JP5095665B2 - Resin composition and multilayer structure using the same - Google Patents

Description

  The present invention provides a film surface abnormality caused by poor dispersion of EVOH when a resin composition comprising a polyolefin and a saponified ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as EVOH) is melt-molded. More specifically, the present invention relates to a resin composition in which generation of EVOH agglomerates in a microscopic region and generation of a wave pattern on the surface of a molded article are improved, and a multilayer structure including a layer formed of the resin composition.

  A resin composition obtained by blending polyolefin and EVOH is known (see Patent Document 1). However, this resin composition generally has poor compatibility, and when a film, a sheet, a bottle, or the like is formed by extrusion molding, it is not uniform. It is known that a phase-separated foreign matter is likely to be generated, and this foreign matter increases particularly when operated for a long time, and the appearance of the molded product is remarkably impaired (decrease in long-run moldability). It is also known that so-called “eyes” that are generated around the die outlet during extrusion of the resin composition are likely to cause problems such as mixing into the molded product and leading to quality degradation.

In order to improve such a poor compatibility between polyolefin and EVOH, it is effective to add a higher fatty acid metal salt having 8 to 22 carbon atoms, an ethylenediaminetetraacetic acid metal salt and / or a hydrotalcite compound. Is known (see Patent Document 1 and Patent Document 2). In addition to these combinations, in addition to polyolefin and EVOH, hydrotalcite compounds, higher fatty acids having 8 or more carbon atoms, boron compounds, phosphoric acid and / or alkali (earth) metal hydrogen phosphate -By blending a lower fatty acid metal salt with 7 or less carbon atoms, etc., long run property and heat resistance during melt molding of a composition mainly composed of polyolefin and EVOH (retaining physical properties against repeated thermal history during regrinding) Is disclosed (see Patent Document 3, Patent Document 4, and Patent Document 5). However, in these documents, the evaluation regarding the fish eye occurrence state at the time of film forming is conducted by examining the number of fish having a diameter of 0.2 mm or more per 100 cm ² .

  On the other hand, when a resin composition comprising polyolefin and EVOH is melt-molded, polyolefin and EVOH are used as polyolefin and EVOH as a resin composition that improves the generation of a wave pattern on the surface of the molded product, which is caused by flow abnormality due to poor compatibility. In addition to the above-mentioned higher fatty acid metal salt having 8 to 22 carbon atoms, ethylenediaminetetraacetic acid metal salt and hydrotalcite, ethylene content is 68 to 98 mol%, vinyl acetate unit saponification degree is 20 % Of ethylene-vinyl acetate copolymer saponified product (hereinafter sometimes referred to as S-EVOH) improves the compatibility of the resulting resin composition and the surface wave pattern of the molded product It is disclosed that the scrap composition such as regrind is effectively reused (see Patent Document 6).

Furthermore, by adding an acid graft-modified polyolefin-based resin and a polyhydric alcohol compound to the collected product of the laminate including the thermoplastic resin layer and the EVOH layer, the resulting resin composition has no gelation during melt molding. In addition, it is disclosed that the generation of wave patterns and fish eyes in a molded product is prevented, the long-run moldability is excellent, and the effect of preventing generation of phase-separated foreign matters (eyes) is effective (see Patent Document 7). However, in this document, the fish-eye evaluation is performed by examining the number of layers having a diameter per 100 cm ² of 0.4 mm or more in the regrind layer of the laminate.

On the other hand, a method for producing a vinyl acetate polymer in which a conjugated polyene compound having a boiling point of 20 ° C. or higher is added to an ethylene-vinyl acetate copolymer, and a vinyl acetate polymer to saponify the vinyl acetate polymer obtained by such a method. A method for producing a combined saponified product is disclosed, and EVOH obtained by this method is said to be high in quality with little coloration and less gelled formation during molding (see Patent Document 8).

  By the techniques disclosed in Patent Documents 2 to 7, the compatibility of EVOH and polyolefin in the resin composition obtained by blending polyolefin and EVOH is considerably improved, and the appearance of the molded product can be improved. However, in recent trends in environmental measures (reducing packaging materials and reducing waste), the trend toward thinner layers for cups, bottles, films, etc. has become stronger. In thick packaging materials, at a level that was not a problem due to the effect of transparency, occurrence of poor appearance due to poor dispersibility and abnormal flow in a finer region in a resin composition blended with polyolefin and EVOH There is still a need for improvement in terms of suppression. Patent Document 8 discloses a technique relating to reducing gelled spots in a molded product of EVOH alone, and there is no teaching or suggestion about a resin composition obtained by blending EVOH and polyolefin.

JP 60-199040 A JP-A-6-87195 JP-A-10-001569 JP-A-10-001570 Japanese Patent Application Laid-Open No. 09-278952 Japanese Patent Laid-Open No. 03-72542 JP 2008-115367 A JP 09-71620 A

The inventor of the present invention has a film surface abnormality that is caused when a resin composition obtained by blending a polyolefin and EVOH is melt-molded, and is caused by poor dispersion of EVOH. It was found that this is caused by the formation of EVOH aggregates in the microscopic region.
Accordingly, an object of the present invention is to improve the dispersion of EVOH by suppressing the formation of aggregates in such a microscopic region, and to generate a wave pattern on the surface of the molded product due to a flow abnormality caused by the aggregates. It is to suppress the appearance defect and thereby effectively reuse a scrap portion such as a laminate having a polyolefin layer and an EVOH layer as a regrind layer to obtain a molded article having a beautiful appearance.

  According to the present invention, the object is to saponify the ethylene-vinyl acetate copolymer (B) (polyolefin (A), ethylene content 20 to 65 mol%, vinyl acetate unit saponification degree 96% or more). Hereinafter, simply referred to as EVOH (B)), higher fatty acid metal salt (C) having 8 to 22 carbon atoms (hereinafter simply referred to as higher fatty acid metal salt (C)), conjugated polyene compound (D) having a boiling point of 20 ° C. or higher (Hereinafter simply referred to as conjugated polyene compound (D)), ethylene-vinyl acetate copolymer (E) (hereinafter referred to as EVAc (E)), and divalent to 15-valent polyhydric alcohol (F) (hereinafter referred to as And a mass ratio of polyolefin (A) to EVOH (B) of 60:40 to 99.9: 0.1, and a higher fatty acid metal salt (C ) Polyolefin In the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of A) and EVOH (B), the conjugated polyene compound (D) is added to 100 parts by mass of polyolefin (A) and EVOH (B). On the other hand, in the range of 0.000001 to 1 part by mass, the total amount of EVAc (E) and polyhydric alcohol (F) is 0.000 to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B). This is achieved by providing a resin composition contained in a range of 3 parts by mass or more.

  The above-described resin composition is preferably obtained by previously melt-kneading the polyolefin (A), the higher fatty acid metal salt (C), EVAc (E) and the polyhydric alcohol (F) to obtain a master batch, It is obtained by melt-kneading polyolefin (A), EVOH (B) and conjugated polyene compound (D).

When the master batch obtained above is analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR), the signal Ja derived from the hydrogen atom bonded to the carbon atom to which the acetoxy group is bonded and the carbon to which the hydroxyl group is bonded In the resin composition of the present invention, the intensity ratio of the signal Jb derived from the hydrogen atom bonded to the atom is in the range of Ja: Jb = 99.5: 0.5 to 70.0: 30.0. This is a preferred embodiment.

