JPH06128433A - Resin composition and structure member - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a saponified ethylene-vinyl ester copolymer, inorganic fine particles, a higher fatty acid, etc., and having excellent gas-barrier properly, ultraviolet-absorbing function and transparency and to provide a structure member having a layer of the resin composition. CONSTITUTION:The resin composition contains (A) 100 pts.wt. of a saponified ethylene-vinyl ester copolymer having an ethylene content of 20-65mol% (preferably 25-50mol%) and a saponification degree of the vinyl ester component of >=90mol% (preferably >=94mol%), (B) 0.01-5 pts.wt. (preferably 0.05-4 pts.wt.) of inorganic fine particles having particle diameter of <=0.1mum (preferably <=0.08mum) (preferably titanium oxide) and optionally surface-treated with silicon oxide, fatty acid, etc., and (C) 0.005-5 pts.wt. (preferably 0.01-4 pts.wt.) of one or more compounds selected from 4-24C higher fatty acid, its metal salt, ester and amide. The structure member contains at least one layer composed of the composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition and a structure having both a gas barrier property and an ultraviolet ray absorbing function.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a structure having both a gas barrier property and an ultraviolet ray shielding function and excellent transparency, a vinylidene chloride copolymer, a vinyl alcohol copolymer, an acrylonitrile copolymer is used as a gas barrier resin. A method is known in which a polymer or the like is used to have a UV blocking function, and a UV absorber such as a benzophenone derivative, a salicylic acid derivative, a benzoic acid derivative, or a benzotriazole derivative is kneaded into a resin, an adhesive, an ink or the like to form a multilayer. However, many organic UV absorbers have a problem that they cannot block UV rays around 250 nm and that the UV absorber itself deteriorates to lower its absorption ability. In addition, the method of kneading these organic UV absorbers into the resin has a problem of migration to the contents. There is also a method of kneading these organic UV absorbers into adhesives and inks, but when processing them, the UV absorbers were kneaded with the adhesives and inks that had been used in the processing equipment until then. Since it was necessary to replace with adhesives or inks, loss of time and adhesives or inks occurred, which was a factor of high cost. On the other hand, it is possible to obtain a structure having both a gas barrier property and an ultraviolet ray blocking function by laminating aluminum foil, but it is opaque and the visibility of the contents is poor.

In Japanese Patent Laid-Open No. 1-253442, 55 to 97% by weight of an ethylene-vinyl alcohol copolymer resin containing 20 to 50 mol% of an ethylene monomer unit and at least one selected from polyamide, polyolefin, polyester and polycarbonate. A gas barrier multilayer package having an intermediate layer of a composition comprising 45 to 3% by weight of a resin is described, and the composition of the intermediate layer includes:
It is described that calcium stearate may be contained as a stabilizer and titanium oxide may be contained as a colorant. However, the titanium oxide of the publication is used as a colorant, has a larger particle size than the titanium oxide of the present invention, and is added for concealment (opacity). Is also different. Moreover, since calcium stearate is also added as a stabilizer, there is no description about the improvement of the ultraviolet blocking property.

JP-A-3-72541 discloses a polyolefin, an ethylene-vinyl acetate copolymer saponified product having an ethylene content of 20 to 65 mol% and a saponification degree of a vinyl acetate component of 96 mol% or more, and titanium oxide. 8 to 22 carbon atoms
Compositions of higher fatty acid metal salts are described. However, the publication relates to eliminating charring, eye blemishes and abnormal flow, and titanium oxide is used for improving the compatibility of polyolefin and EVOH.
There is no description about the fact that titanium oxide having a specific particle size has an ultraviolet blocking property. Moreover, titanium oxide is not included in the listed ultraviolet absorbers.
Furthermore, it is stated that the higher fatty acid metal salt having 8 to 22 carbon atoms is particularly effective in eliminating charring, eye blemishes and abnormal flow when it contains a titanium compound which is a residual catalyst of polyolefin, and has an improved UV blocking property. There is no description about things.

[0005]

As described above, there is still no sufficient method for obtaining a structure having both gas barrier property and ultraviolet blocking function and excellent transparency, and a structure having such characteristics is not available yet. Has been desired for many years.

The present invention was devised in order to solve the above-mentioned drawbacks of the prior art, and an object thereof is to obtain a structure excellent in transparency having both a gas barrier property and an ultraviolet ray blocking function. To do.

