Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2553/00—Packaging equipment or accessories not otherwise provided for
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention may be referred to as a thermoplastic resin containing no polar group, a thermoplastic resin containing a polar group, or an ethylene-vinyl alcohol-based copolymer having an ethylene content of 20 to 60 mol% (hereinafter, referred to as "EVOH").
• EVOH ethylene-vinyl alcohol-based copolymer having an ethylene content of 20 to 60 mol%
• the present invention relates to a resin composition containing.), And more particularly, to a resin composition having excellent mechanical strength.
• a laminate containing a thermoplastic resin layer containing no polar group such as polyethylene and polypropylene and a layer made of EVOH having excellent gas barrier properties (hereinafter, may be abbreviated as "EVOH layer”) has been used.
• EVOH layer a layer made of EVOH having excellent gas barrier properties
• Films, sheets, cups, trays, bottles, etc. and are applied to various applications by taking advantage of their characteristics, and are especially commercialized as packaging materials for foods and chemicals.
• unnecessary parts such as scraps and edges, defective products, or the molded product thereof. Scraps such as dust are generated after using the product for various purposes.
• Such scrap amounts to 30-50% (area ratio) of the original laminate. Therefore, this scrap is collected, melt-molded, and the recovered product is applied to at least one layer of the laminate, which is a recycled layer (so-called regrind layer, and in the present invention, the recycled layer is referred to as a "regrind layer”. There is a case) and it may be reused.
• thermoplastic resin containing no polar group and EVOH are incompatible with each other, the recovered product of the thermoplastic resin layer containing no polar group and the laminate having the EVOH layer is remelted to be remelted or recycled.
• a thermoplastic resin that does not contain a polar group at the time of melting and EVOH tend to cause poor compatibility.
• it has been a cause of poor appearance such as rheumatism during the production of the molded product, fish eyes and holes in the molded product, and wavy patterns on the surface.
• an ethylene-vinyl acetate-based copolymer having a high ethylene content (hereinafter, may be referred to as "EVA”) is blended.
• EVA ethylene-vinyl acetate-based copolymer having a high ethylene content
• the EVA saponified product having a high ethylene content has a characteristic that the ethylene content is 70 mol% or more and the compatibility with the polyolefin is high.
• the EVOH which is also an EVA kenside, has an ethylene content of 20 to 60 mol% and is characterized by excellent gas barrier properties.
• the present inventor tried the methods described in Patent Documents 1 to 3, and found that these techniques were compared with respect to the problems associated with the low compatibility between the thermoplastic resin containing no polar group and EVOH. It was found that although good results were obtained, there was a problem that the obtained regrind layer turned yellow or red. Therefore, in order to suppress such discoloration, the present inventor has also tried a method of reducing the content of EVA saponified products having a high ethylene content, but the compatibility effect is reduced and problems associated with poor compatibility (machinery). Since the improvement of (decrease in target strength) is insufficient, further improvement is required.
• Patent Documents a resin composition using a resin in which EVA and an EVA saponified product having a high ethylene content are used in combination as a base resin.
• the present invention has been made in view of such circumstances, such as a thermoplastic resin containing no polar group, a thermoplastic resin containing a polar group, scraps of a product generated during the production of a laminate containing EVOH, an end portion, and the like. Even when the unnecessary parts and defective products of the above, or the collected products such as dust after using the molded product for various purposes are reused as a resin composition, the obtained molded product has excellent mechanical strength. To provide a resin composition.
• the present invention also provides a method for producing the above resin composition, a molded product, a multilayer structure and a packaging body.
• thermoplastic resin (A) containing no polar group a thermoplastic resin (B) containing a polar group, EVOH (C), acetic acid and / or The salt (D), an aliphatic carboxylic acid (E) having 3 or more carbon atoms, and an aliphatic carboxylic acid metal salt (F) which is a metal salt of the aliphatic carboxylic acid (E) are used in combination and contain the above polar group.
• a resin composition having excellent mechanical strength can be obtained by setting the contents of the thermoplastic resin (A) and EVOH (C) that do not exist within a specific range.
• an aliphatic carboxylic acid metal salt promotes the thermal decomposition of EVOH and lowers the mechanical strength of the resin composition containing EVOH. Therefore, those skilled in the art should avoid blending an aliphatic carboxylic acid metal salt for the purpose of improving the mechanical strength of the resin composition containing EVOH.
• the present inventor has made a polar group-free thermoplastic resin, a polar group-containing thermoplastic resin, EVOH, acetic acid and / or a salt thereof, an aliphatic carboxylic acid having 3 or more carbon atoms, and an aliphatic carboxylic acid thereof. It was found that when the metal salts of the above were used together to satisfy a specific relationship, the mechanical strength was improved contrary to the conventional expectation.
• the present invention relates to a thermoplastic resin (A) containing no polar group, a thermoplastic resin (B) containing a polar group, EVOH (C), acetic acid and / or a salt thereof (D), and 3 carbon atoms.
• the content of the resin (A) is 66 to 99% by weight based on the total amount of the resin composition, and the content of the EVOH (C) is 0.1 to 25% by weight based on the total amount of the resin composition.
• the resin composition is the first gist.
• the second gist is a method for producing a resin composition in which the resin composition of the first gist is melt-kneaded and pelletized, and the third gist is a molded product using the resin composition of the first gist.
• the fourth gist is a multi-layer structure having at least one layer made of the resin composition of the first gist, and the fifth gist is a package made of the multi-layer structure of the fourth gist. be.
• the resin composition of the present invention comprises a polar group-free thermoplastic resin (A), a polar group-containing thermoplastic resin (B), EVOH (C), acetic acid and / or a salt thereof (D), and 3 carbon atoms.
• thermoplastic resin (A) containing no polar group is at least one selected from a polyolefin resin and a polystyrene resin, it is more excellent in recyclability and economy.
• thermoplastic resin (A) containing no polar group is at least one selected from polyethylene, polypropylene, and polystyrene, it is further excellent in recyclability and economy.
• thermoplastic resin (B) containing the polar group when the content of the thermoplastic resin (B) containing the polar group is 0.1 to 50% by weight based on the total amount of the resin composition, it is more excellent in mechanical strength, recyclability and economy. ing.
• thermoplastic resin (B) containing the polar group is a modified thermoplastic resin containing a carboxy group or an acid anhydride group, it is further excellent in mechanical strength, recyclability and economic efficiency.
• thermoplastic resin (B) containing the polar group is at least one selected from a modified polyolefin resin containing a carboxy group or an acid anhydride group and a polyvinyl acetate resin, it is particularly mechanical. Excellent in strength, recyclability and economy.
• the mechanical strength is more excellent.
• the mechanical strength is more excellent. There is.
• the mechanical strength is more excellent.
• the manufacturing method of the above resin composition is a manufacturing method having more excellent mechanical strength.
• the molded product obtained by using the above resin composition is a molded product having excellent mechanical strength.
• the multilayer structure having at least one layer made of the above resin composition is a multilayer structure having excellent mechanical strength.
• the package of the present invention is composed of the above-mentioned multi-layer structure, the obtained package is also excellent in mechanical strength.
• y and / or z (y, z are arbitrary constituents or components) means three combinations of y only, z only, and y and z.
• the resin composition of the present invention contains a polar group-free thermoplastic resin (A) [hereinafter, may be simply referred to as "thermoplastic resin (A)”], and a polar group-containing thermoplastic resin (B) [ Hereinafter, it may be simply referred to as “thermoplastic resin (B)”], EVOH (C), acetic acid and / or a salt thereof (D), an aliphatic carboxylic acid (E) having 3 or more carbon atoms, and the above-mentioned aliphatic carboxylic acid. It contains an aliphatic carboxylic acid metal salt (F) which is a metal salt of the acid (E).
• the polar group-free thermoplastic resin (A) used in the present invention is, for example, a polar group-free thermoplastic resin such as a hydroxyl group, a carboxy group, an amino group, and an amide group, and the type thereof is not particularly limited. ..
• the thermoplastic resin (A) include polyolefin-based resins, polystyrene-based resins, fluororesins, and the like. These may be used alone or in combination of two.
• polystyrene-based resin examples include polyethylenes such as linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ultra-low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).
• LLDPE linear low-density polyethylene
• LDPE low-density polyethylene
• VLDPE ultra-low-density polyethylene
• MDPE medium-density polyethylene
• HDPE high-density polyethylene
• PE polyethylene
• PP polyethylene
• PP polyethylene
• block or random copolymer propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymer
• polyethylene- ⁇ -olefin (carbon number 4) ⁇ 20 ⁇ -Olefin) copolymers polyethylenes, polypentenes, polymethylpentenes and other olefins alone or copolymers, polycyclic olefins, blends thereof and the like can be mentioned. These may be used alone or in combination of two or more.
• polyethylene (PE), ethylene-propylene (block or random) copolymer, polypropylene (PP) and blends thereof are preferable in terms of economy and mechanical properties, and polyethylene (PE) and polypropylene ( PP) and ethylene-propylene (block or random) copolymers are particularly preferable because the effects of the present invention are particularly excellent.
• the ethylene or ⁇ -olefin of the polyolefin-based resin may be a plant-derived ethylene or ⁇ -olefin derived from bioethanol, or a non-plant-derived ethylene or ⁇ -olefin, that is, petroleum-derived ethylene or ⁇ -olefin. Often, these two types may be used in combination. Since a wide variety of petroleum-derived ⁇ -olefins are available, the physical characteristics of the polyolefin-based resin can be easily adjusted by producing them. By using plant-derived ethylene and ⁇ -olefin, the biomass degree of the final product can be further increased, and the burden on the environment can be reduced.
• a sugar solution or starch obtained from plants such as sugar cane, corn, and sweet potato is fermented by microorganisms such as yeast to produce bioethanol according to a conventional method. Then, this is heated in the presence of a catalyst, and plant-derived ethylene and ⁇ -olefin (1-butene, 1-hexene, etc.) can be obtained by an intramolecular dehydration reaction or the like. Further, using the obtained plant-derived ethylene and ⁇ -olefin, a plant-derived polyethylene-based resin can be produced in the same manner as in the production of a petroleum-derived polyethylene-based resin.
• the method for producing the above-mentioned plant-derived ethylene, ⁇ -olefin and plant-derived polyethylene-based resin is described in detail in, for example, Japanese Patent Publication No. 2011-506628.
