JPH09109335A - Laminated structure and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated structure having excellent gas barrier properties, organic solvent resistance and low-temperature impact resistance and a vessel for volatile compound using the laminated structure. SOLUTION: A resin composition layer made of saponified ethylene-vinyl acetate copolymer containing 10 to 70mol% of ethylene content and degree of saponification of 85mol% or more and end adjusting polyamide resin so regulated that the number (x) of end COOH group and the number (y) of end CONRR' group (where R is 1-22C hydrocarbon group, R' is hydrogen or 1-22C hydrocarbon group) satisfy 100×y/(x+y)>=5, and a resin composition layer that 0.5 to 40 pts.wt. of saponified ethylene-vinyl chloride copolymer having 10 to 70mol% of ethylene content is dispersed to 100 pts.wt. of polyolefin resin and degree of saponification of 85mol% are laminated.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas barrier property,
The present invention relates to a laminated structure excellent in organic solvent resistance (solvent crack resistance), low temperature impact resistance, and the like, and a container using the laminated structure.

[0002]

2. Description of the Related Art Generally, a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, antistatic property, oil resistance, solvent resistance, gas barrier property, aroma retaining property and the like. For applications intended for packaging materials, gas barrier properties, aroma retention properties, food discoloration prevention properties, etc. are obtained by laminating films of low density polyethylene, polypropylene, nylon, polyester, etc. on both front and back sides of EVOH film. It is the fact that it is used for various packaging applications by compensating for the defects of EVOH such as drop strength, thermoformability and moisture resistance while maintaining the characteristics of EVOH. Recently, not only for packaging such as food bottles as described above, but also for transportation and storage of volatile compounds (various organic solvents, fuels, etc.) mainly containing hydrocarbons such as agricultural chemicals, reagents, and kerosene. It has come to be used as a bottle, a tank, a drum, etc.

However, although EVOH is generally excellent in gas barrier properties and solvent resistance as described above, its deterioration cannot be denied when exposed to such a hydrocarbon-based organic solvent (volatile compound). In the formed film / sheet, container or the like, so-called solvent crack (stress crack) occurs in which stress strain during stretching causes cracks due to the influence of the organic solvent.

In order to avoid such adverse effects, a layer in which a gas barrier resin (polyamide, polyvinyl alcohol, EVOH, etc.) is dispersed as a discontinuous phase in a polyethylene resin is used as an intermediate layer, and a polyethylene resin layer is used as an inner and outer layer. It has a three-layer structure (JP-A-6-218891), EVOH is blended with at least one thermoplastic resin selected from polyamide, polyolefin and polyester (JP-A-7-52333), E
A layer in which a VOH is mixed with a plasticizer and a thermoplastic resin layer such as polyamide or polyolefin are laminated (Japanese Patent Laid-Open No. 6-3
No. 28634), a polyolefin layer treated with a halogen-based compound or a sulfur-based compound and a resin layer containing EVOH or polyamide are laminated (JP-A-6-34).
In addition, a specific modified polyolefin resin is used as an adhesive resin for lamination in a laminate of a polyolefin resin layer and a polyamide or EVOH layer (JP-A-64-38232, JP-A-6432 / 6432). -38
No. 233 and Japanese Patent Publication No. 60-34461) have been proposed.

[0005]

However, it is difficult to develop a barrier property sufficient to meet the recent market demands, and the solvent crack resistance is still insufficient. In addition, there is room for improvement in barrier properties.
There is a concern that the adhesive strength between the OH layer and the adhesive layer will decrease,
There are still problems with safety during processing (deterioration of working environment, etc.), and even low temperature impact resistance (when the molded product is dropped) and lack of solvent crack resistance are mentioned, and there is still no satisfactory laminate. Is the reality.

[0006]

[Means for Solving the Problems] Therefore, as a result of intensive studies in view of the above circumstances, the present inventors have found that the ethylene content is 10 to 70 mol% and the saponification degree is 85 mol% or more. Terminal COOH with EVOH (A1) and terminal modifier
The number of groups (x) and a terminal CONRR 'group (wherein R is a hydrocarbon group having 1 to 22 carbon atoms, R'is hydrogen or 1 to 22 carbon atoms).
Number of hydrocarbon groups (y) is 100 × y / (x + y)
An ethylene content of 10 per 100 parts by weight of a resin composition layer (A) made of a terminal-adjusted polyamide resin (A2) adjusted to satisfy ≧ 5 and 100 parts by weight of a polyolefin resin (B1).
EVOH (B of 70 mol% or more and saponification degree of 85 mol% or more
2) Resin composition layer (B) in which 0.5 to 40 parts by weight are dispersed
The laminated structure is excellent in gas barrier property and organic solvent resistance, and the container using the laminated structure is a volatile compound containing various kinds of organic compounds such as agricultural chemicals / reagents and kerosene as a main component. It has been found that a laminated structure which is very useful for a container for fuel, etc., and in which a polyolefin-based resin layer (C) is further provided on both outer sides of the laminated structure can be particularly expected to exert the effect of the present invention. It came to completion.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. EVOH used for the resin composition layer (A) of the present invention
As (A1), the ethylene content is 10 to 70 mol% (preferably 20 to 60 mol%), and the degree of saponification of vinyl acetate units is 85 mol% or more (preferably 90 mol% or more, more preferably 95 mol%). The above) is used. When the ethylene content is less than 10 mol%, the melt moldability is deteriorated. Conversely, when the ethylene content exceeds 70 mol%, the gas barrier property is deteriorated, and when the saponification degree is less than 85 mol%, the gas barrier property and the gas barrier property are deteriorated. Insufficient resistance to organic solvents and inappropriate.

