JP2002146135A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition excellent in gas barrier property and external appearance. SOLUTION: This resin composition is obtained by melt blending of an ethylene-vinyl acetate copolymer (A), an organic substance-containing layered inorganic compound (B) and a polyamide resin (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition obtained by melt-mixing a saponified ethylene-vinyl acetate copolymer (A), a layered inorganic compound (B) containing an organic substance, and a polyamide resin (C). More specifically, the present invention relates to a resin composition having excellent gas barrier properties and appearance characteristics.

[0002]

2. Description of the Related Art In general, saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, antistatic property, oil resistance, solvent resistance, gas barrier property, fragrance retention property and the like. It is also a thermoplastic resin that can be melt-molded, and is used for various packaging materials such as food packaging. In order to further improve gas barrier properties,
Attempts have been made to mix inorganic substances with VOH.

For example, JP-A-5-86241 describes a resin composition in which EVOH is mixed with a mixture of a water-swellable phyllosilicate and a polyamide.
JP-A-00-264328 discloses a resin composition in which a mixture of a polyamide as a matrix and a water-swellable phyllosilicate dispersed therein is mixed with EVOH.

[0004]

However, as a result of a detailed study of the disclosed technology described in the above-mentioned publication, the inventors of the present invention have found that in the former technology, a water-swellable phyllosilicate is present in the presence of water. Is added, and a water / alcohol solution of EVOH is further added, so-called mamako is likely to be generated. Therefore, it is difficult to uniformly disperse the water-swellable phyllosilicate. It is necessary and found that there may be cases where sufficient gas barrier properties cannot be exhibited, and since the latter technique, which is presumed to be an improvement of such a technique, is also an interlayer polymerization method, a water-swellable phyllosilicate is contained in the polyamide resin. It is necessary to increase the amount of the polyamide resin in order to uniformly disperse the resin at a high concentration, and as a result, the gas barrier property is reduced, and further improvement is desired. A.

[0005]

Means for Solving the Problems Accordingly, the present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that EVOH
(A) It has been found that a resin composition obtained by melt-mixing a layered inorganic compound (B) containing an organic substance and a polyamide resin (C) can solve the above-mentioned problems, thereby completing the present invention. Reached.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The EVOH (A) used in the present invention is not particularly limited, but has an ethylene content of 5 to 60 mol% (further 10 to 60 mol%, particularly 20 to 55 mol%, particularly 25
To 50 mol%), and the ethylene content is 5%.
If the amount is less than mol%, the water resistance becomes insufficient, and conversely, 60 mol%
If it exceeds, the gas barrier properties are undesirably reduced.

The degree of saponification of the vinyl acetate component is preferably 90 mol% or more (more preferably 95 mol% or more, particularly 99 mol% or more, particularly 99.5 mol% or more). If it is less than mol%, gas barrier properties and heat resistance become insufficient, which is not preferable.

The above EVOH (A) may be copolymerized with an ethylenically unsaturated monomer copolymerizable within a range not impairing the effects of the present invention (about 10 mol% or less). Examples of the compound include olefins such as propylene, 1-butene, and 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 esters having 1 to 18 carbon atoms, acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or a acid thereof Acrylamides such as salts or quaternary salts thereof, methacrylamide, having 1 to 18 carbon atoms N- alkylmethacrylamide,
Methacrylamides such as N, N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt or a quaternary salt thereof, N-vinylpyrrolidone, N-vinylformamide, N N-vinylamides such as vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers, vinyl chloride, vinylidene chloride, fluorine Vinyl halides such as vinyl chloride, vinylidene fluoride, and vinyl bromide, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamide-3-dime Rupuropiru) - ammonium chloride, and the like acrylamido-2-methylpropanesulfonic acid. Also, as long as the spirit of the present invention is not impaired,
Post-modification such as urethanization, acetalization, and cyanoethylation may be used. Also, as EVOH (A),
For example, EVOH containing silicon as described in JP-A-60-144304 can be used.

In the present invention, the EVOH (A) preferably contains a boron compound (A1), sodium acetate (A2) and magnesium acetate (A3), and the content thereof is not particularly limited. EVOH (A)
On the other hand, the boron compound (A1) is 0.00
5 to 0.3% by weight, sodium acetate (A2) and magnesium acetate (A3) were 0.001 to 0.
When the content of the boron compound (A1) is less than 0.005% by weight in terms of boron, the effect of improving the long-run property is not sufficient.
If the content exceeds 3% by weight, gels and fish eyes tend to occur frequently, which is not preferable. If the content of sodium acetate (A2) is less than 0.001% by weight in terms of metal, the effect of improving long-run property is not sufficient. If the content exceeds 0.02% by weight, the appearance of the obtained molded article may be deteriorated, and the content of magnesium acetate (A3) is 0.1% in terms of metal.
If it is less than 001, the effect of improving the long-run property is not sufficient, and if it exceeds 0.02% by weight, the melt viscosity is too low, and it becomes difficult to form a film or the like.

A more preferred lower limit of the content of the boron compound (A1) is 0.01% by weight, particularly 0.015% by weight, particularly 0.02% by weight in terms of boron, and conversely, The preferred upper limit is 0.2% by weight, especially 0.15% by weight, especially 0.1% by weight, and sodium acetate (A2)
Is more preferably 0.001 in terms of metal.
5% by weight, particularly 0.002% by weight; conversely, a more preferred upper limit is 0.015% by weight, particularly 0.01% by weight.
Further, the more preferable lower limit of the content of magnesium acetate (A3) is 0.0015% by weight and particularly 0.002% by weight in terms of metal, and the more preferable upper limit is 0.015% by weight. In particular, it is 0.01% by weight.

As described above, E containing boron compound (A1), sodium acetate (A2) and magnesium acetate (A3)
There is no particular limitation in obtaining VOH (A), and the method for preparing such EVOH (A) is described below, but is not limited thereto. The above (A1) to EVOH
In order to contain (A3), it is sufficient to treat with the aqueous solution of (A1) to (A3). Usually, the ethylene-vinyl acetate copolymer is sodium hydroxide, potassium hydroxide, sodium methylate, and methanol in a methanol medium. The EVOH obtained by saponifying with an alkali such as potassium methylate and then neutralizing with acetic acid and the like contains sodium by-products and the like as by-products, so that the aqueous solution of the above (A1) to (A3) It is preferable to wash with acetic acid aqueous solution and water before the treatment.