• Examples of the plant-derived polyethylene-based resin preferably used in the present invention include green PE manufactured by Braskem SA.
• the polyolefin-based resin is produced by using a Ziegler-type catalyst, and chlorine caused by the catalyst is 0.01 to 500 ppm, preferably 0.1 to 400 ppm, and more preferably 1 to 300 ppm. Particularly preferably, a polyolefin resin containing 5 to 150 ppm is preferable. By using such a polyolefin-based resin, the effect of the present invention can be obtained more remarkably.
• polystyrene-based resin examples include homopolymers of styrene-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, and bromostyrene, or copolymers thereof.
• a copolymer of a styrene-based monomer as a main component and a styrene-based monomer and a polymerizable vinyl monomer a copolymer of a styrene-based monomer and a rubber component such as butadiene, a homopolymer of a styrene-based monomer, or a polymer thereof.
• examples thereof include so-called high-impact polystyrene, which is a mixture or polymer of a copolymer or a copolymer of a styrene-based monomer and a vinyl monomer and a diene-based rubber-like polymer.
• These polystyrene-based resins may be used alone or in combination of two or more.
• Examples of the vinyl monomer that can be polymerized with the styrene-based monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cetyl (meth) acrylate, and (meth) acrylonitrile. , Dimethylmaleate, dimethyl fumarate, diethyl fumarate, ethyl fumarate, divinylbenzene, alkylene glycol dimethacrylate and other bifunctional monomers and the like. These vinyl monomers may be used alone or in combination of two or more.
• diene-based rubber-like polymer examples include polybutadiene, styrene-butadiene copolymer, ethylene-propylene-non-conjugated diene three-dimensional copolymer and the like.
• polystyrene-based resin a polystyrene-based resin containing 50% by mass or more of styrene is preferable, and polystyrene is more preferable from the viewpoint of economy.
• thermoplastic resins (A) at least one selected from polyolefin-based resin and polystyrene-based resin is preferable, and at least one selected from polyethylene, polypropylene, and polystyrene is preferable from the viewpoint of excellent recyclability and economic efficiency. It is more preferably a seed, especially polypropylene.
• the melt flow rate (MFR) (230 ° C., load 2160 g) of the thermoplastic resin (A) is usually 0.1 to 100 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes. ..
• the content of the thermoplastic resin (A) is 66 to 99% by weight with respect to the total amount of the resin composition. It is preferably 70 to 98% by weight, more preferably 80 to 95% by weight. In the present invention, since the content of the thermoplastic resin (A) is in the above range, the mechanical strength is excellent. Further, if the content of the thermoplastic resin (A) is too small, the mechanical strength becomes insufficient, and if the content is too large, the gas barrier property and heat resistance rigidity of the laminated structure become insufficient.
• thermoplastic resin (B) containing a polar group used in the present invention is not particularly limited as long as it is a resin other than EVOH (C) described later.
• an unsaturated carboxylic acid or an anhydride thereof can be used as the above-mentioned thermoplastic resin.
• a modified thermoplastic resin containing a carboxy group or an acid anhydride group obtained by chemically bonding to (A) by an addition reaction, a graft reaction, or the like, or Examples thereof include a polyvinyl acetate-based resin, a polyvinyl alcohol-based resin, an ionomer-based resin modified with metal ions, a polyamide-based resin, a polyester-based resin, a polyurethane-based resin, a polycarbonate-based resin, and an acrylic-based resin. These may be used alone or in combination of two or more.
• a modified thermoplastic resin containing a carboxy group or an acid anhydride group is preferable from the viewpoint of excellent mechanical strength, recyclability and economy. Further, from the viewpoint of excellent mechanical strength, recyclability and economy, at least one selected from a polyolefin resin containing a carboxy group or an acid anhydride group and a polyvinyl acetate resin is preferable, and a carboxy group is preferable. Alternatively, it is more preferable to use a polyolefin resin containing an acid anhydride group and a polyvinyl acetate resin in combination.
• thermoplastic resin (A) used for the modified thermoplastic resin containing the carboxy group or acid anhydride group is preferably the polyolefin-based resin or polystyrene-based resin described in the thermoplastic resin (A).
• Examples of the unsaturated carboxylic acid used in the modified thermoplastic resin containing the carboxy group or the acid anhydride group include an unsaturated dicarboxylic acid and an unsaturated monocarboxylic acid.
• Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, chloromaleic acid, hymic acid, citraconic acid, and itaconic acid
• examples of the unsaturated monocarboxylic acid include acrylic acid, butanoic acid, and crotonic acid.
• Examples of the unsaturated carboxylic acid anhydride include the acid anhydride of the unsaturated dicarboxylic acid or the unsaturated monocarboxylic acid. Specific examples thereof include maleic anhydride, hymic anhydride, itaconic anhydride, citraconic anhydride, and acrylate anhydrides. Two or more kinds of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride may be used in combination. Of these, maleic anhydride is particularly suitable from the viewpoint of more effectively obtaining the effects of the invention, and further being recyclable and economical.
• the acid value of such a modified thermoplastic resin is usually 0.01 to 120 mgKOH / g, preferably 0.5 to 10 mgKOH / g, more preferably 0.5 to 7 mgKOH / g, still more preferably 0. It is .5 to 5 mgKOH / g, and particularly preferably 0.5 to 3 mgKOH / g. If the acid value of the modified thermoplastic resin is too low, the dispersibility of EVOH (C) in the resin composition tends to decrease, and the mechanical strength of the obtained molded product tends to decrease.
• the acid value of the modified thermoplastic resin is defined as the weighted average of the acid values of each resin by the mixed mass ratio.
• polyvinyl acetate-based resin for example, a resin having a vinyl acetate content measured by JIS K6924-1 of 0.01 to 60% by weight based on all the monomer components can be used, and further, the effect of the invention. Is preferably 0.02 to 50% by weight, and particularly preferably 0.03 to 30% by weight.
• the polyvinyl acetate-based resin is a monomer component that can be copolymerized with vinyl acetate as a monomer component other than vinyl acetate, for example, an olefin-based monomer such as ethylene and propylene; acrylic acid, methacrylic acid, maleic acid, and fumal.
• Carboxyl group-containing monomer such as acid, crotonic acid, itaconic acid; carboxylic acid anhydride group-containing monomer such as maleic anhydride; (meth) acrylic such as (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group.
• Acid ester hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate; epoxy group-containing copolymerizable monomer such as glycidyl (meth) acrylate; N, N-dimethylamino Amino group-containing copolymerizable monomer such as ethyl (meth) acrylic acid alkyl ester; amide group-containing copolymerizable monomer such as (meth) acrylamide; cyano group-containing copolymerizable monomer such as (meth) acrylonitrile; styrene such as styrene Monomer; Dienes such as butadiene and isoprene may be contained.
• the ethylene-vinyl acetate copolymer is particularly suitable from the viewpoint that the effects of the invention can be easily obtained.
• the polyvinyl acetate resin may be saponified. That is, the polyvinyl acetate-based resin may have a vinyl alcohol unit as the monomer unit.
• the saponification degree of the polyvinyl acetate resin is usually 20 mol% or more, and more preferably 40 to 99.5 mol%, particularly 70 to 99 mol%, so that the effect of the invention is more effective. It is preferable from the viewpoint that it is easy to obtain.
• the saponified polyvinyl acetate resin is contained in EVOH (C) described later, it is not included in the thermoplastic resin (B).
• the melt flow rate (MFR) (190 ° C., load 2160 g) of the polyvinyl acetate resin is usually 0.1 to 100 g / 10 minutes, and further 0.5 to 50 g / 10 minutes, particularly 1 to 1. 30 g / 10 minutes is preferable from the viewpoint that the effect of the invention can be easily obtained.
• the polyvinyl acetate-based resin is a modified product containing a carboxy group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof by an addition reaction, a graft reaction, or the like to the extent that the gist of the present invention is not impaired. There may be.
• the amount of such modification is preferably 10 mol% or less, for example.
• Examples of the unsaturated carboxylic acid or its anhydride include ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, etacrilic acid and crotonic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid and maleic acid.
• Examples thereof include ethylenically unsaturated dicarboxylic acids such as monomethyl, monoethyl maleate, and maleic anhydride, their anhydrides, and half esters.
• maleic anhydride is used from the viewpoint that the effects of the invention can be obtained more effectively. It is preferably used.
• polyvinyl acetate-based resin can be used alone or in combination of two or more different types such as vinyl acetate content, saponification degree, molecular weight, MFR, density, modifying group and its modified amount.
• the polyvinyl alcohol-based resin (hereinafter, may be referred to as "PVOH") is a resin usually produced by saponifying a vinyl ester-based polymer obtained by polymerizing a vinyl ester-based compound.
• the production method is also not particularly limited, and can be produced by a known method.
• vinyl ester compound examples include vinyl formate, vinyl acetate, trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatic acid, vinyl palmitate, vinyl stearate and the like. Can be mentioned. Although these are used alone or in combination of two or more, vinyl acetate is practically preferable.
• the PVOH may be a copolymer of the vinyl ester compound and a copolymerizable monomer.
• the content of the monomer copolymerizable with the vinyl ester compound in the PVOH is preferably less than 20 mol%, more preferably 10 mol% or less, and particularly preferably 7 mol% or less.
• Examples of the monomer copolymerizable with the vinyl ester compound include olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene, acrylic acid, methacrylic acid, crotonic acid and malein.
• Unsaturated acids such as acids, maleic anhydrides and itaconic acids or salts thereof or mono or dialkyl esters, nitriles such as acrylonitrile and metaacrylonitrile, amides such as acrylamide and methacrylicamide, ethylene sulfonic acid, allyl sulfonic acid and meta.
• Olefin sulfonic acid such as allyl sulfonic acid or a salt thereof, alkyl vinyl ethers, polyoxyethylene (meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) Polyoxyalkylene (meth) acrylates such as acrylates and polyoxypropylene (meth) acrylates, polyoxyalkylene (meth) acrylamides such as polyoxyethylene (meth) acrylamides and polyoxypropylene (meth) acrylamides, polyoxyethylene [1- (Meta) acrylamide-1,1-dimethylpropyl] ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, diacrylic acetone amide , N-acrylamide methyltrimethylammonium
• PVOH can be obtained by saponifying the vinyl ester-based polymer obtained by polymerizing the vinyl ester-based compound or the like.