If EVOH (A1) is in a small amount,
It may be "copolymer-modified" with other comonomers such as α-olefin, unsaturated carboxylic acid compound, unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, vinyl chloride and styrene. . Further, within the range that does not impair the gist of the present invention,
"Post-modification" such as urethanization, acetalization, cyanoethylation, etc. may be performed.

The terminal-adjusting polyamide-based resin (A2) used in the resin composition layer (A) of the present invention includes the number (x) of terminal COOH groups and the terminal CONRR 'group (where R is carbon A hydrocarbon group having 1 to 22 carbon atoms, R'is hydrogen or a hydrocarbon group having 1 to 22 carbon atoms, and the number (y) is 10
An end-adjusted polyamide-based resin adjusted to satisfy 0xy / (x + y) ≧ 5 is used. Such a terminal-adjusted polyamide resin (A2) is produced by polycondensing a polyamide raw material in the presence of a monoamine having 1 to 22 carbon atoms or a monocarboxylic acid having 2 to 23 carbon atoms.

As the polyamide raw material, lactams (ε-caprolactam, enanthlactam, capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, etc.), ω-amino acids (6-aminocaproic acid, 7-aminoheptane) are used. Acid, 9-aminononanoic acid, 11
-Aminoundecanoic acid, etc.), dibasic acid (adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadioic acid, hexadecanedioic acid, eicosadiendioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, xylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
(Terephthalic acid, isophthalic acid, etc.), diamines (hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4 (or 2,2,4-) trimethylhexamethylenediamine , Bis- (4,4′-aminocyclohexyl) methane, metaxylenediamine and the like).

Examples of monoamines having 1 to 22 carbon atoms include aliphatic monoamines (methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine. , Dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine), alicyclic monoamines (cyclohexylamine,
Methylcyclohexylamine, etc.), aromatic monoamines (benzylamine, β-phenylethylamine, etc.), symmetrical secondary amines (N, N-dibutylamine, N, N-dihexylamine, N, N-dioctylamine, N, N- Didecylamine, etc.), mixed secondary amine (N-methyl-N-
Ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecylamine, N
-Ethyl-N-octadecylamine, N-propyl-N
-Hexadecylamine, N-methyl-N-cyclohexylamine, N-methyl-N-benzylamine, etc.) and the like.

As the monocarboxylic acid having 2 to 23 carbon atoms, aliphatic monocarboxylic acids (acetic acid, propionic acid,
Butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid,
Capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myritoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Arachidic acid, behenic acid, etc.), alicyclic monocarboxylic acids (cyclohexanecarboxylic acid, methylcyclohexanecarboxylic acid, etc.), aromatic monocarboxylic acids (benzoic acid, toluic acid, ethylbenzoic acid, phenylacetic acid, etc.) and the like. .

If necessary, in addition to the above monoamine or the above monocarboxylic acid, an aliphatic diamine (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylene). Diamine, dodecamelenediamine, 2,2,4- (or 2,
4,4-) trimethylhexamethylenediamine) etc.),
Alicyclic diamine (cyclohexanediamine, bis-
(4,4′-aminocyclohexyl) methane, etc., aromatic diamine (xylenediamine, etc.), aliphatic dicarboxylic acid (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid) , Dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosadionic acid, eicosendioic acid, docosanedioic acid, 2,2,4-trimethyladipic acid, alicyclic dicarboxylic acid ( It is also possible to coexist diamines and dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid) and aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, xylenedicarboxylic acid, etc.).

In producing the terminal-adjusted polyamide resin (A2), the above-mentioned polyamide raw material may be used and the reaction may be started according to a conventional method. The above-mentioned carboxylic acid and amine start the reaction under reduced pressure from the start of the reaction. Can be added at any stage up to. Further, the carboxylic acid and the amine may be added simultaneously or separately.

The amount of carboxylic acid and amine used is 2 to 20 meq / mol, preferably 3 as the carboxyl group and the amount of amine, per 1 mol of the polyamide raw material (monomer constituting the repeating unit or 1 mol of monomer unit). .About.19 meq / mol (the equivalent of amino group is 1 equivalent of the amount of amino group that reacts with 1 equivalent of carboxylic acid in a ratio of 1: 1 to form an amide bond). If this amount is too small, it becomes impossible to produce a polyamide-based resin having the effect of the present invention. On the contrary, if it is too large, it becomes difficult to produce a polyamide having a high viscosity, and the physical properties of the polyamide-based resin are adversely affected. become.