[0007]

The above objects are (A) saponified ethylene-vinyl ester copolymer having an ethylene content of 20 to 65 mol% and a saponification degree of a vinyl ester component of 90 mol% or more, and (B) particles. A fine particle inorganic material having a diameter of 0.1 μm or less and (C) one or more kinds selected from higher fatty acids having 4 to 24 carbon atoms, metal salts, esters and amides thereof, and (A) relative to 100 parts by weight. (B)
This is achieved by providing a resin composition containing 0.01 to 5 parts by weight and (C) 0.005 to 5 parts by weight.

The present invention will be described in more detail below. In the present invention, known EVOH can be used, and the production method is exemplified by ethylene and vinyl ester in a solvent such as methanol, t-butanol or dimethyl sulfoxide under pressure, benzoyl peroxide and azobis. Polymerized by a known method using a polymerization initiator such as isobutyronitrile,
Examples thereof include those obtained by saponification with an acid or alkali catalyst. Examples of the fatty acid vinyl ester include vinyl acetate, propionate vinyl ester, versatic acid vinyl ester, pivalic acid vinyl ester and the like. Aromatic carboxylic acid vinyl ester and the like can also be used, but from the viewpoint of price, vinyl acetate ester However, from the viewpoint of gas barrier properties, vinyl pivalate is preferable. The ethylene content of EVOH is 20 to 65 mol%, preferably 25 to 50 mol%, and the degree of saponification of the vinyl ester component is 90 mol% or more, preferably 94 mol% or more. When the ethylene content is less than 20 mol%, the gas barrier property at high humidity is deteriorated, and when it exceeds 65 mol%, sufficient gas barrier property cannot be obtained. On the other hand, when the saponification degree is less than 90 mol%, not only the gas barrier property at high humidity is deteriorated but also the thermal stability of EVOH is deteriorated, and gel is apt to be generated on the obtained film surface.

Further, EVOH contains a smaller amount of propylene, isobutene, 4-methylpentene-1, hexene,
Α-Olefins such as octene, unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof, vinyltrimethoxysilane, etc. The vinylsilane compound, unsaturated sulfonic acid, salt thereof, alkyl thiols, N-vinylpyrrolidone and other copolymerization components may be contained.

EVOH may be a mixture of two or more kinds of EVOH having different ethylene contents, and
It may be a mixture of two or more kinds of EVOH having different degrees of polymerization and saponification. Further, the ethylene content and the degree of polymerization or the degree of saponification may be different.

Furthermore, the EVOH layer may be a multilayer body of two or more kinds of EVOH having different ethylene contents. In such a case, all layers may be the composition of the present invention, or only specific layers may be the composition of the present invention. In the EVOH multilayer body, all layers may be biaxially stretched, only specific layers may be biaxially stretched, or all layers may be unstretched. The surface of the EVOH layer may be cross-linked with various aldehydes such as boric acid and formalin. Further, a metal such as aluminum, aluminum oxide, or silicon oxide and a metal oxide may be vapor-deposited on the surface.

[0012] Further, EVOH includes, in a range that does not impair the present invention, an antioxidant, a colorant, an organic ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a cross-linking agent such as boric acid, an inorganic filler, You may mix | blend various additives, such as an inorganic desiccant, and various resins, such as polyamide, polyolefin, and a superabsorbent resin.

In the present invention, the fine particle inorganic substance (B) includes fine particles of titanium oxide (whether rutile type or anatase type), iron oxide, zinc oxide, talc, kaolin, calcium carbonate, etc. It is preferable to use titanium oxide, which has a large size and is chemically stable. The inorganic fine particles have a particle diameter of 0.1 μm or less, preferably 0.08 μm or less, more preferably 0.06 μm, depending on the type of inorganic substance.
It is important that the size is m or less. Particle size is 0.1μ
If it exceeds m, absorption tends to occur not only in the ultraviolet region but also in the visible region, and moreover, it tends to become opaque. Particle size 0.0
Materials having a particle size of less than 01 μm can be used, but if they are too small, they may be inferior in UV blocking property, and if they are fine particles, it becomes difficult to completely disperse them. In some cases, there may be no great difference in the result from the case where fine particles having a particle size of 001 μm or more are dispersed. Note that the particle size was observed at 50,000 times with a transmission electron microscope, and the size of any 20 particles in the 1 μm square field of view (in the case of secondary aggregation, the primary particles constituting the particle) The average of the measured values of the diameter (diameter when it is needle-shaped or rugby ball-shaped and not spherical).