• the saponification of the vinyl ester-based polymer is carried out by dissolving the vinyl ester-based polymer in an alcohol (methanol, ethanol, butanol, etc.) and using an alkaline catalyst (sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, etc.). It is carried out in the presence of alkali metal hydroxides such as potassium methylate and alcohols).
• the average saponification degree of PVOH is usually preferably 70 to 99.9 mol%, more preferably 75 to 99 mol%.
• two or more kinds of PVOH having different saponification degrees may be mixed and used, if necessary.
• the ionomer-based resin modified with the metal ion is a known resin, and is a thermoplastic resin having an ionic group in the side chain with respect to the hydrophobic polymer main chain.
• ionomer-based resins include sulfonic acid-based ionomers having a structure in which some or all of the sulfonic acid groups of the sulfonic acid group-containing polymer are neutralized with metal ions, and carboxy of an ethylene-unsaturated carboxylic acid copolymer. Examples thereof include carboxylic acid ionomers having a structure in which part or all of the groups are neutralized with metal ions.
• Metal ions that neutralize the acid moiety are usually monovalent metal ions such as lithium, sodium, potassium, rubidium, and cesium, and calcium, magnesium, iron, zinc, and the like. Examples thereof include divalent metal ions, trivalent metal ions such as iron and aluminum.
• the metal cation content in the ionomer is usually in the range of 0.4-4 mol, preferably 0.6-2 mol per kg of ionomer.
• the degree of neutralization is preferably one in which 15 to 80%, preferably 20 to 60% of the amount of acid in the copolymer component is neutralized with the cations of the metal.
• a divalent metal ion neutralized product is preferable from the viewpoint of affinity with EVOH (C), and a zinc ion neutralized product is particularly preferable.
• the sulfonic acid-based ionomer examples include polystyrene sulfonate (PSS) ionomer, ethylene-based sulfonate ionomer, and the like.
• Specific examples of the carboxylic acid ionomer include carboxylate ionomers such as an ethylene-unsaturated carboxylic acid copolymer. Among them, from the viewpoint of affinity with EVOH (C), it is preferable to use a carboxylic acid-based ionomer, and in particular, an ethylene-unsaturated carboxylic acid copolymer ionomer is preferably used.
• Examples of the unsaturated carboxylic acid in the ionomer of the ethylene-unsaturated carboxylic acid copolymer include (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, maleic acid monomethyl ester, and maleic acid monoethyl ester. These can be mentioned, and these can be used alone or in combination of two or more at the same time. Of these, (meth) acrylic acid is particularly preferable.
• the ionomer of the ethylene-unsaturated carboxylic acid copolymer may contain a small amount of other monomers that can be copolymerization components (for example, less than 20% by weight).
• the other monomer include vinyl esters such as vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, and (meth).
• Unsaturated (meth) acrylic acid esters such as isooctyl acrylate and the like can be mentioned.
• a divalent metal ion-neutralized product of an ethylene- (meth) acrylic acid-based copolymer is preferable, and a zinc ion-neutralized product of an ethylene- (meth) acrylic acid-based copolymer is particularly preferable. Is.
• polyamide-based resin known homopolyamide-based resins and copolymerized polyamide-based resins can be used.
• the homopolyamide resin include polycoupled (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), and polylauryl lactam. (Nylon 12) and the like.
• the copolymerized polyamide resin include polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon).
• Nylon 610 Polyhexamethylene dodecamide (Nylon 612), Polyoctamethylene adipamide (Nylon 86), Polydecamethylene adipamide (Nylon 108), Caprolactam / Lauryl lactam copolymer (Nylon 6/12), Caprolactam / ⁇ -aminononanoic acid copolymer (nylon 6/9), caprolactam / hexamethylene diammonide adipate copolymer (nylon 6/66), lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/66) , Ethylenediamine adipamide / hexamethylenediammonide adipate copolymer (nylon 26/66), caprolactam / hexamethylenediammonide adipate / hexamethylenediammonium sevacate copolymer (nylon 66/610), ethyleneammonium adip
• the polyamide-based resin may be a terminal-modified polyamide-based resin in which the ends of the homopolyamide-based resin or the copolymerized polyamide-based resin are modified. These may be used alone or in combination of two or more. Of these, a terminal-modified polyamide-based resin is preferable.
• polyester-based resin examples include polymers or copolymers obtained by a condensation reaction containing a dicarboxylic acid and a diol or an ester derivative thereof as main components.
• aromatic dicarboxylic acids are preferable, and for example, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropyridendicarboxylic acid, 1,2-bis (phenoxy) ethane Examples thereof include -4,4'-dicarboxylic acid, 2,5-anthracendicarboxylic acid, 2,6-anthracendicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid. Two or more of these dicarcinol, 4,4'-b
• one or more adipic acid, azelaic acid, sebacic acid, dodecanoic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids may be mixed and used together with the above aromatic dicarboxylic acid. You can.
• diol examples include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol, 1,4.
• aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol, 1,4.
• -Alicyclic diols such as cyclohexanedimethanol, and mixtures thereof.
• polyester-based resins include, for example, polyethylene terephthalate (hereinafter referred to as "PET”), polypropylene terephthalate, polybutylene terephthalate (hereinafter referred to as “PBT”), polyhexylene terephthalate, and polyethylene naphthalate (hereinafter referred to as "PBT”).
• PET polyethylene terephthalate
• PBT polypropylene terephthalate
• PBT polybutylene terephthalate
• PBT polyhexylene terephthalate
• PBT polyethylene naphthalate
• PEN polybutylene terephthalate
• PBN polybutylene terephthalate
• polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate etc.
• polyethylene isophthalate / Examples thereof include copolymerized polyesters such as terephthalate and polybutylene terephthalate / isophthalate.
• PET, PBT, PBN, and PEN with well-balanced mechanical properties and the like can be preferably used.
• thermoplastic resin (B) used in the present invention is obtained by acid-modifying the same type of thermoplastic resin as the thermoplastic resin (A) from the viewpoint of excellent compatibility with the thermoplastic resin (A). preferable.
• the thermoplastic resin (A) is polypropylene
• the thermoplastic resin (B) is preferably acid-modified polypropylene
• the thermoplastic resin (B) is preferably acid-modified polyethylene.
• the dispersion size of EVOH (C) present in the resin composition can be increased by using the thermoplastic resin (B). Since the resin composition is made finer, it is presumed that the resin composition easily absorbs energy when it undergoes external deformation, and as a result, the mechanical strength is improved.
• the melt flow rate (MFR) (190 ° C., load 2160 g) of the thermoplastic resin (B) is usually 0.01 to 1000 g / 10 minutes, preferably 0.05 to 800 g / 10 minutes, particularly. It is preferably 0.1 to 200 g / 10 minutes, and particularly preferably 0.5 to 50 g / 10 minutes.
• MFR melt flow rate
• the content of the thermoplastic resin (B) is preferably 0.1 to 50% by weight, more preferably 0.1 to 50% by weight, based on the total amount of the resin composition, from the viewpoints of mechanical strength, recyclability and economic efficiency. It is 0.3 to 25% by weight, more preferably 0.5 to 15% by weight, and particularly preferably 1.0 to 10% by weight. If the content of the thermoplastic resin (B) is too small, the dispersibility of EVOH (C) is lowered, and the mechanical strength of the molded product tends to be insufficient, and the content is too large.
• EVOH (C) used in the present invention is a resin usually obtained by copolymerizing an ethylene-vinyl ester-based copolymer obtained by copolymerizing ethylene and a vinyl ester-based monomer, and is an ethylene-vinyl alcohol.
• the polymerization method any known polymerization method, for example, solution polymerization, suspension polymerization, or emulsion polymerization can be used, but solution polymerization using methanol as a solvent is generally used.
• the obtained ethylene-vinyl ester copolymer can also be saponified by a known method.
• EVOH (C) used in the present invention is mainly composed of an ethylene structural unit and a vinyl alcohol structural unit, and contains a small amount of vinyl ester structural unit remaining without saponification.
• vinyl ester-based monomer vinyl acetate is typically used because it is easily available on the market and the processing efficiency of impurities during production is good.
• Other vinyl ester-based monomers include, for example, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatic acid and the like.
• examples thereof include aliphatic vinyl esters and aromatic vinyl esters such as vinyl benzoate.
• an aliphatic vinyl ester having 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms is preferable. These are usually used alone, but if necessary, a plurality of types may be used at the same time.
• the EVOH (C) may further contain a structural unit derived from the comonomer shown below in addition to the ethylene structural unit and the vinyl alcohol structural unit (including the unsaponified vinyl ester structural unit). good.
• the comonomer include ⁇ -olefins such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, and ⁇ -octadecene; 3-butene-1-ol, 4-pentene-1-ol, 3-butene-1, Hydroxy group-containing ⁇ -olefins such as 2-diols and their esterified products, hydroxy group-containing ⁇ -olefin derivatives such as acylated products; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2- Hydroxymethylvinylidene diacetates such as methylenepropane, 1,3-dibutyronyloxy-2-methylene
• EVOH "post-modified” EVOH such as urethanization, acetalization, cyanoethylation, and oxyalkyleneization can also be used.
• EVOH in which a primary hydroxyl group is introduced into the side chain by copolymerization is preferable because it improves secondary moldability such as stretching treatment and vacuum / pressure forming.
• EVOH having a 1,2-diol structure in the side chain is preferable.
• the content of ethylene structural unit in the above EVOH (C) is a value measured based on ISO14663, which is 20 to 60 mol%, preferably 25 to 50 mol%, and particularly preferably 25 to 35 mol%. .. If the content is too small, the gas barrier property and melt moldability at high humidity are lowered, and if the content is too high, the gas barrier property is lowered.
• the degree of saponification of EVOH (C) is a value measured based on JIS K6726 (however, EVOH is a solution uniformly dissolved in water / methanol solvent), and is usually 90 to 100 mol%, preferably 95. It is -100 mol%, particularly preferably 99-100 mol%. If the saponification degree is too low, the gas barrier property, thermal stability, moisture resistance and the like tend to decrease.
• the melt flow rate (MFR) (210 ° C., load 2160 g) of EVOH (C) is usually 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, and particularly preferably 3 to 35 g. / 10 minutes. If the MFR is too high, the film-forming property tends to decrease. Further, if the MFR is too low, melt extrusion tends to be difficult.
