JP2002161212A - Resin composition having excellent gas barrier property and light screening property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent screening function of visible light and ultraviolet light and gas barrier properties, and to obtain a molding composed of the resin composition. SOLUTION: This resin composition (F) comprises a gas-barrier resin (A), an inorganic filler (B) having 0.01-0.5 μm particle diameter, an inorganic filler (C) having 0.6-2.5 μm particle diameter and >=5 weight-average aspect ratio, a hydrotalcite compound (D) and at least one kind of compound (E) selected from a 4-24C higher fatty acid, its metal salt, ester and amide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition excellent in a function of shielding visible light and ultraviolet rays and a gas barrier property, and a molded article comprising the resin composition.

[0002]

2. Description of the Related Art Various types of containers are filled in a packaging container having a single-layer or multi-layer structure. However, the contents must be easily deteriorated by light, such as some chemicals and foods. There are many. In order to stably store such contents for a long period of time, a single-layer or multilayer structure having excellent gas barrier properties and excellent light blocking properties is required. In particular, the content of alcoholic beverages (especially sake and wine with a low alcohol content) and some chemicals can be degraded by visible light, so they are excellent in both ultraviolet light and visible light. Desirable.

Conventionally, as a multi-layer container including a layer made of a resin composition in which an inorganic filler is added to an ethylene-vinyl alcohol copolymer, Japanese Patent Application Laid-Open No. 5-193076 discloses an ethylene content of 20 to 60 mol% and a saponification degree of 95. Mol% or more of ethylene-vinyl alcohol copolymer 50 to 95
A multilayer container is disclosed in which a resin composition (A) composed of 50% by weight and 50 to 5% by weight of an inorganic filler is used as an intermediate layer, and a moisture-resistant thermoplastic resin (B) is provided in the inner and outer layers of the intermediate layer.
However, an object of the present invention is to obtain a package excellent in thermoformability and gas barrier property during retort,
No light blocking property is described. Also, EVO
As an inorganic filler to be added to H, a particle diameter of 0.01 to
0.5 μm inorganic filler and particle size 0.6 to 2.5
There is no description that an inorganic filler having a μm and a weight average aspect ratio of 5 or more is used in combination.

Japanese Patent Application Laid-Open No. 5-140345 discloses that ethylene-vinyl alcohol copolymers 50 to 99 are used.
% By weight and a layer of a resin composition comprising 1 to 50% by weight of an inorganic filler, and has a surface glossiness of at least one surface of 6%.
No more than 0% functional films are disclosed. However, as the inorganic filler to be incorporated into EVOH, an inorganic filler having a particle diameter of 0.01 to 0.5 μm and a particle diameter of 0.1 to 0.5 μm are used.
There is no description that an inorganic filler having a weight average aspect ratio of 5 to 6 μm and a weight average aspect ratio of 5 or more is used in combination.

[0005] Further, a method of increasing the heat insulating effect by evacuating the inside of a structure sealed with a container or an outer wrapping material formed of a gas barrier material has been conventionally known. A vacuum heat insulating material in which a core material is filled in the inside of the structure and evacuated is also known. In such a vacuum heat insulating material, the gas heat transfer is reduced by maintaining the inside at a high degree of vacuum to improve the heat insulating property. It is necessary to use a material having extremely excellent gas barrier performance for the body.

As such a material, a resin, particularly a thermoplastic resin, is preferably used from the viewpoint of moldability, but polyvinylidene chloride (PVDC) or an ethylene-vinyl alcohol copolymer (PVDC) which is a typical example of a resin having excellent gas barrier properties is used. However, the gas barrier property of such a material is not sufficient as a vacuum heat insulating material, and it has been difficult to maintain the heat insulating property of the obtained structure for a long period of time. Therefore, for the purpose of improving the gas barrier properties of the resin, for example, JP-A-63-279083 and JP-A-63-233284 describe a metal laminate in which an aluminum foil is laminated on a thermoplastic resin film. .

However, the vacuum heat insulator made of the above-mentioned metal laminate can maintain a high degree of vacuum for a long period of time. However, metals such as aluminum have a large thermal conductivity (for example, aluminum has a thermal conductivity of about 200 W). / M ・
K is about 0.23W for polypropylene resin
/ M · K, about 0.02 W / m · K in air), a so-called heat bridge in which heat moves along a metal portion is likely to occur, and there is a possibility that the heat insulation performance may be reduced.

Although it has been considered to reduce the thickness of the metal layer for the purpose of suppressing the heat bridge, in general, when laminating a metal on a thermoplastic resin layer, a metal such as aluminum is vaporized once at a high temperature and the resin is laminated. In many cases, a metal foil is separately formed by vapor deposition or rolling on the surface of the layer, and then laminated on the resin layer. In these methods, if the thickness of the metal layer is reduced, sufficient flexibility and impact resistance may not always be obtained, and pinholes and the like are generated in a distribution process such as transportation, and the gas barrier is provided even though the metal layer is provided. Properties and light blocking properties may be reduced, and long-term heat insulation performance may be reduced.

When aluminum foil is used, recycling cannot always be said to be easy. Further, at the time of incineration, there is a possibility that aluminum vapor is condensed in a water pipe of a heat exchanger installed in an incinerator to deteriorate thermal efficiency. was there.

[0010]

Therefore, there is a need for a resin composition having an excellent function of shielding visible light and ultraviolet light and excellent gas barrier properties.

[0011]

The object of the present invention is to provide a barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm, and a weight average aspect ratio. Contains 5 or more inorganic filler (C), hydrotalcite compound (D), and at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof. This is achieved by providing a resin composition (F) comprising:

That is, the present invention provides a barrier resin (A),
Inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm, and a weight average aspect ratio of 5
At least one selected from the above inorganic filler (C), hydrotalcite compound (D), and higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof.
The present invention relates to a resin composition (F) containing a compound (E).

In a preferred embodiment, the resin composition (F) of the present invention comprises 70 to 95% by weight of a barrier resin (A) and inorganic fillers (B) 1 to 15 having a particle diameter of 0.01 to 0.5 μm.
3% to 25% by weight of an inorganic filler (C) having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more,
0.001 to 5% by weight of a hydrotalcite compound (D), and a higher fatty acid having 4 to 24 carbon atoms, and a metal salt thereof;
Consisting of 0.001 to 10% by weight of at least one compound (E) selected from esters and amides.

In a preferred embodiment, the barrier resin (A) used in the present invention is at least one selected from ethylene-vinyl alcohol copolymer and polymethaxylylene adipamide, and particularly preferably contains ethylene. An ethylene-vinyl alcohol copolymer having an amount of 5 to 60 mol% and a saponification degree of 90% or more.

[0015] In a preferred embodiment, the inorganic filler (B) used in the present invention is titanium oxide. In a preferred embodiment, the inorganic filler (C) used in the present invention is talc.

In a preferred embodiment, the molded product comprising the resin composition (F) of the present invention comprises 100 parts by weight of the barrier resin (A), 60 to 98% by weight of the barrier resin (A), and a particle size of 0.1%. 50 to 250 parts by weight of a resin composition (f1) comprising 6 to 2.5 μm and 2 to 40% by weight of an inorganic filler (C) having a weight average aspect ratio of 5 or more, and 50 to 98% by weight of a barrier resin (A) , Particle size 0.01-0.5μ
m to 2 to 45% by weight of an inorganic filler (B), 0.001 to 5% by weight of a hydrotalcite compound (D), and
At least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof
Resin composition (f2) 1 consisting of 0.001 to 15% by weight
It is characterized by being obtained by mixing 0 to 400 parts by weight at once and then melt-mixing.

In a preferred embodiment, the resin composition (F) of the present invention is used after being melt-molded into a film or sheet. A preferred embodiment of the present invention is a film or sheet obtained by stretching a film or sheet comprising the resin composition (F) of the present invention at least two times in a uniaxial direction.

In a preferred embodiment, the film made of the resin composition (F) of the present invention has a thickness of 3 to 100 μm.
And the total haze is 50% or more. In a further preferred embodiment, the difference between the total haze and the internal haze of the stretched film is 30% or less.

The present invention also relates to a multilayer structure comprising at least one layer comprising the resin composition (F) of the present invention. In a preferred embodiment, the multilayer structure is a multilayer structure including at least one layer made of a film or sheet made of the resin composition (F) of the present invention.

In a preferred embodiment, the film or sheet comprising the resin composition (F) of the present invention is used as a multilayer structure obtained by dry laminating the film or sheet on a substrate. A preferred embodiment of the multilayer structure is a paper container, and another preferred embodiment is a wallpaper or a decorative board. Further, the multilayer structure is suitably used as a vacuum heat insulating material.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Barrier resin used in the present invention
(A) is a resin having gas barrier properties. Such ba
As the rear resin (A), the oxygen permeation amount is 100 ml.
20 μm / m ^Two・ Day (measured at 20 ° C-65% RH)
Value). The upper limit of oxygen permeation is
More preferably, 10 ml · 20 μm / m^Two・ Day ・ at
m, more preferably 5 ml · 20 μm / m^Two
· Day · atm or less, particularly preferably 1 ml · 2
0 μm / m^Two· Day · atm or less.

It is also preferable to use at least one selected from the group consisting of polyvinyl alcohol resins and polyamides as the barrier resin (A) used in the present invention.

The polyvinyl alcohol-based resin in the present invention refers to a resin obtained by saponifying a vinyl ester polymer or a copolymer of a vinyl ester and another monomer using an alkali catalyst or the like. As a vinyl ester, vinyl acetate is mentioned as a typical one,
Other fatty acid vinyl esters (vinyl propionate,
Vinyl pivalate) can also be used.

The degree of saponification of the vinyl ester component of the polyvinyl alcohol resin of the present invention is preferably at least 90%, more preferably at least 95%, even more preferably at least 99%. If the saponification degree is less than 90 mol%,
There is a possibility that the gas barrier properties under high humidity may decrease. When the polyvinyl alcohol-based resin is composed of a mixture of two or more kinds of polyvinyl alcohol-based resins having different degrees of saponification, the average value calculated from the blending weight ratio is defined as the degree of saponification. The saponification degree of such a polyvinyl alcohol-based resin can be determined by a nuclear magnetic resonance (NMR) method.

The polyvinyl alcohol-based resin of the present invention is an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) from the viewpoint of melt molding and good gas barrier properties under high humidity. ) Is preferred.

The EVOH used in the present invention is preferably one obtained by saponifying an ethylene-vinyl ester copolymer.
It is preferably 0 mol%. The lower limit of the ethylene content is more preferably at least 15 mol%, even more preferably at least 25 mol%. The upper limit of the ethylene content is more preferably 55 mol% or less, and still more preferably 50 mol% or less. If the ethylene content is less than 5 mol%, the melt moldability may deteriorate, and if it exceeds 60 mol%, the barrier properties may be insufficient.

