JP6450069B2 - Resin composition for melt molding, film, laminate, packaging material and method for producing film - Google Patents

Description

  The present invention relates to a resin composition containing an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as “EVOH”), a film formed from the resin composition, a laminate having a layer comprising the film, the film or The present invention relates to a packaging material provided with a laminate, and a method for producing a film using the resin composition.

  EVOH resin compositions have excellent gas barrier properties, are formed into films, sheets, containers and the like, and are widely used as various packaging materials. For example, an EVOH film constitutes a laminate together with a thermoplastic resin film excellent in moisture resistance, mechanical properties, etc., particularly a polyolefin resin film, and is used in various fields as a packaging material. Such packaging materials are widely used in the fields of foods, cosmetics, medicinal chemicals, toiletries, vacuum insulation plates, etc. in the form of bags, tubes, cups, pouches, etc., for example, as containers having excellent oxygen barrier properties. Moreover, it is used also in the field | area where the barrier property of gasoline vaporization is calculated | required like the gasoline tank of a motor vehicle. EVOH resin compositions used for packaging materials in these fields are required to satisfy the following various characteristics.

  The EVOH resin composition is required to have high appearance characteristics even after melt molding, such as no yellow coloring on the roll end surface after being wound up as a roll in the film forming step.

  In addition, the EVOH resin composition can reduce film breakage that may occur due to the tension between rolls in a film unwinding process or the like when laminating another thermoplastic resin layer on the EVOH film or when forming a vapor deposition layer. (Film break resistance) and high slipperiness (blocking resistance) between films when stored as a film roll or between a roll and EVOH film in a production process at the time of lamination are also required.

  Furthermore, if a vapor deposition defect such as a pinhole occurs during the vapor deposition process, the gas barrier performance deteriorates (see Japanese Patent Application Laid-Open No. 2005-290108). Therefore, the vapor deposition defect occurs during the vapor deposition process and the defect increases over time. It is demanded to suppress this.

  Moreover, in the laminated body which has a vapor deposition layer, it is also requested | required that the adhesion strength of a vapor deposition layer and an EVOH film should be improved, and the delamination etc. which may cause the appearance defect may be suppressed.

  In response to these requirements, in order to prevent the occurrence of coloring such as yellowing in melt molding, acids such as carboxylic acid and phosphoric acid, and metal salts such as alkali metal salts and alkaline earth metals at an appropriate content. A method of inclusion has been proposed (see JP 2001-146539 A). In addition, in order to improve the slipperiness and blocking resistance of the film, it has been proposed to contain an oxide and a boride (see JP 2000-265024 A). Furthermore, with respect to the suppression of gas barrier performance degradation due to pinholes in vapor deposition, a surface treatment resin film having a molar ratio of oxygen atoms to carbon atoms on the film surface of 0.24 or more is used, and is treated with metal aluminum or silicon oxide. It has been proposed to use a multilayer structure including at least one layer (see JP-A-2005-290108).

  However, the method of adding an acid or metal salt in an appropriate amount described in JP-A No. 2001-146539 cannot sufficiently suppress the occurrence of coloring such as yellowing in melt molding. In addition, the addition of the oxide and boron compound described in JP-A-2000-265024 improves the slipperiness and blocking resistance of the film, but does not sufficiently suppress the generation of pinholes in the vapor deposition process and the laminate processability. . Furthermore, in the multilayer structure disclosed in Japanese Patent Application Laid-Open No. 2005-290108, the generation of pinholes in a layer treated with metal aluminum or silicon oxide cannot be reduced. Thus, the conventional resin composition cannot satisfy the above requirements. In addition, from the environmental point of view, it is necessary to consider the odor during molding.

JP-A-2005-290108 JP 2001-146539 A JP 2000-265024 A

  The present invention has been made on the basis of the circumstances as described above, and its purpose is the appearance characteristics after melt molding, such as the color of the film end (roll end), film breakage resistance, blocking resistance, and vapor deposition. An object of the present invention is to provide a resin composition that is excellent in defect suppression and adhesion strength of a deposited layer.

  The invention made to solve the above problems contains an ethylene-vinyl alcohol copolymer (A) (hereinafter also referred to as “EVOH (A)”), inorganic particles (B), and a saturated ketone (C). The resin composition has a content of the inorganic particles (B) of 50 ppm to 5,000 ppm and a content of the saturated ketone (C) of 0.01 ppm to 100 ppm.

  The resin composition of the present invention contains EVOH (A), inorganic particles (B) and saturated ketone (C), and contains a specific amount of inorganic particles (B) and saturated ketone (C), thereby being melt-molded. It is excellent in later appearance characteristics, film breakage resistance, deposition defect suppression and adhesion strength of the deposited layer. The reason why such an effect is exhibited is not necessarily clear, but can be inferred as follows, for example. That is, the resin composition contains a specific amount of inorganic particles (B) and saturated ketone (C), thereby improving the blocking resistance and slipping property of the film surface by the inorganic particles (B), and saturated ketone (C It is considered that the suppression of the occurrence of gelled blisters and the like is exhibited. Moreover, saturated ketone (C) interacts effectively on the surface of inorganic particle (B), disperses inorganic particle (B) in the said resin composition, and increases the effect of said inorganic particle (B). Can be considered. As a result, it is possible to improve appearance characteristics after melt molding of the resin composition, film breakage resistance, vapor deposition defect suppression, and adhesion strength of the vapor deposition layer.

  The mass ratio of the inorganic particles (B) to the saturated ketone (C) is preferably 1 or more and 100,000 or less. By setting the mass ratio of the inorganic particles (B) to the saturated ketone (C) within the above range, it is considered that the inorganic particles (B) can be appropriately dispersed as described above, and the arithmetic average roughness of the film surface (Ra) and the average length (RSm) of the contour curve element can be set in a more appropriate range. As a result, the film fracture resistance of the resin composition and the adhesion strength of the vapor deposition layer can be further improved.

  The average particle size of the inorganic particles (B) is preferably 0.5 μm or more and 10 μm or less. The said resin composition can make arithmetic mean roughness (Ra) of a film surface further moderate by making the average particle diameter of an inorganic particle (B) into the said range. As a result, it is possible to further improve the film breakage resistance, the vapor deposition defect suppression property, and the adhesion strength of the vapor deposition layer.

  The metal element constituting the inorganic particle (B) is preferably at least one selected from the group consisting of silicon, aluminum, magnesium, zirconium, cerium, tungsten and molybdenum. Moreover, as an inorganic substance which comprises the said inorganic particle (B), the oxide of the said element is preferable. The said resin composition can further improve the external appearance characteristic after melt molding, etc. by containing the said specific inorganic particle (B).

  The saturated ketone (C) is preferably a saturated aliphatic ketone. The saturated aliphatic ketone is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone and 2-hexanone. By containing these saturated aliphatic ketones, it is possible to further improve the appearance characteristics after melt molding, the film breakage resistance, the vapor deposition defect suppression property, and the adhesion strength of the vapor deposition layer.

  The film of the present invention is formed from the resin composition. By forming the film from the resin composition, the film is excellent in appearance characteristics, film break resistance, and blocking resistance.

  The arithmetic average roughness (Ra) of at least one surface measured according to JIS B0601 of the film is preferably 0.05 μm or more and 1 μm or less. The said film is more excellent in film breakability by making arithmetic mean roughness (Ra) into the said range.

  Moreover, as an average length (RSm) of the contour curve element of at least one surface measured based on JIS B0601 of the said film, 50 micrometers or more and 1,000 micrometers or less are preferable. The said film is further excellent in film fracture resistance by making the average length (RSm) of a contour curve element into the said specific range.

The laminated body of this invention has the layer which consists of the said film, and the layer which consists of another component.
Moreover, it is preferable that the layer which consists of said other component is a metal vapor deposition layer, and the thickness of this metal vapor deposition layer is 30 nm or more and 150 nm or less. Since the laminate has a metal vapor deposition film having a thickness in the specific range, there are few vapor deposition defects, and the adhesion strength between the metal vapor deposition layer and another resin layer is excellent.

The packaging material of the present invention includes the film or the laminate.
Since the packaging material includes the film or the laminate described above, the packaging material is excellent in appearance characteristics and film breakage resistance.

The manufacturing method of the film of this invention has the process of cast-molding the said resin composition.
Moreover, the manufacturing method of another film of this invention has the process of extending | stretching the film obtained from the said resin composition.
According to the manufacturing method of the said film, the film which is excellent by an external appearance characteristic, film fracture resistance, and blocking resistance can be obtained by having the said process.

  Here, the “metal element” is a concept that includes both transition metal elements and typical metal elements, and also includes so-called metalloid elements such as Si and Ge.

