WO2024034519A1 - Polyolefin resin composition, molded body, and laminate - Google Patents

Polyolefin resin composition, molded body, and laminate Download PDF

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Publication number
WO2024034519A1
WO2024034519A1 PCT/JP2023/028455 JP2023028455W WO2024034519A1 WO 2024034519 A1 WO2024034519 A1 WO 2024034519A1 JP 2023028455 W JP2023028455 W JP 2023028455W WO 2024034519 A1 WO2024034519 A1 WO 2024034519A1
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Prior art keywords
weight
oil
polyolefin resin
laminate
resin composition
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PCT/JP2023/028455
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French (fr)
Japanese (ja)
Inventor
郁人 浦野
貴之 美濃
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住友化学株式会社
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Publication of WO2024034519A1 publication Critical patent/WO2024034519A1/en

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Classifications

    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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

Definitions

  • the present invention relates to a polyolefin resin composition, a molded article, and a laminate.
  • polyolefin resin compositions are used in the layers of food packaging films and food packaging laminates.
  • Patent Document 1 discloses that a polyolefin resin and a packaged object formed of a polyolefin resin composition containing a specific ester compound, etc., a specific alkali metal sulfonic acid salt, etc., and specific inorganic particles, etc. come into contact with each other. It is described that there is provided a packaging film having a layer having the following properties and having excellent antifogging properties, smoothness, and antiblocking properties at the same time without impairing transparency.
  • Patent Document 2 discloses a retort in which a polyethylene resin and a surface-treated synthetic silica-based anti-blocking agent are blended, and the surface treatment includes coating the silica surface with silicone oil or the like.
  • a resin composition for retort food packaging which has excellent anti-blocking properties, suppresses decreases in impact resistance and transparency after retort processing, and suppresses occurrence of yuzu skin caused by oily foods, etc. It is stated that.
  • polyolefin resin compositions are required to be able to be kneaded without oil leaking out or the screws of the kneader spinning idly (hereinafter sometimes referred to as processability of polyolefin resin compositions). .
  • the present inventor has developed the present invention as a polyolefin resin composition that is suitable for containers and bottles where the contents of mayonnaise, sauce, etc. tend to come out (flow easily) and has good processability. .
  • the present invention includes a polyolefin resin composition that has excellent separation properties such that the contents easily come out (flows down easily), and excellent processability that allows kneading without idling the screws of a kneading machine, and the resin compositions thereof.
  • the object is to provide a molded body and a laminate.
  • the present invention provides any of the following.
  • the oil absorption amount of filler (B) measured based on ISO 787-5:1980 is 40 mL/100 g or more and 500 mL/100 g or less (requirement (I))
  • the Hansen solubility parameter (HSP value) of the oil (C) is 10 MPa 1/2 or more and 36 MPa 1/2 or less (requirement (II)),
  • the weight ratio of the weight of oil (C) to the weight of filler (B) (oil (C)/filler (B), unit: weight/weight) is 0.2 or more and 10.0 or less (requirement (III))
  • Filler (B) is at least one member selected from the group consisting of titanium oxide, calcium carbonate, alumina, silica, diatomaceous earth, iron oxide, ferrite, zeolite, talc, wollastonite, mica, and clay. , the polyolefin resin composition according to [1].
  • a molded article comprising the polyolefin resin composition according to any one of [1] to [3].
  • a polyolefin resin composition that has excellent separation properties such that the contents easily come out (flows down easily), and excellent processability that allows kneading without the screws of a kneading machine idling, and the resin composition. Molded bodies and laminates containing the above can be provided.
  • the polyolefin resin (A) is a resin containing an olefin polymer.
  • the polyolefin resin include polyethylene resin, polypropylene resin, and the like.
  • the polyolefin resin is preferably a polyethylene resin.
  • Polyethylene resin is a resin containing an ethylene polymer.
  • An ethylene polymer is a polymer containing more than 50% by mass of monomer units derived from ethylene, that is, an ethylene homopolymer or an ethylene polymer containing more than 50% by mass of monomer units derived from ethylene. It is a copolymer.
  • the ethylene polymer is preferably an ethylene homopolymer or an ethylene copolymer containing 90% by mass or more of monomer units derived from ethylene, and more preferably an ethylene homopolymer.
  • one type of ethylene polymer may be used alone, or two or more types may be used in combination.
  • monomeric unit in terms such as “monomeric unit derived from ethylene” means a polymerized unit of a monomer. Therefore, for example, "a monomer unit derived from ethylene” means a monomer unit of -CH 2 CH 2 -.
  • ethylene homopolymers examples include high-pressure low-density polyethylene (with a density of 910 kg/m 3 to 935 kg/m 3 ) in which repeating units of ethylene are randomly bonded in a branched structure by high-pressure radical polymerization using a radical initiator. LDPE).
  • ethylene copolymer examples include a copolymer of ethylene and ⁇ -olefin, and a copolymer of ethylene and ⁇ -olefin substituted with an alicyclic compound.
  • copolymers of ethylene and ⁇ -olefin examples include linear low-density polyethylene with crystallinity, elastomers of copolymers of ethylene and ⁇ -olefin with low crystallinity and rubber-like elastic properties, etc. can be mentioned.
  • the density of the linear low density polyethylene is preferably 900 kg/m 3 to 940 kg/m 3 . Further, the density of the elastomer of the copolymer of ethylene and ⁇ -olefin is preferably 860 kg/m 3 to 900 kg/m 3 .
  • the ⁇ -olefin is preferably an ⁇ -olefin having 3 to 10 carbon atoms.
  • ⁇ -olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 3-methyl-1- Examples include butene.
  • the ⁇ -olefin having 3 to 10 carbon atoms is preferably an ⁇ -olefin having 4 to 10 carbon atoms, more preferably 1-butene, 1-hexene or 1-octene.
  • Examples of the ⁇ -olefin substituted with an alicyclic compound include vinylcyclohexane.
  • the content of monomer units derived from ⁇ -olefin in the ethylene copolymer is preferably 4% by mass to 20% by mass.
  • the copolymer of ethylene and ⁇ -olefin examples include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-octene copolymer. Examples include decene copolymer and ethylene-(3-methyl-1-butene) copolymer. Note that the copolymer of ethylene and ⁇ -olefin may be used singly or in combination of two or more. Further, the ethylene polymer may be a mixture of an ethylene homopolymer and a copolymer of ethylene and ⁇ -olefin.
  • the melt flow rate (MFR) of the ethylene polymer measured at a temperature of 190° C. and a load of 2.16 kg is preferably 0.1 g/10 minutes to 50 g/10 minutes, more preferably 0.3 g/10 minutes to 30 g/10 minutes, more preferably 0.3 g/10 minutes to 20 g/10 minutes. Note that MFR is measured according to method A specified in JIS K7210-1.
  • a polypropylene resin is a resin containing a propylene polymer.
  • a propylene-based polymer is a polymer containing more than 50% by mass of monomer units derived from propylene, that is, a propylene homopolymer or a propylene-based polymer containing more than 50% by mass of monomer units derived from propylene. It is a copolymer (random polypropylene, heterophasic polypropylene).
  • the propylene copolymer is preferably a copolymer of propylene and ethylene and/or an ⁇ -olefin having 4 to 10 carbon atoms.
  • the propylene homopolymer preferably has a melt flow rate (MFR) of 0.1 g/10 minutes to 50 g/10 minutes, measured at a temperature of 230° C. and a load of 2.16 kg.
  • MFR melt flow rate
  • the copolymer of ethylene and/or ⁇ -olefin having 4 to 10 carbon atoms and propylene preferably has a melt flow rate (MFR) of 1 g/10 min to 200 g measured at a temperature of 230°C and a load of 2.16 kg. /10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, even more preferably 1 g/10 minutes to 10 g/10 minutes.
  • MFR is measured according to method A specified in JIS K7210-1.
  • Monomer derived from ethylene and/or ⁇ -olefin having 4 to 10 carbon atoms when the total mass of the copolymer of ethylene and/or ⁇ -olefin having 4 to 10 carbon atoms and propylene is 100% by mass
  • the content of monomeric units is preferably 0.1% by mass to 40% by mass, and the content of monomer units derived from propylene is preferably 60% by mass to 99.9% by mass.
  • Examples of ⁇ -olefins having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.
  • the ⁇ -olefin having 4 to 10 carbon atoms is preferably 1-butene, 1-hexene or 1-octene.
  • a copolymer of ethylene and/or an ⁇ -olefin having 4 to 10 carbon atoms and propylene specifically, for example, a copolymer of propylene and ethylene, a copolymer of propylene and an ⁇ -olefin having 4 to 10 carbon atoms, copolymers of propylene, ethylene, and ⁇ -olefins having 4 to 10 carbon atoms, etc.
  • the copolymer of propylene and ethylene and/or ⁇ -olefin having 4 to 10 carbon atoms may be used alone or in combination of two or more.
  • the propylene-based polymer may be a mixture of a propylene homopolymer and a copolymer of propylene and ethylene and/or an ⁇ -olefin having 4 to 10 carbon atoms.
  • copolymers of propylene and ⁇ -olefin having 4 to 10 carbon atoms include propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-1-octene copolymer. Examples include 1-decene copolymer.
  • Copolymers of propylene, ethylene, and ⁇ -olefin having 4 to 10 carbon atoms include, for example, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1 -octene copolymer, propylene-ethylene-1-decene copolymer, and the like.
  • Filler (B) is a filler used in a polyolefin resin composition that forms a layer with which the packaged object comes into contact, and filler (B) includes 1) oxide-based inorganic particles, 2) silicate-based Inorganic particles, 3) organic crosslinked particles, and 4) any mixture of any two or more of the above 1) to 3) are included.
  • oxide-based inorganic particles as the filler (B) examples include silica, diatomaceous earth, alumina, iron oxide, ferrite, etc. Among them, silica and diatomaceous earth are preferred, and silica is more preferred.
  • silicate-based inorganic particles as the filler (B) examples include zeolite, talc, wollastonite, mica, clay, etc. Among them, zeolite, talc, and wollastonite are preferred, and zeolite and talc are more preferred.
  • organic crosslinked particles as the filler (B) examples include crosslinked silicone particles, crosslinked polyamide particles, crosslinked polytriazine particles, crosslinked polyacrylic particles, crosslinked polystyrene particles, etc. Particles are preferred, and crosslinked polyacrylic particles are particularly preferred.