  A resin composition obtained by adding 0.0001 to 10 parts by mass of the hydrotalcite compound (G) to 100 parts by mass of the total amount of the polyolefin (A) and EVOH (B) in the above resin composition. Is also a preferred embodiment of the present invention.

  Furthermore, at least a layer made of any of the above resin compositions and a layer made of a saponified ethylene-vinyl acetate copolymer having an ethylene content of 20 to 65 mol% and a saponification degree of vinyl acetate units of 96% or more. A multilayer structure comprising two layers is also a preferred embodiment of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can suppress the production | generation of the EVOH aggregate in a micro area | region, improves dispersibility, and can suppress generation | occurrence | production of the fluid abnormality resulting from this aggregate is provided. be able to. The resin composition of the present invention can be used as a recovered regrind layer even when a scrap of a laminate having a polyolefin layer and an EVOH layer is used as a raw material, and a molded product having no appearance defect can be obtained.

  The resin composition of the present invention comprises a polyolefin (A), EVOH (B), a higher fatty acid metal salt (C), a conjugated polyene compound (D), EVAc (E) and a polyhydric alcohol (F). The mass ratio of A) to EVOH (B) is 60:40 to 99.9: 0.1, and the higher fatty acid metal salt (C) is 100 parts by mass of the total amount of polyolefin (A) and EVOH (B). In the range of 0.0001 to 10 parts by mass relative to 100 parts by mass of the conjugated polyene compound (D) with respect to 100 parts by mass of polyolefin (A) and EVOH (B), EVAAc (E ) And polyhydric alcohol (F) as a total amount of both in a range of 0.3 parts by mass or more with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B).

  Examples of the polyolefin (A) in the present invention include polyethylene (low density, linear low density, medium density, high density, etc.); α such as ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene, etc. -Ethylene copolymers copolymerized with olefins or acrylic esters; polypropylene (homopolypropylene, random polypropylene, block polypropylene, etc.); propylene and ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, etc. Propylene copolymer obtained by copolymerization of α-olefins; modified polypropylene blended with rubber polymer; poly (1-butene), poly (4-methyl-1-pentene), maleic anhydride added to the above-mentioned polyolefin Modified polyolefins that have been acted on; including ionomer resins. In the present invention, as the polyolefin (A), it is preferable to use a polypropylene resin such as polypropylene or a propylene copolymer, or a polyethylene resin such as polyethylene or an ethylene copolymer, among which a polypropylene resin is used. Is more preferable. These polyolefin (A) may be used individually by 1 type, and may mix and use 2 or more types. Of these polyolefins (A), polyolefins containing 1 to 300 ppm, preferably 3 to 150 ppm of halogen compounds as impurities contained in polymerization catalyst residues or additives such as fillers and pigments are used. In such a case, the effects of the present invention can be obtained more remarkably.

  EVOH (B) used in the present invention is a saponified (hydrolyzed) vinyl acetate unit in an ethylene-vinyl acetate copolymer. EVOH having a low ethylene content and a high saponification degree (hydrolysis degree) of vinyl acetate units tends to have poor compatibility with polyolefins. On the other hand, EVOH having a high ethylene content and a low saponification degree (hydrolysis degree) of vinyl acetate units tends to be poor in thermal stability of EVOH itself. From this viewpoint, the ethylene content of EVOH (B) used in the present invention is in the range of 20 to 65 mol%, preferably in the range of 20 to 60 mol%, and in the range of 20 to 50 mol%. Is more preferable. On the other hand, the saponification degree of the vinyl acetate unit of EVOH (B) is preferably 96% or more, more preferably 98% or more, and further preferably 99% or more. In particular, EVOH having an ethylene content in the range of 20 to 65 mol% and a saponification degree of 99% or more can be used as a container excellent in properties such as gas barrier properties by being laminated with the polyolefin (A). Since it is obtained, it is particularly important as an application target of the present invention.

  EVOH (B) may be modified with other polymerizable monomers within a range not inhibiting the effects of the present invention, generally within a range of 5 mol% or less. Examples of the polymerizable monomer include α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene; esters such as acrylic acid esters and methacrylic acid esters; maleic acid, fumaric acid, Higher fatty acid such as itaconic acid or vinyl ester thereof; alkyl vinyl ether; N- (2-dimethylaminoethyl) methacrylamide or quaternized product thereof, N-vinylimidazole or quaternized product thereof, N-vinylpyrrolidone, N, N- Examples include butoxymethylacrylamide, vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane.

  EVOH (B) has a melt index (MI; measured at 190 ° C. under a load of 2160 g) of 0.1 g / 10 min or more, preferably 0.5 g / 10 min or more, and preferably 100 g / 10 min or less. Is preferably 50 g / 10 min or less, and most preferably 30 g / 10 min or less. At this time, from the viewpoint of dispersibility of EVOH (B), when MI of EVOH (B) is MI (B) and MI of polyolefin (A) (measured at 190 ° C. under a load of 2160 g) is MI (A) The MI (B) / MI (A) is preferably in the range of 0.1 to 100, and more preferably in the range of 0.3 to 50.

  The mass ratio of polyolefin (A) and EVOH (B) in the resin composition of the present invention is in the range of polyolefin (A): EVOH (B) = 60: 40 to 99.9: 0.1, It is important for obtaining the effect of the present invention remarkably. In such a mass ratio, when EVOH (B) is present in a larger amount than 60:40, it is difficult to sufficiently obtain an effect of suppressing aggregation in the microscopic region of EVOH (B), while 99.9: 0. When the amount of polyolefin (A) is larger than 1., the effect of the present invention cannot be sufficiently confirmed. From this viewpoint, the mass ratio of the polyolefin (A) to EVOH (B) is more preferably in the range of 65:35 to 99.7: 0.3.

  As the higher fatty acid metal salt (C) used in the present invention, a metal salt such as lauric acid, stearic acid, myristic acid, particularly a metal salt of Group I, Group II or Group III of the periodic table, such as sodium salt, A potassium salt, a calcium salt, a magnesium salt, and a zinc salt are mentioned. Among these, a metal salt of Group II of the periodic table such as calcium salt and magnesium salt is preferable because the effects of the present invention can be obtained with a small amount of addition.

  If the amount of the higher fatty acid metal salt (C) is too small, the effects of the present invention cannot be sufficiently obtained. On the other hand, if it is too large, the thermal degradation of EVOH (B) is promoted, and foaming due to decomposition gas or coloring There is a concern that causes. For this reason, the addition amount of the higher fatty acid metal salt (C) is in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polyolefin (A) and EVOH (B), and 0.001 to 1 More preferably, it is in the range of parts by mass.