• the EVOH (C) used in the present invention may be a mixture with other EVOHs different from each other, and such other EVOHs include, for example, those having a different ethylene content and those having a different degree of saponification. Examples thereof include those having a different melt flow rate (MFR), those having a different other copolymerization component, those having a different amount of modification (for example, those having a different content of structural units containing a primary hydroxyl group in the side chain). ..
• MFR melt flow rate
• those having a different other copolymerization component those having a different amount of modification (for example, those having a different content of structural units containing a primary hydroxyl group in the side chain).
• the content of EVOH (C) is 0.1 to 25% by weight, preferably 0.3 to 20% by weight, more preferably 0.3 to 20% by weight, based on the total amount of the resin composition, from the viewpoint of excellent mechanical strength. It is 0.5 to 15% by weight. If the content of EVOH (C) is too small, the gas barrier property of the molded product becomes insufficient, and if the content is too large, the mechanical strength of the molded product becomes insufficient.
• the resin composition of the present invention contains acetic acid and / or a salt (D) thereof, and specific examples of the acetic acid and / or the salt (D) thereof include acetic acid, sodium acetate, and acetic acid.
• Potassium, calcium acetate, magnesium acetate, manganese acetate, copper acetate, cobalt acetate, zinc acetate and the like can be mentioned, and these can be used alone or in combination of two or more.
• acetic acid, sodium acetate, potassium acetate, calcium acetate and magnesium acetate are preferable, acetic acid, sodium acetate and potassium acetate are particularly preferable, and acetic acid and sodium acetate are more preferable.
• the content of the acetic acid and / or its salt (D) in terms of acetate ions is preferably 0.01 to 1000 ppm, more preferably 0.01 to 1000 ppm, based on the total amount of the resin composition, from the viewpoint of excellent mechanical strength. Is 0.1 to 800 ppm, particularly preferably 5 to 600 ppm, and particularly preferably 10 to 400 ppm. If the content is too small, the mechanical strength tends to decrease due to the thermal decomposition product of the aliphatic carboxylic acid metal salt (F) described later, and if the content is too large, the effect of the invention cannot be sufficiently obtained. Tend.
• the content of the above acetic acid and / or its salt (D) in terms of acetate ion is not particularly limited and can be measured by a known analytical method. For example, it can be evaluated by using liquid chromatography-mass spectrometry (LC / MS), gas chromatography-mass spectrometry (GC / MS), or the like.
• LC / MS liquid chromatography-mass spectrometry
• GC / MS gas chromatography-mass spectrometry
• the ion-equivalent content / (D) acetate ion-equivalent content) is usually 0.001 ⁇ ((F) / (D)) ⁇ 1.3 on a weight basis, preferably 0.005 ⁇ ((F) / (D)) ⁇ 1.3.
• the resin composition of the present invention contains an aliphatic carboxylic acid other than acetic acid, that is, an aliphatic carboxylic acid (E) having 3 or more carbon atoms [hereinafter, may be referred to as "aliphatic carboxylic acid (E)"].
• the number of carbon atoms of the aliphatic carboxylic acid (E) is usually 3 to 30, preferably 4 to 20, and particularly preferably 5 to 14. When the carbon number of the aliphatic carboxylic acid (E) is within the above range, it is preferable from the viewpoint of economy.
• Examples of the aliphatic carboxylic acid (E) include an aliphatic monocarboxylic acid having one carboxy group, an aliphatic dicarboxylic acid having two carboxy groups, and an aliphatic tricarboxylic acid having three carboxy groups. ..
• aliphatic monocarboxylic acid examples include butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, 12 -Saturated aliphatic acids such as hydroxystearic acid, arachidic acid, henicosyl acid, bechenic acid, lignoseric acid, montanic acid, melisic acid, tartron acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid, gluconic acid, mevalonic acid, pantoic acid, etc.
• aliphatic dicarboxylic acid examples include saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and unsaturated aliphatic dicarboxylic acids such as eikosazienoic acid and docosadienoic acid. Be done.
• saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid
• unsaturated aliphatic dicarboxylic acids such as eikosazienoic acid and docosadienoic acid. Be done.
• aliphatic tricarboxylic acid examples include saturated aliphatic tricarboxylic acids such as citric acid, isocitric acid, and aconitic acid.
• These aliphatic carboxylic acids (E) can be used alone or in combination of two or more
• an aliphatic monocarboxylic acid having one carboxy group is preferable, and a saturated aliphatic monocarboxylic acid is more preferable.
• Particularly preferred are stearic acid, caproic acid, capric acid, lauric acid and behenic acid.
• the content of the aliphatic carboxylic acid (E) in terms of carboxylic acid ion is preferably 0.0001 to 150 ppm, more preferably 0.0001 to 150 ppm, based on the total amount of the resin composition, from the viewpoint of excellent mechanical strength. It is 0.001 to 100 ppm, particularly preferably 0.005 to 75 ppm, and particularly preferably 0.01 to 50 ppm. If the content is too small, the thermal stability of the aliphatic carboxylic acid metal salt (F) described later becomes insufficient, and as a result, the effects of the invention tend not to be sufficiently obtained.
• the aliphatic carboxylic acid (E) itself acts as a plasticizing agent, and the effects of the invention tend not to be sufficiently obtained.
• the content of the aliphatic carboxylic acid (E) in terms of carboxylic acid ion can be determined by a method described later.
• the resin composition of the present invention contains an aliphatic carboxylic acid metal salt (F), which is a metal salt of the aliphatic carboxylic acid (E).
• Examples of the metal species of the aliphatic carboxylic acid metal salt (F) include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as beryllium, magnesium, calcium and barium, chromium, cobalt, nickel and copper. Transition metals such as iron and zinc can be mentioned, preferably sodium, potassium, calcium, magnesium, iron and zinc, particularly preferably sodium, calcium, magnesium and zinc, particularly in which the effects of the invention can be easily obtained. Preferably, it is zinc which has a particularly excellent effect and is inexpensive and easily available.
• thermoplastic resin in the resin composition can be obtained by using the aliphatic carboxylic acid metal salt (F).
• thermoplastic resin in the resin composition can be obtained by using the aliphatic carboxylic acid metal salt (F).
• anion species of the aliphatic carboxylic acid metal salt (F) those exemplified as the aliphatic carboxylic acid (E) can be used. Further, in the present invention, it is important that the anionic species of the aliphatic carboxylic acid metal salt (F) and the anionic species of the aliphatic carboxylic acid (E) are the same species. When the anionic species of the aliphatic carboxylic acid metal salt (F) and the aliphatic carboxylic acid (E) are the same species, a resin composition having excellent mechanical strength can be obtained.
• the resin composition of the present invention contains a plurality of the aliphatic carboxylic acids (E) or a plurality of the aliphatic carboxylic acid metal salts (F), at least one kind of the aliphatic carboxylic acid (E) And the anion species of the above-mentioned aliphatic carboxylic acid metal salt (F) may be the same species.
• the aliphatic carboxylic acid (E) is considered to interact with the metal species of the aliphatic carboxylic acid metal salt (F) and exist in a state like a metal complex, and the aliphatic carboxylic acid metal salt (F) is considered to exist.
• the content of the aliphatic carboxylic acid metal salt (F) in terms of metal ions is preferably 0.01 to 90 ppm, more preferably 0.01 to 90 ppm, based on the total amount of the resin composition, from the viewpoint of excellent mechanical strength. Is 0.05 to 80 ppm, particularly preferably 0.08 to 60 ppm, and particularly preferably 0.1 to 50 ppm. If the content of the aliphatic carboxylic acid metal salt (F) is too small or too large, the effect of the invention tends not to be sufficiently obtained.
• the content of the aliphatic carboxylic acid metal salt (F) in terms of metal ions and the content of the aliphatic carboxylic acid (E) in terms of carboxylic acid ions are not particularly limited, and a known analysis method can be used. Can be measured. For example, the following methods can be obtained alone or in combination.
• [Content of aliphatic carboxylic acid metal salt (F) in terms of metal ions] The dried sample is precisely weighed, placed in a constant weight platinum evaporating dish, charred with an electric heater, then heated with a gas burner until no smoke is emitted, and the above platinum evaporating dish is placed in an electric furnace. The temperature is raised to completely incinerate.
• the ion-equivalent content / ((E) carboxylic acid ion-equivalent content) is usually 0.11 ⁇ ((F) / (E)) ⁇ 100, more preferably 0.13 ⁇ ((F) ⁇ ((F) / (E)) ⁇ 100 on a weight basis.
• the aliphatic carboxylic acid (E) itself acts as a plasticizer, so that the effect of the present invention (mechanical strength improving effect) can be sufficiently obtained. It is presumed that it cannot be done.
• thermoplastic resins In the resin composition of the present invention, other thermoplastic resins other than the thermoplastic resin (A), the thermoplastic resin (B), and EVOH (C) are used within a range that does not impair the effects of the present invention (for example, a resin). It may be contained in an amount of 30% by weight or less, preferably 10% by weight or less based on the total amount of the composition. By blending other thermoplastic resins, the strength can be further increased or other functions can be imparted.
• thermoplastic resin examples include polyvinyl chloride, polyvinylidene chloride, acrylic resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, halogenated polyolefin such as chlorinated polypropylene, aromatic or aliphatic polyketones and the like. Can be mentioned. These may be used alone or in combination of two or more.
• Additions to the resin composition of the present invention are generally blended with the resin composition within a range that does not impair the effects of the present invention (for example, usually 30% by weight or less, preferably 10% by weight or less of the resin composition).
• Agents such as heat stabilizers, inorganic fillers, antioxidants, antioxidants, colorants, UV absorbers, lubricants (eg saturated aliphatic amides such as stearic acid amides, unsaturated fatty acid amides such as oleic acid amides) , Bis fatty acid amides such as ethylene bisstearic acid amides), plasticizers (eg, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, hexanediol, etc.), light stabilizers, surfactants, antibacterial agents, desiccants, Antiblocking agents, flame retardants, cross-linking agents, foaming agents, crystal nucleating agents, antifogging agents, biodegradation additives, silane coupling agents, oxygen absorbers, phosphoric acid and / or salts thereof, cinnamic acid and / or its It contains known additives such as salts, conjugated polyene compounds, endiol group-containing substances
• examples of the inorganic filler include hydrotalcite compounds, mica, talcite, calcium carbonate, titanium oxide, kaolin, clay, glass flakes, glass beads, vermiculite, smectite, and the like. Two or more types may be used in combination.
