WO2013084707A1 - Resin composition, and packaging film and method for producing same - Google Patents

Resin composition, and packaging film and method for producing same Download PDF

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Publication number
WO2013084707A1
WO2013084707A1 PCT/JP2012/079965 JP2012079965W WO2013084707A1 WO 2013084707 A1 WO2013084707 A1 WO 2013084707A1 JP 2012079965 W JP2012079965 W JP 2012079965W WO 2013084707 A1 WO2013084707 A1 WO 2013084707A1
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WIPO (PCT)
Prior art keywords
vegetable oil
resin composition
epoxidized vegetable
acid
mass
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PCT/JP2012/079965
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French (fr)
Japanese (ja)
Inventor
保 西澤
田中　一也
高木　潤
藤田　篤志
智 今中
Original Assignee
三菱樹脂株式会社
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Priority claimed from JP2011269764A external-priority patent/JP2013119623A/en
Priority claimed from JP2011269763A external-priority patent/JP2013119622A/en
Priority claimed from JP2011269765A external-priority patent/JP2013119624A/en
Priority claimed from JP2012047473A external-priority patent/JP2013181148A/en
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Publication of WO2013084707A1 publication Critical patent/WO2013084707A1/en

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    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a resin composition, which is a resin composition containing a thermoplastic resin and a specific plasticizer, and particularly suitable for molding soft materials such as food packaging films, table mats, and dicing tapes. Related to things. Moreover, this invention relates to the film for packaging which uses said resin composition as a raw material, and its industrially advantageous manufacturing method.
  • thermoplastic resins such as vinyl chloride resins and olefin resins have been used as the main material of soft materials.
  • various plasticizers are usually added to the resin in order to develop the soft properties required for the product.
  • these plasticizers are low molecular weight and low boiling point components, they tend to bleed out on the surface of the molded product, and measures for preventing bleed out are being studied.
  • an isocyanate compound having an average functional group number of more than 2 and a polyol of 30 to 150 parts by weight, a polyol of 1 to 8 parts by weight with respect to 100 parts by weight of a vinyl chloride resin There has been proposed a soft vinyl chloride resin composition obtained by adding an isocyanate group such that the ratio of isocyanate group / hydroxyl group in an isocyanate compound is 0.3 to 1.3, and heating and melting and mixing under a shearing force (for example, patents) Reference 1).
  • an object of the present invention is to provide a new resin composition capable of sufficiently preventing bleeding out of a plasticizer while exhibiting desired soft characteristics.
  • Another object of the present invention is to provide a packaging film using the above-mentioned new resin composition as a raw material and an industrially advantageous production method thereof.
  • the present invention comprises a group of related inventions, and the gist of each invention is as follows.
  • a first gist of the present invention is a resin composition comprising 20 to 60 parts by mass of a modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass based on 100 parts by mass of a thermoplastic resin.
  • the second gist of the present invention resides in a packaging film comprising the above resin composition.
  • the third gist of the present invention is a method for producing a packaging film using the above resin composition as a raw material, wherein the resin composition contains a thermoplastic resin, an epoxidized vegetable oil, and an active hydrogen-containing compound.
  • a process for producing a packaging film comprising a step of preparing a modified epoxidized vegetable oil by a reaction between an epoxidized vegetable oil and an active hydrogen-containing compound in the thermoforming step.
  • the fourth gist of the present invention is a method for producing a packaging film using the above resin composition as a raw material, and is a epoxidation thermoplastic resin having a peroxide value of 13.1-18.0 meq / kg.
  • the manufacturing method of the film for packaging characterized by including the thermoforming process of the resin composition containing a vegetable oil, modifying
  • the present invention it is possible to sufficiently prevent bleeding out of a plasticizer while expressing desired soft characteristics, and to produce soft material products such as a table mat and a dicing tape in addition to a food packaging film.
  • a resin composition suitable for is provided.
  • the film for packaging which uses said resin composition as a raw material, and its industrially advantageous manufacturing method are provided.
  • the resin composition of the present invention contains a thermoplastic resin and a modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass as essential components.
  • thermoplastic resin Since the thermoplastic resin is excellent in compatibility with the modified epoxidized vegetable oil, the thermoplastic resin is preferably a polar thermoplastic resin.
  • the thermoplastic resin having polarity include polyester resins, polystyrene resins, chlorine-containing resins, fluorine-containing resins, polyamide resins, polyimide resins, polyamideimide resins, polyarylate resins, polyurethane resins, and polyureas. Resin, acrylic resin, ether resin and the like. You may use these in combination of 2 or more type. Among these, a chlorine-containing resin or a polyester-based resin is particularly preferable because of compatibility with the modified epoxidized vegetable oil and excellent bleed resistance.
  • the chlorine-containing resin is not particularly limited, and preferable examples include vinyl chloride resins, chlorinated vinyl chloride resins, and vinylidene chloride resins. Among these, a vinyl chloride resin is particularly preferable.
  • vinyl chloride resin in addition to a vinyl chloride homopolymer, a copolymer with a monomer copolymerizable with vinyl chloride (hereinafter referred to as a vinyl chloride copolymer), this vinyl chloride copolymer
  • a vinyl chloride copolymer examples thereof include a graft copolymer obtained by graft-copolymerizing vinyl chloride to a polymer other than the polymer (hereinafter referred to as vinyl chloride-based graft copolymer). Since the mechanical properties of the vinyl chloride copolymer decrease as the content of constituent units other than vinyl chloride in the copolymer increases, the proportion of vinyl chloride in the vinyl chloride copolymer is usually 60%. ⁇ 99% by mass.
  • the vinyl chloride homopolymer and the vinyl chloride copolymer can be polymerized by an arbitrary method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method and the like.
  • the monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule, for example, ⁇ -olefins such as ethylene, propylene, butylene; vinyl acetate, vinyl propionate, etc.
  • Vinyl esters such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate and phenyl methacrylate; styrene Aromatic vinyls such as ⁇ -methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. You may use these in combination of 2 or more type.
  • the polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate / carbon monoxide copolymer, Ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated Examples include polypropylene. You may use these in combination of 2 or more type.
  • the average degree of polymerization of the vinyl chloride resin is usually 800 to 1,400. If the average degree of polymerization is 800 or more, sufficient mechanical strength can be obtained. On the other hand, if the average degree of polymerization is 1,400 or less, heat generation due to an increase in melt viscosity does not occur, and the occurrence of coloring due to decomposition can be eliminated. Therefore, from this viewpoint, the average degree of polymerization of the vinyl chloride resin is preferably 900 to 1,350, more preferably 1,000 to 1,300.
  • the polyester resin is not particularly limited, and examples thereof include aromatic polyester resins, aliphatic polyester resins, aliphatic-aromatic polyester resins, and the like. Among these, an adipic acid ester compound, a sebacic acid ester compound, a succinic acid ester compound, and a polyester polyol are particularly preferable because of compatibility with epoxidized vegetable oil and excellent bleed resistance.
  • epoxidized vegetable oil (Modified epoxidized vegetable oil) Specific examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil, epoxidized fatty acid ester, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, and epoxidized castor oil. You may use these in combination of 2 or more type.
  • Epoxidized vegetable oil is basically composed of monomers, but forms a multimer by a modification reaction in which an epoxy group is ring-opened.
  • epoxidized vegetable oil may contain a trace amount of dimer or higher multimer due to various factors, and the content thereof is usually 4% by mass or less, preferably based on the total mass of the epoxidized vegetable oil. Is 2% by mass or less.
  • the modified epoxidized vegetable oil used in the present invention has a multimer content of 5 to 65% by mass. In this case, the proportion of the monomer is 95 to 35% by mass.
  • the multimer content is in the above range, both the plasticization of the thermoplastic resin with the modified epoxidized vegetable oil and the bleed resistance of the modified epoxidized vegetable oil can be achieved. That is, when the ratio of the multimer is 65% by mass or less, the thermoplastic resin is sufficiently plasticized and excellent flexibility can be obtained. On the other hand, if the ratio of the multimer is 5% by mass or more, the bleed-out amount of the modified epoxidized vegetable oil can be sufficiently suppressed.
  • the multimer content is preferably 5 to 60% by mass, more preferably 6 to 60% by mass. The method for measuring the multimer content will be described in Examples below.
  • Examples of the modification reaction used for adjusting the multimer content include (i) a modification reaction using an active hydrogen-containing compound, (ii) a modification reaction using a peroxide group of an epoxidized vegetable oil, (i) and Examples include a denaturation reaction combining (ii). And if said modification
  • Active hydrogen-containing compounds include compounds having various reactive functional groups such as compounds having a carboxyl group, such as acids, compounds having a hydroxyl group, compounds having an amino group, and acid anhydrides (“modified compounds”). "). In these, an acid is preferable from a viewpoint of the ease of the ring-opening reaction of an epoxy group.
  • acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, etc.
  • Saturated carboxylic acid Saturated carboxylic acid; unsaturated carboxylic acid such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, sorbic acid, docosahexaenoic acid, eicosapentaenoic acid; hydroxy acid such as lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, Aromatic carboxylic acids such as isophthalic acid, terephthalic acid and salicylic acid; and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid and maleic acid.
  • unsaturated carboxylic acid such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, sorbic acid, docosahexaenoic acid, eicosapentaenoic acid
  • hydroxy acid such
  • carboxylic acid derivatives such as oxocarboxylic acid, aconitic acid, amino acid, nitrocarboxylic acid and the like. You may use these in combination of 2 or more type.
  • unsaturated carboxylic acid, dicarboxylic acid, and tricarboxylic acid are preferable from the viewpoint of reactivity with epoxidized vegetable oil, and dicarboxylic acid is particularly preferable.
  • Epoxidized vegetable oil obtained by a method of epoxidizing vegetable oil using hydrogen peroxide as an oxidizing agent has a high peroxide group content (for example, 20 to 40). It can be reduced by heat treatment under reduced pressure.
  • Various epoxidized vegetable oils having different peroxide values are commercially available. The method for measuring the peroxide value will be described in the examples below.
  • the peroxide value of the epoxidized vegetable oil used in the present invention is generally 13.1-18.0 meq / kg, preferably 13.3-17.5 meq / kg, more preferably 13.5- 17.0 meq / kg.
  • the peroxide value of the epoxidized vegetable oil is less than 13.1 meq / kg, there are few peroxide groups in the epoxidized vegetable oil, and sufficient multimerization is achieved at the time of melt-kneading in the thermoplastic resin. Is difficult.
  • the peroxide value exceeds 18.0 milliequivalents / kg, for example, the odor when formed into a film is severe and it may be difficult to use as a food packaging material.
  • the ratio of each component when using an active hydrogen-containing compound in the modification reaction of the epoxidized vegetable oil is as follows. That is, the active hydrogen-containing compound is usually 0.01 to 8 parts by mass, preferably 0.05 to 6 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the epoxidized vegetable oil.
  • the active hydrogen-containing compound in the above range a modified epoxidized vegetable oil particularly suitable for a vinyl chloride resin can be obtained, and a resin composition containing both is excellent in thermal stability, flexibility and bleed resistance.
  • the ratio of each component in the case of performing a modification reaction in a thermoplastic resin is as follows.
  • epoxidized vegetable oil is 20 to 60 parts by mass
  • active hydrogen-containing compound is 0.01 to 50 parts by mass, preferably 0.05 to 4 parts by mass, more preferably 0.1 to 100 parts by mass of the thermoplastic resin. ⁇ 3 parts by mass.