[0012] The washing conditions are 0.001 to 1% by weight, preferably 0.1 to 100% by weight of EVOH.
After adding 50 to 500 parts by weight, preferably 100 to 400 parts by weight of an aqueous solution of acetic acid of 0.5 to 0.5% by weight and stirring at 10 to 50 ° C., preferably 20 to 40 ° C. for 10 minutes to 5 hours,
The EVOH is filtered, an equal amount of water is added, and washing is performed in the same manner. The washing is repeated 2 to 5 times. Acetic acid should be removed as much as possible by the water washing (0.01% by weight or less, further 0.005% by weight or less, particularly 0.005% by weight or less).
1% by weight or less), and sodium acetate is desirably 0.001% by weight or less in terms of metal. If the content of acetic acid exceeds 0.01% by weight, the appearance of the resulting molded product is undesirably reduced.

Next, the above-mentioned water-washed EVOH is treated with an aqueous solution of a boron compound (A1), sodium acetate (A2), and magnesium acetate (A3) so as to be adjusted to predetermined contents. However, as the preparation method, treatment with a mixed aqueous solution of a boron compound (A1), sodium acetate (A2) and magnesium acetate (A3), or treatment with a boron compound (A1), sodium acetate (A2), magnesium acetate (A3 ), One or two aqueous solutions, and then the remaining aqueous solution may be used. However, the boron compound (A1), sodium acetate (A2), magnesium acetate (A3 ) Since the respective adsorptive properties are different from each other, it is preferable to treat with the mixed aqueous solution, since the respective contents can be easily controlled.

The boron compound (A) used in the present invention
1) includes boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum / potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate, Ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, Potassium octaborate, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (sodium metaborate) , Sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc.), boric acid Lead (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate,
Nickel diborate, nickel tetraborate, nickel octaborate, etc., barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (orthoborate) Magnesium borate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc., manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (Lithium metaborate, lithium tetraborate,
Lithium pentaborate, etc.), borax, carnite,
Examples include borate minerals such as inyoite, dwarfite, zyanite, and ziberite, and preferably borax, boric acid, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, pentaborate) Sodium, sodium hexaborate, sodium octaborate, etc.) are used.

As the treatment method, specifically, 0.0001 to 1.5% by weight, preferably 0.001 to 0.2% by weight of a boron compound (A1) in terms of boron is added to 100 parts by weight of the above-mentioned water-washed EVOH. %, Further 0.001 to 0.0
2% by weight and sodium acetate (A2)
01-0.1% by weight, preferably 0.001-0.05
% By weight, more preferably 0.001 to 0.02% by weight, and magnesium acetate (A3) is 0.0005 to 0.1% by weight, preferably 0.0005 to 0.05% by weight, more preferably 0. It is immersed in 200 parts by weight of an aqueous solution containing 0005 to 0.02% by weight at 10 to 50 ° C. for 2 to 10 hours, or treated with stirring. As the water to be used, it is preferable to use ion-exchanged water from the viewpoint that the concentration of various components can be easily adjusted, but it is not limited to this. The above processing can be performed by either a batch method or a continuous method.

After the treatment, the solution is filtered and dried in a drier at 90 to 12%.
By drying at 0 ° C. for 5 to 48 hours, the desired EVOH can be obtained.

The layered inorganic compound (B) containing an organic substance used in the present invention is one containing an organic substance between layers of the layered inorganic compound. Examples of the layered inorganic compound include, but are not particularly limited to, clay minerals such as smectite and vermiculite, and further include synthetic mica, and specific examples of the former smectite include montmorillonite, beidellite, nontronite, saponite, hectite. Light, sauconite, stevensite and the like. These may be natural or synthetic. Among these, smectite, particularly montmorillonite, is preferred because it allows organic substances to easily enter between layers of the layered inorganic compound. Na type fluorine tetrasilicic mica, Na type teniolite, Li type teniolite, N
Water-swellable fluoromica-based minerals such as a-hectorite are also preferably used. The aspect ratio of the layered inorganic compound is not particularly limited, but is preferably 500 or more.

The organic substance contained in the layered inorganic compound is not particularly limited, but in consideration of the insertability into the layered inorganic compound, a compound having an organic onium ion is preferable, and the compound having such an organic onium ion is contained. Specifically, this is performed by adding an organic agent comprising an organic onium ion having a hydroxyl group to the layered inorganic compound and treating it.

The organic onium ion is not particularly limited, but may be a monoalkyl primary to quaternary ammonium ion, a dialkyl secondary to tertiary ammonium ion, or a trialkyl tertiary to quaternary ammonium ion. Examples thereof include an ammonium ion and a tetraalkylammonium ion. The alkyl chain has a carbon number of 4 to 30.
Are preferred, more preferably 6 to 20, particularly preferably 8 to 18. In addition to the alkyl chain, primary to quaternary ammonium ions having a polyethylene glycol chain having ethylene oxide as a structural unit (monoethylene glycol, diethylene glycol, triethylene glycol,
The ammonium ion of tetraethylene glycol may be used. Or a higher or lower fatty acid ester of a higher fatty acid, a higher or lower fatty acid ester, or a higher or lower alcohol. Further, those having plural kinds of molecular chains may be used. Further, a secondary or quaternary ammonium ion obtained by adding these molecular chains to a fatty acid amide may be used.

It is preferable that the average interplanar spacing of the layer of the layered inorganic compound is 10 ° or more by such treatment,
0 to 100 °, particularly 12 to 40 °, is preferable. If the average plane distance is less than 10 °, dispersion in EVOH may not be sufficient, which is not preferable. The average interplanar spacing of the layer of the layered inorganic compound was determined by wide-angle X-ray diffraction (WAXD).
Using an apparatus, Cuk-α1 was used as an X-ray light source, light was emitted at a voltage of 40 kV and a current of 40 mA, the divergence slit was 1 deg, the scattering slit was 1 deg, the light receiving slit was 0.3 mm, and the scanning speed was 2 mm. ° / m
in, the scan step is 0.02 ° and the scan axis 2θ /
It can be obtained by measuring θ.

