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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • 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
  • 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
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D129/00—Coating compositions based on 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; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
  • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
  • C09D129/04—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
  • B32B2250/00—Layers arrangement
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2439/02—Open containers
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/80—Medical packaging
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2423/10—Homopolymers or copolymers of propene
  • C08J2423/14—Copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/10—Applications used for bottles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films

Definitions

• the present invention relates to a resin composition containing an ethylene-vinyl alcohol copolymer and a polypropylene resin containing 14 carbon atoms. It also relates to a molded article, sheet, film, bottle, tube, container, or multilayer structure having a layer containing the resin composition, and a method for producing the resin composition.
• ethylene-vinyl alcohol copolymer (hereinafter referred to as "EVOH”) has been mainly used as a food packaging material due to its excellent gas barrier properties and transparency.
• EVOH ethylene-vinyl alcohol copolymer
• the sheets, films, etc. used as the food packaging material can be made from the above-mentioned EVOH alone, but they are often mixed with other thermoplastic resins to improve physical properties, or multi-layered structures with layers of polyolefin resins, etc. to impart other functions.
• the present invention provides an EVOH resin composition containing polypropylene that has excellent thermal stability.
• a resin composition according to [1] wherein the mass ratio [(A)/(B)] of the EVOH (A) to the polypropylene resin containing 14 carbon atoms (B) is 10 to 90 to 99/1.
• [4] The resin composition according to any one of [1] to [3], wherein the content of the polypropylene resin (B) containing carbon 14 relative to the entire resin composition is 1 to 90 mass%.
• [5] The resin composition according to any one of [1] to [4], wherein the content of the boron compound (C) relative to the entire resin composition is 1 to 10,000 ppm by mass.
• [6] A molded article comprising the resin composition according to any one of [1] to [5].
• [7] A sheet comprising the resin composition according to any one of [1] to [5].
• [8] A film comprising the resin composition according to any one of [1] to [5].
• [9] A bottle comprising the resin composition according to any one of [1] to [5].
• a tube comprising the resin composition according to any one of [1] to [5].
• a container comprising the resin composition according to any one of [1] to [5].
• a multilayer structure having a layer containing the resin composition according to any one of [1] to [5].
• a method for producing a resin composition comprising the step of mixing EVOH (A), a carbon-14 containing polypropylene resin (B), and a boron compound (C).
• the resin composition of the present invention has excellent thermal stability and can therefore be suitably used as a raw material for molded articles and multilayer structures.
• the reason why the resin composition of the present invention has excellent thermal stability is believed to be that the polypropylene resin containing carbon-14 has stronger bond energy due to the primary isotope effect compared to petroleum-derived polypropylene resin not containing carbon-14, which slows down decomposition and increases thermal stability, and also due to a synergistic effect with the boron compound (C) which has a thermal degradation inhibitory effect.
• the upper limit or lower limit of a numerical range described in stages can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
• the upper limit or lower limit of the numerical range can be replaced with a value shown in the examples.
• the term “film” also includes the terms “tape” and "sheet.”
• the term “main component” means a component that has a significant effect on the properties of the target object, and the content of the component in the target object is usually 50 mass % or more, preferably 55 mass % or more, more preferably 60 mass % or more, and even more preferably 70 mass % or more, and may be 100 mass %.
• a resin composition according to an example of an embodiment of the present invention contains EVOH (A), a polypropylene resin containing carbon-14 (B), and a boron compound (C). Each component will be described below.
• the EVOH (A) is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin.
• the polymerization of ethylene and vinyl ester monomers can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, or emulsion polymerization, and solution polymerization using methanol as a solvent is generally used.
• the saponification of the resulting ethylene-vinyl ester copolymer can also be carried out using known methods.
• the EVOH (A) produced in this manner is mainly composed of structural units derived from ethylene and vinyl alcohol structural units, and usually contains a small amount of vinyl ester structural units that remain unsaponified.
• vinyl ester monomer vinyl acetate is typically used because of its market availability and the efficiency of impurity treatment during production.
• vinyl ester monomers other than vinyl acetate include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate, and aromatic vinyl esters such as vinyl benzoate.
• Aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms, can be used. These can be used alone or in combination of two or more kinds.
• the ethylene content in the EVOH (A) can be controlled by the ethylene pressure when the vinyl ester monomer and ethylene are copolymerized, and is 20 to 60 mol %, preferably 25 to 50 mol %, and particularly preferably 25 to 35 mol %. If the content is too low, the gas barrier properties and melt moldability under high humidity conditions tend to decrease, and conversely, if the content is too high, the gas barrier properties tend to decrease.
• the ethylene content can be measured based on ISO14663.
• the degree of saponification of the vinyl ester component in EVOH (A) can be controlled by the amount, temperature, time, etc. of a saponification catalyst (usually, an alkaline catalyst such as sodium hydroxide is used) used when saponifying an ethylene-vinyl ester copolymer, and is usually 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 99 to 100 mol%. If the degree of saponification is too low, the gas barrier property, thermal stability, moisture resistance, etc. tend to decrease.
• the degree of saponification of the EVOH (A) can be measured based on JIS K6726 (wherein EVOH is used as a solution uniformly dissolved in a water/methanol solvent).
• the melt flow rate (MFR) (210°C, load 2160 g) of the EVOH (A) is usually 0.5 to 100 g/10 min, preferably 1 to 50 g/10 min, and particularly preferably 3 to 35 g/10 min. If the MFR is too high, film-forming properties tend to be unstable, and if it is too low, the viscosity tends to be too high, making melt extrusion difficult.
• the MFR is an index of the degree of polymerization of the EVOH, and can be adjusted by the amount of polymerization initiator and the amount of solvent used when copolymerizing ethylene and vinyl ester monomers.
• EVOH (A) may further contain structural units derived from the comonomers shown below within a range that does not impair the effects of the present invention (for example, 10 mol % or less of EVOH).
• the comonomer include olefins such as propylene, 1-butene, and isobutene; hydroxyl-containing ⁇ -olefins such as 3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, and 5-hexene-1,2-diol, and derivatives thereof such as esters and acylation products; hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyryloxy-2-methylenepropane, and 1,
• -Hydroxyalkylvinylidene diacetates such as 2-methylenepropane
• unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, or their salts or mono- or dialkyl esters in which the alkyl group has 1 to 18 carbon atoms
• Acrylamides methacrylamide, N-alkyl methacrylamides in which the alkyl group has 1 to 18 carbon atoms, N,N-dimethyl methacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidepropyldimethylamine or an acid salt or a quaternary salt thereof; N-vinyl amides such as N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers in which the alkyl group has 1 to 18 carbon atoms, hydrochloride, etc.
• vinyl ethers examples include vinyl ethers such as alkoxyalkyl vinyl ether and alkoxyalkyl vinyl ether; halogenated vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxyvinylsilane; halogenated allyl compounds such as allyl acetate and allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; and comonomers such as trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride and acrylamido-2-methylpropanesulfonic acid. These can be used alone or in combination of two or more.
• EVOH copolymerized with a hydroxy group-containing ⁇ -olefin i.e., EVOH having a primary hydroxyl group in the side chain
• EVOH having a primary hydroxyl group in the side chain is preferred in that it exhibits good secondary moldability while retaining gas barrier properties, and among these, EVOH having a 1,2-diol structure in the side chain is preferred.
• the content of structural units derived from a monomer having the primary hydroxyl group is usually 0.1 to 20 mol %, preferably 0.5 to 15 mol %, and particularly preferably 1 to 10 mol %.
• the EVOH (A) used in this embodiment may be "post-modified" by, for example, urethane, acetalization, cyanoethylation, or oxyalkylenation.
• the EVOH (A) used in this embodiment may be a mixture of two or more types of EVOH (A), for example, EVOH (A) having different ethylene contents, different degrees of saponification, different degrees of polymerization, different copolymerization components, etc.
• the content of EVOH (A) in the resin composition is usually 1% by mass or more, preferably 10 to 99% by mass, more preferably 30 to 95% by mass, and further preferably 50 to 90% by mass, based on the total mass of the resin composition. When such a value is within the above range, the effects of the present invention tend to be more effectively obtained.