The reaction pressure is preferably such that the end of the reaction is 400 Torr or less, preferably 300 Torr or less. If the pressure at the end of the reaction is high, a desired relative viscosity cannot be obtained. The low pressure is not particularly inconvenient. The reduced pressure reaction time is preferably 0.5 hours or longer, usually about 1 to 2 hours.

The hydrocarbon group represented by R or R'in the -CONRR 'group at the terminal of the terminal-adjusted polyamide resin (A2) is an aliphatic hydrocarbon group (methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, tetradecyl group, tetradecylene group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, eicosyl group, docosyl group, etc., alicyclic hydrocarbon group (cyclohexyl group, methylcyclohexyl group, cyclohexylmethyl group, etc.), aromatic Examples thereof include group hydrocarbon groups (phenyl group, toluyl group, benzyl group, β-phenylethyl group, etc.).

Terminal adjustment of terminal of polyamide resin (A2)-
The conversion ratio of the COOH group to the -CONRR 'group is adjusted by the presence of an amine or a carboxylic acid with the amine during the production of the polyamide resin. In the present invention, the degree of this conversion depends on the number of terminal -COOH groups ( x) and the end-
The relationship with the number of CONRR 'groups (y) is 100 × y /
(X + y) ≧ 5, preferably 100 × y / (x + y) ≧
10 is satisfied, the -COOH group is -CONRR '
The amount of unconverted —COOH groups is preferably 50 μeq / g · polymer or less, preferably 40 μeq / g · polymer or less, and particularly preferably 20 μeq / g · polymer or less. Is desirable. If the degree of conversion is small, the effect of the present invention cannot be expected, and on the contrary, increasing the degree of conversion does not cause any inconvenience from the viewpoint of physical properties, but since it becomes difficult to manufacture, the amount of unmodified terminal carboxyl group is 1 μeq. It is a good idea to limit the amount to / g · polymer.

The hydrocarbon group represented by -CONRR 'can be measured by gas chromatography after hydrolyzing the polyamide resin with hydrochloric acid. -C
The OOH group can be measured by dissolving a polyamide resin in benzyl alcohol and titrating with 0.1N caustic soda. As the terminal group of the polyamide resin, the above-mentioned
In addition to the CONRR ′ group, there are —COOH group and —NH ₂ group derived from the above polyamide raw material.

The terminal amino group may or may not be modified, but it is preferably modified with the above-mentioned hydrocarbon group because it has good fluidity and melt heat stability.

The resin composition layer (A) contains the above E
In addition to VOH (A1) and terminal-adjusted polyamide-based resin (A2), hindered phenol-based compounds (A3), aliphatic carboxylic acid alkaline earth metal salts (for improving melt heat stability and molding processing stability) ( A4) and ethylene bis fatty acid amide, higher fatty acid metal salt, polymer ester, fatty acid ester, or at least one compound selected from at least one compound (A5) selected from hydrocarbon compounds are also useful, As the hindered phenol compound (A3), N, N'-hexamethylenebis (3,5-di-
t-butyl-4-hydroxyhydrocinnamide), 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol),
4,4'-thiobis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like, preferably N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- ( 3,5-di-t-butyl-4
-Hydroxyphenyl) propionate].

Aliphatic carboxylic acid alkaline earth metal salt (A
Examples of 4) include beryllium salts, magnesium salts, calcium salts, strontium salts and barium salts of aliphatic carboxylic acids having about 1 to 9 carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid and caprylic acid. Particularly, magnesium salts and calcium salts of aliphatic carboxylic acids having 2 to 4 carbon atoms are important.

As the compound (A5), ethylene bis fatty acid such as ethylene bis-stearyl amide (having 16 to 16 carbon atoms)
18) Higher fatty acid metal salts such as amide, zinc stearate, aluminum stearate, calcium stearate and magnesium stearate, adipate condensate of polypropylene glycol, sebacate condensate of polypropylene, polymer ester [eg, spalm aceti Made), Hoechst wax-E (made by Hoechst Japan), lytol (made by Sanwa Yushi), wood wax (made by Noda wax)], fatty acid ester [for example, butyl stearate, Nissan caster wax-A (made by NOF Corporation), TB-121 (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.)], a low molecular weight polyolefin such as polyethylene having a molecular weight of 900 to 30,000 by the viscosity method, a molecular weight of 1,000 to the viscosity method.
Examples thereof include low molecular weight polyolefins such as modified polyethylene and modified polypropylene having an acid value of 20,000 in the range of 5 to 100, and preferably ethylene bis fatty acid (having 16 carbon atoms).
-18) Amide, zinc stearate, lead stearate, calcium stearate, magnesium stearate, modified polyethylene having a molecular weight of 1000 to 20000 by a viscosity method and an acid value of 5 to 100, and modified polypropylene are mentioned, and particularly preferably. , Zinc stearate, calcium stearate.

