JP2001323175A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a resin composition that has visible light and UV light shielding function, gas barrier properties and moldability at the same time. SOLUTION: The resin composition comprises (A) a gas barrier resin, (B) an inorganic substance having a particle size of 0.1-0.5 μm, (C) an inorganic substance having a particle size of 0.01-0.06 μm and, as an optional component, (D) one or more than one compound selected from a 4-24C higher fatty acid, its metal salt, its ester and its amide and contains, per 100 pts.wt. the component (A), 1-15 pts.wt. the component (B), 0.5-5 pts.wt. the component (C) and 0-0.5 pts.wt. the component (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition having a function of shielding visible light and ultraviolet light, a gas barrier property and a moldability.

[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 have excellent light shielding in both ultraviolet and visible light. Desirable.

Conventionally, as a method for obtaining a structure having gas barrier properties and also having a function of blocking ultraviolet rays, Japanese Patent Application Laid-Open No.
Japanese Patent No. 128433 discloses a saponified ethylene-vinyl ester copolymer having an ethylene content of 20 to 65 mol%, a saponification degree of a vinyl ester component of 90 mol% or more, a fine particle inorganic material having a particle diameter of 0.1 μm or less, and a carbon number of 4 (A) 100 or more selected from higher fatty acids, metal salts, esters and amides thereof.
(B) 0.01 to 5 parts by weight, (C) 0.0 to parts by weight
A resin composition containing 0.5 to 5 parts by weight is disclosed.
Such a resin composition has an excellent gas barrier property and an ultraviolet blocking effect, but cannot sufficiently block visible light.

A resin composition obtained by adding an inorganic substance to an ethylene-vinyl alcohol copolymer is disclosed in JP-A-5-140.
No. 345, a functional film comprising a resin composition layer comprising 50 to 99% by weight of an ethylene-vinyl alcohol copolymer and 1 to 50% by weight of an inorganic filler, and having at least one surface having a surface gloss of 60% or less. Is disclosed, but there is no description about ultraviolet blocking properties.

As a method for obtaining a structure having gas barrier properties and a function of shielding visible light and ultraviolet light, vinylidene chloride copolymer as a gas barrier resin,
Using a vinyl alcohol copolymer, acrylonitrile copolymer, etc., the ultraviolet blocking function is a benzophenone derivative,
There is known a method of kneading an ultraviolet absorbent such as a salicylic acid derivative, a benzoic acid derivative, or a benzotriazole derivative into a resin, an adhesive, an ink, or the like to form a multilayer. However, many of the organic UV absorbers have a problem that they cannot block UV light having a wavelength of around 250 nm, and the absorption capacity is deteriorated due to deterioration of the UV absorber itself. In addition, the method of kneading these organic ultraviolet absorbers into a resin also has a problem of transfer to contents. There is also a method of kneading these organic UV absorbers into adhesives and inks, but when processing them, the adhesives and inks used up to that time in the processing equipment are removed.
It is necessary to replace the ultraviolet absorbent with an adhesive or ink into which the kneaded material has been kneaded, which results in a loss of time and adhesive or ink, which has been a factor of high cost.

On the other hand, by laminating aluminum foil, it is possible to obtain a structure having both gas barrier properties and light shielding properties, but it is not always possible to obtain sufficient flexibility and impact resistance. In some cases, pinholes and the like are generated in a distribution process such as transportation, and gas barrier properties and light blocking properties may be reduced. In addition, when aluminum foil is used, recycling is not always easy, and furthermore, at the time of incineration, there is a possibility that aluminum vapor condenses on a water pipe of a heat exchanger installed in an incinerator, thereby deteriorating thermal efficiency. .

[0007]

Accordingly, a resin composition having both a function of shielding visible light and ultraviolet light, a gas barrier property and a moldability, and a single-layer or multilayer structure formed by molding the resin composition Is desired.

[0008]

The object of the present invention is to provide a barrier resin (A), an inorganic substance (B) having a particle size of 0.1 to 0.5 μm,
An inorganic substance (C) having a particle size of 0.01 to 0.06 μm;
It is composed of one or more compounds (D) selected from the optional higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof, and 100 parts by weight of (A) and (B) This is achieved by providing a resin composition containing 1 to 15 parts by weight, (C) 0.5 to 5 parts by weight, and (D) 0 to 0.5 part by weight.

That is, the present invention provides a barrier resin (A),
Inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, and a particle diameter of 0.1 to 0.5 μm.
An inorganic substance (C) having a particle size of from 0.01 to 0.06 μm and one or more compounds (D) selected from higher fatty acids having 4 to 24 carbon atoms as an optional component, metal salts, esters and amides thereof; And (A) 100 parts by weight,
The present invention relates to a resin composition containing (B) 1 to 15 parts by weight, (C) 0.5 to 5 parts by weight, and (D) 0 to 0.5 part by weight.

In a preferred embodiment, the resin composition of the present invention comprises a barrier resin (A), an inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, and an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm. ) And one or more compounds (D) selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof, and (B) based on 100 parts by weight of (A) 1 to 15 parts by weight, (C) 0.5 to 5 parts by weight, and (D) 0.05 to 0.5 parts by weight.