• the "resin composition" in the "whole resin composition” that is the basis for the content of EVOH (A) refers to the EVOH resin composition as a final product that contains EVOH resin (A), polypropylene resin containing 14 carbon atoms (B), boron compound (C), various additives that are blended as necessary, etc. The same applies in the following explanation.
• the carbon-14-containing polypropylene resin (B) used in the resin composition means a polypropylene resin obtained by chemical or biological synthesis using renewable biomass resources as raw materials.
• the carbon-14-containing polypropylene resin (B) has the characteristic that even if it is incinerated, it does not increase the carbon dioxide concentration in the atmosphere due to the carbon neutrality of biomass.
• the polypropylene resin (B) containing carbon-14 is preferably biopropylene derived from biopropanol obtained from plant raw materials.
• the polypropylene resin (B) containing carbon-14 is preferably a plant-derived polypropylene resin.
• polypropylene resin derived from plants (biomass resources) and polypropylene resin derived from petroleum do not differ in physical properties such as molecular weight and mechanical properties. Therefore, the biobased degree is generally used to distinguish between them.
• the biobased degree is an index of the content of plant-derived biopolypropylene resin, which is measured by accelerator mass spectrometry, since the carbon of petroleum-derived polypropylene resin does not contain 14 C (radioactive carbon- 14 , half-life 5730 years). Therefore, if a film is made of plant-derived polypropylene resin, the biobased degree of the film will be determined according to the content of plant-derived polypropylene resin.
• polypropylene resin (B) containing carbon-14 means that it contains radioactive carbon ( 14 C).
• the biobased content can be determined, for example, by heating and stirring the resin composition in a water/methanol mixed solvent to dissolve the EVOH (A), and measuring the carbon-14 ( 14 C) content of the remaining polypropylene resin using the following method.
• the sample to be measured is burned to generate carbon dioxide, which is purified in a vacuum line and reduced with hydrogen using iron as a catalyst to generate graphite.
• This graphite is then attached to a tandem accelerator-based 14 C-AMS dedicated device (manufactured by NEC Corporation) to measure the 14 C count, 13 C concentration ( 13 C/ 12 C), and 14 C concentration ( 14 C/ 12 C), and the ratio of the 14 C concentration of the sample carbon to the standard modern carbon is calculated from the measured values, and the biobased content is determined in accordance with ASTM D6866. Furthermore, in order to distinguish between polypropylene resin derived from plants (biomass resources) and polypropylene resin derived from petroleum, the aforementioned bio-based content is used, and the measurement method is also as described above.
• the carbon-14 content in the carbon-14-containing polypropylene resin (B) is not particularly limited, but the ratio of carbon-14 to total carbon in the carbon-14-containing polypropylene resin (B) is usually 1.0 ⁇ 10-14 or more, preferably 1.0 ⁇ 10-13 or more. The upper limit is usually 1.2 ⁇ 10-12 .
• this resin composition contains polypropylene resin (B) containing carbon-14, it has better thermal stability than resin compositions containing conventional petroleum-derived polypropylene resins. The reason for this is presumably that polypropylene resin containing carbon-14 has stronger bond energy due to the primary isotope effect, which slows decomposition and increases thermal stability.
• the biobased content of the carbon-14-containing polypropylene resin (B) used in this resin composition is usually 1 to 99%, preferably 5 to 95%, and particularly preferably 10 to 90%.
• polypropylene in the above-mentioned polypropylene resin (B) containing carbon 14 is not particularly limited, and may be a homopolypropylene or a copolymer of propylene and a small amount of a comonomer.
• the copolymer may be in the form of a block copolymer or a random copolymer.
• a copolymer consisting of propylene and less than 50% by mass of other ⁇ -olefin monomers, or a non-olefin monomer having a functional group with a mass fraction of 3% or less can be used.
• ⁇ -olefins examples include ethylene, ⁇ -olefins having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl 1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene
• non-olefin monomer examples include styrene monomers, diene monomers, cyclic monomers, and oxygen atom-containing monomers. These may be used alone or in combination of two or more kinds.
• styrene monomer examples include styrene, 4-methylstyrene, and 4-dimethylaminostyrene.