• hydrotalcite-based compound examples include hydrotalcite-based solid solutions represented by the following general formula (1).
• Mg and Ca are preferable as M 1 2+
• Zn and Cd are preferable as M 2 2+
• examples of M x 3+ include Al, Bi, In, Sb, B, Ga, Ti and the like, and these are used alone or in combination of two or more, but Al is practical among them. ..
• Examples of the compounds represented by the general formula (2) specifically, Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O, Mg 5 Al 2 (OH) 14 CO 3 ⁇ 4H 2 O, Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4H 2 O, Mg 8 Al 2 (OH) 20 CO 3 ⁇ 5H 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 , and the like.
• Mg 2 Al (OH) 9 ⁇ 3H 2 in which a part of OH in O is not explicitly shown in the formula such as those substituted with CO 3 or HPO 4 or more crystalline
• compounds in which M is Mg and E is CO 3 are suitable from the viewpoint of recyclability.
• the average particle size of the hydrotalcite compound for example, is usually 10 ⁇ m or less, more preferably 5 ⁇ m or less, and particularly preferably 1 ⁇ m or less. That is, when the average particle size is too large, the effect of the present invention tends not to be sufficiently obtained.
• the average particle size referred to here is a value measured by the LUZEX method.
• hydrotalcite-based solid solution represented by the above general formula (1) it is particularly preferable to use the hydrotalcite-based solid solution represented by the above general formula (1) from the viewpoint of high molding stability.
• the average particle size of the inorganic filler other than the hydrotalcite compound is usually preferably 1 to 20 ⁇ m, more preferably 3 to 18 ⁇ m, and particularly preferably 5 to 15 ⁇ m. If the average particle size is less than 1 ⁇ m, gel due to the aggregation of the particles will be generated in the molded product, the heat resistance and rigidity of the laminated structure will be insufficient, and if it exceeds 20 ⁇ m, the increase in resin pressure can be suppressed. It gets harder.
• the content of the inorganic filler is usually preferably 0.001 to 30% by weight, more preferably 0.005 to 20% by weight, and particularly preferably 0.01 to 10% by weight, based on the total amount of the resin composition. By weight%.
• antioxidants examples include hindered phenolic compounds: dibutylhydroxytoluene, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis.
• Trialkyl phosphite such as alkylaryl phosphite, triisooctyl phosphite, tristearyl phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, etc .; thioether compound: pentaerythritol -Tetrakiss- ( ⁇ -laurylthiopropionate), tetrakis [methylene-3- (dodecylthio) propionate] methane, bis [2-methyl-4- ⁇ 3-n-alkylthiopropionyloxy ⁇ -5-t-butylphenyl ] Sulfide, dilauryl-3,3'-thiodipropionate, dimystylyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythryl
• hindered phenolic antioxidants are preferable, and in particular, pentaerythritol-tetrakis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and octadecyl-3- (3,5-) are preferable.
• Di-t-butyl-4-hydroxyphenyl) propionate is preferably used because it is excellent in reducing thermal deterioration of the resin composition of the present invention.
• the content of the antioxidant is usually 0.001 to 10% by weight, preferably 0.005 to 5% by weight, particularly preferably 0.01 to 3% by weight, based on the total amount of the resin composition. be.
• phosphoric acid and / or a salt thereof include, for example, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, and phosphoric acid.
• Calcium monohydrogen, calcium dihydrogen phosphate, tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, zinc hydrogen phosphate, barium hydrogen phosphate, manganese hydrogen phosphate, etc. can be mentioned. , These can be used alone or in combination of two or more.
• phosphoric acid sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, and zinc hydrogen phosphate are preferable, and phosphoric acid and sodium dihydrogen phosphate are particularly preferable.
• the content of the phosphoric acid and / or a salt thereof is usually preferably 0.001 to 300 ppm or less, more preferably 0.005 to 200 ppm, still more preferably 0.01 to 100 ppm, based on the total amount of the resin composition. Is.
• cinnamic acid and / or a salt thereof include cis-cinnamic acid and trans-cinnamic acid, and trans-cinnamic acid is preferably used from the viewpoint of stability and price.
• the cinnate salt include alkali metal silicates such as lithium cinnate, sodium cinnate, and potassium cinnate, alkaline earth metal salts of cinnate such as magnesium cinnate, calcium cinnate, and barium cinnate. Can be mentioned.
• These cinnamic acids and / or salts thereof can be used alone or in combination of two or more. Of these, it is preferable to use trans-cinnamic acid alone.
• the content of the cinnamic acid and / or a salt thereof is usually 0.1 to 120 ppm, preferably 0.1 to 100 ppm, and more preferably 1 to 80 ppm, based on the total amount of the resin composition. It is preferably 1.5 to 50 ppm.
• the conjugated polyene compound has 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, so-called conjugated double bonds. It is a compound having.
• a conjugated polyene compound 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 carbon-. It may be a conjugated triene having a structure in which 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. ..
• the number of conjugated carbon-carbon double bonds is 8 or more, there is a concern that the molded product will be colored by the color of the conjugated polyene compound itself, so the number of conjugated carbon-carbon double bonds is 7 or less. It is preferably a certain polyene.
• the above-mentioned conjugate double bond composed of two or more carbon-carbon double bonds may be formed in a plurality of pairs in one molecule without being conjugated with each other.
• a compound having three conjugated trienes in the same molecule, such as tung oil is also included in the conjugated polyene compound.
• conjugated polyene compound examples include a conjugated diene compound having two carbon-carbon double bonds such as isoprene, milsen, farnesene, sembrene, sorbic acid, sorbic acid ester, sorbate, and avietic acid; 1,3.
• Conjugated triene compounds having three carbon-carbon double bonds such as 5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, and cholecalciferol; cyclooctatetraene, Examples thereof include conjugated polyene compounds having four or more carbon-carbon double bonds such as 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoic acid. These conjugated polyene compounds may be used alone or in combination of two or more.
• the content of the conjugated polyene compound is usually preferably 0.001 to 1000 ppm, more preferably 0.01 to 100 ppm, and particularly preferably 0.05 to 50 ppm, based on the total amount of the resin composition.
• the method for producing the resin composition of the present invention is not particularly limited, and examples thereof include the methods shown in (I) to (IV) below.
• the methods shown in (I) to (IV) below may be used in combination of two or more.
• Pellets of thermoplastic resin (A), thermoplastic resin (B), EVOH (C), acetic acid and / or a salt thereof (D), aliphatic carboxylic acid (E), aliphatic carboxylic acid metal salt A method in which at least one of F) is blended in a predetermined ratio and dry-blended (dry blend method).
• At least one pellet of the thermoplastic resin (A), the thermoplastic resin (B), and the EVOH (C) is subjected to acetic acid and / or a salt thereof (D), an aliphatic carboxylic acid (E), and an aliphatic carboxylic acid.
• a method in which at least one type is blended in a predetermined ratio and melt-kneaded, and then pellets are prepared (melt-kneading method).
• At least one of the above aliphatic carboxylic acid metal salts (F) is added and mixed, and then the solvent in the solution is removed (solution mixing method).
• a method of blending at least one salt (F) in a predetermined ratio, melt-kneading, and then producing pellets (melt-kneading method) is practical and industrially preferable in terms of productivity and economy.
• a resin composition containing the other thermoplastic resin or additive can be obtained by following the methods (I) to (IV) above.
• a known mixing device such as a locking mixer, a ribbon blender, or a line mixer can be used.
• the water content of at least one pellet of the thermoplastic resin (A), the thermoplastic resin (B), and the EVOH (C) is set to 0.1 to 5% by weight (further, 0.5 to 4). It is preferable to adjust the weight to%, particularly 1 to 3% by weight).
• the acetic acid and / or its salt (D), the aliphatic carboxylic acid (E), and the aliphatic carboxylic acid metal salt (F) is likely to fall off and the adhesion distribution is large. It tends to be non-uniform.
• at least one of the acetic acid and / or its salt (D), the aliphatic carboxylic acid (E), and the aliphatic carboxylic acid metal salt (F) are aggregated and the adhesion distribution is non-uniform. Tends to be.
• thermoplastic resin (A), thermoplastic resin (B), and EVOH (C) pellets The water content of at least one of the above-mentioned thermoplastic resin (A), thermoplastic resin (B), and EVOH (C) pellets is measured and calculated by the following method.
• the acetic acid and / or a salt (D) thereof is placed on the outside of at least one pellet of the thermoplastic resin (A), the thermoplastic resin (B), and the EVOH (C).
• the pellet to which at least one component of the aliphatic carboxylic acid (E) and the aliphatic carboxylic acid metal salt (F) is attached can be obtained.
• melt-kneading device such as a kneader, a ruder, an extruder, a mixing roll, a Banbury mixer, or a plast mill can be used, and usually 150 to It is preferable to melt-knead at 300 ° C. (more preferably 180 to 280 ° C.) for about 1 to 20 minutes.
• a vent suction device such as a gear pump device, a screen device, or the like, if necessary.
• the extruder in order to remove water and by-products (pyrolytic low molecular weight substances, etc.), the extruder is provided with one or more vent holes for suction under reduced pressure, and oxygen is prevented from being mixed into the extruder.
• an inert gas such as nitrogen
• the method of supplying to a melt-kneading device such as an extruder is not particularly limited.
• Method of blending and supplying to the extruder in a batch 2 At least one pellet of the thermoplastic resin (A), the thermoplastic resin (B), and the EVOH (C) is supplied to the extruder to be melted, and there.
• a method of supplying solid acetic acid and / or a salt thereof (D), an aliphatic carboxylic acid (E), and an aliphatic carboxylic acid metal salt (F) (solid side feed method). 3) Acetic acid and / or a salt thereof (D) in a molten state when at least one pellet of the thermoplastic resin (A), the thermoplastic resin (B), and the EVOH (C) is supplied to an extruder and melted. ), The aliphatic carboxylic acid (E), and the aliphatic carboxylic acid metal salt (F) (melt side feed method). Among them, the method 1) is practical in terms of the simplicity of the apparatus, the cost of the blended product, and the like.
• scrap containing a layer made of a thermoplastic resin (A) and a layer made of EVOH (C) as raw materials are also preferable.