  The conjugated polyene compound (D) used in the present invention is a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, and the number of carbon-carbon double bonds is two or more. , A compound having a so-called conjugated double bond. The conjugated polyene compound (D) is a conjugated diene having a structure in which two carbon-carbon double bonds and one carbon-carbon single bond are alternately connected, three carbon-carbon double bonds and two. A conjugated triene having a structure in which carbon-carbon single bonds are alternately connected, or a conjugated polyene compound having a structure in which a larger number of carbon-carbon double bonds and carbon-carbon single bonds are alternately connected. May be. However, if the number of conjugated carbon-carbon double bonds is 8 or more, the molded product may be colored by the color of the conjugated polyene compound itself, so the number of conjugated carbon-carbon double bonds is 7 or less. A certain polyene is preferred. Further, a plurality of conjugated double bonds composed of two or more carbon-carbon double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated trienes in the same molecule such as tung oil is also included in the conjugated polyene compound (D). In addition to the conjugated double bond, the conjugated polyene compound (D) further includes other functional groups such as carboxyl groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, imino groups, amide groups, cyano groups. Group, diazo group, nitro group, sulfone group, sulfoxide group, sulfide group, thiol group, sulfonic acid group and its salt, phosphoric acid group and its salt, phenyl group, halogen atom, double bond, triple bond, etc. It may have a functional group.

  Specific examples of the conjugated polyene compound (D) 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 Butadiene, 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, fulvene, tropone, oximene, ferrandrene, myrcene, farnesene, semblene, sorbine Conjugated diene compounds comprising a conjugated structure of two carbon-carbon double bonds such as acid, sorbic acid ester, sorbate, and abietic acid; 1,3,5-hexatriene, 2,4,6-octatriene-1 -Conjugated trie composed of a conjugated structure of three carbon-carbon double bonds such as carboxylic acid, eleostearic acid, tung oil, cholecalciferol, etc. Compound; cyclooctatetraene, 2,4,6,8 Dekatetoraen-1-carboxylic acid, retinol, carbon atoms such as retinoic acid - such as conjugated polyene compound comprising carbon double bond of four or more conjugated structure. As these conjugated polyene compounds (D), one type of compound may be used alone, or two or more types of compounds may be used in combination.

  The addition amount of the conjugated polyene compound (D) is in the range of 0.000001 to 1 part by mass and in the range of 0.00001 to 1 part by mass with respect to 100 parts by mass of the total amount of the polyolefin (A) and EVOH (B). It is more preferable that When the addition amount is less than 0.00001 parts by mass with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B), the effect of the present invention is not sufficiently obtained, while the addition amount is polyolefin ( When the amount exceeds 1 part by mass with respect to 100 parts by mass of the total amount of A) and EVOH (B), there is a concern of promoting gelation of the resulting resin composition.

  The conjugated polyene compound (D) may be blended directly into the mixture of the polyolefin (A) and EVOH (B). However, when the addition amount is very small, from the viewpoint of being uniformly dispersed in the resin composition of the present invention, It is preferable to blend in EVOH (B) having good compatibility in advance.

  EVAAc (E) used in the present invention is a random copolymer obtained by polymerizing ethylene and vinyl acetate by a known method, a terpolymer obtained by copolymerization with other monomers, or a modification modified by grafting or the like. EVAAc may be used. 2-40 mol% is suitable for content of the vinyl acetate unit of EVAAc (E), and it is more preferable that it is 5-25 mol%. When the content of vinyl acetate units is less than 2 mol% or more than 40 mol%, a sufficient effect for preventing aggregation of EVOH (B) may not be obtained. Moreover, the melt index (MI; measured at 190 ° C. under a load of 2160 g) of EVAc (E) is preferably 0.1 to 50 g / 10 min or more, and preferably 0.5 to 30 g / 10 min or more. More preferably, it is more preferably 1 to 20 g / 10 minutes or more.

  The polyhydric alcohol (F) used by this invention is a 2-15 valent alcohol compound which has a hydroxyl group. The polyhydric alcohol (F) preferably has a melting point of 300 ° C. or lower, more preferably 200 ° C. or lower, from the viewpoint that it is preferably a liquid during melt kneading to obtain the resin composition of the present invention. It is preferably 150 ° C. or lower. The boiling point of the polyhydric alcohol (F) is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and particularly preferably 200 ° C. or higher. From these things, it is preferable that the valence of a polyhydric alcohol (F) is 3-10 valence, and it is more preferable that it is 3-8 valence. Moreover, carbon number of a polyhydric alcohol (F) is 2-20 normally, it is preferable that it is 4-15, and it is more preferable that it is 6-10. Furthermore, the molecular weight of the polyhydric alcohol (F) is usually 50 to 1000, preferably 50 to 500, and more preferably 80 to 200.

  Specific examples of the polyhydric alcohol (F) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol and other alkylene glycols; 1,2-propanediol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5 -Aliphatic dihydric alcohols such as hexanediol; diethanolamine, triethanolamine, di-2-amino-2-hydroxymethyl-1,3-propanediol, tri-2-amino-2-hydroxymethyl-1,3 -Propanediol, poly Amino group-containing dihydric alcohols such as 2-amino-2-hydroxymethyl-1,3-propanediol; 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol, 2- ( Aliphatic trihydric alcohols such as 2-hydroxypropyl) propane-1,3-diol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, glycerin, trimethylolmethane, trimethylolethane, and trimethylolpropane Diglycerin, polyglycerin, di-trimethylol methane, tri-trimethylol methane, di-trimethylol ethane, tri-trimethylol ethane, di-trimethylol propane, tri-trimethylol propane, pentaerythritol, di-pentaerythritol , Tri-pentaerythrito ; Can be exemplified or ester, polyethylene oxide adducts of these with a carboxylic acid and the like; mannitol, sorbitol, fructose, glucose, arabinitol like. These polyhydric alcohols may be used alone or in combination of two or more.

  Among these, as polyhydric alcohol (F), glycerols such as glycerol, diglycerol and polyglycerol; trimethylolpropane such as trimethylolpropane, di-trimethylolpropane, tri-trimethylolpropane and poly-trimethylolpropane The use of sorbitol is preferred from the standpoint of more remarkable effects of the present invention, and trimethylolpropane and diglycerin are particularly preferred from the viewpoint of inhibiting aggregation of EVOH (B).

  The added amount of EVAc (E) and polyhydric alcohol (F) in the resin composition of the present invention is such that the total amount of both is 0.3 with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B). It is at least 0.5 parts by mass, more preferably at least 0.5 parts by mass. When the addition amount is less than 0.3 parts by mass, the effect of adding EVAc (E) and polyhydric alcohol (F) cannot be sufficiently obtained. On the other hand, the upper limit of the addition amount is not particularly limited, but even if the addition amount is increased, the EVOH dispersibility is not improved beyond a certain level, so 30 parts by mass or less is sufficient for practical use.

  In addition, although there is no restriction | limiting in a strict meaning in the ratio of EVAAc (E) and polyhydric alcohol (F) to add, from a viewpoint which show | plays the effect of this invention effectively, normally EVAAc (E ): Polyhydric alcohol (F) = 99.9: 0.1 to 70.0: 30.0, preferably EVAc (E): polyhydric alcohol (F) = 99.5: 0. The range of 5-85.0: 15.0 is more preferable.

  As components constituting the resin composition of the present invention, the above-described polyolefin (A), EVOH (B), higher fatty acid metal salt (C), conjugated polyene compound (D), EVAc (E) and polyhydric alcohol (F ), Hydrotalcite (G) can be further added. When hydrotalcite (G) is used as a constituent of the resin composition of the present invention, it is preferable because the dispersibility of EVOH (B) in the resin composition can be improved.