• diene monomer examples include 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, and dicyclooctadiene.
• DMDT 4,8-dimethyl-1,4,8-decatriene
• cyclic monomers examples include methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and cyclopentene.
• oxygen atom-containing monomer examples include hexenol, hexenoic acid, and methyl octenoate.
• the above-mentioned other ⁇ -olefins and non-olefin monomers may be made from renewable biomass resources or from petroleum.
• renewable biomass resources the bio-based content of the final product can be further increased.
• petroleum-based raw materials a wide variety of products are available, so by using these to manufacture the product, the physical properties of the carbon-14-containing polypropylene resin (B) can be easily adjusted.
• the polypropylene resin (B) containing carbon 14 is obtained by homopolymerization of propylene or copolymerization of propylene with a comonomer, and the polymerization or copolymerization can be carried out in accordance with a conventional method using a metallocene catalyst or a Ziegler-Natta catalyst. Of these, it is preferable to use a metallocene catalyst.
• the polypropylene resin (B) containing carbon 14 may be used alone or in combination of two or more kinds, but in particular, it is preferable to use homopolypropylene derived from biopropylene, or ethylene-propylene block copolymer, ethylene-propylene random copolymer, or impact copolymer derived from biopropylene in terms of moldability, handling, and thermal stability.
• the melt flow rate (MFR) (230°C, load 2160 g) of the above-mentioned carbon-14-containing polypropylene resin (B) is usually 0.1 to 100 g/10 min, preferably 0.5 to 90 g/10 min, and particularly preferably 2 to 80 g/10 min. If the MFR is too large, the film-forming properties tend to be unstable, and if it is too small, the viscosity tends to be high, making melt extrusion difficult.
• polypropylene resin (B) containing carbon 14 that is preferably used in this embodiment is HP640J manufactured by LyondellBasell.
• the content of the polypropylene resin (B) containing carbon-14 in the resin composition is usually 0.5% by mass or more, preferably 1 to 90% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 50% by mass, based on the total resin composition.
• the mass ratio [(A)/(B)] of EVOH (A) to the above-mentioned polypropylene resin containing carbon-14 (B) is usually 10/99 to 99/1, preferably 30/70 to 95/5, and more preferably 50/50 to 90/10.
• the mass ratio of EVOH (A) to the polypropylene resin containing carbon-14 (B) is within the above range, a resin composition with better thermal stability is obtained.
• the proportion of the total content of EVOH (A) and polypropylene resin (B) containing carbon 14 in the entire resin composition is not particularly limited, but is usually 70 mass% or more, preferably 80 mass% or more, and more preferably 90 mass% or more.
• the boron compound (C) used in the present resin composition may be boric acid or a metal salt thereof, for example, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, potassium octaborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.), calcium borate, barium borate (barium orthoborate, barium metaborate, barium diborate, barium tetraborate, etc.), magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc.), manganese borate (boric acid, manga
• the boron compound (C) may be in any form, such as a solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, or emulsion (aqueous dispersion), but a powder form is preferred.
• the amount of the boron compound (C) is usually 1 to 10,000 ppm, preferably 10 to 5,000 ppm, more preferably 50 to 2,500 ppm, and even more preferably 100 to 1,500 ppm, by mass based on the total amount of the resin composition. If the content of the boron compound (C) is too high, it tends to impair thermal stability, and if it is too low, it tends to impair the moldability of the resin composition.
• the content of the boron compound (C) in the resin composition can be measured, for example, by the following method. That is, first, 0.1 g of the resin composition is treated with concentrated nitric acid by microwave decomposition to obtain a solution, which is then diluted to a constant volume (0.75 mg/mL) with pure water to prepare a test solution, which is then measured with an inductively coupled plasma atomic emission spectrometer (ICP-AES) (Model 720-ES, manufactured by Agilent Technologies). The boron content measured in this way corresponds to the amount of boron derived from the boron compound.
• ICP-AES inductively coupled plasma atomic emission spectrometer
• the layer of the resin composition to be measured can be removed from the multi-layer structure by any method, and the boron content can be quantified by the same method as above.