The resin composition layer (A) of the present invention comprises EVOH (A1) and end-adjusted polyamide resin (A
2), preferably hindered phenolic compound (A3), aliphatic carboxylic acid alkaline earth metal salt (A4)
And ethylene bis fatty acid amide, higher fatty acid metal salt,
(A1) and (A2), which also contain at least one compound selected from one or more compounds (A5) selected from polymer esters, fatty acid esters and hydrocarbon compounds.
The blending ratio with is preferably from 70:30 to 96: 4 by weight, and when the blending ratio of the end-adjusted polyamide resin (A2) is less than the weight ratio, solvent crack resistance and low temperature impact resistance. Inferiority and conversely many, EVO
The gas barrier property of H (A1) tends to be impaired, and more preferably 70:30 to 90:10.

Further, a hindered phenol compound (A
The blending ratio of 3) is preferably in the range of 0.01 to 1% by weight based on the total amount of (A1) and (A2), and the blending ratio of the hindered phenolic compound (A3) is more than the above range. When the amount is too small, the antioxidant property is insufficient, so that an oxidative heat-deteriorated product is likely to occur during molding. Conversely, even if the compounding ratio is increased beyond the above range, the addition effect does not improve so much, which is a cost disadvantage. Becomes More preferably from 0.03
0.9% by weight, particularly preferably 0.05-0.8% by weight
It is.

Further, the mixing ratio of the aliphatic carboxylic acid alkaline earth metal salt (A4) is 0.5 to 15 μmol / g, preferably 1 in terms of metal, based on the total amount of (A1) and (A2). 10μmol / g is preferable, 0.5μ
If it is less than mol / g, the melt viscosity is increased, and conversely 15μ.
If it exceeds mol / g, foaming may occur at the time of molding or the interlayer adhesive strength may be deteriorated, which is not preferable. The compounding ratio of the compound (A5) is preferably 0.01 to 1% by weight based on the total amount of (A1) and (A2), and 0.0
If the amount is less than 1% by weight, the amount of the retained material in the extruder or the die is increased. On the contrary, if the amount exceeds 1% by weight, the surging phenomenon increases during molding, and a stable multilayer structure cannot be obtained, which is not preferable. More preferably, it is 0.1 to 1% by weight.

The resin composition layer (B) of the present invention contains EVOH (B) based on 100 parts by weight of the polyolefin resin (B1).
2) 0.5 to 40 parts by weight (preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight) of a resin composition, and the amount of EVOH (B2) is 0.5. If it is less than 10 parts by weight, the gas barrier property and solvent crack resistance are deteriorated, while if it exceeds 40 parts by weight, the low temperature impact resistance is deteriorated and the object of the present invention cannot be achieved. In addition, the resin composition layer (B) contains EV in the continuous phase of the polyolefin resin (B1).
OH (B2) dispersed resin composition layer, preferably EV
It is preferable that OH (B2) is dispersed in a thin layer as a discontinuous layer, and various kinds of polyolefin resin (B1) can be used. Specifically, high density polyethylene, medium density polyethylene, low density polyethylene, Ultra low density polyethylene, vinyl acetate, acrylic acid ester or polyethylene copolymerized with α-olefins such as butene, hexene and 4-methyl-1-pentene, polypropylene homopolymer, polypropylene grafted with ethylene, 4-methyl Polypropylene copolymerized with α-olefins such as -1-pentene, poly-1-butene, poly-4-methyl-1-pentene, and the above-mentioned polyolefins with unsaturated carboxylic acid or acid anhydride thereof, vinylsilane compound, epoxy Modified polio prepared by copolymerization or graft polymerization of group-containing compounds Such fins based resins.
Preferably high density polyethylene, medium density polyethylene,
Low-density polyethylene and ultra-low-density polyethylene are used, and it is also possible to use two or more kinds of polyolefin resins together, as described later.

The EVOH (B2) blended with the polyolefin resin (B1) has an ethylene content of 10 to 10.
It should be 70 mol% (preferably 15-65 mol%, more preferably 20-60 mol%) and the saponification degree is 85 mol% or more (preferably 90 mol% or more, more preferably 95 mol% or more). Ethylene content is 10 mol%
If it is less than 70% by weight, melt moldability is deteriorated, while if it exceeds 70 mol%, sufficient gas barrier properties cannot be obtained. If the degree of saponification is less than 85 mol%, the gas barrier property and the resistance to organic solvents (volatile compounds containing hydrocarbon as the main component) deteriorate.

EVOH (B2) is the above EVOH.
Similar to (A1), a small amount of propylene, isobutene, α-octene, α-dodecene, α-octadecene, and other α-olefins and unsaturated carboxylic acids within a range that does not impair properties such as transparency, gas barrier properties, and solvent resistance. Or a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile,
It may include a comonomer such as an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof. Also, EVOH
(A1) and EVOH (B2) can use the same EVOH or different EVOH at the same time.