As hydrotalcite (G) in the present invention, in particular,
_{M x Al y (OH) 2x} + 3y-2z (A) z · aH 2 O
(M represents Mg, Ca or Zn, A represents CO ₃ or HPO ₄ , x, y and z are positive integers, and a is an integer of 0 or more)
The hydrotalcite compound which is a double salt represented by the following can be exemplified, and among them, the following are particularly preferable.
Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O
_{Mg 8 Al 2 (OH) 20} CO 3 · 5H 2 O
Mg ₅ Al ₂ (OH) ₁₄ CO ₃ .4H ₂ O
_{Mg 10 Al 2 (OH) 22} (CO 3) 2 · 4H 2 O
_{Mg 6 Al 2 (OH) 16} HPO 4 · 4H 2 O
Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O
Zn ₆ Al ₆ (OH) ₁₆ CO ₃ .4H ₂ O

  When hydrotalcite (G) is further added, the addition amount is in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B), and 0.001 More preferably, it is in the range of ˜1 part by mass. When the addition amount is less than 0.0001 parts by mass with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B), the effect of the present invention is not sufficiently obtained, while the addition amount is polyolefin ( If the total amount of A) and EVOH (B) exceeds 10 parts by mass with respect to 100 parts by mass, the thermal degradation of EVOH in the resulting resin composition is promoted to cause foaming or coloring due to decomposition gas. There is.

  Adding a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof to the resin composition of the present invention is also effective in suppressing aggregation in the microscopic region of EVOH (B). Here, the modified polyolefin resin is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, its ester or its anhydride; methyl acrylate, methyl methacrylate From unsaturated carboxylic acid derivatives such as ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, sodium acrylate, sodium methacrylate; A polyolefin resin modified with at least one selected unsaturated carboxylic acid or derivative thereof. Preferred examples of the polyolefin resin before modification include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, and the like.

  In addition, as long as various known additives for improving various characteristics such as thermal stability during melt extrusion molding of EVOH are within a range that does not impair the effects of the present invention, the EVOH constituting the resin composition of the present invention Since the deterioration suppression of (B) can be expected, it is preferably added. These additives include organic acids such as acetic acid and lactic acid, inorganic acids such as hydrochloric acid and phosphoric acid, and metal salts with periodic group I, II and III metals, and boron such as boric acid. Examples thereof include higher fatty acids such as compounds and stearic acid. In particular, the addition of boric acid is effective in suppressing aggregation of EVOH (B), and the preferred addition amount is 0.0001 to 0.1 mass with respect to 100 mass parts of the total amount of polyolefin (A) and EVOH (B). Part range. When boric acid is added, if the added amount exceeds 0.1 parts by mass with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B), EVOH (B) tends to aggregate. Become.

  Next, the polyolefin (A), EVOH (B), higher fatty acid metal salt (C), conjugated polyene compound (D), EVAc (E) and polyhydric alcohol (F) are mixed and the resin composition of the present invention. And a method for molding such a resin composition will be described.

  The mixing method for obtaining the resin composition of the present invention is not particularly limited, and polyolefin (A), EVOH (B), higher fatty acid metal salt (C), conjugated polyene compound (D), EVAc (E) and polyvalent Method of dry blending alcohol (F) at a time and melt-kneading; pre-blending higher fatty acid metal salt (C) and / or conjugated polyene compound (D) into polyolefin (A) and / or EVOH (B), Is exemplified by a method of dry blending together with the remaining components and melt-kneading, and a suitable example is a mixture in which polyolefin (A) and conjugated polyene compound (D) are previously blended in EVOH (B), Dry blend of polyolefin (A) with a mixture of higher fatty acid metal salt (C), EVAc (E) and polyhydric alcohol (F) in advance And a method of melt kneading.

  In particular, as described above, when the conjugated polyene compound (D) is preliminarily blended with EVOH (B), the effect of the present invention can be enhanced even if the addition amount of the conjugated polyene compound (D) is reduced. . The method of pre-blending the conjugated polyene compound (D) with EVOH (B) is not particularly limited, but EVOH (B) is dissolved in a good solvent of EVOH (B) such as a water / methanol mixed solvent. B) 0.000001-10 parts by mass of the conjugated polyene compound (D) is dissolved with respect to 100 parts by mass, the mixed solution is extruded into a poor solvent from a nozzle or the like, precipitated and solidified, washed and dried. Examples thereof include a method of obtaining EVOH (B) containing the conjugated polyene compound (D).

  On the other hand, the method of previously blending the higher fatty acid metal salt (C), EVAc (E) and the polyhydric alcohol (F) with the polyolefin (A) is not particularly limited, but the polyolefin (A), the higher fatty acid metal salt (C), Method of dry blending EVAAc (E) and polyhydric alcohol (F); Method of melt kneading and pelletizing polyolefin (A), higher fatty acid metal salt (C), EVAc (E) and polyhydric alcohol (F) That is, a method of obtaining a master batch is exemplified. Among these methods, the latter method is preferred from the viewpoint that the higher fatty acid metal salt (C) is usually a powder because the handling becomes easier.

Further, a composition in which a higher fatty acid metal salt (C), EVAc (E), and a polyhydric alcohol (F) are mixed in advance with polyolefin (A), preferably the above-described master batch, is prepared by nuclear magnetic resonance spectroscopy ( ¹ H-NMR), the signal derived from the hydrogen atom bonded to the carbon atom to which the acetoxy group is bonded is Ja, and the signal derived from the hydrogen atom bonded to the carbon atom to which the hydroxyl group is bonded is Jb. The strength ratio is preferably in the range of Ja: Jb = 99.5: 0.5 to 70.0: 30.0. In other words, in the resin composition of the present invention, there are carbon atoms to which acetoxy groups are bonded and carbon atoms to which hydroxyl groups are bonded, and the molar ratio thereof is 99.5: 0.5 to 70.0: 30.0. It is suitable from the viewpoint of improving the dispersibility of EVOH (B). When the intensity ratio is less than 0.5 or exceeds 30, there is a concern that the effect of improving the dispersibility of EVOH (B) cannot be obtained sufficiently.

  In addition, as a method for making the intensity ratio of Ja and Jb to be in the range of Ja: Jb = 99.5: 0.5 to 70.0: 30.0, EVAAc (E) and polyhydric alcohol (F) Examples thereof include a method for appropriately adjusting the mixing ratio, a method for adjusting the molecular weight and valence of the polyhydric alcohol (F) to be used, and a method for appropriately adjusting the ethylene content of EVAc (E).

  There is no particular limitation on the blending method in the case of adding hydrotalcite (G), and polyolefin (A), EVOH (B), higher fatty acid metal salt (C), conjugated polyene compound (D), EVAc (E) and The mixture of polyhydric alcohol (F) and hydrotalcite (G) may be dry blended and melt kneaded. In the case where a polyolefin (A), a higher fatty acid metal salt (C), EVAc (E) and a polyhydric alcohol (F) are previously melt-kneaded and pelletized to obtain a masterbatch, If talcite (G) is also blended and pelletized at the same time, it is preferable from the viewpoint of reducing the number of materials to be handled during the final melt-kneading of the resin composition of the present invention.