  • oxide-based inorganic particles and silicate-based inorganic particles are preferred, and silica, zeolite, talc, and calcium carbonate are more preferred.
  • the present invention does not particularly limit the average particle diameter of the oxide-based inorganic particles, silicate-based inorganic particles, and organic crosslinked particles as the filler (B), those having an average particle diameter of 0.5 to 10 ⁇ m are preferable. , 1 to 5 ⁇ m is more preferable.
  • the oxide-based inorganic particles and silicate-based inorganic particles as component C may be naturally occurring minerals or may be artificially synthesized. Further, these may be used as they are without any particular treatment, or may be used after being treated with a ball mill, an acid, a silane coupling agent, or the like.
  • Filler (B) has an oil absorption amount of 40 mL/100 g or more and 500 mL/100 g or less (requirements (I)) is a filler.
  • the oil absorption amount is preferably 40 mL/100 g or more and 500 mL/100 g or less, more preferably 40 mL/100 g or more and 300 mL/100 g or less, and still more preferably 40 mL/100 g or more and 240 mL/100 g or less.
  • the oil (C) can be retained during kneading, and the molded product has good releasability.
  • the amount of oil (C) added is close to the oil absorption amount, and the amount of oil (C) discharged from the filler (B) to the polyolefin resin (A) is stabilized. Therefore, it is preferable.
  • the filler (B) is preferably selected from the group consisting of titanium oxide, calcium carbonate, alumina, crystalline silica, amorphous silica, diatomaceous earth, iron oxide, ferrite, zeolite, talc, wollastonite, mica, and clay. At least one kind is selected, and among them, amorphous silica is more preferable from the viewpoint of safety.
  • ⁇ Oil (C)> water-containing or O/W type emulsion is used as the content, so an oil-based liquid that is immiscible with the water-containing content is used as the oil (C), but generally After filling the packaging container with the contents, discharging the contents, and selectively extracting and removing the contents, the amount of liquid remaining on the inner surface of the container (liquid permeable surface) is the retention amount (0. 5 to 50 g/m2, especially 1 to 50 g/m2), such as silicone oil, glycerin fatty acid esters such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, liquid paraffin, and the group of edible fats and oils.
  • the oil whose surface tension is significantly different from that of the contents has a higher lubricating effect and is suitable for the present invention.
  • the oil whose surface tension is significantly different from that of the contents has a higher lubricating effect and is suitable for the present invention.
  • such oily liquids naturally have low volatility and have a vapor pressure that does not volatilize even when the packaging container is opened.
  • the oil most suitably used for the water-containing contents as described above is one having a surface tension within the above-mentioned range, particularly silicone oil, glycerin fatty acid ester such as fatty acid triglyceride, and fluid.
  • a hydrophilic liquid that is immiscible with the oil-containing content is used as the oil (C) based on the same idea as above.
  • the oil (C) a hydrophilic liquid that is immiscible with the oil-containing content
  • the oil (C) based on the same idea as above.
  • at least one selected from the group of glycerin fatty acid esters such as fatty acid monoglycerides, alcohols such as octadecanol, and polyhydric alcohols such as glycerin may be used.
  • the oil whose surface tension is significantly different from that of the contents has a higher lubricating effect and is suitable for the present invention.
  • the oil (C) has a Hansen solubility parameter (HSP value) of 10 MPa 1/2 or more and 36 MPa 1/2 or less (requirement (II)).
  • the Hansen solubility parameter (HSP value) of oil (C) is defined by the following three-dimensional parameters ( ⁇ D, ⁇ P, ⁇ H), and is expressed by the following formula (1).
  • This idea (theory) proposed by Hansen is described in Hansen Solubility Parameter: A User's Handbook, Second Edition, C. M. Hansen (2007), Taylor and Francis Group, LLC (HSPiP Manual).
  • HSP2 ( ⁇ D)2+( ⁇ P)2+( ⁇ H)2...Formula (1)
  • ⁇ D London dispersion force term
  • ⁇ P Molecular polarization term (dipole force term)
  • ⁇ H Hydrogen bond term
  • ⁇ D, ⁇ P and ⁇ H can be calculated from the chemical structural formula of the oil (C), for example, by using the computer software Hansen Solubility Parameters in Practice (HSPiP).
  • HSP value of the oil (C) used in the present invention is based on HSPiP ver. The value obtained by calculation according to 5.4.01 is used.
  • the HSP value of ethanol is 25.0 MPa 1/2
  • the HSP value of propanol is 22.6 MPa 1/2
  • the HSP value of propanol is 22.6 MPa 1/2
  • the HSP value of octadecanol is 17.8 MPa 1/2.
  • the HSP value of glycerin is 35.7 MPa 1/2 .
  • the oil (C) is preferably at least one selected from the group consisting of silicone oil, glycerin fatty acid ester, liquid paraffin, edible fat, alcohol, and polyhydric alcohol. Oil (C) can be appropriately selected depending on the contents. If the HSP value is preferably 10 MPa 1/2 to 36 MPa 1/2 , more preferably 10 MPa 1/2 to 25 MPa 1/2 , even more preferably 14 MPa 1/2 to 22 MPa 1/2 , the polyolefin resin of the present invention It is possible to exhibit releasability to the contents suitably used as the contents of the composition.
  • the polyolefin resin composition of the present invention contains a polyolefin resin (A) of 2% to 98.9% by weight, a filler (B) of 0.1% to 49% by weight, and an oil (C). 1.0% by weight or more and 49% by weight or less. However, the total of the polyolefin resin (A), filler (B), and oil (C) is 100% by weight.
  • the weight ratio of the weight of oil (C) to the weight of filler (B) is preferably 0.2 or more and 10.0 or less, more preferably 0. 5 or more and 5.0 or less (requirement (III)).
  • a sufficient and appropriate amount of oil (C) is discharged onto the surface of the molded product, and separation properties are developed, making it possible to avoid processing troubles such as idling in the screws of the kneading machine.
  • the water-containing content to be filled is not particularly limited, but is generally a fluid substance in the form of a viscous paste or slurry (e.g. Products with a viscosity of 100 mPa ⁇ s or more at 25°C), specifically cosmetics and liquids such as ketchup, water-based glue, honey, various sauces, mayonnaise, low-calorie mayonnaise, mustard, jam, chocolate syrup, and milky lotion.
  • a viscous paste or slurry e.g. Products with a viscosity of 100 mPa ⁇ s or more at 25°C
  • specifically cosmetics and liquids such as ketchup, water-based glue, honey, various sauces, mayonnaise, low-calorie mayonnaise, mustard, jam, chocolate syrup, and milky lotion.
  • Detergents, shampoos, conditioners, etc. are suitable as contents. That is, in the present invention, even such a viscous fluid substance can be quickly discharged without remaining attached to the inner surface of the container by tilting or in
  • the contents of the packaging container containing the polyolefin resin composition of the present invention are particularly suitable for contents containing a large amount of water, such as ketchup, various sauces, honey, mayonnaise, Calorie-free mayonnaise, mustard, jam, chocolate syrup, milky lotion, etc. are preferred.
  • calorie-off mayonnaise generally refers to a mayonnaise-like food with an oil content of less than 65%, and includes emulsifiers and thickeners (e.g., pectin, starch, polysaccharide thickener, xanthan gum, etc.) as ingredients. It is known as a mayonnaise-like food with added .
  • emulsifiers and thickeners e.g., pectin, starch, polysaccharide thickener, xanthan gum, etc.
  • the molded article of the present invention is a molded article containing the polyolefin resin composition of the present invention.
  • the molded body include a laminate, and examples thereof include a laminate having a layer containing the polyolefin resin composition of the present invention as the innermost layer of the laminate.
  • a laminate in which one of the layers is a gas barrier layer, and a laminate in which the gas barrier layer contains ethylene/vinyl alcohol resin can be mentioned.
  • the laminate include a multilayer bottle and a multilayer film.
  • an example of the laminate of the present invention is a multilayer extrusion molded product.
  • the multilayer extrusion molded product may be provided with other resin layers as necessary.
  • Other resin layers that may be provided include, for example, ethylene-vinyl alcohol copolymers, vinyl alcohol polymers, saponified ethylene-vinyl acetate copolymers, and vinyl acetate for the purpose of preventing the permeation of gases such as oxygen. Examples include a layer containing a saponified copolymer, an adhesive layer for the purpose of improving adhesion between layers, and a layer using recycled extrusion products.
  • the method of molding the multilayer extrusion molded product is not particularly limited, and may be a molding method using a normal extrusion molding machine.
  • the extrusion molding machine include a blown film manufacturing device, a T-die cast film manufacturing device, a blow molding machine, a tube molding machine, and the like.
  • Examples of the multilayer molding method in the multilayer extrusion molding method include a method of coextruding the polyolefin resin composition of the present invention and other resins (referred to as coextrusion method), a method of extrusion coating (extrusion coating method or extrusion lamination). law), etc.
  • Oil absorption amount (unit: mL/100g) A value measured based on ISO 787-5:1980 (General methods of test for pigments and extenders-Part 5: Determination of oil absorption value) was used.
  • Solubility parameter (unit: MPa 1/2 ) Values calculated using the computer software Hansen Solubility Parameter in Practice (HSPiP) ver. 5.4.01 were used.
  • Calorie-off type mayonnaise A Calorie-off type mayonnaise with a fat weight ratio of 20% to 30% by weight
  • Calorie-off type mayonnaise B Fat weight ratio of 30% by weight or more Calorie-off type mayonnaise with a content of 40% by weight or less
  • Okonomiyaki sauce A Rich sauce specified by JAS standards (general name: Okonomiyaki sauce)
  • Conditioner A Conditioner whose main ingredients are dipotassium glycyrrhizinate and water.
  • A-1 Polyethylene: Sumikasen (registered trademark) F108-1 (manufactured by Sumitomo Chemical Co., Ltd., manufacturing method: high-pressure radical polymerization method, monomer unit derived from ethylene: 100 mol%, density: 921 kg/m 3 , MFR: 0.6g/10min)
  • A-2) Polyethylene: Sumikasen E MB CMB-735 (manufactured by Sumitomo Chemical Co., Ltd., antioxidant masterbatch)
  • B-1 Amorphous silica: Silicia 430 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 226 mL/100 g)
  • B-2 Amorphous silica: Cyrophobic 120 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 232 mL/100 g)
  • B-3 Amorphous silica: Cyrophobic 505 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 105 mL/100 g)
  • Silica Gasil AB905 (manufactured by PQ Corporation, oil absorption 36mL/100g)
  • C-1 Glycerin fatty acid ester: Coconade MT (ingredient name: fatty acid triglyceride ((caprylic acid/capric acid) triglyceride), HSP value: 17.1 MPa 1/2 , manufactured by Kao Corporation)
  • Judgment criteria for separation All the sample has flowed down from the dropping position. ⁇ : Part of the sample (less than half) remained at the dropping position. ⁇ : The sample (more than half) remained at the dropping position or did not slide down.

