JP2005054195A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in barrier properties, mechanical strengths, flexibility, stretchability, melt stability, scrap recoverability, thermal adhesiveness, coatability, stain resistance, transparency and the like, comprises an ethylene-vinyl alcohol copolymer and a thermoplastic resin whose solubility parameter (calculated from Fedors' equation) is not more than 11, and is good in compatibility. <P>SOLUTION: The resin composition comprises (A) an ethylene-vinyl alcohol copolymer, (B) a polyamide resin, (C) an ethylene-unsaturated carboxylic acid random copolymer or its metal salt, and (D) another thermoplastic resin. The compounding weight ratios satisfy the following formulae (1)-(4): (1): 0.6≤(A+D)/(T)≤0.995; (2): 0.005≤(B+C)/(T)≤0.4; (3): 0.01≤(A)/(A+D)≤0.99 and (4): 0.02≤(B)/(B+C)≤0.98. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is an ethylene-vinyl alcohol copolymer having excellent barrier properties, mechanical strength, flexibility, stretchability, melt stability, scrap recoverability, thermal adhesiveness, paintability, stain resistance, transparency and the like ( A), a polyamide resin (B), an ethylene-unsaturated carboxylic acid random copolymer or a metal salt thereof (C), and a thermoplastic resin other than the above resin having a solubility parameter of 11 or less (calculated from the Fedors equation) ( D) and a resin composition having good compatibility.

  Hydrophobic thermoplastic resins such as polyolefin and polystyrene are used for non-food products such as films, bottles and cups in the food packaging field because of their excellent melt moldability, secondary processability, mechanical properties and economy. In the field, it is widely used for daily necessities, home appliance parts, automobile parts and the like. A multilayer structure of these resins and an ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) is widely used in the food field where barrier properties against oxygen, flavor and the like are required.

  Thus, by laminating the hydrophobic thermoplastic resin and EVOH, it is possible to take advantage of the characteristics of both, but a method of blending and using both is also widely used. However, EVOH is a highly hydrophilic resin, which has a problem in compatibility when blended with a hydrophobic thermoplastic resin, and has a problem that a resin composition having good physical properties cannot be obtained. So far, various compatibilizers represented by polyolefin resins having polar functional groups have been studied, but the effect is not always sufficient, and high-performance compatibilizers that can be compatible with each other well. Development is desired.

  The method of laminating EVOH with a hydrophobic thermoplastic resin such as polyolefin or polystyrene is useful, but when the shape of the molded product is complex or the molded product is small, it is difficult to mold both layers Therefore, development of a thermoplastic single-layer barrier material having barrier properties is desired. As an example of a single-layer barrier material having a barrier property, three components of polyolefin, EVOH having a melting point of 135 ° C. or higher, and EVOH having a melting point of 130 ° C. or lower are used for the mouth of a two-piece tube-shaped container having a mouth and a cylindrical body. A method of using a resin composition comprising: is known (for example, see Patent Document 1). However, the oral head obtained by this method does not necessarily satisfy the required performance such as barrier properties, mechanical strength, and adhesive strength between the oral head and the cylindrical body.

  In addition, hydrophobic thermoplastic resins such as polyolefin and polystyrene have various drawbacks because they are hydrophobic. For example, when obtaining a coated molded product, the surface of the molded product is non-polar, so the adhesion (adhesion) with the paint vehicle is poor, and generally it is necessary to maintain adhesion by performing a primer treatment. There is a disadvantage that the coating cost is high. Furthermore, in recent years, from the viewpoint of global environmental problems, paints have also been moving from organic solvent-based paints to water-based paints, but in the case of water-based paints, the adhesiveness with hydrophobic thermoplastic resins is further low, Development of a thermoplastic resin with improved adhesion is further desired.

  On the other hand, EVOH has been recognized for its effectiveness in films for food packaging and the like, particularly in the food field where barrier properties against oxygen, odor, flavor and the like are necessary. However, since EVOH itself lacks toughness, there are almost no cases where EVOH is used alone. For example, the EVOH film has a drawback that pinholes are easily generated when subjected to deformation such as repeated bending.

  As a method for improving the flexibility, which is a drawback of EVOH, EVOH is often used as a multilayer structure by laminating thermoplastic resin layers such as polyethylene, polypropylene, and polyamide and various adhesive resin layers. . However, as described above, when the shape of the molded product is complicated or the molded product is small, it is difficult to produce a multilayer structure of a thermoplastic resin and EVOH, so it is used in a single layer structure. You may have to do that. Even when used as a multilayer structure, the EVOH resin layer is insufficiently flexible, so that the performance as a whole becomes insufficient, and the use may be limited. Therefore, development of a resin composition having flexibility while maintaining the barrier property of EVOH is desired.

  In order to improve these drawbacks, many methods have been reported so far for blending ethylene-based polymers having excellent flexibility with EVOH. In many cases, however, the effect of improving flexibility and stretchability has been reported. The current situation is that it has not been widely adopted because it is insufficient or the transparency of EVOH is greatly impaired. Therefore, development of a resin composition excellent in flexibility, stretchability and transparency is desired.

  In addition, EVOH is excellent in chemical resistance, oil resistance, stain resistance, and plasticizer shielding. Therefore, it is widely used to laminate EVOH film on the surface of various interior materials such as wallpaper, decorative plywood and PVC leather. It has been broken. However, EVOH film has a high glossiness, and in applications such as wallpaper and leather that require matting, matte rolls are thermocompression bonded and matted, but in cases where sufficient pressure is not applied, There is a problem that the gloss cannot be sufficiently erased. In general, as a method for delustering the film, in addition to the above-described mat roll, (1) sand blasting method, (2) surface treatment method with chemicals, (3) method of blending powdered inorganic substances, etc. ing. However, these methods have disadvantages such as high cost and poor productivity and film forming property. In particular, in the method of blending the powdered inorganic substance (3), in the case of EVOH, if the powdered inorganic substance is blended in such a large amount that a sufficient matting effect can be obtained, the film has a hole and cannot be formed.

  As a method for solving this problem, a matte film comprising EVOH 95 to 50% by weight and carboxylic acid-modified polyethylene resin 5 to 50% by weight and having a surface glossiness of at least 60% or less is known (for example, patents). Reference 2). However, this configuration is still insufficient in terms of the thermal stability of the blend resin composition.

  When a multilayer container (bottle, cup, etc.) made of a thermoplastic resin and an EVOH resin is produced, scrap (bottle burrs, cup punching waste) is generated in the production process. As a method for collecting and utilizing such scrap, a method is generally employed in which a scrap collecting layer is interposed between a thermoplastic resin layer and an EVOH layer. However, when the scrap recovery layer containing the thermoplastic resin and the EVOH resin is melt-extruded, a flow abnormality that is considered to be caused by poor compatibility of the EVOH and the thermoplastic resin in the recovery layer or thermal degradation of the EVOH occurs. Wave patterns may occur in the multilayer sheet including the scrap collection layer and the thermoformed product thereof. In order to solve this problem, an ethylene content of 68 to 98 is used as a compatibilizing agent for blending EVOH having a ethylene content of 20 to 65 mol% and a vinyl acetate component having a saponification degree of 96% or more and a thermoplastic resin. A method of blending EVOH having a mol% and a vinyl acetate component having a saponification degree of 20% or more has been proposed (for example, see Patent Document 3). However, there is no improvement effect that completely eliminates the wave pattern generated in the multilayer sheet and its molded product, and development of a higher performance compatibilizer is desired.

  By the way, the graft polymer 0.1 obtained by graft-reacting 50 to 99.5% by weight of polyolefin, 0.4 to 50% by weight of EVOH, and ethylenically unsaturated carboxylic acid or its derivative to polyolefin and further melt-mixing with polyamide. A polyolefin resin composition having a gas barrier property of ˜15% by weight is known (see, for example, Patent Document 4). Further, comprising 0.4 to 50% by weight of polyolefin, 50 to 99.5% by weight of EVOH, and 0.1 to 15% by weight of the graft polymer, water resistance, gas barrier property under high humidity atmosphere, stretchability and flexibility. EVOH-based resin compositions excellent in the above are known (for example, see Patent Document 5). However, the modified polyolefin that is melt-mixed with the polyamide is obtained by grafting an unsaturated carboxylic acid or derivative thereof to the polyolefin, and is not a random copolymer as in the present invention. As shown in the comparative examples described later, the use of the graft copolymer cannot achieve the object of the present invention.

  A thermoplastic resin composition comprising 50 to 85 parts by weight of EVOH, 10 to 40 parts by weight of an ionomer of an ethylene-unsaturated carboxylic acid copolymer having an unsaturated carboxylic acid content of 4 to 15 mol%, and 1 to 25 parts by weight of polyamide. However, it is known that it is excellent in gas barrier properties, impact resistance, pinhole resistance, stretchability, drawability, and transparency (see, for example, Patent Document 6). Moreover, the resin composition which mix | blended 0.01-3 weight part of fatty acid metal salt with respect to 100 weight part of said resin compositions, and improved thermal stability is also well-known (for example, refer patent document 7). However, in this resin composition, as shown in Comparative Examples described later, the effect of improving the flexibility, particularly the bending resistance, as a resin composition containing EVOH as a main component is still insufficient. Further, there is no description about further blending a specific hydrophobic thermoplastic resin with the resin composition comprising these three components.