Further, the saponification degree of the vinyl ester component of EVOH used in the present invention is preferably at least 90%. The saponification degree of the vinyl ester component is more preferably 95% or more, and most preferably 99% or more. If the saponification degree is less than 90%, the gas barrier properties and the thermal stability may be insufficient.

A typical example of the vinyl ester used in the production of EVOH is vinyl acetate.
Other fatty acid vinyl esters (vinyl propionate,
Vinyl pivalate) can also be used. Also, EVOH
Is a vinyl silane compound as a copolymer component 0.0002 to
0.2 mol% can be contained. Here, as the vinylsilane-based compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β
-Methoxy-ethoxy) silane and γ-methacryloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used. Further, other comonomer such as propylene, butylene, or unsaturated monomer such as (meth) acrylic acid, methyl (meth) acrylate or ethyl (meth) acrylate, as long as the object of the present invention is not hindered. A carboxylic acid or an ester thereof and vinylpyrrolidone such as N-vinylpyrrolidone can also be copolymerized.

Further, a boron compound may be blended with EVOH within a range not to impair the object of the present invention.
Here, examples of the boron compound include boric acids, borate esters, borates, borohydrides, and the like. Specifically, as boric acids, orthoboric acid, metaboric acid,
Tetraboric acid and the like, boric acid esters such as triethyl borate and trimethyl borate, and borate salts of the above-mentioned various boric acids such as alkali metal salts, alkaline earth metal salts, and borax. No. Of these compounds, orthoboric acid (hereinafter sometimes simply referred to as boric acid) is preferred.

When the boron compound is blended, the content of the boron compound is preferably 20 to 2 in terms of boron element.
000 ppm, more preferably 50 to 1000 ppm. By being in this range, it is possible to obtain EVOH in which torque fluctuation during heating and melting is suppressed. If it is less than 20 ppm, such an effect is small, and if it exceeds 2,000 ppm, gelation is likely to occur, resulting in poor moldability.

The alkali metal salt is added to the EVOH used in the present invention in an amount of 5 to 50 in terms of an alkali metal element.
It is also preferable that the content is contained at 00 ppm because it is effective for improving interlayer adhesion and compatibility. The more preferable content of the alkali metal salt is 20 to
It is 1000 ppm, furthermore 30-500 ppm.
Here, as the alkali metal, lithium, sodium,
Potassium and the like can be mentioned, and examples of the alkali metal salt include a monovalent metal aliphatic carboxylate, an aromatic carboxylate, a phosphate and a metal complex. For example, sodium acetate, potassium acetate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid and the like can be mentioned. Among them, sodium acetate and potassium acetate are preferred.

Further, a phosphoric acid compound is added to the EVOH used in the present invention in an amount of 20 to 500 ppm in terms of a phosphate group.
More preferably 30-300 ppm, optimally 50-20.
It is also preferable to contain 0 ppm. By incorporating a phosphoric acid compound in such a range, the melt moldability and thermal stability of EVOH can be improved. In particular, by including a phosphoric acid compound in such a range, when melt molding is performed for a long time using EVOH, generation of gel-like bumps and coloring can be effectively suppressed.

The kind of the phosphoric acid compound to be mixed in the EVOH is not particularly limited. Various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. The phosphate may be contained in any form of a first phosphate, a second phosphate, and a third phosphate, and the cationic species thereof is not particularly limited. And alkaline earth metal salts. Among them, it is preferable to add a phosphate compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

Further, a heat stabilizer, an antioxidant, and a plasticizer such as glycerin or glycerin monostearate can be blended with EVOH within a range not to impair the object of the present invention.

Suitable melt flow rate (MFR) of EVOH used in the present invention (at 190 ° C. under a load of 2160 g)
Is 0.1 to 50 g / 10 min, more preferably 0.3 to 50 g / 10 min.
-40 g / 10 min, more preferably 0.5-30 g / 10 min
Minutes. However, the melting point is around 190 ° C or 190 ° C
Over 2160 g, measured at a plurality of temperatures above the melting point under a load of 2160 g.
The logarithm of FR is plotted on the vertical axis and represented by a value extrapolated to 190 ° C. These EVOH resins can be used alone or in combination of two or more.

The polyamide used as the barrier resin (A) of the present invention is a polymer having an amide bond, for example, polycaproamide (nylon-6), polyundecaneamide (nylon-11), polylauryl. Homopolymers such as lactam (nylon-12), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-6,12), and caprolactam / lauryl lactam copolymer (nylon- 6 /
12), caprolactam / aminoundecanoic acid polymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid polymer (nylon-6,9), caprolactam / hexamethylene diammonium adipate copolymer (nylon-6 / 6) , 6), caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon-6 / 6,6)
/ 6, 12), polymethaxylylene adipamide (hereinafter, referred to as
MXD-6), or aromatic nylon which is a polymer of hexamethylenediamine and m, p-phthalic acid. These polyamides can be used alone or in combination of two or more.

Among these polyamides, from the viewpoint of gas barrier properties, polymethaxylylene adipamide (MXD-
6) and polycaproamide (nylon-6) are preferred, especially polymethaxylylene adipamide (MXD-
6) is preferred.

Among the barrier resins (A) exemplified above, ethylene-vinyl alcohol copolymer (EVOH) and polymethaxylylene adipamide (MXD-6) are preferred from the viewpoint of gas barrier properties. It is preferable to use EVOH.

In a preferred embodiment, the molded article comprising the resin composition of the present invention is used for shielding light, for example, as a constituent material of a wallpaper or a paper container. In such an embodiment, the resin of the present invention is used. Molded articles composed of the composition are usually
Exposed to light for a long time. However, as described below, the inorganic filler (B) used in the present invention is preferably titanium oxide. As a result of detailed studies by the present inventors, when a molded product (such as a film) made of the barrier resin (A) containing titanium oxide was exposed to light for a long time, the barrier resin (A) Part of the molded product
It has been found that yellowing may occur slightly. According to the study of the present inventors, when a polyvinyl alcohol-based resin is compared with a polyamide, the occurrence of such yellowing is suppressed when a polyvinyl alcohol-based resin is used as the barrier resin (A). In particular, E is used as a barrier resin (A).
By using VOH, the resin composition of the present invention containing the inorganic filler (B) as an essential component can withstand long-time light exposure and significantly suppress yellowing.
From this viewpoint, EVOH is used as the barrier resin (A).
It is preferable to use

The resin composition (F) of the present invention may optionally contain a thermoplastic resin other than the barrier resin (A) as long as the effects of the present invention are not impaired. As the thermoplastic resin, various polyolefins (polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, copolymer of ethylene and α-olefin having 4 or more carbon atoms, polyolefin Copolymer of ethylene and maleic anhydride, ethylene-vinyl ester copolymer, ethylene-acrylate ester copolymer, or modified polyolefin obtained by graft-modifying these with unsaturated carboxylic acid or a derivative thereof), polyurethane, polyacetal, etc. Is mentioned.

However, the resin composition (F) of the present invention
From the viewpoint of the gas barrier property of the resin, it is preferable that the blending amount of the thermoplastic resin other than the barrier resin (A) is small. In the thermoplastic resin constituting the resin composition (F), the content of the thermoplastic resin other than the barrier resin (A) is preferably 20% by weight or less, more preferably 10% by weight or less, More preferably 5% by weight or less,
The content is particularly preferably 3% by weight or less, and most preferably, the thermoplastic resin constituting the resin composition (F) is substantially composed of only the barrier resin (A).

The particle size used in the present invention is from 0.01 to 0.1.
The inorganic filler (B) having a thickness of 5 μm is not particularly limited, and examples thereof include titanium oxide, zinc white, lead white, and zinc sulfide. Among them, it is preferable to use rutile-type titanium oxide from the viewpoint of being chemically stable, having a large refractive index, and being excellent in light blocking properties.

The particle size of the inorganic filler (B) used in the present invention is 0.01 to 0.5 μm. Particles having a particle diameter of less than 0.01 μm are not always easy to produce, and thus may be difficult to obtain. Further, by using an inorganic filler (B) having a particle diameter of 0.01 μm or more, the dispersibility of the inorganic filler (B) in the barrier resin (A) is improved, and the resin composition (F ), The appearance and the light-shielding property of the molded article composed of the above-mentioned composition become particularly good. From the viewpoint of emphasizing the dispersibility of the inorganic filler (B) in the barrier resin (A),
The lower limit of the particle diameter of the inorganic filler (B) is preferably at least 0.05 μm, more preferably at least 0.08 μm, particularly preferably at least 0.1 μm. When the particle size of the inorganic filler (B) exceeds 0.9 μm, the surface smoothness of a molded product made of the resin composition (F) is reduced. In particular, when the molded product is a film, the tendency becomes remarkable. The upper limit of the particle size of the inorganic filler (B) is preferably 0.6 μm or less, more preferably 0.4 μm or less.

In order to improve the dispersibility of the inorganic filler (B) in the barrier resin (A), it is preferable to treat the surface of the inorganic filler (B) particles with aluminum oxide, stearic acid or the like. More preferably, the particle surface is treated with aluminum oxide. The surface treatment is particularly effective when the inorganic filler (B) is titanium oxide.

The inorganic filler (B) has a particle diameter of 0.1.
When an inorganic filler having a particle size of from 01 μm to less than 0.05 μm is used, it is preferable to perform the above-mentioned surface treatment in order to obtain sufficient dispersibility. After the treatment with aluminum oxide, it is particularly preferable to further treat the surface with an organosiloxane. preferable. On the other hand, as the inorganic filler (B), a particle diameter of 0.0
When an inorganic filler having a particle size of 5 μm to 0.9 μm is used, the dispersibility in the barrier resin (A) is relatively good as compared with an inorganic filler having a particle size of less than 0.05 μm.
In many cases, sufficient dispersibility can be obtained only by aluminum oxide treatment.

The particle size of the inorganic filler (B) in the present invention can be determined by observing the particles with a transmission electron microscope at a magnification of 50,000 to 150,000 times. , Constituent primary particles).

The particle size used in the present invention is 0.6 to 2.5.
Preferred examples of the inorganic filler (C) having a μm and a weight average aspect ratio of 5 or more include, but are not limited to, mica, sericite, glass flake, and talc. These inorganic fillers can be used alone or in combination. Among the inorganic fillers (C) exemplified above, it is particularly preferable to use talc from the viewpoint of obtaining a stretched film having a large weight average aspect ratio (α) and particularly excellent light blocking properties and gas barrier properties.

The weight average aspect ratio (α) of the inorganic filler (C) used in the present invention is 5 or more. The weight average aspect ratio (α) of the inorganic filler (C) is preferably 10 or more, and more preferably 13 or more. If the weight average aspect ratio (α) of the inorganic filler (C) is less than 5, the effect of imparting oxygen barrier properties and light blocking properties will be reduced, and the effect of improving pinhole resistance will be insufficient.