  • the proportion of the modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass is 20 to 60 parts by mass, preferably 25 to 55 parts by mass, more preferably 100 parts by mass of the thermoplastic resin.
  • the amount is preferably 30 to 50 parts by mass.
  • the reaction temperature for the modification reaction of the epoxidized vegetable oil is usually 100 to 220 ° C., and the reaction time is usually 10 minutes to 2 hours.
  • the reaction temperature is usually 180 to 220 ° C., preferably 185 to 215 ° C., and the reaction time is usually 30 seconds to 3 minutes. Therefore, when a raw material resin composition containing necessary components is extruded to produce a film, the modification reaction of the epoxidized vegetable oil can be completed within the normal residence time of the extrusion process.
  • an antifogging agent a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, an antistatic agent, a lubricant, Additives such as pigments and dyes can be blended.
  • the above-mentioned necessary components are used, for example, a method of mixing by a mixer such as a V-type blender, a ribbon blender, a Henschel mixer, an extruder, a mixing roll, a Banbury mixer, a kneader.
  • a mixer such as a V-type blender, a ribbon blender, a Henschel mixer, an extruder, a mixing roll, a Banbury mixer, a kneader.
  • a method of kneading with a kneader such as the above
  • a method of mixing and kneading by combining a mixer and a kneader are examples thereof.
  • the resin composition of the present invention suppresses bleeding out of the modified epoxidized vegetable oil by the action of the multimer, particularly the dimer contained in the modified epoxidized vegetable oil, and is excellent in flexibility.
  • the composition containing the thermoplastic resin, the epoxidized vegetable oil, and the active hydrogen-containing compound has a low viscosity in the initial state before heating and is easy to mold, or is mixed uniformly. Is easy. And when this is heated, the epoxidized vegetable oil reacts with the active hydrogen-containing compound, and the modified epoxidized vegetable oil in which the content of the dimer, and possibly the trimer or higher is higher than the epoxidized vegetable oil Produces.
  • the packaging film of the present invention comprises the above resin composition and can be obtained by a known molding method such as a T-die method or an inflation method.
  • a known molding method such as a T-die method or an inflation method.
  • the method of modifying the epoxidized vegetable oil in the thermoplastic resin in the extrusion process is recommended as a simple method for producing a packaging film comprising the resin composition of the present invention.
  • thermoplastic resin is used as the resin composition of the present invention. It is a vinyl chloride resin, and further contains a polyester compound having a weight average molecular weight of 3,000 to 10,000, and the content ratio of the polyester compound with respect to 100 parts by mass of the vinyl chloride resin is 1 to 30 masses. It is preferable to use a resin composition that is part. The reason is as follows.
  • the modified epoxidized vegetable oil obtained by polymerizing the epoxidized vegetable oil is used as the plasticizer instead of the epoxidized vegetable oil.
  • Foods with excellent safety and flexibility and heat stability, which can suppress the bleed-out amount of modified epoxidized vegetable oil to isooctane measured by the evaporation residue test method (single-sided method) A packaging film can be provided.
  • the polyester compound used in the present invention has a weight average molecular weight of 3,000 to 10,000. If the weight average molecular weight is 3,000 or more, bleeding out of the polyester compound can be suppressed, which is preferable for safety. On the other hand, if the weight average molecular weight is 10,000 or less, the compatibility with the vinyl chloride resin is good, the occurrence of bleeding out to the surface of the molded product can be suppressed, and a sufficient plasticizing effect can be obtained. .
  • the weight average molecular weight of the polyester compound is preferably 4,000 to 9,000, and more preferably 5,000 to 8,000.
  • polyester compounds include adipic acid ester compounds, sebacic acid ester compounds, succinic acid ester compounds, polyester polyols, and the like. In these, since it is excellent in compatibility with vinyl chloride resin, an adipate ester compound, polyester polyol, or a mixture thereof is preferable.
  • adipic acid ester compound examples include a reaction product of adipic acid and a dihydric alcohol.
  • adipic acid ester compounds include, for example, poly (propylene glycol / adipic acid) ester, poly (1,3-butanediol / adipic acid) ester, poly (1,4-butanediol / adipic acid) ester , Poly (ethylene glycol / adipic acid) ester, poly (1,6-hexanediol / butanediol / adipic acid) ester, poly (butanediol / ethylene glycol / adipic acid) ester, poly (ethylene glycol / propylene glycol / butane) Diol / adipic acid) ester and the like.
  • poly (1,3-butanediol / adipic acid) ester or poly (1,4-butanediol / adipic acid) ester because of excellent compatibility with vinyl chloride resin and bleed resistance. Or a mixture of these.
  • the dihydric alcohol is not particularly limited.
  • ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like are used. You may use it in combination.
  • polyester polyol examples include those obtained by polycondensation of an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid and a dihydric alcohol.
  • aliphatic dicarboxylic acid examples include succinic acid, adipic acid, sebacic acid, glutaric acid, and azelaic acid.
  • aromatic dicarboxylic acid examples include isophthalic acid and terephthalic acid.
  • ethylene glycol diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentadiol, neopentyl glycol, 1,4-dihydroxymethylcyclohexane, etc. Is mentioned.
  • polyester polyol examples include, for example, polyethylene adipate diol, polybutylene adipate diol, pohexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate Diol etc. are mentioned.
  • polyneopentyl adipate diol is preferred because it is excellent in compatibility with vinyl chloride resin and bleed resistance.
  • the content of the polyester compound relative to 100 parts by mass of the vinyl chloride resin is 1 to 30 parts by mass, preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass.
  • a Ca—Zn stabilizer may be added to further improve the thermal stability of the packaging film.
  • the Ca—Zn stabilizer is a mixture of calcium fatty acid salt and zinc fatty acid salt.
  • fatty acids include behenic acid, stearic acid, lauric acid, oleic acid, palmitic acid, ricinoleic acid, benzoic acid and the like, and can be used in combination of two or more according to the purpose. From the viewpoint of moldability, stearates are preferred.
  • the ratio of calcium to zinc is usually 1: 2 to 1: 3 as a mass ratio. If the ratio of zinc is less than 2 relative to calcium, a redness peculiar to calcium salts will appear. On the other hand, if the ratio of zinc is greater than 3 relative to calcium, zinc chloride produced during molding will be vinyl chloride. It becomes a decomposition catalyst for the resin, and sudden blackening and decomposition called “zinc burn” occurs.
  • the addition amount of the Ca—Zn stabilizer is usually 0.1 to 2.0 parts by mass, preferably 0.3 to 1.8 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If it is 0.1 parts by mass or more, the effect of imparting thermal stability can be obtained, and if it is 2.0 parts by mass or more, rapid blackening and decomposition called “zinc burn” can be prevented. .
  • an ester compound of a polyhydric alcohol and a fatty acid may be blended in order to impart antifogging properties to the packaging film.
  • esters of polyhydric alcohol and fatty acid examples include monoglycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether and the like.
  • the monoglycerin fatty acid ester is preferably a monoglycerin ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include monoglycerol laurate, monoglycerol myristate, monoglycerol palmitate, monoglycerol stearate, monoglycerol oleate, and monoglycerol linoleate.
  • the polyglycerol fatty acid ester is preferably a polyglycerol ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol stearate, polyglycerol oleate, polyglycerol linoleate and the like.
  • the sorbitan fatty acid ester is preferably a saturated or unsaturated fatty acid sorbitan ester having 12 to 18 carbon atoms. Specifically, sorbitan laurate, sorbitan myristate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan linoleate and the like can be mentioned.
  • the polyoxyethylene alkyl ether is preferably a saturated alcohol polyoxyethylene alkyl ether having 12 to 18 carbon atoms, more preferably a polyoxyethylene alkyl ether having 3 to 7 added moles of ethylene oxide.
  • Specific examples include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether, and the like.
  • film refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) Industrial standard JISK6900), and in general, “sheet” refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • sheet refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width.
  • Odor Sensory evaluation is performed in a thermostatic chamber at 23 ° C. for the films prepared in Examples and Comparative Examples. Evaluation was made in the following two stages. A: The odor is not unpleasant or weak. B: The odor is unpleasant or strong.
  • Examples 1 to 5 and Comparative Examples 1 to 3 ⁇ Materials used> (1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050 (2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd. (3) Epoxidized soybean oil (4) Succinic acid (saturated dicarboxylic acid) (5) Oleic acid (saturated monocarboxylic acid) (6) Plasticizer (DOP: Dioctyl phthalate)
  • epoxidized soybean oil reacts with dicarboxylic acid or monocarboxylic acid by heating to 180-220 ° C. to form dimers, trimers and higher multimers. Confirmed to do. Therefore, it was confirmed that the modified epoxidized soybean oil was contained after the reaction.
  • epoxidized soybean oil does not contain an acid
  • Comparative Example 2 when only a plasticizer that is not an epoxidized vegetable oil is used (Comparative Example 2), and only an epoxidized soybean oil Is used (Comparative Example 3), modified epoxidized soybean oil is not produced.
  • Examples 6 to 10 and Comparative Examples 4 to 5 ⁇ Materials used> (1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050 (2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd. (3) Modified epoxidized soybean oil-1: Obtained by stirring and mixing 100 parts by mass of epoxidized soybean oil and 1.2 parts by mass of oleic acid at 200 ° C. for 1 hour. (4) Modified epoxidized soybean oil-2: obtained by reacting 100 parts by mass of epoxidized soybean oil and 6 parts by mass of oleic acid with stirring at 200 ° C. for 1 hour.
  • Modified epoxidized soybean oil-3 Obtained by stirring and mixing 100 parts by mass of epoxidized soybean oil and 1.2 parts by mass of succinic acid at 200 ° C. for 1 hour.
  • Epoxidized soybean oil (7) Polyester compound-1: DIC Corporation trade name “Polysizer W-360-EL” (poly (1,3-butanediol / adipic acid) ester, weight average molecular weight: 6,000) (8) Polyester compound-2: Trade name “Polylite OD-X-2044” of DIC Corporation (polyneopentyl adipate diol, weight average molecular weight: 6,800)
  • Examples 11 to 15 and Reference Examples 1 to 4 ⁇ Materials used> (1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050 (2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd.
  • Epoxidized soybean oil-4 Epoxidized soybean oil having a peroxide value of 13.3
  • Epoxidized soybean oil-5 Epoxidized soybean oil having a peroxide value of 15.1
  • Epoxidized soybean oil 6 Epoxidized soybean oil with a peroxide value of 10.1
  • Epoxidized soybean oil -7 Epoxidized soybean oil with a peroxide value of 18.6
  • Polyester compound Trade name “Polycizer” of DIC Corporation W-360-EL ”(poly (1,3-butanediol / adipic acid) ester, weight average molecular weight: 6,000)

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

Proposed is a novel resin composition which can exhibit a desired flexible property and, at the same time, does not undergo the bleeding out of a plasticizer therefrom. A resin composition produced by mixing 100 parts by mass of a thermoplastic resin with 20 to 60 parts by mass of a modified epoxidized plant oil containing a polymer at a content of 5 to 65 mass%.