  Here, “ppm” is a mass ratio of the corresponding component in the resin composition, and 1 ppm is 0.0001 mass%. The “average particle size” is a value measured by a laser diffraction method.

  The resin composition of the present invention is excellent in appearance characteristics after melt molding, such as the color of the film end (roll end), film breakage resistance, blocking resistance, deposition defect suppression, and adhesion strength of the deposited layer. The film of the present invention is excellent in appearance characteristics such as the color of the film end (for example, roll end), film breakage resistance and blocking resistance. According to the film production method of the present invention, it is possible to produce a film that is superior in appearance characteristics such as the color of the film edge (for example, roll edge), film breakage resistance, and blocking resistance. The laminate of the present invention has few vapor deposition defects and is excellent in adhesion strength between the vapor deposition layer and the film. The packaging material of the present invention is excellent in appearance characteristics and film breakage resistance. Therefore, these can be suitably used as various packaging materials.

  Embodiments of the present invention will be described below. However, the present invention is not limited to the following description. Moreover, as long as there is no description in particular, the material illustrated below may be used individually by 1 type, and may use 2 or more types together.

<Resin composition>
The resin composition contains EVOH (A), inorganic particles (B), and saturated ketone (C). The resin composition may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, EVOH (A), inorganic particles (B), saturated ketone (C), and other optional components will be described in detail.

<EVOH (A)>
EVOH (A) is a copolymer obtained by saponifying a copolymer of ethylene and vinyl ester.

  Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate and the like, and vinyl acetate is preferable. These vinyl esters may be used alone or in combination of two or more.

  EVOH (A) may contain other structural units derived from monomers other than ethylene and vinyl ester. Examples of such monomers include vinyl silane compounds and other polymerizable compounds. As content of said other structural unit, it is 0.0002 mol% or more and 0.2 mol% or less with respect to all the structural units of EVOH (A), for example.

  Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, and γ-methacryloxypropylmethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

Examples of the other polymerizable compounds include unsaturated hydrocarbons such as propylene and butylene;
Unsaturated carboxylic acids such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate or esters thereof;
And vinyl pyrrolidone such as N-vinyl pyrrolidone.

  The ethylene content of EVOH (A) is usually 20 mol% or more and 60 mol% or less, preferably 24 mol% or more and 55 mol% or less, more preferably 27 mol% or more and 45 mol% or less, and more preferably 27 mol% or more. 42 mol% or less is still more preferable, and 27 mol% or more and 38 mol% or less are especially preferable. If the ethylene content is less than 20 mol%, the water resistance of the packaging material obtained from the resin composition, the hot water resistance, and the gas barrier property under high humidity may be lowered, or the melt moldability may be deteriorated. is there. On the other hand, when ethylene content exceeds 60 mol%, there exists a possibility that gas barrier properties, such as a packaging material obtained from the said resin composition, may fall.

  The saponification degree of the structural unit derived from the vinyl ester of EVOH (A) is usually 85% or more, preferably 90% or more, more preferably 98% or more, and further preferably 99% or more. If the degree of saponification is less than 85%, the thermal stability may be insufficient.

  As content of EVOH (A) in the said resin composition, it is 95 mass% or more normally, 98.0 mass% or more is preferable, 99.0 mass% is more preferable, 99.5 mass% or more is further more preferable. . By setting the EVOH (A) content to 95% by mass or more, the advantageous properties possessed by EVOH can be sufficiently exerted, and thus molded articles obtained from the resin composition are excellent in gas shielding properties, oil resistance, and the like. .

  The lower limit of the EVOH (A) melt flow rate is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes, further preferably 1 g / 10 minutes, and particularly preferably 3 g / 10 minutes. The upper limit of the EVOH (A) melt flow rate is preferably 200 g / 10 minutes, more preferably 50 g / 10 minutes, still more preferably 30 g / 10 minutes, and particularly preferably 15 g / 10 minutes. By setting the melt flow rate of EVOH (A) within the above range, the melt molding property of the obtained resin composition is improved, and more excellent appearance characteristics and long run properties (such as fish eyes and streaks in long-time molding) Can be obtained). The melt flow rate is a value measured at a temperature of 210 ° C. and a load of 2,160 g in accordance with JIS K7210.

<Inorganic particles (B)>
The resin composition of the present invention has an appropriate arithmetic average roughness (Ra) on the surface of a film formed from the resin composition, and improves blocking resistance and slipperiness. Here, an inorganic particle means the particle | grains which have an inorganic substance as a main component. The main component refers to a component having the largest content, for example, a component having a content of 50% by mass or more.

  The inorganic substance constituting the inorganic particles (B) is preferably at least one selected from the group consisting of silicon, aluminum, magnesium, zirconium, cerium, tungsten and molybdenum. Among these, at least one selected from the group consisting of silicon, aluminum, and magnesium is more preferable because it is easily available.

  Examples of the inorganic material include oxides, nitrides, and oxynitrides of the exemplified elements, and oxides are preferable.

  The lower limit of the average particle diameter of the inorganic particles (B) is preferably 0.5 μm, more preferably 1.5 μm, and further preferably 2.5 μm. The upper limit of the average particle diameter of the inorganic particles (B) is preferably 10 μm, more preferably 8 μm, and even more preferably 5 μm. By setting the average particle diameter of the inorganic particles (B) within the above range, the arithmetic average roughness (Ra) of the surface of the film formed from the resin composition becomes appropriate, and the blocking resistance and slipping property are improved. To do. As a result, the resin composition can improve the film rupture resistance, the deposition defect suppressing ability and the adhesion strength of the deposition layer, and can further improve the adhesion strength of the film.

  As a minimum of content of an inorganic particle (B), it is 50 ppm to the resin composition concerned, 100 ppm is preferred, and 150 ppm is more preferred. As an upper limit of content of an inorganic particle (B), it is 5,000 ppm with respect to the said resin composition, 4,000 ppm is preferable and 3,000 ppm is more preferable. By setting the content of the inorganic particles (B) in the above range, the arithmetic average roughness (Ra) of the surface of the film formed from the resin composition becomes appropriate, and the blocking resistance and slipping property are improved. . As a result, the resin composition is excellent in film rupture resistance and vapor deposition defect suppression, and can improve the adhesion strength of the resulting film. As an inorganic particle (B), 1 type, or 2 or more types of particle | grains may be included. Moreover, one particle | grain may be formed from 1 type, or 2 or more types of inorganic substances.

<Saturated ketone (C)>
Saturated ketone (C) increases the effect of inorganic particles (B) by suppressing the generation of gelled particles and improving the dispersibility of inorganic particles (B) in the resin composition. is there. Here, the saturated ketone (C) refers to a ketone that does not contain an unsaturated bond in a portion other than the carbonyl group in the molecule. As long as the saturated ketone (C) does not contain an unsaturated bond in a portion other than the carbonyl group, it may be a linear ketone or a branched ketone, and a ketone having a ring structure in the molecule. It may be. The number of carbonyl groups in the molecule of the saturated ketone (C) may be 1 or 2 or more.

  Examples of the saturated ketone (C) include saturated aliphatic ketones and saturated cyclic ketones.

  Examples of saturated aliphatic ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 3-methyl-2-butanone, 2-hexanone, 3-hexanone, 4-methyl-2-pentanone, 2-methyl-3- Pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-hexanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, 2-octanone, 3-methyl-2-heptanone, 5-methyl-3-heptanone, 3-octanone, 6-methyl-2-heptanone, 2-nonanone, 5-nonanone, 2,6-dimethyl-4-heptanone, 2,2,4,4-tetramethyl-3-pentanone, 6-undecanone, 2-undecanone, 7-tridecanone, 18-pen Triacontanyl Non, methylcyclopentyl ketone, methyl cyclohexyl ketone, ethyl cyclopentyl ketone, ethyl cyclohexyl ketone.

  Examples of saturated cyclic ketones include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecanone, cyclopentadecanone, cyclohexanone. Examples include sadecanone, cycloheptadecanone, cyclooctadecanone, and cyclononadecanone.

  As carbon number of saturated ketone (C), from a viewpoint of the water solubility improvement of saturated ketone (C), 3-50 are preferable, 3-15 are more preferable, and 3-8 are more preferable. As the saturated ketone (C), among the exemplified examples, saturated aliphatic ketones are preferable from the viewpoint of suppressing generation of defects and coloring due to melt molding and improving long run properties, and acetone, methyl ethyl ketone, and 2-hexanone are more preferable. Acetone is more preferred.