• Pellets containing a melt-kneaded aliphatic carboxylate metal salt (F) and scrap containing a layer made of a thermoplastic resin (A) and a layer made of EVOH (C) are dry-blended and collectively supplied to an ex
• Method 6) Contains a layer made of a thermoplastic resin (A), a layer made of acetic acid and / or a salt thereof (D), an aliphatic carboxylic acid (E), an aliphatic carboxylic acid metal salt (F), and an EVOH (C).
• a method in which the scrap to be processed and the thermoplastic resin (B) are dry-blended and collectively supplied to the extruder include a method in which the scrap to be processed and the thermoplastic resin (B) are dry-blended and collectively supplied to the extruder.
• the methods 4) and 6) are practical in terms of convenience and cost of the apparatus.
• the scrap is a collection of edges and defective products generated when manufacturing a multi-layer structure or a molded product, and further, the scrap is a multi-layer structure containing a recovered material layer containing scrap.
• a multi-layer structure and a molded body containing a recovered material layer made of a resin composition obtained from an end portion or a defective product generated when the multi-layer structure and the molded body are manufactured are manufactured, and the multi-layer structure and the molded body are manufactured.
• the scrap of the molded product may be collected and used as a raw material for the resin composition of the present invention.
• the scrap is preferably crushed to an appropriate size, and as the scrap, scrap obtained from one type of multi-layer structure and molded body may be used, or two or more types of multi-layer structure and molding may be used. Scrap obtained from the body may be mixed and used.
• the scrap may consist of a multi-layer structure and a molded product discarded by general consumers as plastic waste. That is, the multilayer structure and the molded product discarded from general consumers as plastic waste may be collected, and the scrap recovered product of the multilayer structure and the molded product may be used as a raw material for the resin composition of the present invention.
• a known method can be used, and examples thereof include a strand cut method and a hot cut method (air cut method, underwater cut method).
• the strand cut method is preferable.
• a known good solvent may be used.
• water and an aliphatic alcohol having 1 to 4 carbon atoms are typical good solvents for EVOH (C).
• a mixed solvent with and is used preferably a mixed solvent of water and methanol.
• the aliphatic carboxylate metal salt (F) may be blended.
• acetic acid and / or a salt thereof (D), an aliphatic carboxylic acid (E), and an aliphatic carboxylic acid metal salt (F) can be blended in a solid state, a solution, a dispersion liquid, or the like.
• the resin composition solution or paste that has been uniformly stirred is pelletized by the above-mentioned known method. In terms of industrial productivity, the underwater cut method is preferable. The obtained pellets are dried by a known method.
• any shape such as a spherical shape, an oval shape, a cylindrical shape, a cubic shape, and a rectangular parallelepiped shape can be adopted.
• it is an oval type or a cylindrical shape, and the size thereof is usually 1 to 6 mm, preferably 2 to 5 mm, and a major axis in the case of the oval type from the viewpoint of convenience when it is used as a molding material later.
• the diameter of the bottom surface is usually 1 to 6 mm, preferably 2 to 5 mm
• the length is usually 1 to 6 mm, preferably 2 to 5 mm.
• the molded product of the present invention is melt-molded from the above-mentioned resin composition of the present invention.
• the above-mentioned molded body can be used as it is for various shapes (for example, films, sheets, cups, trays, bottles, tanks, pipes, tubes, transport pallets, chairs, desks, piles, etc.), but it is necessary. (Heating) stretching treatment is performed accordingly.
• the stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching.
• the stretching method a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, vacuum compressed air forming, or the like, which has a high stretching ratio, can also be adopted.
• the stretching temperature is usually selected from the range of 40 to 170 ° C., preferably about 60 to 160 ° C. If the stretching temperature is too low, the stretchability tends to be poor, and if it is too high, it tends to be difficult to maintain a stable stretched state.
• the molded product may be heat-fixed for the purpose of imparting dimensional stability after stretching.
• the heat treatment can be carried out by a well-known means.
• the stretched multilayer structure (stretched film) is kept in a tense state at usually 80 to 180 ° C., preferably 100 to 165 ° C. for usually 2 to 600 seconds. Perform degree heat treatment.
• the above heat fixing is not performed in order to impart heat shrinkage, for example, after stretching.
• the film may be cooled and fixed by applying cold air to the film.
• a cup or tray-shaped single-layer container from the molded product of the present invention.
• a draw forming method is usually adopted, and specific examples thereof include a vacuum forming method, a vacuum forming method, a vacuum forming method, a plug-assisted vacuum forming method, and the like.
• a blow molding method is adopted, specifically, an extrusion blow molding method (for example, a double-headed type).
• Mold moving type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison type blow molding method, injection blow molding method, biaxial stretching blow molding method (for example, extrusion cold parison biaxial) Stretch blow molding method, injection cold parison biaxial stretch blow molding method, injection molding in-line biaxial stretch blow molding method, etc.) and the like can be mentioned.
• the molded body of the present invention is subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry laminating treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing and the like, as necessary. be able to.
• the thickness of the molded product (including the stretched product) of the present invention is appropriately set depending on the intended use, packaging form, required physical properties, and the like.
• the thickness of the molded product (including the stretched product) of the present invention is usually 10 to 500,000 ⁇ m, preferably 30 to 300,000 ⁇ m, and particularly preferably 50 to 200,000 ⁇ m. If the thickness of the molded product is too thin, the mechanical strength tends to decrease. Further, if the thickness of the molded product is too thick, the mechanical strength becomes excessive and unnecessary raw materials are used excessively, which is economically unfavorable.
• the multilayer structure of the present invention has at least one layer made of the resin composition of the present invention.
• the layer made of the resin composition of the present invention (hereinafter, simply referred to as "resin composition layer”) can be further increased in strength or imparted with other functions by laminating with another base material.
• Examples of the other base material include a layer made of an adhesive resin (hereinafter, simply referred to as an "adhesive resin layer”), a layer made of a polyamide resin (hereinafter, simply referred to as a “polyamide layer”), and EVOH (C).
• a layer made of (hereinafter, simply referred to as “EVOH layer”) and a layer made of a thermoplastic resin other than EVOH (hereinafter, simply referred to as “thermoplastic resin layer”) are preferably used.
• the layer structure of the multilayer structure is such that the resin composition layer of the present invention is R (R1, R2, 7), The EVOH layer is ⁇ ( ⁇ 1, ⁇ 2, 7), And the adhesive resin layer is ⁇ ( ⁇ 1, ).
• the polyamide layer is ⁇ ( ⁇ 1, ⁇ 2, 7),
• the thermoplastic resin layer is ⁇ ( ⁇ 1, ⁇ 2, 7), ⁇ / R / ⁇ / ⁇ , ⁇ 1 / R / ⁇ 2 / ⁇ 3, ⁇ / R / ⁇ 1 / ⁇ / ⁇ 2, ⁇ 1 / R / ⁇ / / / ⁇ 2, R1 / ⁇ 1 / ⁇ / ⁇ 2 / R2, R1 / ⁇ 1 / ⁇ 2 / ⁇ 3 / R2, ⁇ 1 / R1 / ⁇ 1 / ⁇ / ⁇ 2 / R2 / ⁇ 2, ⁇ 1 / R1 / ⁇ 1 / / ⁇ 2
• polyamide resin known ones can be used. Specifically, for example, polycapramid (nylon 6), poly- ⁇ -aminoheptanoic acid (nylon 7), poly- ⁇ -aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryl lactam (nylon 12). ) And the like, and among them, polycapramide (nylon 6) is preferable.
• polycapramide nylon 6
• the copolymerized polyamide resin include polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon).
• nylon 612 polyhexamethylene dodecamide
• nylon 86 polyoctamethylene adipamide
• nylon 108 polydecamethylene adipamide
• caprolactam / lauryllactam copolymer nylon 6/12
• caprolactam / ⁇ -Aminononanoic acid copolymer nylon 6/9
• caprolactam / hexamethylene diammonide adipate copolymer nylon 6/66
• lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/66)
• Aromatic polyamides such as amide / terephthalamide copolymers, poly-p-phenylene terephthalamide, poly-p-phenylene 3,4'-diphenyl ether terephthalamide, amorphous polyamides, and methylenebenzyl for these polyamide-based resins.
• Examples thereof include those modified with aromatic amines such as amines and polymer amines, and polymers such as metal xylylene diam adipates.
• these terminal-modified polyamide-based resins may be used, preferably terminal-modified polyamide-based resins.
• thermoplastic resin other than EVOH examples include linear low-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymer, and ethylene-.
• Polyolefin resins such as ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers, polypropylene, polypropylene resins such as propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers, (Unmodified) polyolefin-based resins such as polybutene, polypentene, and polycyclic olefin resins (polymers having a cyclic olefin structure in the main chain and / or side chains) and these polyolefins with unsaturated carboxylic acids or esters thereof.
• ⁇ -olefin ⁇ -olefin having 4 to 20 carbon atoms copolymers
• polypropylene such as propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers
• (Unmodified) polyolefin-based resins such as polybutene
• polyolefin resins including modified olefin resins such as graft-modified unsaturated carboxylic acid-modified polyolefin resins, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers.
• hydrophobic resins such as polyolefin resins, polyester resins, and polystyrene resins are preferable, and polyethylene resins, polypropylene resins, polycyclic olefin resins, and these are more preferable.
• a polyolefin-based resin such as an unsaturated carboxylic acid-modified polyolefin-based resin, and in particular, a polycyclic olefin-based resin is preferably used as a hydrophobic resin.
• the ethylene or ⁇ -olefin of the polyolefin-based resin may be a plant-derived ethylene or ⁇ -olefin derived from bioethanol, or a non-plant-derived ethylene or ⁇ -olefin, that is, a petroleum-derived ethylene or ⁇ -olefin. These two types may be used in combination. Since a wide variety of petroleum-derived ⁇ -olefins are available, the physical characteristics of the polyolefin-based resin can be easily adjusted by producing them. Further, by using plant-derived ethylene and ⁇ -olefin, the biomass degree of the final product can be further increased, and the burden on the environment can be reduced.
• bioethanol is produced by fermenting sugar solution or starch obtained from plants such as sugar cane, corn, and sweet potato with microorganisms such as yeast according to a conventional method. , This can be heated in the presence of a catalyst to obtain plant-derived ethylene and ⁇ -olefins (1-butene, 1-hexene, etc.) by an intramolecular dehydration reaction or the like.
• the plant-derived polyethylene-based resin can be produced by using the obtained plant-derived ethylene and ⁇ -olefin in the same manner as in the production of the petroleum-derived polyethylene-based resin.