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Abstract

Provided are: a polyolefin resin composition having excellent releasability that allows contents to exit easily (flow down easily) and excellent workability that allows the stirring blades of a kneader to knead without idling; and a molded body and a laminate that contain the resin composition.　A polyolefin resin composition that contains 2-98.9 wt% inclusive of a polyolefin resin (A), 0.1-49 wt% inclusive of a filler (B), and 1.0-49 wt% inclusive of an oil (C), the oil absorption value of the filler (B) measured based on ISO 787-5:1980 being 40-500 mL/100 g inclusive, the Hansen solubility parameter (HSP value) of the oil (C) being 10 MPa1/2 to 36 MPA1/2 inclusive, and the weight ratio (oil (C)/filler (B), unit: weight/weight) of the weight of the oil (C) to the weight of the filler (B) being 0.2-10.0 inclusive.

Description

ポリオレフィン系樹脂組成物、成形体および積層体Polyolefin resin compositions, molded bodies and laminates
　本発明は、ポリオレフィン系樹脂組成物、成形体および積層体に関するものである。 The present invention relates to a polyolefin resin composition, a molded article, and a laminate.
　従来から、ポリオレフィン系樹脂組成物は、食品包装用フィルムや食品包装用積層体の層に用いられることが知られている。 It has been known that polyolefin resin compositions are used in the layers of food packaging films and food packaging laminates.
　例えば、特許文献１には、ポリオレフィン系樹脂と、特定のエステル化合物等、特定のスルホン酸アルカリ金属塩等及び特定の無機粒子等を含むポリオレフィン系樹脂組成物で形成した被包装物が接触することとなる層を有する包装用フィルムであって、透明性を損なうことなく、優れた防曇性、平滑性及びアンチブロッキング性を同時に有する包装用フィルムを提供することが記載されている。 For example, Patent Document 1 discloses that a polyolefin resin and a packaged object formed of a polyolefin resin composition containing a specific ester compound, etc., a specific alkali metal sulfonic acid salt, etc., and specific inorganic particles, etc. come into contact with each other. It is described that there is provided a packaging film having a layer having the following properties and having excellent antifogging properties, smoothness, and antiblocking properties at the same time without impairing transparency.
　また、特許文献２には、ポリエチレン系樹脂と、表面処理が施された合成シリカ系のアンチブロッキング剤が配合され、表面処理がシリコーンオイル等を用いてシリカ表面を被覆することを特徴とするレトルト食品包装用樹脂組成物であって、アンチブロッキング性、レトルト処理後の衝撃性や透明性の低下抑制、更に油性食品等によるユズ肌の発生抑制に優れたレトルト食品包装用樹脂組成物を提供することが記載されている。 Further, Patent Document 2 discloses a retort in which a polyethylene resin and a surface-treated synthetic silica-based anti-blocking agent are blended, and the surface treatment includes coating the silica surface with silicone oil or the like. Provided is a resin composition for retort food packaging, which has excellent anti-blocking properties, suppresses decreases in impact resistance and transparency after retort processing, and suppresses occurrence of yuzu skin caused by oily foods, etc. It is stated that.
　一般に、樹脂製容器やボトルには、その樹脂製容器やボトルに充填された内容物が出やすいこと（内容物が流れ落ちやすいこと）が求められる。そして、内容物がマヨネーズやソースのように油成分を含み粘性である場合、特許文献１に記載された包装用フィルムや、特許文献２に記載されたレトルト食品包装用樹脂組成物からなる容器やボトルに充填された内容物の出やすさ（流れ落ちやすさ）について（以下身離れ性と称することがある）、更なる改良が求められている。 In general, resin containers and bottles are required to allow the contents filled in the resin container or bottle to easily come out (the contents can easily flow down). When the contents are viscous and contain oil components such as mayonnaise or sauce, containers made of the packaging film described in Patent Document 1 or the resin composition for retort food packaging described in Patent Document 2, or There is a need for further improvement in the ease with which the contents filled in the bottle come out (flow down) (hereinafter sometimes referred to as detachability).
　また、ポリオレフィン系樹脂組成物がオイルを含む場合、ポリオレフィン系樹脂組成物からオイルが漏れ出すことがあり、オイルが漏れ出した場合、ポリオレフィン系樹脂組成物を混練機で混練する時に、混練機のスクリューなどが空転し、混練できないことがある。そのためポリオレフィン系樹脂組成物には、オイルが漏れ出すことなく、混練機のスクリューが空転することなく、混練できること（以下、ポリオレフィン系樹脂組成物の加工性と称することがある）が求められている。 In addition, if the polyolefin resin composition contains oil, the oil may leak from the polyolefin resin composition. The screws may run idly, making it impossible to mix. Therefore, polyolefin resin compositions are required to be able to be kneaded without oil leaking out or the screws of the kneader spinning idly (hereinafter sometimes referred to as processability of polyolefin resin compositions). .
　かかる状況の下、本発明者は、マヨネーズやソース等の内容物が出やすい（流れ落ちやすい）容器やボトルに適しており、良好な加工性を有するポリオレフィン系樹脂組成物として、本発明に至った。 Under such circumstances, the present inventor has developed the present invention as a polyolefin resin composition that is suitable for containers and bottles where the contents of mayonnaise, sauce, etc. tend to come out (flow easily) and has good processability. .
特開２００５－２００６２８JP2005-200628 特開２００３－４１０６８JP2003-41068
　本発明は、内容物が出やすい（流れ落ちやすい）という身離れ性に優れ、混練機のスクリューなどが空転することなく、混練できるという加工性に優れるポリオレフィン系樹脂組成物、その樹脂組成物を含む成形体および積層体を提供することを目的とする。 The present invention includes a polyolefin resin composition that has excellent separation properties such that the contents easily come out (flows down easily), and excellent processability that allows kneading without idling the screws of a kneading machine, and the resin compositions thereof. The object is to provide a molded body and a laminate.
　上記の課題を解決するために、本発明は以下の何れかのものを提供する。 In order to solve the above problems, the present invention provides any of the following.
［１］ポリオレフィン系樹脂（Ａ）を２重量％以上９８．９重量％以下と、
フィラー（Ｂ）を０．１重量％以上４９重量％以下と、
オイル（Ｃ）を１．０重量％以上４９重量％以下と、を含有し（ただし、（Ａ）と（Ｂ）と（Ｃ）の合計を１００重量％とする）、
フィラー（Ｂ）のＩＳＯ　７８７－５：１９８０に基づいて測定された吸油量が４０ｍＬ／１００ｇ以上５００ｍＬ／１００ｇ以下であり（要件（Ｉ））
オイル（Ｃ）のハンセンの溶解度パラメーター（ＨＳＰ値）が１０ＭＰａ１／２以上３６ＭＰａ１／２以下であり（要件（ＩＩ））、
フィラー（Ｂ）の重量に対するオイル（Ｃ）の重量の重量比（オイル（Ｃ）／フィラー（Ｂ）、単位：重量／重量）が０．２以上１０．０以下である（要件（ＩＩＩ））、
ポリオレフィン系樹脂組成物。 [1] Polyolefin resin (A) in an amount of 2% by weight or more and 98.9% by weight or less,
The filler (B) is 0.1% by weight or more and 49% by weight or less,
Contains 1.0% by weight or more and 49% by weight or less of oil (C) (however, the total of (A), (B), and (C) is 100% by weight),
The oil absorption amount of filler (B) measured based on ISO 787-5:1980 is 40 mL/100 g or more and 500 mL/100 g or less (requirement (I))
The Hansen solubility parameter (HSP value) of the oil (C) is 10 MPa 1/2 or more and 36 MPa 1/2 or less (requirement (II)),
The weight ratio of the weight of oil (C) to the weight of filler (B) (oil (C)/filler (B), unit: weight/weight) is 0.2 or more and 10.0 or less (requirement (III)) ,
Polyolefin resin composition.
［２］オイル（Ｃ）が、シリコーンオイル、グリセリン脂肪酸エステル、流動パラフィン、食用油脂、アルコール、及び、多価アルコールからなる群から選ばれる少なくとも１種である、［１］に記載のポリオレフィン系樹脂組成物。 [2] The polyolefin resin according to [1], wherein the oil (C) is at least one selected from the group consisting of silicone oil, glycerin fatty acid ester, liquid paraffin, edible oil and fat, alcohol, and polyhydric alcohol. Composition.
［３］フィラー（Ｂ）が、酸化チタン、炭酸カルシウム、アルミナ、シリカ、珪藻土、酸化鉄、フェライト、ゼオライト、タルク、ウォラストナイト、マイカ、及び、クレーからなる群から選ばれる少なくとも１種である、［１］に記載のポリオレフィン系樹脂組成物。 [3] Filler (B) is at least one member selected from the group consisting of titanium oxide, calcium carbonate, alumina, silica, diatomaceous earth, iron oxide, ferrite, zeolite, talc, wollastonite, mica, and clay. , the polyolefin resin composition according to [1].
［４］［１］から［３］のいずれか１項に記載のポリオレフィン系樹脂組成物を含む成形体。 [4] A molded article comprising the polyolefin resin composition according to any one of [1] to [3].
［５］積層体であって、最内層として、［１］から［３］のいずれか１項に記載のポリオレフィン系樹脂組成物を含む層を有する積層体。 [5] A laminate having a layer containing the polyolefin resin composition according to any one of [1] to [3] as the innermost layer.
［６］積層体のいずれか１層がガスバリア層である、［５］に記載の積層体。 [6] The laminate according to [5], wherein any one layer of the laminate is a gas barrier layer.
［７］ガスバリア層にエチレン・ビニルアルコール樹脂を含む、［６］に記載の積層体。 [7] The laminate according to [6], wherein the gas barrier layer contains ethylene/vinyl alcohol resin.
［８］積層体が多層ボトルである、［５］から［７］のいずれか１項に記載の積層体。 [8] The laminate according to any one of [5] to [7], wherein the laminate is a multilayer bottle.