  Thermoplastic polymer having a carbonyl group in at least one main chain or side chain selected from the group consisting of 30 to 98 parts by weight of low density polyethylene, 2 to 70 parts by weight of EVOH, and ionomer or polyamide 0.5 to 15 A resin composition excellent in processability and gas barrier properties composed of parts by weight is known (see, for example, Patent Document 8). Although there is a description in the patent document that both polyamide and ionomer can be blended, it is not described at all that it is preferable to blend them at the same time and the effects obtained in that way. Also, there is no description about the blending ratio of polyamide and ionomer. It should be noted that the effects of the present invention cannot be achieved when either polyamide or ionomer is missing, as shown in the comparative examples described later.

JP 6-80150 A JP-A 64-74252 JP-A-3-215032 Japanese Patent Laid-Open No. 4-164941 JP-A-4-164944 JP-A-8-217934 Japanese Patent Laid-Open No. 9-77945 Japanese Patent Publication No. 51-41657

  From the background described above, the object of the present invention is to provide a resin having excellent compatibility such as barrier properties, mechanical strength, flexibility, stretchability, melt stability, thermal adhesiveness, paintability, stain resistance, and transparency. An object of the present invention is to provide a resin composition that is excellent in scrap recoverability without generation of wave patterns in a multilayer structure of a thermoplastic resin and EVOH. The barrier property referred to in the present invention is not limited to the barrier property against gas such as oxygen, nitrogen, carbon dioxide gas, that is, the gas barrier property, and is not limited to fragrance components (for example, limonene, etc.), odor components ( For example, it includes non-adsorbability and non-permeability to hydrocarbons such as skatole) or gasoline.

  The above-mentioned purpose is that ethylene-vinyl alcohol copolymer (A), polyamide resin (B), ethylene-unsaturated carboxylic acid random copolymer or metal salt thereof (C), and a solubility parameter of 11 or less (from Fedors' formula) It is achieved by providing a resin composition having a blending weight ratio satisfying the following formulas (1) to (4). 0.6 ≦ W (A + D) / W (T) ≦ 0.995 (1) 0.005 ≦ W (B + C) / W (T) ≦ 0.4 (2) 0.01 ≦ W (A) / W (A + D) ≦ 0.99 (3) 0.02 ≦ W (B) / W (B + C) ≦ 0.98 (4) (W (A); weight of (A) in composition W (B ); Weight (B) of (B) in the composition; weight W (D) of (C) in the composition; weight W (T) of (D) in the composition; total weight of the composition)

  At this time, the total weight of the resin composition includes 0.01 to 3 parts by weight of at least one selected from a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound, or a blending weight ratio W (B ) / W (B + C) is preferably 0.5 or less.

Here, it is preferable that the thermoplastic resin (D) is a matrix phase and the ethylene-vinyl alcohol copolymer (A) is a dispersed phase, or the ethylene-vinyl alcohol copolymer (A) is a matrix phase and a thermoplastic. In some cases, it is preferable that the resin (D) becomes a dispersed phase. In the latter case, the elastic modulus at 20 ° C. of the thermoplastic resin (D) is preferably 500 kg / cm ² or less.

  As a preferred method for producing such a resin composition, a polyamide resin (B) and an ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof are first melt-mixed, and then an ethylene-vinyl alcohol copolymer ( Examples thereof include a method for producing a resin composition that is melt-mixed with A) and the thermoplastic resin (D).

  Preferred embodiments using the resin composition of the present invention include a multilayer structure comprising at least one layer composed of the resin composition, a molded product in which a coating is applied to the mouth and the surface of a tubular container, thermoforming Examples thereof include a container, a flexible film, and a matte film having a surface glossiness of 60% or less on at least one side.

  Furthermore, using a polyamide resin (B) and an ethylene-unsaturated carboxylic acid random copolymer or a metal salt thereof (C) as a compatibilizing agent, an ethylene-vinyl alcohol copolymer (A) and a solubility parameter of 11 or less A scrap recovery method for recovering a scrap of a molded product mainly composed of a thermoplastic resin (D) other than the above resin (calculated from the Fedors equation) is also a useful embodiment of the present invention. At this time, a scrap recovery method in which the compatibilizer contains at least one of a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound is suitable. A multilayer structure including at least one scrap recovery layer made of the resin composition obtained by the recovery method is also a preferred embodiment.

  According to the present invention, ethylene-vinyl alcohol copolymer (A), polyamide resin (B), ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof having excellent compatibility, and a solubility parameter of 11 or less There is provided a resin composition comprising a thermoplastic resin (D) other than the resin having (calculated from the Fedors equation). Such a resin composition has excellent barrier properties, mechanical strength, flexibility, stretchability, melt stability, scrap recoverability, thermal adhesiveness, paintability, stain resistance, transparency, etc., and is useful for various applications. .

  EVOH (A) used in the present invention is obtained by saponifying an ethylene-vinyl ester copolymer, and has an ethylene content of 15 to 70 mol%, preferably 20 to 65 mol%, and optimally 25. Further, those having a saponification degree of 85% or more, preferably 90% or more can be used. If the ethylene content is less than 15 mol%, the melt moldability is poor, and the water resistance and hot water resistance are lowered. On the other hand, when it exceeds 70 mol%, the barrier property is insufficient. On the other hand, when the degree of saponification is less than 85%, the barrier property and the thermal stability are deteriorated. Further, if the ethylene content exceeds 70 mol% or the saponification degree is less than 85%, the stain resistance of the obtained film is lowered, and this film is laminated on polyvinyl chloride containing a plasticizer. When used for wallpaper, etc., the ability to suppress bleed out of the plasticizer is also reduced.

  A typical vinyl ester used in EVOH production is vinyl acetate, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used. Moreover, EVOH can contain 0.0002-0.2 mol% of vinyl silane compounds as a copolymerization component. Here, examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Of these, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used. Further, other comonomer [for example, propylene, butylene, unsaturated carboxylic acid or ester thereof {(meth) acrylic acid, methyl (meth) acrylate, (meth) acrylic] within the range in which the object of the present invention is not inhibited. Ethyl acid etc.} and vinyl pyrrolidone (N-vinyl pyrrolidone etc.) can also be copolymerized.

  A suitable melt index (MI) (190 ° C., under a load of 2160 g) of EVOH used in the present invention is 0.1 to 50 g / 10 min. , Optimally 0.5-30 g / 10 min. It is. However, when the melting point is around 190 ° C. or exceeds 190 ° C., measurement is performed under a load of 2160 g and at a plurality of temperatures equal to or higher than the melting point. The value is extrapolated to 190 ° C. These EVOH resins can be used alone or in combination of two or more.

  The polyamide resin (B) used in the present invention is a polymer having an amide bond, for example, polycaproamide (nylon-6), polyundecanamide (nylon-11), polylauryllactam (nylon-12). , Homopolymers such as polyhexamethylene adipamide (nylon-6, 6), polyhexamethylene sebamide (nylon-6, 12), 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 / hexamethylene diammonium adipate / hexamethylene di Ammonium sebacate copolymer (nylon-6 / 6,6 / 6,12), a polymer of adipic acid and metaxylylenediamine, or a polymer of hexamethylenediamine and m, p-phthalic acid A family nylon and the like. These polyamide resins can be used alone or in combination of two or more.

  Of these polyamide resins (B), polyamides containing a nylon 6 component (for example, nylon-6, nylon-6, 12, nylon-6 / 12, nylon-6 / 6, nylon-6 / 6, among these polyamide resins (B) from the viewpoint of compatibility with EVOH. 6 etc.) is preferable. Since EVOH and nylon react and gel in the melting process, it is preferable to use a nylon having a melting point of 240 ° C. or lower, preferably 230 ° C. or lower from the viewpoint of suppressing thermal deterioration of the blend composition.

  A suitable melt index (MI) (210 ° C., under a load of 2160 g) of the polyamide (B) used in the present invention is 0.1 to 50 g / 10 min. , Optimally 0.5-30 g / 10 min. It is. However, when the melting point is around 210 ° C. or exceeds 210 ° C., it is measured at a plurality of temperatures above the melting point under a load of 2160 g. The value is extrapolated to 210 ° C.

  The ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) used in the present invention is a polymer obtained by random copolymerization of ethylene and an unsaturated carboxylic acid, or neutralizes the carboxylic acid component. It is a so-called ionomer that is a metal salt obtained in this way. Here, it is extremely important that ethylene and unsaturated carboxylic acid are randomly copolymerized. When a copolymer obtained by grafting unsaturated carboxylic acid onto polyethylene is used, as shown in a comparative example described later. In addition, the effects of the present invention cannot be achieved. The reason why the random copolymer or its metal salt is superior to the graft copolymer is not clear, but the random copolymer is more compatible with the polyamide resin (B) than the graft copolymer. It is believed that there is. Furthermore, in the case of a graft copolymer, gel and fish eyes are likely to be generated because a hydroxyl group in EVOH and a carboxyl group in the graft copolymer react with each other. In particular, the occurrence of gel and fish eyes is remarkable when performing melt molding for a long time. Moreover, in this resin composition, the reason why it is better to use an ionomer that is a metal salt than an ethylene-unsaturated carboxylic acid random copolymer is not clear, but the ionomer has better compatibility with nylon. It is thought that there is.

  The content of unsaturated carboxylic acid is preferably 2 to 15 mol%, more preferably 3 to 12 mol%. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, and maleic anhydride, and acrylic acid or methacrylic acid is particularly preferable. Other monomers that may be contained in the copolymer include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, and acrylic acid n. Examples thereof include unsaturated carboxylic acid esters such as butyl, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate and diethyl maleate, and carbon monoxide.