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

In a preferred embodiment, the resin composition of the present invention is used after being molded into a container. In another preferred embodiment, the resin composition of the present invention is used after being formed into a film or a sheet.

In a preferred embodiment, the film formed by molding the resin composition of the present invention has a thickness of 5 to 200 μm.
m, and the total haze is 60% or more. In a further preferred embodiment, the difference between the total haze and the internal haze of the film is 10% or less.

In a preferred embodiment, the film comprising the resin composition of the present invention is obtained by stretching at least two times in the uniaxial direction.

In a preferred embodiment, the resin composition of the present invention is used as a multilayer structure having at least one layer made of the resin composition of the present invention. A preferred embodiment of the multilayer structure is a paper container, and another preferred embodiment is a wallpaper or a decorative board.

In a preferred embodiment, the resin composition of the present invention comprises an inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm, and a carbon number of 4 After mixing at least one compound (D) selected from the group consisting of -24 to higher fatty acids, metal salts, esters and amides thereof, a barrier resin (A) is blended.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Barrier resin used in the present invention
(A) is a resin having gas barrier properties. Such ba
The rear resin (A) has an oxygen permeation amount of 100 cc
20 μm / m ^Two・ Day (measured at 20 ° C-65% RH)
Value). The upper limit of oxygen permeation is
More preferably, 10 cc · 20 μm / m^Two・ Day ・ at
m, more preferably 5 cc · 20 μm / m^Two
· Day · atm or less, particularly preferably 1 cc · 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 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%, and even more preferably at least 99%. If the saponification degree is less than 90 mol%,
There is a possibility that the gas barrier property under high humidity may decrease, and the gasoline barrier property may become insufficient. Here,
When the polyvinyl alcohol-based resin is composed of a blend of two or more types of polyvinyl alcohol-based resins having different degrees of saponification, the average 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.

As the polyvinyl alcohol resin of the present invention, from the viewpoints of being capable of being melt-molded, having good gas barrier properties under high humidity, and having excellent gasoline barrier properties, ethylene-vinyl alcohol copolymer ( Hereinafter, E
VOH).

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

Furthermore, 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 such as the above-mentioned alkali metal salts of various boric acids, 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 phosphate 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 type of the phosphoric acid compound to be incorporated into 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 minutes, more preferably 0.3 to 50 g / 10 minutes.
-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 is 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), polymetaxylylene 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, polymetaxylylene 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. The inorganic substance (B) and the inorganic substance (C) used in the present invention are preferably titanium oxide, but as a result of detailed studies by the present inventors, a barrier resin (A) containing an oxidation catalyst such as titanium oxide If a molded article (such as a film) made of
It became clear that the molded product made of the barrier resin (A) tends to be yellowed. Further, when a polyvinyl alcohol-based resin and a polyamide are compared, when a polyvinyl alcohol-based resin is used as the barrier resin (A), the occurrence of such yellowing is suppressed, and in particular, EVOH is used as the barrier resin (A). Accordingly, even when titanium oxide is used as the inorganic substance (B) and / or the inorganic substance (C), it is possible to withstand long-time light exposure and to significantly suppress yellowing. From this point of view,
It is preferable to use EVOH as the barrier resin (A).

The resin composition 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, from the viewpoint of the gas barrier properties of the resin composition, it is preferable that the amount of the thermoplastic resin other than the barrier resin (A) is small. The thermoplastic resin constituting the resin composition preferably has a content of the thermoplastic resin other than the barrier resin (A) of 20% by weight or less,
The content is more preferably 10% by weight or less, further preferably 5% by weight or less, particularly preferably 3% by weight or less, and the thermoplastic resin constituting the resin composition is substantially a barrier resin ( Optimally, it consists only of A).

The inorganic substance (B) used in the present invention is responsible for shielding visible light and has a particle diameter of 0.1 to 0.6.
μm, preferably 0.15 to 0.5 μm, more preferably 0.2 to 0.4 μm.

When the particle size of the inorganic substance (B) is less than 0.1 μm, the visible light shielding property becomes insufficient. It is very important that the particle diameter of the inorganic substance (B) is 0.6 μm or less. Heretofore, in order to impart a higher barrier property to EVOH (JP-A-5-140344)
Japanese Patent Application Laid-Open No.
Japanese Patent Publication No. 140345/1992) discloses a technique of adding an inorganic substance such as talc. In these examples, an inorganic substance having a particle diameter of more than 1 μm is added. However,
As a result of detailed studies by the present inventors, when the particle diameter of the inorganic substance (B) exceeds 0.6 μm, the barrier resin (A)
Because the internal haze of a film composed of a resin composition in which an inorganic substance (B) is blended is reduced, it is clarified for the first time that a sufficient visible light shielding property cannot be obtained when the film is multilayered to form a composite film. (See Comparative Example 7 of the present application).