  In the saturated ketone (C), part or all of the hydrogen atoms may be substituted with a substituent as long as the effects of the present invention are not impaired. Examples of the substituent include a halogen atom, a hydroxy group, an amino group, an amide group, and a cyano group.

  The lower limit of the saturated ketone (C) content in the resin composition is 0.01 ppm, preferably 0.05 ppm, more preferably 0.1 ppm, further preferably 0.15 ppm, and particularly preferably 0.2 ppm. . The upper limit of the content of the saturated ketone (C) is 100 ppm, preferably 95 ppm, more preferably 50 ppm, still more preferably 30 ppm, and particularly preferably 20 ppm. When the content of the saturated ketone (C) is less than the above lower limit, the effect of containing the saturated ketone (C), for example, the suppression of the occurrence of gelled particles due to the saturated ketone (C), the dispersion of the inorganic particles (B) The effect of improving the properties cannot be obtained sufficiently. On the other hand, if the content of the saturated ketone (C) exceeds the above upper limit, oxidation and cross-linking with the saturated ketone (C) of the resin composition at the time of melt molding are likely to occur, which may induce the formation of gelled blisters. In addition, the resin composition is easily colored.

<Other optional components>
The base film may contain other optional components as long as the effects of the present invention are not impaired. Examples of other optional components include boron compounds, carboxylic acids and ions thereof, metal ions, conjugated polyene compounds, phosphorus compounds, and other additives. The resin composition may contain two or more of these optional components, and the total content of the optional components is preferably 1% by mass or less in the resin composition.

(Carboxylic acid and its ions)
Carboxylic acid and its ions improve coloration resistance during melt molding of the resin composition.

  Carboxylic acid is a compound having one or more carboxyl groups in the molecule. In addition, the carboxylate ion is one in which the hydrogen ion of the carboxyl group of the carboxylic acid is eliminated. The carboxylic acid contained in the resin composition may be a monocarboxylic acid, a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule, or a combination thereof. The polyvalent carboxylic acid does not include a polymer. The polyvalent carboxylate ion is one in which at least one hydrogen ion of the carboxyl group of the polyvalent carboxylic acid is eliminated. The carboxylate ion may form a salt with a metal ion.

  The monocarboxylic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, acrylic acid, methacrylic acid, benzoic acid, and 2-naphthoic acid. These carboxylic acids may have a hydroxyl group or a halogen atom. Examples of the carboxylate ion include those from which the hydrogen ion of the carboxyl group of the carboxylic acid is eliminated. The pKa of the monocarboxylic acid (including a polycarboxylic acid that gives a monocarboxylic acid ion) is preferably 3.5 or more, more preferably 4 or more, from the viewpoint of the pH adjusting ability and melt moldability of the resin composition. preferable. Examples of such monocarboxylic acids include formic acid (pKa = 3.68), acetic acid (pKa = 4.74), propionic acid (pKa = 4.85), butyric acid (pKa = 4.80), and the like. Acetic acid is preferred because it is easy to handle.

  The polyvalent carboxylic acid is not particularly limited as long as it has two or more carboxyl groups in the molecule. For example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, Aliphatic dicarboxylic acids such as adipic acid and pimelic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as aconitic acid; 1,2,3,4-butanetetracarboxylic acid and ethylenediaminetetraacetic acid Carboxylic acids having 4 or more carboxyl groups such as tartaric acid, citric acid, isocitric acid, malic acid, mucinic acid, tartronic acid, citramalic acid and the like; oxaloacetic acid, mesooxalic acid, 2-ketoglutaric acid, 3- Ketocarboxylic acids such as ketoglutaric acid; amino such as glutamic acid, aspartic acid, 2-aminoadipic acid Etc. The. Among these, succinic acid, malic acid, tartaric acid, and citric acid are preferable because they are easily available. Examples of the polyvalent carboxylic acid ion include anions derived from the polyvalent carboxylic acid.

  The upper limit of the content of carboxylic acid and carboxylate ion is preferably 20 μmol / g, more preferably 15 μmol / g, and even more preferably 10 μmol / g in terms of carboxylic acid root, from the viewpoint of color resistance during melt molding. On the other hand, the lower limit of the content is preferably 0.01 μmol / g, more preferably 0.05 μmol / g, further preferably 0.5 μmol / g in terms of carboxylic acid radical.

(Metal ions)
Metal ions improve the adhesion between layers when packaging materials and the like are molded. By containing metal ions, the resin composition can improve adhesion between layers when a packaging material or the like is molded, and as a result, durability of the packaging material or the like can be improved. The reason why such metal ions improve interlaminar adhesion is not necessarily clear. However, when one of adjacent layers has a functional group capable of reacting with the hydroxyl group of EVOH (A) in the molecule, the hydroxyl group is used. It is conceivable that the bond formation reaction between the functional group and the functional group is accelerated by the presence of a metal ion.

  Examples of the metal ions include alkali metal ions and alkaline earth metal ions. These metal ions may be used alone or in combination of two or more.

  As a metal ion, an alkali metal ion is preferable. Examples of the alkali metal ion include lithium, sodium, potassium, rubidium, cesium and the like, and sodium ion and potassium ion are preferable from the viewpoint of industrial availability. By including alkali metal ions, the resin composition can improve the interlaminar adhesive strength when used as a long run property in melt molding and a packaging material.

  Although it does not specifically limit as a compound containing the said alkali metal ion, For example, Alkali metal salts, such as aliphatic carboxylates, such as lithium, sodium, and potassium, Aromatic carboxylates, and phosphates; Metal complexes etc. are mentioned. . Examples of the alkali metal salt include sodium acetate, potassium acetate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, diphosphate phosphate. Examples thereof include lithium hydrogen, trilithium phosphate, sodium stearate, potassium stearate, and a sodium salt of ethylenediaminetetraacetic acid. Among these, sodium acetate, potassium acetate, and sodium dihydrogen phosphate are preferable because they are easily available.

  As the metal ion, an alkaline earth metal ion is also preferable. Alkaline earth metal ions include ions such as beryllium, magnesium, calcium, strontium, and barium, but magnesium ions and calcium ions are preferred from the viewpoint of industrial availability. In the resin composition, the metal ion is an alkaline earth metal ion, so that deterioration when the formed packaging material and the like are repeatedly reused is suppressed, and the molded product is reduced due to the reduction of defects such as gel-like material. The appearance can be improved.

  The lower limit of the metal ion content (content in the dry resin composition) is preferably 2.5 μmol / g, more preferably 3.5 μmol / g, and even more preferably 4.5 μmol / g. The upper limit of the metal ion content is preferably 22 μmol / g, more preferably 16 μmol / g, and even more preferably 10 μmol / g. If the metal ion content is less than the above lower limit, the interlaminar adhesion may be reduced. On the other hand, when the content of the metal ions exceeds the above upper limit, it is difficult to reduce the color of the resin composition by containing the saturated ketone (C), and the appearance characteristics after melt molding may be deteriorated.

(Phosphorus compound)
The phosphorus compound suppresses generation and coloring of defects such as streak and fish eye, and improves long run properties. Examples of the phosphorus compound include phosphates such as phosphoric acid and phosphorous acid.

  As said phosphate, any form of a 1st phosphate, a 2nd phosphate, and a 3rd phosphate may be sufficient. Moreover, although it does not specifically limit also about the cation seed | species of a phosphate, An alkali metal salt and alkaline-earth metal salt are preferable, Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, hydrogen phosphate 2 Sodium and dipotassium hydrogen phosphate are more preferable, and sodium dihydrogen phosphate and dipotassium hydrogen phosphate are more preferable.

  As a minimum of content of a phosphorus compound in the resin composition, 1 ppm is preferred, 2 ppm is more preferred, 3 ppm is still more preferred, and 5 ppm is especially preferred. As an upper limit of content of a phosphorus compound, 200 ppm is preferable, 150 ppm is more preferable, and 100 ppm is further more preferable. When the content of the phosphorus compound is less than the above lower limit or exceeds the above upper limit, the thermal stability is reduced, and there is a risk that gelled spots and coloration are likely to occur during long-time melt molding. .

(Boron compound)
The boron compound suppresses gelation during melt molding and suppresses torque fluctuations (viscosity change during heating) of an extruder or the like.

Examples of the boron compound include boric acids such as orthoboric acid, metaboric acid, and tetraboric acid; boric acid esters such as triethyl borate and trimethyl borate;
Borate salts such as alkali metal salts or alkaline earth metal salts of borates, borax;
Examples thereof include borohydrides. Among these, boric acids are preferable, and orthoboric acid (hereinafter also referred to as “boric acid”) is more preferable.

