquid.
1 to 0000 ppm and / or carboxylic acid metal salt
It is also preferable to contain 15000 ppm and / or 1 to 50000 ppm of carboxylic acid ester, and further it is preferable to contain 50 to 5000 ppm of carboxylic acid and / or 10 to 5000 ppm of metal salt of carboxylic acid and / or 10 to 10,000 ppm of carboxylic acid ester. preferable. By containing carboxylic acids in the above range in the coagulation bath, EVOH (A
1) It becomes possible to obtain pellets more suitably.

The carboxylic acid is not particularly limited, but includes formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, crotonic acid,
Maleic acid, itaconic acid and the like can be mentioned, but acetic acid is preferably used. The metal salt of carboxylic acid is not particularly limited, and sodium formate, potassium formate, magnesium formate, calcium formate, sodium acetate, potassium acetate, magnesium acetate and the like are used, but sodium acetate is preferably used. The carboxylic acid ester is not particularly limited, but methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl acetoacetate, ethyl acetoacetate and the like can be used. Preferably methyl acetate is used.

The temperature at which the EVOH (A1) solution is brought into contact with the coagulating liquid is preferably -10 to 40 ° C, more preferably 0 to 20.
C., in particular 0-10.degree. The EVOH (A1) solution is extruded in a strand shape into the coagulating liquid as described above by a nozzle having an arbitrary shape. The shape of such a nozzle is not particularly limited, but a cylindrical shape is preferable and The length is preferably 1 to 100 cm, more preferably 3 to 30 cm, and the inner diameter is preferably 0.1 to 10 cm,
Furthermore, it is 0.2 to 5.0 cm.

Thus, the EVOH (A1) (solution) is extruded from the nozzle in the form of a strand, but the number of strands is not necessarily one and can be extruded in any number between several and several hundred. is there.

EVO finally extruded in a strand shape
H (A1) is cut after it has sufficiently solidified, pelletized, and then washed with water. As for the shape of such pellets, those having a cylindrical shape having a diameter of 1 to 10 mm and a length of 1 to 10 mm (further, each having a diameter of 2 to 6 mm), and those having a spherical shape having a diameter of 1 to 10 mm (further Is preferably 2 to 6 mm).

As the washing condition, the pellets are washed in a water bath at a temperature of 10 to 40 ° C (further 20 to 40 ° C). By such a water washing treatment, oligomers and impurities in EVOH (A1) are removed. Further, after the water washing treatment, or instead of the water washing treatment, the EVOH (A1) may be treated with an aqueous solution containing various acids or metal salts so that the EVOH (A1) contains the acid or metal salt. The EVOH (A1) and the composition (A) after blending are improved in color tone, thermal stability, long-run moldability, appearance of the resulting squeezed multilayer container, interlayer adhesion, heat stretch moldability, regrindability, etc. Preferred in terms of the acid component, such acid components include acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, organic acids such as behenic acid and sulfuric acid, sulfurous acid, carbonic acid, boric acid, inorganic acids such as phosphoric acid. The metal salts include metal salts of the above-mentioned acids such as alkali metals, alkaline earth metals and transition metals, and acetic acid, phosphoric acid, boric acid and alkali metal salts thereof, and alkaline earth metal salts are particularly effective. Favored in terms Used well.

By the above method, EVOH (A
1) Pellets are obtained, but EV before melt-kneading
When adjusting the water content of the OH (A1) pellets, known drying treatment (hot air drying, dielectric heating drying, microwave irradiation drying, etc.) or removal of water adhering to the surface of the water-containing pellets may be performed in advance if necessary. In terms of stability of melt-kneading, it is preferable.

Subsequently, the EVOH (A1) having a water content of 1 to 60% by weight obtained above, a saponified product of an olefin-carboxylic acid vinyl ester copolymer (A2) and an olefin-
A method for melt-kneading the unsaturated carboxylic acid copolymer (A3) to obtain the resin composition (A) will be specifically described.