Further, in the multilayer structure including the layer composed of the resin composition of the present invention, the layer composed of the resin composition of the present invention has good embossability (see Example 10 of the present application), but the particle diameter is small. When a resin composition containing an inorganic substance (B) exceeding 0.6 μm is used, embossability decreases (see Comparative Example 8 of the present application).

From the viewpoint of obtaining sufficient visible light blocking properties, the inorganic substance (B) preferably has a high refractive index. The inorganic substance (B) used in the present invention is not particularly limited, but titanium oxide (irrespective of rutile type or anatase type) iron oxide,
Fine particles such as zinc oxide, talc, kaolin, and calcium carbonate are preferable, and titanium oxide having a large refractive index and being chemically stable is particularly preferable.

The inorganic substance (C) used in the present invention is responsible for shielding ultraviolet rays and has a particle diameter of 0.01 to 0.0.
It is important that it is 6 μm. The particle diameter of the inorganic substance (C) is from 0.01 to 0.06 μm, preferably from 0.0 to 0.06 μm.
15 to 0.05 μm, more preferably 0.02 to 0.0
4 μm. If the particle size is less than 0.01 μm, it is not always easy to obtain and manufacture. Particle size 0.06
If it exceeds μm, sufficient ultraviolet blocking properties cannot be obtained.

The inorganic substance (C) used in the present invention is not particularly limited, but titanium oxide (irrespective of rutile type or anatase type) which has a large refractive index, is chemically stable, and is easily available is preferable.

The particle diameters of the inorganic substance (B) and the inorganic substance (C) in the present invention are observed at a magnification of 50,000 using a transmission electron microscope. , Primary particles constituting the particles) are the average values of the measured values of arbitrary 20 diameters.

The inorganic fine particles as described above can be obtained by pulverizing the inorganic materials with a mill or the like, but are not particularly limited. As a preferable method for producing the inorganic substance (B) and the inorganic substance (C), when (B) and / or (C) is titanium oxide, titanium tetrachloride is hydrolyzed in a gas phase in an oxygen / hydrogen flame. A method in which titanium alkoxide is atomized and then hydrolyzed in an oxygen-containing flame, and a method in which titanium hydroxide obtained by hydrolyzing titanyl sulfate is calcined.

When (B) and / or (C) is iron oxide, a method of heating hydrated iron oxide to remove water of crystallization, mixing iron oxide and barium carbonate, sintering or coprecipitation.
There is a method in which barium ferrite is once obtained by a salt catalyst method, and barium is removed therefrom.

When the inorganic substance (B) and / or the inorganic substance (C) is zinc oxide, basic zinc carbonate, zinc oxalate, zinc hydroxide or the like is decomposed by heating,
A method of calcining at a dehydration temperature may be used.

These inorganic substances (B) and inorganic substances (C)
Is coated with a barrier resin (A) (particularly preferably EVO).
From the viewpoint of improving the affinity with H), it is preferable to perform a surface treatment with aluminum oxide (alumina), an organic siloxane, silicon oxide, a fatty acid, or the like, and in particular, the surfaces of (B) and (C) are treated with alumina. Is preferred. Further, as for the inorganic substance (C), an embodiment in which the surface is treated with alumina and then the surface is further treated with organosiloxane is particularly preferable. Such an inorganic substance (C)
Is used, it is possible to effectively suppress the aggregation of the inorganic substance (C) in the barrier resin (A) and obtain good dispersibility, and to mold the resin composition of the present invention into a film or the like. In the case of (C), the cohesion of (C) is small and the appearance is excellent.
In addition, it is possible to obtain a molded product having excellent light blocking properties.

Further, from the viewpoint of the thermal stability of the resin composition,
The above-mentioned inorganic substance (B) and inorganic substance (C) are preferably the same compound that differs only in the particle diameter. Although the detailed reason is unknown, when the inorganic substance (B) and the inorganic substance (C) are different compounds, the thermal stability of the resin composition may be adversely affected.

The resin composition of the present invention comprises a barrier resin (A), an inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm, and optionally It is composed of one or more compounds (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof, and (B) per 100 parts by weight of (A) 1 to 15 parts by weight, (C) 0.5 to 5 parts by weight, and (D) 0 to 0.5 parts by weight. By using such a resin composition, it is possible to obtain a molded product excellent in a function of shielding visible light and ultraviolet light and a gas barrier property.

In the present invention, the particle diameter is 0.1 to 0.6 μm.
The amount of the inorganic substance (B) to be added is such that the barrier resin (A) 100
1 to 15 parts by weight with respect to parts by weight, preferably 3 to 15 parts by weight.
It is 13 parts by weight, more preferably 5 to 10 parts by weight.
When the addition amount of (B) is more than 15 parts by weight, surface irregularities become severe when a film made of the resin composition is formed, and wrinkles occur when bonding with another material using an adhesive. There is a problem that is likely to occur. When the amount of (B) added is 1
If the amount is less than the weight, the effect of blocking visible light is reduced.