• plant-derived ethylene, ⁇ -olefin and plant-derived polyethylene-based resin are described in detail in, for example, Japanese Patent Publication No. 2011-506628.
• plant-derived polyethylene-based resin preferably used in the present invention include green PE manufactured by Braskem SA.
• the adhesive resin which is the material for forming the adhesive resin layer a known adhesive resin can be used, and it may be appropriately selected according to the type of the thermoplastic resin used for the other thermoplastic resin as the base material.
• a modified polyolefin-based polymer containing a carboxy group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to a polyolefin-based resin by an addition reaction, a graft reaction, or the like can be mentioned.
• maleic anhydride graft-modified polyethylene maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft.
• the content of the unsaturated carboxylic acid or its anhydride in the modified polyolefin-based polymer containing a carboxy group is usually 0.001 to 3% by weight based on the total amount of the modified polyolefin-based polymer containing a carboxy group. Yes, preferably 0.01 to 1% by weight, particularly preferably 0.03 to 0.5% by weight. If the content (modification amount) of the unsaturated carboxylic acid or its anhydride is small, the adhesiveness tends to be insufficient, and conversely, if it is large, a cross-linking reaction tends to occur and the moldability tends to deteriorate.
• adhesive resins can be blended with rubber / elastomer components such as ethylene-vinyl alcohol-based copolymers, polyisobutylene, and ethylene-propylene rubber, and resins of a polyolefin-based resin layer.
• rubber / elastomer components such as ethylene-vinyl alcohol-based copolymers, polyisobutylene, and ethylene-propylene rubber
• resins of a polyolefin-based resin layer In particular, it is also possible to blend a polyolefin-based resin different from the polyolefin-based resin that is the base of the adhesive tree fat.
• the adhesive resin layer, polyamide layer, and thermoplastic resin layer are provided with acetic acid and / or used in the present invention within a range that does not impair the gist of the present invention (for example, 30% by weight or less, preferably 10% by weight or less).
• acetic acid for example, 30% by weight or less, preferably 10% by weight or less.
• plasticizers for example, ethylene glycol, glycerin, hexanediol, etc.
• fillers for example, for example.
• Montmorillonite, etc. colorants, antioxidants, antioxidants, lubricants (eg, alkali metal salts of higher fatty acids with 8 to 30 carbon atoms, alkaline earth metal salts, higher fatty acid esters (eg, methyl esters of higher fatty acids, etc.) Isopropyl ester, butyl ester, octyl ester, etc.), higher fatty acid amides (eg, saturated aliphatic amides such as stearic acid amides and behenic acid amides, unsaturated fatty acid amides such as oleic acid amides and erucic acid amides, ethylene bisstearic acid amides).
• lubricants eg, alkali metal salts of higher fatty acids with 8 to 30 carbon atoms, alkaline earth metal salts, higher fatty acid esters (eg, methyl esters of higher fatty acids, etc.) Isopropyl ester, butyl
• Ethylene bisoleic acid amide Ethylene bisoleic acid amide, ethylene bisuelca acid amide, bis fatty acid amide such as ethylene bislauric acid amide
• low molecular weight polyolefin for example, low molecular weight polyethylene having a molecular weight of about 500 to 10000, or low molecular weight polypropylene
• nucleating agent for example, low molecular weight polyethylene having a molecular weight of about 500 to 10000, or low molecular weight polypropylene
• nucleating agent for example, low molecular weight polyethylene having a molecular weight of about 500 to 10000, or low molecular weight polypropylene
• nucleating agent for example, low molecular weight polyethylene having a molecular weight of about 500 to 10000, or low molecular weight polypropylene
• nucleating agent for example, low molecular weight polyethylene having a molecular weight of about 500 to 10000, or low molecular weight polypropy
• thermoplastic resin (A), the thermoplastic resin (B), the EVOH (C), the acetic acid and / or its salt (D), and the aliphatic It is also preferable to blend at least one selected from the group consisting of the carboxylic acid (E) and the aliphatic carboxylic acid metal salt (F).
• the laminating method in the case of laminating the resin composition layer with the other base material to prepare a multilayer structure can be performed by a known method.
• a method of melt-extruding and laminating another base material on a film, sheet or the like made of the resin composition of the present invention conversely, a method of melt-extruding and laminating the resin composition of the present invention on another base material, a method of melt-extruding and laminating the resin of the present invention.
• a method of coextruding the composition and another base material, a film (layer) made of the resin composition of the present invention and another base material (layer) are prepared, and these are made into an organic titanium compound, an isocyanate compound, and a polyester.
• Examples thereof include a method of dry laminating using a known adhesive such as a system compound and a polyurethane compound, and a method of applying a solution of the resin composition of the present invention on another substrate and then removing the solvent.
• the coextrusion molding method is preferable from the viewpoint of cost and environment.
• the multilayer structure is then subjected to (heating) stretching treatment as necessary.
• the stretching treatment may be either uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching.
• a roll stretching method a tenter stretching method, a tubular stretching method, a stretching blow method, a vacuum compressed air forming method, or the like, which has a high stretching ratio, can also be adopted.
• the stretching temperature is usually selected from the range of 40 to 170 ° C., preferably about 60 to 160 ° C. If the stretching temperature is too low, the stretchability becomes poor, and if it is too high, it becomes difficult to maintain a stable stretched state.
• heat fixing may be performed next for the purpose of imparting dimensional stability after stretching.
• Heat treatment can be carried out by a well-known means.
• the stretched multilayer structure is usually held at 80 to 180 ° C., preferably 100 to 165 ° C. for about 2 to 600 seconds while maintaining a tense state. Perform heat treatment.
• the above heat fixing is not performed in order to impart heat shrinkage, for example, a film after stretching.
• the film may be cooled and fixed by applying cold air to the film.
• a cup or tray-shaped multi-layer container from the multi-layer structure of the present invention.
• a drawing molding method is usually adopted, and specific examples thereof include a vacuum forming method, a vacuum forming method, a vacuum forming method, a plug-assisted vacuum forming method, and the like.
• a blow molding method is adopted, specifically, an extrusion blow molding method (for example, double-headed molding, mold).
• the multilayer laminate of the present invention can be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry laminating treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc., as necessary. Can be done.
• the thickness of the multilayer structure (including stretched one) of the present invention, and the thickness of the resin composition layer, EVOH layer, polyamide resin layer, adhesive resin layer, and other thermoplastic resin layers constituting the multilayer structure are , The layer structure, the type of thermoplastic resin, the type of polyamide resin, the type of adhesive resin, the application and packaging form, the required physical properties, and the like.
• the total thickness of the multilayer structure (including stretched one) of the present invention is usually 10 to 5000 ⁇ m, preferably 30 to 3000 ⁇ m, and particularly preferably 50 to 2000 ⁇ m. If the total thickness of the multilayer structure is too thin, the gas barrier property and mechanical strength may decrease. Further, when the total thickness of the multilayer structure is too thick, the gas barrier property and the mechanical strength become excessive performance, and unnecessary raw materials are used in excess, which tends to be uneconomical.
• the resin composition layer (R) is usually 5 to 3000 ⁇ m, preferably 10 to 2000 ⁇ m, particularly preferably 20 to 1000 ⁇ m, and the EVOH layer ( ⁇ ) is usually 1 to 500 ⁇ m, preferably 3 to 300 ⁇ m, particularly.
• the thermoplastic resin layer ( ⁇ ) is usually 5 to 3000 ⁇ m, preferably 10 to 2000 ⁇ m, particularly preferably 20 to 1000 ⁇ m, and the adhesive resin layer ( ⁇ ) is usually 0.5 to 3000 ⁇ m. It is 250 ⁇ m, preferably 1 to 150 ⁇ m, and particularly preferably 3 to 100 ⁇ m.
• the above numerical values are when two or more layers of at least one of the resin composition layer (R), the EVOH layer ( ⁇ ), the adhesive resin layer ( ⁇ ), and the thermoplastic resin layer ( ⁇ ) are present. Is the total thickness of layers of the same type.
• the ratio of the thickness of the EVOH layer ( ⁇ ) to the resin composition layer (R) in the multilayer structure (EVOH layer ( ⁇ ) / resin composition layer (R)) is the thickest when there are a plurality of layers.
• the ratio between the layers is usually 1/99 to 50/50, preferably 2/98 to 45/55, particularly preferably 5/95 to 40/60, and particularly preferably 10/90 to 35/65. ..
• the effect of the present invention tends to be obtained more remarkably, and when it is smaller than the above range, the gas barrier property and mechanical strength tend to be insufficient, and when it is larger than the above range, it tends to be insufficient.
• the multi-layer structure tends to crack easily.
• the thickness ratio of the EVOH layer ( ⁇ ) to the polyamide layer ( ⁇ ) in the multilayer structure (EVOH layer ( ⁇ ) / polyamide layer ( ⁇ )) is the ratio of the thickest layers when there are a plurality of layers. It is usually 10/90 to 99/1, preferably 20/80 to 80/20, and particularly preferably 40/60 to 60/40. When such a value is within the above range, the effect of the present invention tends to be obtained more remarkably, when it is smaller than the above range, the gas barrier property tends to be insufficient, and when it is larger than the above range, the mechanical strength tends to be insufficient. Tends to be inadequate.
• the thickness ratio (EVOH layer ( ⁇ ) / adhesive resin layer ( ⁇ )) of the EVOH layer ( ⁇ ) to the adhesive resin layer ( ⁇ ) in the multilayer structure is the thickest layer when there are a plurality of layers.
• the ratio is usually 10/90 to 99/1, preferably 20/80 to 95/5, and particularly preferably 50/50 to 90/10.
• the effect of the present invention tends to be obtained more remarkably, when it is smaller than the above range, the gas barrier property tends to be insufficient, and when it is larger than the above range, the adhesive strength tends to be insufficient. It tends to be inadequate.
• the multilayer structure containing the layer made of the above resin composition includes various foods such as general foods, seasonings such as mayonnaise and dressings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, and pharmaceuticals. It is useful as a raw material for packaging.