  Examples of the metal ion in the ionomer include alkali metals such as lithium, sodium, and potassium, and alkaline earth metals such as zinc, magnesium, and calcium, and the use of zinc is particularly preferable from the viewpoint of compatibility with nylon. The neutralization degree in the ionomer is preferably 100% or less, particularly 90% or less, and more preferably 70% or less. The lower limit of the degree of neutralization is usually preferably 5% or more, particularly 10% or more, and more preferably 30% or more.

  The suitable melt index (MI) (190 ° C., 2160 g load) of the ethylene-unsaturated carboxylic acid random copolymer or its metal salt used in the present invention is preferably 0.05 to 50 g / 10 min, more preferably 0.5 to 30 g / 10 min. These ethylene-unsaturated carboxylic acid random copolymers or metal salts thereof can be used alone or in combination of two or more.

  The thermoplastic resin (D) used in the present invention is a thermoplastic resin different from the components (A), (B), and (C), and it is important that the solubility parameter is 11 or less. That is, the solubility parameter (calculated from the Fedors equation) of the thermoplastic resin (D) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) is close, resulting in four components (A). , (B), (C) and (D) are improved in compatibility. When the solubility parameter of the thermoplastic resin (D) is 11 or more, the compatibility between the four components (A), (B), (C), and (D) decreases, and the scrap recoverability of the blend resin composition In addition, thermoformability, mechanical strength, transparency and the like are significantly reduced. Examples of the thermoplastic resin (D) having a solubility parameter of 11 or less include polyolefin resins, styrene resins, and polyvinyl chloride resins. Among these, polyolefin resins are most preferable, and α-olefins selected from homopolymers of α-olefins such as high-density or low-density polyethylene, polypropylene, and polybutene-1, ethylene, propylene, butene-1, hexene-1, and the like. Examples include copolymers of olefins. Moreover, what copolymerized the following components to the alpha olefin is also contained. Examples of the copolymer component with the α-olefin include diolefins, vinyl compounds such as vinyl chloride and vinyl acetate, unsaturated carboxylic acids such as maleic acid, acrylic acid and methacrylic acid, and anhydrides thereof. Examples of the styrene resin include polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS), and acrylonitrile-styrene copolymer resin (AS). These thermoplastic resins can be used alone or in combination of two or more.

  The suitable melt index (MI) (190 ° C., under a load of 2160 g) of the thermoplastic resin (D) used in the present invention is preferably 0.05 to 100 g / 10 minutes, more preferably 0.05 to 50 g / 10 minutes. Optimally, it is 0.5 to 30 g / 10 min. However, when the melting point is around 190 ° C. or exceeds 190 ° C., measurement is performed under a load of 2160 g and at a plurality of temperatures equal to or higher than the melting point. The value is extrapolated to 190 ° C.

  In the present invention, when compatibilizing EVOH (A) and thermoplastic resin (D), polyamide (B) and an ethylene-unsaturated carboxylic acid random copolymer or a metal salt (C) 2 are used as compatibilizing agents. It is the most characteristic to use components, and EVOH (A) and thermoplastic resin can be obtained by using a combination of polyamide (B) and ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof. The compatibility between (D) can be remarkably improved, and a resin composition having excellent characteristics can be obtained. In other words, as a measure for improving the compatibility between the resin having poor compatibility, that is, a resin having greatly different solubility parameters, EVOH (A) and the thermoplastic resin (D), compatibility with EVOH (A) is achieved. The resin composition of the present invention is obtained by using an ethylene-unsaturated carboxylic acid random copolymer or a metal salt (C) thereof having good compatibility with a good polyamide (B) and thermoplastic resin (D) as a compatibilizing agent. I came to find something.

  The blending weight ratio of each component in the resin composition of the present invention satisfies the following formulas (1) to (4). 0.6 ≦ W (A + D) / W (T) ≦ 0.995 (1) 0.005 ≦ W (B + C) / W (T) ≦ 0.4 (2) 0.01 ≦ W (A) / W (A + D) ≦ 0.99 (3) 0.02 ≦ W (B) / W (B + C) ≦ 0.98 (4) (W (A); weight of (A) in composition W (B ); Weight (B) of (B) in the composition; weight W (D) of (C) in the composition; weight W (T) of (D) in the composition; total weight of the composition) Each of the formulas (1) to (4) is preferably 0.65 ≦ W (A + D) / W (T) ≦ 0.99 (1 ′) 0.01 ≦ W (B + C) / W (T) ≦ 0.35 (2 ′) 0.02 ≦ W (A) / W (A + D) ≦ 0.98 (3 ′) 0.04 ≦ W (B) / W (B + C) ≦ 0.96 (4 ′) More preferably, 0.70 ≦ W (A + D) / W (T) ≦ 0.985 (1 ” 0.015 ≦ W (B + C) / W (T) ≦ 0.30 (2 ″) 0.03 ≦ W (A) / W (A + D) ≦ 0.97 (3 ″) 0.05 ≦ W (B) /W(B+C)≦0.95(4 ″).

  When W (A + D) / W (T) exceeds 0.995 or W (B + C) / W (T) is less than 0.005, the compatibility of EVOH (A) with the thermoplastic resin (D) The effect of the present invention cannot be obtained. When W (A + D) / W (T) is less than 0.6 or W (B + C) / W (T) exceeds 0.4, EVOH (A) in the total amount of the composition Since the ratio of the thermoplastic resin (D) is reduced, performance such as barrier properties inherently possessed by EVOH (A) and melt moldability possessed by the thermoplastic resin (D) is degraded. When W (A) / W (A + D) is less than 0.01, the gas barrier property of the composition is insufficient, and when W (A) / W (A + D) exceeds 0.99, the composition is flexible. The improvement effect is insufficient. Moreover, when W (B) / W (B + C) is less than 0.02, the compatibility between EVOH (A) and the polyamide resin (B) is lowered, and W (B) / W (B + C) is 0.98. When exceeding, the compatibility of an ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) and a thermoplastic resin (D) falls. A decrease in the compatibility between the components leads to a decrease in the mechanical strength of the resin composition itself, or a decrease in barrier properties, thermal adhesiveness, paintability, matteness, flexibility, and stretchability. Also, thermoplastic resins and EVOH In the recovery of scrap generated at the time of manufacturing a multilayer container composed of the above, a wave pattern is caused in the multilayer sheet including the scrap recovery layer and its thermoformed product.

  Further, the blending weight ratio W (B) / W (B + C) of the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof is 0.5 or less. It is preferable from the viewpoint of thermal stability, more preferably 0.45 or less, and optimally 0.4 or less. When the blending weight ratio W (B) / W (B + C) is in such a range, the melt stability of the resin composition is improved, and a molded product having a good appearance can be obtained even in a long-time melt molding. , Improve productivity. The reason for this is not clear, but it is thought that the reaction between EVOH and polyamide adversely affects the melt stability.

  When blended in the above blending ratio, the dispersion form of each resin is not particularly limited, but it is preferable that the thermoplastic resin (D) is a matrix phase and EVOH (A) is a dispersed phase depending on the application. On the contrary, it may be preferable that EVOH (A) is the matrix phase and the thermoplastic resin (D) is the dispersed phase.

  The resin composition in which the thermoplastic resin (D) is the matrix phase and the EVOH (A) is the dispersed phase, while retaining the characteristics of the thermoplastic resin as a whole, can impart its characteristics by blending EVOH. Useful in that it can. That is, it is useful for applications such as the mouth of a tubular container that can improve barrier properties while maintaining thermal adhesiveness and mechanical strength, and molded products that can improve paintability while maintaining mechanical strength. It is also widely used as a scrap recovery composition in which a thermoplastic resin is the main component and the EVOH component is a minor component. Such a dispersion form can be obtained by reducing the value of W (A) / W (A + D), or by making the melt viscosity of (A) larger than the melt viscosity of (D). At this time, the value of W (A) / W (A + D) is preferably 0.65 or less, and more preferably 0.6 or less. When the value of W (A) / W (A + D) exceeds 0.65, it becomes difficult for the thermoplastic resin to form a matrix phase.

  Conversely, the resin composition in which EVOH (A) is the matrix phase and the thermoplastic resin (D) is the dispersed phase should contain the thermoplastic resin while maintaining the excellent performance of EVOH as a whole. It is useful in that the characteristics can be imparted. That is, in applications such as a film with improved flexibility and stretchability while retaining the excellent barrier properties possessed by EVOH, and a matte film with reduced gloss while retaining the excellent stain resistance possessed by EVOH. Useful. Such a dispersion form can be obtained by increasing the value of W (A) / W (A + D) or by making the melt viscosity of (A) smaller than the melt viscosity of (D). At this time, the value of W (A) / W (A + D) is preferably 0.65 or more, and more preferably 0.7 or more. When the value of W (A) / W (A + D) is less than 0.65, it becomes difficult for EVOH to form a matrix phase.

When EVOH (A) is the matrix phase and the thermoplastic resin (D) is the dispersed phase, the thermoplastic resin (D) preferably has an elastic modulus (ASTM D882) at 20 ° C. of 500 kg / cm ² or less. More preferably, it is 400 kg / cm ² or less, and further preferably 300 kg / cm ² or less. EVOH has higher rigidity and lacks flexibility than a general polymer, and thus has low resistance to bending, and is often not usable in flexible packaging applications. Further, in a process having a stretching process such as skin pack packaging, shrink packaging, thermoformed film or sheet, there is a problem of deterioration of gas barrier property due to poor thickness distribution of thermoformed product due to stretching unevenness, and further poor appearance. Therefore, in order to develop good bending resistance and stretchability, a composition having a low Young's modulus that can be stretched with a smaller force is desired. In response to such a demand, it is effective to add the thermoplastic resin (D) to EVOH (A), and it is particularly effective to set the elastic modulus at 20 ° C. of the thermoplastic resin (D) to 500 kg / cm ² or less. It is. Examples of the thermoplastic resin (D) having an elastic modulus of 500 kg / cm ² or less include very low density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), and ethylene-methyl methacrylate copolymer (EMAA). , Ethylene-ethyl acrylate copolymer (EEA), ethylene-propylene copolymer (EPR), styrene elastomer (SEBS resin and the like), and the like.