The weight average aspect ratio (α) of the inorganic filler (C) in the present invention is defined as the weight average flake diameter L
And a value calculated using the formula (1) from the weight average flake thickness d of the inorganic filler measured by the following method. α = L / d (1) The weight average flake diameter L of the inorganic filler (C) in the formula (1) is determined by classifying the powder with a micro sieve or sieve having various openings, and determining the result by Rosin-Rammlar.
Plotted on a diagram, the aperture L of a microsieve or sieve through which 50% by weight of the total weight of the powder used for measurement passes
_This is a value equivalent to ₅₀ . That is, the weight average flake diameter L of the powder is defined by the formula (2) or (3). L = L ₅₀ (in the case of micro sieve) (2) L = 2 ^0.5 · L ₅₀ (in the case of sieve) (3) Here, a portion of the powder having a large particle size is classified by the sieve. The portion having a small particle size is classified by a micro sieve.

On the other hand, the weight average flake thickness d of the inorganic filler refers to C.I. E. FIG. Capes et al. Reported a single-particle water surface membrane method {C. E. FIG. Capes and R.A. C. Cole
man. Ind. Eng. Chem. Fundam. ,
Vol. 12, No. 2, P. 124-126 (197
3) The occupied area S of the flake on the water surface measured by｝
Is a value calculated from the following equation (4) using d = W / {ρ (1-ε) · S} (4) where W is the weight of the powder used for measurement, ρ is the specific gravity of the powder,
(1- [epsilon]) is the occupancy when the powder is in a close-packed state on the water surface, and the powder was calculated by setting (1- [epsilon]) to 0.9.

In order to improve the affinity with the barrier resin (A) and prevent perforation during stretching, a surface treatment agent (for example, a silane coupling agent, It is also preferable to perform a treatment with a titanate-based coupling agent, an aluminum-based coupling agent, or the like.

The particle size of the inorganic filler (C) used in the present invention is 0.6 to 2.5 μm, preferably 0.8 to 2.5 μm.
To 2.5 μm, more preferably 0.8 to 1.8 μm. In addition, the particle diameter of the inorganic filler (C) in the present invention refers to the above-mentioned weight average flake diameter L. When the particle size of the inorganic filler (C) is less than 0.6 μm, the light blocking property, particularly the visible light blocking property becomes insufficient.

By using the inorganic filler (C) having a particle diameter of 2.5 μm or less, the appearance and the light blocking property of the molded article comprising the resin composition (F) of the present invention are particularly good. Becomes In particular, this is extremely remarkable when the molded product is a film stretched at least twice in the uniaxial direction.

A particularly preferred embodiment of the present invention is a stretched film obtained by stretching a film or sheet comprising the resin composition (F) of the present invention at least two times in a uniaxial direction. Such a stretched film has extremely excellent ultraviolet and visible light shielding properties and gas barrier properties. As a result of detailed studies by the present inventors, the above-mentioned Japanese Patent Application Laid-Open
The particle size of the inorganic filler contained in the barrier resin (A) is not particularly limited under mild stretching conditions described in JP-A-193076, such as obtaining a multilayer container by thermoforming a multilayer sheet. When performing high-magnification stretching as required in the invention, the particle size of the inorganic filler is 2.5
It became clear for the first time that it was essential that it be less than μm. When the particle size of the inorganic filler (C) used in the present invention exceeds 2.5 μm, the stretchability of the resin composition comprising the barrier resin (A) and the inorganic filler (C) becomes unsatisfactory. As a result, the film may be broken by the stretching treatment, and the film thickness after stretching may be non-uniform.

As the hydrotalcite compound (D) used in the present invention, in particular, M _x Al _y (OH) _{2x + 3y-2z}
(A) _z · aH ₂ O (M is Mg, Ca or Zn, A is C
O ₃ or HPO ₄ , x, y, z, and a are positive numbers). Particularly preferred examples include the following hydrotalcite compounds.

[0056] _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O Mg 8 Al 2 (OH) 20 CO 3 · 5H 2 O Mg 5 Al 2 (OH) 14 CO 3 · 4H 2 O Mg 10 Al 2 ( _{OH) 22 (CO 3) 2} · 4H 2 O Mg 6 Al 2 (OH) 16 HPO 4 · 4H 2 O Ca 6 Al 2 (OH) 16 CO 3 · 4H 2 O Zn 6 Al 6 (OH) 16 CO 3 _{· 4H 2 O Mg 4. 5} Al 2 (OH) 13 CO 3 · 3.5H 2 O

The hydrotalcite compound (D)
JP-A-1-308439 (USP 49545)
[Mg _0.75 Zn _0.25 ] _0.67 Al _0.33 (OH) which is a hydrotalcite-based solid solution described in 57).
₂ (CO ₃ ) _0.167 · 0.45 H ₂ O can also be used.

The higher fatty acid having 4 to 24 carbon atoms used in the present invention and at least one compound selected from metal salts, esters and amides thereof (E) The higher fatty acid having 4 to 24 carbon atoms used in the present invention, In at least one compound (E) selected from the group consisting of metal salts, esters and amides, the higher fatty acids having 4 to 24 carbon atoms are linear or branched saturated and unsaturated fatty acids, butyric acid, isobutyric acid, Acid, pentanoic acid, caproic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, elaidic acid, stearic acid, isostearic acid, ricinoleic acid, erucic acid,
Behenic acid and the like are exemplified.

When the compound (E) has less than 4 carbon atoms, the inorganic filler (B) and the inorganic filler (C)
The effect of improving the dispersibility in the barrier resin (A) becomes insufficient, so that lumps are easily generated, and this tendency is particularly remarkable in the dispersibility of the inorganic filler (B).
From the viewpoint of improving the dispersibility of the inorganic filler (B) in the barrier resin (A), the compound (E) preferably has 10 or more carbon atoms. On the other hand, when the carbon number of (E) is 2
If it exceeds 4, the dispersibility of the compound (E) itself in the barrier resin (A) becomes poor, and the effect of suppressing the torque fluctuation during the heating and melting of the resin composition cannot be sufficiently obtained.

Examples of metal salts of higher fatty acids having 4 to 24 carbon atoms include salts of the above higher fatty acids with metals such as lithium, sodium, potassium, calcium, barium, aluminum and zinc.

The ester of a higher fatty acid having 4 to 24 carbon atoms is an ester of the higher fatty acid and a compound having a hydroxyl group. Examples of the compound having a hydroxyl group include methanol, ethanol, ethylene glycol, n-propyl alcohol and isopropyl. Alcohol, propylene glycol,
Examples thereof include alcohols such as glycerin, pentaerythritol, sorbitan, sucrose, n-butyl alcohol, isobutyl alcohol, octanol, ethylhexyl alcohol, lauryl alcohol, oleyl alcohol, and stearyl alcohol.

The amide of a higher fatty acid having 4 to 24 carbon atoms is an amide of the higher fatty acid and a compound having an amino group. Examples of the compound having an amino group include ammonia,
Methylamine, ethylamine, ethylenediamine, methylolamine, n-butylamine, isobutylamine,
Examples include amines such as octylamine, ethylhexylamine, laurylamine, oleylamine, stearylamine and the like.

In the present invention, the at least one compound (E) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof includes higher fatty acids exemplified above and higher fatty acids thereof. It is possible to use one or a mixture of two or more selected from metal salts, esters and amides of the above. Among these,
It is preferable to use ethylene bisstearic acid amide, magnesium stearate, and calcium stearate.

The resin composition (F) of the present invention comprises a barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio. It consists of an inorganic filler (C) having a ratio of 5 or more, a hydrotalcite compound (D), and at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof. It is a resin composition. In a preferred embodiment, the above (A), (B),
The content of (C), (D) and (E) is (A) 70 to
95% by weight, (B) 1 to 15% by weight, (C) 3 to 25% by weight, (D) 0.001 to 5% by weight and (E) 0.0
01 to 10% by weight.

In the resin composition (F) of the present invention, the lower limit of the content of the barrier resin (A) is more preferably at least 75% by weight from the viewpoint of the moldability of the resin composition (F). . The upper limit of the content of the barrier resin (A) is 9
More preferably, it is 0% by weight or less. When the content of the gas barrier resin (A) is less than 70% by weight, the moldability of the resin composition (F) may be reduced, and particularly when the resin composition (F) is molded into a molded product such as a film, the surface smoothness may be reduced. And the appearance may deteriorate. On the other hand, when the content of the barrier resin (A) exceeds 95% by weight, sufficient light blocking properties may not be obtained.

In the resin composition (F) of the present invention, the content of the inorganic filler (B) is preferably from 1 to 15% by weight. The lower limit of the content of the inorganic filler (B) is more preferably 2% by weight, and still more preferably 3% by weight. The upper limit of the content of the inorganic filler (B) is more preferably 12% by weight, and further preferably 10% by weight. When the content of the inorganic filler (B) is less than 1% by weight, the light blocking property may be insufficient. Also,
When the content of the inorganic filler (B) exceeds 15% by weight, the inorganic filler (B) is contained in the resin composition (F).
May easily occur, and the appearance of a molded product made of the resin composition (F) may be poor.

In the resin composition (F) of the present invention, the content of the inorganic filler (C) is preferably from 3 to 25% by weight. When the content of the inorganic filler (C) is less than 3% by weight, the light blocking property and the gas barrier property may be insufficient. In particular, a preferred embodiment of the present invention is a stretched film obtained by stretching a film or sheet comprising the resin composition (F) of the present invention at least twice in at least one axial direction. If the content is less than 3% by weight, the effect of improving the bending resistance of such a stretched film may not be sufficiently obtained. When the content of the inorganic filler (C) is more than 25% by weight, the effect of improving the moldability of the resin composition (F) may be reduced. In this case, the smoothness of the surface may be reduced and the appearance may be deteriorated.

In the resin composition (F) of the present invention, the content of the hydrotalcite compound (D) is from 0.001 to
Preferably it is 5% by weight. From the viewpoint of improving the dispersibility of the inorganic filler (B) in the resin composition (F), the lower limit of the content of the hydrotalcite compound (D) is more preferably 0.005% by weight, and Preferably 0.
01% by weight. The upper limit of the content of the hydrotalcite compound (D) is more preferably 1% by weight,
More preferably, it is 0.5% by weight. When the content of the hydrotalcite compound (D) is more than 5% by weight, the thermal stability of the resin composition (F) may be reduced, and a molded article made of the resin composition (F) may not be obtained. The appearance may be deteriorated, for example, it may be easily colored.

The resin composition (F) of the present invention contains a hydrotalcite compound (D) as an essential component. The resin composition (F) of the present invention comprises an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm and an inorganic filler (C) having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more. The dispersibility of the inorganic filler (B) in the barrier resin (A) is remarkably improved by blending the hydrotalcite compound (D). In particular,
When the inorganic filler (B) is titanium oxide, the effect of improving dispersibility is large.