Such fine particles of inorganic matter can be obtained by pulverizing the inorganic matter with a mill or the like. With titanium oxide, titanium tetrachloride is hydrolyzed in a gas phase in oxygen / hydrogen flame, and alkoxide of titanium is atomized. Then, a method of hydrolyzing in an oxygen-containing flame, a method of hydrolyzing titanyl sulfate, and calcining the obtained titanium hydroxide can be mentioned. In the case of iron oxide, there is a method of heating hydrous iron oxide to remove the water of crystallization, a method of mixing iron oxide and barium carbonate / calcination method or coprecipitation / salt catalyst method to obtain barium ferrite, and then removing barium from it. To be With zinc oxide, heat decomposition of basic zinc carbonate, zinc oxalate, zinc hydroxide, etc.,
Examples include a method of calcining at a dehydration temperature. The manufacturing method is not important, but the particle size described above is important. The surface of these inorganic fine particles may be surface-treated with aluminum oxide, organic siloxane, silicon oxide, fatty acid, or the like.

In the present invention, the addition amount of the fine particle inorganic material (B) having a particle diameter of 0.1 μm or less is EVOH (A) 100.
The amount of (B) is 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, and more preferably 0.1 to 4 parts by weight with respect to parts by weight. If the addition amount of (B) is less than 0.01 parts by weight, the ultraviolet ray blocking property is poor, and if the addition amount exceeds 5 parts by weight, the ultraviolet ray blocking property is the same, but seeds are generated due to poor dispersion or even in the visible region. Absorption appears and tends to be opaque.

The number of carbon atoms used in the present invention is 4 to 2.
4 higher fatty acids, their metal salts, esters, amides (C)
In the above, the higher fatty acid having 4 to 24 carbon atoms is a saturated or unsaturated fatty acid having 4 to 24 carbon atoms having a straight chain or a branch, butyric acid, isobutyric acid, pentanoic 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 number of carbon atoms is less than 4, the fine particle inorganic material (B) is poorly dispersed in the EVOH (A) and is likely to cause lumps. When the carbon number exceeds 24, the dispersion of (C) itself into EVOH (A) becomes poor. 4 to 4 carbon atoms
In the case of 24, E of fine particle inorganic substances (B) and (C) itself
Not only does the dispersion in VOH (A) become good and the spots are less likely to occur, but also the ultraviolet blocking property becomes good even if the addition amount of (B) is the same.

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

The ester of higher fatty acid having 4 to 24 carbon atoms is an ester of the higher fatty acid and a compound having a hydroxyl group, and examples of the compound having a hydroxyl group include methanol, ethanol, ethylene glycol, n-propyl alcohol and isopropyl. Alcohol, propylene glycol,
Examples 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 above-mentioned higher fatty acid and a compound having an amino group, and the compound having an amino group is ammonia,
Methylamine, ethylamine, ethylenediamine, methylolamine, n-butylamine, isobutylamine,
Examples include amines such as octylamine, ethylhexylamine, laurylamine, oleylamine and stearylamine.

In the present invention, as (C), the higher fatty acids exemplified above, and the metal salts of the higher fatty acids,
It is possible to use one kind or a mixture of two or more kinds selected from ester and amide.

In the present invention, the addition amount of (C) is EV
0.005 to 5 parts by weight with respect to 100 parts by weight of OH (A),
Preferably 0.01 to 4 parts by weight, more preferably 0.1.
It is from 03 to 3 parts by weight. If the amount is less than 0.005 part by weight, the fine particle inorganic material (B) is poorly dispersed in the EVOH (A), and seeds are easily generated. On the other hand, even if it exceeds 5 parts by weight, there is no change in the dispersibility of the fine particle inorganic material (B) in the EVOH (A),
(C) Porosity may occur due to poor dispersion of itself.

In the present invention, it is important to use (B) and (C) in combination, and by using them in combination, the ultraviolet blocking property is remarkably improved. This is described in Example 1 below.
It is also clear that {combined use of (B) and (C)} is significantly superior to Comparative Example 1 {using only (C)} and Comparative Example 2 {using only (B)}.