  The lower limit of the boron compound content in the resin composition is preferably 100 ppm, more preferably 150 ppm. The upper limit of the boron compound content is preferably 5,000 ppm, more preferably 4,000 ppm, and even more preferably 3,000 ppm. If the boron compound content is less than the above lower limit, torque fluctuations in an extruder or the like may not be sufficiently suppressed. On the other hand, if the content of the boron compound exceeds the above upper limit, gelation tends to occur during melt molding, and the appearance of the molded product may be deteriorated. In addition, content of a boron compound is boron element conversion content of the boron compound in a dry resin composition.

(Conjugated polyene compound)
The conjugated polyene compound suppresses oxidative degradation during melt molding. Here, the conjugated polyene compound is a so-called conjugated double compound having a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected and having two or more carbon-carbon double bonds. A compound having a bond. This conjugated polyene compound may be a conjugated diene having two conjugated double bonds, a conjugated triene having three, or a conjugated polyene having more than that number. Further, a plurality of sets of the conjugated double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated triene structures in the same molecule such as tung oil is also included in the conjugated polyene compound.

  The number of conjugated double bonds in the conjugated polyene compound is preferably 7 or less. When the resin composition contains a conjugated polyene compound having 8 or more conjugated double bonds, the molded product is highly likely to be colored.

  In addition to conjugated double bonds, the conjugated polyene compounds include carboxyl groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, imino groups, amide groups, cyano groups, diazo groups, nitro groups, sulfones. It may have other functional groups such as a group and a salt thereof, a sulfonyl group, a sulfoxide group, a sulfide group, a thiol group, a phosphate group and a salt thereof, a phenyl group, a halogen atom, a double bond, and a triple bond.

Examples of the conjugated polyene compound include isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3- Pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2- Methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4- Hexadiene, 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-diphenyl-1,3-butyl Tadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3-butadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene Butadiene, chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1,3-butadiene, oxime, ferrandrene, myrcene, farnesene, semblene, sorbic acid, sorbic acid Conjugated diene compounds such as esters, sorbates and abietic acids;
Conjugated triene compounds such as 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, cholecalciferol, fulvene, and tropone;
Examples thereof include conjugated polyene compounds such as cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoic acid. The said conjugated polyene compound may be used individually by 1 type, and may use 2 or more types together.

  As carbon number of a conjugated polyene compound, 4-30 are preferable and 4-10 are more preferable. Among the exemplified conjugated diene compounds, sorbic acid, sorbic acid ester, sorbate, myrcene, and a mixture of two or more thereof are preferable, and sorbic acid, sorbate, and a mixture thereof are more preferable. Sorbic acid, sorbate and a mixture thereof are highly effective in suppressing oxidative degradation at high temperatures, and are also widely used industrially as food additives, and thus are preferable from the viewpoint of hygiene and availability.

  The molecular weight of the conjugated polyene compound is usually 1,000 or less, preferably 500 or less, and more preferably 300 or less. When the molecular weight of the conjugated polyene compound exceeds 1,000, the dispersion state of the conjugated polyene compound in EVOH (A) may be deteriorated, and the appearance after melt molding may be deteriorated.

  As a minimum of content of a conjugated polyene compound in the resin composition, 0.01 ppm is preferred, 0.1 ppm is more preferred, 0.5 ppm is still more preferred, and 1 ppm is especially preferred. The upper limit of the content is preferably 1,000 ppm, more preferably 800 ppm or less, and even more preferably 500 ppm or less. If the content of the conjugated polyene compound is less than the above lower limit, the effect of suppressing oxidative deterioration during melt molding may not be sufficiently obtained. On the other hand, when the content of the conjugated polyene compound exceeds the upper limit, gelation of the resin composition may be promoted.

(Other additives)
The resin composition of the present invention includes an alkali metal, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, a filler, a heat stabilizer, and a drying agent as long as the effects of the present invention are not impaired. It is also possible to add an appropriate amount of an agent, a crosslinking agent, a reinforcing agent such as various fibers, and the like.

(Alkali metal)
Examples of the alkali metal include lithium, sodium, potassium and the like. Examples of the alkali metal salts include monovalent metal aliphatic carboxylates, aromatic carboxylates, metal complexes, and the like. Specifically, sodium acetate, potassium acetate, sodium stearate, Examples include potassium stearate and sodium salt of ethylenediaminetetraacetic acid. Among these, sodium acetate and potassium acetate are preferable. The alkali metal content in the resin composition is preferably 20 ppm to 1,000 ppm, more preferably 50 ppm to 500 ppm.

(Antioxidant)
Examples of the antioxidant include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis (6-t-butylphenol), 2,2 Examples include '-methylene-bis (4-methyl-6-tert-butylphenol), octadecyl-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate.

(UV absorber)
Examples of ultraviolet absorbers include ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, and 2- (2′-hydroxy-5′-methyl). Phenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, Examples include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-oxybenzophenone and the like.

(Plasticizer)
Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, and phosphate ester.

(Antistatic agent)
Examples of the antistatic agent include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, polyethylene glycol (trade name: carbowax) and the like.

(Lubricant)
Examples of the lubricant include ethylene bisstearamide and butyl stearate.

(Coloring agent)
Examples of the colorant include carbon black, phthalocyanine, quinacridone, indoline, azo pigment, and bengara.

(filler)
Examples of the filler include glass fiber, wollastonite, calcium silicate, talc, and montmorillonite.

(Heat stabilizer)
Examples of the heat stabilizer include hindered phenol compounds and hindered amine compounds.

  In addition, an appropriate amount of a thermoplastic resin other than EVOH (A) can be blended within a range that does not impair the effects of the present invention. Examples of thermoplastic resins other than EVOH (A) include various polyolefins (polyethylene, polypropylene, poly (1-butene), poly (4-methyl-1-pentene), ethylene-propylene copolymers, ethylene and 4 or more carbon atoms. Copolymers with α-olefins, polyolefins modified with maleic anhydride, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, or graft-modified with unsaturated carboxylic acids or derivatives thereof Modified polyolefin, etc.), various nylons (nylon-6, nylon-66, nylon-6 / 66 copolymer, etc.), polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene, polyacrylonitrile, polyurethane, polyacetal, modified polyvinyl alcohol resin Etc. That. When a thermoplastic resin other than EVOH (A) is contained, the content thereof is preferably 50% by mass or less, and more preferably 10% by mass or less with respect to the resin composition.

  The lower limit of the melt flow rate of the resin composition is preferably 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes, further preferably 1 g / 10 minutes, and particularly preferably 3 g / 10 minutes. The upper limit of the melt flow rate of the resin composition is preferably 200 g / 10 minutes, more preferably 50 g / 10 minutes, further preferably 30 g / 10 minutes, particularly preferably 15 g / 10 minutes, and most preferably 10 g / 10 minutes. preferable. By making the melt flow rate of the said resin composition into the said range, melt moldability improves and it can exhibit the more outstanding external appearance characteristic and long run property. The melt flow rate is a value measured at a temperature of 210 ° C. and a load of 2,160 g in accordance with JIS K7210.

<Method for producing resin composition>
The method for producing the resin composition is not particularly limited as long as EVOH (A), inorganic particles (B), and saturated ketone (C) can be blended uniformly.

As a method of uniformly blending the inorganic particles (B) and the saturated ketone (C) in the resin composition with the above specific content,
In the method for producing an ethylene-vinyl alcohol copolymer, (1) a step of copolymerizing ethylene and a vinyl ester, and (2) a step of saponifying the copolymer obtained in step (1), for example,
A method of adding one or both of a specific amount of inorganic particles (B) and saturated ketone (C) in the step (1),
A method of adding one or both of a specific amount of inorganic particles (B) and saturated ketone (C) in the step (2),
A method of adding one or both of a specific amount of inorganic particles (B) and saturated ketone (C) to EVOH obtained by the above step (2),
A method of adding one or both of a specific amount of inorganic particles (B) and saturated ketone (C) when melt-forming EVOH obtained by the above step (2),
The method etc. which use these methods together are mentioned.

  In addition, the specific amount of inorganic particles (B) or saturated ketone (C) is added in the step (1) or a specific amount of inorganic particles (B) or saturated in the step (2). When adopting a method of adding either one or both of ketones (C), it is necessary to add them in a range that does not inhibit the polymerization reaction in step (1) and the saponification reaction in step (2). .

  Among these methods, from the viewpoint of easy control of the content of the inorganic particles (B) and the saturated ketone (C) in the resin composition, the EVOH obtained in the step (2) has a specific amount of inorganic particles ( B) or a method of adding one or both of saturated ketone (C), either a specific amount of inorganic particles (B) or saturated ketone (C) when melt-forming EVOH obtained in step (2) A method of adding one or both of them is preferred, and a method of adding one or both of a specific amount of inorganic particles (B) and saturated ketone (C) to EVOH obtained in step (2) is more preferred.