  When the resin composition of the present invention contains at least one of a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound, the heat of EVOH caused by the reaction of EVOH (A) with the polyamide resin (B). Deterioration can be prevented, and, as is clear from the examples described later, an excellent molded product having no wave pattern can be obtained on the multilayer coextruded sheet containing a scrap layer.

Here, as the hydrotalcite compound, M _x Al _y (OH) _{2x + 3y−2z} (A) _z · aH ₂ O (M is Mg, Ca or Zn, A is CO ₃ or HPO ₄ , x, y, z) , A is a positive number), and the hydrotalcite compound which is a double salt represented by the following can be exemplified.

Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ OMg ₈ Al ₂ (OH) ₂₀ CO ₃ .5H ₂ OMg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ OMg ₁₀ Al ₂ (OH) ₂₂ (CO ₃ ) ₂ · 4H ₂ OMg ₆ Al ₂ (OH) ₁₆ HPO ₄ · 4H ₂ OCa ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ OZn ₆ Al ₆ (OH) ₁₆ CO ₃ · 4H ₂ OMg _4.5 Al _{2 (OH) 13 CO 3 · 3.5H} 2 O

Further, as the hydrotalcite compound, [Mg _0.75 Zn _0.25 ] _0.67 Al _0.33 (OH), which is a hydrotalcite-based solid solution described in JP-A-1-308439 (USP 4945557). ₂ (CO ₃ ) _0.167 · 0.45H ₂ O can also be used.

  The higher aliphatic carboxylic acid metal salt is a metal salt of a higher fatty acid having 8 to 22 carbon atoms, and examples of the higher fatty acid having 8 to 22 carbon atoms include lauric acid, stearic acid, myristic acid, and the like. Examples thereof include sodium, potassium, magnesium, calcium, zinc, barium, aluminum and the like. Of these, alkaline earth metals such as magnesium, calcium and barium are preferred.

  The content of the metal salt of these higher aliphatic carboxylic acids and the hydrotalcite compound is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2.5 parts by weight based on the total weight of the resin composition. Parts by weight. In addition, the resin composition of the present invention contains other additives (such as a heat stabilizer, a plasticizer, an ultraviolet absorber, an antioxidant, a colorant, a filler, and other resins) within a range where the object of the present invention is not hindered. It is free to use in.

  The composition of this invention can be easily obtained by melt-kneading each component with a normal melt-kneading apparatus. The blending method is not particularly limited, but EVOH (A), polyamide resin (B), ethylene-unsaturated carboxylic acid random copolymer or metal salt thereof (C), thermoplastic resin (D) By simultaneously pelletizing with a single screw or twin screw extruder or drying, or first melt mixing and cooling polyamide resin (B) and ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof -After pelletizing, dry-blending to EVOH (A) and a thermoplastic resin (D), pelletizing with a single screw or a twin screw extruder etc., and the like etc. are mention | raise | lifted. In particular, as shown in Examples described later, first, polyamide resin (B) and ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof are melt-blended, and then EVOH ( The object of the present invention can be effectively achieved by the method of melt blending with A) and the thermoplastic resin (D). The reason for this is not necessarily clear, but the polyamide resin (B), which acts as a compatibilizer for EVOH (A) and the thermoplastic resin (D), and an ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof. By preparing the blend in advance, the compatibility between EVOH (A) and the thermoplastic resin (D) is improved, and the resin composition composed of four components seems to form a stable morphology. In the melt blending operation, blending may become non-uniform, and gels and blisters may be generated and mixed. For this reason, blend pelletization should be performed using an extruder with a high kneading degree as much as possible. It is desirable to seal with nitrogen gas and extrude at low temperatures.

  The resin composition comprising EVOH (A), polyamide resin (B), ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) thereof and thermoplastic resin (D) of the present invention is a simple substance of this composition. Although it can also be set as the molded object of a layer structure, it can also be used as a molded object of another various base material and 2 or more types of multilayer structures. As this composition layer and the thermoplastic resin layer adjacent thereto, high density, medium density, or low density polyethylene, vinyl acetate, acrylate ester, polyethylene copolymerized with α-olefins such as butene and hexene, Polyolefins such as ionomer resins, polypropylene homopolymers, polypropylenes copolymerized with α-olefins such as ethylene, butene, hexene, modified polypropylenes blended with rubber polymers, or addition of maleic anhydride to these resins, Or the grafted thermoplastic resin is mentioned as a suitable thing. Still other thermoplastic resin layers include polyamide resins, polyester resins, polystyrene resins, polyvinyl chloride resins, acrylic resins, polyurethane resins, polycarbonate resins, and polyvinyl acetate resins.

  Moreover, you may have an adhesive resin layer between the composition layer of this invention, and the thermoplastic resin layer adjacent to it. The adhesive resin is not particularly limited, but an unsaturated carboxylic acid or an anhydride thereof (such as maleic anhydride) is replaced with an olefin polymer or copolymer (for example, LLDPE, VLDPE, etc.), ethylene-vinyl acetate copolymer. Typical examples include polymers grafted to ethylene- (meth) acrylic acid ester copolymers.

  The method for obtaining the multilayer structure is not particularly limited, but is an extrusion lamination method, a dry lamination method, an extrusion blow molding method, a coextrusion lamination method, a coextrusion sheet molding method, a coextrusion pipe molding method, a coextrusion method. Examples include blow molding, co-injection molding, and solution coating. Next, the laminate can be subjected to secondary processing after being reheated in the range below the melting point of EVOH by vacuum / pneumatic deep drawing or blow molding.

  The layer structure of the multilayer structure is not particularly limited, but in consideration of moldability, cost, etc., thermoplastic resin layer / resin composition layer / thermoplastic resin layer, resin composition layer / adhesive resin Typical examples include layer / thermoplastic resin layer, thermoplastic resin layer / adhesive resin layer / resin composition layer / adhesive resin layer / thermoplastic resin layer. When the thermoplastic resin layers are provided on both outer layers, different resins may be used, or the same one may be used. Further, scrap generated when performing extrusion molding, blow molding, thermoforming, or the like may be blended with the thermoplastic resin layer or provided as a separate recovery layer.

  By using the resin composition of the present invention, molding excellent in barrier properties, mechanical strength, flexibility, stretchability, melt stability, scrap recoverability, thermal adhesiveness, paintability, stain resistance, transparency, etc. Since a product can be obtained, it is effective for various applications.

  For example, a resin composition in which a thermoplastic resin (D) is a matrix phase and EVOH (A) is a dispersed phase is a single-layer barrier material having a barrier property, such as a mouthpiece of a two-piece tubular container, a small single unit. It can be used for a layer barrier container (bottle, cup, etc.), a paper container, or a barrier spout (spout) for a bag-in-box. In addition, the present invention is useful for plastic household goods or household electrical appliance parts having stain resistance, such as plastic automobile parts with improved paintability. Further, it can be used for a fuel tank or a fuel tube utilizing barrier properties against an organic solvent.

  Here, a case where a resin composition in which the thermoplastic resin (D) is a matrix phase and EVOH (A) is a dispersed phase is used as the mouth of a two-piece tubular container will be described. When used in this application, the use of such a resin composition is effective in that the barrier property can be improved while maintaining thermal adhesiveness and mechanical strength. As the thermoplastic resin (D) used in this case, polyolefin is preferable from the viewpoint of mechanical strength and thermal adhesiveness with the tube portion, and polyethylene is particularly preferable. Further, the value of the blending weight ratio W (A) / W (A + D) of the thermoplastic resin (D) and EVOH (A) is preferably 0.2 or more from the viewpoint of securing good barrier properties, It is more preferably 0.3 or more, and most preferably 0.4 or more.

  Next, a case where a resin composition in which the thermoplastic resin (D) is a matrix phase and EVOH (A) is a dispersed phase is used as a molded product having a coating applied on the surface thereof will be described. When used in this application, the use of such a resin composition is effective in that a molded product that can improve paintability while maintaining mechanical strength is obtained. As the thermoplastic resin (D) used in this case, polyolefin is preferable from the viewpoint of mechanical strength, rigidity, impact resistance, etc., and polypropylene is particularly optimal. As EVOH (A) to be used, from the viewpoint of improving paintability efficiently, the ethylene content is preferably 50 mol% or less, more preferably 45 mol% or less, and 40 mol% or less. Is the best. The saponification degree is preferably 90% or more, more preferably 92 to 98%, and most preferably 93 to 97%. Further, the blending weight ratio W (A) / W (A + D) of the thermoplastic resin (D) and EVOH (A) impairs the mechanical strength, rigidity, impact resistance, etc. of the thermoplastic resin (D). In consideration of economic efficiency, it is preferably 0.3 or less, more preferably 0.2 or less, and most preferably 0.15 or less. For the same reason, the blending weight ratio of the total amount of the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) to the total weight of the resin composition W (B + C) / W (T ) Is preferably 0.15 or less, and more preferably 0.1 or less.

  On the other hand, the resin composition in which EVOH (A) is the matrix phase and the thermoplastic resin (D) is the dispersed phase can obtain EVOH with improved flexibility, stretchability, and transparency, It is useful for bag-in-boxes that require bending resistance, skin pack packaging that requires stretchability and thermoformability, shrink packaging, thermoforming containers, and the like.