The method of blending the resin composition comprising (A), (B) and (C) and the order of blending are not particularly limited, and known methods can be employed. For example, a mixture of EVOH (whether in the form of powder, pellets, flakes, etc.), fine-particle inorganic substances, higher fatty acids or their derivatives (metal salts, esters, amides) is used with a single-screw extruder or a twin-screw extruder. A method of pelletizing and filming (a dry blending step may be performed first). A method of pelletizing and film-forming a mixture of EVOH, fine particle inorganic matter, higher fatty acid or its derivative using a single-screw extruder or a twin-screw extruder equipped with a screw having a kneading part (a dry blending step may be performed first) . EVOH,
A method of kneading a mixture of a fine particle inorganic substance, a higher fatty acid or a derivative thereof with a mixer under melting (first may be a dry blending step), and then pelletizing and filming using a single screw extruder or a twin screw extruder ( A screw with a kneading part may be attached). Further, a mixture of fine particle inorganic matter, higher fatty acid or its derivative is
A method of kneading in VOH by the above method. A method of obtaining pellets or a film by dispersing a mixture of a fine particle inorganic substance and a higher fatty acid or a derivative thereof in a solution of EVOH (a known solvent, for example, a mixed solvent of water and n-propyl alcohol) and then removing the solvent. After dispersing the fine particle inorganic substance in water or alcohol or a mixed solvent of water and alcohol, E
Examples include a method of dissolving a mixture of VOH and a higher fatty acid or a derivative thereof, and then removing a solvent to obtain a pellet or a film. Methanol as alcohol,
Ethanol, ethylene glycol, propylene glycol, glycerin, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, octanol,
Examples thereof include ethylhexyl alcohol.

In the present invention, the structure having a layer made of the resin composition may be a single layer structure of the resin layer,
A multilayer structure including at least one resin layer may be used. In the case of a multilayer structure, there is no particular limitation on the arrangement of EVOH layers.
Examples of the form include a film, a sheet, a bag, a lid, a tray, a cup, a bottle and a tube.

In the present invention, examples of the laminated thermoplastic resin (D) used for forming the multilayer structure include those for imparting strength and / or heat sealability to the structure, and are representative. Specific examples thereof include polyethylene, polypropylene, polystyrene, polyester, polyamide, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polycarbonate. They may be used alone or two or more kinds of plastics may be used in multiple layers. Good, or may be used by blending. In addition, various additives such as an antioxidant, a colorant, an ultraviolet absorber, a slip agent, an antistatic agent, a plasticizer, a cross-linking agent, an inorganic filler, and an inorganic desiccant are added to these plastics within a range that does not impair the present invention. You may mix | blend various resins, such as an agent and a thermoplastic resin.

As the polyethylene used for the thermoplastic resin (D) layer, high density polyethylene which is a homopolymer of ethylene, medium density polyethylene, low density polyethylene, and propylene containing ethylene as a main component,
Butene-1,4-methylpentene-1,1-hexene,
1-octene, 5-ethylidene-2-norbornene, 5
-Methylene-2-norbornene, styrene, vinyl acetate, butyl acetate, methyl acrylate, ethyl acrylate, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, copolymers with glycidyl methacrylate and the like can be mentioned. The copolymer with acrylic acid or methacrylic acid among the copolymers may be cross-linked with sodium, zinc, aluminum or the like, and the copolymer with vinyl acetate is a part of the vinyl acetate component or All may be saponified. The polyethylene may be graft-modified with a carboxylic acid such as maleic anhydride.

The polypropylene used in the thermoplastic resin (D) layer includes homopolymers of propylene and ethylene, butene-1, pentene-1, 4-methylpentene-1, and hexene-1 containing propylene as a main component. ,
Octene-1,5-ethylidene-2-norbornene, 5
-Methylene-2-norbornene, 1,4-hexadiene, copolymers with styrene and the like, and those graft-modified with a carboxylic acid such as maleic anhydride.

Further, as polystyrene used in the thermoplastic resin (D) layer, homopolymer of styrene and α-methylstyrene, vinyltoluene, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylic acid containing styrene as a main component. Examples thereof include copolymers with ronitrile and butadiene.

Further, as the polyester used in the thermoplastic resin (D) layer, ethylene glycol, diethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2 , 2
-Bis (4-hydroxyphenyl) propane, 1,1-
Polyhydric alcohol components such as bis (4-hydroxyphenyl) cyclohexane, glycerin, trimethylolpropane and pentaerythritol, hydroxycarboxylic acid components such as parahydroxybenzoic acid, δ-valerolactone, ε-caprolactone and tartaric acid, and terephthalic acid Polyesters obtained from polycarboxylic acids such as isophthalic acid, 2,6-naphthalene dicarboxylic acid, azelaic acid, sebacic acid, pimelic acid, adipic acid, glutaric acid, succinic acid and trimellitic acid, and their ester components as raw materials Is mentioned.