Description

樹脂組成物、包装用フィルム及びその製造方法Resin composition, packaging film and method for producing the same
　本発明は、樹脂組成物に関し、熱可塑性樹脂と特定の可塑剤を含む樹脂組成物であって、特に、食品包装用フィルム、テーブルマット、ダイシングテープといった軟質材料を成形するのに適した樹脂組成物に関する。また、本発明は、上記の樹脂組成物を原料とする包装用フィルム及びその工業的に有利な製造方法に関する。 The present invention relates to a resin composition, which is a resin composition containing a thermoplastic resin and a specific plasticizer, and particularly suitable for molding soft materials such as food packaging films, table mats, and dicing tapes. Related to things. Moreover, this invention relates to the film for packaging which uses said resin composition as a raw material, and its industrially advantageous manufacturing method.
　食品包装用フィルムには、従来、塩化ビニル系樹脂やオレフィン系樹脂などの熱可塑性樹脂が軟質材料の主材として使用されてきた。この種の軟質材料においては、製品に要求される軟質特性を発現させるために、通常、樹脂に各種の可塑剤を添加することが行われている。しかし、これらの可塑剤は、低分子量かつ低沸点成分であることから、成形品の表面にブリードアウトし易いため、ブリードアウトを防止するための対策が検討されている。そして、その一つとして、塩化ビニル系樹脂１００重量部に対し、可塑剤３０重量部以上１５０重量部以下、ポリオール１重量部以上８重量部以下と平均官能基数が２を超えるイソシアネート化合物をポリオールとイソシアネート化合物におけるイソシアネート基／水酸基の比が０．３～１．３になるように添加し、剪断力下、加熱溶融混合して得られる軟質塩化ビニル系樹脂組成物が提案されている（例えば特許文献１）。 For food packaging films, thermoplastic resins such as vinyl chloride resins and olefin resins have been used as the main material of soft materials. In this type of soft material, various plasticizers are usually added to the resin in order to develop the soft properties required for the product. However, since these plasticizers are low molecular weight and low boiling point components, they tend to bleed out on the surface of the molded product, and measures for preventing bleed out are being studied. As one of them, an isocyanate compound having an average functional group number of more than 2 and a polyol of 30 to 150 parts by weight, a polyol of 1 to 8 parts by weight with respect to 100 parts by weight of a vinyl chloride resin There has been proposed a soft vinyl chloride resin composition obtained by adding an isocyanate group such that the ratio of isocyanate group / hydroxyl group in an isocyanate compound is 0.3 to 1.3, and heating and melting and mixing under a shearing force (for example, patents) Reference 1).
特開平７－１３８４３８号公報JP 7-138438 A
　しかしながら、上記のような軟質塩化ビニル系樹脂組成物では、所望の軟質特性を発現させつつ、同時に可塑剤のブリードアウトを十分に防止することは困難である。 However, with the soft vinyl chloride resin composition as described above, it is difficult to sufficiently prevent bleed-out of the plasticizer while exhibiting desired soft characteristics.
　そこで、本発明の目的は、所望の軟質特性を発現させつつ、同時に可塑剤のブリードアウトを十分に防止することができる、新たな樹脂組成物を提供することにある。また、本発明の他の目的は、上記の新たな樹脂組成物を原料とする包装用フィルム及びその工業的に有利な製造方法を提供することにある。 Therefore, an object of the present invention is to provide a new resin composition capable of sufficiently preventing bleeding out of a plasticizer while exhibiting desired soft characteristics. Another object of the present invention is to provide a packaging film using the above-mentioned new resin composition as a raw material and an industrially advantageous production method thereof.
　本発明は連関する一群の発明から成り、各発明の要旨は以下のとおりである。 The present invention comprises a group of related inventions, and the gist of each invention is as follows.
　本発明の第１の要旨は、熱可塑性樹脂１００質量部に対し多量体含有量５～６５質量％の変性エポキシ化植物油２０～６０質量部を配合して成ることを特徴とする樹脂組成物に存する。 A first gist of the present invention is a resin composition comprising 20 to 60 parts by mass of a modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass based on 100 parts by mass of a thermoplastic resin. Exist.
　本発明の第２の要旨は、上記の樹脂組成物から成ることを特徴とする包装用フィルムに存する。 The second gist of the present invention resides in a packaging film comprising the above resin composition.
　本発明の第３の要旨は、原料として、上記の樹脂組成物を使用する包装フィルムの製造方法であって、熱可塑性樹脂、エポキシ化植物油、活性水素含有化合物を含有する樹脂組成物の加熱成形工程を包含し、当該加熱成形工程におけるエポキシ化植物油と活性水素含有化合物との反応により変性エポキシ化植物油を調製することを特徴とする包装用フィルムの製造方法。 The third gist of the present invention is a method for producing a packaging film using the above resin composition as a raw material, wherein the resin composition contains a thermoplastic resin, an epoxidized vegetable oil, and an active hydrogen-containing compound. A process for producing a packaging film, comprising a step of preparing a modified epoxidized vegetable oil by a reaction between an epoxidized vegetable oil and an active hydrogen-containing compound in the thermoforming step.
　本発明の第４の要旨は、原料として、上記の樹脂組成物を使用する包装フィルムの製造方法であって、熱可塑性樹脂、過酸化物価１３．１～１８．０ミリ当量／ｋｇのエポキシ化植物油を含有する樹脂組成物の加熱成形工程を包含し、当該加熱成形工程により上記のポキシ化植物油を変性させて変性エポキシ化植物油を調製することを特徴とする包装用フィルムの製造方法。 The fourth gist of the present invention is a method for producing a packaging film using the above resin composition as a raw material, and is a epoxidation thermoplastic resin having a peroxide value of 13.1-18.0 meq / kg. The manufacturing method of the film for packaging characterized by including the thermoforming process of the resin composition containing a vegetable oil, modifying | denaturing said poxylated vegetable oil by the said thermoforming process, and preparing modified | denatured epoxidized vegetable oil.
　本発明によれば、所望の軟質特性を発現させつつ、同時に可塑剤のブリードアウトを十分に防止することができ、食品包装用フィルムの他、テーブルマット、ダイシングテープといった軟質材料製品を作製するのに好適な樹脂組成物が提供される。
　更に、本発明によれば、上記の樹脂組成物を原料とする包装用フィルム及びその工業的に有利な製造方法が提供される。 According to the present invention, it is possible to sufficiently prevent bleeding out of a plasticizer while expressing desired soft characteristics, and to produce soft material products such as a table mat and a dicing tape in addition to a food packaging film. A resin composition suitable for is provided.
Furthermore, according to this invention, the film for packaging which uses said resin composition as a raw material, and its industrially advantageous manufacturing method are provided.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
＜樹脂組成物＞
　本発明の樹脂組成物は、必須成分として熱可塑性樹脂と多量体含有量５～６５質量％の変性エポキシ化植物油を含有する。 <Resin composition>
The resin composition of the present invention contains a thermoplastic resin and a modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass as essential components.
（熱可塑性樹脂）
　熱可塑性樹脂は、変性エポキシ化植物油との相溶性に優れることから、極性を有する熱可塑性樹脂であるのが好ましい。極性を有する熱可塑性樹脂としては、例えば、ポリエステル系樹脂、ポリスチレン系樹脂、塩素含有樹脂、フッ素含有樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリアミドイミド系樹脂、ポリアリレート系樹脂、ポリウレタン系樹脂、ポリウレア系樹脂、アクリル系樹脂、エーテル系樹脂などが挙げられる。これらは２種以上を組み合わせて使用してもよい。これらの中では、変性エポキシ化植物油との相溶性や耐ブリード性に優れることから、特に塩素含有樹脂又はポリエステル系樹脂が好ましい。 (Thermoplastic resin)
Since the thermoplastic resin is excellent in compatibility with the modified epoxidized vegetable oil, the thermoplastic resin is preferably a polar thermoplastic resin. Examples of the thermoplastic resin having polarity include polyester resins, polystyrene resins, chlorine-containing resins, fluorine-containing resins, polyamide resins, polyimide resins, polyamideimide resins, polyarylate resins, polyurethane resins, and polyureas. Resin, acrylic resin, ether resin and the like. You may use these in combination of 2 or more type. Among these, a chlorine-containing resin or a polyester-based resin is particularly preferable because of compatibility with the modified epoxidized vegetable oil and excellent bleed resistance.
　塩素含有樹脂としては、特に限定されず、例えば、塩化ビニル系樹脂、塩素化塩化ビニル系樹脂、塩化ビニリデン系樹脂などを好ましく例示することができる。これらの中では、特に塩化ビニル系樹脂が好ましい。 The chlorine-containing resin is not particularly limited, and preferable examples include vinyl chloride resins, chlorinated vinyl chloride resins, and vinylidene chloride resins. Among these, a vinyl chloride resin is particularly preferable.
　塩化ビニル系樹脂としては、塩化ビニル系単独重合体の他、塩化ビニルと共重合可能な単量体との共重合体（以下、塩化ビニル系共重合体とする）、この塩化ビニル系共重合体以外の重合体に塩化ビニルをグラフト共重合させたグラフト共重合体（以下、塩化ビニル系グラフト共重合体）等が挙げられる。塩化ビニル系共重合体は、共重合体中の塩化ビニル以外の構成単位の含有量が多くなると機械的特性が低下するため、塩化ビニル系共重合体中に占める塩化ビニルの割合は、通常６０～９９質量％である。なお、塩化ビニル系単独重合体、及び、塩化ビニル系共重合体は、任意の方法、例えば、乳化重合法、懸濁重合法、溶液重合法、塊状重合法などで重合することができる。 As the vinyl chloride resin, in addition to a vinyl chloride homopolymer, a copolymer with a monomer copolymerizable with vinyl chloride (hereinafter referred to as a vinyl chloride copolymer), this vinyl chloride copolymer Examples thereof include a graft copolymer obtained by graft-copolymerizing vinyl chloride to a polymer other than the polymer (hereinafter referred to as vinyl chloride-based graft copolymer). Since the mechanical properties of the vinyl chloride copolymer decrease as the content of constituent units other than vinyl chloride in the copolymer increases, the proportion of vinyl chloride in the vinyl chloride copolymer is usually 60%. ~ 99% by mass. The vinyl chloride homopolymer and the vinyl chloride copolymer can be polymerized by an arbitrary method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method and the like.
　塩化ビニルと共重合可能な単量体としては、分子中に反応性二重結合を有するものであればよく、例えば、エチレン、プロピレン、ブチレン等のα－オレフィン類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；ブチルビニルエーテル、セチルビニルエーテル等のビニルエーテル類；アクリル酸、メタクリル酸などの不飽和カルボン酸類；アクリル酸メチル、メタクリル酸エチル、メタクリル酸フェニル等のアクリル酸またはメタクリル酸のエステル類；スチレン、α－メチルスチレン等の芳香族ビニル類；塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル類；Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－置換マレイミド類などが挙げられる。これらは２種以上を組み合わせて使用してもよい。また、塩化ビニル系共重合体以外の重合体としては、塩化ビニルをグラフト共重合できるものであればよく、例えば、エチレン・酢酸ビニル共重合体、エチレン・酢酸ビニル・一酸化炭素共重合体、エチレン・エチルアクリレート共重合体、エチレン・エチルアクリレート・一酸化炭素共重合体、エチレン・メチルメタクリレート共重合体、エチレン・プロピレン共重合体、アクリロニトリル・ブタジエン共重合体、ポリウレタン、塩素化ポリエチレン、塩素化ポリプロピレン等が挙げられる。これらは２種以上を組み合わせて使用してもよい。 The monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule, for example, α-olefins such as ethylene, propylene, butylene; vinyl acetate, vinyl propionate, etc. Vinyl esters such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate and phenyl methacrylate; styrene Aromatic vinyls such as α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. You may use these in combination of 2 or more type. The polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate / carbon monoxide copolymer, Ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated Examples include polypropylene. You may use these in combination of 2 or more type.