In melting and kneading EVOH (A1) having a water content of 1 to 60% by weight, a saponified product of an olefin-carboxylic acid vinyl ester copolymer (A2) and an olefin-unsaturated carboxylic acid copolymer (A3), It can be carried out using a known melt-kneading device such as a melt extruder, a kneader ruder, a mixing roll, a Banbury mixer, a plastomill, etc., but it is usually industrially preferable to use a single-screw or twin-screw extruder. Especially, a twin-screw extruder is preferably used in view of stability of melt-kneading and homogeneity of blend, and a method using such a twin-screw extruder will be described in more detail.

The twin-screw extruder to be used is not particularly limited, but has an inner diameter of 20 mm or more (further, 30 to 150 m).
m) is preferable, and if the inner diameter is less than 20 mm, productivity is poor, and L / D is 20.
-80 (further, 30-60) is preferable, and such L /
If the D diameter is less than 20, the ability to remove water may be insufficient, whereas if it exceeds 80, the residence time of the resin in the extruder becomes longer than necessary, which is unfavorable because of its thermal deterioration. Also, it is sufficient if there is at least one vent, especially 2
It is preferable that there are more than one place, and it is preferable that at least one of them is sucked under reduced pressure from the viewpoint of drying efficiency and quality of the obtained resin. For the shape of the die hole,
Although not limited, the diameter is 1 to 7 mm (further 2 to 5 mm) in consideration of obtaining a pellet having an appropriate shape and size.
(mm) circular shape is preferable, and the number of the holes is preferably about 3 to 100 (more preferably 10 to 50) in terms of production. Furthermore, it is also preferable to provide one or more mesh screens (especially two or more) between the extruder and the entrance of the die for removing foreign matters and stabilizing the resin pressure (stabilization of extrusion). In consideration of the above, it is also preferable to provide a gear pump, a heat exchanger, or the like.

The cylinder temperature of such an extruder is usually
It is preferable to select from the range of room temperature to 300 ° C (further, 50 to 280 ° C). Further, by the above temperature setting, the molten resin composition (A) is supplied to a die and extruded, but the temperature of the resin composition (A) in the die (resin temperature) is 150 to 300 ° C. It is also preferable to adjust the extrusion conditions (set temperature, screw shape, screw rotation speed, etc.) so as to be (more preferably 180 to 280 ° C.), and if the temperature is less than 150 ° C., extrusion may become unstable. Conversely, if the temperature exceeds 300 ° C., the quality of the composition (A) may deteriorate (heat deterioration), which is not preferable.

The rotation speed of the screw is 50 to 300 r.
If it is selected from the range of pm (further 80 to 200 rpm) and the number of rotations is less than 50 rpm, the ability to remove water may be insufficient, and conversely, if it exceeds 300 rpm, the quality of the resin composition (A) may be reduced. May decrease (heat deterioration), which is not preferable, and the discharge rate of the resin composition (A) is 10 to 400 kg / hr (further 20 to 3 kg).
00 kg / hr), and when the discharge rate is less than 10 kg / hr, it is unproductive and conversely 400 kg / hr.
If it exceeds kg / hr, sufficient water removal may not be possible, which is not preferable, and the residence time of the resin composition (A) in the extruder is selected from the range of 10 to 600 seconds (further 10 to 180 seconds). , If the residence time is less than 10 seconds,
In some cases, sufficient water removal may not be possible, and conversely, if it exceeds 600 seconds, the quality of the resin composition (A) may deteriorate (heat deterioration), which is not preferable, and the pressure applied to the resin composition (A) (resin Pressure) is selected from the range of 5 to 300 kg / cm ² (further 10 to 200 kg / cm ² ), and the applied pressure is less than 5 kg / cm ² and 300 kg / cm ^2.
Exceeding cm ² is not preferable because the extrusion may become unstable. It is also preferable to seal the inside of the hopper and around the vent hole with nitrogen in order to prevent thermal deterioration of the resin composition (A).