• the resin composition may contain, depending on various purposes, EVOH (A) and resins other than the polypropylene resin (B) containing carbon-14 (e.g., petroleum-derived polypropylene resins, other types of resins), and any additives other than the boron compound (C) (hereinafter, these are referred to as "other components"), within the scope that does not significantly impair the effects of the present invention. Only one type of other component may be used, or two or more types may be used in any combination and ratio.
• the above additives include, for example, antioxidants, ultraviolet absorbers, plasticizers, lubricants, fillers, and antistatic agents.
• the total content of these components is generally 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the resin composition.
• the resin composition can be produced by mixing the essential components EVOH (A), the polypropylene resin containing carbon-14 (B), and the boron compound (C), as well as the other components as necessary.
• the mixing method include known methods such as a dry blend method, a melt mixing method in which a compound is obtained using a single-screw extruder or a twin-screw extruder, a solution mixing method, and an impregnation method, and these methods can be used in any combination.
• the resin composition thus obtained is less susceptible to decomposition at high temperatures and has excellent thermal stability, compared to conventional resin compositions obtained by combining EVOH and petroleum-derived polypropylene.
• the biobased content of the resin composition can be determined, for example, by measuring the carbon-14 ( 14 C) content of the resin composition by the following method.
• the sample to be measured is burned to generate carbon dioxide, which is purified in a vacuum line and reduced with hydrogen using iron as a catalyst to generate graphite.
• This graphite is then attached to a tandem accelerator-based 14 C-AMS dedicated device (manufactured by NEC Corporation) to measure the 14 C count, 13 C concentration ( 13 C/ 12 C), and 14 C concentration ( 14 C/ 12 C), and the ratio of the 14 C concentration of the sample carbon to standard modern carbon is calculated from these measurements, and the biobased content is determined in accordance with ASTM D6866.
• the content of carbon-14 in the resin composition is not particularly limited, but the ratio of carbon-14 to the total carbon in the resin composition is usually 1.0 ⁇ 10 or more, and preferably 1.0 ⁇ 10 or more.
• the upper limit is usually 1.2 ⁇ 10 .
• the biobased content of the resin composition is usually 0.01 to 99.99%, preferably 0.1 to 99.9%, more preferably 1 to 99%, even more preferably 1 to 90%, and particularly preferably 10 to 90%, 2 to 70%, or 4 to 50%.
• a resin composition with superior thermal stability can be obtained.
• melt flow rate (MFR) of this resin composition (210°C, load 2160 g) is usually 0.1 to 100 g/10 min, preferably 0.5 to 90 g/10 min, and particularly preferably 2 to 80 g/10 min.
• the water content of this resin composition is usually 0.01 to 0.5% by mass, preferably 0.02 to 0.35% by mass, and particularly preferably 0.05 to 0.3% by mass.
• the water content of the resin composition is measured and calculated by the following method.
• the mass (W 1 ) of the resin composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150° C. for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W 2 ) is weighed and calculated according to the following formula.
• Moisture content (mass%) [(W 1 - W 2 )/W 1 ] x 100
• the reduction temperature difference of the present resin composition is usually 10° C. or more, preferably 11° C. or more, more preferably 12° C. or more, and further preferably 13° C. or more.
• the temperature loss difference can be calculated by measuring the mass loss rate when the temperature is increased at 10° C./min in a nitrogen atmosphere using a thermogravimetric analyzer (Perkin Elmer, Pyris 1 TGA), and then subtracting the temperature at which the resin composition has lost 5% mass from the temperature at which the resin composition has lost 10% mass (temperature loss difference). The higher this value, the slower the decomposition of the resin composition is, and the more excellent the thermal stability of the resin composition is.
• the present resin composition is prepared in various forms, such as pellets or powder, and is provided as a material for various molded bodies and multilayer structures. As described above, the present resin composition has excellent thermal stability, so that molded bodies using the present resin composition or multilayer structures having a layer using the present resin composition are of excellent quality. In particular, in this embodiment, when the present resin composition is provided as a material for melt molding, the effects of the present invention tend to be obtained more efficiently, which is preferable.
• a molded article according to one embodiment of the present invention (hereinafter, referred to as the present molded article) is obtained by molding the present resin composition.