Inorganic filler (B) used in the present invention
Is preferably titanium oxide as described above. Titanium oxide is generally used by being blended with various resins, for example, polyolefin and the like, but usually its dispersibility does not matter. However, as a result of the study by the present inventors, when the inorganic filler (B) typified by titanium oxide is blended with the barrier resin (A), particularly EVOH, the dispersibility may not always be satisfactory. It became clear. In particular, when the inorganic filler (B) and the inorganic filler (C) having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more are simultaneously added to the barrier resin (A), the tendency is increased. It turned out to be remarkable.

The present inventor has further studied and found that the barrier resin (A), the inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, the particle diameter of 0.6 to 2.5 μm, and the weight average aspect ratio are lower. 5 or more inorganic filler (C) and 4 to 4 carbon atoms
By adding a hydrotalcite compound (D) to at least one compound (E) selected from the group consisting of a higher fatty acid, a metal salt, an ester and an amide thereof, the barrier resin of the inorganic filler (B) ( A very surprising fact was revealed that the dispersibility in A) was significantly improved.

In the resin composition (F) of the present invention, the content of at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof is 0.001 to 10 % By weight.
When the content of the compound (E) is less than 0.001% by weight, the effect of improving the moldability of the resin composition (F) may be reduced, and particularly, the resin composition (F) is formed into a thin molded product such as a film. In this case, the smoothness of the surface may be reduced and the appearance may be deteriorated. Further, when the content of the compound (E) is 10
If the amount exceeds the above range, the effect of improving the moldability of the resin composition (F) may be reduced, and the compound (E) may bleed on the outer surface of the molded article made of the resin composition (F). May go out. For this reason, in the multilayer structure including the layer composed of the resin composition (F) of the present invention,
The interlayer adhesion between the layer comprising the resin composition (F) of the present invention and another layer may be reduced.

The method for producing the resin composition (F) of the present invention is not particularly limited. ,
(B), (C), (D) and (E) are mixed by dry blending or the like, and then the mixture is blended with (A) to form a pellet. Suitable methods include, for example, a method of adding and mixing (C), (D) and (E) and then removing the solvent to obtain pellets or a film. (A), (B),
When the resin composition (F) is obtained by melt-mixing (C), (D) and (E), (A), (B), (C), and (D)
The moisture content of (E) and (E) is preferably 1% or less, more preferably 0.5% or less. With such a water content, generation of bumps in the resin composition during melt-kneading can be more effectively avoided.

In the melt compounding operation, it is particularly preferable to pelletize using a twin-screw extruder having a high kneading degree from the viewpoint of improving the dispersibility of (B) and (C) with respect to (A). Furthermore, since the blend may be non-uniform, gels and butters may be generated and mixed, the blend pelletization uses an extruder with a high degree of kneading as much as possible, sealing the hopper port with nitrogen gas, It is desirable to extrude at a low temperature.

In particular, in order to sufficiently exhibit the effects of the present invention, the resin composition (f1) comprising (A) and (C) is required.
And a resin composition (f2) composed of (A), (B), (D) and (E) in advance, and melt-mixing (f1) and (f2) to obtain a resin composition of the present invention. The method of obtaining (F) is preferred. Further, a further preferred embodiment of the present invention is an embodiment in which a pellet made of the barrier resin (A), a pellet made of the above (f1) and a pellet made of the above (f2) are mixed at once to produce a molded product. It is.

That is, pellets comprising a resin composition containing the barrier resin (A) and a high concentration of (C) (hereinafter referred to as pellets)
Masterbatch pellet (f1)),
And a resin in which (B) and (C) are diluted by melt-molding pellets (hereinafter sometimes abbreviated as masterbatch pellets (f2)) comprising a resin composition containing a high concentration of (B). An embodiment for obtaining a molded article comprising the composition is particularly preferred.

As a specific example, 100 parts by weight of (A) and 25 parts by weight of (C) are mixed, and the mixture is formed into a blend pellet to prepare a pellet made of the resin composition (f1). This is referred to as a batch pellet (f1). Subsequently, (A) 100 parts by weight, (B) 30 parts by weight,
0.5 parts by weight of (D) and 0.6 parts by weight of (E) were mixed at once, and the mixture was formed into a blend pellet to prepare a pellet composed of the resin composition (f2). I do. Then, 100 parts by weight of the barrier resin (A) and the master batch pellet (f1)
50 parts by weight and master batch pellets (f2) 11
By mixing 5 parts by weight and melt-molding, (A) 8
6.82% by weight, (B) 4.34% by weight, (C) 8.6
8% by weight, (D) 0.07% by weight and (E) 0.09%
A molded product comprising the resin composition (F) consisting of 100% by weight can be obtained.

As described above, by using the master batch (f1) and the master batch (f2) to obtain the resin composition (F) of the present invention and a molded product comprising the resin composition (F), The following benefits can be enjoyed.

One is that it is possible to diversify the brands of products that can be produced. In general, when using a molded article composed of the resin composition (F) of the present invention, the molded article changes the content of the inorganic filler (B) and / or the inorganic filler (C) according to the embodiment and the required performance. It is desirable to do. When a masterbatch is not used, each time the content of (B) and / or (C) is changed, the mixing ratio of each component must be changed, and the operating conditions must be changed as necessary. . However,
Master batch (f1), master batch (f2)
By appropriately adjusting the mixing ratio of the masterbatch and the barrier resin (A) for diluting the masterbatch, the inorganic filler (B) in the resin composition is used.
And / or the content of the inorganic filler (C) can be freely controlled. For this reason, the resin composition (F)
And the productivity at the time of manufacturing a molded article using the same can be significantly improved.

Further, after mixing the master batch (f1) and the master batch (f2), melt molding is performed, so that the appearance of the molded product can be further improved.
A more preferred embodiment is an embodiment in which the masterbatch (f1), the masterbatch (f2) and the barrier resin (A) are mixed and then melt-molded to obtain a molded product.
In order to obtain a molded product comprising the resin composition (F) of the present invention, after (A), (B), (C), (D) and (E) are collectively mixed, melt molding is carried out to obtain a resin composition. Obviously, it is also possible to obtain a molded product comprising (F), and the molded product has an excellent appearance.

However, the master batch (f)
1) and the masterbatch (f2) are prepared in advance, and the masterbatch (f1) and the masterbatch (f2) are prepared.
And the barrier resin (A) are mixed and then melt-molded to obtain a molded product, whereby the secondary aggregation of the inorganic filler (B) and the inorganic filler (C) is more effectively suppressed, and further the resin composition The appearance of the molded product made of (F) can be improved. In particular, the effect of improving the dispersibility of the inorganic filler (B) is great. This effect of improving the appearance is particularly remarkable when the molded article is a thin molded article such as a film.

From the viewpoint of sufficiently obtaining the effect of suppressing secondary aggregation of the inorganic filler (B) and the inorganic filler (C), the master batch (f1) and the master batch (f
As the barrier resin (A) that dilutes both of the two, the content of the inorganic filler (B) and the inorganic filler (C) is 10 parts by weight or less based on 100 parts by weight of the barrier resin (A). The barrier resin (A) to be mixed with the masterbatch (f1) and the masterbatch (f2) substantially contains the inorganic filler (B) and the inorganic filler (C). Particularly preferred is an embodiment that does not contain any.

The composition of the masterbatch (f1) comprising the barrier resin (A) and the inorganic filler (C) is not particularly limited, and is arbitrarily selected according to the composition of the finally obtained resin composition (F). You. Preferably, the master batch (f1) comprises 5 to 40 parts by weight of the inorganic filler (C) based on 100 parts by weight of the barrier resin (A). The master batch (f1) is preferably obtained by melt-mixing (A) and (C) and blending into pellets. In the master batch (f1), when the content of (C) exceeds 40 parts by weight with respect to 100 parts by weight of (A), when the master batch pellets (f1) are obtained by blending pellets, the May be insufficiently stable. When the content of (C) is less than 5 parts by weight with respect to 100 parts by weight of (A), the inorganic filler (F) in the resin composition (F) can be obtained by using the master batch (f1). The effect of improving the dispersibility of C) may be unsatisfactory. Master batch (f
1) more preferably comprises 10 to 35 parts by weight of (C) based on 100 parts by weight of (A).

At least one compound selected from a barrier resin (A), an inorganic filler (B), a hydrotalcite compound (D) and a higher fatty acid having 4 to 24 carbon atoms, a metal salt, an ester and an amide thereof ( The composition of the masterbatch (f2) composed of E) is not particularly limited,
It is arbitrarily selected according to the composition of the finally obtained resin composition (F). Preferably, the master batch (f2)
Are (B) 5 to 80 parts by weight, (D) 0.005 to 5 parts by weight and (E) 0.00 based on 100 parts by weight of (A).
It consists of 5 to 10 parts by weight. The master batch (f2)
Is preferably obtained by melt-mixing (A), (B), (D) and (E) and blending into pellets. When the content of (B) exceeds 80 parts by weight with respect to 100 parts by weight of (A) in the masterbatch (f2), when the masterbatch pellets (f2) are obtained by blending pellets, the May be insufficiently stable. When the content of (B) is less than 5 parts by weight based on 100 parts by weight of (A), the inorganic filler (F) in the resin composition (F) can be obtained by using the master batch (f2). The effect of improving the dispersibility of B) may be unsatisfactory.

In the master batch (f2), (B)
Is more preferably 10 to 70 parts by weight based on 100 parts by weight of (A). The content of (D) is more preferably 0.01 to 3 parts by weight of (D) with respect to 100 parts by weight of (A), and still more preferably (D) with respect to 100 parts by weight of (A). 0.1 to 2 parts by weight. Further, the content of (E) is more preferably (A)
It is 0.01 to 5 parts by weight per 100 parts by weight of (E), and more preferably 0.1 to 3 parts by weight per 100 parts by weight of (A).

As described above, when the dispersibility of the inorganic filler (B) in the resin composition (F) is particularly important, the particle size of the inorganic filler (B) is 0.05 μm to 0.9 μm.
It is preferable that the particle size is 0.05 to 0.1.
When a 9 μm inorganic filler (B) is used, the blending amount of the inorganic filler (B) and the hydrotalcite compound (D) in the master batch (f2) preferably satisfies the following formula (1). 20 ≦ W (B) / W (D) ≦ 100 (1) where W (B) is a particle diameter of 0.05 to 0.9 μ with respect to 100 parts by weight of the barrier resin (A) in the master batch (f2).
W (D): Content (weight) of hydrotalcite compound (D) based on 100 parts by weight of barrier resin (A) in masterbatch (f2) Part).

In the above equation (1), W (B) / W
The lower limit of (D) is more preferably 30 or more, and 4
It is more preferably 0 or more, and particularly preferably 45 or more. Further, the upper limit of W (B) / W (D) is more preferably 90 or less, and further preferably 80 or less.