Thus, the resin composition (A) is obtained, and the water content of the finally obtained resin composition (A) is 1% by weight or less (further 0.001 to 0.5% by weight, In particular, 0.01 to 0.35% by weight) is preferable in that troubles such as foaming at the time of melt molding (extrusion blow molding etc.) of the squeezed multilayer container after melt kneading can be reduced.

In order to make the resin composition (A) have such a water content, for example, in the method using the above-mentioned twin-screw extruder, the resin temperature (extruder set temperature) is adjusted by adjusting various conditions. It is possible by adjusting the discharge amount (screw rotation speed and resin charging amount) and the like. The water content of the resin composition (A) after melt-kneading is measured and calculated by the following method.

[Measurement Method of Moisture Content] The resin composition (A) was weighed (W1 g) by an electronic balance, put in a hot air oven type dryer maintained at 150 ° C., and dried for 5 hours.
Further, the weight after allowing to cool in a desiccator for 30 minutes is similarly weighed (W2g) and calculated from the following equation (2). Moisture content (%) = {(W1−W2) / W1} × 100 (2)

Further, after carrying out the above melt-kneading, known drying treatment (hot air drying, dielectric heating drying, microwave irradiation drying, etc.) is carried out as necessary, such as adjustment of the water content of the resin composition (A). It is also possible to carry out together.

In the present invention, as described above, the resin composition (A) may further contain an acid component or a metal salt thereof so that the resin composition (A) has a color tone, thermal stability and long-run moldability. The appearance of the obtained squeezed multilayer container, interlayer adhesion, heat stretch moldability, regrindability and the like are preferable, and such acid components include acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, and oleic acid. ,
Organic acids such as behenic acid, sulfuric acid, sulfurous acid, carbonic acid, boric acid,
Examples of the inorganic acid such as phosphoric acid include metal salts such as alkali metal such as sodium salt, potassium salt, calcium salt, magnesium salt and zinc salt of the above acid, alkaline earth metal, transition metal and the like. In particular, acetic acid, phosphoric acid, boric acid, alkali metal salts thereof and alkaline earth metal salts thereof are preferably used because of their excellent effects.

The content of such acetic acid is 5 to 1000 ppm (more preferably 10 to 5) based on 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, especially 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 saponified product (A2) of the vinyl carboxylate ester copolymer, in advance in the olefin-unsaturated carboxylic acid copolymer (A3), or in the EVOH (A
1) and the saponified product of olefin-carboxylic acid vinyl ester copolymer (A2) and the olefin-unsaturated carboxylic acid copolymer (A3) at the same time when they are blended together, or EVO
H (A1) and a saponified product of an olefin-carboxylic acid vinyl ester copolymer (A2) and an olefin-unsaturated carboxylic acid copolymer (A3) may be contained in the resin composition (A) after blending, The methods can be combined. In order to obtain the effect more remarkably, EVO
It is preferable to add H (A1) to H (A1) because the dispersibility of the acid component and its metal salt is excellent.

As a method of preliminarily containing it in EVOH (A1), the above-mentioned a) EVO having a water content of 20 to 80% by weight is used.
In addition to the method in which the porous precipitate of H (A1) 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) (Method of adding acid component or its metal salt to (water / alcohol solution, etc.), extruding it into a coagulating liquid in a strand form, and then cutting the obtained strand to form pellets, and further drying treatment) A method in which EVOH (A1) and an acid component or its metal salt are mixed together and then melt-kneaded in an extruder, etc. d) The alkali (sodium hydroxide) used in the saponification step during the production of EVOH (A1) , Potassium hydroxide, etc.) with an acid component such as acetic acid, and the amount of residual acid components such as acetic acid and by-produced alkali metal salts such as sodium acetate and potassium acetate are adjusted by washing with water. And so on Kill. 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) (A3) 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 (A3) 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), polylauryl lactam (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.