The polyamide resin (C) used in the present invention is not particularly limited, and various resins can be used. Specific examples of such polyamide resins include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), and polylauryl lactam. (Nylon 12), polyethylene diamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexa Methylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / ω-aminononanoic acid Copolymer (Niro 6/9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12
/ 66), ethylene diamine adipamide / hexamethylene diammonium adipate copolymer (nylon 26 /
66), 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 a polyamide resin modified with an aromatic amine such as methylenebenzylamine or metaxylenediamine And meta-xylylenediammonium adipate.

In the present invention, one or two of these
More than one kind of blend can be used, and nylon 6, nylon 66, and nylon 6/66 are preferably used.

Further, a polyamide resin in which the carboxyl group and / or amino group at the molecular terminal of the polyamide resin has been adjusted (modified) with an alkyl monocarboxylic acid, an alkyl dicarboxylic acid, an alkyl monoamine, an alkyl diamine, or the like can be used. Such a polyamide resin will be described below. As such a polyamide resin, the number of terminal COOH groups (x) and terminal CONR
R ′ group (where R is a hydrocarbon group having 1 to 22 carbon atoms, R ′
Is hydrogen or a hydrocarbon group having 1 to 22 carbon atoms) (y)
However, a terminal-adjusted polyamide resin adjusted so as to satisfy 100 × y / (x + y) ≧ 5 is used. Such a terminal-adjusted polyamide resin 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.

Examples of the polyamide raw materials include lactams (ε-caprolactam, enantholactam, caprylactam, lauryl lactam, α-pyrrolidone, α-piperidone, etc.) and ω-amino acids (6-aminocaproic acid, 7-aminoheptane) Acid, 9-aminononanoic acid, 11
-Aminoundecanoic acid, etc.), dibasic acids (adipic acid, glutaric acid, pimelic acid, spearic acid, azelaic acid, sebacic acid, undecandionic acid, dodecadionic acid, hexadecandionic acid, eicosadienedioic 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, meta-xylenediamine and the like.

Examples of the monoamine 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 monoamine (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.), hybrid 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 and the like).

The monocarboxylic acids having 2 to 23 carbon atoms include aliphatic monocarboxylic acids (acetic acid, propionic acid,
Butyric, valeric, caproic, enanthic, caprylic,
Capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, mylitreic acid, palmetic 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.). .

If necessary, in addition to the above-mentioned monoamine or monocarboxylic acid, aliphatic diamine (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine) Diamine, dodecamediamine, 2,2,4- (or 2,
4,4-) trimethylhexamethylenediamine), etc.),
Alicyclic diamines (cyclohexanediamine, bis-
(4,4'-aminocyclohexyl) methane, etc.), aromatic diamines (xylene diamine, etc.), aliphatic dicarboxylic acids (malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid) Alicyclic dicarboxylic acids such as dodecandionic acid, tetradecandionic acid, hexadecandionic acid, octadecanedioic acid, octadecenedioic acid, eicosadonic acid, eicosenedioic acid, docosandioic acid, 2,2,4-trimethyladipate; Diamines and dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and the like and aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, and xylene dicarboxylic acid) can also be present.

In producing the terminal-adjusted polyamide resin, 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 may be added at any time from the start of the reaction to the start of the reaction under reduced pressure. Can be added at the stage. Further, the carboxylic acid and the amine may be added simultaneously or separately.

The carboxylic acid and amine are used in an amount of 2 to 20 meq / mole, preferably 3 to 20 mq / mole, based on the carboxyl group and amine amount, per mol of the polyamide raw material (1 mol of the monomer or monomer unit constituting the repeating unit). １９19 meq / mol (the equivalent of the amino group is 1 equivalent to the amount of the amino group that forms an amide bond by reacting 1: 1 with 1 equivalent of the carboxylic acid). If this amount is too small, it becomes impossible to produce a polyamide resin having the effect of the present invention, and if it is too large, it becomes difficult to produce a polyamide having a high viscosity, which adversely affects the physical properties of the polyamide resin. become.

The reaction pressure is preferably 400 Torr or less at the end of the reaction, more preferably 300 Torr or less. If the pressure at the end of the reaction is high, the desired relative viscosity cannot be obtained. There is no particular disadvantage that the pressure is low. The reaction time under reduced pressure is preferably 0.5 hour or more, and usually about 1 to 2 hours.

Examples of the hydrocarbon group represented by R or R 'in the -CONRR' group at the terminal of the terminal-adjusting polyamide resin include an aliphatic hydrocarbon group (methyl group, ethyl group, propyl group, butyl group, pentyl group). , Hexyl group,
Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, tetradecylene, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, etc. ), Alicyclic hydrocarbon groups (cyclohexyl group, methylcyclohexyl group, cyclohexylmethyl group, etc.), aromatic hydrocarbon groups (phenyl group, toluyl group, benzyl group, β-phenylethyl group, etc.).

Terminal-COO of terminal-adjusted polyamide resin
The conversion ratio of the H group to the -CONRR 'group is adjusted by the presence of an amine or a carboxylic acid during the production of the polyamide resin. In the present invention, the degree of this conversion is determined by the number of terminal -COOH groups ( x) and terminal -CON
The relationship with the number (y) of RR ′ groups is 100 × y / (x +
y) The amount of -COOH groups preferably converted to -CONRR 'groups, and the amount of unconverted -COOH groups so as to satisfy ≧ 5, preferably 100 × y / (x + y) ≧ 10. Is desirably 50 μeq / g · polymer or less, preferably 40 μeq / g · polymer or less, particularly preferably 20 μeq / g · polymer or less. If the degree of this conversion is too small, the effects of the present invention cannot be expected. Conversely, increasing the degree of conversion is not inconvenient in terms of physical properties, but it makes production difficult, so the amount of unmodified terminal carboxyl groups is reduced. It is advisable to keep the amount to 1 μeq / 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 the polyamide resin in benzyl alcohol and titrating with 0.1 N caustic soda. As the terminal group of the polyamide resin, the above-mentioned-
Other CONRR 'groups are -COOH groups and -NH ₂ group derived from the above-mentioned polyamide material.