A master batch (f1) and a master batch (f2) are prepared in advance, and the master batch (f1),
After the master batch (f2) and the barrier resin (A) are mixed and then melt-molded to obtain a molded product composed of the resin composition (F), the above-mentioned (f1), (f)
The mixing ratio of 2) and (A) is not particularly limited, and (f)
The composition is arbitrarily set according to the respective compositions of 1) and (f2) and the composition of the target resin composition (F). Among them, (f1) 50 to 250 with respect to (A) 100 parts by weight.
An embodiment is preferred in which the mixture is melt-molded by mixing 10 parts by weight and (f2) 10 to 400 parts by weight.

Further, when diluting the master batch (f1) and the master batch (f2) with the barrier resin (A), the MFR of the barrier resin (A) constituting the master batch (f2) converts the master batch into It is preferable that the MFR of the barrier resin (A) to be diluted is larger than the MFR from the viewpoint of further improving the dispersibility of the inorganic filler (B) in the resin composition (F).

For example, the barrier resin (A) used in the present invention is optimally EVOH, and its melt flow rate (MFR) (at 190 ° C. under a load of 2160 g) is 0.1 to 50 g / 10 min. Preferably, there is. Then, the MF of the EVOH constituting the master batch (f2)
R is MFR (f2), E to dilute the master batch
When the MFR of VOH is MFR (A), the dispersibility of the inorganic filler (B) in the resin composition (F) is further improved by satisfying the following expression (2). 1.5 ≦ MFR (f2) / MFR (A) ≦ 20 (2) where, MFR (A): MFR (190) of EVOH mixed with master batch (f1) and master batch (f2)
MFR (f2): E constituting master batch (f2)
VOH MFR (measured at 190 ° C with 2160g load)

In the above equation (2), MFR (f2) /
The lower limit of MFR (A) is more preferably 2 or more. Further, the upper limit of MFR (f2) / MFR (A) is 15 or less, more preferably 10 or less.

[0092] The above-mentioned molded product is not particularly limited, and a film, a sheet, a bottle and the like are preferably exemplified. Further, the above-mentioned molded product includes a pellet. That is, a masterbatch (f1) and a masterbatch (f2) are prepared in advance, and the masterbatch (f1), the masterbatch (f2) and the barrier resin (A) are mixed. It is also possible to produce. However, from the viewpoint of reducing the heat history and suppressing the deterioration of the appearance of the molded article made of the resin composition (F) of the present invention due to thermal deterioration, the pellets composed of the master batch (f1) and the master batch pellets (f2) ) And a barrier resin (A)
It is preferable to mix pellets composed of a tumbler or the like, charge the mixture into an extruder, and melt-mold a molded product such as a film or a sheet without forming a pellet into a blend.

[0093] The method for molding the molded article comprising the resin composition (F) of the present invention is not particularly limited, and examples of suitable methods include extrusion molding, inflation extrusion, blow molding, melt spinning, and injection molding. The melting temperature varies depending on the melting point of the barrier resin (A) constituting the resin composition (F) and the like.
About 50 to 270 ° C is preferable.

The resin composition (F) of the present invention can be used for molding a film, a sheet, etc. of the resin composition (F) of the present invention, in addition to the single-layer molded product of the resin composition (F) as described above. It is often used practically as a multilayer structure having at least one layer. As a layer configuration of the multilayer structure,
When the resin composition of the present invention is represented by F, the adhesive resin is represented by Ad, and the thermoplastic resin is represented by T, F / Ad / T, T / Ad / F / A
d / T and the like, but are not limited thereto. Each layer may be a single layer or may be a multilayer in some cases. When the thermoplastic resin layers are provided on both outer layers, they may be different types or may be the same. Furthermore, a recovered resin layer made of scrap such as trim generated during molding may be separately provided, or the recovered resin may be blended with the thermoplastic resin layer. Although there is no particular limitation on the thickness configuration of the multilayer structure, the thickness ratio of the resin composition (F) layer to the total layer thickness is preferably 2 to 20% in consideration of moldability, cost, and the like. is there.

The method for producing the above-mentioned multilayer structure is not particularly limited. For example, a method of melt-extruding a thermoplastic resin into a molded product (film, sheet, etc.), a method of co-extrusion of the resin composition of the present invention with another thermoplastic resin, a method of coextruding the thermoplastic resin with another thermoplastic resin of the present invention, Co-injection with resin,
Further, a molded product (such as a film or a sheet) obtained from the resin composition of the present invention and a film or sheet of another substrate are formed using a known adhesive such as an organic titanium compound, an isocyanate compound, or a polyester compound. Lamination method and the like can be mentioned.

The thermoplastic resins used include linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene and propylene-α. -Olefin copolymer (carbon number 4
Α-olefins), polybutene, polypentene and other olefins alone or copolymers thereof, polyesters such as polyethylene terephthalate, polyester elastomers, polyamide resins such as nylon-6, nylon-6,6, polystyrene, polyvinyl chloride , Polyvinylidene chloride, acrylic resin, vinyl ester resin, polyurethane elastomer, polycarbonate, chlorinated polyethylene, chlorinated polypropylene and the like.
Among them, polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyamide, polystyrene, and polyester are preferably used.

In laminating the resin composition (F) of the present invention and a thermoplastic resin, an adhesive resin may be used in some cases. The adhesive resin in this case is not particularly limited, but the barrier resin (A) used in the resin composition (F) of the present invention.
Is EVOH, an adhesive resin comprising a carboxylic acid-modified polyolefin is preferred. Here, the carboxylic acid-modified polyolefin is a modified olefin-based polyolefin containing a carboxyl group obtained by chemically (eg, by addition reaction or graft reaction) bonding an ethylenically unsaturated carboxylic acid or its anhydride to an olefin polymer. Refers to merging. The term "olefin polymer" as used herein means polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene, polyolefin such as polypropylene, boribene, and comonomers (vinyl ester, non-polyester) capable of copolymerizing olefin with the olefin. (E.g., a saturated carboxylic acid ester), such as an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer. Among them, linear low-density polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate content 5 to 5)
55% by weight) and ethylene-ethyl acrylate copolymer (content of ethyl acrylate 8 to 35% by weight) are preferable, and linear low-density polyethylene and ethylene-vinyl acetate copolymer are particularly preferable. It is. Ethylenically unsaturated carboxylic acids or anhydrides include ethylenically unsaturated monocarboxylic acids, esters thereof, ethylenically unsaturated dicarboxylic acids, mono or diesters thereof, and anhydrides thereof, and among them, ethylenically unsaturated dicarboxylic acids Anhydrides are preferred. Specific examples include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate, diethyl maleate, monomethyl fumarate, among others, maleic anhydride. Acids are preferred.

The amount of addition or grafting (degree of modification) of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer is 0.01 to 15 with respect to the olefin polymer.
%, Preferably 0.02 to 10% by weight. The addition reaction and graft reaction of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer can be obtained by, for example, a radical polymerization method in the presence of a solvent (such as xylene) and a catalyst (such as peroxide). The carboxylic acid-modified polyolefin thus obtained was heated at 190 ° C., 216 ° C.
The melt flow rate (MFR) measured under a load of 0 g is preferably from 0.2 to 30 g / 10 minutes, more preferably from 0.5 to 10 g / 10 minutes. These adhesive resins may be used alone or in combination of two or more.

In producing a paper container, a wallpaper and a decorative board including a layer comprising the resin composition (F) of the present invention, a molded product (film or sheet) obtained from the resin composition (F) of the present invention is used. And the like, and a film and a sheet of another base material are laminated using a known adhesive such as an organic titanium compound, an isocyanate compound, or a polyester compound, that is, a so-called dry lamination method.
The resin composition (F) of the present invention has very good dispersibility of the inorganic filler (B) and the inorganic filler (C) in the barrier resin (A), and thus has good film-forming properties. On the surface of the film or sheet obtained by the film, secondary aggregation of the inorganic filler (B) and the inorganic filler (C) is effectively suppressed, and the surface is excellent in smoothness. Therefore, the film or sheet comprising the resin composition (F) of the present invention exhibits excellent adhesiveness when laminated with a film of another substrate by a dry lamination method. In addition, since the film or sheet comprising the resin composition (F) of the present invention having such high smoothness exhibits excellent embossability, the film comprising the resin composition (F) of the present invention also has such a viewpoint. Is preferably used as wallpaper or decorative board.

The film or sheet comprising the resin composition (F) of the present invention exhibits excellent performance even in a non-stretched state, but a single layer formed by molding the resin composition (F) used in the present invention. An embodiment using a film obtained by stretching the original film at least twice or more in the uniaxial direction is particularly preferable. By using such a stretched film, pinhole resistance and gas barrier properties can be further improved. In order to obtain a multilayer structure including a layer composed of the above-mentioned stretched film, a single-layer raw film obtained by molding the resin composition (F) used in the present invention is stretched at least twice in at least one direction. It is preferable to prepare a film. As the stretched film to be laminated on the base material, a stretched multilayer structure including at least one layer composed of the resin composition (F) may be used, but the resin composition (F)
From the viewpoint that stretching can be performed under the best stretching conditions, an embodiment in which a single-layer raw film formed by molding the resin composition (F) is particularly preferred. By stretching under favorable conditions for the resin composition (F),
It is possible to further improve the ultraviolet light blocking property, visible light blocking property, gas barrier property and pinhole resistance.

When a multilayer structure is used as the raw material for stretching, the other layers laminated on the layer composed of the resin composition (F) also need to be stretched at the same time. In some cases, stretching cannot be performed under optimal stretching conditions. When a multilayer structure is used as the stretched raw material, at least one of the layers adjacent to the resin composition (F) layer is necessarily stretched. If you want to use a non-stretched layer,
It is necessary to use a stretched film obtained by stretching a single layer stretched raw material made of the resin composition (F).

The stretched raw material comprising the resin composition (F) obtained by the method exemplified above is stretched at least two times in the uniaxial direction to obtain a stretched film comprising the resin composition (F) of the present invention. can get. The production method of the stretched raw material is not particularly limited, but a production method in which a film or a sheet obtained by melt molding is quenched is particularly preferable. By rapidly cooling the film or sheet, it is possible to suppress the promotion of crystallization while the film or sheet immediately after production is cooled and solidified from a molten state, and it is possible to improve the stretchability of the stretched raw material. The method for rapidly cooling the film or sheet obtained by melt molding is not particularly limited, and a known water cooling method, air cooling method, metal roll contact method and the like are exemplified as suitable ones.

When the stretched raw material is uniaxially stretched, the stretching ratio is preferably at least 2 times, more preferably 2.times.
It is 5 times or more, more preferably 3 times or more. The stretching may be either uniaxial stretching or biaxial stretching, but biaxial stretching is preferred from the viewpoint of improving the gas barrier properties and mechanical strength of the stretched film. When the stretched raw material is biaxially stretched, the stretch ratio is preferably 3 times or more, more preferably 4 times or more, particularly preferably 6 times or more in terms of area ratio, from the viewpoint of improving gas barrier properties and mechanical strength. .

