WO2005012422A1 - 塩化ビニリデン系樹脂フィルム、食肉練製品用ケーシング及び包装食肉練製品 - Google Patents
塩化ビニリデン系樹脂フィルム、食肉練製品用ケーシング及び包装食肉練製品 Download PDFInfo
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- WO2005012422A1 WO2005012422A1 PCT/JP2004/010074 JP2004010074W WO2005012422A1 WO 2005012422 A1 WO2005012422 A1 WO 2005012422A1 JP 2004010074 W JP2004010074 W JP 2004010074W WO 2005012422 A1 WO2005012422 A1 WO 2005012422A1
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- vinylidene chloride
- meat
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- resin film
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- 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
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- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
-
- 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
- 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
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D2565/38—Packaging materials of special type or form
- B65D2565/381—Details of packaging materials of special type or form
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
Definitions
- the present invention relates to a vinylidene chloride-based resin film, and more particularly, to a vinylidene chloride-based resin film that is excellent in meat peelability and suitability for automatic filling and packaging, and is suitable as a packaging material for meat-paste products such as kamo sausage. .
- the vinylidene chloride-based resin film of the present invention can be suitably used as a casing for meat and meat products.
- meat dough products such as fish and fish sausage are manufactured and sold in a form packed in a plastic film casing such as a tube for long-term storage and the like.
- the plastic film constituting the casing is excellent in gas barrier properties (oxygen gas barrier properties and water vapor barrier properties), low-temperature flexibility, transparency, heat shrinkage, heat sealing properties, etc., and has good printability.
- Vinylidene resin films are widely used.
- a packaged meat paste product filled and packaged with a meat paste product in a vinylidene chloride resin film casing and heat-sterilized may cause the meat paste product to adhere too tightly to the inner surface of the casing film,
- the meat paste product adheres to the peeled surface of the casing film due to the chemical bond between the film and the Cinda film. If the meat paste product adheres to the peeled surface of the casing film, the contents will decrease, and the appearance of the meat paste product after peeling the casing film will be impaired, and the commercial value will decrease. Therefore, in order to prevent the meat paste product from adhering to the casing film peeling surface, a Shiridani bilidene-based resin film containing various additives generally called "meat peeling agent" has been proposed. .
- Vinylidene chloride-based resin film for example, Japanese Patent Publication No. 44-2010
- Vinylidene chloride-based resin film for example, Japanese Patent Publication No.
- a vinylidene-based resin film (for example, Japanese Patent Publication No. 55-22666) formed by infusion method, and a resin obtained by adding polyglycerin stearate ester to a vinylidene chloride-based resin.
- a vinylidene chloride-based resin film on which a composition is formed (for example, JP-A-6-316641) has been proposed.
- a vinylidene chloride resin film containing a meat exfoliating agent such as sorbitan fatty acid ester or polyglycerin stearate has a meat exfoliating property.
- a meat exfoliating agent such as sorbitan fatty acid ester or polyglycerin stearate
- the Shiridani vinylidene-based resin film used as the wrapping material has not only excellent meat release properties but also It is required to have excellent suitability for automatic filling and packaging machines.
- a seamless single-layer tube formed by molding a vinylidene chloride resin by an inflation method is sometimes used.
- a long film obtained by folding a cylindrical film formed of vinylidene chloride resin by the inflation method to form a flat two-layer film and slitting the two-layer film to a desired width is used as an original. Used as an anti.
- the slit-processed raw film is formed into a tube shape by overlapping the two ends in the width direction into an envelope-stretched shape by a bag making device attached to an automatic filling and packaging machine and welding. ing. High-frequency electrodes are used for film welding.
- the meat dough product material determined by a metering pump is passed through the flow path from the nozzle tip to the tube. Is filled in.
- the tube filled with the raw material is squeezed at regular intervals by a pair of squeezing rollers.
- the tube was filled with the filled raw material, and the tube was ligated at two places with two metal clips.
- the lower metal clip of the two metal clips forms the upper end ligature of the previously filled portion, and the upper metal clip forms the lower end ligature of the later filled portion.
- the cut between the two ligatures results in individual packaged meat products.
- the vinylidene chloride-based resin film has good slipperiness. If the vinylidene chloride-based resin film has poor slipperiness, the length of the packaged meat and meat products will vary, and the high-frequency welded parts will be over-melted, resulting in thinning of seal lines, pinholes, and high pressure due to poor sealing. The bag may break during heat sterilization.
- An object of the present invention is to provide a vinylidene chloride-based resin film which is excellent in meat releasability and suitability for automatic filling and packaging, and is suitable as a packaging material for meat paste products such as kamo sausage.