  As a method of adding a specific amount of inorganic particles (B) and saturated ketone (C) to EVOH, for example, either or both of inorganic particles (B) and saturated ketone (C) are previously blended in EVOH and pelletized. , A method of impregnating a strand precipitated in the step of depositing a paste after saponification of an ethylene-vinyl ester copolymer, a saturated ketone (C) after cutting the precipitated strand, ), A method of adding one or both of inorganic particles (B) and saturated ketone (C) to a redissolved chip of a dry resin composition, EVOH and inorganic particles (B) or saturated ketone (C) A method of melt kneading a blend of either one or both of two or three components, EVOH melt from the middle of the extruder Either one or both of inorganic particles (B) and saturated ketone (C) are used as a method, and one or both of inorganic particles (B) and saturated ketone (C) are blended at a high concentration in a part of EVOH. Examples thereof include a method of preparing a granulated master batch, dry blending with EVOH, and melt-kneading.

  Among these, from the viewpoint that the specific inorganic particles (B) and the saturated ketone (C) can be more uniformly dispersed in EVOH, either one or both of the inorganic particles (B) and the saturated ketone (C) are used. A method of previously blending EVOH with EVOH and granulating the pellet is preferable. Specifically, one or both of inorganic particles (B) and saturated ketone (C) are added to a solution obtained by dissolving EVOH in a good solvent such as a water / methanol mixed solvent, and the mixed solution is added to a nozzle or the like. By extruding into a poor solvent and precipitating and / or solidifying, and washing and / or drying, pellets in which inorganic particles (B) and saturated ketone (C) are uniformly mixed with EVOH can be obtained. .

  Examples of a method of adding other components other than the inorganic particles (B) and the saturated ketone (C) to the resin composition include, for example, a method of mixing and melting and kneading the pellets together with the components, and preparing the pellets. , A method of mixing other components together with the inorganic particles (B) and the saturated ketone (C), a method of immersing the pellet in a solution containing each component, and the like. In addition, a ribbon blender, a high speed mixer kneader, a mixing roll, an extruder, an intensive mixer, etc. can be used for mixing a pellet and another component.

<Molded body>
The resin composition is formed into various molded bodies such as a film, a sheet, a container, a pipe, and a fiber by melt molding or the like. A film usually has a thickness of less than 300 μm, and a sheet usually has a thickness of 300 μm or more. Examples of the melt molding method include extrusion molding, cast molding, inflation extrusion molding, blow molding, melt spinning, injection molding, injection blow molding, and the like. The melt molding temperature is preferably about 150 ° C. to 270 ° C., although it varies depending on the melting point of EVOH (A). Since the said molded object is formed from the said resin composition, it is excellent in an external appearance characteristic. These molded bodies can be pulverized and molded again for the purpose of reuse. It is also possible to uniaxially or biaxially stretch films, sheets, fibers, and the like. The molded body obtained by the above melt molding or the like may be subjected to secondary processing molding such as bending, vacuum molding, blow molding, press molding or the like, if necessary, to obtain a target molded body.

<Film>
The film of the present invention is formed from the resin composition. Since the said film is formed from the said resin composition, it is excellent in an external appearance characteristic and film rupture resistance. Examples of the film include a single layer film and a multilayer film.

  The upper limit of the arithmetic average roughness (Ra) of at least one surface measured according to JIS B0601 of the film is preferably 1.0 μm, more preferably 0.8 μm, still more preferably 0.6 μm, 0 .4 μm is particularly preferred. The lower limit of the arithmetic average roughness (Ra) of at least one surface of the film is preferably 0.05 μm, more preferably 0.10 μm, further preferably 0.15 μm, and particularly preferably 0.20 μm. By setting the arithmetic average roughness (Ra) of at least one surface of the film in the above range, the film break resistance is more excellent.

  As an upper limit of the average length (RSm) of the contour curve element of at least one surface measured according to JIS B0601 of the film, 1,000 μm is preferable, 800 μm is more preferable, 600 μm is further preferable, and 400 μm is preferable. Particularly preferred. The lower limit of the average length (RSm) of the contour curve element on at least one surface of the film is preferably 50 μm, more preferably 100 μm, further preferably 150 μm, and particularly preferably 200 μm. By setting the average length (RSm) of the contour curve element on at least one surface of the film in the above range, the film break resistance is more excellent. The above JIS B0601 represents, for example, JIS B0601-2001.

<Film production method>
The said film can be manufactured by the method similar to what was shown as a method of manufacturing the above-mentioned molded object. Among these, a cast molding step of melt-extruding the resin composition on a casting roll, a step of stretching an unstretched film obtained from the resin composition (uniaxial stretching step, sequential biaxial step, simultaneous biaxial stretching step, A method having an inflation molding step) is preferred. According to the manufacturing method of the said film, film fracture resistance can be improved by having these processes.

<Laminate>
The molded article may be a molded article having a single-layer structure consisting only of a barrier layer (hereinafter also referred to as “barrier layer”) formed from the resin composition. It is preferable to form a laminate having a layer made of another component on one surface. Since the said molded object is equipped with the barrier layer or laminated body formed from the resin composition which has the above-mentioned property, it can be used suitably for boil sterilization or retort sterilization.

As a laminated body, a multilayer sheet, a multilayer pipe, a multilayer hose, a multilayer fiber etc. are mentioned, for example.
As a layer which consists of other components which constitute the above-mentioned layered product, for example, a thermoplastic resin layer formed from a thermoplastic resin is preferred. A laminated body is excellent in an external appearance property, retort resistance, and a processing characteristic by providing a barrier layer and a thermoplastic resin layer.

  The layer structure of the laminate of the present invention is not particularly limited, but the barrier layer or laminate layer is represented by E, the layer obtained from the adhesive resin is Ad, and the layer obtained from the thermoplastic resin is represented by T. , T / E / T, E / Ad / T, T / Ad / E / Ad / T, and the like. Each of these layers may be a single layer or a multilayer.

  It does not specifically limit as a method of manufacturing the said laminated body. For example, a method of melt-extruding a thermoplastic resin into a molded body (film, sheet, etc.) obtained from the resin composition, a method of co-extruding the resin composition and another thermoplastic resin, the resin composition and the thermoplastic A method of co-injecting a resin, the barrier layer or laminate obtained from the resin composition, and a film, sheet, or the like of another substrate with a known adhesive such as an organic titanium compound, an isocyanate compound, or a polyester compound The method of laminating by using, etc. are mentioned.

  Examples of the thermoplastic resin used in the layer made of other components in the laminate include linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer. Polymers, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, olefins such as polybutene and polypentene alone or copolymers thereof, polyesters such as polyethylene terephthalate, polyester elastomers, nylon- 6, polyamide such as nylon-66, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, vinyl ester resin, polyurethane elastomer, polycarbonate, chlorinated polyethylene, chlorinated polypropylene, and the like. Among these, polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyamide, polystyrene, and polyester are preferably used.

  Although it will not specifically limit as said adhesive resin if it has adhesiveness with the said resin composition and thermoplastic resin, The adhesive resin containing carboxylic acid modified polyolefin is preferable. As the carboxylic acid-modified polyolefin, a modified olefin containing a carboxyl group obtained by chemically bonding an ethylenically unsaturated carboxylic acid, its ester or its anhydride to an olefin polymer (for example, addition reaction, graft reaction, etc.) A polymer can be preferably used. Here, the olefin polymer is a polyolefin such as polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene, polypropylene, boribten, olefin and other monomers (vinyl ester, unsaturated carboxylic acid ester, etc.) (For example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ethyl ester copolymer, etc.). Among these, linear low density polyethylene, ethylene-vinyl acetate copolymer (vinyl acetate content 5-55 mass%), ethylene-acrylic acid ethyl ester copolymer (acrylic acid ethyl ester content 8- 35% by mass), linear low density polyethylene and ethylene-vinyl acetate copolymer are particularly preferred. Examples of the ethylenically unsaturated carboxylic acid, its ester or its anhydride include ethylenically unsaturated monocarboxylic acid, its ester, ethylenically unsaturated dicarboxylic acid, its mono or diester, or its anhydride, Of these, ethylenically unsaturated dicarboxylic acid anhydride is preferred. Specific examples include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid diethyl ester, and fumaric acid monomethyl ester. Acid is preferred.