［９］積層体が多層フィルムである、［５］から［７］のいずれか１項に記載の積層体。 [9] The laminate according to any one of [5] to [7], wherein the laminate is a multilayer film.
　本発明によれば、内容物が出やすい（流れ落ちやすい）という身離れ性に優れ、混練機のスクリューなどが空転することなく、混練できるという加工性に優れるポリオレフィン系樹脂組成物、その樹脂組成物を含む成形体および積層体を提供することができる。 According to the present invention, there is provided a polyolefin resin composition that has excellent separation properties such that the contents easily come out (flows down easily), and excellent processability that allows kneading without the screws of a kneading machine idling, and the resin composition. Molded bodies and laminates containing the above can be provided.
＜ポリオレフィン系樹脂（Ａ）＞
　ポリオレフィン系樹脂（Ａ）は、オレフィン系重合体を含む樹脂である。ポリオレフィン系樹脂としては、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂等が挙げられる。ポリオレフィン系樹脂は、好ましくは、ポリエチレン系樹脂である。 <Polyolefin resin (A)>
The polyolefin resin (A) is a resin containing an olefin polymer. Examples of the polyolefin resin include polyethylene resin, polypropylene resin, and the like. The polyolefin resin is preferably a polyethylene resin.
　ポリエチレン系樹脂は、エチレン系重合体を含む樹脂である。エチレン系重合体は、エチレンに由来する単量体単位を５０質量％超含む重合体であり、すなわち、エチレン単独重合体、または、エチレンに由来する単量体単位を５０質量％超含むエチレン系共重合体である。エチレン系重合体は、好ましくは、エチレン単独重合体、または、エチレンに由来する単量体単位を９０質量％以上含むエチレン系共重合体であり、より好ましくは、エチレン単独重合体である。なお、エチレン系重合体は、１種類を単独で用いてもよく、２種類以上を併用してもよい。 Polyethylene resin is a resin containing an ethylene polymer. An ethylene polymer is a polymer containing more than 50% by mass of monomer units derived from ethylene, that is, an ethylene homopolymer or an ethylene polymer containing more than 50% by mass of monomer units derived from ethylene. It is a copolymer. The ethylene polymer is preferably an ethylene homopolymer or an ethylene copolymer containing 90% by mass or more of monomer units derived from ethylene, and more preferably an ethylene homopolymer. In addition, one type of ethylene polymer may be used alone, or two or more types may be used in combination.
　本明細書において、「エチレンに由来する単量体単位」のような用語中の「単量体単位」とは、モノマーの重合単位を意味する。したがって、例えば、「エチレンに由来する単量体単位」は、－ＣＨ２ＣＨ２－なる単量体単位を意味する。 As used herein, "monomeric unit" in terms such as "monomeric unit derived from ethylene" means a polymerized unit of a monomer. Therefore, for example, "a monomer unit derived from ethylene" means a monomer unit of -CH 2 CH 2 -.
　エチレン単独重合体としては、例えば、ラジカル開始剤を用いて高圧ラジカル重合により繰り返し単位のエチレンがランダムに分岐構造をもって結合した、密度が９１０ｋｇ／ｍ３～９３５ｋｇ／ｍ３の高圧法低密度ポリエチレン（ＬＤＰＥ）が挙げられる。 Examples of ethylene homopolymers include high-pressure low-density polyethylene (with a density of 910 kg/m 3 to 935 kg/m 3 ) in which repeating units of ethylene are randomly bonded in a branched structure by high-pressure radical polymerization using a radical initiator. LDPE).
　エチレン系共重合体としては、例えば、エチレンとα－オレフィンとの共重合体、脂環式化合物で置換されたα－オレフィンとエチレンとの共重合体が挙げられる。 Examples of the ethylene copolymer include a copolymer of ethylene and α-olefin, and a copolymer of ethylene and α-olefin substituted with an alicyclic compound.
　エチレンとα－オレフィンとの共重合体としては、例えば、結晶性を有する直鎖状低密度ポリエチレン、結晶性が低くゴム状の弾性特性を有するエチレンとα－オレフィンとの共重合体のエラストマー等が挙げられる。 Examples of copolymers of ethylene and α-olefin include linear low-density polyethylene with crystallinity, elastomers of copolymers of ethylene and α-olefin with low crystallinity and rubber-like elastic properties, etc. can be mentioned.
　直鎖状低密度ポリエチレンの密度は、好ましくは９００ｋｇ／ｍ３～９４０ｋｇ／ｍ３である。また、エチレンとα－オレフィンとの共重合体のエラストマーの密度は、好ましくは８６０ｋｇ／ｍ３～９００ｋｇ／ｍ３である。 The density of the linear low density polyethylene is preferably 900 kg/m 3 to 940 kg/m 3 . Further, the density of the elastomer of the copolymer of ethylene and α-olefin is preferably 860 kg/m 3 to 900 kg/m 3 .
　α－オレフィンは、好ましくは、炭素数３～１０のα－オレフィンである。炭素数３～１０のα－オレフィンとしては、例えば、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン、１－デセン、３－メチル－１－ブテン等が挙げられる。炭素数３～１０のα－オレフィンは、好ましくは、炭素数４～１０のα－オレフィンであり、より好ましくは、１－ブテン、１－ヘキセンまたは１－オクテンである。 The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms. Examples of α-olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 3-methyl-1- Examples include butene. The α-olefin having 3 to 10 carbon atoms is preferably an α-olefin having 4 to 10 carbon atoms, more preferably 1-butene, 1-hexene or 1-octene.
　脂環式化合物で置換されたα－オレフィンとしては、例えば、ビニルシクロヘキサン等が挙げられる。 Examples of the α-olefin substituted with an alicyclic compound include vinylcyclohexane.
　エチレン系共重合体におけるα－オレフィンに由来する単量体単位の含有量は、好ましくは４質量％～２０質量％である。 The content of monomer units derived from α-olefin in the ethylene copolymer is preferably 4% by mass to 20% by mass.
　エチレンとα－オレフィンとの共重合体として、具体的には、例えば、エチレン－１－ブテン共重合体、エチレン－１－ヘキセン共重合体、エチレン－１－オクテン共重合体、エチレン－１－デセン共重合体、エチレン－（３－メチル－１－ブテン）共重合体等が挙げられる。なお、エチレンとα－オレフィンとの共重合体は、１種類を単独で用いてもよく、２種類以上を併用してもよい。また、エチレン系重合体は、エチレン単独重合体と、エチレンとα－オレフィンとの共重合体との混合物であってもよい。 Specific examples of the copolymer of ethylene and α-olefin include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-octene copolymer. Examples include decene copolymer and ethylene-(3-methyl-1-butene) copolymer. Note that the copolymer of ethylene and α-olefin may be used singly or in combination of two or more. Further, the ethylene polymer may be a mixture of an ethylene homopolymer and a copolymer of ethylene and α-olefin.
　エチレン系重合体は、温度１９０℃、荷重２．１６ｋｇで測定されるメルトフローレート（ＭＦＲ）が、好ましくは０．１ｇ／１０分～５０ｇ／１０分であり、より好ましくは０．３ｇ／１０分～３０ｇ／１０分であり、さらに好ましくは０．３ｇ／１０分～２０ｇ／１０分である。なお、ＭＦＲは、ＪＩＳ　Ｋ７２１０－１に規定されたＡ法に従って測定される。 The melt flow rate (MFR) of the ethylene polymer measured at a temperature of 190° C. and a load of 2.16 kg is preferably 0.1 g/10 minutes to 50 g/10 minutes, more preferably 0.3 g/10 minutes to 30 g/10 minutes, more preferably 0.3 g/10 minutes to 20 g/10 minutes. Note that MFR is measured according to method A specified in JIS K7210-1.
　ポリプロピレン系樹脂は、プロピレン系重合体を含む樹脂である。プロピレン系重合体は、プロピレンに由来する単量体単位を５０質量％超含む重合体であり、すなわち、プロピレン単独重合体、または、プロピレンに由来する単量体単位を５０質量％超含むプロピレン系共重合体（ランダムポリプロピレン、ヘテロファジックポリプロピレン）である。プロピレン系共重合体は、好ましくは、エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体である。 A polypropylene resin is a resin containing a propylene polymer. A propylene-based polymer is a polymer containing more than 50% by mass of monomer units derived from propylene, that is, a propylene homopolymer or a propylene-based polymer containing more than 50% by mass of monomer units derived from propylene. It is a copolymer (random polypropylene, heterophasic polypropylene). The propylene copolymer is preferably a copolymer of propylene and ethylene and/or an α-olefin having 4 to 10 carbon atoms.
　プロピレン単独重合体は、温度２３０℃、荷重２．１６ｋｇで測定されるメルトフローレート（ＭＦＲ）が、好ましくは０．１ｇ／１０分～５０ｇ／１０分である。エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体は、温度２３０℃、荷重２．１６ｋｇで測定されるメルトフローレート（ＭＦＲ）が、好ましくは１ｇ／１０分～２００ｇ／１０分、より好ましくは１ｇ／１０分～５０ｇ／１０分、さらに好ましくは１ｇ／１０分～１０ｇ／１０分である。なお、ＭＦＲは、ＪＩＳ　Ｋ７２１０－１に規定されたＡ法に従って測定される。 The propylene homopolymer preferably has a melt flow rate (MFR) of 0.1 g/10 minutes to 50 g/10 minutes, measured at a temperature of 230° C. and a load of 2.16 kg. The copolymer of ethylene and/or α-olefin having 4 to 10 carbon atoms and propylene preferably has a melt flow rate (MFR) of 1 g/10 min to 200 g measured at a temperature of 230°C and a load of 2.16 kg. /10 minutes, more preferably 1 g/10 minutes to 50 g/10 minutes, even more preferably 1 g/10 minutes to 10 g/10 minutes. Note that MFR is measured according to method A specified in JIS K7210-1.
　エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体の全質量を１００質量％としたときに、エチレンおよび／または炭素数４～１０のα－オレフィンに由来する単量体単位の含有量は、好ましくは０．１質量％～４０質量％であり、プロピレンに由来する単量体単位の含有量は、好ましくは６０質量％～９９．９質量％である。 Monomer derived from ethylene and/or α-olefin having 4 to 10 carbon atoms, when the total mass of the copolymer of ethylene and/or α-olefin having 4 to 10 carbon atoms and propylene is 100% by mass The content of monomeric units is preferably 0.1% by mass to 40% by mass, and the content of monomer units derived from propylene is preferably 60% by mass to 99.9% by mass.