- Another object of the present invention is to provide a vinylidide chloride having excellent meat release properties and suitability for an automatic filling and packaging machine. It is an object of the present invention to provide a casing for meat and meat products comprising a resin-based resin film. Further, an object of the present invention is to provide a packaged meat dough product in which the meat dough product is filled and packaged in such a meat dough product casing.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, a specific polyglycerin fatty acid ester exhibited excellent performance as a meat release agent for a vinylidene chloride-based resin film. It was found that the suitability of the filling and packaging machine was not impaired. The present invention has been completed based on these findings.
- the ester of the fatty acid component having 19 to 25 carbon atoms and the polyglycerin component is added to 0.05 to 1.5 parts by weight based on 100 parts by weight of the vinylidene chloride resin.
- the present invention provides a vinylidene chloride-based resin film formed from a resin composition containing:
- a casing for meat and meat products formed from the above-mentioned Shiridani vinylidene-based resin film.
- a packaged meat paste product in which the meat paste product is filled and packaged in the meat paste product casing.
- the vinylidene chloride resin (hereinafter sometimes referred to as “PVDC resin”) used in the present invention is 60 to 98% by weight of vinylidene chloride and another monomer copolymerizable with vinylidene chloride. (Co-monomer) A copolymer with 2 to 40% by weight.
- Examples of the comonomer include, for example, Shiri-Dai-Biel; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, radiuryl acrylate, and stearyl acrylate.
- alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, radiuryl acrylate, and stearyl acrylate.
- the number of carbon atoms in the alkyl group is 1 to 18
- alkyl methacrylates such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate (the number of carbon atoms in the alkyl group).
- cyanided burs such as atarilonitrile and metathalonitrile
- aromatic butyls such as styrene
- Butyl ester of an aliphatic carboxylic acid having 1 to 18 carbon atoms such as butyl acetate; alkylbutyl ether having 1 to 18 carbon atoms; such as ataryl acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid Bull polymerizable unsaturated carboxylic acid; alkyl ester of bullet polymerizable unsaturated carboxylic acid such as maleic acid, fumaric acid, itaconic acid (including partial ester, alkyl group having 1 to 18 carbon atoms); Monomers; functional group-containing monomers; and polyfunctional monomers.
- comonomers can be used alone or in combination of two or more.
- comonomers biel chloride, methyl acrylate, and lauryl acrylate are preferred, and butyl chloride is particularly preferred.
- the copolymerization ratio of the comonomer is preferably 3 to 35 weight. / 0 , more preferably 8 to 25% by weight.
- the reduced viscosity [ ⁇ sp / C] of the vinylidene chloride resin is preferably from 0.035 to 0.070 from the viewpoint of processability when forming into a film, suitability for an automatic filling and packaging machine, and cold resistance. More preferably, it is from 0.040 to 0.065, particularly preferably from 0.045 to 0.063. If the reduced viscosity of the vinylidene chloride-based resin is too low, the processability is lowered, and if it is too high, a coloring tendency is exhibited. Two or more kinds of vinylidene chloride resins having different reduction viscosities can be used in combination, whereby the workability and the color tone can be highly balanced. When two or more vinylidene chloride resins are used in combination, the reduced viscosity of each resin is preferably within the above range.
- the vinylidene chloride resin can be blended with another resin if desired.
- other resins include ethylene monoacetate butyl copolymer, (meth) acrylate (co) polymer, and methyl methacrylate butadiene-styrene copolymer.
- the (meth) acrylic acid ester (co) polymer include a homopolymer or copolymer of an alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group [for example, (meth) acrylic acid Methyl- (meth) butyl acrylate copolymer].
- Other resins are vinylidene chloride resins. It is usually used in a proportion of 20 parts by weight or less based on parts by weight.
- the vinylidene chloride-based resin used in the present invention can be synthesized by any polymerization method such as suspension polymerization, emulsion polymerization, and solution polymerization. Among these, those synthesized by the suspension polymerization method are preferable.
- the vinylidene chloride resin is generally mixed with an additive component as a powder resin to form a powdery compound. This powdery compound is used as a material for forming a film.
- a vinylidene chloride-based resin can be synthesized as a powder resin having a particle size of about 40 to 600 / m without requiring a pulverization step after polymerization. 2.
- the polyglycerin fatty acid ester used in the present invention is an ester of a fatty acid component having 19 to 25 carbon atoms and a polyglycerin component.
- Typical fatty acid components having 19 to 25 carbon atoms include icosanoic acid and behenic acid, and among these, behenic acid [CH 3 (CH 2 ) 20 COOH] is preferred.
- the fatty acid component may be in the form of a free acid, or in the form of a salt or an alkyl ester upon esterification.
- polyglycerin component polyglycerols having various degrees of polymerization can be used, but diglycerin, triglycerin, and tetraglycerin are preferable from the viewpoints of meat releasability, compatibility and the like.
- the polyglycerin fatty acid ester may be any of monoester, diester, triester and the like, and may be a mixture thereof.
