CN1829768A - 1,1-vinylidene chloride resin film, casing for meat paste product, and packed meat paste product - Google Patents
1,1-vinylidene chloride resin film, casing for meat paste product, and packed meat paste product Download PDFInfo
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- CN1829768A CN1829768A CNA2004800219672A CN200480021967A CN1829768A CN 1829768 A CN1829768 A CN 1829768A CN A2004800219672 A CNA2004800219672 A CN A2004800219672A CN 200480021967 A CN200480021967 A CN 200480021967A CN 1829768 A CN1829768 A CN 1829768A
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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
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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
- 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
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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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
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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
- 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
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- Polymers & Plastics (AREA)
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- Materials Engineering (AREA)
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- Packages (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
A vinylidene chloride resin film formed from a resin composition which comprises 100 pts.wt. of a vinylidene chloride resin and 0.05 to 1.5 pts.wt. of an ester of a C19-25 fatty acid ingredient with a polyglycerol ingredient; a casing for meat paste products which comprises the film; and a packed meat paste product which comprises the casing and a meat paste product packed thereinto.
Description
Technical field
The present invention relates to a kind of vinylidene chloride resin film, relate to a kind of meat separability and automatic vinylidene chloride resin film packing suitability excellence, that be suitable as the wrapping material of meat emulsion products such as breaded fish stick, sausage in more detail.Vinylidene chloride resin film of the present invention can be suitable as casing for meat paste product.
Background technology
All the time, the meat emulsion product of breaded fish stick, fish sausage etc. is a purpose with prolonged preservation etc., sells with the form manufacturing of packing in the casing of the plastic film system of the such shape of pipe.As the plastic film that constitutes casing, be extensive use of the vinylidene chloride resin film, because excellences such as its barrier properties for gases (oxygen-barrier property and water vapour barrier), low-temperature pliability, the transparency, heat-shrinkable, heat sealability, and the printing suitability is good.
But, 1, in the casing of 1-vinylidene chloride resin film system packing meat emulsion product and carried out the packed meat paste product of heat sterilization, because meat emulsion product and packing film inner face excessively produce Chemical bond etc. between bonding, meat emulsion product and the packing film, so when the human consumer peels off packing film, on the release surface of meat emulsion product attached to packing film.If on the release surface of meat emulsion product attached to packing film, then content reduces, and in addition, peels off the appearance damage of the meat emulsion product behind the packing film, and commodity value descends.Therefore, in order to prevent that meat emulsion product to the adhering to of packing film release surface, having proposed to be combined with the vinylidene chloride resin film of the various additives that are commonly referred to as " meat stripper ".
People have for example proposed, will be 1, the resin combination that has added sorbitan fatty(acid)ester or polyoxyethylene sorbitan fatty acid ester in the 1-vinylidene chloride resin carries out film forming and the breaded fish stick packaging vinylidene chloride resin film (for example, special public clear 44-2108 communique) that obtains; The resin combination that utilizes inflation method will be mixed with nonionogenic tenside and other processing aids in the vinylidene chloride resinoid carries out film forming and the vinylidene chloride resin film (for example, special public clear 46-2382 communique) that obtains; Utilize the inflation method will be 1, the resin combination that adds the sorbitan fatty(acid)ester of the fatty acid component contain carbonatoms 20～24 in the 1-vinylidene chloride resin carries out film forming and the vinylidene chloride resin film (for example, special public clear 55-2266 communique) that obtains; Vinylidene chloride resin film (for example, the spy opens flat 6-316641 communique) that the resin combination that has added poly-stearin in the vinylidene chloride resinoid is carried out film forming and obtain etc.
Contain 1 of meat strippers such as sorbitan fatty(acid)ester, poly-stearin, the 1-vinylidene chloride resin film, be endowed the meat separability,, then can have suppressed meat emulsion product adhering to the packing film release surface if use the casing of this film system to come the packing meat emulsion product.