　炭素数４～１０のα－オレフィンとしては、例えば、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン、１－デセン等が挙げられる。炭素数４～１０のα－オレフィンは、好ましくは、１－ブテン、１－ヘキセンまたは１－オクテンである。 Examples of α-olefins having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. The α-olefin having 4 to 10 carbon atoms is preferably 1-butene, 1-hexene or 1-octene.
　エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体として、具体的には、例えば、プロピレンとエチレンとの共重合体、プロピレンと炭素数４～１０のα－オレフィンとの共重合体、プロピレンとエチレンと炭素数４～１０のα－オレフィンとの共重合体等が挙げられる。なお、エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体は、１種類を単独で用いてもよく、２種類以上を併用してもよい。また、プロピレン系重合体は、プロピレン単独重合体と、エチレンおよび／または炭素数４～１０のα－オレフィンとプロピレンとの共重合体との混合物であってもよい。 As a copolymer of ethylene and/or an α-olefin having 4 to 10 carbon atoms and propylene, specifically, for example, a copolymer of propylene and ethylene, a copolymer of propylene and an α-olefin having 4 to 10 carbon atoms, copolymers of propylene, ethylene, and α-olefins having 4 to 10 carbon atoms, etc. The copolymer of propylene and ethylene and/or α-olefin having 4 to 10 carbon atoms may be used alone or in combination of two or more. Further, the propylene-based polymer may be a mixture of a propylene homopolymer and a copolymer of propylene and ethylene and/or an α-olefin having 4 to 10 carbon atoms.
　プロピレンと炭素数４～１０のα－オレフィンとの共重合体としては、例えば、プロピレン－１－ブテン共重合体、プロピレン－１－ヘキセン共重合体、プロピレン－１－オクテン共重合体、プロピレン－１－デセン共重合体等が挙げられる。 Examples of copolymers of propylene and α-olefin having 4 to 10 carbon atoms include propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-1-octene copolymer. Examples include 1-decene copolymer.
　プロピレンとエチレンと炭素数４～１０のα－オレフィンとの共重合体としては、例えば、プロピレン－エチレン－１－ブテン共重合体、プロピレン－エチレン－１－ヘキセン共重合体、プロピレン－エチレン－１－オクテン共重合体、プロピレン－エチレン－１－デセン共重合体等が挙げられる。 Copolymers of propylene, ethylene, and α-olefin having 4 to 10 carbon atoms include, for example, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1 -octene copolymer, propylene-ethylene-1-decene copolymer, and the like.
＜フィラー（Ｂ）＞
　フィラー（Ｂ）は、被包装物が接触することとなる層を形成するポリオレフィン系樹脂組成物に用いるフィラーであり、フィラー（Ｂ）には、１）酸化物系無機粒子、２）珪酸塩系無機粒子、３）有機架橋粒子、４）以上の１）～３）のうちでいずれか二つ以上の任意の混合物が含まれる。 <Filler (B)>
Filler (B) is a filler used in a polyolefin resin composition that forms a layer with which the packaged object comes into contact, and filler (B) includes 1) oxide-based inorganic particles, 2) silicate-based Inorganic particles, 3) organic crosslinked particles, and 4) any mixture of any two or more of the above 1) to 3) are included.
　フィラー（Ｂ）としての酸化物系無機粒子としては、シリカ、珪藻土、アルミナ、酸化鉄、フェライト等が挙げられるが、なかでもシリカ、珪藻土が好ましく、シリカがより好ましい。 Examples of the oxide-based inorganic particles as the filler (B) include silica, diatomaceous earth, alumina, iron oxide, ferrite, etc. Among them, silica and diatomaceous earth are preferred, and silica is more preferred.
　フィラー（Ｂ）としての珪酸塩系無機粒子としては、ゼオライト、タルク、ウォラストナイト、マイカ、クレー等が挙げられるが、なかでもゼオライト、タルク、ウォラストナイトが好ましく、ゼオライト、タルクがより好ましい。 Examples of the silicate-based inorganic particles as the filler (B) include zeolite, talc, wollastonite, mica, clay, etc. Among them, zeolite, talc, and wollastonite are preferred, and zeolite and talc are more preferred.
　フィラー（Ｂ）としての有機架橋粒子としては、架橋シリコーン粒子、架橋ポリアミド粒子、架橋ポリトリアジン粒子、架橋ポリアクリル粒子、架橋ポリスチレン粒子等が挙げられるが、架橋シリコーン粒子、架橋ポリアクリル粒子、架橋ポリスチレン粒子が好ましく、なかでも架橋ポリアクリル粒子がより好ましい。 Examples of the organic crosslinked particles as the filler (B) include crosslinked silicone particles, crosslinked polyamide particles, crosslinked polytriazine particles, crosslinked polyacrylic particles, crosslinked polystyrene particles, etc. Particles are preferred, and crosslinked polyacrylic particles are particularly preferred.
　以上説明したフィラー（Ｂ）において、なかでも酸化物系無機粒子、珪酸塩系無機粒子が好ましく、シリカ、ゼオライト、タルク、炭酸カルシウムがより好ましい。本発明はフィラー（Ｂ）としての酸化物系無機粒子、珪酸塩系無機粒子、有機架橋粒子の平均粒子径を特に制限するものではないが、平均粒子径が０．５～１０μｍのものが好ましく、１～５μｍのものが更に好ましい。Ｃ成分としての酸化物系無機粒子、珪酸塩系無機粒子は天然に産出する鉱物を用いてもよいし、人工合成物であってもよい。また、これらは特に処理を行うことなくそのまま用いてもよいし、ボールミル、酸、シランカップリング剤処理等の処理を行った後に用いてもよい。 Among the fillers (B) described above, oxide-based inorganic particles and silicate-based inorganic particles are preferred, and silica, zeolite, talc, and calcium carbonate are more preferred. Although the present invention does not particularly limit the average particle diameter of the oxide-based inorganic particles, silicate-based inorganic particles, and organic crosslinked particles as the filler (B), those having an average particle diameter of 0.5 to 10 μm are preferable. , 1 to 5 μm is more preferable. The oxide-based inorganic particles and silicate-based inorganic particles as component C may be naturally occurring minerals or may be artificially synthesized. Further, these may be used as they are without any particular treatment, or may be used after being treated with a ball mill, an acid, a silane coupling agent, or the like.
　フィラー（Ｂ）は、ISO 787-5:1980（General　methods　of　test　for　pigments　and　extenders―Part　5：Determination　of　oil　absorption　value）に基づいて測定される吸油量が４０ｍＬ／１００ｇ以上５００ｍＬ／１００ｇ以下（要件（Ｉ））のフィラーである。吸油量は、好ましくは４０ｍＬ／１００ｇ以上５００ｍＬ／１００ｇ以下であり、さらに好ましくは４０ｍＬ／１００ｇ以上３００ｍＬ／１００ｇ以下であり、さらに好ましくは４０ｍＬ／１００ｇ以上２４０ｍＬ／１００ｇ以下である。吸油量がこの範囲内であると、混練時にオイル（Ｃ）を保持でき、成形体は身離れ性が良好である。吸油量がこの範囲内であると、吸油量に対して添加するオイル（Ｃ）の量が近くなり、フィラー（Ｂ）からポリオレフィン系樹脂（Ａ）へのオイル（Ｃ）の排出量が安定するため好ましい。 Filler (B) has an oil absorption amount of 40 mL/100 g or more and 500 mL/100 g or less (requirements (I)) is a filler. The oil absorption amount is preferably 40 mL/100 g or more and 500 mL/100 g or less, more preferably 40 mL/100 g or more and 300 mL/100 g or less, and still more preferably 40 mL/100 g or more and 240 mL/100 g or less. When the oil absorption is within this range, the oil (C) can be retained during kneading, and the molded product has good releasability. When the oil absorption amount is within this range, the amount of oil (C) added is close to the oil absorption amount, and the amount of oil (C) discharged from the filler (B) to the polyolefin resin (A) is stabilized. Therefore, it is preferable.
フィラー（Ｂ）として、好ましくは、酸化チタン、炭酸カルシウム、アルミナ、結晶質シリカ、非晶質シリカ、珪藻土、酸化鉄、フェライト、ゼオライト、タルク、ウォラストナイト、マイカ、及び、クレーからなる群から選ばれる少なくとも１種であり、中でも安全性の観点から非晶質シリカがより好ましい。 The filler (B) is preferably selected from the group consisting of titanium oxide, calcium carbonate, alumina, crystalline silica, amorphous silica, diatomaceous earth, iron oxide, ferrite, zeolite, talc, wollastonite, mica, and clay. At least one kind is selected, and among them, amorphous silica is more preferable from the viewpoint of safety.
＜オイル（Ｃ）＞
　本発明では、例えば、内容物として水分含有またはＯ/Ｗ型エマルジョンのものが使用されるため、オイル（Ｃ）として、水分含有内容物と混和しない油性液体が使用されるが、一般的には、包装容器内に内容物を充填した後、内容物を排出し且つ内容物を選択的に抽出除去した後、容器内面（液浸透性面）に残存する液量が前述した保持量（０．５乃至５０ｇ／ｍ２、特に１乃至５０ｇ／ｍ２）の範囲内となるようなオイル、例えば、シリコーンオイル、脂肪酸モノグリセリド、脂肪酸ジグリセリド、脂肪酸トリグリセリドなどのグリセリン脂肪酸エステル、流動パラフィン、及び、食用油脂の群から選ばれる少なくとも１種を使用すればよい。特に、オイルの表面張力が、内容物と大きく異なるものほど、潤滑効果が高く、本発明には好適である。例えば、表面張力が１６乃至４０ｍＮ／ｍ、さらに好ましくは１６乃至３５ｍＮ／ｍの範囲にある食用油脂等をオイルとして用いるのが良い。 　また、かかる油性液体は、当然、揮発性が低く、包装容器を開封した状態においても、揮散しないような蒸気圧を有している。 <Oil (C)>
In the present invention, for example, water-containing or O/W type emulsion is used as the content, so an oil-based liquid that is immiscible with the water-containing content is used as the oil (C), but generally After filling the packaging container with the contents, discharging the contents, and selectively extracting and removing the contents, the amount of liquid remaining on the inner surface of the container (liquid permeable surface) is the retention amount (0. 5 to 50 g/m2, especially 1 to 50 g/m2), such as silicone oil, glycerin fatty acid esters such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, liquid paraffin, and the group of edible fats and oils. At least one selected from the following may be used. In particular, the oil whose surface tension is significantly different from that of the contents has a higher lubricating effect and is suitable for the present invention. For example, it is preferable to use an edible oil or fat having a surface tension in the range of 16 to 40 mN/m, more preferably 16 to 35 mN/m, as the oil. Moreover, such oily liquids naturally have low volatility and have a vapor pressure that does not volatilize even when the packaging container is opened.