- the compounding ratio When the fatty acid component of the polyglycerin fatty acid ester has 18 or less carbon atoms (for example, stearic acid), the compounding ratio must be relatively large in order to obtain sufficient meat release properties.
- the number of carbon atoms in the fatty acid component is in the range of 19 to 25
- a sorbitan behenate ester other than polyglycerin fatty acid ester is used, the meat peeling property is insufficient, and Relatively large Even with this, it is difficult to obtain sufficient flaking properties.
- polyglycerin behenate is preferable.
- the polyglycerin behenate include at least one polyglycerin behenate selected from the group consisting of diglycerin monobenate, diglycerin dibehenate, triglycerin monobehenate, and triglycerin dibehenate.
- Esters are preferred.
- mixed esters such as diglycerin mono 'diester (a mixture of diglycerin monoester and diglycerin diester) and triglycerin monodiester (a mixture of triglycerin monoester and triglycerin diester) can be used.
- the proportion of the monoester-diester component in the mixed ester is arbitrary.
- polyglycerol fatty acid esters cannot always be fully specified due to the large number of hydroxyl groups.
- Polyglycerin fatty acid esters are often obtained as mixed esters.
- Specific examples of the polyglycerin fatty acid ester used in the present invention include the following diglycerin monobehenate, diglycerin monobehenate, triglycerin monobehenate, and triglycerin dibehenate.
- diglycerin monobehenate examples include the following formula (1)
- diglycerin dibehenate examples include the following formula (2)
- the polyglycerin fatty acid ester is used as a meat release agent for a bi-lidene chloride resin film, and the compounding ratio is 0.0 with respect to 100 parts by weight of the bi-lidene chloride resin. 5 to: L. 5 parts by weight, preferably 0.1 to 1.3 parts by weight, more preferably 0.2 to 1.0 parts by weight.
- the blending ratio of polyglycerol fatty acid ester to 100 parts by weight of vinylidene chloride-based resin is in the range of 0.4 to 0.8 parts by weight, the balance between meat release properties and suitability for automatic filling and packaging machines can be improved. It is possible to obtain a vinylidene chloride-based resin film that is excellent and has good film characteristics such as transparency.
- Vinylidene chloride resin has a plasticizer, a heat stabilizer, an antioxidant, a lubricant, a filler, a matting agent, a coloring agent, a UV absorber, a surfactant, and a pH adjuster during polymerization and during compound formation. And various other additives.
- plasticizer examples include octyl phthalate, tributyl acetyl citrate (namely, acetyl tributyl citrate), dibutyl sebacate, octyl sebacate, acetylated monoglyceride, acetylated diglyceride, acetyl ditriglyceride, and the like.
- polyester plasticizers such as acetylated glycerides containing two or three, adipic acid and 1,3-butanediol, adipic acid and 1,4-butanediol, and mixtures of two or more of these. It is listed as.
- the plasticizer is generally used in a proportion of 0.05 to 10 parts by weight based on 100 parts by weight of the Shiridani vinylidene-based resin. If the mixing ratio of the plasticizer is too large, the plasticizer tends to bleed.
- heat stabilizer examples include epoxidized vegetable oil, epoxidized animal oil, and epoxy Fatty acid esters, epoxy resin prepolymers, glycidyl group-containing (meth) acrylic resins and the like are used.
- the epoxidized vegetable oil and the epoxidized animal oil are not particularly limited as long as they have been conventionally used as heat stabilizers for vinylidene chloride-based resins.
- epoxidation with acetic acid or the like a compound in which a double bond has been modified into an oxysilane ring can be used.
- Preferred epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.
- Epoxidized fatty acid esters include epoxy products of unsaturated fatty acid esters such as epoxidized octyl stearate.
- Epoxy resin prepolymers include, for example, bisphenol A glycidyl ether.
- a (meth) acrylate copolymer containing a glycidyl ester of a butyl polymerizable unsaturated organic acid as a copolymerization component is exemplified.
- these epoxy compounds epoxidized vegetable oils widely used in the field of food packaging are preferred.
- the heat stabilizer is used in an amount of usually 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the vinylidene chloride resin. If the compounding ratio of the heat stabilizer is too large, bleeding occurs on the surface of the vinylidene chloride resin film, blocking tends to occur, and the gas barrier property tends to decrease.
- antioxidants examples include 2,6-di-tert-butyl-4-methyl-phenol (BHT) and triethylene glycol-bis [3- (3-tert-butyl-15-methyl-4-hydroxyphenyl).
- BHT 2,6-di-tert-butyl-4-methyl-phenol
- Propionate Irgano 245, manufactured by Chipagagi Co., Ltd.
- 2,4-dimethinole 6-S-anolequinolephenol 2,4-dimethyl-16- (1-methylpentadecyl) phenol
- a phenolic antioxidant such as Irganoxll 41 manufactured by Chipagagi Co., Ltd .