  Moreover, it is also free to mix | blend other additives other than having mentioned above with the resin composition of this invention in the range which does not inhibit the effect of this invention. Examples of such additives include antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, or other polymer compounds. Specific examples of the additive include the following.

  Antioxidant: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis (6-t-butylphenol), 2,2′-methylenebis ( 4-methyl-6-t-butylphenol), octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis (6-t-butylphenol), etc. .

  UV absorber: ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-) 5'-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.

Plasticizer: Dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc.
Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax, etc.
Lubricant: Ethylene bisstearamide, butyl stearate, etc.

Colorant: Titanium oxide, carbon black, phthalocyanine, quinacridone, indoline, azo pigment, bengara, etc.
Filler: Glass fiber, asbestos, ballastite, calcium silicate, etc.

  Of these additives, colorants and fillers often contain impurities that promote aggregation in the microscopic region of EVOH (B) constituting the resin composition of the present invention. Therefore, when these additives are included, the higher fatty acid metal salt (C) and / or the conjugated polyene compound (D) and / or EVAc (E) and / or the polyhydric alcohol (F) as necessary. In some cases, it is necessary to increase the blending amount.

  Many other polymer compounds can also be blended in the resin composition of the present invention to the extent that the effects of the present invention are not inhibited.

  Examples of the means for mixing the components for obtaining the resin composition of the present invention include a ribbon blender, a high-speed mixer / conical mixer, a mixing roll, an extruder, and an intensive mixer.

  In addition, the resin composition of the present invention uses a well-known melt extrusion molding machine, compression molding machine, transfer molding machine, injection molding machine, blow molding machine, thermoforming machine, rotational molding machine, dip molding machine, etc. It can be formed into an arbitrary molded product such as a film, sheet, tube, bottle, or cup. The extrusion temperature at the time of molding is the type of polyolefin (A) constituting the resin composition of the present invention, the melt index of polyolefin (A) and EVOH (B), the composition ratio of polyolefin (A) and EVOH (B), or molding Although it is appropriately selected depending on the type of the machine, it is often in the range of 170 to 350 ° C.

When using the resin composition of this invention as a layer structure of the multilayered structure containing the layer which consists of polyolefin and EVOH, the layer structure which has arrange | positioned at least 1 layer in arbitrary positions can be taken. As such a layer structure, when the resin composition of the present invention is represented by F, polyolefin is A, EVOH is B, and adhesive resin is AD, for example, the following layer structure is represented. Here, as the AD, the above-described modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof can be preferably used.
3 layers A / F / B
4 layers F / B / AD / A, A / F / AD / B
5 layers F / AD / B / AD / F, A / F / B / AD / A, A / F / B / F / A
6 layers A / F / AD / B / AD / A
7 layers A / F / AD / B / AD / F / A

  In such a multilayer structure, the resin composition of the present invention can be substituted with a melt-kneaded scrap of the multilayer structure. In addition to the multilayer structure, other polyolefin molded body scraps can be mixed and melt-kneaded. Therefore, when an AD layer is present in the multilayer structure, AD is included as a constituent in the resin composition of the present invention.

  Since the multilayer structure having the above-described layer structure contains EVOH excellent in gas barrier properties, it is useful as a packaging material for foods, pharmaceuticals, medical devices and the like that require gas barrier properties.

  As a multilayer molding method, generally, a number of extruders corresponding to the type of the resin layer are used, and so-called coextrusion molding is performed in which the melted resin flows in the extruder are co-extruded in a layered state. The method carried out by is preferred. As another method, a multilayer molding method such as extrusion coating or dry lamination may be employed. In addition, by carrying out stretching such as uniaxial stretching, biaxial stretching or blow stretching of a single molded article of the resin composition of the present invention or a multilayer structure containing the resin composition of the present invention, mechanical properties, gas barrier properties, etc. Can be obtained.

  The molded product obtained by using the resin composition of the present invention has a beautiful appearance, and aggregation of EVOH in the micro area in the resin composition of the present invention is suppressed and uniformly dispersed. Since it has excellent mechanical properties and gas barrier properties, its industrial significance is great.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the following production examples, examples and comparative examples, (part) is expressed on a mass basis unless otherwise specified.

[Method for quantifying conjugated polyene compound (D) blended in EVOH]
The amount of the conjugated polyene compound (D) contained in EVOH was quantified by the following procedure. EVOH containing the conjugated polyene compound (D) was pulverized, and 10 g of coarse particles removed by a 100 mesh sieve were Soxhlet extracted with 100 ml of chloroform for 48 hours. The amount of the conjugated polyene compound in the extract was quantified by high-performance liquid chromatography by preparing a calibration curve using each conjugated polyene compound sample.

[NMR analysis]
Various masterbatches containing EVAc (E) and polyhydric alcohol (F) obtained in the production examples described later were mixed in a mixture of orthodichlorobenzene / orthodichlorobenzene-d ₄ = 80/20 (volume ratio). It is dissolved in a solvent at a concentration of 5% by mass, and ¹ H-NMR (500 MHz, measurement temperature 120 ° C., integration count 1024 times, TMS, δ (ppm)) is measured and bonded to a carbon atom to which a hydroxyl group is bonded. From the area ratio of the signal Jb near 3.58 ppm derived from the hydrogen atom and the signal Ja near 5.05 ppm derived from the hydrogen atom bonded to the carbon atom to which the acetoxy group is bonded, the intensity ratio of both signals is Calculated.

Production Example 1
(1) Intrinsic viscosity [η] _ph measured at 30 ° C. using a mixed solution of ethylene content of 32 mol%, saponification degree of 99.8 mol%, water / phenol = 15/85 (mass ratio) as 0 0.092 l / g of EVOH 2000 parts was put into 18000 parts of a mixed solvent of water / methanol = 40/60 (mass ratio) and stirred at 60 ° C. for 6 hours to completely dissolve the mixture. To this solution, 2 parts of sorbic acid as a conjugated polyene compound (D) was added, and further stirred at 60 ° C. for 1 hour to completely dissolve sorbic acid, thereby obtaining an EVOH solution containing sorbic acid. This EVOH solution was continuously extruded from a nozzle having a diameter of 4 mm into a coagulation bath of water / methanol = 5/95 (mass ratio) adjusted to 0 ° C. to coagulate EVOH in a strand form. This strand was introduced into a pelletizer to obtain a porous EVOH chip.

  (2) The porous EVOH chip obtained in the above (1) was washed sequentially at 20 ° C. using 2000 parts of 0.1 mass% acetic acid aqueous solution and then 2000 parts of ion-exchanged water per 100 parts of the chip. It was immersed in 2000 parts of an aqueous solution containing 092% boric acid at 20 ° C. for 4 hours. After the EVOH chip was removed and separated, it was dried with a hot air dryer at 80 ° C. for 4 hours, and further dried at 100 ° C. for 16 hours to obtain an EVOH chip. The boric acid content in the obtained EVOH chip was 0.11 part with respect to 100 parts of EVOH, and the sorbic acid content was 0.01 part. Further, the melt index (ASTM-D1238, 190 ° C., 2160 g load) of this EVOH was 1.6 g / 10 min. This EVOH chip is referred to as EVOH (B1).