When the polyamide resin (A4) is contained, the EVOH (A1), the saponified product of the olefin-carboxylic acid vinyl ester copolymer (A2) and the olefin-unsaturated carboxylic acid copolymer (A3) are mixed. It is also possible to add them simultaneously at the time of mixing such as melt kneading, or to mix them in advance with EVOH (A1) or olefin-unsaturated carboxylic acid copolymer (A3) 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 (more preferably 5 parts by weight) with respect to 100 parts by weight of the olefin-unsaturated carboxylic acid copolymer (including ionomer) (A3). ˜80 parts by weight, especially 20 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 resin composition. The thermal stability of (A) may deteriorate, which is not preferable.

Further, in the present invention, a saturated aliphatic amide (such as stearic acid amide) and an unsaturated fatty acid amide (such as oleic acid amide) are added to the resin composition (A) as long as the object of the present invention is not impaired. , Bis fatty acid amides (eg ethylene bis stearic acid amides), higher fatty acid metal salts (eg calcium stearate, magnesium stearate, zinc stearate etc.), low molecular weight polyolefins (eg 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, polyolefin resin, polyamide resin, polyester resin, etc.) 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 resin composition (A) layer as an intermediate layer and the 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 the polyolefin resin (B) is laminated on both sides of the resin composition (A) to form a multi-layer parison (a hollow tubular pre-blank 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 bottle-shaped or tube-shaped hollow container (blow molding). ).

The blow molding method is also not particularly limited, and the extrusion direct blow molding method (double head type, mold 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 inline 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, for the tubular squeezed multilayer container, a laminated sheet having the above-mentioned structure is produced by coextrusion molding or the like, and the laminated sheets are laminated and joined to form a tubular shape. By attaching a screw-shaped extrusion port formed by injection molding of a thermoplastic resin and a conical shoulder portion continuous to this part, the other end of the tubular body is closed by fusion or the like. It is also possible to produce.

Thus, a squeezed multilayer container can be 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 multilayer container is b / a / b, where a is a layer made of the resin composition (A) and b is a layer made of a 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 multi-layer container, a large amount of scraps, unnecessary portions at the ends, and defective products are usually generated, which is industrially involved. From the viewpoint of economy, it is necessary to recycle the composition (scrap composition) consisting of scraps generated at the time of molding, and it is possible 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 multi-layer 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 multi-layer container of the present invention, an adhesive resin is not necessary between the layers, probably because the resin composition (A) has excellent affinity and adhesiveness with the polyolefin resin (B). In the range which does not impair the object of the invention,
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-out multilayer container of the present invention thus obtained cannot be generally stated 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.

Further, the thickness of all layers of the squeezed-out multi-layer container of the present invention cannot be unequivocally determined depending on the layer constitution, container form, use of container, required physical properties and the like, 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 composed of the bottles, tubes and the like obtained as described above is used in addition to 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.

[0085]

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. Further, for the measurement of the alkali (earth) metal content, EVOH (A1), saponified product of olefin-carboxylic acid vinyl ester copolymer (A2) and resin composition (A) are ashed and then added to a hydrochloric acid aqueous solution. It was performed by dissolving and quantifying alkali (earth) metal by atomic absorption spectrometry. The saponification degree of the carboxylic acid vinyl ester component of the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer was determined by measuring the content of the carboxylic acid vinyl ester component according to JIS-K7192. .

Example 1 [Preparation of resin composition (A)] Ethylene content 32 mol%
To 1000 parts of a methanol solution containing 40% of the ethylene-vinyl acetate copolymer, 40 parts of a methanol solution containing 6% of sodium hydroxide and 2500 parts of methanol are continuously supplied, and methyl acetate and extra methanol by-produced. While distilling from the system, the saponification reaction is carried out at 110 ° C. for 2.5 hours, and the saponification degree of the vinyl acetate component is 99.5.
Obtained mol% EVOH. Next, in the saponification reaction completion liquid,
Excess methanol was distilled off while supplying 450 parts of 50% water-containing methanol at an azeotropic point to obtain a water / methanol mixed solution of EVOH [water / methanol = 50/50 (weight ratio), resin concentration 40%]. .