Further, as the polyamide used in the thermoplastic resin (D) layer, hexamethylenediamine, piperazine, tetramethylenediamine, ethylenediamine, metaxylylenediamine, 3,3'-dimethyl-
A diamine component such as 4,4′-diaminodicyclohexylmethane, δ-valerolactam, ε-caprolactam,
Aminocarboxylic acid components such as ω-laurolactam, ω-aminoundecanoic acid and ω-aminododecanoic acid, and 2,6-
Examples thereof include polyamides obtained from polyvalent carboxylic acid components such as naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, azelaic acid, sebacic acid, pimelic acid, adipic acid, glutaric acid and succinic acid as raw materials.

As the polyacrylonitrile used in the thermoplastic resin (D) layer, nitriles such as acrylonitrile, methacrylonitrile, fumaronitrile and maleonitrile are the main components, and styrene, methylstyrene, ethylstyrene, divinylbenzene, halogen-substituted styrene are used. , Sulfonic acid-substituted styrene, methacrylic sulfonic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, methacrylic acid,
Acrylic acid, methyl fumarate, methyl itaconate, methyl maleate, ethyl fumarate, ethyl itaconate, ethyl maleate, fumaric acid, itaconic acid, maleic acid, etc. as a hard phase copolymer, butadiene, styrene , Acrylonitrile, ethylene, isoprene, divinylbenzene, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, 1,3-
Examples thereof include a copolymer such as butylene glycol dimethacrylate in an elastic phase.

Further, as the polyvinyl chloride used in the thermoplastic resin (D) layer, a homopolymer of vinyl chloride and vinyl chloride as main components, vinyl acetate, ethylene, propylene, alkyl vinyl ester, alkyl vinyl ether, acryl Examples thereof include copolymers of acid and its ester, maleic acid and its ester, and the like.

Further, as the polyvinylidene chloride used in the thermoplastic resin (D) layer, a vinylidene chloride homopolymer and a copolymer containing vinylidene chloride as a main component and containing vinyl chloride, acrylonitrile, methyl acrylate, ethyl acrylate, etc. Is mentioned.

Typical examples of the polycarbonate used in the thermoplastic resin (D) layer include carbonic acid esters obtained from bisphenol A and carbonyl chloride or diphenyl carbonate.

The layer structure of the thus obtained multilayer structure is as follows: D layer / resin composition layer of the present invention, D layer / resin composition layer of the present invention / D layer, D layer / of the present invention Examples include resin composition layer / D layer / resin composition layer of the present invention, D layer / resin composition layer of the present invention / D layer / resin composition layer of the present invention / D layer, and the like. An adhesive resin layer or an adhesive layer may be provided between these layers as needed.

The structure obtained by using the resin composition of the present invention is excellent in ultraviolet ray blocking property and gas barrier property, and is fruit juice drink such as tomato juice and orange juice, alcoholic drink such as sake and beer, and tomato. Seasonings such as ketchup, soy sauce, mayonnaise, miso, edible oil, instant noodles, kiribushi,
Oily foods such as cherry prawns, potato chips, peanuts, hams, sausages, cherry rice balls, tsukudani, cod roe, Japanese mackerel, and other processed foods, such as green tea and pickled pickles, and other foods that are susceptible to light degradation. Medicines, cosmetics, hydrangea, pudding,
Jelly, sweets such as honey beans, mainspring, pickles such as warabi, sawan, rapeseed, processed foods such as sausage and kamaboko, corn soup, meat sauce, rice cooked with meat, potatoes and other side dishes are susceptible to oxidative deterioration It can be suitably applied to foods. Further, since the structure comprising a single layer of the resin composition of the present invention is excellent in transparency, it can be applied in a single layer or by laminating a transparent D layer on the structure (field such as container) where transparency is required. Can also be applied to.

It is also possible to laminate with an opaque single-layer body or a multi-layer body including an aluminum foil, a colored film or sheet, a steel plate, a plywood and the like. When laminated on these opaque single-layered or multi-layered products, the surface is often printed, and is used for visibility of printing and prevention of discoloration of printing, wallpaper, Building materials, signboards, birds and beast damage prevention tools (dove threat), etc. are exemplified.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. All parts and% are based on weight unless otherwise specified.