- a phosphite-based antioxidant such as diphosphite
- the antioxidant is usually used in an amount of 0.0001 to 0.001 per 100 parts by weight of the Shiridani vinylidene resin. It is used in a proportion of 0.5 parts by weight.
- the lubricant examples include waxes such as oxidized polyethylene wax, paraffin wax, polyethylene wax, estenole wax montanate, and calcium montanate; and fatty acid esters such as glycerin monoester.
- waxes such as oxidized polyethylene wax, paraffin wax, polyethylene wax, estenole wax montanate, and calcium montanate
- fatty acid esters such as glycerin monoester.
- mono- or bis-amides of fatty acids such as stearic acid amide can be mentioned.
- These lubricants are usually used in a proportion of 0.001 to 2 parts by weight based on 100 parts by weight of the vinylidene chloride resin.
- Examples of the filler include silicon dioxide and calcium carbonate. Silicon dioxide and calcium carbonate also act as a maturing agent and a film slipperiness (packing machine suitability) agent. Silicon dioxide also acts as an inorganic lubricant.
- An appropriate amount of the filler and the matting agent is used in an amount of usually 1 part by weight or less, preferably 0.5 part by weight or less, based on 100 parts by weight of the vinylidene chloride-based resin. When a filler is used, its lower limit is usually 0.001 part by weight based on 100 parts by weight of the Shiridani vinylidene-based resin.
- the ultraviolet absorber examples include 2- (2'-hydroxy-13 ', 5'-di-tert-ptinolepheninole) -5-chlorobenzototriazole, and an appropriate amount is used as needed. .
- an ultraviolet absorber When an ultraviolet absorber is used, it is usually used in a proportion of 0.001 to 1 part by weight based on 100 parts by weight of the vinylidene chloride resin.
- the surfactant for example, a nonionic surfactant such as sorbitan fatty acid ester, other polyglycerin fatty acid ester, or polyoxyethylene sorbitan fatty acid ester is used in an appropriate amount as necessary.
- these surfactants also act as a meat release agent for a packaging film, they can be used in combination with the meat release agent of the present invention, if necessary. However, these surfactants may reduce the properties such as slipperiness, delamination, and stickiness, so even if they are used, the proportion of these surfactants depends on the amount of polyglycerin fatty acid ester used in this invention. It is preferably smaller than the ratio. When these surfactants are used, the ratio is more preferably 0.01 to 0.1 part by weight based on 100 parts by weight of the vinylidene chloride-based resin.
- Other stabilizers include, for example, inorganic bases such as magnesium hydroxide, magnesium oxide and calcium hydroxyphosphate; organic weak acid salts such as citric acid and alkali metal citrate; ethylenediaminetetraacetate; Can be used.
- Examples of the pH adjuster include sodium pyrophosphate and sodium dihydrogen pyrophosphate.
- An appropriate amount of the pH adjuster is used within a range of 0.5 part by weight or less based on 100 parts by weight of the vinylidene chloride-based resin.
- the colorant examples include organic pigments such as azo pigments, phthalocyanine pigments, and quinatalidone pigments; inorganic pigments such as titanium oxide, aluminum-based pigments, My power and carbon black; and constitutions such as calcium carbonate and magnesium oxide. Pigments are used. Among these, red pigments such as Pigment 'Red and yellow pigments such as Pigment Yellow are widely used in the packaging film field for meat and meat products such as fish sausage. The colorants can be used alone or in combination of two or more.
- the colorant is usually used in an appropriate amount of 1 part by weight or less based on 100 parts by weight of the vinylidene chloride-based resin. However, in the case of a titanium oxide pigment, it may be mixed up to 10 parts by weight. When a colorant is used, its lower limit is usually about 0.01 part by weight based on 100 parts by weight of the vinylidene chloride-based resin.
- a powdery resin of the vinylidene chloride-based resin and various additives are blended to produce a powdery mixture (compound).
- liquid additives such as epoxidized vegetable oils and plasticizers are absorbed by the powder resin of vinylidene chloride resin.
- the powder additive adheres around the powder resin of the vinylidene chloride resin. If necessary, a part or all of the liquid plasticizer or stabilizer is added from the vinylidene chloride resin (composition) added during the polymer production process at the start or end of polymerization. Powdered resin may be used.
- Each component can be mixed using a blender such as a blade blender, a repump blender, and a Henschel mixer.
- a blender such as a blade blender, a repump blender, and a Henschel mixer.
- aggregation of the additive components easily occurs. If a large amount of aggregates are present in the vinylidene chloride-based resin composition, processability, extrudability, film formability, stretchability, etc. will be impaired, and further, the appearance of the film will be impaired due to the formation of fish shreds. Therefore, in order to enhance the dispersibility of the additive component and to suppress the formation of aggregates, it is preferable to use a dispersing aid or to devise the mixing order. If the formation of aggregates is still unavoidable, remove the aggregates by sieving.