• the shapes of the molded products include, for example, films, sheets, tapes, cups, trays, tubes, bottles, containers, pipes, filaments, irregular cross-section extrusions, various irregularly shaped objects, etc.
• molding method for this resin composition there are no particular limitations on the molding method for this resin composition, and any molding method that is applicable to general resin compositions can be used. Examples of molding methods include extrusion molding, blow molding, injection molding, and thermoforming.
• a multilayer structure according to one embodiment of the present invention (hereinafter, referred to as the present multilayer structure) has at least one layer containing the present resin composition.
• the present multilayer structure can be laminated with another substrate (hereinafter referred to as a "substrate resin") mainly composed of a thermoplastic resin other than the present resin composition, to impart further strength or other functions to the structure.
• the base resin may be, for example, polyethylene resins such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene (block and random) copolymers, and ethylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers; polypropylene resins such as polypropylene and propylene- ⁇ -olefin ( ⁇ -olefin having 4 to 20 carbon atoms) copolymers; (unmodified) polyolefin resins such as polybutene, polypentene, and polycyclic olefin resins (polymers having a cyclic olefin structure in at least one of the main chain and side chain); and unsaturated carboxylic acid resins obtained by mixing these polyolefins.
• polyethylene resins such as linear low-density polyethylene, low-density
• polyolefin resins in the broad sense, including modified olefin resins such as unsaturated carboxylic acid modified polyolefin resins graft-modified with acids or their esters, ionomers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polyester resins, polyamide resins (including copolymerized polyamides), polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene resins, vinyl ester resins, polyester elastomers, polyurethane elastomers, polystyrene elastomers, halogenated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, and aromatic or aliphatic polyketones.
• modified olefin resins such as unsaturated carboxylic acid modified polyolefin resins graft-modified with acids or their est
• polyamide resins polyolefin resins, polyester resins, and polystyrene resins are preferred from the standpoint of economy and productivity, and more preferred are polyolefin resins such as polyethylene resins, polypropylene resins, polycyclic olefin resins, and unsaturated carboxylic acid modified polyolefin resins of these.
• the layer structure of the multilayer structure can be any combination of a/b, b/a/b, a/b/a, a1/a2/b, a/b1/b2, b2/b1/a/b1/b2, b2/b1/a/b1/a/b1/b2, etc., where a is the resin composition layer (a1, a2, 7) and b is the base resin layer (b1, b2, ). It is also possible to provide a recycled layer containing a mixture of the resin composition and base resin, which is obtained by remelting and molding the ends and defective products generated during the manufacturing process of the multilayer structure.
• the total number of layers in the multilayer structure is usually 2 to 15, and preferably 3 to 10.
• an adhesive resin layer containing an adhesive resin may be interposed between each layer as necessary.
• any known adhesive resin can be used, and it may be appropriately selected according to the type of thermoplastic resin used in the base resin layer "b".
• Representative examples include modified polyolefin polymers containing carboxy groups obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to a polyolefin resin by addition reaction, graft reaction, or the like.
• modified polyolefin polymers containing carboxy groups include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-propylene (block and random) copolymers, maleic anhydride grafted ethylene-ethyl acrylate copolymers, maleic anhydride grafted ethylene-vinyl acetate copolymers, maleic anhydride modified polycyclic olefin resins, maleic anhydride grafted polyolefin resins, etc. One or a mixture of two or more selected from these can be used.
• an adhesive resin layer is used between the resin composition layer and the base resin layer in this multilayer structure, since the adhesive resin layers are located on both sides of the resin composition layer, it is preferable to use an adhesive resin with excellent hydrophobicity.
• the base resin and adhesive resin may contain conventionally known plasticizers, fillers, clays (montmorillonite, etc.), colorants, antioxidants, antistatic agents, lubricants, core materials, antiblocking agents, waxes, etc., within the range that does not impair the purpose of the present invention (for example, 30% by mass or less, preferably 10% by mass or less, based on the total resin).
• Lamination of the resin composition with the above-mentioned base resin can be performed by a known method.