The terminal amino group may be modified or unmodified, but is preferably modified with the above-mentioned hydrocarbon group because of its good fluidity and melt heat stability.

The resin composition of the present invention comprises the above-mentioned EVO
H (A), a layered inorganic compound (B) containing an organic substance, and a polyamide resin (C). The content ratio of (A) to (C) is not particularly limited, In order to obtain the effects of the present invention efficiently,
(B) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of (A). If (B) is less than 0.5 part by weight, the effect of improving gas barrier properties is poor, and conversely, 10 parts by weight. Exceeding the part is undesirable because the appearance of the obtained molded article is deteriorated. The lower limit of (B) is more preferably 1.0 part by weight, further 1.5 parts by weight, particularly 2.0 parts by weight, and the more preferable upper limit is 9.5 parts by weight. 9.
0 parts by weight, especially 8.5 parts by weight.

The content of (C) is preferably 1 to 40 parts by weight based on 100 parts by weight of (A).
If (C) is less than 1 part by weight, the dispersibility of (B) will be insufficient, and if it exceeds 40 parts by weight, the gas barrier properties will decrease,
In addition, gel and fish eyes are undesirably generated.
It is to be noted that a more preferred lower limit of (C) is 1.5 parts by weight, further 2.0 parts by weight, particularly 2.5 parts by weight, and a more preferred upper limit is 35 parts by weight. 5
Parts by weight, especially 30 parts by weight.

In the present invention, the above (A) to (C)
Are melt-mixed to obtain a resin composition, and it is necessary to mix them in a molten state.

There is no particular limitation on melt-mixing of the above (A) to (C). For example, a known melt-kneading (mixing) apparatus such as a melt extruder, a kneader-ruder, a mixing roll, a Banbury mixer, and a plast mill is used. It is sufficient to mix in a molten state in the apparatus, it is usually industrially preferable to use a single-screw or twin-screw extruder, and in particular, a twin-screw extruder is suitably used in view of stability of melt-kneading, The method using such a twin-screw extruder will be described in more detail, but is not limited thereto.

The twin-screw extruder used is not particularly limited, but has an inner diameter of 15 mm or more (more preferably 20 to 150 m).
m) is preferable, and when the inner diameter is less than 15 mm, productivity is poor, which is not preferable.
To 80 (more preferably 30 to 60), and such L / D
If the diameter is less than 20, the mixing ability may be insufficient,
Conversely, if it exceeds 80, the residence time of the resin in the extruder becomes unnecessarily long, which is not preferable since thermal degradation is a concern.
The direction of rotation of the screw is not particularly limited, but a different-direction twin-screw extruder is preferable in terms of the kneading effect.

There is no particular limitation on the supply of the above (A) to (C) to the twin-screw extruder. A method in which a mixture obtained by dry blending (A) to (C) in advance is supplied to a hopper of the extruder, A method in which (A) to (C) are directly supplied to the hopper of the extruder collectively by melt-mixing (B) and (C) in advance to obtain a blend (B + C). B + C) to the hopper of the extruder;
(A) is supplied to the hopper of the extruder and the (B +
C) is supplied from a part of the barrel of the extruder (side feed). Conversely, (B + C) is supplied to a hopper of the extruder and (A) is supplied from a part of the barrel of the extruder. And (A) and (C) are melt-mixed in advance to obtain (A + C), and (B) and (A + C) are supplied to the hopper of the extruder.
, Are preferred.

That is, a molten mixture of a layered inorganic compound (B) containing an organic substance and a polyamide resin (C) and a saponified ethylene-vinyl acetate copolymer (A) are melt-mixed to obtain a resin composition of the present invention. The method for obtaining the product is preferable in view of the dispersibility of (B). In obtaining a molten mixture of (B) and (C), (C) is supplied to a hopper of a twin-screw extruder,
Blend (B + C) can be obtained by supplying (B) from a part of the barrel of the extruder and melt-kneading the mixture at a temperature not lower than the melting point of (C).

Thus, the resin composition of the present invention is obtained. In the present invention, it is preferable that the viscosity behavior of the resin composition shows the following viscosity behavior. That is, D
10 from the melting point measured by SC (differential scanning calorimeter)
The relationship between the heating temperature and the discharge speed in the Koka type flow tester at at least one point at
The discharge speed at any heating time within 5 minutes to 2 hours is in the range of 0.1 to 50 times the discharge speed after 15 minutes, and the discharge at any heating time within 2 hours to 10 hours. In the relationship between the time and the torque measured by the torque detection type rheometer at at least one point at a temperature where the speed is less than twice the discharge speed after 15 minutes and 30 to 60 ° C. higher than the melting point measured by DSC, It is preferable from the viewpoint of long run property that the torque value in an arbitrary heating time within 1 hour to 2 hours shows a viscosity behavior in the range of 1/6 to 5/6 of the maximum torque value appearing within 20 minutes.

The melting point is a value indicated by a main endothermic peak temperature by a DSC (differential scanning calorimeter; heating rate: 10 ° C./min). The discharge rate measured by a Koka flow tester is 1 mm in diameter. 10k using a 10mm long nozzle
The measurement was carried out under a load of g / cm ² , and the measurement time was a time including a preheating time of 5 minutes. In addition, the relationship between time and torque is measured using a torque detection type rheometer. As such a torque detection type rheometer, for example, `` Plasticorder '' manufactured by Brabender and `` Toyo Seiki Seisakusho '' Labo Plastmill "and the like. The measurement is carried out using a measuring mixer having a chamber capacity of 60 cc and a roller-type blade. As the roller-type blade, "Plastic coder" is used for "roller mixer W50", and "Laboplast mill" is used for "roller". Shape blade R60B "is used. In the measurement, 55 g of a sample (filling rate: 90 to 100% by volume) was charged from the supply port under air, the lid was sealed with a load of 7 kg, and the rotation speed was increased to 50 rpm within 30 seconds after preheating for 5 minutes. 60
The torque value at the time of kneading is detected.

In imparting the viscosity behavior as described above to the resin composition of the present invention, there is no particular limitation, but a large amount of an alkaline earth metal such as calcium or magnesium for adhering a higher fatty acid salt to the surface of the resin composition. Although it is possible by performing a treatment such as impregnating with water containing, industrially, it is preferable to adhere a higher fatty acid salt to the surface of the resin composition, such a method is described below,
It is not limited to this method.