  The addition amount or graft amount (modification degree) of the ethylenically unsaturated carboxylic acid or its anhydride to the olefin polymer is 0.0001 to 15% by mass, preferably 0.001 to 10%, based on the olefin polymer. % By mass. The addition reaction or grafting reaction of ethylenically unsaturated carboxylic acid or its anhydride to olefin polymer, for example, is performed by radical polymerization method in the presence of solvent (such as xylene) and catalyst (such as peroxide). Can do. The melt flow rate (MFR) measured at 210 ° C. of the carboxylic acid-modified polyolefin thus obtained is preferably 0.2 to 30 g / 10 minutes, and more preferably 0.5 to 10 g / 10 minutes. These adhesive resins may be used alone or in combination of two or more.

  The co-extrusion method of the resin composition and the thermoplastic resin or the like is not particularly limited, and examples thereof include a multi-manifold merging method T-die method, a feed block merging method T-die method, and an inflation method.

  Moreover, a laminated body can also be formed by laminating | stacking a vapor deposition layer on the at least one surface of the said film mentioned above. Moreover, this laminated body may laminate | stack the other resin layer on the surface of the vapor deposition layer side and / or the opposite side. By making the said film into the said laminated body, gas barrier property and moisture resistance can be improved. Moreover, since the obtained laminated body uses the film formed from the said resin composition, there are few vapor deposition defects, and it is excellent in the adhesive strength of a vapor deposition layer and an EVOH film layer.

  Examples of the substance that forms the vapor deposition layer include metals such as aluminum, zinc, magnesium, and tin; metals such as silica, alumina, and magnesia, or oxides of semimetals. Among these, metals are preferable and aluminum is more preferable from the viewpoints of the gas barrier properties, moisture resistance, and easiness of vapor deposition.

  The thickness of the vapor deposition layer is preferably 30 nm to 150 nm, more preferably 35 nm to 140 nm, and still more preferably 40 nm to 130 nm. The said laminated body can raise both the adhesive strength of gas barrier property and moisture proofness, and a vapor deposition layer and another resin layer by making the thickness of the said vapor deposition layer into the said range.

<Packaging materials>
The film and laminate obtained as described above can be used as a packaging material. Furthermore, you may obtain packaging materials (a film, a sheet | seat, a tube, a bottle, etc.) by carrying out the secondary process of the said film and laminated body. Examples of the packaging material obtained by the secondary processing include (1) a multilayer co-stretched sheet or film obtained by stretching and heat-treating a film and a laminate in a uniaxial or biaxial direction, and (2) a film and a laminate. A multilayer rolled sheet or film obtained by rolling the body, (3) a multilayer tray cup-shaped container obtained by thermoforming the film and laminate, such as vacuum forming, pressure forming, vacuum pressure forming, etc. (4) Examples thereof include bottles and cup-shaped containers obtained by subjecting the laminate to stretch blow molding or the like.

  In addition, as a secondary processing method, it is not limited to each method illustrated above, For example, well-known secondary processing methods other than the above, such as blow molding, can be used suitably.

  Since the laminate has a layer obtained from the resin composition having excellent appearance characteristics and long run properties, it is less colored such as fish eyes, streaks, and yellowing. For example, deep drawn containers, cup-shaped containers, bottles It can be suitably used as a food container or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.

  Analysis and evaluation of EVOH resin compositions and the like in Examples and Comparative Examples were performed by the following methods.

(1) Measurement of water content of water-containing EVOH pellets Water content of water-containing EVOH pellets using a halogen moisture analyzer “HR73” manufactured by METTLER TOLEDO at a drying temperature of 180 ° C., a drying time of 20 minutes, and a sample amount of about 10 g. The rate was measured. The moisture content of the water-containing EVOH shown below is mass% based on the dry mass of EVOH.

(2) Ethylene content and saponification degree of EVOH (A) Using a nuclear magnetic resonance apparatus (“Superconducting nuclear magnetic resonance apparatus Lambda500” manufactured by JEOL Ltd.), DMSO-d ₆ as a measurement solvent, and ¹ H-NMR Asked.

(3) Quantification of carboxylic acid and carboxylate ion The dried EVOH pellets were pulverized by freeze pulverization. The obtained pulverized EVOH was divided by a sieve having a nominal size of 1 mm (conforming to standard fluid standard JIS Z8801-3). 10 g of EVOH powder and 50 mL of ion exchanged water that passed through the sieve were put into a 100 mL Erlenmeyer flask with a stopper, and a cooling condenser was attached, followed by stirring at 95 ° C. for 10 hours. 2 mL of the obtained solution was diluted with 8 mL of ion exchange water. The amount of the carboxylic acid and the carboxylate ion was calculated by quantifying the amount of the carboxylate ion of this diluted solution according to the following measurement conditions using ion chromatography “ICS-1500” manufactured by Yokogawa Electric Corporation. A calibration curve prepared using monocarboxylic acid or polyvalent carboxylic acid was used for quantification.

(Measurement condition)
Column: “IonPAC ICE-AS1 (9φ × 250 mm, electrical conductivity detector)” from DIONEX

Eluent: 1.0 mmol / L Octanesulfonic acid aqueous solution Measurement temperature: 35 ° C
Eluent flow rate: 1 mL / min.
Analytical volume: 50 μL

(4) Quantification of inorganic particles (B) and metal ions 0.5 g of dry EVOH pellets were charged into a Teflon (registered trademark) pressure vessel made by Actac, and 5 mL of nitric acid for precision analysis from Wako Pure Chemical Industries, Ltd. was further added. After standing for 30 minutes, the container is covered with a cap lip with a rupture disk, treated at 150 ° C for 10 minutes and then at 180 ° C for 10 minutes with Actac's microwave high-speed decomposition system "Speedwave MWS-2", and dried EVOH The pellet was broken down. When the decomposition of the dry EVOH pellets was not completed, the processing conditions were adjusted as appropriate. The obtained decomposition product was diluted with 10 mL of ion exchange water, and all the liquids were transferred to a 50 mL volumetric flask and the volume was adjusted with ion exchange water to obtain a decomposition product solution.

  By using the ICP emission spectroscopic analyzer “Optima 4300 DV” of PerkinElmer Japan, the obtained decomposition product solution is quantitatively analyzed at each observation wavelength shown below, whereby each inorganic particle (B), metal ion, The amounts of phosphate compound and boron compound were quantified. The content of each inorganic particle (B) was calculated as an oxide conversion value by quantifying the metal element. That is, it calculated as silicon oxide, aluminum oxide, magnesium oxide, zirconium oxide, cerium oxide, tungsten oxide, and molybdenum oxide. When a plurality of metals were included, the amount was calculated as a plurality of metal oxide amounts. The amount of the phosphoric acid compound was calculated as a phosphate radical equivalent value by quantifying phosphorus element. The boron compound content was calculated as a boron element equivalent value.

Na: 589.592 nm
K: 766.490 nm
Mg: 285.213 nm
Ca: 317.933 nm
P: 214.914 nm
B: 249.667 nm
Si: 251.611 nm
Al: 396.153 nm
Zr: 343.823 nm
Ce: 413.764 nm
W: 207.912 nm
Mo: 202.031 nm

(5) Determination method of saturated ketone (C) 50 mg of 2,4-dinitrophenylhydrazine (DNPH) solution 200 mg, 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) 50 mL, acetic acid 11.5 mL and 8 mL of ion exchange water were added to prepare a DNPH solution. Thereafter, 1 g of the dried resin composition pellets was added to 20 mL of the DNPH solution and dissolved by stirring at 35 ° C. for 1 hour. Acetonitrile was added to this solution to precipitate EVOH, followed by filtration and concentration to obtain an extracted sample. Saturated ketone (C) was quantified by quantitatively analyzing the extracted sample by high performance liquid chromatography. For quantification, a calibration curve prepared using a standard obtained by reacting the corresponding saturated ketone (C) with a DNPH preparation solution was used.

(6) Preparation of inorganic particles (B) having different particle diameters In the case of inorganic particles (B) containing silicon atoms, “Silicia 380” (average particle diameter 9.0 μm) or Silysia 310P (average particle diameter) manufactured by Fuji Silysia Chemical Ltd. 2.7 μm) was classified by pulverization and sieving, and adjusted to a desired size.

Similarly, commercially available SiO ₂ · Al ₂ O ₃ , SiO ₂ · MgO, CeO ₂ , ZrO ₂ , WO ₃ and MoO ₃ were classified by pulverization and sieving, and adjusted to a desired size.