The particle size in the present invention is 0.01 to 0.06.
The addition amount of the inorganic substance (C) of μm is determined by the barrier resin (A) 1
The amount is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight based on 00 parts by weight. The amount of addition of the inorganic substance (C) is 0.5
When the amount is less than 5 parts by weight, the ultraviolet shielding property is insufficient, and when the amount of the inorganic substance (C) exceeds 5 parts by weight, secondary aggregation is liable to occur, which causes the occurrence of dust due to poor dispersion.

In the present invention, at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof,
The higher fatty acid having 4 to 24 carbon atoms is a saturated or unsaturated fatty acid having a straight or branched chain, butyric acid, isoacid,
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.

In the present invention, the compound (D) is not an essential component, but the compound (D) is further added to a resin composition comprising the barrier resin (A), the inorganic substance (B) and the inorganic substance (C). Thereby, it is possible to effectively suppress the secondary aggregation of the inorganic substance (B) and the inorganic substance (C), and to suppress the occurrence of bumps in a molded product obtained by molding the resin composition, and to improve moldability. In particular, it is possible to obtain a resin composition which is particularly excellent. In addition, since the dispersibility of the inorganic substance (B) and the inorganic substance (C) in the barrier resin (A) is improved, the effect of blocking visible light and ultraviolet light is further improved. These tendencies are particularly remarkable in a molded article having a small thickness such as a film. In addition, it is preferable to add the compound (D) from the viewpoint of suppressing the torque fluctuation during the heating and melting of the resin composition by adding the compound (D).

When the number of carbon atoms of the compound (D) is less than 4, the dispersibility of the inorganic substance (B) and the inorganic substance (C) in the barrier resin (A) is poor, so that lumps are easily generated. On the other hand, when the carbon number of (D) exceeds 24, compound (D)
The dispersibility of the resin composition in the barrier resin (A) is deteriorated, and the effect of suppressing the torque fluctuation during the heating and melting of the resin composition cannot be sufficiently obtained. From the viewpoint of dispersibility of the inorganic substance (B) and the inorganic substance (C) in the barrier resin (A), the compound (D)
It is particularly preferred that the carbon number of is 10 or more.

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.

The at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides in the present invention includes the higher fatty acids exemplified above and the higher fatty acids 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 amount of the at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof used in the present invention is 100% of the barrier resin (A). 0.05 parts by weight
To 0.5 parts by weight, more preferably 0.1 to 0.4 parts by weight, even more preferably 0.15 to 0.5 parts by weight.
0.3 parts by weight. When the amount of compound (D) added is 0.05
If the amount is less than 0.5 parts by weight, the effect of improving the dispersibility of the inorganic substance (B) and the inorganic substance (C) may be insufficient. If the amount is more than 0.5 part by weight, unevenness may occur due to poor dispersion of the compound (D) itself. Sometimes.

The resin composition of the present invention comprises a barrier resin (A), an inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, and an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm. However, the manufacturing method is not particularly limited. (A),
A method in which (B) and (C) are collectively mixed to form a blend pellet; a method in which (B) and (C) are mixed by dry blending and the like; a method in which the mixture is blended with (A) to form a pellet; A method in which (B) and (C) are added to the solution (A), mixed, and then the solvent is removed to obtain a pellet or a film is exemplified as a suitable method. As the solvent used for the solution of the barrier resin (A), when the barrier resin (A) is EVOH, water-
Alcohol mixed solvents are particularly preferred.

In a preferred embodiment, the resin composition of the present invention comprises a barrier resin (A) having a particle diameter of 0.1 to 0.5 μm.
m or an inorganic substance (B), an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm, and a higher fatty acid having 4 to 24 carbon atoms, or one or two selected from metal salts, esters and amides thereof.
It comprises at least one kind of compound (D), but its production method is not particularly limited. A method in which (A), (B), (C) and (D) are collectively mixed to form a blend pellet, (B),
(C) and (D) are mixed by dry blending or the like, and then the mixture is blended with (A) to form a pellet. (B), (C) and (D) are added to a solution of the barrier resin (A). A method in which a solvent is removed after addition and mixing to obtain a pellet or a film, and the like are exemplified as preferable examples.

In particular, after mixing (B), (C) and (D), it is preferable to blend the mixture with the barrier resin (A). (B), (C) and (D)
Is not particularly limited, but a method of dry blending using a known Henschel mixer having a high shear rate is particularly preferable. The method of mixing the thus obtained mixture of (B), (C) and (D) with the barrier resin (A) is optional, but the mixture is dispersed in a solution of the barrier resin (A). And removing the solvent to obtain pellets or a film, or a method of blending the mixture with the barrier resin (A) using a known tumbler, Henschel mixer or the like, and is preferable.
From the viewpoint of productivity and the like, a method of blending the barrier resin (A) and the mixture using a known tumbler, Henschel mixer or the like is particularly preferable. By adopting such a production method, secondary aggregation of the inorganic substance (B) and the inorganic substance (C) can be effectively suppressed, and (B) and (C)
Has good dispersibility in the barrier resin (A).