The higher fatty acid salt is preferably adhered to the surface of the resin composition after the resin composition of the present invention is formed into pellets in advance. Examples of such higher fatty acid salts include salts of fatty acids having 8 or more carbon atoms, and specifically, lauric acid, tridecylic acid,
Myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, oleic acid,
Alkali metal salts such as sodium salt and potassium salt of higher fatty acids such as capric acid, behenic acid and linoleic acid, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, zinc metal salts and the like can be mentioned. it can. Among them, stearic acid, oleic acid and lauric acid
Valent metal salts (magnesium salts, calcium salts, zinc salts)
Is preferably used.

The application of the higher fatty acid salt to the surface of the resin composition (pellet) is not particularly limited, as long as the higher fatty acid salt is finally attached to the surface of the resin composition (pellet). A method of blending a higher fatty acid salt with the resin composition (pellet) having a water content of 1 to 5% by weight; a method of blending a molten higher fatty acid salt with the heated resin composition (pellet); A method of blending a higher fatty acid salt with the resin composition (pellet) mixed with oil, a method of blending a higher fatty acid salt with the resin composition (pellet) containing a liquid plasticizer, and the resin composition (pellet) And a method of blending a higher fatty acid salt dissolved in a small amount of a solvent.

The method will be described more specifically, but is not limited thereto. In adhering the higher fatty acid salt to the surface of the resin composition (pellet), the water content is adjusted to 1 to 5% by weight (furthermore, 2 to 3% by weight) in order to improve the adhesion of the higher fatty acid salt. When the water content is less than 1% by weight, the higher fatty acid salt drops off and the adhesion (attachment) becomes non-uniform, and when it exceeds 5% by weight, the higher fatty acid salt aggregates and Adhesion (attachment) becomes uneven, which is not preferable. In addition, a device such as a rocking mixer, a ribbon blender, and a super mixer can be used for blending.

Thus, the higher fatty acid salt is attached to the surface of the resin composition (pellet), and the amount of the attached fatty acid is 30 to 300 ppm (more preferably 50 to 250 ppm, particularly 100 to 250 ppm, based on the resin composition). When the amount is less than 30 ppm, the long-run moldability is deteriorated. On the contrary, when the amount exceeds 300 ppm, generation of gas due to decomposition is extremely undesirable.

Thus, the resin composition of the present invention having the above-mentioned viscosity behavior is obtained. Such a resin composition is firstly heated to a temperature of 10 to 80 ° C. from the melting point measured by DSC.
Regarding the relationship between the heating temperature and the discharge rate in the Koka type flow tester at at least one point of high temperature, the discharge rate in any heating time within 15 minutes and within 2 hours is 15 points.
In the range of 0.1 to 50 times the discharge speed after one minute,
If the magnification is less than 0.1, processing becomes inferior due to vigorous thickening, while if it exceeds 50, molding may become difficult due to vigorous thinning. When the discharge speed is less than twice the discharge speed after 15 minutes, and when the magnification is twice or more, the generation of gas due to decomposition may become remarkable, and the temperature may be 30 to 60 ° C. higher than the melting point measured by DSC. In the relationship between the time and the torque measured by the torque detection type rheometer at at least one point, the torque value in an arbitrary heating time within 1 hour to 2 hours is 1/6 to 5/5 of the maximum value of the torque appearing within 20 minutes. 6 (further 1/3 to 2/3), and when the ratio is less than 1/6, the viscosity is greatly reduced and molding is disadvantageous. Preferred to drop Wards.

The resin composition of the present invention thus obtained is
It has excellent gas barrier properties and appearance properties, and is widely used for molded products. It is formed into films, sheets, containers, fibers, rods, pipes, various molded products, etc. by melt molding and the like. The product can be again subjected to melt molding using such a method as when the product is reused. Examples of such a melt molding method include extrusion molding methods (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.), The injection molding method is mainly employed. Melt molding temperature is 150-30
It is often selected from the range of 0 ° C.

Further, the resin composition of the present invention can be used as a single molded product. However, when the resin composition is applied to a molded product of a laminate (multilayer structure), the resin composition of the present invention can sufficiently exhibit the effects and effects. Specifically, it is useful to use a layer composed of the resin composition as a multilayer structure in which a thermoplastic resin layer or the like is laminated on at least one surface.

In producing the multilayer structure, another substrate is laminated on one or both sides of a layer composed of the resin composition. The lamination method is, for example, a film or a film composed of the resin composition. A method of melt-extruding a thermoplastic resin into a sheet, a method of melt-extruding the resin composition on a substrate such as a thermoplastic resin, a method of co-extruding the resin composition with another thermoplastic resin, A method of dry laminating a film or sheet made of the resin composition of the present invention and a film of another substrate, a sheet with a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester-based compound, or a polyurethane compound. No. It is also preferable that the resin composition of the present invention is subjected to co-extrusion molding.

In the case of coextrusion, the other resin is a polyolefin resin, polyester resin, polyamide resin, copolymerized polyamide, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride, acrylic resin, or the like.
Examples thereof include vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene, aromatic and aliphatic polyketones, aliphatic polyalcohols, and the like. Polyolefin resins are preferably used.

Specific examples of the polyolefin resin include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE). ), Ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer Coalesce, ethylene-methacrylic acid ester copolymer, polypropylene, propylene-α-olefin (C 4-20 α-olefin) copolymer, polybutene, polypentene, homo- or copolymer of olefin such as polymethylpentene, Alternatively, these olefins are simply Examples include polyolefin resins in a broad sense, such as those obtained by graft-modifying a homopolymer or a copolymer with an unsaturated carboxylic acid or an ester thereof, and blends thereof. Among them, linear low-density polyethylene (L
LDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), and ionomer are excellent in bending fatigue resistance, vibration fatigue resistance, and the like of the obtained laminated packaging material. It is preferred in that respect.

Further, a molded product such as a film or a sheet is once obtained from the resin composition of the present invention, and another substrate is extrusion-coated thereon, or a film or sheet of another substrate is formed by using an adhesive. In the case of laminating, any substrate (paper, metal foil, non-stretched, uniaxial or biaxially stretched plastic film or sheet and its inorganic deposit, woven fabric, nonwoven fabric, metal flocculent, woody etc. ) Can be used.