Subsequently, the EVOH solution (liquid temperature 50 ° C.) was maintained at 5 ° C. with a nozzle having a hole diameter of 4 mm, and the EVOH solution (water 9
5%, methanol 5%) is extruded into a strand into a tank to solidify EVOH into a strand, and then the strand EVOH is led to a take-up roller attached to the end of the water tank and cut with a cutter. , Diameter 4 mm,
White porous pellets with a length of 4 mm were obtained.

Further, the obtained white porous pellets were washed with 0.5% acetic acid aqueous solution, and then washed with 0.1% acetic acid.
Pour into an aqueous solution containing 0.03% magnesium acetate and 0.02% calcium acetate and stir at 30 ° C. for 5 hours to prepare water-containing EVOH (A1) pellets [after drying EVOH
(A1) in acetic acid 100ppm, magnesium acetate 35p
pm (calculated as magnesium), calcium acetate 20ppm
(Containing calcium)] was obtained. Such hydrous EVO
The H (A1) pellets (water content 60%) were brought into contact with nitrogen gas in an atmosphere of 80 ° C. for 40 minutes by a tower fluidized bed dryer to obtain a water content of 25% and MFR 3.5 g / 10 minutes ( EVOH (A1) of 210 ℃, measured at a load of 2160g)
Pellets were obtained.

Next, 80 parts of the obtained water-containing EVOH (A1) pellets and a saponified product of ethylene-vinyl acetate copolymer [ethylene content 89 mol%, saponification degree of vinyl acetate component 95.5 mol%, MFR 4. 5g / 10 minutes (190
℃, measured at a load of 2160g), sodium acetate 150p
pm (sodium equivalent)] (A2) 15 parts and ionomer of ethylene-methacrylic acid copolymer [methacrylic acid content 9%, ionic species Na ⁺ , density 0.94 g / c
m ³ , MFR 1.2g / 10 minutes (190 ° C, load 216
0 g)] (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 cut with a pelletizer. Then, the water content is 0.15%, the acetic acid content is 80 ppm, and the sodium acetate content is 22 ppm.
(Sodium equivalent), magnesium acetate content is 28p
pm (calculated as magnesium), calcium acetate content is 1
6 ppm (calcium equivalent) resin composition (A) pellets were obtained.

The resin composition (A) pellets thus obtained were visually observed, but colorless and no yellow coloring was observed. Further, such a composition could be efficiently obtained at a rate of 50 kg / hr. Further, the pelletizing is continuously performed for 10 times.
After a long period of time, strand breakage, foreign matter, eye blemishes, etc. were not observed at all, and pellets were obtained stably.

[Conditions for Melt Pelletization by Twin-screw Extruder] Screw outer diameter 30 mmΦ L / D 42 Strand die shape 2-hole screen mesh with diameter 3.5 mmΦ 90/90 mesh vent C4 is opened, C6 is a nitrogen seal in a vacuum hopper. The screw rotation speed is 120 rpm

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

[0095] [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

[0096] [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) The bottle surface obtained above was sealed with an aluminum metal plate to measure the oxygen permeability (temperature was 23 ° C., outside 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 to easily extrude the contents (bottle of the bottle). 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) In the bottle obtained above, it was visually observed whether light yellow eye tars (phase-separated foreign matter) were mixed in between the regrinding layer / adjacent layer and in the regrinding 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 In Example 1, as the component (A2), a saponified product of ethylene-vinyl acetate copolymer [ethylene content 89 mol%, saponification degree of vinyl acetate component 99.1 mol%, MFR
6.8 g / 10 minutes (measured at 190 ° C. and a load of 2160 g), sodium acetate 600 ppm (converted to sodium)
Containing a resin composition (A) [resin composition (A)
The water content is 0.15%, the acetic acid content is 80 ppm, the sodium acetate content is 90 ppm (sodium conversion),
The content of magnesium acetate was 28 ppm (calculated as magnesium), and the content of calcium acetate was 16 ppm (calculated as calcium)]. Layer (2
(0 μm) / regrind layer (170 μm) / inner low-density polyethylene (B) layer (100 μm), and a similar squeezed multilayer container (bottle) was prepared and evaluated in the same manner. The resin composition (A) layer was at a position of about 73 to 78% from the inner side to the outer side in the thickness direction, and the thickness of the resin composition (A) layer was 5.4% of the total layer thickness.