　塩化ビニル系樹脂の平均重合度は通常８００～１，４００である。平均重合度が８００以上であれば、十分な機械強度を得ることができる。一方、平均重合度が１，４００以下であれば、溶融粘度の増加に伴う発熱が生じることなく、分解による着色の発生を無くすことができる。よって、斯かる観点から、塩化ビニル系樹脂の平均重合度は、好ましくは９００～１，３５０、更に好ましくは１，０００～１，３００である。 The average degree of polymerization of the vinyl chloride resin is usually 800 to 1,400. If the average degree of polymerization is 800 or more, sufficient mechanical strength can be obtained. On the other hand, if the average degree of polymerization is 1,400 or less, heat generation due to an increase in melt viscosity does not occur, and the occurrence of coloring due to decomposition can be eliminated. Therefore, from this viewpoint, the average degree of polymerization of the vinyl chloride resin is preferably 900 to 1,350, more preferably 1,000 to 1,300.
　ポリエステル系樹脂としては、特に限定されず、芳香族ポリエステル系樹脂、脂肪族ポリエステル系樹脂、脂肪族－芳香族ポリエステル系樹脂などが挙げられる。これらの中では、エポキシ化植物油との相溶性や耐ブリード性に優れることから、特に、アジピン酸エステル系化合物、セバシン酸エステル系化合物、コハク酸エステル系化合物、ポリエステルポリオールが好ましい。 The polyester resin is not particularly limited, and examples thereof include aromatic polyester resins, aliphatic polyester resins, aliphatic-aromatic polyester resins, and the like. Among these, an adipic acid ester compound, a sebacic acid ester compound, a succinic acid ester compound, and a polyester polyol are particularly preferable because of compatibility with epoxidized vegetable oil and excellent bleed resistance.
（変性エポキシ化植物油）
　エポキシ化植物油の具体例としては、エポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化パームオイル、エポキシ化脂肪酸エステル、エポキシ化桐油、エポキシ化魚油、エポキシ化牛脂油、エポキシ化ひまし油などが挙げられる。これらは２種以上を組み合わせて使用してもよい。エポキシ化植物油は、基本的に単量体から構成されるが、エポキシ基が開環する変性反応により多量体を形成する。通常、市販のエポキシ化植物油は、様々な要因により２量体以上の多量体を微量含んでいる場合があり、その含有量は、エポキシ化植物油の全質量に対し、通常４質量％以下、好ましくは２質量％以下である。 (Modified epoxidized vegetable oil)
Specific examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil, epoxidized fatty acid ester, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, and epoxidized castor oil. You may use these in combination of 2 or more type. Epoxidized vegetable oil is basically composed of monomers, but forms a multimer by a modification reaction in which an epoxy group is ring-opened. Usually, commercially available epoxidized vegetable oil may contain a trace amount of dimer or higher multimer due to various factors, and the content thereof is usually 4% by mass or less, preferably based on the total mass of the epoxidized vegetable oil. Is 2% by mass or less.
　本発明で使用する変性エポキシ化植物油は多量体含有量５～６５質量％のものである。この場合、単量体の割合は９５～３５質量％である。多量体含有量が上記の範囲であれば、変性エポキシ化植物油による熱可塑性樹脂の可塑化と変性エポキシ化植物油の耐ブリード性を両立することができる。すなわち、多量体の割合が６５質量％以下であれば、熱可塑性樹脂の可塑化が十分であり、優れた柔軟性を得ることができる。一方、多量体の割合が５質量％以上であれば、変性エポキシ化植物油のブリードアウト量を十分に抑えることができる。多量体含有量は、好ましくは５～６０質量％、更に好ましくは６～６０質量％である。多量体含有量の測定方法は後述の実施例で説明する。 The modified epoxidized vegetable oil used in the present invention has a multimer content of 5 to 65% by mass. In this case, the proportion of the monomer is 95 to 35% by mass. When the multimer content is in the above range, both the plasticization of the thermoplastic resin with the modified epoxidized vegetable oil and the bleed resistance of the modified epoxidized vegetable oil can be achieved. That is, when the ratio of the multimer is 65% by mass or less, the thermoplastic resin is sufficiently plasticized and excellent flexibility can be obtained. On the other hand, if the ratio of the multimer is 5% by mass or more, the bleed-out amount of the modified epoxidized vegetable oil can be sufficiently suppressed. The multimer content is preferably 5 to 60% by mass, more preferably 6 to 60% by mass. The method for measuring the multimer content will be described in Examples below.
　多量体含有量の調整に利用する変性反応としては、例えば、（ｉ）活性水素含有化合物を使用した変性反応、（ii）エポキシ化植物油の過酸化物基を使用した変性反応、（ｉ）及び（ii）を組み合わせた変性反応などが挙げられる。そして、熱可塑性樹脂中で上記の変性反応を行うならば、組成物化を同時に行うことができる利点がある。 Examples of the modification reaction used for adjusting the multimer content include (i) a modification reaction using an active hydrogen-containing compound, (ii) a modification reaction using a peroxide group of an epoxidized vegetable oil, (i) and Examples include a denaturation reaction combining (ii). And if said modification | denaturation reaction is performed in a thermoplastic resin, there exists an advantage which can make composition simultaneously.
（活性水素含有化合物）
　活性水素含有化合物としては、酸などのようにカルボキシル基を有する化合物の他、水酸基を有する化合物、アミノ基を有する化合物、酸無水物など、各種の反応性の官能基を有する化合物（「変性化合物」とも称する）が挙げられる。これらの中では、エポキシ基の開環反応の容易性の観点から、酸が好ましい。 (Active hydrogen-containing compounds)
Active hydrogen-containing compounds include compounds having various reactive functional groups such as compounds having a carboxyl group, such as acids, compounds having a hydroxyl group, compounds having an amino group, and acid anhydrides (“modified compounds”). "). In these, an acid is preferable from a viewpoint of the ease of the ring-opening reaction of an epoxy group.
　酸の具体例としては、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マーガリン酸、ステアリン酸などの飽和カルボン酸；オレイン酸、リノール酸、リノレン酸、アラキドン酸、ソルビン酸、ドコサヘキサエン酸、エイコサペンタエン酸などの不飽和カルボン酸；乳酸、リンゴ酸、クエン酸などのヒドロキシ酸、安息香酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸などの芳香族カルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、フマル酸、マレイン酸などのジカルボン酸が挙げられる。また、オキソカルボン酸、アコニット酸、アミノ酸、ニトロカルボン酸などのカルボン酸誘導体も挙げられる。これらは２種以上を組み合わせて使用してもよい。これらの中では、エポキシ化植物油との反応性の観点から、不飽和カルボン酸、ジカルボン酸、トリカルボン酸が好ましく、特にジカルボン酸が好ましい。 Specific examples of acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, etc. Saturated carboxylic acid; unsaturated carboxylic acid such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, sorbic acid, docosahexaenoic acid, eicosapentaenoic acid; hydroxy acid such as lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, Aromatic carboxylic acids such as isophthalic acid, terephthalic acid and salicylic acid; and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid and maleic acid. Also included are carboxylic acid derivatives such as oxocarboxylic acid, aconitic acid, amino acid, nitrocarboxylic acid and the like. You may use these in combination of 2 or more type. Among these, unsaturated carboxylic acid, dicarboxylic acid, and tricarboxylic acid are preferable from the viewpoint of reactivity with epoxidized vegetable oil, and dicarboxylic acid is particularly preferable.
（高過酸化物価のエポキシ化植物油）
　植物油を酸化剤である過酸化水素を使用してエポキシ化する方法（過酸化水素法）で得られるエポキシ化植物油は、過酸化物基の含有量が高く（例えば２０～４０）、その量は減圧下の加熱処理によって減少化することができる。そして、過酸化物価の異なる種々のエポキシ化植物油が市販されている。過酸化物価の測定方法は後述の実施例で説明する。 (High peroxide value epoxidized vegetable oil)
Epoxidized vegetable oil obtained by a method of epoxidizing vegetable oil using hydrogen peroxide as an oxidizing agent (hydrogen peroxide method) has a high peroxide group content (for example, 20 to 40). It can be reduced by heat treatment under reduced pressure. Various epoxidized vegetable oils having different peroxide values are commercially available. The method for measuring the peroxide value will be described in the examples below.
　本発明で使用する上記のエポキシ化植物油の過酸化物価は、通常１３．１～１８．０ミリ当量／ｋｇ、好ましくは１３．３～１７．５ミリ当量／ｋｇ、更に好ましくは１３．５～１７．０ミリ当量／ｋｇである。エポキシ化植物油の過酸化物価が１３．１ミリ当量／ｋｇを下回る場合、エポキシ化植物油中の過酸化物基が少なく、熱可塑性樹脂の中での溶融混練時において十分な多量体化を図ることが困難である。一方、過酸化物価が１８．０ミリ当量／ｋｇを上回る場合、例えば、フィルム状に成形した際の臭気が酷く、食品包装材として使用することが困難な場合がある。 The peroxide value of the epoxidized vegetable oil used in the present invention is generally 13.1-18.0 meq / kg, preferably 13.3-17.5 meq / kg, more preferably 13.5- 17.0 meq / kg. When the peroxide value of the epoxidized vegetable oil is less than 13.1 meq / kg, there are few peroxide groups in the epoxidized vegetable oil, and sufficient multimerization is achieved at the time of melt-kneading in the thermoplastic resin. Is difficult. On the other hand, when the peroxide value exceeds 18.0 milliequivalents / kg, for example, the odor when formed into a film is severe and it may be difficult to use as a food packaging material.
（各成分の割合）
　エポキシ化植物油の変性反応に活性水素含有化合物を使用する場合の各成分の割合は次のとおりである。すなわち、活性水素含有化合物は、エポキシ化植物油１００質量部に対し、通常０．０１～８質量部、好ましくは０．０５～６質量部、更に好ましくは０．１～３質量部である。活性水素含有化合物の上記範囲の使用により、特に塩化ビニル系樹脂に好適な変性エポキシ化植物油が得られ、両者を含有する樹脂組成物は、熱安定性、柔軟性、耐ブリード性に優れる。一方、熱可塑性樹脂中で変性反応を行う場合の各成分の割合は次のとおりである。すなわち、熱可塑性樹脂１００質量部に対し、エポキシ化植物油は２０～６０質量部、活性水素含有化合物は０．０１～５０質量部、好ましくは０．０５～４質量部、更に好ましくは０．１～３質量部である。 (Ratio of each component)
The ratio of each component when using an active hydrogen-containing compound in the modification reaction of the epoxidized vegetable oil is as follows. That is, the active hydrogen-containing compound is usually 0.01 to 8 parts by mass, preferably 0.05 to 6 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the epoxidized vegetable oil. By using the active hydrogen-containing compound in the above range, a modified epoxidized vegetable oil particularly suitable for a vinyl chloride resin can be obtained, and a resin composition containing both is excellent in thermal stability, flexibility and bleed resistance. On the other hand, the ratio of each component in the case of performing a modification reaction in a thermoplastic resin is as follows. That is, epoxidized vegetable oil is 20 to 60 parts by mass, active hydrogen-containing compound is 0.01 to 50 parts by mass, preferably 0.05 to 4 parts by mass, more preferably 0.1 to 100 parts by mass of the thermoplastic resin. ~ 3 parts by mass.