The layer structure of the multilayer structure is such that a layer composed of the resin composition of the present invention is a (a ₁ , a ₂ ,...) And another base material, for example, a thermoplastic resin layer is b (b ₁ , b ₂ ,...), in the case of a film, a sheet, or a bottle, not only a two-layer structure of a / b but also b / a / b, a / b / a, a ₁ / a ₂
/ B, a / b ₁ / b ₂ , b ₂ / b ₁ / a / b ₁ / b ₂ , b ₁ /
Any combination such as b ₂ / a / b ₃ / b ₄ and a ₁ / b ₁ / a ₂ / b ₂ is possible. In the filament form, a and b are bimetal type, and core (a) -sheath (b). Mold, core (b)-sheath (a)
Any combination such as a mold or an eccentric core-sheath type is possible.

In the above-mentioned layer structure, an adhesive resin layer can be provided between the respective layers as necessary. Various kinds of adhesive resins can be used. Although it differs depending on the type of the resin and cannot be stated unconditionally, the carboxyl obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to an olefin polymer (the above-mentioned polyolefin resin in a broad sense) by an addition reaction, a graft reaction or the like. Examples of the modified olefin polymer having a group include a maleic anhydride-grafted polyethylene, a maleic anhydride-grafted polypropylene, and a maleic anhydride-grafted ethylene-propylene (block or random) copolymer. , Maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride Graft-modified ethylene - one or a mixture of two or more species selected from vinyl acetate copolymers and the like as preferred. At this time, the amount of the unsaturated carboxylic acid or its anhydride contained in the olefin polymer is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, and particularly preferably 0.1 to 1% by weight. 03-
0.5% by weight. When the amount of modification in the modified product is small,
Adhesiveness may be insufficient, and if it is too high, a crosslinking reaction may occur, resulting in poor moldability.
In addition, these adhesive resins may be blended with the resin composition of the present invention, other rubber / elastomer components such as EVOH, polyisobutylene, and ethylene-propylene rubber, as well as the resin of layer b. In particular, blending a polyolefin-based resin different from the base polyolefin-based resin of the adhesive resin is useful because the adhesiveness may be improved.

The thickness of each layer of the multilayer structure cannot be specified unconditionally depending on the layer constitution, the type of b, the use and the form of the container, the required physical properties, etc., but usually the layer a has a thickness of 5 to 500 μm (further 10 to 10 μm). 200 μm), the b layer is 5 to 5000 μm (further 30 to 1000 μm), and the adhesive resin layer is 5 to 400 μm
(Further 10 to 150 μm). If the thickness of the a layer is less than 5 μm, the gas barrier properties are insufficient, and the thickness control becomes unstable. Conversely, if the thickness exceeds 500 μm, the bending fatigue resistance is inferior. Run short, and conversely 50
If it exceeds 00 μm, the bending fatigue resistance is inferior and the weight becomes large, which is not preferable. If the adhesive resin layer is less than 5 μm, the interlayer adhesion becomes insufficient, and the thickness control becomes unstable. And it is not economical and not preferable. In addition, in each layer of the multilayer structure, the above-mentioned various additives and modifiers, fillers, other resins, and the like are added in a range that does not impair the effects of the present invention, in order to improve moldability and various physical properties. You can also.

The multilayer structure is used as it is in various shapes. However, in order to further improve the physical properties of the multilayer structure, it is preferable to carry out a stretching treatment. Any of axial stretching may be used,
Stretching as high as possible gives better physical properties, and a stretched film, a stretched sheet, a stretched container, a stretched bottle, or the like which does not generate pinholes, cracks, stretch unevenness, delamination, and the like during stretching can be obtained.

The stretching method includes a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like.
Among the deep drawing forming, vacuum press forming and the like, those having a high stretching ratio can be employed. In the case of biaxial stretching, any of a simultaneous biaxial stretching method and a sequential biaxial stretching method can be adopted. The stretching temperature is selected from the range of 60 to 170 ° C, preferably about 80 to 160 ° C.

After completion of the stretching, it is also preferable to carry out heat setting. . The heat setting can be carried out by a known means, and the stretched film is kept at a tension of 80 to 1 while being kept in tension.
Heat treatment is performed at 70 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds. For example, when a cup or tray-shaped multilayer container is obtained from a multilayer sheet or a multilayer film, a drawing method is employed, and specifically, a vacuum forming method, a pressure forming method,
Vacuum pressure forming method, plug assist type vacuum pressure forming method and the like can be mentioned.

Further, when a tube or a bottle-shaped multilayer container is obtained from a multilayer parison (a hollow tubular preform before blowing), a blow molding method is employed. Specifically, an extrusion blow molding method (double head type, mold) Mobile, parison shift, rotary, accumulator, horizontal parison, etc.)
Cold parison type blow molding method, injection blow molding method,
Biaxial stretch blow molding (extrusion cold parison biaxial stretch blow molding, injection cold parison biaxial stretch blow molding, injection molding in-line biaxial stretch blow molding, etc.) and the like.

When used for heat shrink wrapping of raw meat, processed meat, cheese, etc., it is not subjected to heat setting after stretching to form a product film, and the raw meat, processed meat, cheese, etc. are stored in the film. After that, 50-130 ° C., preferably 70
The film is subjected to a heat treatment at about 120 ° C. for about 2 to 300 seconds to thermally shrink the film, thereby performing tight packaging.

The shape of the multilayer structure thus obtained may be arbitrary, and examples thereof include a film, a sheet, a tape, a bottle, a pipe, a filament, and an extrudate having a modified cross section. In addition, the obtained multilayer structure is required,
Heat treatment, cooling, rolling, printing, dry laminating, solution or melt coating, bag making, deep drawing, box processing, tube processing, split processing, and the like can be performed.

The containers, cups, trays, tubes, bottles and the like obtained as described above, bags and lids made of stretched films, as well as general foods, seasonings such as mayonnaise and dressing, and fermented foods such as miso , Salad oils and other fat foods, beverages, cosmetics, pharmaceuticals, detergents, cosmetics, industrial chemicals,
It is useful as various containers for agricultural chemicals, fuels, etc., and is particularly useful for fuel containers and the like.