When a mixture comprising the barrier resins (A) and (B), (C) and (D) is blended using a known tumbler, Henschel mixer or the like, the resulting blend is directly melt-molded. However, once the blend is pelletized using a single-screw extruder or a twin-screw extruder having a kneading unit, the dispersion of (B), (C) and (D) in the barrier resin (A) can be improved. It is particularly preferable from the viewpoint of improving the properties. In the melt compounding operation, there is a possibility that the blend becomes non-uniform, and gels and lumps are generated and mixed.Therefore, in the case of blend pelletization, use an extruder with a high degree of kneading as much as possible, and use a nitrogen gas It is desirable to extrude at a low temperature.

The obtained resin composition of the present invention is formed into various molded products such as films, sheets, containers, pipes and fibers by melt molding. These molded products can be crushed and molded again for the purpose of reuse. It is also possible to uniaxially or biaxially stretch films, sheets, fibers and the like. When stretching, at least 2
It is preferable that the film is stretched twice or more. Examples of the melt molding method include extrusion molding, inflation extrusion, blow molding, melt spinning, and injection molding. The melting temperature varies depending on the melting point of the copolymer and the like, but is preferably about 150 to 270 ° C.

The thickness of the film comprising the resin composition of the present invention is not particularly limited, but is preferably from 5 to 200 μm. If it is less than 5 μm, the mechanical strength of the film may be unsatisfactory, and pinholes and the like may easily occur. The thickness of the film is more preferably 1
It is 0 to 100 μm, particularly preferably 10 to 50 μm. Even with such a film thickness, a film made of the resin composition of the present invention is suitable from the viewpoint of having a sufficient visible light and ultraviolet ray shielding function and gas barrier properties.
The thickness of the resin composition of the present invention is 5 to 200 μm.
In the film of m, it is particularly preferable that the total haze is 60% or more from the viewpoint of sufficiently exhibiting the effect of the present application of a visible light blocking function. The total haze of the film is 7
It is more preferably 0% or more, and further preferably 75% or more. Further, the difference between the total haze and the internal haze of the film is preferably 10% or less,
It is more preferably at most 5%. When the difference between the total haze and the internal haze of the film is 10% or less, a good visible light blocking function can be exhibited even when the film is laminated on a film or sheet made of another thermoplastic resin. It is.

Further, a sheet or film made of the resin composition of the present invention is stretched at least two times in a uniaxial direction,
It is also preferable to use a stretched film. By performing the stretching treatment, it is possible to further improve the gas barrier property while maintaining the function of blocking visible light and ultraviolet light.

As described above, the resin composition of the present invention may be obtained by forming at least one layer of a molded product such as a film or sheet made of the composition of the present invention, in addition to the production of a resin molded product having only the resin composition as a single layer. It is often used practically as a multilayer structure. As the layer constitution of the multilayer structure, the resin composition of the present invention is E, the adhesive resin is Ad, and the thermoplastic resin is T.
The expression includes E / Ad / T, T / Ad / E / Ad / T, but is 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. further,
A recovered resin layer made of scrap such as trim generated at the time of 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 layer to the total thickness is preferably 2 to 20% in consideration of moldability, cost, and the like.

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 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 when the barrier resin (A) used in the resin composition of the present invention is EVOH, an adhesive resin made of a carboxylic acid-modified polyolefin is preferable. 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 55% by weight),
Ethylene-ethyl acrylate copolymer (ethyl acrylate content: 8 to 35% by weight) is preferred, and linear low-density polyethylene and ethylene-vinyl acetate copolymer are particularly preferred. 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 anhydride thereof 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.

By subjecting the thus obtained multilayer structure to secondary processing, various molded products (film, sheet,
Tubes, bottles, etc.), for example, the following. (1) Multi-layer co-stretched sheet or film obtained by stretching a multilayer structure (sheet or film etc.) at least twice in at least one axis direction or stretching in bi-axial direction and heat-treating (2) Multi-layer structure (sheet or film etc.) (3) Multi-layered rolled sheet or film (3) Multi-layer tray cup-shaped container by thermo-forming of multi-layer structure (sheet or film, etc.) by vacuum forming, pressure forming, vacuum pressure forming, etc. (4) Multi-layer Bottles and cup-shaped containers by stretch blow molding from a structure (such as a pipe), etc. There is no particular limitation on such a secondary processing method, and a known secondary processing method (such as blow molding) other than the above can also be employed.

The single-layer structure or the multi-layer structure obtained by molding the resin composition of the present invention has excellent gas barrier properties and excellent shielding properties against visible light and ultraviolet light.
It is suitably used as a container for storing alcoholic beverages, industrial goods that are not susceptible to oxidative deterioration, and the like. The form of the container is not particularly limited, but a cup and its lid material, a bottle, a tube, a paper container and the like are exemplified, and a paper container is particularly preferable.

Conventionally, an aluminum foil has been laminated on a paper container filled with contents that are easily 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.