  In addition, a resin composition in which EVOH (A) is a matrix phase and thermoplastic resin (D) is a dispersed phase can reduce gloss while maintaining the excellent stain resistance of EVOH. It is also useful for an eraser film.

  As the thermoplastic resin (D) used for the matte film, polyolefin is preferable from the viewpoint of mechanical strength and economy, and polyethylene is particularly preferable. The polyethylene here is preferably a resin in which 60 mol% or more of its constituent components are composed of an ethylene component. Examples of comonomer components that can be used at a ratio of less than 40 mol% include olefins such as propylene and butylene, dienes such as isoprene and butadiene, styrene and derivatives thereof, various acrylic esters, various methacrylate esters, and vinyl acetate. Etc. Moreover, it has various functional groups such as α, β-unsaturated fatty acid such as maleic anhydride and the carboxylic anhydride, glycidyl methacrylate methacrylate, ethylene oxide, propylene oxide, etc. as comonomer components that can be used at a ratio of 1 mol% or less. Compounds. In particular, a polyethylene resin obtained by copolymerizing or grafting an α, β-unsaturated fatty acid and the carboxylic acid anhydride at a ratio of 0.0005 to 0.5 mol% is particularly preferably used in the present invention.

  The effect of the content of the thermoplastic resin (D) when used in a matte film is 4 to 45% by weight with respect to the total amount of (A), (B), (C) and (D). It is suitable above, and the range of 10 to 30% by weight is more preferable. If it is 4% by weight or less, the glossiness may not be satisfied, and if it exceeds 45% by weight, the morphology may change and the characteristics inherent to the EVOH film may not be maintained.

  The weight ratio of the polyamide resin (B) to the ethylene-unsaturated carboxylic acid random copolymer or metal salt (C) used in the matte film is 2:98 to 70:30, preferably 3:97 to 60. : 40, optimally 5:95 to 50:50. When the ratio of the polyamide resin is less than 2%, the dispersibility of the entire system is insufficient, and not only the glossiness is not satisfactory, but also the mechanical properties are insufficient. If it exceeds 70%, the reaction rate between EVOH and nylon increases, and productivity becomes a problem.

  The total amount of the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) used in the matte film is (A), (B), (C) and (D). It is 1 to 20% by weight, preferably 2 to 15% by weight, optimally 3 to 10% by weight, based on the total amount. If it is less than 1% by weight, the dispersion of the component (A) and the component (B) becomes insufficient, and not only the glossiness is not satisfactory, but also the mechanical properties of the film are deteriorated. If it exceeds 20% by weight, the dispersibility of the thermoplastic resin (D) becomes too good, so that the glossiness cannot be satisfied.

  Further, it is important that the glossiness of at least one surface of the matte film is 60% or less, preferably 50% or less, and optimally 40% or less. Those exceeding 60% are unsuitable as a matte film. The glossiness referred to here is an average value of measured values at arbitrary five locations measured with a Murakami gloss meter.

  Although there is no restriction | limiting in particular about the thickness of a matte film, 10-50 micrometers is preferable. When the thickness exceeds 50 μm, the rigidity of the film increases, and there are cases where the pattern and the like are limited when laminated on a base material for interior materials such as paper wallpaper and polyvinyl chloride wallpaper. By laminating the matte film of the present invention thus obtained on a base material for interior materials such as wallpaper and decorative plywood, it is possible to suppress bleeding of plasticizers and other undesirable substances and to impart stain resistance to various pollutants. At the same time, it is possible to give a high-class feeling with no gloss. Moreover, the same effect can be given also by laminating | stacking on a laser etc.

  As another preferred embodiment of the present invention, when recovering scraps of molded articles mainly composed of EVOH (A) and thermoplastic resin (D), particularly multilayer molded articles having (A) layer and (D) layer. Further, there is a scrap recovery method of a molded product in which a polyamide resin (B) and an ethylene-unsaturated carboxylic acid random copolymer or a metal salt (C) thereof are added as a compatibilizing agent. Here, the molded product containing EVOH (A) and the thermoplastic resin (D) as main components means that the total weight of (A) and (D) occupies half or more of the total molded product weight.

  Multi-layer sheet and its thermoforming due to poor compatibility of EVOH (A) and thermoplastic resin (D) when scrap generated during extrusion molding, blow molding, thermoforming, etc. is used with a separate recovery layer The wave pattern generated in the product is also remarkably improved by blending the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C). Further, the effect becomes particularly remarkable when at least one of a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound is added to (B) and (C). The suitable compounding quantity of the metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound is 0.1-50 weight part with respect to the total amount of (B) + (C).

  The resin composition recovered in this manner is effectively used as a multilayer structure having at least one scrap recovery layer. For example, when a multilayer sheet for thermoforming is used, a thermoformed container having a good appearance can be obtained. In particular, a multilayer structure having at least one EVOH layer in addition to the scrap collection layer is useful from the viewpoint of barrier properties.

  Furthermore, when recovering the scrap of the multilayer structure, as described above, besides the method of directly adding the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) to the scrap Alternatively, it may be blended in advance in any one layer of the multilayer structure, or may be used as any one layer of the multilayer structure, for example, an adhesive layer of EVOH and polyolefin.

  The thermoplastic resin (D) used in such a recovery composition is not particularly limited, but polypropylene is also preferable in terms of mechanical strength, impact resistance, secondary processability, economy, etc. From the viewpoints of glossiness, secondary processability, economy, etc., polystyrene is preferably used. Further, the blending weight ratio W (A) / W (A + D) of the thermoplastic resin (D) and EVOH (A) impairs the mechanical strength, rigidity, impact resistance, etc. of the thermoplastic resin (D). In consideration of economic efficiency, it is preferably 0.3 or less, more preferably 0.25 or less, and most preferably 0.2 or less. For the same reason, the blending weight ratio of the total amount of the polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) to the total weight of the resin composition W (B + C) / W (T ) Is preferably 0.15 or less, more preferably 0.1 or less, and most preferably 0.08 or less.

  As described above, the resin composition of the present invention is excellent in barrier properties, mechanical strength, flexibility, stretchability, melt stability, scrap recoverability, thermal adhesiveness, paintability, stain resistance, transparency, etc. It can be usefully used in various applications.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it is not limited at all by this. In the following examples, <Examples relating to the mouth of a two-piece tube-like container>, <Examples relating to paintability>, <Examples relating to scrap recoverability>, and <Examples relating to a flexible film> Resins shown in Tables 1 to 4 were used as raw materials. Here, Table 1 shows EVOH (A), Table 2 shows polyamide resin (B), Table 3 shows ethylene copolymer resin (C), and Table 4 shows thermoplastic resin (D).

<Example regarding the mouth of a two-piece tubular container>
Example 1-1
Using the resins shown in Tables 1 to 4, EVOH (A-3) 40 parts by weight, polyamide (B-2) 5 parts by weight, ethylene-methacrylic acid random copolymer (EMAA; C-1) 15 parts by weight and high A blend comprising 40 parts by weight of density polyethylene (HDPE; D-1) was obtained by the following method. That is, first, polyamide (B-2) and EMAA (C-1) were put into a twin screw type vent type extruder, extruded and pelletized at 220 ° C. in the presence of nitrogen, and the resulting blend pellet EVOH ( A-3) and HDPE (D-1) were blended again in the same manner to obtain the desired resin composition pellets.

  Next, a tube-shaped container was produced by an injection molding method using a tube-shaped container molding machine by an injection molding method disclosed in JP-A-56-25411 (Japanese Patent Publication No. 64-7850). At this time, while the obtained resin composition pellets were supplied to an injection molding machine, a cylindrical tube serving as a body part prepared in advance was supplied to the mold of the molding machine.

  Here, a 35 mmφ in-line screw type injection molding machine was used as the injection molding machine, and the mouth was molded under conditions of a cylinder temperature of 240 ° C. and a nozzle temperature of 235 ° C. The obtained tube-shaped container had an outer diameter of 35 mmφ, an outer diameter of the mouth squeezing port of 12 mmφ, an inner diameter of 7 mmφ, and an oral thickness of 2 mm. Cylindrical tube is low density polyethylene (LDPE, Mitsui Petrochemical, Ultzex 3520L, thickness 150μ) / adhesive resin (Mitsui Petrochemical, Admer NF500, thickness 20μ) / EVOH (A-1, thickness 20μ) / adhesiveness. A resin (Mitsui Petrochemical, Admer NF500, thickness 20μ) / LDPE (Mitsui Petrochemical, Ultozex 3520L, thickness 150μ) is formed by a coextrusion method using a circular die.

  By observing the obtained oral head with an electron microscope, it was confirmed that HDPE (D-1) was a matrix phase and EVOH (A-3) was a dispersed phase.

  Using the tube-like container thus obtained, storage stability, thermal adhesiveness, oral strength, and oral appearance were evaluated by the following methods. In addition, in order to measure the barrier property of the oral part itself, a resin pellet for the oral part was formed, and the oxygen transmission coefficient (OTR) of the film was measured. The evaluation results are shown in Table 5.

(1) Oxygen transmission coefficient (OTR)
The resin composition was melt-extruded at 235 ° C. by a T-die method to form a film having a thickness of 100 μm, and then 20 ° C.-65% RH using an Ox-Tran 100 type oxygen permeability measuring device manufactured by Modern Control. The oxygen transmission coefficient was measured under the following conditions.