[0066]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 Preparation of Layered Inorganic Compound (B) Containing Organic Substance
natural montmorillonite “AMS” 5 manufactured by nanocor
g was added to 100 ml of distilled water, and the mixture was stirred well to obtain a uniform montmorillonite aqueous dispersion. Thereto, 5 g of aminopropanol was added, and the mixture was stirred well to aggregate montmorillonite. Then, 100 ml of acetone was added,
After suction filtration, the resultant was dried under vacuum at 80 ° C. to obtain a layered inorganic compound containing a compound having onium ions (natural montmorillonite containing an organic substance) (B).

The organic content of the layered inorganic compound is TG
A was 25 wt% by A measurement, and the layer spacing was wide-angle X-ray diffraction (W
AXD) measurement confirmed that the angle was 15 °. W
In the AXD measurement, an X-ray diffractometer “RINT1200” manufactured by Rigaku Denki Kogyo was used, and the light source was a voltage of 40 k.
V, current 40 mA, using Cuk-α1, divergence slit 1 deg, scattering slit 1 deg, light receiving slit 0.
At 3 mm, the scan speed was 2 / min, the scan step was 0.02, and the layer interval was calculated from the peak at the scan axis 2θ / θ.

[Production of Resin Composition] Polyamide resin (C) [Nylon 6, "Novamid 102" manufactured by Mitsubishi Chemical Corporation
2C6 "] at a rate of 80 parts / minute into a twin-screw extruder (30 mmφ with L / D = 42) from the hopper, and the montmorillonite (B) containing the organic substance obtained above was added to the extruder.
The extruder was continuously fed at a rate of parts / minute from the vent of the extruder to perform melt mixing.

The temperature setting zone immediately below the hopper is 2
The temperature was set at 10 ° C., the temperature at the middle part (vent) at 230 ° C., and the temperature at the outlet of the extruder at 240 ° C. And
The composition was extruded in a strand form from a strand die provided at the outlet of the extruder, and cut to obtain a composition pellet (a cylindrical shape having a diameter of 2.5 mm and a length of 3 mm).

Next, the above composition pellets (B + C) 1
0 parts and 90 parts of EVOH (A) [ethylene content 32 mol%, saponification degree 99.7 mol%] were mixed with a twin-screw extruder (L / D =
42, 30 mmφ) to perform melt mixing. still,
The temperature setting zone immediately below the hopper of the extruder was set to 200
° C, and the set temperature of the intermediate part and the outlet part of the extruder were set to 240 ° C. Then, the resin composition melt-mixed in a strand form is extruded from a strand die provided at the outlet of the extruder, cut, and pellets (2.5 mm diameter, 3 mm length cylindrical) of the resin composition of the present invention are cut out. ) Got. The obtained pellets are supplied to a 40 mmφ single screw extruder,
A film was formed by a T-die casting method to obtain a film having a thickness of 30 μm. At this time, the temperature setting zone immediately below the hopper of the extruder was set at 200 ° C., and the set temperatures of the intermediate portion and the outlet portion of the extruder were set at 240 ° C.

The following evaluation was performed on the obtained film. (Oxygen permeability) The obtained film was subjected to an equal pressure method (MOCON) using “OXTRAN 2/20” manufactured by MOCON.
Method) under the conditions of 20 ° C. and 80% RH.

(Appearance Characteristics) In the obtained film,
The number of foreign substances having a diameter of 0.1 mm or more in 10 cm × 10 cm was measured and evaluated according to the following criteria. ◎ ・ ・ ・ 1 or less ○ ・ ・ ・ 2 to 5 × ・ ・ ・ 6 or more

Example 2 In Example 1, the content of EVOH (A) was 32 mol% of ethylene, the saponification degree was 99.7 mol%, boric acid (A1) was 0.02% by weight in terms of boron, and acetic acid was EVOH (A). The same operation was performed except that EVOH containing 0.008% by weight of sodium (A2) in terms of metal and 0.01% by weight of magnesium acetate (A3) in terms of metal and containing 0.001% by weight of acetic acid was used. To obtain a resin composition (pellet), which was similarly evaluated.

Example 3 In Example 1, the EVOH used in Example 2 was used as the EVOH (A), and nylon 6/66 [“UBE nylon 5023D” manufactured by Ube Industries, Ltd.) was used as the polyamide resin (C). ] To obtain a resin composition (pellet), which was evaluated in the same manner.

Example 4 In Example 2, the content of EVOH (A) was 32 mol% of ethylene, the saponification degree was 99.7 mol%, boric acid (A1) was 0.03 wt% in terms of boron, acetic acid was 150 ppm of magnesium stearate adhered to EVOH pellets containing 0.004% by weight of sodium (A2) in terms of metal and 0.005% by weight of magnesium acetate (A3) in terms of metal and containing 0.002% by weight of acetic acid A resin composition (pellet) was obtained in the same manner as above except that the resin composition was used, and evaluated in the same manner.

The melting point (main endothermic peak temperature) of the resin composition measured by DSC (differential scanning calorimeter) is 1
The relationship between the heating temperature and the discharge speed in the Koka type flow tester at 84 ° C. and 56 ° C. higher than this temperature is 2
The discharge speed at the heating time after 0 minute is 0.8 times the discharge speed after 15 minutes, and the discharge speed at the heating time after 1.5 hours is 1.6 times the discharge speed after 15 minutes. And DS
The relationship between time and torque measured by a torque detection type rheometer at a temperature 56 ° C. higher than the melting point measured at C is 1.5% of the maximum torque at which a torque value within a heating time of 1.5 hours appears within 20 minutes. / 5.

Example 5 A resin composition (pellet) was obtained in the same manner as in Example 2, except that a silicon-containing EVOH having a silicon content of 0.25 mol% was used as the EVOH (A). Evaluation was performed similarly.

Example 6 In Example 2, the composition pellets (B + C) and EVO
A resin composition (pellet) was prepared in the same manner except that the mixing ratio of H (A) was adjusted to 20 parts / 80 parts (weight ratio).
And evaluated similarly.