As a method of stretching the stretched raw material, a known stretching method can be employed. Although there is a method of stretching uniaxially or biaxially by a double bubble method, a tenter method, a roll method, or the like, the tenter method is preferable because the film thickness accuracy is excellent. As a stretching method, after first stretching in the longitudinal direction with a longitudinal stretching machine combining several different rolls, it may be stretched in the horizontal direction with a tenter type stretching machine, or conversely, after stretching in the horizontal direction first, It may be stretched in the direction. Also,
A method of simultaneous biaxial stretching with a tenter-type stretching machine may be used.

The stretching temperature is not particularly limited.
It is preferable to perform the treatment at a temperature equal to or lower than the melting point of the barrier resin (A) used in the present invention from the viewpoint of light blocking properties. This tendency is particularly strong when the barrier resin (A) is made of EVOH. When the barrier resin (A) is made of EVOH, the stretching temperature is 20 ° C. higher than the melting point of EVOH used.
Or lower, more preferably 40 ° C. or lower than the melting point of EVOH, and 60 ° C. lower than the melting point of EVOH.
More preferably, the melting point is lower than the melting point of EVOH.
It is particularly preferable that the temperature is lower than 0 ° C. By lowering the stretching temperature, stretching itself may be difficult,
It is preferable to perform a stretching treatment using a stretched raw fabric in a water-containing state. The method for producing the stretched raw fabric in a water-containing state is not particularly limited, and a method in which a resin composition pellet impregnated with water is obtained by melt molding or a method in which the stretched raw fabric is immersed in warm water (preferably at 60 to 90 ° C.) to be wet. A suitable method is exemplified.

The melting point of the barrier resin (A) in the present invention refers to a value obtained by measuring the barrier resin (A) by the method described in JIS K7121 (using iridium and lead for temperature calibration). Was). The stretching temperature in the present invention refers to a value obtained by measuring the surface temperature of the stretched raw material immediately before stretching after heating the stretched raw material for a predetermined time.

The stretched film of the present invention is preferably subjected to a heat treatment from the viewpoint of further improving gas barrier properties and mechanical strength. On the other hand, a stretched film that is not subjected to a heat treatment is suitably used as a heat-shrinkable film. The heat treatment temperature in the present invention refers to a value obtained by measuring the surface temperature of the multilayer structure immediately after heating the stretched film for a predetermined time in the heat treatment step. Although the heat treatment temperature is not particularly limited, the heat treatment is preferably performed under the condition satisfying the following expression (3). 0 ≦ T _m −T ₁ ≦ 80 (3) where Tm: melting point (° C.) of the barrier resin (A) T ₁ : heat treatment temperature (° C.) The heat treatment temperature in the present invention refers to a value obtained by measuring the surface temperature of the stretched film immediately after heating the stretched film for a predetermined time in the heat treatment step.

The thickness of the film comprising the resin composition (F) of the present invention is not particularly limited, but is preferably 3 to 100 μm. If it is less than 3 μm, the mechanical strength of the film may be unsatisfactory, and pinholes and the like may easily occur. If it exceeds 100 μm, the intended use may be limited, and when obtaining a stretched film having a high stretch ratio, the thickness of the stretched raw material is increased, so that uniform stretching may be difficult. . The thickness of the film is more preferably from 5 to 50 μm, particularly preferably from 5 to 20 μm. Even with such a film thickness, a film composed of the resin composition (F) of the present invention is suitable from the viewpoint of having a sufficient visible light and ultraviolet ray shielding function and gas barrier properties.

Further, in the film made of the resin composition (F) of the present invention having a thickness of 3 to 100 μm, the total haze is preferably 50% or more from the viewpoint of sufficiently exhibiting the effect of the present application of a visible light blocking function. Particularly preferred. The total haze of the film is more preferably 60% or more, further preferably 70% or more, and particularly preferably 80% or more. The difference between the total haze and the internal haze of the film is preferably 30% or less, more preferably 20% or less, and further preferably 10% or less. When the difference between the total haze and the internal haze of the film is 30% or less, even when the film is laminated on a film or sheet made of another thermoplastic resin, a particularly good visible light blocking function can be exhibited. It is possible.

Further, in the film made of the resin composition (F) of the present invention having a thickness of 3 to 100 μm, the visible light transmittance is 50% or less and the ultraviolet light transmittance is 30%.
The following is preferable from the viewpoint of obtaining a sufficient light blocking property. The visible light transmittance is more preferably 40% or less, still more preferably 30% or less, and particularly preferably 2% or less.
0% or less, and optimally 10% or less. The UV transmittance is more preferably 20% or less, still more preferably 10% or less, and most preferably 5% or less. In the present invention, the visible light transmittance is a wavelength of 500 nm.
And the ultraviolet transmittance is a wavelength of 35
The light transmittance at 0 nm.

The film made of the resin composition (F) of the present invention and the multilayer structure containing at least one layer made of the film have excellent gas barrier properties and excellent shielding properties against visible light and ultraviolet light. It is suitably used as a container for storing foods, alcoholic beverages, industrial goods that are not susceptible to oxidative deterioration, and the like. The form of the container is not particularly limited, and a flexible pouch, a paper container and the like are exemplified as preferable ones, and a paper container is particularly preferable.

Heretofore, aluminum foil has been laminated on a paper container filled with contents which are liable to be degraded by visible light and ultraviolet rays, from the viewpoint of providing a function of blocking visible light and ultraviolet rays and a gas barrier property with a thin film thickness. However, the multilayer structure using the aluminum foil has a problem in both recyclability and incineration as described above.
However, by using a paper container including a layer made of the resin composition of the present invention, recyclability is greatly improved, and the problem of incineration is solved.

The layer constitution of the paper container is as follows: T is a layer composed of a thermoplastic resin, F is a layer composed of the resin composition of the present invention, Ad is a layer composed of an adhesive resin or a layer composed of an adhesive, and P is a paper. Then, T / P / Ad / F / Ad / T, T / P /
Layer configurations such as Ad / F / Ad / P / T and T / P / Ad / F / Ad are exemplified. However, it is not always necessary to add other layers to these layers at all, and it is limited to the above examples. Not something.

Further, lamination with a single-layer structure or a multilayer structure including a colored film or sheet, steel plate and plywood is also possible. When laminated on these single-layer structures or multilayer structures, they are used for surface protection and matte effect, etc., and are preferably used for wallpaper, decorative boards, building materials, signboards, bird and beast damage prevention tools, etc. Is exemplified. In particular, the layer composed of the resin composition (F) of the present invention is excellent in matting effect and embossability, so that the multilayer structure including the resin composition layer of the present invention is suitably used as a wallpaper or decorative board.

Further, since the film made of the resin composition (F) of the present invention is excellent in the function of shielding visible light and ultraviolet light and the gas barrier property, a multilayer structure containing at least one layer made of the film is used as a vacuum heat insulating material. Very suitable. Since the vacuum heat insulating material generally requires a high gas barrier property, the resin composition (F) of the present invention is particularly preferable.
It is particularly preferable to use a stretched film obtained by stretching a film or sheet composed of at least two times in the uniaxial direction. As described above, conventionally, a multilayer structure including at least one layer made of an aluminum foil has been used as a vacuum heat insulating material in order to provide gas barrier properties and light blocking properties, but problems remain in recyclability and incineration properties. In addition, there still remains a problem of deterioration of the heat insulation performance due to a so-called heat bridge. However, these problems can be solved at once by using a multilayer structure including at least one layer made of a stretched film made of the resin composition (F) of the present invention.

[0116]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Various test methods in the present invention were performed according to the following methods.
All parts and percentages are by weight unless otherwise specified.

<Oxygen permeability> MODERN CONTR
OLS INC. MOCONOX Oxygen Permeation Analyzer
-Measured according to the method described in JIS K7126 (isobaric method) under the conditions of 20 ° C and 65% RH using TRAN2 / 20. Incidentally, the oxygen permeation amount referred to in the present invention is the oxygen permeation amount (ml / m ² · day · atm) measured at an arbitrary film thickness of a film composed of a single layer by a film thickness of 20 μm.
Value converted to (ml · 20 μm / m ² · day · at
m).

<Haze> An integral expression H. manufactured by Nippon Precision Optical Co., Ltd. T. The haze of the films obtained in the examples and comparative examples was measured using an R meter according to JIS D8741. The internal haze is a value measured by applying silicone oil to a thickness of about 2 μm on both surfaces of the film obtained in each of Examples and Comparative Examples.

<Light Transmittance> Using a self-recording spectrophotometer UV-2100 manufactured by Shimadzu Corporation, the light transmittance was measured according to the method described in JIS K7105, and the light transmittance at a wavelength of 500 nm was determined from the measurement diagram. (Visible Light Transmittance)
And the light transmittance (UV transmittance) at a wavelength of 350 nm was determined.

Example 1 (1) Preparation of Master Batch (f1) Ethylene content of 32 mol% as barrier resin (A)
EVOH having a saponification degree of 99.5 mol% (melting point: 183 ° C., EVAL EC-F101A (registered trademark); manufactured by Kuraray Co., Ltd.), talc having a particle diameter of 1.5 μm and a weight average aspect ratio of 15 as an inorganic filler (C) (LMS-200, manufactured by Fuji Talc Corporation) was used. The EVOH1
After mixing 00 parts by weight and 25 parts by weight of the talc with a tumbler, the mixture was pelletized at 230 ° C. using a vented twin screw extruder to obtain a master batch (f1).

(2) Preparation of master batch (f2) Ethylene content of 32 mol% as barrier resin (A)
Degree of saponification 99.5 mol%, MFR 4.4 g / 10 min (1
90 ° C, 2160 g load) EVOH (EVAL EC-
F104A (registered trademark; manufactured by Kuraray Co., Ltd.), titanium oxide having a particle diameter of 0.25 μm (Taipaque CR60, particle surface treated with aluminum oxide; manufactured by Ishihara Sangyo) as an inorganic filler (B), hydrotalcite compound (D ) As DH
T-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) and one or more compounds (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof as ethylene bisstearic acid amide (Alflow H- 50T; manufactured by NOF CORPORATION, hereinafter sometimes abbreviated as EBSA). (A) 100 parts by weight, (B) 30 parts by weight, (D)
After 0.5 parts by weight and 0.6 parts by weight of (E) were mixed at once with a Henschel mixer, the mixture was formed into a blend pellet at 230 ° C. using a twin-screw extruder while sealing the hopper port with nitrogen gas. A pellet consisting of (f2) was obtained. The strands of the masterbatch (f2) at the stage of pelletization were stable, and generation of tarnish was not observed.