Example 3 In Example 2, the water content was 15% and the ethylene content was 29%.
Mol%, saponification degree 99.6 mol%, MFR after drying 4g
/ 10 minutes (210 ℃, load 2160g) EVOH (A
1) [Boric acid 150ppm in EVOH (A1) after drying
(Boron equivalent), sodium acetate containing 100 ppm (sodium equivalent) was used in the same manner as above, except that the resin composition (A) had a water content of 0.13% and a boric acid content of (A). 120 ppm (boron conversion) and sodium acetate content 170 ppm (sodium conversion)] were obtained, and a multilayer container (bottle) was similarly squeezed out and evaluated in the same manner. However, regarding boric acid and sodium acetate in EVOH (A1), as in Example 1, E
A water-methanol solution of EVOH after the saponification step during VOH production was extruded into a water tank in a strand shape to coagulate and cut with a cutter to obtain a pellet-shaped porous precipitate, which was washed with an aqueous acetic acid solution, and then washed with boric acid and It was contained by adding it to an aqueous solution containing sodium acetate and stirring.

Example 4 In Example 2, as the component (A3), an ionomer of an ethylene-methacrylic acid copolymer [methacrylic acid content 11%, ionic species Na ⁺ , density 0.95 g / cm ³ , MF
R2.8 g / 10 min (190 ° C., load 2160 g)] in the same manner except that the resin composition (A) [water content in the resin composition (A) was 0.15%, acetic acid content was 80 pp.
m, sodium acetate content was 90 ppm (sodium conversion), magnesium acetate content was 28 ppm (magnesium conversion), calcium acetate content was 16 ppm (calcium conversion)], and a squeezed multilayer container (bottle) was similarly prepared. And evaluated in the same manner.

Example 5 In Example 2, as the component (A2), a saponified product of ethylene-vinyl acetate copolymer [ethylene content 82 mol%, saponification degree of vinyl acetate component 98.7 mol%, MFR
6.5 g / 10 minutes (measured at 190 ° C., load 2160 g), sodium acetate 700 ppm (sodium conversion)
Is contained as a component (A3), ethylene-methacrylic acid copolymer [methacrylic acid content 9%, density 0.93 g
/ Cm ³ , MFR 8g / 10 minutes (190 ° C, load 216
0 g)] was used in the same manner except that the water content in the resin composition (A) [resin composition (A) was 0.15%, and the acetic acid content was 8].
0ppm, sodium acetate content is 105ppm (sodium conversion), magnesium acetate content is 28ppm
(Calculated as magnesium), calcium acetate content is 16p
pm (calcium equivalent)] was obtained, a multilayer container (bottle) was similarly squeezed out, and the same evaluation was performed.

Example 6 In Example 3, as the component (A2), a saponified product of ethylene-vinyl acetate copolymer [ethylene content 82 mol%, saponification degree of vinyl acetate component 98.7 mol%, MFR
6.5 g / 10 minutes (measured at 190 ° C., load 2160 g), sodium acetate 700 ppm (sodium conversion)
Is contained as a component (A3), ethylene-acrylic acid copolymer [acrylic acid content 8.5%, MFR 7g / 1
0 minutes (190 ° C., load 2160 g)] in the same manner except that the resin composition (A) [water content in the resin composition (A) was 0.13% and boric acid content was 120 ppm (calculated as boron)). , Sodium acetate content was 185 ppm (converted to sodium)] and squeezed out in the same manner to obtain a multi-layer container (bottle)
Was prepared 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 5, the blending ratio of EVOH (A1), a saponified product of ethylene-vinyl acetate copolymer (A2) and ethylene-methacrylic acid copolymer (A3) was changed to EVOH (A1) 90.
Part, saponified product of ethylene-vinyl acetate copolymer (A2) 7
Parts, ethylene-methacrylic acid copolymer (A3) except that the resin composition (A) [resin composition (A)
The water content is 0.15%, the acetic acid content is 90 ppm, the sodium acetate content is 50 ppm (sodium conversion),
A magnesium acetate content of 31 ppm (calculated as magnesium) and a calcium acetate content of 18 ppm (calculated as calcium) were obtained, and a multilayer container (bottle) was similarly squeezed out and evaluated in the same manner.