• a method of melt extrusion laminating the base resin onto a film, sheet, etc. of the resin composition a method of melt extrusion laminating the resin composition onto a base resin layer, a method of co-extruding the resin composition and the base resin, a method of dry laminating the resin composition layer and the base resin layer using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc., a method of applying a solution of the resin composition onto the base resin and then removing the solvent, etc.
• the method of co-extruding the resin composition and the base resin is preferred from the viewpoints of cost and the environment.
• heat setting may be performed after the stretching process.
• Heat setting can be performed by known means, for example, the stretched film is kept in a tensed state and heat-treated at 80 to 180°C, preferably 100 to 165°C, for about 2 to 600 seconds.
• the above-mentioned heat setting may not be performed, and instead, a process such as cooling and setting the film by blowing cold air on it after stretching may be performed.
• the multilayer structure may be used to obtain cup- or tray-shaped multilayer containers.
• a squeeze molding method is usually used, specifically vacuum molding, pressure molding, vacuum pressure molding, plug-assisted vacuum pressure molding, etc.
• a blow molding method is used to obtain a tube- or bottle-shaped multilayer container (laminate structure) from a multilayer parison (a hollow tubular preform before blowing).
• the thickness of this multilayer structure (including the stretched one), and further the thickness of the resin composition layer, base resin layer, and adhesive resin layer that compose the multilayer structure, cannot be generally determined depending on the layer configuration, type of base resin, type of adhesive resin, application, packaging form, required physical properties, etc., but is usually 10 to 5000 ⁇ m, preferably 30 to 3000 ⁇ m, and particularly preferably 50 to 2000 ⁇ m.
• the resin composition layer is usually 1 to 500 ⁇ m, preferably 3 to 300 ⁇ m, and particularly preferably 5 to 200 ⁇ m
• the base resin layer is usually 5 to 3000 ⁇ m, preferably 10 to 2000 ⁇ m, and particularly preferably 20 to 1000 ⁇ m
• the adhesive resin layer is usually 0.5 to 250 ⁇ m, preferably 1 to 150 ⁇ m, and particularly preferably 3 to 100 ⁇ m.
• EVOH Ethylene unit content 29 mol%, MFR (210° C., load 2160 g) 3.8 g/10 min, saponification degree 99.9 mol%
• Polypropylene resin Polypropylene containing carbon-14 (B1): Polypropylene containing carbon-14 (LyondellBasell, HP640J), MFR (230°C, load 2160 g) 3.2 g/10 min, biobased content 40% Petroleum-derived polypropylene (B'1): Polypropylene (manufactured by Japan Polypropylene Co., Ltd., FY6), MFR (230°C, load 2160 g) 2.4 g/10 min
• Example 1 90 parts of EVOH (A1), 10 parts of polypropylene (B1) containing carbon 14, and a predetermined amount of boron compound (C) were mixed together by dry blending, and then fed to a twin-screw kneader at a rate of 8 kg/hour using a mass feeder, and then strand-cut with a drum pelletizer to prepare a pellet-shaped resin composition.
• thermal stability improvement rate was calculated from the following formula when the value of the decrease in temperature difference of the comparative example corresponding to each Example (for example, the comparative example corresponding to Example 1 is Comparative Example 1) was set to 100.
• Thermal stability improvement rate (%) (decrease in temperature difference of the example/decrease in temperature difference of the comparative example corresponding to the example ⁇ 100) ⁇ 100 (Thermal stability improvement rate (%) is rounded off to the nearest whole number.)
• This resin composition has better thermal stability than resin compositions using petroleum-derived polypropylene. Therefore, molded articles made from this resin composition and multilayer structures having a layer containing this resin composition are useful as materials for various packaging containers.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=92905550

Family Applications (1)

Country Status (4)

Citations (5)

• 2024
  • 2024-03-27 JP JP2025511037A patent/JPWO2024204379A1/ja active Pending
  • 2024-03-27 EP EP24780481.8A patent/EP4692217A1/en active Pending
  • 2024-03-27 WO PCT/JP2024/012298 patent/WO2024204379A1/ja not_active Ceased
• 2025
  • 2025-08-06 US US19/292,246 patent/US20250361394A1/en active Pending

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events