　本発明の樹脂組成物において、多量体含有量５～６５質量％の変性エポキシ化植物油の割合は、熱可塑性樹脂１００質量部に対し、２０～６０質量部、好ましくは２５～５５質量部、更に好ましくは３０～５０質量部である。斯かる条件を満足することにより、本発明の樹脂組成物を使用してフィルムを成形した際に可塑剤の耐ブリード性とフィルムの柔軟性を確保することができる。 In the resin composition of the present invention, the proportion of the modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass is 20 to 60 parts by mass, preferably 25 to 55 parts by mass, more preferably 100 parts by mass of the thermoplastic resin. The amount is preferably 30 to 50 parts by mass. By satisfying such conditions, the bleed resistance of the plasticizer and the flexibility of the film can be ensured when the film is formed using the resin composition of the present invention.
　エポキシ化植物油の変性反応の反応温度は通常１００～２２０℃であり、反応時間は通常１０分から２時間である。熱可塑性樹脂中で変性反応を行う場合、反応温度は、通常１８０～２２０℃、好ましくは１８５～２１５℃であり、反応時間は、通常３０秒～３分である。従って、必要成分を含む原料樹脂組成物を押出成形してフィルムを製造する場合は、押出成形工程の通常の滞留時間の範囲内でエポキシ化植物油の変性反応を終えることができる。 The reaction temperature for the modification reaction of the epoxidized vegetable oil is usually 100 to 220 ° C., and the reaction time is usually 10 minutes to 2 hours. When the modification reaction is carried out in the thermoplastic resin, the reaction temperature is usually 180 to 220 ° C., preferably 185 to 215 ° C., and the reaction time is usually 30 seconds to 3 minutes. Therefore, when a raw material resin composition containing necessary components is extruded to produce a film, the modification reaction of the epoxidized vegetable oil can be completed within the normal residence time of the extrusion process.
　本発明の樹脂組成物においては、本発明の効果を損なわない限り、防曇剤、熱安定剤、酸化防止剤、紫外線吸収剤、光安定剤、抗菌・防かび剤、帯電防止剤、滑剤、顔料、染料等の添加剤を配合することができる。 In the resin composition of the present invention, as long as the effects of the present invention are not impaired, an antifogging agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, an antistatic agent, a lubricant, Additives such as pigments and dyes can be blended.
　本発明の樹脂組成物の調製方法としては、前記の必要成分を使用し、例えば、Ｖ型ブレンダー、リボンブレンダー、ヘンシェルミキサー等の混合機により混合する方法、押出機、ミキシングロール、バンバリーミキサー、ニーダ等の混練機により混練する方法、混合機と混練機を組み合わせて混合・混練する方法などが挙げられる。 As a method for preparing the resin composition of the present invention, the above-mentioned necessary components are used, for example, a method of mixing by a mixer such as a V-type blender, a ribbon blender, a Henschel mixer, an extruder, a mixing roll, a Banbury mixer, a kneader. Examples thereof include a method of kneading with a kneader such as the above, and a method of mixing and kneading by combining a mixer and a kneader.
＜樹脂組成物の特性＞
　本発明の樹脂組成物は、変性エポキシ化植物油が含有する多量体、特に２量体の作用により、変性エポキシ化植物油のブリードアウトが抑制され、しかも柔軟性にも優れる。 <Characteristics of resin composition>
The resin composition of the present invention suppresses bleeding out of the modified epoxidized vegetable oil by the action of the multimer, particularly the dimer contained in the modified epoxidized vegetable oil, and is excellent in flexibility.
　また、本発明の樹脂組成物を製造するに際し、熱可塑性樹脂とエポキシ化植物油と活性水素含有化合物を含有する組成物は、加熱前の初期状態において粘度が小さくて成形しやすいばかりか、均一混合が容易であるという特徴を有する。そして、これを加熱すると、エポキシ化植物油と活性水素含有化合物とが反応して、２量体、場合によってその３量体或いはそれ以上の多量体の含有量がエポキシ化植物油より多い変性エポキシ化植物油が生成する。 In producing the resin composition of the present invention, the composition containing the thermoplastic resin, the epoxidized vegetable oil, and the active hydrogen-containing compound has a low viscosity in the initial state before heating and is easy to mold, or is mixed uniformly. Is easy. And when this is heated, the epoxidized vegetable oil reacts with the active hydrogen-containing compound, and the modified epoxidized vegetable oil in which the content of the dimer, and possibly the trimer or higher is higher than the epoxidized vegetable oil Produces.
＜包装用フィルム及びその製造方法＞
　本発明の包装用フィルムは、前記の樹脂組成物から成り、例えば、Ｔダイ法、インフレーション法などの公知の成形方法により得ることができる。特に、押出成形工程の熱可塑性樹脂中でエポキシ化植物油の変性反応を行う方法は、本発明の樹脂組成物からなる包装用フィルムの簡便な製造方法として推奨される。 <Packaging film and manufacturing method thereof>
The packaging film of the present invention comprises the above resin composition and can be obtained by a known molding method such as a T-die method or an inflation method. In particular, the method of modifying the epoxidized vegetable oil in the thermoplastic resin in the extrusion process is recommended as a simple method for producing a packaging film comprising the resin composition of the present invention.
　ところで、本発明の包装用フィルムを食品包装用フィルム（特に精肉、鮮魚、青果等を包装する生鮮食品の包装用フィルム）として使用する場合、前述の本発明の樹脂組成物として、熱可塑性樹脂が塩化ビニル系樹脂であり、更に、重量平均分子量が３，０００～１０，０００のポリエステル系化合物を含有し、塩化ビニル系樹脂の含有量１００質量部に対するポリエステル系化合物の含有割合が１～３０質量部である樹脂組成物を使用するのが好ましい。その理由は次のとおりである。 By the way, when the packaging film of the present invention is used as a food packaging film (particularly a packaging film for fresh foods for packaging meat, fresh fish, fruits and vegetables, etc.), as the resin composition of the present invention, a thermoplastic resin is used. It is a vinyl chloride resin, and further contains a polyester compound having a weight average molecular weight of 3,000 to 10,000, and the content ratio of the polyester compound with respect to 100 parts by mass of the vinyl chloride resin is 1 to 30 masses. It is preferable to use a resin composition that is part. The reason is as follows.
　食品包装用フィルムに関しては、配合剤の衛生性、食品等への移行性が重要視されるため、米国においてはＦＤＡ規格（Ｆｏｏｄ　ａｎｄ　Ｄｒｕｇ　Ａｄｍｉｎｉｓｔｒａｔｉｏｎ）、日本においてはＰＬ規格（塩化ビニル樹脂製包装容器包装等に関する自主規制基準）等が定められており、これらの規格に適合する樹脂、添加剤などが食品包装用フィルムに使用されている。また、食品などへの添加剤の移行性の確認試験として、厚生省告示２０号試験により蒸発残留物試験法として抽出試験が行われている。 For food packaging films, the hygiene of compounding ingredients and the ability to migrate to foods are regarded as important. Therefore, FDA standards (Food and Drug Administration) in the US and PL standards (vinyl chloride resin packaging containers in Japan) Self-regulation standards for packaging, etc.) have been established, and resins and additives that meet these standards are used in food packaging films. In addition, as a test for confirming the transferability of additives to foods and the like, an extraction test is performed as an evaporation residue test method according to the Ministry of Health and Welfare Notification No. 20 test.
　上記のような背景下、塩化ビニル系樹脂を主材とする食品包装用フィルム或いは当該フィルムを作製するための樹脂組成物として、柔軟性を高めるための可塑剤などが添加された数多くの樹脂組成物が提案されている（例えば、特開平２－２６９１４５号公報、特開平８－２７３４１号公報、特開平９－１７６４２４号公報、特開２０１１－１５３２１０号公報）。 Under the background as described above, as a food packaging film mainly composed of a vinyl chloride resin or a resin composition for producing the film, a number of resin compositions to which a plasticizer for increasing flexibility is added. Products have been proposed (for example, JP-A-2-269145, JP-A-8-27341, JP-A-9-176424, JP-A-2011-153210).
　しかしながら、食品包装用フィルムには、成形や使用時において１００℃以上の高温環境下でも黒色化するなどの変質が起こらないような「熱安定性」が求められる場合があるが、従来提案された方法では、柔軟性、耐ブリード性及び熱安定性を全て満足することは困難であった。 However, food packaging films are sometimes required to have “thermal stability” that does not cause alteration such as blackening even in a high temperature environment of 100 ° C. or higher during molding and use. In the method, it was difficult to satisfy all of flexibility, bleed resistance and thermal stability.
　ところが、本発明の前記の好ましい態様によれば、可塑剤として、エポキシ化植物油ではなく、エポキシ化植物油を多量体化してなる変性エポキシ化植物油を使用したことにより、昭和５７年厚生省告示２０号に定める蒸発残留物試験法（片面法）により測定したイソオクタンに対する変性エポキシ化植物油のブリードアウト量を非常に少なく抑えることができ、安全性に優れており、柔軟性、熱安定性にも優れた食品包装用フィルムを提供することができる。 However, according to the preferred embodiment of the present invention, the modified epoxidized vegetable oil obtained by polymerizing the epoxidized vegetable oil is used as the plasticizer instead of the epoxidized vegetable oil. Foods with excellent safety and flexibility and heat stability, which can suppress the bleed-out amount of modified epoxidized vegetable oil to isooctane measured by the evaporation residue test method (single-sided method) A packaging film can be provided.
（ポリエステル系化合物）
　本発明で使用するポリエステル系化合物の重量平均分子量は３，０００～１０，０００である。重量平均分子量が３，０００以上であれば、ポリエステル系化合物のブリードアウトを抑制でき、安全上好ましい。一方、重量平均分子量が１０，０００以下であれば、塩化ビニル系樹脂との相溶性が良く、成形品表面へのブリードアウトの発生を抑制でき、かつ、十分な可塑化効果を得ることができる。ポリエステル系化合物の重量平均分子量は、好ましくは４，０００～９，０００、更に好ましくは５，０００～８，０００である。 (Polyester compound)
The polyester compound used in the present invention has a weight average molecular weight of 3,000 to 10,000. If the weight average molecular weight is 3,000 or more, bleeding out of the polyester compound can be suppressed, which is preferable for safety. On the other hand, if the weight average molecular weight is 10,000 or less, the compatibility with the vinyl chloride resin is good, the occurrence of bleeding out to the surface of the molded product can be suppressed, and a sufficient plasticizing effect can be obtained. . The weight average molecular weight of the polyester compound is preferably 4,000 to 9,000, and more preferably 5,000 to 8,000.
　ポリエステル系化合物の具体例としては、例えば、アジピン酸エステル系化合物、セバシン酸エステル系化合物、コハク酸エステル系化合物、ポリエステルポリオール等が挙げられる。これらの中では、塩化ビニル系樹脂との相溶性に優れることから、アジピン酸エステル系化合物、ポリエステルポリオール或いはこれらの混合物が好ましい。 Specific examples of polyester compounds include adipic acid ester compounds, sebacic acid ester compounds, succinic acid ester compounds, polyester polyols, and the like. In these, since it is excellent in compatibility with vinyl chloride resin, an adipate ester compound, polyester polyol, or a mixture thereof is preferable.