As a method for obtaining each of the above resin compositions,
(A1) and (A2) or (B1) and (B2) (or (B1) ~
(B5)) can be melt-blended with a single-screw or multi-screw extruder (which can be repeated several times if necessary) and dry-blended with a rotary mixer. The former method is practical. Is. Furthermore, the polyolefin resin (B1) and EVOH (B2) in the resin composition layer (B) is 23
Apparent melt viscosity ratio calculated from the respective apparent melt viscosities at a shear rate of 100 cm ^{−1 at} 0 ° C. (apparent melt viscosity of polyolefin resin (B1) / EVOH (B2)
Has an apparent melt viscosity of 0.1 to 50 (further 0.5 to 1)
0, particularly 0.8 to 5), and when the melt viscosity ratio deviates from the above range, the dispersibility of EVOH (B2) in the polyolefin resin (B1) becomes insufficient and gas barrier property And solvent crack resistance tend to decrease.

Further, in order to newly improve low temperature impact resistance and solvent crack resistance, polyolefin resin (B
1) As high density polyethylene, medium density polyethylene,
It is also useful to use a modified polyolefin resin obtained by copolymerizing or graft-polymerizing an unsaturated carboxylic acid or its acid anhydride with polyethylene such as low density polyethylene or ultra low density polyethylene.

In the present invention, the polyolefin resin layer (C) is further laminated on the outside of the laminated structure composed of the resin composition layer (A) and the resin composition layer (B) described above to obtain a laminated structure. The moisture resistance, impact resistance, etc. are further improved and it becomes very practical. Polyolefin resin layer (C)
As the polyolefin-based resin used in, the same polyolefin-based resin as described in the layer (B) can be used.

In the laminated structure of the present invention, each of the above layers is (A) / (B) or (C) / (A) / (B) / (C).
A laminate having a constitution is used, and the method for producing the laminate is not particularly limited, and includes a coextrusion laminating method, a melt extrusion laminating method, and a method of dry laminating each layer (film) using an adhesive resin. , Coextrusion molding method,
A co-injection molding method, a co-extrusion inflation molding method, a solution coating method and the like can be mentioned. More specifically, in (A) / (B), a method of co-extruding each resin composition, each resin composition A method of laminating both layers after producing a material layer, a method of producing one resin composition layer and melt-coating (laminating) another resin composition on the layer, and the like, and the method is preferable, (C) / (A) /
The same can be applied to the laminated body having the configuration of (B) / (C).

Usually, an adhesive resin layer is provided between the layer (C) and the layer (A) or between the layer (A) and the layer (B), and the adhesive resin (D) is not suitable. Density modified with saturated carboxylic acid or its anhydride 0.86-0.95 g / cm
Ethylene -α- olefin copolymer preferably ^three, by copolymerization or graft modification with the above resin composition layer (B) a polyolefin resin and similar resins used or unsaturated carboxylic acid anhydride Modifications that can be obtained, of course, also include blends of unmodified ethylene-α-olefin copolymers with unsaturated carboxylic acids or their anhydrides. Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride and the like. Is preferably used.

At this time, the amount of unsaturated carboxylic acid or its anhydride contained in the ethylene-α-olefin copolymer is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. is there. If the content in the modified product is small, the adhesive strength will be lowered, and conversely, if the content is large, a crosslinking reaction will occur and moldability will be poor, such being undesirable. Such a laminated structure is not only in the form of a sheet or a film, but is also a container such as a pipe / tube or a tank / bottle by the coextrusion molding method, the co-injection molding method, the co-extrusion inflation molding method or the blow molding method. Further, it is also possible to heat the laminated structure again to about 100 to 150 ° C. and stretch it by a roll stretching method, a pantograph stretching method, an inflation stretching method, a blow stretching method or the like.

(A) / (B) or (C) / of the present invention
The thickness of each layer of the laminated structure of (A) / (B) / (C) is
It depends on the application and required physical properties, etc., and cannot be generally stated, but in general, each is 5 to 2000 μm / 30 to 10
000 μm, preferably 10-500 μm / 50-70
00 μm, or 30 to 10000 μm / 5 to 2000
μm / 30 to 10000 μm / 30 to 10000 μm,
Preferably 50-7000 μm / 10-500 μm / 5
0 to 7000 μm / 50 to 7000 μm, particularly when such a laminated structure is used for a container for a volatile compound containing hydrocarbon as a main component, (C) / (A) / (B) /
The laminated structure of (C) is preferable, and [inside] (C) / (A)
/ (B) / (C) [outer side], each layer is arranged, and the layer (A) is preferably located at a position of 20 to 60% from the inner side to the outer side, and further preferably 25 to 55%. .

Incidentally, the volatile compounds containing hydrocarbon as a main component in such a container are pesticides / reagents such as isooctane, thinner, machine oil, silicone oil, toluene, benzene, xylene, kerosene and other fuel oils. (Light oil, heavy oil, gasoline, etc.) and the like.

The features of the laminated structure of the present invention are (A) / (B) or (C) / (A) / (B) / (C) as described above.
(The description of the adhesive resin layer between each layer is omitted, and the same applies to the following.), And in addition to such a laminated structure, (C) / (A) / (B), (A) / ( B) /
(C), (C) / (A) / (B) / (A) / (C),
(C) / (B) / (A) / (B) / (C), (C) /
(A) / (C) / (A) / (B) / (C), (C) /
A laminated structure such as (A) / (A ′) / (B) / (C) may be used. Incidentally, (A ') is a layer of a composition containing the component (A1) as a main component. In addition, each layer of the laminate of the present invention includes an antioxidant, a lubricant, a hydrotalcite, an antistatic agent, a plasticizer, a colorant, an ultraviolet absorber, an inorganic Organic fillers and the like can be added within a range that does not impair the effects of the present invention.