As the layer constitution of the paper container, T is the thermoplastic resin, E is the resin composition, Ad is the adhesive resin layer, and P is the paper.
Then, T / P / Ad / E / Ad / T, T / P / A
Layer configurations such as d / E / Ad / P / T and T / P / Ad / E / Ad are exemplified. However, it is not limited to appropriately add other layers to these, and is limited to the above example. 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, since the layer made of the resin composition of the present invention is excellent in matting effect and embossability, the multilayer structure including the resin composition layer of the present invention is suitably used as a wallpaper or decorative board.

[0078]

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 JIS K7126 (isobaric method) under conditions of 20 ° C. and 65% RH using TRAN2 / 20. Incidentally, the oxygen permeation amount referred to in the present invention is obtained by measuring the oxygen permeation amount (ml / m 2 · day · atm) measured at an arbitrary film thickness of a film having a single layer by a film thickness of 20 μm.
Value converted to the amount of oxygen permeation (ml · 20 μm / m2 ·
day.atm).

<Haze> Integral formula H. manufactured by Japan Precision Optical Co., Ltd. T. The measurement was performed using an R meter according to JIS D8741. The total haze is a value of a film having a thickness of 20 μm, and the internal haze is a value measured by applying silicone oil to a thickness of about 2 μm on both surfaces of the film having a thickness of 20 μm.

<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 700 nm was determined from the measurement diagram. (Visible Light Transmittance)
And the light transmittance (UV transmittance) at a wavelength of 350 nm was determined.

<Moldability> The resin composition was extruded at 230 ° C. using a single-screw extruder, and the appearance of a 20 μm-thick unstretched film obtained 1 hour after the start of film formation was visually evaluated. The judgment was made based on the standard. Judgment: Standard ◎ (Pass): The surface is smooth and no bumps are observed. ○ (Pass): There are some occurrences of bumps, but there is no practical problem. X (Fail): Many occurrences of bumps are observed, and this is not practical.

Example 1 As a barrier resin (A), an ethylene content of 32 mol% was used.
EVOH having a saponification degree of 99.5 mol%, particle diameter of 0.1 to
Titanium oxide having a particle diameter of 0.25 μm (rutile type, surface treated with alumina; Ishihara Sangyo Co., Ltd., Taipaque CR60) having a particle diameter of 0.01 to 0.5 μm as an inorganic substance (B) of 0.5 μm
Particle size 0.03 μm as 0.06 μm inorganic substance (C)
Titanium oxide (rutile type, after alumina surface treatment,
Organosiloxane treatment: 1 selected from the group consisting of Taipaque TTO-55S, manufactured by Ishihara Sangyo Co., Ltd. and higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof.
Ethylene bisstearic acid amide was used as one or more compounds (D). Particle size 0.2 shown above
10 parts of 5 μm titanium oxide, 1.5 parts of titanium oxide having a particle diameter of 0.03 μm, and 0.2 parts of ethylenebisstearic acid amide were mixed with a Henschel mixer. Subsequently, the resulting mixture was treated with an ethylene content of 32 mol% and a saponification degree of 9
After mixing with 100 parts of 9.5 mol% EVOH by a tumbler, the mixture was pelletized at 230 ° C. using a twin screw extruder.
Using a single screw extruder, the obtained resin composition pellets
Extrusion was performed at 0 ° C. to obtain a 20 μm-thick unstretched film.
The appearance of the obtained film was good with a smooth surface and no bumps. The single-layer film had an oxygen transmission rate of 0.2 ml / 20 μm / m 2 · day · atm, a total haze of 85%, an internal haze of 85%, a visible light transmittance of 3%, and an ultraviolet transmittance of 0%. %was.

On both sides of the resin composition film, a polyethylene film having a thickness of 60 μm (Icelo Chemical Co., Ltd.)
Manufactured by Suzuron Co., Ltd.). The adhesive was laminated at a temperature of 70 ° C. using Takeda Pharmaceutical Co., Ltd., Takelac, A385 / A50 at a solid content of 4 g / m 2, and aged at 40 ° C. for 5 days. The visible light transmittance of the composite film was 5%, and the ultraviolet light transmittance was 0%.

Example 2 A film was prepared in the same manner as in Example 1 except that EVOH having an ethylene content of 27 mol% and a saponification degree of 99.5% was used as the barrier resin (A). evaluated. Table 1 shows the evaluation results.

Example 3 A film was prepared in the same manner as in Example 1 except that EVOH having an ethylene content of 47 mol% and a saponification degree of 99.5% was used as the barrier resin (A), and various physical properties were measured. evaluated. Table 1 shows the evaluation results.

Example 4 Same as Example 1 except that calcium stearate was used as at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof. , And various physical properties were evaluated. Table 1 shows the evaluation results.

Example 5 Example 1 was repeated except that magnesium stearate was used as at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof. Films were prepared in the same manner, and various physical properties were evaluated. Table 1 shows the evaluation results.

Example 6 A film was prepared in the same manner as in Example 1 except that ethylene bisstearic acid amide was not added, and various physical properties were evaluated. Table 1 shows the evaluation results.