(7) Measurement of average particle diameter of inorganic particles (B) The average particle diameter of the inorganic particles (B) was measured using a “laser diffraction particle size distribution analyzer SALD-2200” manufactured by Shimadzu Corporation. As an evaluation sample, 5 g of 50 cc pure water and inorganic particles (B) to be measured were added to a glass beaker, stirred using a spatula, and then subjected to dispersion treatment for 10 minutes with an ultrasonic cleaner. Next, when the liquid containing the inorganic particles (B) subjected to the dispersion treatment is added to the sampler portion of the apparatus and the absorbance is stabilized, the measurement is performed. From the light intensity distribution data of the diffraction / scattered light of the particles, The size distribution (particle size and relative particle amount) was calculated. The average particle size was obtained by multiplying the measured particle size by the relative particle amount and dividing by the total relative particle amount. The average particle diameter is the average diameter of the particles.

(8) Production of film Melted at 240 ° C. using dried EVOH pellets, extruded onto a casting roll from a die, and simultaneously blown air with an air knife at a wind speed of 30 m / sec. A stretched film was obtained. This EVOH unstretched film is brought into contact with 80 ° C. warm water for 10 seconds, and stretched 3.2 times in the longitudinal direction and 3.0 times in the transverse direction in a 90 ° C. atmosphere using a tenter simultaneous biaxial stretching machine, Furthermore, the following biaxially stretched film was obtained by performing heat processing for 5 second within the tenter set to 170 degreeC, and cutting a film edge part.

Film thickness: 12 μm
Film width: 50cm
Film winding length: 4,000m
Number: 100

(9) Determination of odor at the time of molding After putting 20 g of sample pellets of the resin composition into a 100 mL glass sample tube and capping the mouth with aluminum foil, it was heated at 220 ° C. for 30 minutes in a hot air dryer. After removing from the dryer and allowing to cool at room temperature for 30 minutes, the sample tube was shaken 2-3 times, and then the lid of the aluminum foil was removed to confirm the odor. The odor intensity of the sample pellets was evaluated according to the following criteria.

(Criteria)
A: No odor B: Weak odor C: Clear odor

(10) Measurement of film end color As an evaluation of appearance characteristics after melt molding of the resin composition, the obtained biaxially stretched film was wound around a paper tube, and the color of the film end was observed with the naked eye. Judgment criteria are as follows.

(Criteria)
A: No coloring B: Light yellow C: Coloring

(11) Measurement of arithmetic average height (Ra) of film surface and average length (RSm) of contour curve element About the surface of the obtained biaxially stretched film, “shape measurement laser microscope VK-X200” of Keyence Corporation In accordance with JIS-B0601: 2001, arithmetic average roughness (Ra) and average length (RSm) of contour curve elements were measured. In each evaluation, the number of measurements was 100, and the average value was taken as each measurement value. Each of the arithmetic average height (Ra) of the film surface and the average length (RSm) of the contour curve element was determined as follows.

(Criteria)
Arithmetic mean roughness (Ra)
A: 0.20 μm or more and 0.40 μm or less B: 0.15 μm or more and less than 0.20 μm or more than 0.40 μm and 0.60 μm or less C: 0.10 μm or more and less than 0.15 μm or more than 0.60 μm and more than 0.80 μm D: 0.05 μm or more and less than 0.10 μm or more than 0.80 μm and 1.00 μm or less E: When less than 0.05 μm or more than 1.00 μm

(Criteria)
Average length of contour curve elements (RSm)
A: 200 μm or more and 400 μm or less B: 150 μm or more and less than 200 μm or more than 400 μm and 600 μm or less C: 100 μm or more and less than 150 μm or more than 600 μm and 800 μm or less D: 50 μm or more but less than 100 μm or more than 800 μm and less than 1,000 μm E: Less than 50 μm or 1 When exceeding, 000μm

(12) Measurement of the number of film breaks When the resin composition and the film breakage resistance of the film obtained therefrom were wound on the resulting biaxially stretched film on a slitter and applied with a tension of 100 N / m on a film roll The number of breaks was evaluated. Judgment criteria are as follows.

(Criteria)
A: 0 to 1 time / 100 lines B: 2 to 4 times / 100 lines C: 5 to 7 times / 100 lines D: 8 to 10 times / 100 lines E: 11 times or more / 100 lines

(13) Manufacture of a laminated body Using the obtained 100 biaxially stretched films, using a “batch type vapor deposition equipment EWA-105” of Nippon Vacuum Technology Co., Ltd., at a film running speed of 200 m / min, on one side of the film Aluminum was vapor-deposited to obtain a laminate.

(14) Measurement of thickness of vapor deposition layer The obtained laminate was cut with a microtome to expose the cross section. This cross section was observed using a scanning electron microscope (SEM) (“ZEISS ULTRA 55” manufactured by S.I. Nano Technology Co., Ltd.), and the thickness of the deposited layer was measured using a backscattered electron detector.

(15) Deposition defect suppression property The following (15-1) to (15-3) were performed as evaluation of the deposition defect suppression property of the resin composition and the laminate obtained therefrom.

(15-1) Measurement of the number of vapor deposition defects The first roll of the laminate obtained above was placed on a slitter and unwound while applying a 100 W fluorescent lamp from the bottom of the film, n = 0.5 m wide and 2 m long. The number of vapor deposition defects was counted at 10, and the average value was regarded as the number of vapor deposition defects per 1 m ² , and the following determination was made.

(Criteria)
A: 0 to 20 pieces / m ²
B: 21-40 pieces / m ²
C: 41-60 pieces / m ²
D: 61-80 pieces / m ²
E: 81-100 pieces / m ²
F: 101 or more / m ²

(15-2) Measurement of the number of deposition defects (the number of deposition defects over time)
Roll the 100th roll of the laminate obtained above with a slitter, unwind while applying a 100 W fluorescent lamp from the bottom of the film, count the number of vapor deposition defects at n = 10 over a width of 0.5 m and a length of 2 m. The value was defined as the number of vapor deposition defects per 1 m ² and determined as follows.

(Criteria)
A: 0 to 20 pieces / m ²
B: 21-40 pieces / m ²
C: 41-60 pieces / m ²
D: 61-80 pieces / m ²
E: 81-100 pieces / m ²
F: 101 or more / m ²

(15-3) Evaluation of the degree of increase in the number of deposition defects over time As an indication of the long run property of melt molding of the EVOH resin composition, the degree of increase in the number of deposition defects over time is evaluated and determined as follows. did.

(Criteria)
A: No difference in vapor deposition defects between the first and 100th vapor deposition films B: One vapor deposition defect rank difference between the first and 100th vapor deposition films C: First and 100th vapor deposition films There were two rank differences in the actual deposition defects

(16) Measurement of adhesion strength between vapor-deposited layer and EVOH film layer The adhesion strength between the vapor-deposited layer and other resin layers in the laminate and film formed from the resin composition was evaluated.

  Adhesive for dry lamination ("Takelac A-385" and "Takelac A-50" from Mitsui Chemicals Inc.) was mixed at a mass ratio of 6/1 to the surface on the vapor deposition layer side of the obtained laminate, After coating with a bar coater and drying with hot air at 50 ° C. for 5 minutes, with a nip roll heated to 80 ° C., PET film (Toyobo E5000) and Lamination was performed. At this time, half of the film was also provided with a portion that was not pasted by sandwiching an aluminum foil between them. Thereafter, the film was cured at 40 ° C. for 72 hours to obtain a laminate film. The obtained laminate film was cut into strips of 100 mm × 15 mm around the boundary of aluminum deposition, and a T-type peel test was performed 5 times with a tensile tester at a pulling rate of 10 mm / min. The average value of the measured values obtained was defined as the adhesion strength. The adhesion strength was determined as follows.

(Criteria)
A: 500 g / 15 mm or more B: 450 or more and less than 500 g / 15 mm C: 400 or more and less than 450 g / 15 mm D: 350 or more and less than 400 g / 15 mm E: Less than 350 g / 15 mm

<Example 1> (Synthesis of hydrous EVOH pellets)
Polymerization was carried out under the following conditions using a 250 L pressurized reaction tank to synthesize an ethylene-vinyl acetate copolymer.