[0039]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "part" and "%" mean weight basis unless otherwise specified. The following (A
1) to (A5), (B1) to (B2) and the adhesive resin (D) were prepared. EVOH (A1) A1-1: ethylene content 29 mol%, saponification degree 99.6
Mol%, MI (melt index) = 3 g / 10 minutes (2
10 ° C., 2160 g load) A1-2: ethylene content 32 mol%, saponification degree 99.6
Mol%, MI = 8 g / 10 min (same as above)

End-adjusted polyamide resin (A2) A2-1: Nylon 6 Terminal COOH group: 9 μeq / g Polymer 100 × y / (x + y) = 87, MI = 2.5 (230 ° C., 2160 g) A2- 2: Nylon 6/66 (Nylon 66 component 25% by weight) Terminal COOH group: 3 μeq / g / polymer 100 × y / (x + y) = 94, MI = 11.2 (same as above) A2-3: Nylon 6 terminal COOH Group: 20 μeq / g · polymer 100 × y / (x + y) = 60, MI = 3.6 (same as above)

Hindered Phenol Compound (A3) A3-1: N, N'-hexamethylenebis (3,5-di-)
t-Butyl-4-hydroxyhydrocinnamide) ("Irganox 1098" manufactured by Ciba-Gayky) A3-2: 1,3,5-trimethyl-2,4,6-tris (3,5-di-) t-butyl-4-hydroxybenzyl)
Benzene (“Irganox 13 manufactured by Ciba-Gayky”
30 ") A3-3: pentaerythrityl-tetrakis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” manufactured by Ciba-Gayky)

Aliphatic carboxylic acid alkaline earth metal salt (A
4) A4-1: magnesium acetate tetrahydrate A4-2: calcium propionate A4-3: magnesium butyrate

Compound (A5) A5-1: Ethylenebisstearyl amide A5-2: Polyethylene (Molecular weight 3200 by viscosity method,
Acid value 20 KOHmg / g) A5-3: Zinc stearate A5-4: Magnesium stearate A5-5: Zinc stearate: Calcium stearate =
1: 0.5 (weight ratio)

Polyolefin resin (B1) B1-1; high-density polyethylene (trade name: Hi-Z H
Z8200B, density 0.956 g / cm ³ , apparent melt viscosity 30000 poise, manufactured by Mitsui Petrochemical Industry Co., Ltd. B1-2; high density polyethylene (trade name: Shorex 4551H, density 0.945 g / cm ³ , apparent melting Viscosity 30000 poise, Showa Denko Engineering Co., Ltd.) The above apparent melt viscosity is 230 ° C. shear rate 1
The apparent melt viscosity at 00 cm ^-1 (capirograph (manufactured by Toyo Seiki Co., Ltd.); length: 10 mm, diameter: measured using an orifice having a diameter of 1 mm), and MI represents a melt flow index at 210 ° C.

EVOH (B2) B2-1; ethylene content 29 mol%, degree of saponification 99.6
Mol%, apparent melt viscosity 12000 poise, MI = 3 g
/ 10 min (same as above) B2-2; ethylene content 32 mol%, saponification degree 99.6.
Mol%, apparent melt viscosity 11,000 poise, MI = 3 g
/ 10 min (same as above) B2-3; ethylene content 29 mol%, degree of saponification 99.6.
Mol%, apparent melt viscosity 7,000 poise, MI = 8 g /
10 minutes (same as above) The above apparent melt viscosity is 230 ° C. at a shear rate of 1
The apparent melt viscosity at 00 cm ^-1 (same as above) is shown.

Adhesive resin (D) D-1; Modified polyolefin resin (trade name: Admer NF450A, manufactured by Mitsui Petrochemical Industry Co., Ltd.)

Example 1 As shown in Table 1, a resin composition for the resin composition layer (A) comprising the components (A1) to (A5) and a resin composition layer (components comprising the components (B1) to (B2) ( Resin composition for B) and both outer layers (C)
Polyolefin resin for use (using the polyolefin resin that is the component (B2) above) and adhesive resin (D) in a coextrusion multilayer direct blow molding machine of 4 types and 6 layers, [inside] ( C) / (adhesive resin) / (A) / (adhesive resin) / (B) / (C) [outside] = (thickness of each layer) 3
00 μm / 100 μm / 100 μm / 100 μm / 35
0 μm / 150 μm multi-layer bottle (about 500 ml capacity)
Was prepared. The EVOH layer (A) is at a position of about 36 to 45% from the inside to the outside in the thickness direction.