(3) Production of Molded Product Made of Resin Composition (F) As the barrier resin (A), EVOH having an ethylene content of 32 mol% and a saponification degree of 99.5 mol% (melting point: 183)
C., Eval EC-F101A (registered trademark); manufactured by Kuraray Co., Ltd.), and the master batch (f1) and the master batch (f2) used above were used. 100 parts by weight of barrier resin (A), 115 parts by weight of master batch (f1), and master batch (f2)
After 50 parts by weight were mixed at once using a tumbler, the mixture was melt-extruded from a flat die at 230 ° C. using a single screw extruder under the following conditions, and brought into contact with a cooling roll at a temperature of 20 ° C. to obtain a resin composition having a thickness of 135 μm ( A stretched raw material consisting of F) was obtained. <Film forming conditions> Model Single screw extruder (non-vent type) L / D 20 Caliber 20mmφ Screw Single full flight type, Surface nitrided steel Screw rotation speed 40rpm Die 300mm width Coat hanger die Lip gap 0.3mm Cylinder, die temperature setting C1 / C2 / C3 / die = 195/230/230/220 (° C)

The surface of the obtained stretched raw material was smooth and free of irregularities, and had good thickness and thinness accuracy. The resin composition (F) constituting the stretched raw material is a barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm and Inorganic filler (C) having a weight average aspect ratio of 5 or more, hydrotalcite compound (D), and at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof ), And the compounding ratio is (A) 86.8.
2% by weight, (B) 4.34% by weight, (C) 8.68% by weight, (D) 0.07% by weight and (E) 0.09% by weight
Met.

Next, the moisture of the stretched raw material was adjusted to 15%, and a biaxial stretching device manufactured by Toyo Seiki Co., Ltd.
At 20 ° C., at a stretching temperature of 80 ° C., at a stretching ratio of 9 (longitudinal 3.0 × horizontal 3.0), and at a stretching speed of 1 m / min. To obtain a stretched film having a thickness of 15 μm. . The obtained stretched film was fixed to a wooden frame,
The heat treatment was performed for minutes. The oxygen permeation amount of the single-layer stretched film is 0.04 ml · 20 μm / m ² · day · at
m, the total haze was 91%, the internal haze was 90%, the visible light transmittance was 0%, and the ultraviolet light transmittance was 0%. Observation of the surface of the obtained stretched film showed no secondary aggregation of the inorganic filler at all, and the stretched film was excellent in appearance.

Further, the obtained stretched film was subjected to a bending resistance test according to the following method. That is,
45 sheets of the above stretched film cut into 21 cm × 30 cm were prepared, and each film was heated at 23 ° C.-50% R
After adjusting to H, according to ASTMF 392-74,
Using a Rigaku Kogyo gelbo flex tester,
Number of bending 150 times, 175 times, 200 times, 250 times, 3
After bending 00 times, 400 times, 500 times, 625 times and 750 times, the number of pinholes was measured. At each bending frequency, the measurement was performed 5 times, and the average value was defined as the number of pinholes.

The number of bends (P) is plotted on the abscissa, and the number of pinholes (N) is plotted on the ordinate. The above measurement results are plotted. (See FIG. 1). Np1 of the stretched film of this example
Was 226 times.

A polyethylene film having a thickness of 60 μm (Icelo Chemical Co., Ltd.)
Manufactured by Suzuron Co., Ltd.). The adhesive was laminated using Takeda Pharmaceutical Co., Ltd., Takelac, A385 / A50 at a solid content of 4 g / m ² at a temperature of 70 ° C. and aged at 40 ° C. for 5 days. The composite film had no delamination and had a good film surface. The composite film had a visible light transmittance of 0% and an ultraviolet light transmittance of 0%.

Example 2 As a barrier resin (A), EVOH having an ethylene content of 32 mol% and a saponification degree of 99.5 mol% (melting point: 183)
C., Eval EC-F101A (registered trademark); manufactured by Kuraray Co., Ltd.), and the master batch (f1) and the master batch (f2) used in Example 1 were used. 100 parts by weight of the barrier resin (A), 115 parts by weight of the master batch (f1), and
2) After 50 parts by weight are mixed at once using a tumbler,
Using a single screw extruder under the same film forming conditions as in Example 1,
Melt extrusion from flat die at 0 ° C, resin composition (F)
And a non-stretched film having a thickness of 15 μm.

The surface of the obtained unstretched film was smooth and free of bumps, no secondary aggregation of the inorganic filler was observed, and the thickness accuracy was good. The composition of the resin composition (F) was the same as that in Example 1. The oxygen permeation amount of the single-layer unstretched film is 0.20 ml · 20 μm / m ^2.
day ・ atm, total haze is 85%, internal haze is 83
%, The visible light transmittance was 0.5%, and the ultraviolet light transmittance was 0.1%.

Further, 45 stretched films cut into 21 cm × 30 cm were prepared, and each film was conditioned at 23 ° C.-50% RH.
Using a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd. according to 92-74, the number of bending times is 50 times, 60 times, 70 times.
After bending 80 times, 90 times, 100 times, 125 times, 150 times and 200 times, the number of pinholes was measured. At each bending frequency, the measurement was performed 5 times, and the average value was defined as the number of pinholes.

The number of bends (P) is plotted on the abscissa and the number of pinholes (N) is plotted on the ordinate. The above measurement results are plotted, and the number of bends when the number of pinholes is one (Np1) is extrapolated. I asked. Np1 of the stretched film of this example was 45 times.

A polyethylene film having a thickness of 60 μm (manufactured by Aicello Chemical Co., Ltd., Suzuron) was attached to both sides of the unstretched film produced above to form a composite film. The adhesive is Takeda Pharmaceutical, Takelac, A385 /
Using A50, the coating amount was set to 4 g / m ^{2 of} solid content, laminated at a temperature of 70 ° C, and aged at 40 ° C for 5 days. The composite film had no delamination and had a good film surface. The composite film had a visible light transmittance of 0% and an ultraviolet light transmittance of 0%.

Example 3 <Preparation of Master Batch (f2)> Barrier Resin (A)
Ethylene content 32 mol%, saponification degree 99.5 mol%, MFR 4.4 g / 10 min (190 ° C., 2160 g
EVOH (Eval EC-F104A (registered trademark); manufactured by Kuraray Co., Ltd.), and titanium oxide having a particle diameter of 0.03 μm (Typeak TTO-5) as an inorganic filler (B).
5S, particle surface treated with aluminum oxide, then treated with organosiloxane; Ishihara Sangyo), DHT-4A (manufactured by Kyowa Chemical) as hydrotalcite compound (D), higher fatty acid having 4 to 24 carbon atoms, and its metal As one or more compounds (E) selected from salts, esters and amides, ethylene bisstearic acid amide (Alflow H-50T; manufactured by NOF CORPORATION, hereinafter sometimes abbreviated as EBSA) was used. 100 parts by weight of the above (A),
(B) 15 parts by weight, (D) 0.5 parts by weight and (E) 1
After the weight parts were mixed at once with a Henschel mixer, the pellets were blended into pellets at 230 ° C. using a twin screw extruder while sealing the hopper port with nitrogen gas to obtain pellets comprising a master batch (f2). The strands of the masterbatch (f2) at the stage of pelletization were stable, and generation of tarnish was not observed.

<Preparation of Molded Product Made of Resin Composition (F)> As the barrier resin (A), EVOH having an ethylene content of 32 mol% and a saponification degree of 99.5 mol% (melting point: 183)
° C, EVAL EC-F101A (registered trademark); manufactured by Kuraray Co., Ltd.), the master batch (f1) used in Example 1 was used, and the master batch (f2) used above was used. Was. Barrier resin (A)
100 parts by weight, 188 parts by weight of master batch (f1),
And 146 parts by weight of the master batch (f2) were mixed at once using a tumbler, and then mixed using a single screw extruder.
In the same manner as in Example 1, melt extruded from a flat die at a temperature of 200 ° C., and brought into contact with a cooling roll at a temperature of 20 ° C. to a thickness of 135 μ
m of the resin composition (F) was obtained.

The resin composition (F) comprises a barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm, and a weight average aspect ratio. 5 or more inorganic fillers (C), hydrotalcite compounds (D), and at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof. The compounding ratio was (A) 86.58% by weight, (B) 4.33% by weight,
(C) 8.66% by weight, (D) 0.14% by weight and (E) 0.29% by weight.

Then, the moisture of the above-mentioned stretched raw material was adjusted to 15%, and a biaxial stretching device manufactured by Toyo Seiki Co., Ltd. was used. The film was simultaneously biaxially stretched at a draw ratio of 3.0 times (× 3.0 times) and at a draw speed of 1 m / min to obtain a stretched film having a thickness of 15 μm. The obtained stretched film was fixed to a wooden frame, and the temperature was 140 ° C.
Heat treated for 10 minutes. The oxygen permeation amount of the single-layer stretched film is 0.04 ml · 20 μm / m ² · day · at
m, the total haze was 90%, the internal haze was 88%, the visible light transmittance was 0%, and the ultraviolet light transmittance was 0%. When the surface of the obtained stretched film was observed, secondary aggregation of the inorganic substance was slightly observed, but the appearance of the film was sufficiently enduring practical use.

A polyethylene film having a thickness of 60 μm (Icelo Chemical Co., Ltd.)
Manufactured by Suzuron Co., Ltd.). The adhesive was laminated using Takeda Pharmaceutical Co., Ltd., Takelac, A385 / A50 at a solid content of 4 g / m ² at a temperature of 70 ° C. and aged at 40 ° C. for 5 days. The composite film had no delamination and had a good film surface. The composite film had a visible light transmittance of 0% and an ultraviolet light transmittance of 0%.

Example 4 As a barrier resin (A), EVOH having an ethylene content of 32 mol% and a saponification degree of 99.5 mol% (melting point: 183)
° C, EVAL EC-F101A (registered trademark); Kuraray Co., Ltd.), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, a particle diameter of 0.6 to 2.5 μm, and a weight average aspect ratio. Is at least one compound selected from the group consisting of an inorganic filler (C) having 5 or more, a hydrotalcite compound (D), and a higher fatty acid having 4 to 24 carbon atoms, a metal salt, an ester and an amide thereof. Example 1
The same one as used in the above was used.

(A) 100 parts by weight, (B) 5 parts by weight,
(C) 10 parts by weight, (D) 0.08 parts by weight and (E)
0.1 parts by weight were mixed at once using a tumbler, and then a single screw extruder was used.
In the same manner as in the above, the mixture was melt-extruded and brought into contact with a cooling roll at a temperature of 20 ° C. to obtain a stretched raw material composed of a resin composition (F) having a thickness of 135 μm. The obtained resin composition (F) is (A) 8
6.82% by weight, (B) 4.34% by weight, (C) 8.6
8% by weight, (D) 0.07% by weight and (E) 0.09%
% By weight.