Example 10 In Example 6, the blending ratio of EVOH (A1), a saponified product of ethylene-vinyl acetate copolymer (A2) and ethylene-acrylic acid copolymer (A3) was adjusted to 70% of EVOH (A1). Department,
Saponified ethylene-vinyl acetate copolymer (A2) 23
Part, ethylene-acrylic acid copolymer (A3) was changed to 7 parts in the same manner, except that the resin composition (A) [boric acid content in the resin composition (A) was 105 ppm (boron conversion), sodium acetate was contained). The amount is 230 ppm (calculated as sodium)], and similarly squeezed to produce a multilayer container (bottle),
It evaluated similarly.

Example 11 In Example 7, the blending ratio of EVOH (A1), the saponified product of ethylene-vinyl acetate copolymer (A2) and the ionomer of ethylene-methacrylic acid copolymer (A3) was changed to EVO.
H (A1) 85 parts, ethylene-vinyl acetate copolymer saponified product (A2) 10 parts, ethylene-methacrylic acid copolymer ionomer (A3) 5 parts in the same manner except that the resin composition (A) [Acetic acid content in the resin composition (A) is 85 p
pm, sodium acetate content is 60 ppm (sodium conversion), magnesium acetate content is 30 ppm (magnesium conversion), calcium acetate content is 17 ppm (calcium conversion)], and a squeezed multilayer container (bottle) is similarly prepared. And evaluated in the same manner.

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.
Similarly, resin composition (A) [water content in resin composition (A) is 0.15%, acetic acid content is 80 ppm, sodium acetate content is 90 ppm (sodium conversion) ), Magnesium acetate content is 28 ppm
(Calculated as magnesium), calcium acetate content is 16p
pm (calcium equivalent)] was obtained, a multilayer container (bottle) was similarly squeezed out, and the same evaluation was performed. However, for (A3) and (A4), those which were melt-mixed and pelletized by a twin-screw extruder in advance were used.

Example 13 In Example 3, the polyamide resin (A4) [copolymer of nylon 6/12, 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.
5: 3.5: 1.5 parts except that the resin composition (A) is the same. [The water content in the resin composition (A) is 0.13%, the boric acid content is 120 ppm (calculated as boron), Sodium acetate content was 170 ppm (calculated as sodium)], and a multilayer container (bottle) was similarly squeezed out, and evaluated in the same manner. However, for (A3) and (A4), those which were melt-mixed and pelletized by a twin-screw extruder in advance were used.

Example 14 In Example 11, 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) = 85: 1.
The resin composition (A) [acetic acid content in the resin composition (A) was 85 pp in the same manner except that the content was 0: 3.8: 1.2 parts.
m, sodium acetate content is 60 ppm (sodium conversion), magnesium acetate content is 30 ppm (magnesium conversion), calcium acetate content is 17 ppm (calcium conversion)], and a multilayer container (bottle) is similarly squeezed out. And evaluated in the same manner. However, (A3)
As for (A4), those which were previously melt-mixed and pelletized by a twin-screw extruder were used.

Comparative Example 1 In Example 1, except that the resin composition (A) did not contain the saponified product of ethylene-vinyl acetate copolymer (A2) and the ionomer of ethylene-methacrylic acid copolymer (A3). In the same manner, a multilayer container (bottle) was squeezed out and evaluated in the same manner.