Example 7 100 parts by weight of EVOH and 10 parts of titanium oxide having a particle size of 0.25 μm (rutile type, surface treated with alumina; Taipaque CR6, manufactured by Ishihara Sangyo Co., Ltd.) obtained in the same manner as in Example 1.
0), 1.5 parts of titanium oxide having a particle size of 0.03 μm (rutile type, surface treated with alumina, then treated with organosiloxane; Ishihara Sangyo Co., Ltd., Taipaek TTO-55S)
And a resin composition pellet composed of 0.2 parts of ethylenebisstearic acid amide at 230 ° C. using a single screw extruder.
And contacted with a cooling roll having a temperature of 10 ° C. to obtain a 180 μm-thick raw stretched sheet. The surface of the obtained stretched raw material was smooth and free of bumps, and the accuracy of thickness and thinness was good.

Then, using a biaxial stretching device manufactured by Toyo Seiki Co., Ltd., preheating at 80 ° C. for 20 seconds, stretching temperature of 80 ° C., stretching ratio of 9 times (3.0 times long × 3.0 times wide), and stretching. Speed 1m /
In 20 minutes to obtain a stretched film having a thickness of 20 μm. The obtained stretched film was fixed to a wooden frame and heat-treated (heat treatment temperature: 140 ° C., 10 minutes). The oxygen permeation amount of the single-layer film is 0.13 ml · 20 μm / m2 · d
ay ・ atm, total haze 87%, internal haze 87%
The visible light transmittance was 3% and the ultraviolet light transmittance was 0%. The stretching temperature in the present invention refers to a value obtained by measuring the surface temperature of a stretched raw material immediately before stretching after heating the stretched raw material for a predetermined time. Further, 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.

On both sides of the resin composition film, a polyethylene film having a thickness of 60 μm (Icelo Chemical Co., Ltd.)
Manufactured by Suzuron Co., Ltd.). The adhesive was laminated at a temperature of 70 ° C. using Takeda Pharmaceutical Co., Ltd., Takelac, A385 / A50 at a solid content of 4 g / m 2, and aged at 40 ° C. for 5 days. The visible light transmittance of the composite film was 3%, and the ultraviolet light transmittance was 0%.

Example 8 Example 1 was repeated except that MXD-6 (MX Nylon 6007 manufactured by Mitsubishi Gas Chemical) was used as the barrier resin (A).
A film was prepared in the same manner as described above, and various physical properties were evaluated.
Table 1 shows the evaluation results.

Example 9 A film was prepared in the same manner as in Example 1 except that nylon-6 (UBE nylon 1024B, manufactured by Ube Industries, Ltd.) was used as the barrier resin (A), and various physical properties were evaluated. Table 1 shows the evaluation results.

[0095]

[Table 1]

Comparative Examples 1 to 6 Inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, and a particle diameter of 0.1 to 0.5 μm.
01-0.06 μm inorganic substance (C) and 4-2 carbon atoms
Example 1 except that the compounding amount of at least one compound (D) selected from the group consisting of higher fatty acids 4, their metal salts, esters and amides was changed as shown in Table 2.
A film was prepared in the same manner as described above, and various physical properties were evaluated.
Table 2 shows the evaluation results.

Comparative Example 7 A film was prepared in the same manner as in Example 1 except that talc having a particle diameter of 0.9 μm was used instead of titanium oxide (inorganic substance (B)) having a particle diameter of 0.25 μm, and various physical properties were measured. evaluated. Table 2 shows the evaluation results.

[0098]

[Table 2]

Example 10 The gloss of the single-layer film produced in Example 1 was measured using a Murakami gloss meter manufactured by Nippon Denshoku Co., Ltd. according to JIS Z8772.
As a result of measurement according to the method described in (1), a good matting degree of 19% was shown. Using a gravure coater, a urethane adhesive Adcoat AD-335A having a solid content of 20% by weight and a curing agent Cat-10 (Toyo Morton Co., Ltd., mixing ratio 17: 1) were applied to the film at a coating amount of 2 g / m ² ( (Based on solid content) and dried at 70 ° C. for 4 minutes.
A polyvinyl chloride resin wallpaper (PVC wallpaper, polyvinyl chloride resin is a plasticizer (di-2-ethylhexyl phthalate)) on which the thus-obtained adhesive-coated film is coated and flame-retardant paper are laminated. (Containing 55 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin)). For the resin composition layer of the present invention in such a multilayered wallpaper, a laminator manufactured by Tokyo Lamix Co., Ltd. is used to form an emboss roll (emboss size 5 mm × 5 m).
m, depth 0.5mm, temperature 130 ° C) and pressure 1.5k
Embossing was performed under the conditions of g / cm ² and a speed of 1.4 m / min. As a result of observing the embossed surface with an optical microscope (magnification: 50 times), no crack was generated on the film surface and good embossability was exhibited.