Then, the water content of the stretched raw material was adjusted to 15%, and a biaxial stretching device manufactured by Toyo Seiki Co., Ltd. was used. The preheating was performed at 80 ° C. (for 20 seconds), the stretching temperature was 80 ° C., and the stretching ratio was 9%. The film was simultaneously biaxially stretched at a draw ratio of 3.0 times (× 3.0 times) and at a draw speed of 1 m / min to obtain a stretched film having a thickness of 15 μm. The obtained stretched film was fixed to a wooden frame, and the temperature was 140 ° C.
Heat treated for 10 minutes. The oxygen permeation amount of the single-layer stretched film is 0.04 ml · 20 μm / m ² · day · at
m, the total haze was 91%, the internal haze was 90%, the visible light transmittance was 0%, and the ultraviolet light transmittance was 0%. Observation of the surface of the obtained stretched film showed some secondary aggregation of the inorganic substance, but the appearance of the film was practical.

A bending resistance test was performed in the same manner as in Example 1. The number of bendings (P) was plotted on the horizontal axis, and the number of pinholes (N) was plotted on the vertical axis. The number of bendings (Np1) when the number of holes was one was determined by extrapolation. Np1 of the stretched film of this example was 220 times.

A polyethylene film having a thickness of 60 μm (Icelo Chemical Co., Ltd.)
Manufactured by Suzuron Co., Ltd.). The adhesive was laminated using Takeda Pharmaceutical Co., Ltd., Takelac, A385 / A50 at a solid content of 4 g / m ² at a temperature of 70 ° C. and aged at 40 ° C. for 5 days. The composite film had no delamination and had a good film surface. The composite film had a visible light transmittance of 0% and an ultraviolet light transmittance of 0%.

Comparative Example 1 A barrier resin (A), an inorganic filler (C) having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more, a hydrotalcite compound (D), and a carbon number of 4 ~ 2
As the at least one compound (E) selected from the higher fatty acids 4, metal salts, esters and amides of 4, the same compounds as those used in Example 4 were used. (A) 100
Parts by weight, (C) 10 parts by weight, (D) 0.08 parts by weight, and (E) 0.1 parts by weight were collectively mixed using a tumbler, and then the same as in Example 4, using a single screw extruder. 23
It was melt-extruded from a flat die at 0 ° C. and brought into contact with a cooling roll at a temperature of 20 ° C. to obtain a 135 μm-thick raw stretched sheet.

A stretched film was prepared in the same manner as in Example 4 using the stretched raw material. The oxygen permeation amount of the single-layer stretched film is 0.04 ml · 20 μm / m ² · day
Atm, total haze was 70%, internal haze was 53%, visible light transmittance was 14%, and ultraviolet transmittance was 6%.

Comparative Example 2 A barrier resin (A), an inorganic filler (B) having a particle size of 0.01 to 0.5 μm, a hydrotalcite compound (D), a higher fatty acid having 4 to 24 carbon atoms, and a metal thereof As at least one compound (E) selected from salts, esters and amides, the same compounds as those used in Example 4 were used. (A) 100 parts by weight, (B) 5 parts by weight,
After 0.08 parts by weight of (D) and 0.1 part by weight of (E) were mixed at once using a tumbler, the mixture was melt-extruded from a flat die at 230 ° C. using a single screw extruder in the same manner as in Example 4. Contact a cooling roll at a temperature of 20 ° C.
An original stretched film of 35 μm was obtained.

A stretched film was produced in the same manner as in Example 4 using the stretched raw material. The oxygen permeation amount of the single-layer stretched film is 0.13 ml · 20 μm / m ² · day
Atm, total haze was 83%, internal haze was 82%, visible light transmittance was 3%, and ultraviolet transmittance was 2%.

In addition, 45 stretched films cut to 21 cm × 30 cm were prepared, and each film was conditioned at 23 ° C.-50% RH.
Using a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd. according to
25 times, 150 times, 175 times, 200 times, 225 times, 2
After bending 50 times and 300 times, the number of pinholes having a diameter of 2 mm or more was measured. At each bending frequency, the measurement was performed 5 times, and the average value was defined as the number of pinholes.

The number of bends (P) is plotted on the abscissa and the number of pinholes (N) is plotted on the ordinate. The above measurement results are plotted, and the number of bends when the number of pinholes is one (Np1) is extrapolated. I asked. Np1 of the stretched film of this comparative example was 132 times.

Comparative Example 3 A barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, and an inorganic filler having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more ( As C) and at least one compound (E) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof, the same compounds as those used in Example 4 were used. (A) 100 parts by weight, (B) 5 parts by weight, (C) 1
After 0 parts by weight and 0.1 parts by weight of (E) were mixed at once using a tumbler, the mixture was melt-extruded from a flat die at 230 ° C. using a single screw extruder in the same manner as in Example 4, and cooled to 20 ° C. The sheet was brought into contact with a roll to obtain a 135 μm-thick stretched raw material. The surface of the obtained stretched raw material had bumps due to thermal deterioration of the resin, and secondary aggregation of the inorganic filler was very frequently observed. Therefore, no stretched film was produced.

Comparative Example 4 A barrier resin (A), an inorganic filler (B) having a particle diameter of 0.01 to 0.5 μm, and an inorganic filler having a particle diameter of 0.6 to 2.5 μm and a weight average aspect ratio of 5 or more ( As C) and the hydrotalcite compound (D), the same compounds as those used in Example 4 were used. (A) 100 parts by weight, (B) 5 parts by weight, (C) 10 parts by weight and (D)
After mixing 0.08 parts by weight at once using a tumbler,
In the same manner as in Example 4, the extruded material was melt-extruded from a flat die at 230 ° C. using a single-screw extruder, and brought into contact with a cooling roll at a temperature of 20 ° C. to obtain a 135 μm-thick raw stretched film. The obtained stretched raw material did not produce a stretched film because some unevenness and secondary aggregation of inorganic filler due to thermal degradation of the resin were observed on the surface and the surface was poor in smoothness.

Comparative Example 5 Talc having a particle diameter of 6 μm and a weight average aspect ratio of 7 (PKP, manufactured by Fuji Talc Industries, Ltd.) was used as the inorganic filler (C).
Except for using -80), an attempt was made to produce a stretched film in the same manner as in Example 4. However, the film was broken by stretching, the film appearance and surface smoothness were poor, and the film was not practical.

The resin compositions of the present invention shown in Examples 1 to 4 were excellent in gas barrier properties and exhibited good light blocking properties. On the other hand, when the stretched film of Example 4 and the stretched film of Comparative Example 1 were compared, the stretched film of Example 4 was more excellent in light blocking property. When the stretched film of Example 4 and the stretched film of Comparative Example 2 were compared, the stretched film of Example 4 was superior in light-shielding properties, gas barrier properties, and bending resistance. In Comparative Examples 3 to 5, good stretched raw materials could not be produced, and stretched films could not be evaluated.

Industrial Applicability The resin composition of the present invention is excellent in a function of shielding visible light and ultraviolet light and gas barrier properties. By performing various melt moldings using the resin composition, various types of foods and processed marine products can be obtained. , Medicine, cosmetics, etc., paper containers, wallpaper, building materials, signboards, etc.

[Brief description of the drawings]

FIG. 1 shows the stretched film produced in Example 1 at 23 ° C.
It is a figure which shows the relationship between the number of times of bending (N) and the number of generation of pinholes (P) in a Gelboflex tester at -50% RH.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/18 CEX C08J 5/18 CEX CFG CFG C08K 3/26 C08K 3/26 5/09 5/09 5 / 10 5/10 5/20 5/20 7/00 7/00 7/04 7/04 C08L 23/08 C08L 23/08 29/04 29/04 S 77/00 77/00 F-term (reference) 3E086 AB01 BA04 BA14 BA15 BA35 BB01 BB22 BB23 BB37 CA01 CA28 4F071 AA01 AA15X AA29 AA29X AA54 AA55 AB18 AB28 AB30 AC09 AC12 AD05 AF30Y AH03 AH05 AH19 4F100 AA01A AA08A AA21A AC01A01A02A01A01A02 JK06 4J002 AA001 BB221 BE021 BE031 CL011 CL031 CL051 DE136 DE288 DJ007 DJ047 DJ057 DL007 EF029 EF059 EG009 EG029 EG039 EG049 EH009 EH039 EH049 EP009 EP019 EP029 FA017 FA047 FD016 FD017GF01GF01GF

Claims (15)

[Claims] 1. A barrier resin (A) having a particle diameter of 0.01 to
0.5 μm inorganic filler (B), particle diameter 0.6 to 2.
At least one compound selected from an inorganic filler (C) having a weight average aspect ratio of 5 or more, a hydrotalcite compound (D), and a higher fatty acid having 4 to 24 carbon atoms, a metal salt, an ester and an amide thereof; (E)
A resin composition (F) comprising: 2. The content of (A), (B), (C), (D) and (E) is (A) 70 to 95% by weight,
(B) 1 to 15% by weight, (C) 3 to 25% by weight, (D)
The resin composition (F) according to claim 1, wherein the content is 0.001 to 5% by weight and (E) 0.001 to 10% by weight. 3. The resin composition (F) according to claim 1, wherein the barrier resin (A) is at least one selected from an ethylene-vinyl alcohol copolymer and polymethaxylylene adipamide. 4. The barrier resin (A) having an ethylene content of 5
The resin composition (F) according to claim 1 or 2, which is an ethylene-vinyl alcohol copolymer having a saponification degree of 90% or more by 60 mol% or more. 5. The resin composition (F) according to claim 1, wherein the inorganic filler (B) is titanium oxide. 6. The resin composition (F) according to claim 1, wherein the inorganic filler (C) is talc. 7. Barrier resin (A) 100 parts by weight, barrier resin (A) 60 to 98% by weight and particle diameter 0.6 to
A resin composition (f) comprising 2 to 40% by weight of an inorganic filler (C) having a thickness of 2.5 μm and a weight average aspect ratio of 5 or more
1) 50 to 250 parts by weight, and barrier resin (A)
50 to 98% by weight, 2 to 45% by weight of an inorganic filler (B) having a particle size of 0.01 to 0.5 μm, 0.001 to 5% by weight of a hydrotalcite compound (D), and 4 carbon atoms
At least one compound (E) selected from the group consisting of a higher fatty acid, a metal salt thereof, an ester and an amide thereof.
Resin composition (f2) consisting of 1 to 15% by weight
The resin composition (F) according to any one of claims 1 to 6, which is obtained by mixing and then melt-mixing 0 parts by weight. 8. A film or sheet comprising the resin composition (F) according to claim 1. 9. A film or sheet obtained by stretching the film or sheet according to claim 8 at least twice in at least one axial direction. 10. The film according to claim 8, which has a thickness of 3 to 100 μm and a total haze of 50% or more. 11. A multilayer structure comprising at least one layer comprising the film or sheet according to claim 8. 12. A multilayer structure obtained by laminating the film or sheet according to claim 8 on a substrate by a dry lamination method. 13. A paper container comprising the multilayer structure according to claim 11. 14. A wallpaper or decorative board comprising the multilayer structure according to claim 11 or 12. 15. A vacuum heat insulating material comprising the multilayer structure according to claim 11.