• Thermoplastic resin (A)] -Polypropylene (a1) ("EA7AD” manufactured by Japan Polypropylene Corporation, MFR 1.4 g / 10 minutes [230 ° C, load 2160 g])
• Thermoplastic resin (B) Maleic anhydride graft-modified polypropylene (b1) (“PLEXAR PX6002” manufactured by Lyondell Basell, MFR 2.3 g / 10 minutes [230 ° C., load 2160 g]) -Polyvinyl acetate resin (b2) [Ethylene-vinyl acetate copolymer (b3) ["Ultrasen 3B53A" manufactured by Tosoh Corporation, vinyl acetate content: 28% by weight, MFR: 5.7 g / 10 minutes (190 ° C.) , Load 2160 g) and ethylene-vinyl acetate copolymer saponified product (b4) ["Mersen H0051K” manufactured by Tosoh Corporation, ethylene content: 89 mol%, saponification degree: 99 mol%, MFR: 6.5 g / 10 Minutes (190 ° C., load 2160 g) are melt-kneaded at b
• EVOH (C) EVOH (c1) [ethylene structural unit content 29 mol%, saponification degree 99.7 mol%, MFR 3.8 g / 10 minutes (210 ° C., load 2160 g)]
• EVOH (c2) [ethylene structural unit content 29 mol%, saponification degree 99.7 mol%, MFR 8.0 g / 10 minutes (210 ° C., load 2160 g)]
• Pellets, acetic acid and / or its salt (D) are sodium acetate (d1), aliphatic carboxylic acid (E) is stearic acid (e1), and aliphatic carboxylic acid metal salt (F) is zinc stearate (f1). board.
• the polypropylene (a1) is 94% by weight based on the total resin composition
• the maleic anhydride graft-modified polypropylene (b1) is 1% by weight based on the total resin composition
• EVOH (c1) is contained in the resin composition.
• the resin composition produced above was heat-press molded at 230 ° C. using a manual hydraulic vacuum heating press (MIC-1867 type) manufactured by Imoto Seisakusho Co., Ltd. to prepare a single-layer sheet having a thickness of 1 mm. Then, by cutting out the obtained single-layer sheet, a strip-shaped test piece having a thickness of 1 mm, a width of 15 mm, and a length of 100 mm was finally produced.
• the strip-shaped test piece prepared above was sandwiched between the test pieces at a distance between the gauge points of 50 mm using a tensile tester "Autograph AGS-X manufactured by Shimadzu Corporation" under the conditions of 23 ° C. and 50% RH.
• Example 2 In Example 1, stearic acid (e1) was 0.11 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc stearate (f1) was used with respect to the total of the resin composition in terms of metal ion. The same procedure was carried out except that 0.3 ppm was used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 3 In Example 1, polypropylene (a1) is 90% by weight based on the total resin composition, maleic anhydride graft-modified polypropylene (b1) is 1% by weight based on the total resin composition, and is thermoplastic.
• polyvinyl acetate resin (b2) pellets were added in an amount of 4% by weight based on the total amount of the resin composition
• EVOH (c1) was used in an amount of 5% by weight based on the total amount of the resin composition
• sodium acetate ( d1) is 22 ppm in terms of acetate ion with respect to the total amount of the resin composition
• stearic acid (e1) 0.11 ppm in terms of carboxylate ion with respect to the total amount of the resin composition
• zinc stearate (f1) The same procedure was carried out except that the total amount of the resin composition was set to 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 4 In Example 1, stearic acid (e1) was 0.45 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc stearate (f1) was added with zinc stearate (f1) in terms of metal ion with respect to the total of the resin composition. A resin composition was prepared in the same manner except that it was set to 0.3 ppm, and evaluated in the same manner as in Example 1.
• Example 5 In Example 1, caprylic acid (e2) was used instead of stearic acid (e1) at 0.06 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc caprylic acid (f1) was used instead of zinc stearate (f1). F2) was carried out in the same manner except that the total amount of the resin composition was 0.5 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 6 In Example 5, caprylic acid (e2) was 0.31 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc caprylic acid (f2) was 2 in terms of metal ion with respect to the total of the resin composition. The same procedure was carried out except that 0.3 ppm was used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 7 In Example 3, caprylic acid (e2) was used instead of stearic acid (e1) at 0.31 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc caprylic acid (f1) was used instead of zinc stearate (f1). F2) was carried out in the same manner except that the total amount of the resin composition was set to 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 8 In Example 5, caprylic acid (e2) was 1.28 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc caprylic acid (f2) was added to the total of the resin composition in terms of metal ion.
• a resin composition was prepared in the same manner except that the pH was set to 3 ppm, and the evaluation was carried out in the same manner as in Example 1.
• Example 9 In Example 1, lauric acid (e3) was used instead of stearic acid (e1) at 0.02 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc laurate (f1) was used instead of zinc stearate (f1). F3) was carried out in the same manner except that the total amount of the resin composition was 0.5 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 10 In Example 9, lauric acid (e3) was 0.08 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc laurate (f3) was used in terms of metal ion with respect to the total of the resin composition.
• a resin composition was prepared in the same manner except that the pH was set to 3 ppm, and the evaluation was carried out in the same manner as in Example 1.
• Example 11 In Example 3, lauric acid (e3) was used instead of stearic acid (e1) at 0.08 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc stearate (f1) was replaced with zinc lauric acid (f1). The same procedure was carried out except that f3) was set to 2.3 ppm in terms of metal ions with respect to the total sum of the resin compositions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 12 In Example 9, lauric acid (e3) was added to the total resin composition at 0.33 ppm in terms of carboxylic acid ion, and zinc laurate (f3) was added to the total resin composition in terms of metal ion. A resin composition was prepared in the same manner except that the pH was set to 3 ppm, and the evaluation was carried out in the same manner as in Example 1.
• Example 13 In Example 1, behenic acid (e4) was used instead of stearic acid (e1) at 0.03 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc behenate (f1) was used instead of zinc stearate (f1). e4) was carried out in the same manner except that the total amount of the resin composition was 0.5 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 14 In Example 13, behenic acid (e4) was 0.13 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc behenate (f4) was used in terms of metal ion with respect to the total of the resin composition.
• a resin composition was prepared in the same manner except that the pH was set to 3 ppm, and the evaluation was carried out in the same manner as in Example 1.
• Example 15 In Example 3, behenic acid (e4) was used instead of stearic acid (e1) at 0.13 ppm in terms of carboxylic acid ion with respect to the total resin composition, and zinc behenate (f1) was used instead of zinc stearate (f1). F4) was carried out in the same manner except that the total amount of the resin composition was set to 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 16 behenic acid (e4) is 0.53 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc behenate (f4) is 9 in terms of metal ion with respect to the total of the resin composition.
• a resin composition was prepared in the same manner except that the pH was set to 3 ppm, and the evaluation was carried out in the same manner as in Example 1.
• Example 17 In Example 1, stearic acid (e1) was added to the total resin composition at 0.69 ppm in terms of carboxylic acid ion, and magnesium stearate (f5) was used instead of zinc stearate (f1) in the resin composition. The same procedure was carried out except that the total amount was 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 18 In Example 3, stearic acid (e1) was added to the total resin composition at 0.69 ppm in terms of carboxylic acid ion, and magnesium stearate (f5) was used instead of zinc stearate (f1) in the resin composition. The same procedure was carried out except that the total amount was 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 19 In Example 1, stearic acid (e1) was added to the total resin composition at 0.15 ppm in terms of carboxylic acid ion, and sodium stearate (e6) was used instead of zinc stearate (f1) in the resin composition. The same procedure was carried out except that the total amount was 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 20 In Example 3, stearic acid (e1) was 0.15 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and sodium stearate (f6) was used instead of zinc stearate (f1) in the resin composition. The same procedure was carried out except that the total amount was 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 1 In Example 1, the same procedure was carried out except that stearic acid (e1) and zinc stearate (f1) were not used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 3 In Example 3, the same procedure was carried out except that stearic acid (e1) and zinc stearate (f1) were not used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 2 In Example 2, the same procedure was carried out except that stearic acid (e1) was not used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 5 polypropylene (a1) is 69% by weight based on the total resin composition, EVOH (c1) is 30% by weight based on the total resin composition, and sodium acetate (d1) is added to the resin composition. 130 ppm of caprylic acid (e2) in terms of acetate ion with respect to the total of substances, 7.7 ppm of carboxylic acid ion in terms of total of resin composition, zinc caprylate (f2) in total of resin composition On the other hand, the same procedure was carried out except that the metal ion equivalent was 55.8 ppm to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 7 polypropylene (a1) is 65% by weight based on the total resin composition, EVOH (c1) is 30% by weight based on the total resin composition, and sodium acetate (d1) is added to the resin composition. 130 ppm of caprylic acid (e2) in terms of acetate ion with respect to the total of substances, 7.7 ppm of carboxylic acid ion in terms of total of resin composition, zinc caprylate (f2) in total of resin composition On the other hand, the same procedure was carried out except that the metal ion equivalent was 55.8 ppm to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 6 In Example 1, stearic acid (e1) was added to the total resin composition at 0.11 ppm in terms of carboxylic acid ion, and zinc gluconate trihydrate (f7) was used instead of zinc stearate (f1). The same procedure was carried out except that the total amount of the resin composition was set to 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 7 zinc stearate (f1) was replaced with zinc gluconate trihydrate (f7) in the same manner except that the total amount of the resin composition was 2.3 ppm in terms of metal ions.
• a composition was prepared and evaluated in the same manner as in Example 1.
• Example 8 In Example 1, stearic acid (e1) was 0.11 ppm in terms of carboxylic acid ion with respect to the total of the resin composition, and zinc citrate dihydrate (f8) was used instead of zinc stearate (f1). The same procedure was carried out except that the total amount of the resin composition was set to 2.3 ppm in terms of metal ions to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• Example 9 In Example 6, EVOH (c2) was used instead of EVOH (c1), and the same procedure was carried out except that sodium acetate (d1) was not used to prepare a resin composition, which was evaluated in the same manner as in Example 1.
• the resin compositions of Comparative Examples 1 to 9 having no characteristic structure of the present invention had low mechanical strength.
• the resin compositions of Examples 1 to 20 having the characteristic constitution of the present invention had excellent mechanical strength.
• the resin composition of the present invention has excellent mechanical strength. Therefore, the multilayer structure and the molded product containing the layer made of the above resin composition include general foods, seasonings such as mayonnaise and dressings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, and cosmetics. It is useful as a raw material for various packages such as pharmaceuticals.

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• 2021
  • 2021-03-18 CN CN202180023023.2A patent/CN115335463A/zh active Pending
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