- the powdery vinylidene chloride resin composition (compound) can be melt-extruded and formed into an unstretched film or sheet or a stretched film.
- Preferred examples of the film forming method include an inflation method using a circuit die. In the inflation method, the film can be stretched in at least a uniaxial direction, preferably in a biaxial direction.
- the biaxially stretched oriented film has heat shrinkability and is suitably used as a retortable heat resistant film.
- the stretching ratio is preferably 2 to 5 times in the vertical direction and 2 to 5 times in the horizontal direction.
- the thickness of the film is usually from 5 to 50 / m2, preferably from 10 to 30 / m, as a single-layer film. It is preferable to use a two-layer film obtained by folding a tubular film obtained by the inflation method and slitting the film to have a desired width. The thickness of a two-layer film is twice that of a single-layer film.
- the heat shrinkage of the stretched film is preferably about 30 to 60% in both the vertical and horizontal directions when measured by immersing it in a glycerin bath at 120 ° C for 3 minutes.
- a biaxially stretched film is produced by the inflation method and then folded flat to form a two-layer film (double-ply film). Then, slits are formed at the ears at both ends of the film, and the film is wound around a core material such as a paper tube to form a roll-shaped raw material.
- the two-layer film material is supplied to an automatic filling and packaging machine, and both ends in the width direction are overlapped in an envelope-like shape and welded (heat-sealed) while forming a tube (including a cylinder).
- high-frequency electrodes are used as welding means.
- the tube thus formed is usually sent continuously to the filling section of the same automatic filling and packaging machine, and after filling the contents, is ligated with a metal clip.
- a package is obtained which is filled with contents such as meat and meat products and both ends are ligated.
- the raw material of the meat paste quantified by the metering pump is passed through the flow path. Is filled into the tube from the nozzle tip.
- the tube filled with the raw material is squeezed at regular intervals by a pair of squeezing rollers.
- the tube was filled with the filled ingredients and was ligated at two places simultaneously with two metal clips.
- the lower metal clip of the two metal clips forms the upper ligature of the previously filled portion, and the upper metal clip forms the lower ligature of the later filled portion.
- the tube between the two metal clips is cut to obtain individual packaged meat products.
- the vinylidene chloride-based resin film of the present invention is excellent in meat release properties, and can exhibit a high degree of meat release properties even when the blending ratio of polydaliserine fatty acid ester is relatively small. Further, the Shiridani vinylidene-based resin film of the present invention is excellent in suitability for an automatic filling and packaging machine, excellent in slipperiness and delamination prevention, and has no stickiness on the surface.
- the salted vinylidene-based resin film of the present invention is particularly suitable as a casing for packing meat and meat products such as fish and soy sage mainly composed of fish meat.
- a packaged meat product in which the vinylidene chloride-based resin film of the present invention is filled and packaged as a casing can withstand retort sterilization at high pressure and high temperature.
- packaged meat paste products that have been subjected to such heat sterilization have strong adhesion between the contents and the casing, and tend to cause a large amount of meaty substances to adhere to the peeled surface of the casing film when the casing is peeled off.
- the casing of the invention is remarkably excellent in meat peelability, and can solve such a problem.
- meat peelability is excellent not only when quenched after heat sterilization but also when chilled.
- the meat-filled package was urged at both ends to a length of 10 cm.
- a force cutter Using a force cutter, a cut was made in the length direction along the high-frequency seal line of the tube, and the film was peeled off at a constant speed and force in the circumferential direction. After this peeling, the ratio of the area where the meat adhered to the film was measured and evaluated in accordance with the following evaluation standard values. The smaller the value of the evaluation criterion, the better the meat peelability.
- the two-layered film with a thickness of 20 ⁇ and a width of 72 mm is overlaid at both ends via a forming plate by an automatic filling and packaging machine (Kureha KAP), and then sealed with a high frequency wave on a stuffer nozzle.
- Kureha KAP automatic filling and packaging machine
- a tube with a fold width of 30 mm was produced.
- the tube was taken out via a tension measuring roller at a take-up speed of 30 mZ, and the tension applied to the measuring roller was measured.
- the slip property of the film was evaluated according to the following criteria.
- Sliding tension is less than 3 kg, applicable to automatic filling packaging,
- Table 1 shows the formulation of the meat ingredients used in the experiment (raw material and sausage ingredients).
- the compound prepared in step 1 was melt-extruded into a tube at a resin temperature of 185 ° C. using a melt extruder having a diameter of 90 mm.