Production Example 2
In Production Example 1 (1), the same operation as in Production Example 1 was carried out except that 2 parts of β-myrcene was used as the conjugated polyene compound (D) instead of 2 parts of sorbic acid, and β- EVOH (B2) containing 0.05 part of myrcene was obtained.

Production Example 3
In Production Example 1 (1), EVOH (B3) was obtained in the same manner as in Production Example 1 except that sorbic acid was not added to the EVOH water / methanol solution.

Production Example 4
In Production Example 1 (1), the same operation as in Production Example 1 was carried out except that the amount of sorbic acid added to the water / methanol solution of EVOH was changed from 2 parts to 0.4 parts, and 100 parts of EVOH was obtained. EVOH (B4) having a sorbic acid content of 0.002 part was obtained.

Production Example 5
In Production Example 1 (1), the same operation as in Production Example 1 was carried out except that the amount of sorbic acid added to the water / methanol solution of EVOH was changed from 2 parts to 0.65 parts, with respect to 100 parts of EVOH. EVOH (B5) having a sorbic acid content of 0.0032 part was obtained.

Production Example 6
(1) Intrinsic viscosity [η] _ph measured at 30 ° C. using a mixed solution of ethylene content of 32 mol%, saponification degree of 99.8 mol%, water / phenol = 15/85 as a solvent is 0.112 l / g Except that EVOH was used, the same operation as in Production Example 1 was performed to obtain a porous EVOH chip.
(2) The porous EVOH chip obtained in (1) above is washed sequentially with a 0.1% by mass acetic acid aqueous solution and ion-exchanged water in the same manner as in Production Example 1 (2), and then into an aqueous solution containing boric acid. A drying operation was performed in the same manner as in Production Example 1 (2) without immersing to obtain EVOH (B6). The melt index (ASTM-D1238, 190 ° C., 2160 g load) of this EVOH was 1.5 g / 10 min.

Production Example 7
Low-density polyethylene {LDPE, melt index 1.5 g / 10 min (ASTM-D1238, 190 ° C.), hereinafter simply referred to as LDPE} 40 parts, 2 parts calcium stearate, a higher fatty acid metal salt (C), vinyl acetate unit And 55.2 parts of EVAc (hereinafter referred to as EVAc (E1)) having a content of 7.0 mol% and a melt index (ASTM-D1238, 190 ° C., 2160 g load) of 2.7 g / 10 minutes, and polyvalent 4.8 parts of alcohol (F), trimethylolpropane (molecular weight 134.2, melting point 61 ° C., boiling point 292 ° C., hereinafter referred to as TMP) was dry blended, and the resulting mixture was subjected to 30 mmφ co-directional biaxial extrusion. Using a machine (TEX-30N (trade name), manufactured by Nippon Steel Works) at a extrusion temperature of 200 ° C. and then pelletized, It was obtained Star batch (MB1). When this master batch (MB1) was subjected to NMR analysis, a signal Ja derived from a hydrogen atom bonded to a carbon atom to which an acetoxy group is bonded and a signal derived from a hydrogen atom bonded to a carbon atom to which a hydroxyl group is bonded. The strength ratio of Jb was Ja: Jb = 93.9: 6.1.

Production Example 8
In Production Example 7, 2 parts of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O as hydrotalcite (F) was further added and dry blended, and the resulting mixture was the same as in Production Example 7. To obtain a master batch (MB2).

Production Example 9
In Production Example 7, pelletization was performed in the same manner as in Production Example 7 except that TMP as EVAc (E1) and polyhydric alcohol (F) was not added, to obtain a master batch (MB3).

Production Example 10
In Production Example 7, a master batch (MB4) was obtained by pelletizing in the same manner as in Production Example 7 except that calcium stearate was not added.

Production Example 11
In Production Example 7, pelletization was performed in the same manner as in Production Example 7 except that 60 parts of EVAc (E1) was used instead of 55.2 parts of EVAc (E1) and 4.8 parts of TMP to obtain a master batch (MB5). It was.

Production Example 12
In Production Example 7, pelletization was performed in the same manner as in Production Example 7 except that 2 parts of magnesium stearate was used instead of 2 parts of calcium stearate as the higher fatty acid metal salt (C) to obtain a master batch (MB6).

Production Example 13
In Production Example 7, instead of 55.2 parts of EVAc (E1) and 4.8 parts of TMP which is polyhydric alcohol (F), 55.5 parts of EVAc (E1) and diglycerin which is polyhydric alcohol compound (F) A master batch (MB7) was obtained by pelletizing in the same manner as in Production Example 7 except that 4.5 parts (molecular weight 166.2, boiling point 265 to 270 ° C .; hereinafter referred to as DG) was used. When this master batch (MB7) was subjected to NMR analysis, a signal Ja derived from a hydrogen atom bonded to a carbon atom to which an acetoxy group is bonded and a signal derived from a hydrogen atom bonded to a carbon atom bonded to a hydroxyl group. The strength ratio of Jb was Ja: Jb = 93.9: 6.1.

Production Example 14
In Production Example 7, the same procedure was conducted as in Production Example 7, except that the amount of EVAc (E1) added was changed from 55.2 parts to 12.88 parts and the amount of TMP added was changed from 4.8 parts to 1.12 parts. Pelletization was performed to obtain a master batch (MB8). NMR analysis of this master batch (MB8) revealed that a signal Ja derived from a hydrogen atom bonded to a carbon atom to which an acetoxy group is bonded and a signal derived from a hydrogen atom bonded to a carbon atom to which a hydroxyl group is bonded. The strength ratio of Jb was Ja: Jb = 93.9: 6.1.

Example 1
As the polyolefin (A), polypropylene {melt index 5.4 g / 10 min (ASTM-D1238, 230 ° C.), hereinafter referred to as PP} was used. 88 parts of this PP, 10 parts of EVOH (B1), and 5.1 parts of master batch (MB1) were dry blended to obtain a mixture. The composition of this mixture is 88 parts PP of polyolefin (A), 2 parts of LDPE, 10 parts of EVOH (B), 0.1 part of calcium stearate, higher fatty acid metal salt (C), conjugated polyene compound (D) sorbic acid is 0.001 part, EVAc (E1) is 2.76 parts, and TMP which is a polyhydric alcohol (F) is 0.24 parts. Using a 20 mmφ single screw extruder (Laboplast Mill manufactured by Toyo Seiki Co., Ltd.) and a 300 mm width T die, a 40 μm thick single layer film of this mixture was formed. The film forming temperature was 190 to 230 ° C for the extruder and 220 ° C for the die. The screw rotation speed was 40 rpm, and the discharge rate was 0.95 kg / hour. One hour after the mixture was put into the extruder hopper, a film sample of about 50 m was taken. A 10 cm × 10 cm frame was written at the center of the frame, and the frame was held in front of a desktop fluorescent lamp. The number of EVOH aggregates having a diameter (maximum diameter) of about 200 μm or more in the frame was counted. This count measurement was carried out at a total of 100 locations every 20 cm in the length direction of the film, and the average number of EVOH aggregates per 100 cm ² was calculated to be 0.09.