Comparative Example 2 A squeezed multilayer container (bottle) was prepared in the same manner as in Example 1 except that the saponified product of ethylene-vinyl acetate copolymer (A2) was not added, and the same evaluation was performed. .

Comparative Example 3 A squeezed multilayer container (bottle) was prepared in the same manner as in Example 1 except that the ionomer (A3) of the ethylene-methacrylic acid copolymer was not added, and the same evaluation was performed.

Table 1 shows the evaluation results of the examples and comparative examples.

[Table 1] Appearance Gas barrier property Delamination strength Squeezability Removability (g / 15 mm) Example 1 ○ 0.007 61 ○ ○ 〃 2 ○ 0.006 67 ◎ ○ 〃 3 ○ 0.005 66 ◎ ○ 〃 4 ○ 0.006 67 ◎ ○ 〃 5 ○ 0.006 70 ◎ ○ 〃 6 ○ 0.005 69 ◎ ○ 〃 7 ○ 0.008 65 ◎ ○ 〃 8 ○ 0.006 72 ◎ ○ 〃 9 ○ 0.005 65 ◎ ○ 〃 10 ○ 0.007 78 ◎ ○ 〃 11 ○ 0.007 61 ◎ ○ 〃 12 ○ 0.006 69 ◎ ○ 〃 13 ○ 0.005 69 ◎ ○ 〃 14 ○ 0.007 63 ◎ ○ Comparative example 1 △ 0.004 9 × × 〃 2 × 0.006 23 × △ 〃 3 ○ 0.006 43 × ○ Note) gas barrier properties of units, cc / bottle · day · air

[0121]

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 CA10 FA01 FA04 FA11 FA15 GA01 GA02 HA02 HA03 4F100 AK03A AK03B AK03C AK03J AK06B AK06C AK21A AK21J AK46A AK62B AK62C AK66B AK66C AK68A AK69A AK70A AK71A AL01A AL05A 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 BB08Y BB09Y BB22W BB22X BB23Y CL00Z GF00 GG01

Claims (10)

[Claims] 1. An ethylene-vinyl acetate copolymer saponified product (A1), an olefin-carboxylic acid vinyl ester copolymer saponified product (A2) and an olefin-unsaturated carboxylic acid copolymer (A3) are contained. A squeezed multi-layer container comprising a resin composition (A) layer as an intermediate layer, and a polyolefin resin (B) layer disposed on both sides thereof. 2. The total amount of the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer and the olefin-unsaturated carboxylic acid copolymer (A3) based on the saponified product of the ethylene-vinyl acetate copolymer (A1). Content ratio (A1 / A2 + A3)
Is 50/50 to 99/1 (weight ratio), wherein the squeezed multilayer container according to claim 1. 3. The content ratio (A2 / A3) of the saponified product (A2) of the olefin-carboxylic acid vinyl ester copolymer and the olefin-unsaturated carboxylic acid copolymer (A2 / A3) is 50/50.
It is -99/1 (weight ratio), It is characterized by the above-mentioned.
Alternatively, the squeezed-out multilayer container according to item 2. 4. The saponified product (A2) of an olefin-carboxylic acid vinyl ester copolymer has an ethylene content of 70-9.
The squeezed multilayer container according to any one of claims 1 to 3, which is a partially saponified ethylene-vinyl acetate copolymer having a vinyl acetate component saponification degree of 20 to 99.9 mol%. 5. The olefin-unsaturated carboxylic acid copolymer (A3) 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. 6. 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 5. 7. The squeezed multilayer container according to claim 1, further comprising a resin composition (A) containing a polyamide resin (A4). 8. At least a polyolefin resin (B)
The squeezed multilayer container according to any one of claims 1 to 7, which has a laminated structure of layers / resin composition (A) layer / regrind (C) layer / polyolefin resin (B) layer. 9. 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. 10. The squeezed multilayer container according to claim 1, wherein the content is at least one selected from mayonnaise, ketchup and sauce.