- the melt-extruded tubular body was quenched in a 6 ° C bath to make it amorphous. After passing the amorphous tubular body through a 20 ° C preheating bath to raise the temperature, air is blown into the tubular body while passing between two pairs of pinch rolls with different speeds.
- Biaxial stretching was performed 2.72 times in the direction and 3.63 times in the width direction.
- the obtained biaxially stretched film was folded by a pinch knurl on the take-up side to obtain a flat long double-layer film (double ply film) having a width of 120 Omm and a thickness of 40 / m.
- the double-ply film obtained in step 2 was slit to a width of 72 mm, and the slit double-ply film having a length of 150 Om was wound in layers on a paper tube to obtain a raw material for an automatic filling and packaging machine.
- This web is suspended on an automatic filling and packaging machine (KAP manufactured by Kureha Chemical Industry Co., Ltd.), and both ends in the film width direction are overlapped via an forming plate in the form of an envelope (folding width: 30 mm).
- Example 3 was carried out in the same manner as in Example 1 except that in step 3 of the example 1, "Kamasaki 1" was replaced with “Sausage 1" shown in Table 1. Table 2 shows the results. Example 3
- step 1 of Example 1 the meat release agent was changed from TGMDB to diglycerin mono'dibehenate (a mixture of diglycerin monobehenate and diglycerin dibehenate, hereinafter abbreviated as "DGMDB"). Except for the above, the procedure was the same as in Example 1. Table 2 shows the results. Example 4
- step 1 of Example 1 except that the meat release agent was changed from TGMDB to triglycerin mono-distearate (a mixture of triglycerin monostearate and triglycerin distearate; hereinafter abbreviated as "TGMDS") Performed in the same manner as in Example 1.
- TGMDS triglycerin mono-distearate
- step 1 of Example 1 a meat release agent was added from diglycerin mono and distearate (diglycerin monostearate and diglycerin distearate) from TGMDB. mixture.
- diglycerin mono and distearate diglycerin monostearate and diglycerin distearate
- Table 2 shows the results. Comparative Example 4
- Example 1 was the same as Example 1 except that in Step 1 of Example 1, the meat release agent was changed from TGMDB to S BMDB, and in Step 3 ⁇ Kamazaki 1 '' was changed to ⁇ Sausage 1 '' shown in Table 1. Went similarly. Table 2 shows the results.
- Meat release agent (parts by weight) Suitable for automatic filling and packaging machine
- Vinylidene chloride monochloride Bulle copolymer obtained by suspension polymerization [chloride Biniri den 89 weight 0/0 / vinyl chloride 1 1 wt 0/0, reduced viscosity (sp / C) 0.
- the mixture prepared in Step 1 was melt-extruded into a tube at a resin temperature of 185 ° C. using a melt extruder having a diameter of 90 mm.
- the melt-extruded tubular body was quenched in a 6 ° C bath to make it amorphous. After passing the amorphous tubular body through a preheating bath at 20 ° C to raise the temperature, air is blown into the tubular body while passing between two pairs of pinch ports with different speeds.
- a biaxial extension of 2.72 times in the width direction and 3.63 times in the width direction was performed.
- the biaxially stretched film was folded by a pinch roll on the winding side to obtain a flat long double-ply film having a width of 1200 mm and a thickness of 40 ⁇ .
- the double ply film obtained in step 2 is slit to a width of 72 mm, and the slit double ply film having a length of 150 Om is wound up in layers on a paper tube.
- the material was used for filling and packaging machines.
- This web is suspended on an automatic filling and packaging machine (KAP manufactured by Kureha Chemical Industry Co., Ltd.), and both ends in the film width direction are overlapped via an forming plate in the form of an envelope (folding width: 30 mm).
- One end of the tube was ligated with an aluminum wire, the other end was filled with sausage raw material according to the formulation of "Sausage 2" shown in Table 1, and then this end was ligated with an aluminum wire. .
- 100 meat-filled packages weighing 62 g and having a length between two ligatures of 235 mm were prepared. These packages are put in a can with a gauge pressure of 2.
- Example 6 A retort treatment was performed at 5 kg / cm 2 at 120 ° C. for 15 minutes, and then cooled in the same manner as in Example 1 to obtain a meat-filled package sample. Table 3 shows the results.
- Example 6 A retort treatment was performed at 5 kg / cm 2 at 120 ° C. for 15 minutes, and then cooled in the same manner as in Example 1 to obtain a meat-filled package sample. Table 3 shows the results. Example 6
- Example 5 was carried out in the same manner as in Example 5 except that the mixing ratio of the meat release agent, TGMDB, was changed from 0.3 parts by weight to 0.4 parts by weight in step 1 of Example 5. Table 3 shows the results.
- Example 7
- Example 5 was carried out in the same manner as in Example 5, except that the mixing ratio of the meat release agent, TGMDB, was changed from 0.3 parts by weight to 0.6 parts by weight in step 1 of Example 5. Table 3 shows the results.