　本発明において、上記のような水分含有の内容物に対して最も好適に使用されるオイルは、表面張力が前述した範囲にあるものであり、特にシリコーンオイル、脂肪酸トリグリセリドなどのグリセリン脂肪酸エステル、流動パラフィン、食用油脂である。これらの物質は、揮散し難く、しかも、食品添加物として認可されており、さらには、無臭であり、内容物のフレーバ－を損なわないという利点もある。 In the present invention, the oil most suitably used for the water-containing contents as described above is one having a surface tension within the above-mentioned range, particularly silicone oil, glycerin fatty acid ester such as fatty acid triglyceride, and fluid. Paraffin, edible oil and fat. These substances are difficult to volatilize, are approved as food additives, and have the further advantage of being odorless and not impairing the flavor of the contents.
　一方で、例えば、内容物として油分含有またはＷ/Ｏ型エマルジョンのものが使用されるため、オイル（Ｃ）として、上述と同様の思想にて、油分含有内容物と混和しない親水性液体が使用される。例えば、脂肪酸モノグリセリドなどのグリセリン脂肪酸エステルの群、オクタデカノールなどのアルコール、グリセリンなどの多価アルコールから選ばれる少なくとも１種を使用すればよい。特に、オイルの表面張力が、内容物と大きく異なるものほど、潤滑効果が高く、本発明には好適である。 On the other hand, for example, since the content is oil-containing or a W/O type emulsion, a hydrophilic liquid that is immiscible with the oil-containing content is used as the oil (C) based on the same idea as above. be done. For example, at least one selected from the group of glycerin fatty acid esters such as fatty acid monoglycerides, alcohols such as octadecanol, and polyhydric alcohols such as glycerin may be used. In particular, the oil whose surface tension is significantly different from that of the contents has a higher lubricating effect and is suitable for the present invention.
　つまり、オイル（Ｃ）と内容物の組み合わせとしては、オイル（Ｃ）と内容物が混和しない組み合わせが重要であり、それを満たす表面張力、または、ハンセンの溶解度パラメーターを持つものを使用するのが好ましい。 In other words, it is important for the combination of oil (C) and contents to be such that they are not miscible, and it is best to use a combination that has the surface tension or Hansen's solubility parameter that satisfies this. preferable.
　オイル（Ｃ）は、ハンセンの溶解度パラメーター（ＨＳＰ値）が１０ＭＰａ１／２以上３６ＭＰａ１／２以下（要件（ＩＩ））のオイルである。 The oil (C) has a Hansen solubility parameter (HSP value) of 10 MPa 1/2 or more and 36 MPa 1/2 or less (requirement (II)).
　オイル（Ｃ）のハンセン溶解度パラメーター（ＨＳＰ値）は、下記の（δＤ、δＰ、δＨ）の３次元のパラメーターで定義され、下記式（１）により表される。ハンセンが提唱したこの考え方（理論）は、ハンセン溶解度パラメーター：Ａ 　Ｕｓｅｒ’ｓ 　Ｈａｎｄｂｏｏｋ，Ｓｅｃｏｎｄ 　Ｅｄｉｔｉｏｎ，Ｃ．Ｍ．Ｈａｎｓｅｎ（２００７），Ｔａｙｌｏｒ 　ａｎｄ 　Ｆｒａｎｃｉｓ 　Ｇｒｏｕｐ，ＬＬＣ（ＨＳＰｉＰマニュアル）に記載されている。
ＨＳＰ２＝（δＤ）２＋（δＰ）２＋（δＨ）２ 　・・・式（１）
δＤ：Ｌｏｎｄｏｎ分散力項
δＰ：分子分極項（双極子間力項）
δＨ：水素結合項 The Hansen solubility parameter (HSP value) of oil (C) is defined by the following three-dimensional parameters (δD, δP, δH), and is expressed by the following formula (1). This idea (theory) proposed by Hansen is described in Hansen Solubility Parameter: A User's Handbook, Second Edition, C. M. Hansen (2007), Taylor and Francis Group, LLC (HSPiP Manual).
HSP2=(δD)2+(δP)2+(δH)2...Formula (1)
δD: London dispersion force term δP: Molecular polarization term (dipole force term)
δH: Hydrogen bond term
　δＤ、δＰおよびδＨは、例えば、コンピュータソフトウェアＨａｎｓｅｎ 　Ｓｏｌｕｂｉｌｉｔｙ 　Ｐａｒａｍｅｔｅｒｓ 　ｉｎ 　Ｐｒａｃｔｉｃｅ（ＨＳＰｉＰ）を用いることによって、オイル（Ｃ）の化学構造式から計算することができる。本発明で用いるオイル（Ｃ）のＨＳＰ値は、ＨＳＰｉＰ 　ｖｅｒ．５．４．０１による計算によって得られた値を用いる。例えば、エタノールのＨＳＰ値は２５．０ＭＰａ１／２、プロパノールのＨＳＰ値は２２．６ＭＰａ１／２、プロパノールのＨＳＰ値は２２．６ＭＰａ１／２、オクタデカノールのＨＳＰ値は１７．８ＭＰａ１／２、グリセリンのＨＳＰ値は３５．７ＭＰａ１／２である。 δD, δP and δH can be calculated from the chemical structural formula of the oil (C), for example, by using the computer software Hansen Solubility Parameters in Practice (HSPiP). The HSP value of the oil (C) used in the present invention is based on HSPiP ver. The value obtained by calculation according to 5.4.01 is used. For example, the HSP value of ethanol is 25.0 MPa 1/2 , the HSP value of propanol is 22.6 MPa 1/2 , the HSP value of propanol is 22.6 MPa 1/2 , and the HSP value of octadecanol is 17.8 MPa 1/2. 2. The HSP value of glycerin is 35.7 MPa 1/2 .
　オイル（Ｃ）として、好ましくは、シリコーンオイル、グリセリン脂肪酸エステル、流動パラフィン、食用油脂、アルコール、及び、多価アルコールからなる群から選ばれる少なくとも１種である。オイル（Ｃ）は内容物によって適宜選択することができる。ＨＳＰ値が好ましくは１０ＭＰａ１／２～３６ＭＰａ１／２、より好ましくは１０ＭＰａ１／２～２５ＭＰａ１／２、さらに好ましくは１４ＭＰａ１／２～２２ＭＰａ１／２であれば、本発明のポリオレフィン系樹脂組成物の内容物として好適に用いられる内容物に対して身離れ性を発現できる。 The oil (C) is preferably at least one selected from the group consisting of silicone oil, glycerin fatty acid ester, liquid paraffin, edible fat, alcohol, and polyhydric alcohol. Oil (C) can be appropriately selected depending on the contents. If the HSP value is preferably 10 MPa 1/2 to 36 MPa 1/2 , more preferably 10 MPa 1/2 to 25 MPa 1/2 , even more preferably 14 MPa 1/2 to 22 MPa 1/2 , the polyolefin resin of the present invention It is possible to exhibit releasability to the contents suitably used as the contents of the composition.
　本発明のポリオレフィン系樹脂組成物は、ポリオレフィン系樹脂（Ａ）を２重量％以上９８．９重量％以下と、フィラー（Ｂ）を０．１重量％以上４９重量％以下と、オイル（Ｃ）を１．０重量％以上４９重量％以下とを含有する。ただし、ポリオレフィン系樹脂（Ａ）とフィラー（Ｂ）とオイル（Ｃ）の合計を１００重量％とする。 The polyolefin resin composition of the present invention contains a polyolefin resin (A) of 2% to 98.9% by weight, a filler (B) of 0.1% to 49% by weight, and an oil (C). 1.0% by weight or more and 49% by weight or less. However, the total of the polyolefin resin (A), filler (B), and oil (C) is 100% by weight.
　フィラー（Ｂ）の重量に対するオイル（Ｃ）の重量の重量比（オイル（Ｃ）／フィラー（Ｂ）、単位：重量／重量）は好ましくは０．２以上１０．０以下、さらに好ましくは０．５以上５．０以下である（要件（ＩＩＩ））。重量比がこの範囲にある場合、成形体表面にオイル（Ｃ）が十分量かつ適切量排出され、身離れ性が発現し、混練機のスクリューなどで空転する等の加工トラブルを回避可能である The weight ratio of the weight of oil (C) to the weight of filler (B) (oil (C)/filler (B), unit: weight/weight) is preferably 0.2 or more and 10.0 or less, more preferably 0. 5 or more and 5.0 or less (requirement (III)). When the weight ratio is within this range, a sufficient and appropriate amount of oil (C) is discharged onto the surface of the molded product, and separation properties are developed, making it possible to avoid processing troubles such as idling in the screws of the kneading machine.
　本発明のポリオレフィン系樹脂組成物を含む包装容器において、充填される水分含有内容物は、特に制限されるものではないが、一般的には、粘稠なペースト乃至スラリー状の流動性物質（例えば２５℃での粘度が１００ｍＰａ・ｓ以上のもの）、具体的には、ケチャップ、水性糊、蜂蜜、各種ソース類、マヨネーズ、カロリーオフマヨネーズ、マスタード、ジャム、チョコレートシロップ、乳液等の化粧液、液体洗剤、シャンプー、リンスなどが内容物として好適である。即ち、本発明では、このような粘稠な流動物質であっても、容器を傾倒或いは倒立させることにより、容器の内面に付着残存させることなく、速やかに排出することができるからである。 In the packaging container containing the polyolefin resin composition of the present invention, the water-containing content to be filled is not particularly limited, but is generally a fluid substance in the form of a viscous paste or slurry (e.g. Products with a viscosity of 100 mPa・s or more at 25°C), specifically cosmetics and liquids such as ketchup, water-based glue, honey, various sauces, mayonnaise, low-calorie mayonnaise, mustard, jam, chocolate syrup, and milky lotion. Detergents, shampoos, conditioners, etc. are suitable as contents. That is, in the present invention, even such a viscous fluid substance can be quickly discharged without remaining attached to the inner surface of the container by tilting or inverting the container.