　アジピン酸エステル系化合物としては、例えば、アジピン酸と二価アルコールとの反応物が挙げられる。アジピン酸エステル系化合物の具体例としては、例えば、ポリ（プロピレングリコール／アジピン酸）エステル、ポリ（１，３－ブタンジオール／アジピン酸）エステル、ポリ（１，４－ブタンジオール／アジピン酸）エステル、ポリ（エチレングリコール／アジピン酸）エステル、ポリ（１、６－ヘキサンジオール／ブタンジオール／アジピン酸）エステル、ポリ（ブタンジオール／エチレングリコール／アジピン酸）エステル、ポリ（エチレングリコール／プロピレングリコール／ブタンジオール／アジピン酸）エステル等が挙げられる。これらの中では、塩化ビニル系樹脂との相溶性や耐ブリード性に優れることから、ポリ（１，３－ブタンジオール／アジピン酸）エステル、若しくはポリ（１，４－ブタンジオール／アジピン酸）エステル、又はこれらの混合物を使用することが好ましい。二価アルコールとしては、特に限定されないが、例えば、エチレングリコール、プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１、６－ヘキサンジオール等が使用され、これらは２種類以上を組み合せて使用してもよい。 Examples of the adipic acid ester compound include a reaction product of adipic acid and a dihydric alcohol. Specific examples of adipic acid ester compounds include, for example, poly (propylene glycol / adipic acid) ester, poly (1,3-butanediol / adipic acid) ester, poly (1,4-butanediol / adipic acid) ester , Poly (ethylene glycol / adipic acid) ester, poly (1,6-hexanediol / butanediol / adipic acid) ester, poly (butanediol / ethylene glycol / adipic acid) ester, poly (ethylene glycol / propylene glycol / butane) Diol / adipic acid) ester and the like. Among these, poly (1,3-butanediol / adipic acid) ester or poly (1,4-butanediol / adipic acid) ester because of excellent compatibility with vinyl chloride resin and bleed resistance. Or a mixture of these. The dihydric alcohol is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like are used. You may use it in combination.
　ポリエステルポリオールとしては、例えば、脂肪族ジカルボン酸および／または芳香族ジカルボン酸と、二価アルコールとを重縮合させたものを挙げることができる。脂肪族ジカルボン酸としては、例えば、コハク酸、アジピン酸、セバチン酸、グルタル酸、アゼライン酸などが挙げられ、芳香族ジカルボン酸としては、例えば、イソフタル酸、テレフタル酸などが挙げられ、二価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタジオール、ネオペンチルグリコール、１，４－ジヒドロキシメチルシクロヘキサン等が挙げられる。 Examples of the polyester polyol include those obtained by polycondensation of an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid and a dihydric alcohol. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, glutaric acid, and azelaic acid. Examples of the aromatic dicarboxylic acid include isophthalic acid and terephthalic acid. As, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentadiol, neopentyl glycol, 1,4-dihydroxymethylcyclohexane, etc. Is mentioned.
　ポリエステルポリオールの具体例としては、例えば、ポリエチレンアジペートジオール、ポリブチレンアジペートジオール、ポヘキサメチレンアジペートジオール、ポリネオペンチルアジペートジオール、ポリエチレン／ブチレンアジペートジオール、ポリ－３－メチルペンタンアジペートジオール、ポリブチレンイソフタレートジオール等が挙げられる。これらの中では、塩化ビニル系樹脂との相溶性や耐ブリード性に優れることから、ポリネオペンチルアジペートジオールが好ましい。 Specific examples of the polyester polyol include, for example, polyethylene adipate diol, polybutylene adipate diol, pohexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate Diol etc. are mentioned. Among these, polyneopentyl adipate diol is preferred because it is excellent in compatibility with vinyl chloride resin and bleed resistance.
　塩化ビニル系樹脂の含有量１００質量部に対するポリエステル系化合物の含有割合は、前述のとおり１～３０質量部であるが、好ましくは３～２５質量部、更に好ましくは５～２０質量部である。 As described above, the content of the polyester compound relative to 100 parts by mass of the vinyl chloride resin is 1 to 30 parts by mass, preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass.
（その他の成分）
　本発明においては、包装用フィルムの熱安定性を更に向上させるため、Ｃａ－Ｚｎ系安定剤を配合してもよい。Ｃａ－Ｚｎ系安定剤とは、カルシウムの脂肪酸塩と亜鉛の脂肪酸塩の混合物である。 (Other ingredients)
In the present invention, a Ca—Zn stabilizer may be added to further improve the thermal stability of the packaging film. The Ca—Zn stabilizer is a mixture of calcium fatty acid salt and zinc fatty acid salt.
　脂肪酸の具体例としては、ベヘニン酸、ステアリン酸、ラウリン酸、オレイン酸、パルミチン酸、リシノール酸、安息香酸等が挙げられ、目的に応じて２種以上組み合わせて使用することも可能である。成形性の観点からステアリン酸塩が好ましい。また、カルシウムと亜鉛の比率は、質量比として、通常１：２～１：３である。亜鉛の比率がカルシウムに対して２より少ないとカルシウム塩特有の赤味が出てしまい、一方、亜鉛の比率がカルシウムに対して３よりも多いと、成形加工中に生成する塩化亜鉛が塩化ビニル系樹脂の分解触媒となり、「亜鉛焼け」と呼ばれる急激な黒化、分解が生じる。 Specific examples of fatty acids include behenic acid, stearic acid, lauric acid, oleic acid, palmitic acid, ricinoleic acid, benzoic acid and the like, and can be used in combination of two or more according to the purpose. From the viewpoint of moldability, stearates are preferred. The ratio of calcium to zinc is usually 1: 2 to 1: 3 as a mass ratio. If the ratio of zinc is less than 2 relative to calcium, a redness peculiar to calcium salts will appear. On the other hand, if the ratio of zinc is greater than 3 relative to calcium, zinc chloride produced during molding will be vinyl chloride. It becomes a decomposition catalyst for the resin, and sudden blackening and decomposition called “zinc burn” occurs.
　Ｃａ－Ｚｎ系安定剤の添加量は、塩化ビニル系樹脂１００質量部に対し、通常０．１～２．０質量部、好ましくは０．３～１．８質量である。０．１質量部以上であれば、熱安定性の付与効果を得ることができる、２．０質量部以上であれば、「亜鉛焼け」と呼ばれる急激な黒化、分解を防止することができる。 The addition amount of the Ca—Zn stabilizer is usually 0.1 to 2.0 parts by mass, preferably 0.3 to 1.8 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. If it is 0.1 parts by mass or more, the effect of imparting thermal stability can be obtained, and if it is 2.0 parts by mass or more, rapid blackening and decomposition called “zinc burn” can be prevented. .
　本発明においては、包装用フィルムの防曇性を付与するために多価アルコールと脂肪酸のエステル化合物を配合してもよい。 In the present invention, an ester compound of a polyhydric alcohol and a fatty acid may be blended in order to impart antifogging properties to the packaging film.
　多価アルコールと脂肪酸のエステルとしては、モノグリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル等が挙げられる。 Examples of esters of polyhydric alcohol and fatty acid include monoglycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether and the like.
　モノグリセリン脂肪酸エステルとしては、炭素原子数が１２～１８の飽和または不飽和脂肪酸のモノグリセリンエステルが好ましい。具体的には、モノグリセリンラウレート、モノグリセリンミリステート、モノグリセリンパルミテート、モノグリセリンステアレート、モノグリセリンオレート、モノグリセリンリノレート等が挙げられる。 The monoglycerin fatty acid ester is preferably a monoglycerin ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include monoglycerol laurate, monoglycerol myristate, monoglycerol palmitate, monoglycerol stearate, monoglycerol oleate, and monoglycerol linoleate.
　ポリグリセリン脂肪酸エステルとしては、炭素原子数が１２～１８の飽和または不飽和脂肪酸のポリグリセリンエステルが好ましい。具体的には、ポリグリセリンラウレート、ポリグリセリンミリステート、ポリグリセリンパルミテート、ポリグリセリンステアレート、ポリグリセリンオレート、ポリグリセリンリノレート等が挙げられる。 The polyglycerol fatty acid ester is preferably a polyglycerol ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol stearate, polyglycerol oleate, polyglycerol linoleate and the like.
　ソルビタン脂肪酸エステルとしては、炭素原子数が１２～１８の飽和または不飽和脂肪酸のソルビタンエステルが好ましい。具体的には、ソルビタンラウレート、ソルビタンミリステート、ソルビタンパルミテート、ソルビタンステアレート、ソルビタンオレート、ソルビタンリノレート等が挙げられる。 The sorbitan fatty acid ester is preferably a saturated or unsaturated fatty acid sorbitan ester having 12 to 18 carbon atoms. Specifically, sorbitan laurate, sorbitan myristate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan linoleate and the like can be mentioned.
　ポリオキシエチレンアルキルエーテルとしては、炭素数が１２～１８の飽和アルコールのポリオキシエチレンアルキルエーテルが好ましく、更に好ましくは、エチレンオキサイドの付加モル数が３～７であるポリオキシエチレンアルキルエーテルである。具体的には、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンミリスチルエーテル、ポリオキシエチレンパルミチルエーテル、ポリオキシエチレンステアリルエーテル等が挙げられる。 The polyoxyethylene alkyl ether is preferably a saturated alcohol polyoxyethylene alkyl ether having 12 to 18 carbon atoms, more preferably a polyoxyethylene alkyl ether having 3 to 7 added moles of ethylene oxide. Specific examples include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, polyoxyethylene stearyl ether, and the like.
＜用語の説明＞
　一般的に「フィルム」とは、長さ及び幅に比べて厚みが極めて小さく、最大厚みが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいい（日本工業規格ＪＩＳＫ６９００）、一般的に「シート」とは、ＪＩＳにおける定義上、薄く、一般にその厚みが長さと幅のわりには小さく平らな製品をいう。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。 <Explanation of terms>
In general, "film" refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) Industrial standard JISK6900), and in general, “sheet” refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.
　以下、本発明を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。なお、以下の諸例における各物性の測定法および評価方法は次のとおりである。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, the measuring method and evaluation method of each physical property in the following examples are as follows.
（１）フィルムの貯蔵弾性率（Ｅ′）（柔軟性）の評価：
　動的粘弾性測定機（アイティ計測（株）製、商品名：粘弾性スペクトロメーターＤＶＡ－２００）を使用し、振動周波数：１０Ｈｚ、昇温速度：３℃／分、歪０．１％の条件で、貯蔵弾性率（Ｅ’）を－１００℃から２００℃まで測定し、得られたデータから２５℃における貯蔵弾性率（Ｅ’）を読み取った。そして、次の３段階で評価した。Ａは合格であり、Ｂ及びＣは不合格である。
　Ａ：１００～１０００ＭＰａ
　Ｂ：５０ＭＰａ以上、１００ＭＰａ未満、もしくは、１０００ＭＰａ超過、１５００ＭＰａ以下
　Ｃ：５０ＭＰａ未満、もしくは、１５００ＭＰａ超過 (1) Evaluation of storage elastic modulus (E ′) (flexibility) of film:
Using a dynamic viscoelasticity measuring machine (product name: Viscoelasticity spectrometer DVA-200, manufactured by IT Measurement Co., Ltd.), vibration frequency: 10 Hz, temperature rising rate: 3 ° C./min, strain 0.1% Then, the storage elastic modulus (E ′) was measured from −100 ° C. to 200 ° C., and the storage elastic modulus (E ′) at 25 ° C. was read from the obtained data. And it evaluated in the following three steps. A is acceptable and B and C are unacceptable.