(Preparation amount)
Vinyl acetate: 83.0kg
Methanol: 17.4kg
2,2′-azobisisobutylnitrile: 66.4 g

(Polymerization conditions)
Polymerization temperature: 60 ° C
Polymerization tank ethylene pressure: 3.9 MPa
Polymerization time: 3.5 hours

  The polymerization rate of vinyl acetate in the above polymerization was 36%. After adding sorbic acid to the obtained copolymerization reaction liquid, it is supplied to the purge tower, unreacted vinyl acetate is removed from the top of the tower by introducing methanol vapor from the bottom of the tower, and an ethylene-vinyl acetate copolymer is obtained. Of 41% by mass in methanol was obtained. The ethylene content of this ethylene-vinyl acetate copolymer was 32 mol%. This methanol solution of ethylene-vinyl acetate copolymer was charged into a saponification reactor, and caustic soda / methanol solution (80 g / L) was added so as to be 0.4 equivalent with respect to the vinyl ester unit in the copolymer. Further, methanol was added to adjust the copolymer concentration to 20% by mass. This solution was heated to 60 ° C. and reacted for about 4 hours while blowing nitrogen gas into the reactor. After the reaction, acetic acid and water were added for neutralization, and the reaction solution was neutralized to stop the reaction. To this solution, Fuji Silicia Chemical Co., Ltd. synthetic silica “Silysia 310P” (average particle diameter measured by laser method: 2.7 μm) is added to EVOH at 300 ppm, and a ketone is added to EVOH to form a gold having a circular opening. Water-containing EVOH pellets having a diameter of about 3 mm and a length of about 5 mm were obtained by extruding the plate from the plate to cause precipitation. The water content of the obtained hydrous EVOH pellets was 110% by mass.

  The above is obtained in an aqueous solution obtained by dissolving each component so as to be 0.79 g / L of acetic acid, 0.53 g / L of sodium acetate, 0.012 g / L of phosphoric acid, and 0.42 g / L of boric acid in water. The hydrated EVOH pellets were added and immersed for 6 hours with occasional stirring. The water-containing EVOH pellets after soaking were dehydrated by centrifugation and then dried in a hot air dryer at 80 ° C. for 3 hours and then at 120 ° C. for 35 hours to obtain a dry EVOH resin composition (dried EVOH pellets).

  The obtained dry EVOH resin composition was analyzed for ethylene content and saponification degree according to the above method. The ethylene content (Et) was 32.0 mol% and the saponification degree (DS) was 99.98 mol% or more. It was. As a result of analysis according to the above method, the inorganic particles (B) were converted to silicon dioxide at 300 ppm, saturated ketone (C) at 2.9 ppm, acetic acid and acetate ions at 8.00 μmol / g, sodium ions at 6.96 μmol / g, The phosphate compound contained 10 ppm in terms of phosphate radical and the boron compound contained 201 ppm in terms of boron element.

<Production of film by biaxial stretching>
The obtained EVOH resin composition was formed into a film, a film was produced according to a method using a simultaneous biaxial stretching machine, and each physical property was evaluated. The arithmetic average of the film surface measured according to JIS B0601 The roughness (Ra) was 0.28 μm and the average length (RSm) of the contour curve elements was 298 μm. Moreover, yellow coloring was not seen in the roll end surface after winding up as a roll, but it was A determination. Furthermore, the number of breaks during film processing was 1 and was A. The thickness of the vapor deposition layer in the manufactured laminated body (laminated body which has an aluminum vapor deposition layer) was 50 nm. The vapor deposition defect of the first laminate was 9 pieces / m ² , and the vapor deposition defect of the 100th laminate was 12 pieces / m ² , both of which were A judgments. From this, the increase in deposition defects over time was A. The adhesion strength between the vapor-deposited layer and the EVOH film layer of the laminate was 530 g / 15 mm, which was A judgment.

<Manufacture of film by casting method>
About the obtained EVOH resin composition, it melted at 240 degreeC, it extruded on the casting roll from die | dye, and the film roll was obtained by winding after cut | disconnecting a film edge part. A film roll excellent in appearance could be obtained.

<Manufacture of packaging materials (pouches)>
The obtained laminated body (laminated body having an aluminum vapor-deposited layer) EVOH film is an intermediate layer, and PET film (Toyobo's “E5000”) is an outer layer (the vapor-deposited layer side of the laminated body (laminated body having an aluminum vapor-deposited layer)) One side of PET with an unstretched polypropylene film (hereinafter referred to as “CPP”; “RXC-18” of Tosero Corporation, thickness 60 μm) as an inner layer (EVOH layer side of a laminate (a laminate having an aluminum vapor deposition layer)) And an adhesive for dry lamination on one side of CPP (Mitsui Chemical's “Takelac A-385” and “Takelac A-50” are mixed in a mass ratio of 6/1 to obtain an ethyl acetate solution having a solid content concentration of 23% by mass. The film was coated with a bar coater, dried with hot air at 50 ° C. for 5 minutes, and then the PET EV film was sandwiched between the adhesive surfaces. Laminated with CPP film, it performed 5 days aging at 40 ° C., to obtain a laminate having a layer structure of PET / adhesive layer / EVOH layer / adhesive layer / CPP. Next, the obtained laminate was heat-sealed to form a pouch and filled with 100 g of water.

<Examples 2-39 and Comparative Examples 1-8>
In Example 1, the dry EVOH resin composition was the same as Example 1 except that the types and amounts of the inorganic particles (B) and the saturated ketone (C) and the thickness of the vapor deposition layer were changed as shown in Table 1. A film and a laminate (a laminate having an aluminum vapor deposition layer) were obtained. Table 2 shows the evaluation results of the obtained EVOH resin compositions, films and laminates.

  As is clear from the results in Table 2, the films of the examples are excellent in appearance characteristics and film break resistance. Moreover, the laminated body obtained by vapor-depositing a metal on a film among laminated bodies has few vapor deposition faults, and is excellent in the adhesive strength of a vapor deposition layer and an EVOH film layer. On the other hand, the thing of the comparative example whose content of an inorganic particle (B) or saturated ketone (C) content is outside a regulation range is inferior to these characteristics.

  The resin composition of the present invention is excellent in appearance characteristics after melt molding, such as the color of the film end (roll end), film breakage resistance, blocking resistance, deposition defect suppression, and adhesion strength of the deposited layer. The film of the present invention is excellent in appearance characteristics such as the color of the film end (for example, roll end), film breakage resistance and blocking resistance. According to the film production method of the present invention, it is possible to produce a film that is superior in appearance characteristics such as the color of the film edge (for example, roll edge), film breakage resistance, and blocking resistance. The laminate of the present invention has few vapor deposition defects and is excellent in adhesion strength between the vapor deposition layer and the film. The packaging material of the present invention is excellent in appearance characteristics and film breakage resistance. Therefore, these can be suitably used as various packaging materials.

Claims (17)

Containing ethylene-vinyl alcohol copolymer (A), inorganic particles (B) and saturated ketone (C) having 3 to 8 carbon atoms ,
The content of the inorganic particles (B) is 50 ppm or more and 5,000 ppm or less,
A resin composition for melt molding, wherein the content of the saturated ketone (C) is from 2.9 ppm to 100 ppm.   The resin composition for melt molding according to claim 1, wherein the ethylene content of the ethylene-vinyl alcohol copolymer (A) is 20 mol% or more and 60 mol% or less.   The resin composition for melt molding according to claim 1 or 2, wherein a mass ratio of the inorganic particles (B) to the saturated ketone (C) is 1 or more and 100,000 or less.   4. The resin composition for melt molding according to claim 1, wherein the inorganic particles (B) have an average particle size of 0.5 μm or more and 10 μm or less.   The metal element constituting the inorganic particles (B) is at least one selected from the group consisting of silicon, aluminum, magnesium, zirconium, cerium, tungsten, and molybdenum. The resin composition for melt molding as described.   The resin composition for melt molding according to claim 5, wherein the inorganic substance constituting the inorganic particles (B) is an oxide of the metal element.   The resin composition for melt molding according to any one of claims 1 to 6, wherein the saturated ketone (C) is a saturated aliphatic ketone.   The resin composition for melt molding according to claim 7, wherein the saturated aliphatic ketone is at least one selected from the group consisting of acetone, methyl ethyl ketone and 2-hexanone.   The film formed from the resin composition for melt molding of any one of Claims 1-8.   The film according to claim 9, wherein the arithmetic average roughness (Ra) of at least one surface measured according to JIS B0601 is 0.05 μm or more and 1 μm or less.   The film according to claim 9 or 10, wherein an average length (RSm) of a contour curve element on at least one surface measured in accordance with JIS B0601 is 50 µm or more and 1,000 µm or less. A layer comprising the film according to claim 9, claim 10, or claim 11,
A laminate having a layer made of another component.   The layered product according to claim 12, wherein the layer composed of the other component is a metal vapor deposition layer, and the thickness of the metal vapor deposition layer is 30 nm or more and 150 nm or less.   A packaging material comprising the film according to claim 9, claim 10 or claim 11.   A packaging material comprising the laminate according to claim 12. The manufacturing method of the film which has the process of cast-molding the resin composition for melt molding of any one of Claims 1-8. The manufacturing method of a film which has the process of extending | stretching the film obtained from the resin composition for melt molding of any one of Claims 1-8.