- Example 8
- Example 5 was carried out in the same manner as in Example 5 except that the blending ratio of the meat release agent, TGMDB, was changed from 0.3 parts by weight to 0.8 parts by weight in step 1 of Example 5. Table 3 shows the results. Comparative Example 7
- Example 5 was carried out in the same manner as in Example 5, except that the meat peeling agent was changed from TGMDB to triglycerin mono-distearate (TGMDS) in Step 1 of Example 5. Table 3 shows the results. Comparative Example 8
- Comparative Example 7 was carried out in the same manner as in Comparative Example 7, except that the mixing ratio of D003 was changed from 0.3 parts by weight to 0.4 parts by weight. Table 3 shows the results. Comparative Example 9
- Comparative Example 10 The same procedure was performed as in Comparative Example 7, except that the blending ratio of TGMDS was changed from 0.3 parts by weight to 0.6 parts by weight. Table 3 shows the results. Comparative Example 10
- Comparative Example 7 was carried out in the same manner as in Comparative Example 7, except that the blending ratio of Det 01 ⁇ 03 was changed from 0.3 parts by weight to 0.8 parts by weight. Table 3 shows the results. Comparative Example 11
- Example 5 was carried out in the same manner as in Example 5, except that in Step 1 the meat release agent was changed from TGMDB to sorbitan mono-dibehenate (SBMDB). Table 3 shows the results. Comparative Example 12
- Comparative Example 11 was carried out in the same manner as in Comparative Example 11, except that the mixing ratio of 3808 was changed from 0.3 parts by weight to 0.6 parts by weight. Table 3 shows the results. Comparative Example 14
- T GMD B Triglycerin mono dibehenate
- T GMD S Triglycerin mono ⁇ distearate
- the vinylidene chloride resin film of the present invention is excellent in meat peelability and suitability for automatic filling and packaging, and is suitable as a packaging material for meat paste products such as kamo sausage.
- INDUSTRIAL APPLICABILITY The vinylidene chloride-based resin film of the present invention has good slipperiness, hardly causes delamination, and has no stickiness on the surface.
- the Shiridani vinylidene-based resin film of the present invention is excellent in transparency, heat sealing properties (for example, high frequency welding properties) and the like.
- the casing made of the vinylidene chloride-based resin film of the present invention When the casing made of the vinylidene chloride-based resin film of the present invention is used, the sticking of the meat paste product to the peeling surface of the casing film during the case peeling is suppressed, and the commercial value of the packaged meat paste product can be increased.
- the Shiridani vinylidene-based resin film of the present invention is excellent in meat releasability and suitability for an automatic filling and packaging machine, and is suitable for meat kneading such as fish and sausage containing fish as a main component. It can be suitably used as a casing for packaging products.
- the vinylidene chloride-based resin film of the present invention can be used in the field of packaging materials that require a high degree of meat peelability.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Food Science & Technology (AREA)
- Zoology (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Wrappers (AREA)
- Packages (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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KR1020067001601A KR101100499B1 (ko) | 2003-07-30 | 2004-07-08 | 염화비닐리덴계 수지 필름, 식육 연제품용 케이싱 및 포장식육 연제품 |
Applications Claiming Priority (2)
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JP2003283162A JP4634701B2 (ja) | 2003-07-30 | 2003-07-30 | 塩化ビニリデン系樹脂フィルム、食肉練製品用ケーシング及び包装食肉練製品 |
JP2003-283162 | 2003-07-30 |
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WO2005012422A1 true WO2005012422A1 (ja) | 2005-02-10 |
Family