[0039]

【Example】

Example 1 100 parts of EVOH having an ethylene content of 47 mol%, a saponification degree of a vinyl ester component of 99.5 mol%, and a particle diameter of 0.0
1 part of particulate titanium oxide of 2 to 0.05 μm (rutile type,
Alumina surface treatment) and 2 parts of ethylenebisstearic acid amide were pelletized at 210 ° C. using a twin-screw extruder having a kneading section, and then extruded at 210 ° C. using a single-screw extruder to obtain a film having a thickness of 30 μm. . The obtained film was transparent and had a good appearance.

Biaxially oriented polypropylene with a thickness of 20 μm {“Tocello OP U- manufactured by Tokyo Cellophane Paper Co., Ltd.
1 "} on the corona-treated surface of a two-component curing adhesive {Takeda Pharmaceutical Co., Ltd." A-385 / A-50 "} at a solid content of 3 g / m ↑ 2, and the solvent at 70 ° C. After evaporation, the EVOH film was laminated to obtain a composite film.

The ultraviolet transmittance of the composite film is 25.
The barrier property is 2% at 0 nm, which is good, and 20 ° C, 6
The amount of oxygen permeation at 5% RH is also 2 ml / m ↑ 2 ・ day ・ a
It was excellent at tm. The EVOH layer was placed inside and heat-sealed to obtain a multilayer bag having a good appearance.

Comparative Example 1 A composite film was obtained under the same conditions as in Example 1 except that the fine titanium oxide particles having a particle diameter of 0.02 to 0.05 μm were not added. 2 of the composite film
Oxygen permeation rate at 0 ° C and 65% RH is 2ml / m ↑ 2 ・ d
It was excellent at ay atm, but the UV transmittance was 250.
The blocking property was 85% in nm, which was poor.

Comparative Example 2 A composite film was obtained under the same conditions as in Example 1 except that ethylene bisstearic acid amide was not added. 20 ° C, 65% RH of the composite film
The oxygen transmission rate at 2 ml / m ↑ 2 ・ day ・ atm was excellent, but the UV transmission was 23 at 250 nm.
%, The barrier property was poor, and the film had a lot of spots and had a poor appearance.

Comparative Example 3 A composite was prepared under the same conditions as in Example 1 except that the fine titanium oxide particles having a particle diameter of 0.02 to 0.05 μm were replaced with titanium oxide particles having a particle diameter of 0.2 to 1 μm. I got a film. The oxygen permeation amount of the composite film at 20 ° C. and 65% RH was excellent at 2 ml / m 2 · day · atm, but the film was white and opaque. Example 2

50 parts of EVOH having an ethylene content of 44 mol% and a saponification degree of the vinyl ester component of 99.5 mol%, ethylene content of 32 mol%, 50 parts of EVOH having a saponification degree of the vinyl ester component of 99.5 mol% or more, and a particle diameter. 0.0
1 part of particulate titanium oxide of 2 to 0.05 μm (rutile type,
Alumina / organosiloxane surface treatment) and 1 part of ethylenebisstearic acid amide were pelletized at 220 ° C. using a twin-screw extruder having a kneading part.

Polypropylene homopolymer {MA-8 manufactured by Mitsubishi Yuka Co., Ltd.} 40% by weight, block copolymer of polypropylene {8100J manufactured by Mitsubishi Kasei Co., Ltd.} 45% by weight, and low-density polyethylene {Mitsubishi Yuka Co., Ltd. ) H
E-30} 15% by weight of composition layer as both outer layers, and adhesive polypropylene {ADMER manufactured by Mitsui Petrochemical Industry Co., Ltd.
QF550} as both intermediate layers and the EVOH composition as the central layer, each thickness 470 μm / 20 μm / 20 μm
/ 20 μm / 470 μm 3 type 5 layer coextrusion sheet 2
The film was formed at 40 ° C.

The ultraviolet transmittance of the composite sheet is 250.
The blocking property is 3% at 3 nm, which is good at 20 ° C and 65%.
The oxygen transmission rate at% RH is also 0.5 ml / m ↑ 2 ・ day ・
It was excellent with atm. When the sheet was thermoformed at 150 ° C., a round cup having an excellent appearance with a drawing ratio of 0.4 was obtained.