Example 2
A dry blend mixture was obtained in the same manner as in Example 1 except that 10 parts of EVOH (B2) containing β-myrcene was used instead of 10 parts of EVOH (B1) containing sorbic acid. A single layer film was formed from such a mixture, and the number of EVOH aggregates in the obtained film was counted, and found to be 0.13 per 100 cm ² .

Example 3
In Example 1, instead of dry blending 5.1 parts of the master batch (MB1), the same as Example 1 except that 5.2 parts of the master batch (MB2) containing hydrotalcite (F) was dry blended. A dry blend mixture was obtained, a single layer film was formed from the mixture, and the number of EVOH agglomerates in the obtained film was counted to be 0.06 per 100 cm ² .

Comparative Example 1
In Example 1, 90 parts of PP and 10 parts of EVOH (B3) containing no conjugated polyene compound (D) were dry blended. Using this mixture, a single-layer film was formed in the same manner as in Example 1, and the number of EVOH aggregates in the obtained film was counted. As a result, the number was 100 or more per 100 cm ² .

Comparative Example 2
In Example 1, in place of 5.1 parts of master batch (MB1), the same as Example 1 except that 5 parts of master batch (MB4) not containing calcium stearate, which is a higher fatty acid metal salt (C), was used. Thus, a single layer film was formed, and the number of EVOH aggregates in the obtained film was counted and found to be 6.13 per 100 cm ² .

Comparative Example 3
Example 1 is the same as Example 1 except that 2.1 parts of master batch (MB3) not containing EVAc (E1) and polyhydric alcohol (F) was used instead of 5.1 parts of master batch (MB1). Similarly, when a single layer film was formed and the number of EVOH aggregates in the obtained film was counted, it was 6.12 per 100 cm ² .

Comparative Example 4
In Example 1, a single layer was formed in the same manner as in Example 1 except that 5.1 parts of the master batch (MB5) not containing the polyhydric alcohol (F) was used instead of 5.1 parts of the master batch (MB1). The film was formed, and the number of EVOH aggregates in the obtained film was counted. As a result, it was 4.33 per 100 cm ² .

Example 4
In Example 1, a master containing 68 parts of PP, 30 parts of EVOH (B5), calcium stearate which is a higher fatty acid metal salt (C), EVAc (E1), and TMP which is a polyhydric alcohol (F) except that 5.1 parts of dry-blended batch (MB1) is to form a film of single-layer film in the same manner as in example 1, was counted EVOH number of aggregates in the obtained film, 100 cm ² per 0.21 It was a piece.

Example 5
In Example 1, a monolayer film was formed in the same manner as in Example 1 except that 10 parts of EVOH (B6) containing no boric acid was used instead of 10 parts of EVOH (B1). When the number of EVOH aggregates in the film was counted, it was 0.39 per 100 cm ² .

Example 6
In Example 1, a single layer was formed in the same manner as in Example 1 except that 5.1 parts of master batch (MB6) containing magnesium stearate was used instead of 5.1 parts of master batch (MB1) containing calcium stearate. A film was formed, and the number of EVOH aggregates in the obtained film was counted. As a result, it was 0.08 per 100 cm ² .

Comparative Example 5
In Example 1, a monolayer film was formed in the same manner as in Example 1 except that 10 parts of EVOH (B3) not containing the conjugated polyene compound (D) was used instead of 10 parts of EVOH (B1). When the number of EVOH aggregates in the obtained film was counted, it was 0.92 per 100 cm ² .

Comparative Example 6
In Example 1, a monolayer film was formed in the same manner as in Example 1 except that 48 parts of PP, 50 parts of EVOH (B4), and 5.1 parts of master batch (MB1) were dry blended. When the number of EVOH aggregates in the obtained film was counted, it was 2.98 per 100 cm ² .

Comparative Example 7
88 parts of PP, 10 parts of EVOH (B1) containing a conjugated polyene compound (D) and 5.1 parts of masterbatch (MB1) were dry blended, and 19.9 parts of calcium stearate was further added and dry blended. Using this mixture, an attempt was made to form a single-layer film in the same manner as in Example 1. However, liquid calcium stearate separated from the resin was ejected from the lip portion of the T-die and a large number of films were formed on the film. Because of the holes, it was not possible to count the number of EVOH aggregates.

Example 7
In Example 1, a monolayer film was formed in the same manner as in Example 1 except that 2.8 parts of master batch (MB8) was used instead of 5.1 parts of master batch (MB1). The number of EVOH aggregates in the obtained film was counted and found to be 0.35 per 100 cm ² .

Example 8
In Example 1, EVOH (B3) containing no conjugated polyene compound (D) was used in place of 10 parts of EVOH (B1), and dry blended in the same manner as in Example 1 to obtain the resulting mixture. 0.001 part of sorbic acid, which is a conjugated polyene compound (D), was further dry blended with 10 parts of EVOH (B3). Using the obtained mixture, a single layer film was formed in the same manner as in Example 1, and the number of EVOH aggregates in the obtained film was counted. As a result, it was 0.30 per 100 cm ² .

Example 9
In Example 1, a monolayer film was formed in the same manner as in Example 1 except that 5.1 parts of master batch (MB7) was used instead of 5.1 parts of master batch (MB1). The number of EVOH aggregates in the resulting film was counted and found to be 0.29 per 100 cm ² .

Example 10
In Example 1, high-density polyethylene {melt index 0.9 g / 10 min (ASTM-D1238, 190 ° C), hereinafter referred to as HDPE}} 88 parts was used as the polyolefin (A) instead of PP88 parts. A single-layer film was formed in the same manner as in Example 1, and the number of EVOH aggregates in the obtained film was counted and found to be 0.15 per 100 cm ² .

Comparative Example 8
In Example 1, 88 parts of PP, 10 parts of EVOH (B3) not containing conjugated polyene compound (D), and 5.1 parts of masterbatch (MB1) were dry blended, and further conjugated polyene compound (D) 5 parts of sorbic acid was added and uniformly dry blended. Using this mixture, a single-layer film was formed in the same manner as in Example 1, and the number of EVOH aggregates in the obtained film was counted. As a result, the number was 100 or more per 100 cm ² .

Comparative Example 9
In Example 10, a monolayer film was formed in the same manner as in Example 10 except that 90 parts of HDPE was used and the master batch (MB1) was not added, and the number of EVOH aggregates in the obtained film was counted. As a result, it was 4.56 per 100 cm ² .

Example 11
A coextrusion film forming test including the resin composition layer of the present invention was carried out using the following four types of seven-layer coextrusion cast film forming equipment.
Extruder (1): uniaxial, screw diameter 65 mm, L / D = 22, for outer layer polyolefin Extruder (2): uniaxial, screw diameter 40 mm, L / D = 26, extruder for resin composition of the present invention (3 ): Single screw, screw diameter 40 mm, L / D = 22, Adhesive resin extruder (4): Single screw, screw diameter 40 mm, L / D = 26, EVOH Extruder (1) PP and extruder ( 2) In the same manner as in Example 1, 88 parts of PP, 10 parts of EVOH (B1), and 5.1 parts of masterbatch (MB1) were dry-blended, and the resulting mixture was added to the maleic anhydride in the extruder (3). An acid-modified polypropylene-based adhesive resin (ADMER QF-500 (trade name), manufactured by Mitsui Chemicals) was fed to the extruder (4) with EVOH (B1), and co-extrusion film formation was performed. The extrusion temperature is 200 to 240 ° C. for the extruder (1), 160 to 220 ° C. for the extruder (2), 160 to 230 ° C. for the extruder (3), and 170 to 210 ° C. for the extruder (4). The die was set at 220 ° C. The composition and thickness of the formed multilayer film were as follows: PP / resin composition of the present invention / adhesive resin / EVOH / adhesive resin / resin composition of the present invention / PP = 30/15 / 2.5 / 5/2. .5 / 15/30 .mu.m, total thickness of 100 .mu.m, 4 types and 7 layers were used.
When the multilayer film after 2 hours from the start of film formation was sampled and the appearance was observed, the appearance defect due to aggregation of EVOH was hardly recognized, and a multilayer film having no practical problem was obtained.