　また、本発明のポリオレフィン系樹脂組成物を含む包装容器の内容物は、オイル（Ｃ）の選択の幅が大きいことから、特に水分を多く含むもの、例えばケチャップ、各種ソース類、蜂蜜、マヨネーズ、カロリーオフマヨネーズ、マスタード、ジャム、チョコレートシロップ、乳液などが好ましい。 In addition, since there is a wide range of oil (C) to choose from, the contents of the packaging container containing the polyolefin resin composition of the present invention are particularly suitable for contents containing a large amount of water, such as ketchup, various sauces, honey, mayonnaise, Calorie-free mayonnaise, mustard, jam, chocolate syrup, milky lotion, etc. are preferred.
　ここで、「カロリーオフマヨネーズ」とは、一般に、油分が６５％未満のマヨネーズ様食品のことを指し、成分として、乳化剤や増粘剤（例えば、ペクチン、デンプン、増粘多糖類、キサンタンガム等）が添加されているマヨネーズ様食品として知られている。 Here, "calorie-off mayonnaise" generally refers to a mayonnaise-like food with an oil content of less than 65%, and includes emulsifiers and thickeners (e.g., pectin, starch, polysaccharide thickener, xanthan gum, etc.) as ingredients. It is known as a mayonnaise-like food with added .
　本発明の成形体は、本発明のポリオレフィン系樹脂組成物を含む成形体である。
成形体としては積層体が挙げられ、その積層体の最内層として本発明のポリオレフィン系樹脂組成物を含む層を有する積層体が挙げられる。
　また、積層体のいずれか１層がガスバリア層である積層体が挙げられ、そのガスバリア層にエチレン・ビニルアルコール樹脂を含む積層体が挙げられる。
　そして、積層体としては多層ボトル、多層フィルムが挙げられる。
　さらに、本発明の積層体の例として、多層押出成形体が挙げられる。 The molded article of the present invention is a molded article containing the polyolefin resin composition of the present invention.
Examples of the molded body include a laminate, and examples thereof include a laminate having a layer containing the polyolefin resin composition of the present invention as the innermost layer of the laminate.
Further, there may be mentioned a laminate in which one of the layers is a gas barrier layer, and a laminate in which the gas barrier layer contains ethylene/vinyl alcohol resin can be mentioned.
Examples of the laminate include a multilayer bottle and a multilayer film.
Further, an example of the laminate of the present invention is a multilayer extrusion molded product.
　多層押出成形体には、必要に応じて他の樹脂層を設けてもよい。設けてもよい他の樹脂層としては、例えば、酸素等の気体の透過防止を目的とするエチレン－ビニルアルコール共重合体、ビニルアルコール重合体、エチレン・酢酸ビニル共重合体の鹸化物、酢酸ビニル共重合体の鹸化物等を含有する層、層同士の接着の向上を目的とする接着層や、押出成形体の再生物等を用いた層が挙げられる。 The multilayer extrusion molded product may be provided with other resin layers as necessary. Other resin layers that may be provided include, for example, ethylene-vinyl alcohol copolymers, vinyl alcohol polymers, saponified ethylene-vinyl acetate copolymers, and vinyl acetate for the purpose of preventing the permeation of gases such as oxygen. Examples include a layer containing a saponified copolymer, an adhesive layer for the purpose of improving adhesion between layers, and a layer using recycled extrusion products.
　多層押出成形体の成形方法は、特に制限されるものではなく、通常の押出成形機を用いる成形方法である。押出成形機としては、例えば、インフレーションフィルム製造装置、Ｔダイキャストフィルム製造装置、ブロー成形機、チューブ成形機等が挙げられる。 The method of molding the multilayer extrusion molded product is not particularly limited, and may be a molding method using a normal extrusion molding machine. Examples of the extrusion molding machine include a blown film manufacturing device, a T-die cast film manufacturing device, a blow molding machine, a tube molding machine, and the like.
　多層押出成形体の成形方法における多層成形の方法としては、本発明のポリオレフィン系樹脂組成物およびその他の樹脂を共押出する方法（共押出法という）、押出コーティングする方法(押出コーティング法または押出ラミネート法という)等が挙げられる。 Examples of the multilayer molding method in the multilayer extrusion molding method include a method of coextruding the polyolefin resin composition of the present invention and other resins (referred to as coextrusion method), a method of extrusion coating (extrusion coating method or extrusion lamination). law), etc.
　以下、実施例および比較例によって、本発明をより詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
　＜測定方法＞
　実施例および比較例での各項目の測定値は、次の方法に従って測定した。 <Measurement method>
The measured values of each item in Examples and Comparative Examples were measured according to the following method.
（1）吸油量（単位：ｍＬ／１００ｇ）
　ISO 787-5:1980（General　methods　of　test　for　pigments　and　extenders―Part　5：Determination　of　oil　absorption　value）に基づいて測定した値を用いた。 (1) Oil absorption amount (unit: mL/100g)
A value measured based on ISO 787-5:1980 (General methods of test for pigments and extenders-Part 5: Determination of oil absorption value) was used.
（2）溶解度パラメーター（単位：ＭＰａ１／２）
　コンピュータソフトウェアＨａｎｓｅｎ 　Ｓｏｌｕｂｉｌｉｔｙ 　Ｐａｒａｍｅｔｅｒ 　ｉｎ 　Ｐｒａｃｔｉｃｅ（ＨＳＰｉＰ）ｖｅｒ５．４．０１によって算出した値を用いた。 (2) Solubility parameter (unit: MPa 1/2 )
Values calculated using the computer software Hansen Solubility Parameter in Practice (HSPiP) ver. 5.4.01 were used.
　＜評価方法＞
（1）加工性
　バンバリーミキサーにて混練中、オイル成分の漏出が確認されたもの、およびバンバリーミキサーのローター部で空転が生じ混練が不可であったものを×評価とした。上述のような不具合が発生せずに混練が可能であったものを○評価とした。 <Evaluation method>
(1) Processability Those in which leakage of oil components was confirmed during kneading in the Banbury mixer, and those in which idling occurred in the rotor of the Banbury mixer and kneading was impossible were rated x. Those in which kneading was possible without the occurrence of the above-mentioned problems were given a rating of ○.
（2）身離れ性
　作製したプレスシート表面に身離れ性評価試料として（１）カロリーオフタイプマヨネーズＡ、（２）カロリーオフタイプマヨネーズＢ、（３）お好み焼き用ソースＡ、（４）コンディショナーＡをそれぞれ0.2ｇずつ滴下した後、プレスシートを垂直に立てて10分間静置し各試料の滑落挙動を観察した。10分後、滴下位置に試料が残存していないものを○評価、液滴が滑落したが滴下位置に残留分が確認できるものを△評価、液滴が滑落しなかったものを×評価とした。
　評価試料は以下のものを用いた。
（１）カロリーオフタイプのマヨネーズＡ：脂質の重量比率が20重量％以上30重量％未満の範囲であるカロリーオフタイプマヨネーズ
（２）カロリーオフタイプのマヨネーズＢ：脂質の重量比率が30重量％以上40重量％以下の範囲であるカロリーオフタイプマヨネーズ
（３）お好み焼き用ソースＡ：JAS規格に定められている濃厚ソース（一般名称：お好み焼き用ソース）
（４）コンディショナーＡ：グリチルリチン酸ジカリウム、および、水を主成分とするコンディショナー (2) Separation properties As samples for evaluation of separation properties, (1) calorie-off type mayonnaise A, (2) calorie-off type mayonnaise B, (3) okonomiyaki sauce A, and (4) conditioner A were placed on the surface of the prepared press sheet. After dropping 0.2 g of each sample, the press sheet was stood vertically and allowed to stand for 10 minutes, and the sliding behavior of each sample was observed. After 10 minutes, a sample with no sample remaining at the droplet position was evaluated as ○, a droplet slipped but a sample remained at the droplet position was confirmed with a △ rating, and a droplet did not slide down with a × rating. .
The following evaluation samples were used.
(1) Calorie-off type mayonnaise A: Calorie-off type mayonnaise with a fat weight ratio of 20% to 30% by weight (2) Calorie-off type mayonnaise B: Fat weight ratio of 30% by weight or more Calorie-off type mayonnaise with a content of 40% by weight or less (3) Okonomiyaki sauce A: Rich sauce specified by JAS standards (general name: Okonomiyaki sauce)
(4) Conditioner A: Conditioner whose main ingredients are dipotassium glycyrrhizinate and water.
＜原料＞
ポリオレフィン系樹脂（Ａ）として、下記を用いた。
（Ａ－１）　ポリエチレン：　スミカセン（登録商標）Ｆ１０８－１（住友化学株式会社製、製造方法：高圧ラジカル重合法、エチレンに由来する単量体単位：１００モル％、密度：９２１ｋｇ／ｍ３、ＭＦＲ：０．６ｇ／１０分）
（Ａ－２）　ポリエチレン：　スミカセンＥ　ＭＢ　ＣＭＢ－７３５（住友化学株式会社製、酸化防止剤マスターバッチ） <Raw materials>
The following was used as the polyolefin resin (A).
(A-1) Polyethylene: Sumikasen (registered trademark) F108-1 (manufactured by Sumitomo Chemical Co., Ltd., manufacturing method: high-pressure radical polymerization method, monomer unit derived from ethylene: 100 mol%, density: 921 kg/m 3 , MFR: 0.6g/10min)
(A-2) Polyethylene: Sumikasen E MB CMB-735 (manufactured by Sumitomo Chemical Co., Ltd., antioxidant masterbatch)
フィラー（Ｂ）として、下記を用いた。
（Ｂ－１）　非晶質シリカ：　サイリシア４３０（富士シリシア化学株式会社製、吸油量２２６ｍＬ／１００ｇ）
（Ｂ－２）　非晶質シリカ：　サイロホービック１２０（富士シリシア化学株式会社製、吸油量２３２ｍＬ／１００ｇ）
（Ｂ－３）　非晶質シリカ：　サイロホービック５０５（富士シリシア化学株式会社製、吸油量１０５ｍＬ／１００ｇ）
（Ｂ－４）　シリカ：　Ｇａｓｉｌ 　ＡＢ９０５（ＰＱコーポレーション株式会社製、吸油量３６ｍＬ／１００ｇ） The following was used as the filler (B).