Example 3 In Example 2, ethylene bisstearic acid amide 1
The same as Example 2 except that the parts were changed to 2 parts of magnesium stearate and the fine titanium oxide particles having a particle diameter of 0.02 to 0.05 μm were changed to fine iron oxide particles having a particle diameter of 0.04 to 0.06 μm. A composite film was obtained under the conditions. The oxygen permeation amount of the composite film at 20 ° C. and 65% RH was excellent at 0.6 ml / m ↑ 2 · day · atm, and the ultraviolet transmissivity was 4% at 250 nm, which was a good barrier property. A sheet having a good appearance and no scratches was obtained. When the sheet was thermoformed at 150 ° C., a round cup having an excellent appearance with a drawing ratio of 0.4 was obtained.

Example 4 100 parts of EVOH having an ethylene content of 32 mol%, a saponification degree of a vinyl ester component of 99.5 mol%, and a particle size of 0.0
2 parts of fine titanium oxide of 2 to 0.05 μm (rutile type,
Alumina surface treatment) and 0.3 part of calcium stearate were dissolved and dispersed in a mixed solvent of n-propyl alcohol: water = 65: 35, and then the solvent was evaporated on a drum at 80 ° C. to obtain a 15 μm film. . The obtained film was transparent and had a good appearance.

Two-component curing type adhesive on the corona-treated surface of a biaxially stretched polyester having a thickness of 16 μm (“DIAFOIL H 500” manufactured by DIAFOIL Co., Ltd.) {Takeda Pharmaceutical Co., Ltd.
Manufactured "A-385 / A-50"} as solid content 3 g / m
↑ Apply 2 and evaporate the solvent at 70 ℃.
A μm biaxially stretched nylon {“Bonil W” manufactured by Kojin Co., Ltd.) was attached, the adhesive was further applied, and after evaporation, the EVOH film was attached to obtain a composite film.

The ultraviolet transmittance of the composite film is 32.
It has a good blocking property of 1% at 0 nm, and is at 20 ° C, 6
Oxygen permeation rate at 5% RH is also 0.4ml / m ↑ 2 ・ day
・ Atm was excellent. The EVOH layer was placed inside and heat-sealed to obtain a multilayer bag having a good appearance.

Example 5 A composite film was obtained under the same conditions as in Example 1 except that EVOH having an ethylene content of 32 mol% and a saponification degree of the vinyl ester component of 99.5 mol% was used. . On the EVOH surface of the obtained composite film, a two-component curing type adhesive {“A-385 / A- manufactured by Takeda Pharmaceutical Co., Ltd.”
50 "} as a solid content at 3 g / m ↑ 2 and after evaporating the solvent at 70 ° C, the corona-treated surface of an unstretched polyethylene film {" Sironlon L S201 "by Aicero Chemical Co., Ltd.} is attached, Heat sealing was performed with the polyethylene film inside, and a 10 cm × 10 cm multilayer bag with a good appearance was obtained.

The inside of the multi-layer bag was replaced with nitrogen and dried cherry shrimp 5 g
Was packaged and stored at 20 ° C. and 65% RH for one month at the window, and the preserved state of dried cherry shrimp was good.

Comparative Example 4 A storage test was conducted in the same manner as in Example 5 except that fine particle titanium oxide and ethylenebisstearic acid amide were not added. As for the storage condition for one month, the dried cherry shrimp faded and the commercial value was lost.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

Industrial Applicability As described above, the structure obtained by using the resin composition of the present invention has a good appearance, excellent gas barrier properties and ultraviolet blocking properties, and is a fruit juice drink, alcoholic drink, seasoning. , Oily foods, livestock / seafood products, luxury items,
Confectionery, pickles, side dishes, medicines, cosmetics, wallpaper, building materials,
It can be suitably applied to signboards and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C08K 5/10 KEQ 7242-4J 5/20 KEW 7242-4J C08L 29/04 LGM 6904-4J LGP 6904 -4J LGQ 6904-4J

Claims (2)

[Claims] 1. A saponified ethylene-vinyl ester copolymer having (A) an ethylene content of 20 to 65 mol%, a saponification degree of a vinyl ester component of 90 mol% or more, and (B) a fine particle inorganic substance having a particle diameter of 0.1 μm or less. And (C) carbon number 4
To 24 higher fatty acids, one or more selected from metal salts, esters and amides thereof, and 0.01 to 5 parts by weight of (B) and 0 of (C) per 100 parts by weight of (A). A resin composition containing 0.005 to 5 parts by weight. 2. A structure having a layer made of the resin composition according to claim 1.