Comparative Example 8 The glossiness of the single-layer film produced in Comparative Example 7 was measured using a Murakami gloss meter manufactured by Nippon Denshoku Co., Ltd. according to JIS Z8772.
As a result of measurement according to the method described in, the glossiness was 26%. A multilayer wallpaper was produced and embossed in the same manner as in Example 10 except that this single-layer film was used. As a result of observing the embossed surface with an optical microscope (magnification: 50 times), cracks were observed on the film surface, and the film was not usable.

The resin compositions of Examples 1 to 6 satisfying the constitution of the present invention exhibited excellent performances in all functions of shielding visible light and ultraviolet light, gas barrier properties and moldability. In Example 6, in which at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof was not used, the moldability was slightly reduced and the visible light transmittance was lower. Although the improvement effect was slightly reduced,
It was practical. Moreover, the stretched film made of the resin composition of the present invention maintained an excellent function of shielding visible light and ultraviolet light, and was further improved in gas barrier properties (Example 7).

On the other hand, in the case of Comparative Example 1, which did not contain the inorganic substance (B) and the inorganic substance (C), a sufficient function of shielding visible light and ultraviolet light could not be obtained. In Comparative Example 2 in which the content of the inorganic substance (B) was less than 1 part by weight, a sufficient visible light blocking function was not obtained, and Comparative Example 2 in which the content of the inorganic substance (C) was less than 0.5 part by weight. Did not provide a sufficient ultraviolet blocking function.

In Comparative Example 4 in which the content of at least one compound (D) selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof exceeds 0.5 part by weight, Deteriorated, and a number of bumps were observed in the film. Also, in Comparative Example 5 in which the content of the inorganic substance (B) exceeds 15 parts by weight, and in Comparative Example 6 in which the content of the inorganic substance (C) exceeds 5 parts by weight, the moldability was deteriorated, and many irregularities were observed in the film. Was done.

The particle diameter of the inorganic substance (B) is 0.6 μm
In the case of Comparative Example 7, the difference between the total haze and the internal haze of the film formed from such a resin composition exceeds 30%, and the composite film obtained from the film has a sufficient visible light blocking function. I couldn't.

[0105]

Industrial Applicability The resin composition of the present invention is excellent in the function of shielding visible light and ultraviolet light, gas barrier properties and moldability, and is used for containers of various foods, processed marine products, medicines, cosmetics, etc.
Especially preferably used as paper containers, wallpaper, building materials,
It is suitably used for signboards and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/20 C08J 5/18 CEX 5/18 CEX C08K 3/00 C08K 3/00 5/04 5/04 C08L 23/26 C08L 23/26 29/04 S 29/04 77/06 77/06 B65D 1/00 A B F term (reference) 3E033 AA20 BA13 BA21 BB04 BB08 CA16 4F070 AA13 AA26 AA54 AC15 AC22 AC40 AC43 AC47 AE01 AE09 FA03 FA12 FC02 4F071 AA15 AA15X AA29 AA29X AA55 AF07 AH04 AH05 BA01 BB06 BB07 BB08 BC01 BC07 4F100 AA01A AA21 AK01A AK69A AL05A AT00B DE02A051DEB0102 J051 DJ036 DJ046 EF058 EH038 EH048 EP018 EP028 FB076 FB077 FB096 FB097 FB236 FB237 FD016 FD017 FD178

Claims (14)

[Claims] 1. A barrier resin (A) having a particle size of 0.1 to 1.
0.5 μm inorganic substance (B), particle size 0.01 to 0.06
μm inorganic substance (C) and optional component having 4 to 4 carbon atoms
24 higher fatty acids, one or more compounds selected from metal salts, esters and amides thereof (D), and (B) 1 to 15 parts by weight, C) 0.5 to 5 parts by weight and (D) 0 to 0.5
A resin composition containing parts by weight. 2. The resin composition according to claim 1, wherein the compound (D) is contained in an amount of 0.05 to 0.5 part by weight based on 100 parts by weight of the barrier resin (A). 3. The resin composition 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 according to claim 3, which is an ethylene-vinyl alcohol copolymer having a saponification degree of 90% or more and 60 mol% or less. 5. A container comprising the resin composition according to claim 1. 6. A film or sheet comprising the resin composition according to claim 1. 7. The film according to claim 6, which has a thickness of 5 to 200 μm and a total haze of 60% or more. 8. The film according to claim 7, wherein the difference between the total haze and the internal haze is 10% or less. 9. The film according to claim 6, which is obtained by stretching at least two times in the uniaxial direction. 10. A multilayer structure comprising at least one layer comprising the resin composition according to claim 1. 11. The multilayer structure according to claim 10, which is obtained by stretching at least two times in the uniaxial direction. 12. A paper container comprising the multilayer structure according to claim 10. 13. A wallpaper or decorative board comprising the multilayer structure according to claim 10. 14. An inorganic substance (B) having a particle diameter of 0.1 to 0.5 μm, and an inorganic substance (C) having a particle diameter of 0.01 to 0.06 μm.
And at least one selected from the group consisting of higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof.
The method for producing a resin composition according to any one of claims 2 to 4, wherein the barrier resin (A) is blended after mixing the seed compound (D).