Toluene was filled in such a bottle, sealed, and the amount of permeation of toluene (g / day) measured at 40 ± 2 ° C. from the weight change of the bottle was 0.005 g / da.
It was y. Further, after the bottle filled with such toluene was left at 40 ± 2 ° C. for 8 weeks, the amount of permeation (g / day) of toluene was measured again and found to be 0.005 g / da.
y, and in order to investigate the stress crack resistance of this bottle (after being left standing), the cross section of the bottle was observed with an optical microscope, but no stress cracking due to the solvent was observed. On the other hand, the low temperature impact resistance was examined by dropping the bottle after such a standing treatment at a temperature of -40 ° C from a height of 5 m on a concrete surface, and it was found that the bottle was broken (visual observation) or cracked on the surface or cross section. (Observation with optical microscope as above) was not observed.

Examples 2 to 13 and Comparative Examples 1 to 4 Using the resins shown in Table 1, bottles were prepared according to Example 1 and evaluated in the same manner. In Examples 4 and 5, the thickness of each layer of the bottle is [inside] (C) / (adhesive resin) / (A) / (adhesive resin) / (B) / (C).
[Outside] = (thickness of each layer) 300 μm / 100 μm / 1
00 μm / 100 μm / 500 μm / 200 μm (EV
The position of the OH layer (A) was about 31 to 38% from the inside to the outside in the thickness direction.

The evaluation results of the examples and comparative examples are also shown in Tables 1-5. In addition, the numbers of the components (A3) and (A4) shown in Tables 1 to 5 represent the respective compounding ratios with respect to the total amount of the components (A1) and (A2) in ppm value. The numerical value after the metal name represents the compounding amount (μmol / g) of the metal with respect to the total amount of (A1) and (A2).

[0051]

[Table 1] Example 1 Example 2 Example 3 Example 4 (A1) component A1-1 90 parts A1-1 80 parts A1-1 70 parts A1-2 70 parts (A2) component A2-1 10 parts A2 -1 20 parts A2-1 30 parts A2-1 30 parts (A3) component A3-1 4000ppm A3-3 4000ppm A3-2 8000ppm A3-14000ppm (A4) component A4-1 Mg 3.5 A4-1 Mg 2.0 A4- 3 Mg 2.3 A4-2 Ca 6.0 (A5) component A5-5 1700 ppm A5-5 1500 ppm A5-3 1300 ppm A5-4 1500 ppm (B1) component B1-1 100 parts B1- * 100 parts B1-2 100 parts B1-1 100 parts (B2) component B2-1 15 parts B2-1 20 parts B2-2 15 parts B2-2 15 parts (C) component B1-1-B1-1-B1-2-B1-1- (D) component D-1-D-1-D-1-D-1- Toluene permeation amount (g / day) Before standing 0.005 0.006 0.007 0.007 After standing 0.005 0.0006. 007 0.007 stress crack resistance No change No change No change No change low-temperature impact resistance No change No change No problem Teeth * (B1) component of Example 2, using a mixture of B1-1 and maleic anhydride modified polyethylene (weight ratio = 100/5).

[0052]

[Table 2] Example 5 Example 6 Example 7 Example 8 (A1) component A1-1 90 parts A1-1 90 parts A1-1 90 parts A1-1 90 parts (A2) component A2-2 10 parts A2 −3 10 parts A2-1 10 parts A2-1 10 parts (A3) component A3−2 1000ppm A3−3 4000ppm − A3−3 5000ppm (A4) component A4-1 Mg 2.0 A4−2 Ca 4.0− (A5) Component A5-2 5000ppm A5-1 5000ppm --- (B1) Component B1-1 100 parts B1-1 100 parts B1-1 100 parts B1-1 100 parts (B2) Component B2-1 10 parts B2-2 20 parts B2 -1 10 parts B2-1 10 parts (C) Component B1-1-B1-2-B1-1- (D) Component D-1-D-1-D-1-D-1- Toluene permeation amount ( g / day) Before standing 0.005 0.004 0.007 0.005 After standing 0.005 0.004 0.009 0.005 No stress cracking No abnormality No abnormality No abnormality No abnormality Low temperature impact resistance No abnormality No abnormality No abnormality No abnormality

[0053]

[Table 3] Example 9 Example 10 Example 11 Example 12 (A1) component A1-1 90 parts A1-1 90 parts A1-1 90 parts A1-1 90 parts (A2) component A2-2 10 parts A2 −3 10 parts A2-1 10 parts A2-1 10 parts (A3) component − − A3−3 4000ppm A3−3 4000ppm (A4) component A4-1 Mg 2.0 − A4-1 Mg 3.5 − (A5) component − A5 -1 5000ppm-A5-4 3000ppm (B1) component B1-1 100 parts B1-1 100 parts B1-1 100 parts B1-1 100 parts (B2) component B2-1 10 parts B2-2 20 parts B2-110 Part B2-1 10 parts (C) Component B1-1-B1-2-B1-1- (D) Component D-1-D-1-D-1-D-1- Toluene permeation rate (g / day) ) Before leaving 0.005 0.004 0.005 0.005 After leaving 0.005 0.004 0.005 0.005 Stress crack resistance No abnormalities No abnormalities No abnormalities No abnormalities No low temperature impact resistance No abnormalities Abnormalities None No abnormality No abnormality