Example 7 In Example 4, as EVOH (A), boric acid (A1) was 0.04% by weight in terms of boron, ethylene content was 32 mol%, saponification degree was 99.7 mol%, and acetic acid was EVO containing 0.01% by weight of sodium (A2) in terms of metal and 0.014% by weight of magnesium acetate (A3) in terms of metal
Resin composition (pellet) was prepared in the same manner except that H was used.
And evaluated similarly.

The melting point (main endothermic peak temperature) of the above resin composition measured by DSC (differential scanning calorimeter) is 1
The relationship between the heating temperature and the discharge speed in the Koka type flow tester at 84 ° C. and 56 ° C. higher than this temperature is 2
The discharge speed at the heating time after 0 minutes is 0.7 times the discharge speed after 15 minutes, and the discharge speed at the heating time after 1.5 hours is 1.5 times the discharge speed after 15 minutes. And DS
The relationship between the time and the torque measured by a torque detection type rheometer at a temperature 56 ° C. higher than the melting point measured at C is 1.5% of the torque value at the heating time after 1.5 hours that appears within 20 minutes. / 9.

Example 8 The same procedure as in Example 1 was carried out except that the EVOH (A) used had an ethylene content of 35 mol%, a saponification degree of 99.7 mol%, boric acid (A1) of 0.05% by weight in terms of boron, and acetic acid. The same procedure was performed except that EVOH containing 0.009% by weight of sodium (A2) in terms of metal and 0.009% by weight of magnesium acetate (A3) in terms of metal and containing 0.002% by weight of acetic acid was used. To obtain a resin composition (pellet), which was similarly evaluated.

Comparative Example 1 A resin composition was obtained in the same manner as in Example 1 except that normal natural montmorillonite containing no organic substance was used as (B), and a resin composition was evaluated in the same manner.

Table 1 shows the results of Examples and Comparative Examples.

[0085]

[0086]

EFFECT OF THE INVENTION The resin composition of the present invention comprises EVOH
(A) Since the layered inorganic compound (B) containing an organic substance and the polyamide resin (C) are melt-mixed, they are excellent in gas barrier properties and appearance characteristics. Such a resin composition can be used as a film, sheet or container. It is provided and is useful as various packaging materials such as general foods, retort foods, pharmaceuticals, industrial chemicals, and agricultural chemicals, and it is also effective to use it by laminating with various resins, particularly useful for fuel containers and the like.

[Procedure amendment]

[Submission date] October 24, 2001 (2001.10.
24)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction contents]

The melting point is a value indicated by a main endothermic peak temperature by a DSC (differential scanning calorimeter; heating rate: 10 ° C./min). The discharge rate measured by a Koka flow tester is 1 mm in diameter. 10k using a 10mm long nozzle
The measurement was carried out under a load of g / cm ² , and the measurement time was a time including a preheating time of 5 minutes. In addition, the relationship between time and torque is measured using a torque detection type rheometer. As such a torque detection type rheometer, for example, `` Plasticorder '' manufactured by Brabender and `` Toyo Seiki Seisakusho '' Labo Plastmill "and the like. The measurement is performed using a mixer having a chamber capacity of 60 cc and a roller-type blade. As such a roller -type blade, in the case of “Plastic coder”, “Roller Mixer W50” is used, and “Laboplast Mill” is used. In this case, a " roller blade R60B" is used. In the measurement, 55 g of a sample (filling rate: 90 to 100% by volume) was charged from the supply port under air, the lid was sealed with a load of 7 kg, and the rotation speed was increased to 50 rpm within 30 seconds after preheating for 5 minutes. The torque value after 60 minutes of kneading is detected.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction contents]

In producing the multilayer structure, another substrate is laminated on one or both sides of a layer composed of the resin composition. The lamination method is, for example, a film or a film composed of the resin composition. A method of melt-extruding a thermoplastic resin into a sheet, a method of melt-extruding the resin composition on a substrate such as a thermoplastic resin, a method of co-extruding the resin composition with another thermoplastic resin, A method of dry laminating a film or sheet made of the resin composition of the present invention and a film of another substrate, a sheet with a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester-based compound, or a polyurethane compound. No.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction contents]

[Production of Resin Composition] Polyamide resin (C) [Nylon 6, "Novamid 102" manufactured by Mitsubishi Chemical Corporation
2C6 "] at a rate of 80 parts / minute into a twin-screw extruder (L / D = 42 , 30 mmφ) from a hopper, and the montmorillonite (B) containing an organic substance obtained above was added to the extruder.
The extruder was continuously fed at a rate of parts / minute from the vent of the extruder to perform melt mixing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 29/04 C08L 29/04 S 77/00 77/00 (72) Inventor Takeo Yamamoto Muroyama, Ibaraki-shi, Osaka 2-13-1 Nippon Gosei Chemical Co., Ltd. Central Research Laboratory F term (reference) 4J002 BB22W BE03W CL01X CL03X CL05X DJ006 DK007 EG028 EG039 FB086 FD016 FD207 FD208 FD209 GG00

Claims (5)

[Claims] 1. A resin composition obtained by melt-mixing a saponified ethylene-vinyl acetate copolymer (A), a layered inorganic compound (B) containing an organic substance, and a polyamide resin (C). . 2. A layered inorganic compound (B) containing an organic substance in an amount of 0.5 to 10 parts by weight and a polyamide resin (C) based on 100 parts by weight of a saponified ethylene-vinyl acetate copolymer (A). The resin composition according to claim 1, wherein 1 to 40 parts by weight are mixed. 3. The saponified ethylene-vinyl acetate copolymer (A) is obtained by converting the boron compound (A1) to 0.001 in terms of boron.
5 to 0.3% by weight, sodium acetate (A2) and magnesium acetate (A3) were each 0.001 to 0.
The resin composition according to claim 1, wherein the content of the resin composition is 02% by weight. 4. The resin composition according to claim 3, wherein the saponified ethylene-vinyl acetate copolymer (A) further contains 0.01% by weight or less of acetic acid (A4). 5. A method comprising melting and mixing a melt mixture of a layered inorganic compound (B) containing an organic substance, a polyamide resin (C) and a saponified ethylene-vinyl acetate copolymer (A). The resin composition according to claim 1.