A: 100 to 1000 MPa
B: 50 MPa or more, less than 100 MPa, or more than 1000 MPa, 1500 MPa or less C: less than 50 MPa, or more than 1500 MPa
（２）透明性の評価：
　実施例および比較例で得たフィルムを重ね合わせて２ｍｍ厚みのプレスシート（プレス条件：温度１８０℃、プレス時間１０分、圧力３０ｋｇ／ｃｍ２）を作製し、黒色紙上に並べて目視で透明性を評価した。そして、次の３段階で評価した。
　Ａ：黒色紙がはっきり確認できる透明性を有している。
　Ｃ：シートが白濁し黒色紙がはっきり確認できない。
　Ｂ：上記の中間位置にある。 (2) Evaluation of transparency:
The films obtained in the examples and comparative examples are overlapped to produce a 2 mm-thick press sheet (press conditions: temperature 180 ° C., press time 10 minutes, pressure 30 kg / cm 2 ), which are arranged on black paper and visually transparent. evaluated. And it evaluated in the following three steps.
A: Transparency that allows black paper to be clearly confirmed.
C: The sheet is cloudy and black paper cannot be clearly confirmed.
B: Located at the intermediate position.
（３）プレス時の噴出しの評価：
　実施例および比較例で得たフィルムを重ね合わせて２ｍｍ厚みのプレスシート（プレス条件：温度１８０℃、プレス時間１０分、圧力３０ｋｇ／ｃｍ２）を作製し、プレス完了後の化粧板への噴出し（汚れ）を目視評価した。そして、次の３段階で評価した。
　Ａ：吹き出しが少なく鏡面状態がはっきり確認できる。
　Ｃ：吹き出しが多く化粧板の鏡面状態がはっきり確認できない。
　Ｂ：上記の中間位置にある。 (3) Evaluation of ejection during pressing:
The films obtained in Examples and Comparative Examples were superimposed to produce a 2 mm-thick press sheet (press conditions: temperature 180 ° C., press time 10 minutes, pressure 30 kg / cm 2 ), and jetted onto the decorative board after the press was completed (Stain) was visually evaluated. And it evaluated in the following three steps.
A: There are few balloons and a mirror surface state can be confirmed clearly.
C: There are many balloons and the mirror surface state of a decorative board cannot be confirmed clearly.
B: Located at the intermediate position.
（４）耐ブリード性の評価：
　実施例および比較例で得た０．０１ｍｍのフィルムを測定サンプルとして、厚生省告示２０号に定める蒸発残留物試験法（片面法）に基づき、溶媒としてイソオクタンを使用し、溶媒との接触面積：２５ｃｍ２、溶媒量：２ｍＬ／ｃｍ２、試験温度：２５℃、試験時間：３０分の条件で、イソオクタンに対する可塑剤のブリードアウト量を測定した。そして、次の２段階で評価した。Ａは合格であり、Ｂは不合格である。
　Ａ：９０ｐｐｍ以下
　Ｂ：９０ｐｐｍ超過 (4) Evaluation of bleed resistance:
Based on the evaporation residue test method (single-sided method) defined in the Ministry of Health and Welfare Notification No. 20, using the 0.01 mm film obtained in Examples and Comparative Examples as a solvent, isooctane was used as the solvent, and the contact area with the solvent: 25 cm 2 , Solvent amount: 2 mL / cm 2 , Test temperature: 25 ° C., Test time: 30 minutes The plasticizer bleed-out amount with respect to isooctane was measured. And it evaluated in the following two steps. A is acceptable and B is unacceptable.
A: 90 ppm or less B: Over 90 ppm
（２）熱安定性：
　実施例および比較例で作製したフィルムを長さ５０ｍｍ×幅５０ｍｍに裁断し、得られた評価用サンプルを、ベーキング試験装置（大栄科学精器製作所製「ＤＫＳ－５Ｓ」）内に静置し、２１０℃で６０分間加熱した。試験後にサンプルを目視し、次の２段階で評価した。
　Ａ：黒色化しなかった。
　Ｂ：黒色化した。 (2) Thermal stability:
The films produced in the examples and comparative examples were cut into a length of 50 mm and a width of 50 mm, and the obtained evaluation sample was left in a baking test apparatus (“DKS-5S” manufactured by Daiei Scientific Instruments Co., Ltd.) Heated at 210 ° C. for 60 minutes. After the test, the sample was visually observed and evaluated in the following two stages.
A: Not blackened.
B: Blackened.
（５）臭気
　実施例および比較例で作製したフィルムについて、２３℃の恒温室にて官能評価を行っい。次の２段階で評価した。
　Ａ：臭気が不快でないか或いは弱い。
　Ｂ：臭気が不快であるか或いは強い。 (5) Odor Sensory evaluation is performed in a thermostatic chamber at 23 ° C. for the films prepared in Examples and Comparative Examples. Evaluation was made in the following two stages.
A: The odor is not unpleasant or weak.
B: The odor is unpleasant or strong.
（５）変性エポキシ化大豆油中の多量体量の測定方法
　ゲルパーミエーションクロマトグラフィー（カラム：東ソー（株）の商品名ＴＳＫｇｅｌＧ２０００ＨＸＬ）を使用し、溶媒としてＴＨＦ（溶液濃度２．５ｍｇ／ｍＬ、溶液注入量０．０５ｍＬ、流速１ｍＬ／分、温度４０℃）を使用して測定を行った。得られたチャートより、エポキシ化植物油の単量体の割合を算出し、以下の式にて多量体の割合を求めた。
　多量体の割合（質量％）＝１００（質量％）－「単量体の割合（質量％）」 (5) Method for measuring the amount of multimers in modified epoxidized soybean oil Gel permeation chromatography (column: TSKgel G2000HXL, trade name of Tosoh Corp.) is used, and THF (solution concentration 2.5 mg / mL, solution) Measurement was performed using an injection volume of 0.05 mL, a flow rate of 1 mL / min, and a temperature of 40 ° C.). From the obtained chart, the proportion of the monomer of the epoxidized vegetable oil was calculated, and the proportion of the multimer was determined by the following formula.
Multimer ratio (mass%) = 100 (mass%) − “monomer ratio (mass%)”
（６）エポキシ化植物油の過酸化物価の測定：
　基準油脂分析法（２．５．２過酸化物価、基準油脂分析試験法（Ｉ）、日本油化学会制定、２００３年版、社団法人日本油化学会）の酢酸・イソオクタン法に基づき、エポキシ化植物油にヨウ化カリウムを加えた際に遊離したエポキシ化植物油１ｋｇ当たりのヨウ素のミリ当量数（ミリ当量／ｋｇ）から求めた。 (6) Measurement of peroxide value of epoxidized vegetable oil:
Epoxidized vegetable oil based on the acetic acid / isooctane method of the standard fat analysis method (2.5.2 Peroxide value, standard fat analysis test method (I), Japan Oil Chemistry Society established, 2003 edition, Japan Oil Chemistry Society) It was determined from the number of milliequivalents of iodine per milligram of epoxidized vegetable oil liberated when potassium iodide was added to (equivalent to milliequivalents / kg).
　実施例１～５及び比較例１～３：
＜使用材料＞
（１）塩化ビニル樹脂：ポリ塩化ビニル、平均重合度１０５０
（２）金属石鹸系安定剤：旭電化工業（株）の商品名アデカスタブＳＰ－７６（Ｃａ－Ｚｎ系安定剤）
（３）エポキシ化大豆油
（４）コハク酸（飽和ジカルボン酸）
（５）オレイン酸（飽和モノカルボン酸）
（６）可塑剤（ＤＯＰ：フタル酸ジオクチル） Examples 1 to 5 and Comparative Examples 1 to 3:
<Materials used>
(1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050
(2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd.
(3) Epoxidized soybean oil (4) Succinic acid (saturated dicarboxylic acid)
(5) Oleic acid (saturated monocarboxylic acid)
(6) Plasticizer (DOP: Dioctyl phthalate)
＜操作方法＞
　上記の使用材料から選ばれた各成分を、表１に示す割合で混合し、スーパーミキサーに投入し、攪拌しながら材料温度を室温から１３０℃まで昇温した後、材料温度６０℃まで冷却した。得られた混合物を、Ｔダイ（幅３５０ｍｍ、ギャップ０．４ｍｍ）を装着したΦ４０ｍｍ単軸押出機（Ｌ／Ｄ＝２０）にて樹脂温度２００℃で押出成形して厚み０．０１ｍｍのフィルムを得た。そして、得られたフィルムについて、柔軟性、透明性、プレス時の噴出性、耐ブリード性を評価し、その結果を表１に示した。 <Operation method>
Each component selected from the materials used above was mixed in the proportions shown in Table 1, charged into a supermixer, the temperature of the material was raised from room temperature to 130 ° C. with stirring, and then cooled to a material temperature of 60 ° C. . The resulting mixture was extruded at a resin temperature of 200 ° C. with a Φ40 mm single screw extruder (L / D = 20) equipped with a T die (width 350 mm, gap 0.4 mm) to form a film having a thickness of 0.01 mm. Obtained. And the softness | flexibility, transparency, the ejection property at the time of a press, and bleed resistance were evaluated about the obtained film, and the result was shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　上記実施例１～５に関しては、１８０～２２０℃に加熱することでエポキシ化大豆油とジカルボン酸又はモノカルボン酸とが反応して、２量体、３量体及びそれ以上の多量体を形成することが確認された。よって、反応後は、変性エポキシ化大豆油を含むことが確認された。これに対し、エポキシ化大豆油のみで酸を含まない場合（比較例１）や、エポキシ化植物油ではない可塑剤のみを使用した場合（比較例２）、及び、エポキシ化されていない大豆油のみを使用した場合（比較例３）は、変性エポキシ化大豆油が生成されない。 For Examples 1-5 above, epoxidized soybean oil reacts with dicarboxylic acid or monocarboxylic acid by heating to 180-220 ° C. to form dimers, trimers and higher multimers. Confirmed to do. Therefore, it was confirmed that the modified epoxidized soybean oil was contained after the reaction. On the other hand, when only an epoxidized soybean oil does not contain an acid (Comparative Example 1), when only a plasticizer that is not an epoxidized vegetable oil is used (Comparative Example 2), and only an epoxidized soybean oil Is used (Comparative Example 3), modified epoxidized soybean oil is not produced.
　表１の結果より、多量体含有量５～６５質量％の変性エポキシ化大豆油を含む樹脂組成物を使用してフィルムを成形すると、透明で、且つ柔軟性なフィルムを作製できるばかりか、変性エポキシ化大豆油のブリードアウトを効果的に抑えることができることが分かる。 From the results shown in Table 1, when a film is formed using a resin composition containing a modified epoxidized soybean oil having a multimer content of 5 to 65% by mass, a transparent and flexible film can be produced. It turns out that the bleed-out of epoxidized soybean oil can be suppressed effectively.