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PCT/JP2004/010074 WO2005012422A1 (ja) | 2003-07-30 | 2004-07-08 | 塩化ビニリデン系樹脂フィルム、食肉練製品用ケーシング及び包装食肉練製品 |
Country Status (4)
Country | Link |
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JP (1) | JP4634701B2 (ja) |
KR (1) | KR101100499B1 (ja) |
CN (1) | CN100465224C (ja) |
WO (1) | WO2005012422A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019161884A1 (en) * | 2018-02-20 | 2019-08-29 | Emery Oleochemicals Gmbh | Lubricant for processing chlorinated polyvinylchloride |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3967173B2 (ja) * | 2001-05-09 | 2007-08-29 | 株式会社クレハ | ポリ塩化ビニリデン系樹脂組成物及びその製造方法 |
JP5808330B2 (ja) | 2009-09-30 | 2015-11-10 | ダウ グローバル テクノロジーズ エルエルシー | アセチル化ポリグリセリン脂肪酸エステルおよびそれで可塑化されたpvc絶縁体 |
JP5295929B2 (ja) * | 2009-10-29 | 2013-09-18 | 株式会社クレハ | ポリ塩化ビニリデン樹脂組成物、その製造方法、及び該樹脂組成物から形成された成形品 |
JP5501791B2 (ja) * | 2010-02-22 | 2014-05-28 | 旭化成ケミカルズ株式会社 | ポリ塩化ビニリデン系樹脂ラップフィルム及びラップフィルム巻回体 |
JP6285212B2 (ja) * | 2014-03-03 | 2018-02-28 | 株式会社クレハ | 易開封性及びレトルト耐性を有する充填包装体 |
JP6339435B2 (ja) * | 2014-07-23 | 2018-06-06 | 旭化成株式会社 | 塩化ビニリデン系樹脂ラップフィルム |
EP3324748B1 (en) * | 2015-07-17 | 2020-09-02 | Wm. Wrigley Jr. Company | Chewing gum and gum bases containing elastomers derived from edible oil sources |
JP6671907B2 (ja) * | 2015-09-29 | 2020-03-25 | 理研ビタミン株式会社 | 加工食品用ケーシング剥離性向上剤 |
JP6913506B2 (ja) * | 2017-05-16 | 2021-08-04 | 株式会社クレハ | 塩化ビニリデン系樹脂フィルム及び塩化ビニリデン系樹脂組成物 |
TWI747147B (zh) * | 2019-02-08 | 2021-11-21 | 日商瑪魯哈日魯股份有限公司 | 肉品加工食品包裝體 |
US20230167328A1 (en) * | 2020-03-27 | 2023-06-01 | Asahi Kasei Kabushiki Kaisha | Halogenated vinyl polymer water dispersion, multilayer film, and blister pack for medication |
CN117813349A (zh) | 2021-08-30 | 2024-04-02 | 株式会社吴羽 | 偏氯乙烯系树脂组合物、拉伸膜以及填充包装体 |
CN116003937A (zh) * | 2023-02-20 | 2023-04-25 | 河南双汇投资发展股份有限公司 | 一种提高高温火腿肠剥离效果的薄膜及其生产方法 |
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US4481324A (en) * | 1983-02-25 | 1984-11-06 | Glyco Inc. | Polyglycerol plastic lubricants |
JPH09151290A (ja) * | 1995-09-27 | 1997-06-10 | Kureha Chem Ind Co Ltd | 塩化ビニリデン系重合体組成物およびその成形物 |
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JPS5261261A (en) * | 1975-11-10 | 1977-05-20 | Kureha Chemical Ind Co Ltd | Method of producing packed boiled fish paste |
JPS649260A (en) * | 1987-07-02 | 1989-01-12 | Asahi Chemical Ind | Wrapping film of vinylidene chloride resin |
JP3512831B2 (ja) * | 1993-05-07 | 2004-03-31 | 旭化成ライフ&リビング株式会社 | 塩化ビニリデン系樹脂フィルム |
US6291565B1 (en) * | 1994-05-19 | 2001-09-18 | The Dow Chemical Company | Food packaging film |
NZ507945A (en) * | 1998-05-13 | 2003-02-28 | Dow Global Technologies Inc | Extrudable vinylidene chloride polymer compositions |
JP3802304B2 (ja) * | 2000-01-31 | 2006-07-26 | 理研ビタミン株式会社 | 食品包装用樹脂フィルム及びこれに用いる滑り性向上剤組成物 |
JP3967173B2 (ja) * | 2001-05-09 | 2007-08-29 | 株式会社クレハ | ポリ塩化ビニリデン系樹脂組成物及びその製造方法 |
-
2003
- 2003-07-30 JP JP2003283162A patent/JP4634701B2/ja not_active Expired - Lifetime
-
2004
- 2004-07-08 KR KR1020067001601A patent/KR101100499B1/ko not_active IP Right Cessation
- 2004-07-08 WO PCT/JP2004/010074 patent/WO2005012422A1/ja active Application Filing
- 2004-07-08 CN CNB2004800219672A patent/CN100465224C/zh not_active Expired - Fee Related
Patent Citations (2)
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US4481324A (en) * | 1983-02-25 | 1984-11-06 | Glyco Inc. | Polyglycerol plastic lubricants |
JPH09151290A (ja) * | 1995-09-27 | 1997-06-10 | Kureha Chem Ind Co Ltd | 塩化ビニリデン系重合体組成物およびその成形物 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019161884A1 (en) * | 2018-02-20 | 2019-08-29 | Emery Oleochemicals Gmbh | Lubricant for processing chlorinated polyvinylchloride |
Also Published As
Publication number | Publication date |
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CN1829768A (zh) | 2006-09-06 |
JP2005048109A (ja) | 2005-02-24 |
KR101100499B1 (ko) | 2011-12-29 |
KR20060090794A (ko) | 2006-08-16 |
JP4634701B2 (ja) | 2011-02-16 |
CN100465224C (zh) | 2009-03-04 |
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