(2) Preservability Miso was filled from the bottom opening of the molded tube-shaped container, and the tube bottom was sealed by thermal bonding. Next, an aluminum foil (thickness 25 μm) was attached only to the extrusion port, and then the cap was tightened. The tube-shaped container filled with such miso is left in a constant temperature and high-humidity bath at 40 ° C.-50% RH, the tube-shaped container is taken out after 24 hours, and the discoloration of the miso that has been in contact with the inner surface of the mouth of the tube-shaped container The state was observed visually and evaluated according to the following criteria A to D.
A: No discoloration.
B: Discolored to light brown.
C: Discolored to brown.
D: Discolored to reddish brown.

(3) Thermal adhesiveness The tube barrel is 15 mm wide at two locations in the vertical direction, cut to the thermal bonding portion with the oral head so that they face each other, and each end of the trunk incision portion is attached to a tensile test, Based on JISK7127, the peel strength of the thermal bonding part was measured under the condition of 20 ° C.-65% RH.
A: 3.0 kg or more B: 2.5-3.0 kg
C: 2.0-2.5 kg
D: 2.0 kg or less

(4) Oral strength Under a condition of 20 ° C.-65% RH, the cap of the tube-shaped container is repeatedly opened and closed 30 times, and the state of breakage such as chipping and cracking of the oral screw and the occurrence of cracks in the oral cavity are visually observed. The sample was observed with a loupe and evaluated according to the following criteria A to D. However, the cap was tightened using a torque meter with a torque of 5 kg · cm.
A: No crack, chipping or cracking.
B: Confirmation of occurrence of minute cracks with a loupe.
C: The occurrence of minute cracks was confirmed visually.
D: Visually confirmed the occurrence of minute chips and cracks.

(5) Appearance of the Oral Head The appearance of the oral part (surface state, coloring state, occurrence state of gel and fish eyes) was visually evaluated. At this time, the molded product immediately after the start of injection molding and the molded product after 24 hours from the start of molding were evaluated according to the following criteria A to D.
A: No abnormality.
B: Fine gel, fish eye, or surface roughness occurred.
C: Clear gel, fish eye, or surface roughness partially occurred.
D: A clear gel, fish eye, or rough surface was generated on the entire surface, and the color of the mouth was changed to pale yellow.

  FIG. 1 shows a tubular container according to an embodiment, in which an oral head 2 having a male screw 2a at the upper part of a cylindrical body 1 and a shoulder part 2b at the lower part is thermally bonded at the oral shoulder part 3, The bottom heat bonding portion 4 of the body portion 1 is heat sealed. FIG. 2 shows the configuration of the cylindrical body 1, and from the inner layer side, a heat sealing layer (LDPE) 5, an adhesive resin 6, a barrier resin (EVOH) 7, an adhesive resin 8 and an outer layer (LDPE) 9 are shown. Laminated in order.

Examples 1-2 to 1-8 and Comparative Examples 1-1 to 1-8
Example 1-1 was used except that the resin type and the mixing ratio were changed so that pellets having the resin composition shown in Table 5 were obtained instead of the resin composition pellets composed of the four components prepared in Example 1-1. In the same manner, a tubular container was produced. When the resin composition was composed of two or three components, blending was performed by one kneading operation, and when the resin composition was composed of one component, the kneading operation was not performed. The evaluation results are summarized in Table 5.

Example 1-9
A tubular container was produced in the same manner as in Example 1-1 except that the same composition as in Example 1-1 was used to pelletize the four resin components by only one kneading operation. The evaluation results are shown in Table 5.

<Examples concerning paintability>
Example 2-1
Using the resins shown in Tables 1 to 4, from 10 parts by weight of EVOH (A-1), 1 part by weight of polyamide (B-1), 2 parts by weight of ionomer (C-2) and 87 parts by weight of polypropylene (D-3) The following blend was obtained by the following method. That is, first, polyamide (B-1) and ionomer (C-2) were put into a twin screw type vent type extruder, extruded and pelletized at 220 ° C. in the presence of nitrogen, and the resulting blend pellet EVOH ( A-1) and polypropylene (D-3) were blended again in the same manner to obtain the desired resin composition pellets.

  The obtained pellets were prepared at 220 ° C. using an injection molding machine FS80S manufactured by Nissei Plastic Industry, and various strength measurement test pieces and coating test data pieces were produced. Here, by observing the injection molded product with an electron microscope, it was confirmed that polypropylene (D-3) was a matrix layer and EVOH (A-1) was a dispersion layer. Various performance evaluation was performed by the following method using the obtained test piece. The evaluation results are shown in Table 6.

(1) Tensile strength (kg / cm ² )
Measurement was performed at room temperature according to ASTM D638.
(2) Elongation at break (%)
Measurement was performed at room temperature according to ASTM D638.
(3) Bending strength (kg / cm ² )
Measurement was performed at room temperature according to ASTM D790.
(4) Impact strength (kg · cm / cm)
According to ASTM D256, measurement was performed under a condition of 20-65% RH with a notch using a 3.2 mm-thick specimen.

(5) Coating test The test piece was wiped with gauze containing isopropyl alcohol, a urethane paint was applied under the condition of no primer, and baked at 80 ° C. for 30 minutes to form a coating film. The obtained coated film-formed body was allowed to stand for 24 hours or more under the condition of 23 ° C.-65% RH, and then the adhesion strength (primary adhesion strength) was measured by a cross-cut peel test in accordance with JIS D02024.15. Further, the adhesion strength (secondary adhesion strength) was similarly evaluated for the coating film after being immersed in warm water at 40 ° C. for 240 hours. The rank of evaluation was performed according to the following film surface states.
A: The surface gloss is good and no peeling occurs.
B: No peeling occurred, but the surface gloss slightly decreased.
C: No peeling occurred, but the surface gloss was considerably lowered.
D: Peeling occurred.

(6) Appearance of molded product A to C criteria shown below visually for the appearance of the molded product immediately after the start of injection molding and the appearance of the molded product after the lapse of 24 hours (surface condition, occurrence of gel and fish eyes). It was evaluated with.
A: No abnormality.
B: Fine gel, fish eye, or surface roughness occurred.
C: Clear gel, fish eye, or surface roughness partially occurred.

Examples 2-2 to 2-4 and comparative examples 2-1 to 2-6
Example 2-1 except that the resin type and blending ratio were changed so that pellets of the resin composition shown in Table 6 were obtained instead of the resin composition pellets consisting of the four components prepared in Example 2-1. Samples were prepared and evaluated in the same manner as described above. When the resin composition was composed of two or three components, blending was performed by one kneading operation, and when the resin composition was composed of one component, the kneading operation was not performed. The evaluation results are summarized in Table 6.

Example 2-5
A sample piece was prepared and evaluated under the same conditions as in Example 2-1, except that the same composition as Example 2-1 was used to pelletize the four types of resin components by only one kneading operation. Went. The evaluation results are shown in Table 6.

<Example of scrap recovery>
Example 3-1.
Resins used in the following examples are shown in Tables 1 to 4. First, a three-layer coextruded sheet (560 μm / 100 μm / 560 μm) having a polypropylene (PP; D-4) layer on both sides of the EVOH (A-2) layer is formed, and the resulting sheet is crushed and scraped { (A-2) :( D-4) = 10 parts by weight: 86 parts by weight} was obtained. On the other hand, 1 part by weight of polyamide (B-1) and 3 parts by weight of ionomer (C-2) were put into a twin screw type vent type extruder, and extrusion pelletized at 220 ° C. in the presence of nitrogen. Subsequently, 96 parts by weight of the scrap made of EVOH (A-2) and polypropylene (D-4) and 4 parts by weight of the resin composition pellets made of polyamide (B-1) and ionomer (C-2) were blended. And it pelletized with the full flight type single screw extruder. Through the above operation, a resin comprising four components of 10 parts by weight of EVOH (A-2), 1 part by weight of polyamide (B-1), 3 parts by weight of ionomer (C-2) and 86 parts by weight of polypropylene (D-4). A composition pellet (hereinafter sometimes abbreviated as REG) was obtained.

  The obtained resin composition pellets composed of four components, EVOH (A-2), polypropylene (D-4) and adhesive resin (maleic anhydride-modified polypropylene) were put in separate extruders, 7-layer sheet co-extruded to form PP / REG / adhesive resin / EVOH / adhesive resin / REG / PP (300/150/25/50/25/150 / 300μ) using extrusion equipment (Total layer thickness: 1000 μm) was produced. For extrusion molding, PP is at a temperature of 240 ° C. using a single screw (65 mmφ), REG is at a temperature of 220 ° C. using a single screw (40 mmφ), and the adhesive resin is 220 ° C. using a single screw (40 mmφ). The EVOH was extruded at a temperature of 210 ° C. using a single screw (40 mmφ). The obtained sheet maintained a good appearance even after 24 hours and 72 hours after the start of molding, and there was no occurrence of sheet delamination or wave pattern due to abnormal flow due to poor compatibility in the REG layer. Here, by observing the REG layer of the obtained sheet with an electron microscope, it was confirmed that polypropylene (D-4) was a matrix layer and EVOH (A-2) was a dispersion layer.

Using the thermoforming machine (manufactured by Asano Seisakusho), the sheet obtained 24 hours and 72 hours later was thermoformed into a cup shape (die shape 70φ × 70 mm) (compressed air: 5 kg / cm ² , plug: 45φ). × 65 mm, syntax foam, sheet temperature: 150 ° C., plug temperature: 20 ° C., mold temperature: 70 ° C.). The appearance of the molded cup was visually evaluated. The obtained cup was free from sheet delamination and wave pattern due to poor compatibility in the blend pellets as in the case of the sheet.