Comparative Example 10
Except that the mixture fed to the extruder (2) of Example 11 was changed to a mixture obtained by dry blending 10 parts of PP90 parts EVOH (B3) used in Comparative Example 1, it was the same as Example 11. A multilayer film was obtained. The resulting multilayer film was severely deteriorated in appearance due to EVOH agglomerates and was difficult to put to practical use.

Comparative Example 11
The mixture fed to the extruder (2) of Example 11 was used in Comparative Example 5, 88 parts of PP, 10 parts of EVOH (B3) containing no conjugated polyene compound (D), and higher fatty acid metal salt ( C) A master batch (MB1) containing calcium stearate, EVAc (E1) and TMP, which is a polyhydric alcohol (F), was changed to a mixture obtained by dry blending 5.1 parts in the same manner as in Example 11. A multilayer film was obtained. The appearance of the obtained multilayer film was better than that of the multilayer film obtained in Comparative Example 10, but still poor appearance due to EVOH agglomerates was clearly observed, and it was difficult to put to practical use. It was.

Comparative Example 12
The mixture fed to the extruder (2) of Example 11 was used in Comparative Example 3, which contained 88 parts PP, 10 parts EVOH (B1), and no EVAc (E1) and polyhydric alcohol (F). A multilayer film was obtained in the same manner as in Example 11 except that the master batch (MB3) was changed to a mixture obtained by dry blending 2.1 parts. The appearance of the obtained multilayer film was better than that of the multilayer film obtained in Comparative Example 10, but still poor appearance due to EVOH agglomerates was clearly observed, and it was difficult to put to practical use. It was.

Comparative Example 13
A masterbatch (MB4) containing 88 parts of PP, 10 parts of EVOH (B1), and higher fatty acid metal salt (C) used in Comparative Example 2 for the mixture fed to the extruder (2) of Example 11 ) Was changed to a mixture obtained by dry blending 5 parts to obtain a multilayer film in the same manner as in Example 11. The appearance of the obtained multilayer film was better than that of the multilayer film obtained in Comparative Example 10, but still poor appearance due to EVOH agglomerates was clearly observed, and it was difficult to put to practical use. It was.

Example 12
A masterbatch (MB2) containing 88 parts of PP, 10 parts of EVOH (B1) and hydrotalcite (G) used in Example 3 for the mixture fed to the extruder (2) of Example 11 A multilayer film was obtained in the same manner as in Example 11 except that the mixture was changed to a mixture obtained by dry blending 5.2 parts. The appearance of the obtained multilayer film was even better than that of Example 11, and no appearance defect due to the aggregate of EVOH was observed.

  Tables 1 and 2 collectively show the results of the examples and comparative examples.

  Polyolefin (A), EVOH (B), higher fatty acid metal salt (C), conjugated polyene compound (D), EVAc (E) and polyhydric alcohol (F), and polyolefin (A): EVOH (B) = 60:40 to 99.9: 0.1 (mass ratio), and 0.0001 to 10 mass of the higher fatty acid metal salt (C) with respect to 100 mass parts of the total amount of the polyolefin (A) and EVOH (B). Parts, conjugated polyene compound (D) as a total amount of 0.000001 to 1 part by mass, EVAc (E) and polyhydric alcohol (F) with respect to 100 parts by mass of the total amount of polyolefin (A) and EVOH (B) By providing a resin composition containing a polyolefin (A) and EVOH (B) in a range of 0.3 parts by mass or more based on 100 parts by mass of the total amount of polyolefin (A) and EVOH (B), aggregation of EVOH and aggregation thereof Preventing poor appearance caused by due to the abnormal flow, it is possible to obtain a beautiful appearance moldings.

Claims (5)

Polyolefin (A), ethylene-vinyl acetate copolymer saponified product (B) having an ethylene content of 20 to 65 mol%, a vinyl acetate unit saponification degree of 96% or more, and a higher fatty acid metal salt having 8 to 22 carbon atoms ( C), a conjugated polyene compound (D) having a boiling point of 20 ° C. or higher, an ethylene-vinyl acetate copolymer (E), and a divalent to 15-valent polyhydric alcohol (F), and the polyolefin (A) and the ethylene -Mass ratio of vinyl acetate copolymer saponified product (B) is 60: 40-99.9: 0.1, and the higher fatty acid metal salt (C) is the polyolefin (A) and the ethylene-acetic acid. In a range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the saponified vinyl copolymer (B), the conjugated polyene compound (D) is converted into the polyolefin (A) and the ethylene-vinegar. The ethylene-vinyl acetate copolymer (E) and the polyhydric alcohol (F) are added in the range of 0.000001 to 1 part by mass with respect to 100 parts by mass of the total amount of the saponified vinyl copolymer (B). The resin composition which contains as a total amount in 0.3 mass part or more with respect to 100 mass parts of total amounts of the said polyolefin (A) and the said ethylene-vinyl acetate copolymer saponified material (B). A master batch is obtained by melt-kneading a polyolefin (A), a higher fatty acid metal salt having 8 to 22 carbon atoms (C), an ethylene-vinyl acetate copolymer (E) and a polyhydric alcohol (F) in advance. The resin composition of Claim 1 obtained by melt-kneading a polyolefin (A), a saponified ethylene-vinyl acetate copolymer (B), and a conjugated polyene compound (D) having a boiling point of 20 ° C or higher. When the master batch obtained in claim 2 is analyzed by nuclear magnetic resonance spectroscopy ( ¹ H-NMR), a signal Ja derived from a hydrogen atom bonded to a carbon atom to which an acetoxy group is bonded and a hydroxyl group are bonded. The intensity ratio of the signal Jb derived from a hydrogen atom bonded to a carbon atom to be in the range of Ja: Jb = 99.5: 0.5 to 70.0: 30.0, 2. The resin composition according to 2. Furthermore, hydrotalcite (G) is a total of polyolefin (A) and ethylene-vinyl acetate copolymer saponified product (B) having an ethylene content of 20 to 65 mol% and a saponification degree of vinyl acetate units of 96% or more. The resin composition of any one of Claims 1-3 contained in the range of 0.0001-10 mass parts with respect to 100 mass parts of quantity. A layer comprising the resin composition according to any one of claims 1 to 4, an ethylene-vinyl acetate copolymer ken having an ethylene content of 20 to 65 mol% and a saponification degree of vinyl acetate units of 96% or more. A multi-layer structure comprising at least two layers comprising a compound.