　実施例６～１０及び比較例４～５：
＜使用材料＞
（１）塩化ビニル樹脂：ポリ塩化ビニル、平均重合度１０５０
（２）金属石鹸系安定剤：旭電化工業（株）の商品名アデカスタブＳＰ－７６（Ｃａ－Ｚｎ系安定剤）
（３）変性エポキシ化大豆油－１：エポキシ化大豆油１００質量部とオレイン酸１．２質量部とを２００℃で１時間攪拌混合して反応させて得た。
（４）変性エポキシ化大豆油－２：エポキシ化大豆油１００質量部とオレイン酸６質量部とを２００℃で１時間攪拌混合して反応させて得た。
（５）変性エポキシ化大豆油－３：エポキシ化大豆油１００質量部とコハク酸１．２質量部とを２００℃で１時間攪拌混合して反応させて得た。
（６）エポキシ化大豆油
（７）ポリエステル系化合物－１：ＤＩＣ（株）の商品名「ポリサイザーＷ－３６０－ＥＬ」（ポリ（１，３－ブタンジオール／アジピン酸）エステル、重量平均分子量：６，０００）
（８）ポリエステル系化合物－２：ＤＩＣ（株）の商品名「ポリライトＯＤ－Ｘ－２０４４」（ポリネオペンチルアジペートジオール、重量平均分子量：６，８００） Examples 6 to 10 and Comparative Examples 4 to 5:
<Materials used>
(1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050
(2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd.
(3) Modified epoxidized soybean oil-1: Obtained by stirring and mixing 100 parts by mass of epoxidized soybean oil and 1.2 parts by mass of oleic acid at 200 ° C. for 1 hour.
(4) Modified epoxidized soybean oil-2: obtained by reacting 100 parts by mass of epoxidized soybean oil and 6 parts by mass of oleic acid with stirring at 200 ° C. for 1 hour.
(5) Modified epoxidized soybean oil-3: Obtained by stirring and mixing 100 parts by mass of epoxidized soybean oil and 1.2 parts by mass of succinic acid at 200 ° C. for 1 hour.
(6) Epoxidized soybean oil (7) Polyester compound-1: DIC Corporation trade name “Polysizer W-360-EL” (poly (1,3-butanediol / adipic acid) ester, weight average molecular weight: 6,000)
(8) Polyester compound-2: Trade name “Polylite OD-X-2044” of DIC Corporation (polyneopentyl adipate diol, weight average molecular weight: 6,800)
＜操作方法＞
　上記の使用材料から選ばれた各成分を、表２に示す割合で混合し、スーパーミキサーに投入し、攪拌しながら材料温度を室温から１３０℃まで昇温した。ただし、安定剤は、材料温度の昇温過程で添加した。その後、材料温度７０℃まで冷却した。得られた混合物を、Ｔダイ（幅３５０ｍｍ、ギャップ０．４ｍｍ）を装着したΦ４０ｍｍ単軸押出機（Ｌ／Ｄ＝２０）にて樹脂温度２００℃で押出成形して厚み０．０１ｍｍのフィルムを得た。そして、得られたフィルムについて、熱安定性、柔軟性、耐ブリード性を評価し、その結果を表２に示した。 <Operation method>
Each component selected from the above materials used was mixed in the proportions shown in Table 2, charged into a supermixer, and the material temperature was raised from room temperature to 130 ° C. while stirring. However, the stabilizer was added during the temperature raising process of the material temperature. Then, it cooled to material temperature 70 degreeC. The resulting mixture was extruded at a resin temperature of 200 ° C. with a Φ40 mm single screw extruder (L / D = 20) equipped with a T die (width 350 mm, gap 0.4 mm) to form a film having a thickness of 0.01 mm. Obtained. And about the obtained film, thermal stability, a softness | flexibility, and bleeding resistance were evaluated, and the result was shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　実施例１１～１５及び参考例１～４：
＜使用材料＞
（１）塩化ビニル樹脂：ポリ塩化ビニル、平均重合度１０５０
（２）金属石鹸系安定剤：旭電化工業（株）の商品名アデカスタブＳＰ－７６（Ｃａ－Ｚｎ系安定剤）
（３）エポキシ化大豆油－４：過酸化物価１３．３のエポキシ化大豆油
（４）エポキシ化大豆油－５：過酸化物価１５．１のエポキシ化大豆油
（５）エポキシ化大豆油－６：過酸化物価１０．１のエポキシ化大豆油
（６）エポキシ化大豆油－７：過酸化物価１８．６のエポキシ化大豆油
（７）ポリエステル系化合物：ＤＩＣ（株）の商品名「ポリサイザーＷ－３６０－ＥＬ」（ポリ（１，３－ブタンジオール／アジピン酸）エステル、重量平均分子量：６，０００） Examples 11 to 15 and Reference Examples 1 to 4:
<Materials used>
(1) Vinyl chloride resin: polyvinyl chloride, average polymerization degree 1050
(2) Metal soap type stabilizer: trade name ADK STAB SP-76 (Ca-Zn type stabilizer) of Asahi Denka Kogyo Co., Ltd.
(3) Epoxidized soybean oil-4: Epoxidized soybean oil having a peroxide value of 13.3 (4) Epoxidized soybean oil-5: Epoxidized soybean oil having a peroxide value of 15.1 (5) Epoxidized soybean oil 6: Epoxidized soybean oil with a peroxide value of 10.1 (6) Epoxidized soybean oil -7: Epoxidized soybean oil with a peroxide value of 18.6 (7) Polyester compound: Trade name “Polycizer” of DIC Corporation W-360-EL ”(poly (1,3-butanediol / adipic acid) ester, weight average molecular weight: 6,000)
＜操作方法＞
　上記の使用材料から選ばれた各成分を、表３に示す割合で混合し、スーパーミキサーに投入し、攪拌しながら材料温度を室温から１３０℃まで昇温した。ただし、エポキシ化大豆油は、材料温度の昇温過程で添加した。その後、材料温度７０℃まで冷却した。得られた混合物を、Ｔダイ（幅３５０ｍｍ、ギャップ０．４ｍｍ）を装着したΦ４０ｍｍ単軸押出機（Ｌ／Ｄ＝２０）にて樹脂温度２００℃で押出成形して厚み０．０１ｍｍのフィルムを得た。そして、得られたフィルムについて、熱安定性、柔軟性、耐ブリード性、臭気を評価し、その結果を表３に示した。 <Operation method>
Each component selected from the above materials used was mixed in the proportions shown in Table 3, charged into a supermixer, and the material temperature was raised from room temperature to 130 ° C. while stirring. However, the epoxidized soybean oil was added in the course of raising the material temperature. Then, it cooled to material temperature 70 degreeC. The resulting mixture was extruded at a resin temperature of 200 ° C. with a Φ40 mm single screw extruder (L / D = 20) equipped with a T die (width 350 mm, gap 0.4 mm) to form a film having a thickness of 0.01 mm. Obtained. And about the obtained film, thermal stability, a softness | flexibility, bleed resistance, and an odor were evaluated, and the result was shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Claims (11)

  1. 　熱可塑性樹脂１００質量部に対し多量体含有量５～６５質量％の変性エポキシ化植物油２０～６０質量部を配合して成ることを特徴とする樹脂組成物。 A resin composition comprising 20 to 60 parts by mass of a modified epoxidized vegetable oil having a multimer content of 5 to 65% by mass based on 100 parts by mass of a thermoplastic resin.
  2. 　変性エポキシ化植物油がエポキシ化植物油と活性水素含有化合物との反応によって調製されたものである請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the modified epoxidized vegetable oil is prepared by a reaction between an epoxidized vegetable oil and an active hydrogen-containing compound.
  3. 　変性エポキシ化植物油が過酸化物価１３．１～１８．０ミリ当量／ｋｇのエポキシ化植物油の加熱変性によって調製されたものである請求項１に記載の樹脂組成物。 2. The resin composition according to claim 1, wherein the modified epoxidized vegetable oil is prepared by heat modification of an epoxidized vegetable oil having a peroxide value of 13.1-18.0 meq / kg.
  4. 　エポキシ化植物油がエポキシ化大豆油である請求項１～３の何れかに記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the epoxidized vegetable oil is epoxidized soybean oil.
  5. 　熱可塑性樹脂が塩化ビニル系樹脂であり、更に、重量平均分子量が３，０００～１０，０００のポリエステル系化合物を含有し、塩化ビニル系樹脂の含有量１００質量部に対する、ポリエステル系化合物の含有割合が１～３０質量部である請求項１～４の何れかに記載の樹脂組成物。 The thermoplastic resin is a vinyl chloride resin, further contains a polyester compound having a weight average molecular weight of 3,000 to 10,000, and the content of the polyester compound relative to 100 parts by mass of the vinyl chloride resin The resin composition according to any one of claims 1 to 4, wherein is from 1 to 30 parts by mass.
  6. 　ポリエステル系化合物が、アジピン酸エステル系化合物、ポリエステルポリオール、または、アジピン酸エステル系化合物とポリエステルポリオールの混合物である請求項５に記載の脂組成物。 6. The fat composition according to claim 5, wherein the polyester compound is an adipic acid ester compound, a polyester polyol, or a mixture of an adipic acid ester compound and a polyester polyol.
  7. 　アジピン酸エステル系化合物が、ポリ（１，３－ブタンジオール／アジピン酸）エステル、ポリ（１，４－ブタンジオール／アジピン酸）エステル、または、これらの混合物である請求項６に記載の樹脂組成物。 The resin composition according to claim 6, wherein the adipic acid ester compound is a poly (1,3-butanediol / adipic acid) ester, a poly (1,4-butanediol / adipic acid) ester, or a mixture thereof. object.
  8. 　ポリエステルポリオールがポリネオペンチルアジペートジオールである請求項６に記載の樹脂組成物。 The resin composition according to claim 6, wherein the polyester polyol is polyneopentyl adipate diol.
  9. 　請求項１～８の何れかに記載の樹脂組成物から成ることを特徴とする包装用フィルム。 A packaging film comprising the resin composition according to any one of claims 1 to 8.
  10. 　原料として、請求項１記載の樹脂組成物を使用する包装フィルムの製造方法であって、熱可塑性樹脂、エポキシ化植物油、活性水素含有化合物を含有する樹脂組成物の加熱成形工程を包含し、当該加熱成形工程におけるエポキシ化植物油と活性水素含有化合物との反応により変性エポキシ化植物油を調製することを特徴とする包装用フィルムの製造方法。 It is a manufacturing method of the packaging film which uses the resin composition of Claim 1 as a raw material, Comprising: The thermoforming process of the resin composition containing a thermoplastic resin, an epoxidized vegetable oil, and an active hydrogen containing compound is included, The said A method for producing a packaging film, comprising preparing a modified epoxidized vegetable oil by a reaction between an epoxidized vegetable oil and an active hydrogen-containing compound in a heat forming step.
  11. 　原料として、請求項１記載の樹脂組成物を使用する包装フィルムの製造方法であって、熱可塑性樹脂、過酸化物価１３．１～１８．０ミリ当量／ｋｇのエポキシ化植物油を含有する樹脂組成物の加熱成形工程を包含し、当該加熱成形工程により上記のポキシ化植物油を変性させて変性エポキシ化植物油を調製することを特徴とする包装用フィルムの製造方法。 A method for producing a packaging film using the resin composition according to claim 1 as a raw material, comprising a thermoplastic resin and an epoxidized vegetable oil having a peroxide value of 13.1-18.0 meq / kg A method for producing a packaging film comprising a step of heat-molding a product, wherein the modified epoxidized vegetable oil is prepared by modifying the poxylated vegetable oil by the heat-forming step.
PCT/JP2012/079965 2011-12-09 2012-11-19 Resin composition, and packaging film and method for producing same WO2013084707A1 (en)

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JP2011-269764 2011-12-09
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JP2011269765A JP2013119624A (en) 2011-12-09 2011-12-09 Vinyl chloride-based flexible resin composition and plastic wrap
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