The evaluation of sheet appearance or cup appearance was determined according to the following criteria.
A: Uniform and good film surface without wave pattern and delamination.
B: Uniform and good film surface without delamination, but with a slight wave pattern in part.
C: A clear wave pattern and delamination occurred on the entire surface.
D: A clear wave pattern, delamination and gel fish eyes were generated on the entire surface.
Table 7 shows the evaluation results.

Examples 3-2 to 3-5 and Comparative Examples 3-1 to 3-6
Example 3-1 except that the resin type and blending ratio were changed so that pellets of the resin composition shown in Table 7 were obtained instead of the resin composition pellets consisting of the four components prepared in Example 3-1. In the same manner, a resin composition was obtained. At this time, when the resin composition was composed of two or three components, blending was performed by one kneading operation. A 7-layer sheet having the same configuration as in Example 3-1 except for the resin composition layer was prepared in the same manner as in Example 3-1, except that the obtained resin composition was used, and a cup was formed by thermoforming. did. The evaluation results are summarized in Table 7.

Example 3-6
Instead of 4 parts by weight of the blend of polyamide (B-1) and ionomer (C-2) used in Example 3-1 (blend ratio: 25/75 parts by weight), calcium stearate was added to 4 parts by weight of the blend. A resin composition was obtained in the same manner as in Example 3-1, except that 1 part by weight (manufactured by NOF Corporation) was dry blended. A 7-layer sheet having the same configuration as in Example 3-1 except for the resin composition layer was prepared in the same manner as in Example 3-1, except that the obtained resin composition was used, and a cup was formed by thermoforming. did. Table 7 shows the evaluation results.

Example 3-7
A resin composition was obtained in the same manner as in Example 3-1, except that hydrotalcite (DHT-4A, manufactured by Kyowa Chemical) was used instead of the calcium stearate used in Example 3-6. A 7-layer sheet having the same configuration as in Example 3-1 except for the resin composition layer was prepared in the same manner as in Example 3-1, except that the obtained resin composition was used, and a cup was formed by thermoforming. did. Table 7 shows the evaluation results.

Example 3-8
With the same composition as Example 3-1, the polyamide (B-1) and ionomer (C-2) were kneaded in advance, and the four types of resin components were kneaded by only one kneading operation to be pelletized. Except for this, a resin composition was obtained in the same manner as in Example 3-1. A 7-layer sheet having the same configuration as in Example 3-1 except for the resin composition layer was prepared in the same manner as in Example 3-1, except that the obtained resin composition was used, and a cup was formed by thermoforming. did. Table 7 shows the evaluation results.

Example 3-9
In Example 3-1, three layers having polystyrene (D-5) layers on both sides of the EVOH (A-2) layer using polystyrene (PS; D-5) instead of polypropylene (D-4) A co-extruded sheet (490/100 / 490μ) was prepared, and a resin composition (REG) composed of four components was obtained in the same manner as in Example 3-1, except that the scrap obtained therefrom was used.

  The obtained resin composition pellets composed of 4 components, EVOH (A-2), polystyrene (D-5) and adhesive resin (maleic anhydride-modified ethylene-vinyl acetate copolymer) were put in separate extruders, Using a coextrusion equipment of 4 types and 7 layers, so that the structure is PS / REG / adhesive resin / EVOH / adhesive resin / REG / PS (300/150/25/50/25/150 / 300μ) A seven-layer sheet (total thickness: 1000 μm) was prepared by coextrusion. In the extrusion molding, PS is a temperature of 240 ° C. using a single screw (65 mmφ), REG is a temperature of 220 ° C. using a single screw (40 mmφ), and an adhesive resin is 220 ° C. using a single screw (40 mmφ). The EVOH was extruded at a temperature of 210 ° C. using a single screw (40 mmφ).

Using the thermoforming machine (manufactured by Asano Seisakusho), the sheet obtained 24 hours and 72 hours later was thermoformed into a cup shape (die shape 70φ × 70 mm) (compressed air: 5 kg / cm ² , plug: 45φ). × 65 mm, syntax foam, sheet temperature: 130 ° C., plug temperature: 20 ° C., mold temperature: 70 ° C.). The evaluation results are shown in Table 8.

Examples 3-10 to 3-12 and Comparative Examples 3-6 to 3-9
Example 3-9 except that the resin type and blending ratio were changed so that pellets of the resin composition shown in Table 8 were obtained instead of the resin composition pellets consisting of the four components prepared in Example 3-9. In the same manner, a resin composition was obtained. At this time, when the resin composition was composed of two or three components, blending was performed by one kneading operation. A 7-layer sheet having the same structure as in Example 3-9 except for the resin composition layer was prepared in the same manner as in Example 3-9 except that the obtained resin composition was used, and a cup was formed by thermoforming. did. The evaluation results are summarized in Table 8.

Comparative Example 3-10
In Example 3-1, instead of using polypropylene (D-4), polyethylene terephthalate (PET; D-7) is used, and a polyethylene terephthalate (D-7) layer is provided on both sides of the EVOH (A-2) layer. A three-layer coextruded sheet (370/100 / 370μ) was prepared, and a resin composition (REG) comprising four components was obtained in the same manner as in Example 3-1, except that the scrap obtained therefrom was used.

  The obtained resin composition pellets composed of four components, EVOH (A-2), polyethylene terephthalate (D-7) and adhesive resin (maleic anhydride-modified ethylene-vinyl acetate copolymer) are put in separate extruders. Using a coextrusion equipment of 4 types and 7 layers, so that the composition of PET / REG / adhesive resin / EVOH / adhesive resin / REG / PET (300/150/25/50/25/150 / 300μ) To produce a 7-layer sheet (total layer thickness: 1000 μm). In the extrusion molding, PET is 270 ° C. using a single screw (65 mmφ), REG is 220 ° C. using a single screw (40 mmφ), and the adhesive resin is 270 ° C. using a single screw (40 mmφ). The EVOH was extruded at a temperature of 210 ° C. using a single screw (40 mmφ).

Using the thermoforming machine (manufactured by Asano Seisakusho), the sheet obtained 24 hours and 72 hours later was thermoformed into a cup shape (die shape 70φ × 70 mm) (compressed air: 5 kg / cm ² , plug: 45φ). × 65 mm, syntax foam, sheet temperature: 110 ° C., plug temperature: 20 ° C., mold temperature: 70 ° C.). The evaluation results are shown in Table 8.

Comparative Example 3-11
Comparative Example 3-10 except that the resin type and blending ratio were changed so that pellets of the resin composition shown in Table 8 were obtained instead of the resin composition pellets consisting of the four components prepared in Comparative Example 3-10. In the same manner, a resin composition was obtained. At this time, blending was performed by one kneading operation. A 7-layer sheet having the same configuration as that of Comparative Example 3-10 except for the resin composition layer was prepared in the same manner as in Comparative Example 3-10 except that the obtained resin composition was used, and a cup was formed by thermoforming. did. The evaluation results are shown in Table 8.

<Examples regarding flexible films>
Example 4-1
Using resins shown in Tables 1 to 4, EVOH (A-2) 90 parts by weight, polyamide (B-1) 1 part by weight, ionomer (C-2) 1 part by weight, and ultra-low density polyethylene (D-6) 8 A blend consisting of parts by weight was obtained by the following method. That is, first, polyamide (B-1) and ionomer (C-2) were put into a twin screw type vent type extruder, extruded and pelletized at 220 ° C. in the presence of nitrogen, and the resulting blend pellet EVOH ( A-2) and ultra-low density polyethylene (D-6) were blended again in the same manner to obtain the desired resin composition pellets.

  Using the obtained pellets, a single layer film having a thickness of 25 μm was produced using a flat die having a width of 550 mm using an extruder having a full flight type screw of 40 mmφ, L / D = 24, and compression ratio of 3.5. Filmed. Here, by observing the obtained film with an electron microscope, it was confirmed that EVOH (A-2) was a matrix layer and ultra-low density polyethylene (D-6) was a dispersion layer. The resulting film was evaluated for the haze, flex resistance, Young's modulus, film impact, oxygen permeation amount (OTR), and occurrence of gel fisheye by the following methods. The evaluation results are shown in Table 9.

(1) Haze A 25 μm-thick film was measured using a Japan Integrative Optics Co., Ltd. Poic integrating sphere light transmittance meter.

(2) Flexibility Using a gelboflex tester manufactured by Rigaku Kogyo Co., Ltd., a 12 inch × 8 inch film is formed into a cylindrical shape with a diameter of 3.5 inches, both ends are gripped, and an initial gripping interval is 7 inches. Gripping distance of 1 inch at maximum bending, twist of 440 degrees at the first 3.5 inch of stroke, and then 2.5 inch is a straight horizontal motion, repeated reciprocating motion of 40 times / minute. The number of pinholes in the film after 100 repetitions under the condition of 20 ° C.-65% RH was measured. In addition, the same bending test was performed to measure the number of bendings until the first pinhole was generated.

(3) Young's modulus Measured under conditions of 20 ° C. and 65% RH according to ASTM D-882-67.

(4) Film impact A 0.6-inch hemisphere attached to the tip of the circular film with a constant area stretched horizontally is stuck in the center, and the force when the film bursts is read. The film sample was measured after conditioning for 2 weeks under the condition of 20 ° C.-65% RH. (Equipment used: Toyo Seiki Co., Ltd. Film Impact Tester)

(5) Oxygen transmission rate (OTR)
OX-Tran 10-50A manufactured by Modern Control was used, and the test was performed at 20 ° C. and 65% RH.