(B-1) Amorphous silica: Silicia 430 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 226 mL/100 g)
(B-2) Amorphous silica: Cyrophobic 120 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 232 mL/100 g)
(B-3) Amorphous silica: Cyrophobic 505 (manufactured by Fuji Silicia Chemical Co., Ltd., oil absorption 105 mL/100 g)
(B-4) Silica: Gasil AB905 (manufactured by PQ Corporation, oil absorption 36mL/100g)
オイル（Ｃ）として、下記を用いた。
（Ｃ－１）　グリセリン脂肪酸エステル：　ココナードＭＴ（成分名：脂肪酸トリグリセリド（（カプリル酸・カプリン酸）トリグリセリド）、ＨＳＰ値：１７．１ＭＰａ１／２、花王株式会社製）
（Ｃ－２）　シリコーンオイル：　ＫＦ－９６ＡＤＦ-１００ｃｓ（成分名：ポリジメチルシロキサン、ＨＳＰ値：１４．９ＭＰａ１／２、信越化学工業株式会社製）
（Ｃ－３）　グリセリン脂肪酸エステル：　ホモテックスＰＴ（成分名：脂肪酸モノグリセリド（モノカプリル酸グリセリド）、ＨＳＰ値：２１．３ＭＰａ１／２、花王株式会社製） The following oil was used as the oil (C).
(C-1) Glycerin fatty acid ester: Coconade MT (ingredient name: fatty acid triglyceride ((caprylic acid/capric acid) triglyceride), HSP value: 17.1 MPa 1/2 , manufactured by Kao Corporation)
(C-2) Silicone oil: KF-96ADF-100cs (component name: polydimethylsiloxane, HSP value: 14.9 MPa 1/2 , manufactured by Shin-Etsu Chemical Co., Ltd.)
(C-3) Glycerin fatty acid ester: Homotex PT (ingredient name: fatty acid monoglyceride (monocaprylic acid glyceride), HSP value: 21.3 MPa 1/2 , manufactured by Kao Corporation)
＜成形方法＞
　実施例１から１５および比較例１～３に示す評価用試料は下記の手順によって作製した。 <Molding method>
Evaluation samples shown in Examples 1 to 15 and Comparative Examples 1 to 3 were prepared by the following procedure.
混練、造粒
　［表１］に記載の比率でポリオレフィン系樹脂（Ａ）、フィラー（Ｂ）、オイル（Ｃ）を混合後、バンバリーミキサーを用い、温度１５０℃で均一に混練し、樹脂組成物を得た。該樹脂組成物を６５ｍｍ径のスクリューを有する単軸押出機を用い、温度１８０℃、回転数３０ｒｐｍにて造粒し樹脂組成物のペレットを得た。 Kneading and granulation After mixing the polyolefin resin (A), filler (B), and oil (C) in the ratios listed in Table 1, they were uniformly kneaded at a temperature of 150°C using a Banbury mixer to form a resin composition. I got it. The resin composition was granulated using a single screw extruder having a screw with a diameter of 65 mm at a temperature of 180° C. and a rotation speed of 30 rpm to obtain pellets of the resin composition.
プレスシート作製
　上記で得られたペレットを、１５０℃で５分間静置し（予熱工程）、１５０℃、５ＭＰａで５分間加圧し（プレス工程）、２５℃で５分間徐冷し（徐冷工程）、厚み１．０ｍｍのプレスシートを得た。 Preparation of press sheet The pellets obtained above were left standing at 150°C for 5 minutes (preheating step), pressurized at 150°C and 5 MPa for 5 minutes (pressing step), and slowly cooled at 25°C for 5 minutes (slow cooling step). ), a pressed sheet with a thickness of 1.0 mm was obtained.
評価
　上記で得られたプレスシートを用いて、加工性及び身離れ性を評価した。評価結果を［表１］に示す。 Evaluation Using the press sheet obtained above, processability and detachability were evaluated. The evaluation results are shown in [Table 1].
　評価は、以下の判断基準に従って実施した。
加工性の判断基準
　○：混練(バンバリーミキサー)時のオイル漏れ、空転が無い。
　×：オイル漏れ、空転がある。（身離れ評価は実施しない。） The evaluation was conducted according to the following criteria.
Processability Judgment Criteria ○: No oil leakage or idling during kneading (Banbury mixer).
×: There is oil leakage and idling. (A separate evaluation will not be conducted.)
身離れの判断基準
　〇：滴下位置から試料が全て流れ落ちた。
　△：滴下位置に試料が一部(半分以下)残存した。
　×：滴下位置に試料が(半分以上)残存、または滑落しなかった。 Judgment criteria for separation 〇: All the sample has flowed down from the dropping position.
Δ: Part of the sample (less than half) remained at the dropping position.
×: The sample (more than half) remained at the dropping position or did not slide down.
発明の効果有無の基準
　加工性○かつ、身離れのいずれかに○が付いたら、本発明の効果ありと判断。 Standards for determining whether the invention is effective : If either workability or detachment is marked ○, it is determined that the invention is effective.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (9)

  1. 　ポリオレフィン系樹脂（Ａ）を２重量％以上９８．９重量％以下と、
    フィラー（Ｂ）を０．１重量％以上４９重量％以下と、
    オイル（Ｃ）を１．０重量％以上４９重量％以下と、を含有し（ただし、（Ａ）と（Ｂ）と（Ｃ）の合計を１００重量％とする）、
    フィラー（Ｂ）のＩＳＯ　７８７－５：１９８０に基づいて測定された吸油量が４０ｍＬ／１００ｇ以上５００ｍＬ／１００ｇ以下であり（要件（Ｉ））、
    オイル（Ｃ）のハンセンの溶解度パラメーター（ＨＳＰ値）が１０ＭＰａ１／２以上３６ＭＰａ１／２以下であり（要件（ＩＩ））、
    フィラー（Ｂ）の重量に対するオイル（Ｃ）の重量の重量比（オイル（Ｃ）／フィラー（Ｂ）、単位：重量／重量）が０．２以上１０．０以下である（要件（ＩＩＩ））、
    ポリオレフィン系樹脂組成物。     2% by weight or more and 98.9% by weight or less of polyolefin resin (A),
    The filler (B) is 0.1% by weight or more and 49% by weight or less,
    Contains 1.0% by weight or more and 49% by weight or less of oil (C) (however, the total of (A), (B), and (C) is 100% by weight),
    The oil absorption amount of the filler (B) measured based on ISO 787-5:1980 is 40 mL/100 g or more and 500 mL/100 g or less (requirement (I)),
    The Hansen solubility parameter (HSP value) of the oil (C) is 10 MPa 1/2 or more and 36 MPa 1/2 or less (requirement (II)),
    The weight ratio of the weight of oil (C) to the weight of filler (B) (oil (C)/filler (B), unit: weight/weight) is 0.2 or more and 10.0 or less (requirement (III)) ,
    Polyolefin resin composition.
  2. 　オイル（Ｃ）が、シリコーンオイル、グリセリン脂肪酸エステル、流動パラフィン、食用油脂、アルコール、及び、多価アルコールからなる群から選ばれる少なくとも１種である、請求項１に記載のポリオレフィン系樹脂組成物。 The polyolefin resin composition according to claim 1, wherein the oil (C) is at least one selected from the group consisting of silicone oil, glycerin fatty acid ester, liquid paraffin, edible oil and fat, alcohol, and polyhydric alcohol.
  3. 　フィラー（Ｂ）が、酸化チタン、炭酸カルシウム、アルミナ、シリカ、珪藻土、酸化鉄、フェライト、ゼオライト、タルク、ウォラストナイト、マイカ、及び、クレーからなる群から選ばれる少なくとも１種である、請求項１に記載のポリオレフィン系樹脂組成物。 A claim in which the filler (B) is at least one member selected from the group consisting of titanium oxide, calcium carbonate, alumina, silica, diatomaceous earth, iron oxide, ferrite, zeolite, talc, wollastonite, mica, and clay. 1. The polyolefin resin composition according to 1.
  4. 　請求項１から３のいずれか１項に記載のポリオレフィン系樹脂組成物を含む成形体。 A molded article comprising the polyolefin resin composition according to any one of claims 1 to 3.
  5. 　積層体であって、最内層として、請求項１から３のいずれか１項に記載のポリオレフィン系樹脂組成物を含む層を有する積層体。 A laminate having a layer containing the polyolefin resin composition according to any one of claims 1 to 3 as the innermost layer.
  6. 　積層体のいずれか１層がガスバリア層である、請求項５に記載の積層体。 The laminate according to claim 5, wherein any one layer of the laminate is a gas barrier layer.
  7. 　ガスバリア層にエチレン・ビニルアルコール樹脂を含む、請求項６に記載の積層体。 The laminate according to claim 6, wherein the gas barrier layer contains ethylene/vinyl alcohol resin.
  8. 　積層体が多層ボトルである、請求項５から７のいずれか１項に記載の積層体。 The laminate according to any one of claims 5 to 7, wherein the laminate is a multilayer bottle.
  9. 　積層体が多層フィルムである、請求項５から７のいずれか１項に記載の積層体。 The laminate according to any one of claims 5 to 7, wherein the laminate is a multilayer film.
PCT/JP2023/028455 2022-08-08 2023-08-03 Polyolefin resin composition, molded body, and laminate WO2024034519A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008081719A (en) * 2006-08-30 2008-04-10 Kansai Paint Co Ltd Top coat composition
WO2015012358A1 (en) * 2013-07-26 2015-01-29 東洋製罐グループホールディングス株式会社 Resin structure having liquid layer on surface thereof
JP2017001204A (en) * 2015-06-05 2017-01-05 凸版印刷株式会社 Packaging film and package
WO2017006906A1 (en) * 2015-07-09 2017-01-12 東洋製罐グループホールディングス株式会社 Container in which inner surface is formed from olefin-based resin layer
JP2018123174A (en) * 2017-01-30 2018-08-09 三井化学株式会社 Resin composition and molded body of the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008081719A (en) * 2006-08-30 2008-04-10 Kansai Paint Co Ltd Top coat composition
WO2015012358A1 (en) * 2013-07-26 2015-01-29 東洋製罐グループホールディングス株式会社 Resin structure having liquid layer on surface thereof
JP2017001204A (en) * 2015-06-05 2017-01-05 凸版印刷株式会社 Packaging film and package
WO2017006906A1 (en) * 2015-07-09 2017-01-12 東洋製罐グループホールディングス株式会社 Container in which inner surface is formed from olefin-based resin layer
JP2018123174A (en) * 2017-01-30 2018-08-09 三井化学株式会社 Resin composition and molded body of the same

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