[0054]

[Table 4]

[0055]

[Table 5] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A1) component A1-1 100 parts-A1-1 90 parts A1-1 90 parts (A2) component-A2-1 100 parts A2-1-10 Part A2-1 10 parts (A3) component − − A3-1 4000ppm A3-14000ppm (A4) component − − A4-1 Mg 3.5 A4-1 Mg 3.5 (A5) component − − A5-5 1700ppm A5-5 1700ppm (B1) Component B1-1 100 parts B1-1 100 parts B1-1 100 parts B1-1 100 parts (B2) Component B2-1 15 parts B2-1 15 parts-B2-1 50 parts (C) Component B1- 1-B1-1-B1-1-B1-1- (D) Component D-1-D-1-D-1-D-1- Toluene permeation amount (g / day) Before standing 0.004 0. 08 0.007 0.003 After standing 0.004 0.08 0.0020 0.003 Stress crack resistance No abnormality No abnormality Crack occurrence No abnormality Low temperature impact resistance Crack occurrence No abnormality Crack occurrence Destruction

[0056]

The laminated structure of the present invention has the above-mentioned (A) / (B) or (C) / (A) / (B) / (C).
Since it has a laminated structure, it has excellent gas barrier properties, organic solvent resistance, low temperature impact resistance, etc., and transports and stores volatile compounds (various organic solvents, fuels, etc.) containing hydrocarbons as the main component. It is very useful as a container for carrying out, that is, a bottle for agricultural chemicals / reagents, a tank, a tank for fuel such as drums and kerosene.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/09 KEP C08K 5/09 KEP 5/13 KFY 5/13 KFY 5/20 KEW 5/20 KEW C08L 23/26 LDM C08L 23/26 LDM 31/04 LHJ 31/04 LHJ 77/02 LQS 77/02 LQS

Claims (12)

[Claims] 1. A saponification product (A1) of an ethylene-vinyl acetate copolymer having an ethylene content of 10 to 70 mol% and a saponification degree of 85 mol% or more, and the number of terminal COOH groups (x) by an end adjuster. Terminal CONRR 'group (where R is 1 carbon atom
To 22 hydrocarbon groups, R'is hydrogen or a hydrocarbon group having 1 to 22 carbon atoms), and the number (y) is 100 × y / (x + y) ≧
The ethylene content of 10 to 100 parts by weight of the resin composition layer (A) made of the terminal-adjusted polyamide resin (A2) adjusted to satisfy 5 and 100 parts by weight of the polyolefin resin (B1).
Lamination characterized in that a resin composition layer (B) in which 0.5 to 40 parts by weight of a saponified ethylene-vinyl acetate copolymer (B2) having a proportion of 70 mol% and a saponification degree of 85 mol% or more is dispersed is laminated. Structure. 2. The weight ratio of (A1) :( A2) is from 70:30.
It is 96: 4, The laminated structure of Claim 1 characterized by the above-mentioned. 3. The resin composition layer (A) further comprises a hindered phenolic compound (A3), an aliphatic carboxylic acid alkaline earth metal salt (A4) and ethylenebis fatty acid amide, a higher fatty acid metal salt, a polymer ester, The laminated structure according to claim 1 or 2, wherein at least one selected from the compound (A5) selected from one or more kinds of fatty acid ester and hydrocarbon compound is blended. 4. The blending ratio of (A1) and (A2) when each of (A3) to (A5) is blended,
(A3) is 0.01 to 1% by weight, and (A4) is 0.1 in terms of metal.
The laminated structure according to claim 3, wherein 5 to 15 µmol / g and (A5) is 0.01 to 1% by weight. 5. The hindered phenol compound (A3) is N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), 1,3,5-.
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], at least one selected from the group consisting of :) the laminated structure according to claim 3 or 4. 6. The laminated structure according to claim 3, wherein the aliphatic carboxylic acid alkaline earth metal salt (A4) is a magnesium salt of an aliphatic carboxylic acid having 2 to 4 carbon atoms. . 7. The compound (A5) is an ethylene bis fatty acid amide having 16 to 18 carbon atoms, zinc stearate, lead stearate, calcium stearate, magnesium stearate, a molecular weight of 1000 to 20,000 and an acid value of 5 by the viscosity method. It is at least 1 sort (s) chosen from the low molecular weight polyolefin of the range of 100, The laminated structure in any one of Claims 3-6 characterized by the above-mentioned. 8. The laminated structure according to any one of claims 1 to 7, wherein the polyamide raw material of the end-adjusted polyamide resin (A2) is ε-caprolactam. 9. The laminated structure according to claim 1, further comprising a polyolefin resin layer (C) provided on both outer sides. 10. A container comprising the laminated structure according to claim 1. 11. The container according to claim 10, wherein the layer (A) is located at a position of 20 to 60% from the inside to the outside in the thickness direction of the laminated structure. 12. The container according to claim 10, which is used for a volatile compound containing hydrocarbon as a main component.