(6) Situation of generation of gel and fish eyes The appearance of the film after film formation for 24 hours was visually observed and evaluated according to the following criteria A to D.
A: No gel fish eye was generated.
B: A minute gel fish eye was generated.
C: Minute gel fish eyes were partially generated.
D: A minute gel fisheye was generated on the entire surface.

Examples 4-2 to 4-6 and comparative examples 4-1 to 4-9
Example 4-1 except that the resin type and blending ratio were changed so that pellets of the resin composition shown in Table 9 were obtained instead of the resin composition pellets consisting of the four components prepared in Example 4-1. In the same manner as above, a single layer film was formed and evaluated. When the resin composition was composed of two or three components, blending was performed by one kneading operation, and when the resin composition was composed of one component, the kneading operation was not performed. The evaluation results are summarized in Table 9.

Example 4-7
A single-layer film was formed in the same manner as in Example 4-1, except that the same composition as Example 4-1 was used to pelletize the four types of resin components by only one kneading operation. evaluated. Table 9 shows the evaluation results.

<Test on matte film>
Example 5-1
EVOH pellets having an ethylene content of 44 mol%, a saponification degree of 99.4 mol%, a melt index of 5.1 g / 10 min (under 190 ° C and a load of 2160 g), a melt index of 1.0 g / 10 min (190 ° C) , Under a load of 2160 g) high-density polyethylene resin 10% by weight, polyamide resin (PA-6: Amilan CN1010T manufactured by Toray) 2% by weight, ethylene-methacrylic acid copolymer (methacrylic acid content 3.1 mol%, melt 1.5 g / 10 min index (under conditions of 190 ° C. and load 2160 g)} 3% by weight was blended and pelletized with a twin screw extruder, then formed into a single screw extruder with a T die, and a 20 μm film. Got. The glossiness of this film was 35%. Moreover, by observing the obtained film with an electron microscope, it was confirmed that EVOH was a matrix layer and high-density polyethylene was a dispersed layer.

About the generation | occurrence | production condition of a gel fish eye, the external appearance of the film after film-forming for 8 hours was observed visually, and it evaluated according to the following reference | standard of AD.
A: No gel fish eye was generated.
B: A minute gel fish eye was generated.
C: Minute gel fish eyes were partially generated.
D: A minute gel fisheye was generated on the entire surface.

Examples 5-2 to 5-9, Comparative Examples 5-1 to 5-7
A film in which the compounded resin and the compounding amount of Example 5-1 were changed was prepared in the same manner as in Example 5-1, the glossiness was measured, and the appearance was observed. Table 10 shows the blended resin, blending amount, and measurement results of each example.

EVOH (A) used the following.
・ A-1
EVOH {ethylene content 44 mol%, saponification degree 99.4%, melt index 5.1 g / 10 min (190 ° C, 2160 g load)}
・ A-2
EVOH {ethylene content 27 mol%, saponification degree 99.4%, melt index 1.5 g / 10 min (190 ° C, 2160 g load)}

The polyamide (B) used the following.
・ B-1
6-polyamide (Toray, Amilan CN1010T)
・ B-2
6 / 12-copolymerized polyamide (UBE nylon 7024B)

The ethylene-unsaturated carboxylic acid random copolymer or its metal salt (C) was as follows.
・ C-1
Ethylene-methacrylic acid random copolymer {methacrylic acid content 3.1 mol%, melt index 1.5 g / 10 min (190 ° C., 2160 g load)}
・ C-2
Metal salt of ethylene-methacrylic acid random copolymer (ionomer) {methacrylic acid content 5.3 mol%, neutralization degree 60%, counter ion species Zn, melt index 0.7 g / 10 min (190 ° C, 2160 g load) )}
・ C-3
Metal salt of ethylene-methacrylic acid random copolymer (ionomer) {methacrylic acid content 6.7 mol%, neutralization degree 36%, counter ion species Na, melt index 2.1 g / 10 min (190 ° C, 2160 g load) )}

The following were used for the thermoplastic resin (D).
・ D-1
High density polyethylene {Melt index 1.0g / 10min (190 ° C, 2160g load)}
・ D-2
Low density polyethylene {Melt index 2.5g / 10min (190 ° C, 2160g load)}
・ D-3
Maleic anhydride-modified high-density polyethylene {modified amount 0.09 mol%, melt index 1.0 g / 10 min (190 ° C, 2160 g load)}

Example 5-10
As a model of the polyvinyl chloride wallpaper, 100 parts by weight of polyvinyl chloride (P = 1400), 45 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, 1 part by weight of an epoxy resin stabilizer (trade name EP-828), After stirring 1 part by weight of barium-zinc composite liquid stabilizer, 0.2 part by weight of barium stearate, 0.4 part by weight of zinc stearate, and 1.5 parts by weight of sorbitan monostearate with a super mixer for 10 minutes, 165 It knead | mixed on the mixing roll warmed at (degreeC), and produced the 0.1-mm-thick polyvinyl chloride type film. The EVOH composition film created in Example 5-1 was laminated on this using urethane adhesive AD-335A and curing agent cat-10 (manufactured by Toyo Morton Co., Ltd., mixing ratio 17: 1), and stain resistance, Bleed resistance and gloss were evaluated. The evaluation results are shown in Table 11.

  In addition, evaluation of stain resistance is based on each writing material of water-based pen (Sakura sign pen), oil-based pen (Zebra Mackey extra-fine), lipstick (Shiseido's Leschenage Excellent RD524), and crayon (Sakura crayon thick roll red). A neutral line (Lion Mama Lemon) and an oil-based pen were used to evaluate the degree of discoloration remaining after wiping with a household thinner using a JIS gray scale. As for the bleed resistance, two sheets were laminated so that the laminate film surfaces overlapped at 70 ° C., left under a load of 100 g / cm for 24 hours, and the state of the film surface was visually observed.

Comparative Example 5-8
Evaluation was made in the same manner as in Example 5-10 on the polyvinyl chloride film on which the EVOH composition film was not laminated in Example 5-10. The evaluation results are shown in Table 11.

  When the examples and comparative examples are compared, it is clear that the gloss of the film of the present invention is significantly reduced. It can also be seen from Example 5-10 and Comparative Example 5-8 that the film laminate of the present invention significantly improves the stain resistance and bleed resistance of the substrate.

It is sectional drawing of the tube-shaped container which shows one Example of this invention. It is an expanded sectional view of the tubular container of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cylindrical trunk | drum 2 Oral head 2a Male screw 2b Shoulder part 3 Oral head shoulder part 4 Bottom part junction part 5 Heat seal layer (LDPE)
6 Adhesive resin 7 Barrier resin (EVOH)
8 Adhesive resin 9 Outer layer (LDPE)

Claims (16)

An ethylene-vinyl alcohol copolymer (A), a polyamide resin (B), an ethylene-unsaturated carboxylic acid random copolymer or a metal salt thereof (C), and a solubility parameter of 11 or less (calculated from the Fedors equation) Resin composition which consists of thermoplastic resins (D) other than the said resin to have; and a compounding weight ratio satisfies following formula (1)-(4). 0.6 ≦ W (A + D) / W (T) ≦ 0.995 (1) 0.005 ≦ W (B + C) / W (T) ≦ 0.4 (2) 0.01 ≦ W (A) / W (A + D) ≦ 0.99 (3) 0.02 ≦ W (B) / W (B + C) ≦ 0.98 (4) (W (A); weight of (A) in composition W (B ); Weight (B) of (B) in the composition; weight W (D) of (C) in the composition; weight W (T) of (D) in the composition; total weight of the composition) The resin composition according to claim 1, comprising 0.01 to 3 parts by weight of at least one selected from a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound with respect to the total weight of the resin composition. The resin composition according to claim 1 or 2, wherein the blending weight ratio W (B) / W (B + C) is 0.5 or less. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (D) is a matrix phase and the ethylene-vinyl alcohol copolymer (A) is a dispersed phase. The resin composition according to any one of claims 1 to 3, wherein the ethylene-vinyl alcohol copolymer (A) is a matrix phase and the thermoplastic resin (D) is a dispersed phase. The resin composition according to claim 5, wherein the thermoplastic resin (D) has an elastic modulus at 20 ° C. of 500 kg / cm ² or less. The polyamide resin (B) and the ethylene-unsaturated carboxylic acid random copolymer or metal salt thereof (C) are first melt mixed, and then the ethylene-vinyl alcohol copolymer (A) and the thermoplastic resin (D) The manufacturing method of the resin composition in any one of Claims 1-6 which melt-mixes. A multilayer structure comprising at least one layer comprising the resin composition according to claim 1. An oral head of a tubular container comprising the resin composition according to claim 4. A molded product comprising the resin composition according to claim 4 and having a coating applied on the surface thereof. A thermoformed container having a layer comprising the resin composition according to claim 4. A flexible film comprising the resin composition according to claim 5. A matte film comprising the resin composition according to claim 5 and having a surface glossiness of 60% or less on at least one side. Polyamide resin (B) and ethylene-unsaturated carboxylic acid random copolymer or metal salt thereof (C) are used as compatibilizers, and ethylene-vinyl alcohol copolymer (A) and a solubility parameter of 11 or less (Fedors A scrap recovery method for recovering a scrap of a molded product mainly composed of a thermoplastic resin (D) other than the resin having the formula (1). The scrap recovery method according to claim 14, wherein the compatibilizing agent contains at least one of a metal salt of a higher aliphatic carboxylic acid and a hydrotalcite compound. A multilayer structure comprising at least one scrap recovery layer made of a resin composition obtained by the recovery method according to claim 14 or 15.

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