But, along with to packed meat paste product require the raising of standard to high-qualityization, the development of meat separability is better than 1 of currently available products, 1-diamino vinyl resins film and become the task of top priority by the casing of this film system.More particularly, require a kind of novel meat stripper of exploitation, the problem that it does not have the food sanitation aspect does not have bad influence to membrane property, even interpolation is more a small amount of, its meat separability is also excellent.
In addition, packing forms under high speed because meat emulsion product is to use Autofillingpackagingmachine, so for the vinylidene chloride resin film as wrapping material, except meat separability excellence, require that also Autofillingpackagingmachine is had excellent suitability.
As the packaging raw material film of meat emulsion product, use the mono-layer tube that does not have seam that utilizes inflation method that the moulding of vinylidene chloride resinoid is formed sometimes.But, usually use following long film as the raw material film, described long film is to utilize inflation method to carry out moulding the vinylidene chloride resinoid and obtain tubular membrane, the duplicature folding, that formation is flat is sheared this duplicature the long film that is processed into desired width and obtains.Shearing manufactured long pleurodiaphragmatic in terspace material film, generally is to utilize the bag making device be arranged on the Autofillingpackagingmachine, make the width two ends overlap into envelope applying shape to keep two-layer state, carries out clinkering, thereby is shaped to tubulose.The high frequency electrode is used in the clinkering of film.
In Autofillingpackagingmachine, the pipe of double-deck vinylidene chloride resin film system from above by during below delivering to continuously, by the quantitative meat emulsion product raw material of volume pump through stream, be filled in this pipe from nozzle tip.Smooth out with the fingers with some cycles and get the pipe that is filled with raw material by a pair of roller (drawing roller) of smoothing out with the fingers.The raw material of filling simultaneously carries out ligation by 2 metal clips in 2 places through smoothing out with the fingers the part that only becomes pipe after getting.Downside metal clip in 2 metal clips forms the upper end ligation portion of first filling part, and the upside metal clip forms the lower end ligation portion of back filling part.Part between 2 ligation portions is downcut, can obtain one packed meat paste product.
Using such Autofillingpackagingmachine to carry out high speed when filling, require the sliding of vinylidene chloride resin film good.If the sliding of vinylidene chloride resin film is poor, then the length of packed meat paste product produces inequality, and the excessive fusion at high frequency clinkering position causes the potted line thinning, produces pin hole, produces broken bag when poor sealing causes the high pressure heat sterilization.
In addition, shearing finished duplicature,, then can not form satisfied tubulose casing if with the Autofillingpackagingmachine bag time, produce layering at two interlayers as under the situation of raw material film.And then, if the surfaces of tacky of vinylidene chloride resin film then not only has bad influence to sliding, and reduce goods value.
But there is following problems in existing meat stripper: needs increase with respect to 1, the cooperation ratio of 1-vinylidene chloride resin improves the meat separability, and the sliding of vinylidene chloride resin film reduces, its surfaces of tacky etc., so the Autofillingpackagingmachine suitability is not necessarily abundant.
Summary of the invention
The object of the present invention is to provide a kind of vinylidene chloride resinoid, its meat separability and automatic packing suitability excellence are suitable as the wrapping material of the meat emulsion product of breaded fish stick and sausage etc.
Other purposes of the present invention are to provide a kind of casing for meat paste product, and its vinylidene chloride resin film by meat separability and Autofillingpackagingmachine suitability excellence forms.
And then, the object of the present invention is to provide a kind of in such casing for meat paste product packing the packed meat paste product of meat emulsion product is arranged.
The present inventor has goed deep into research to achieve these goals, found that the meat stripper of specific polyglycerol fatty acid glyceryl ester, can bring into play excellent performance as the vinylidene chloride resin film, and the Autofillingpackagingmachine suitability of not overslaugh vinylidene chloride resin film.The present invention is based on these discoveries and the invention finished.
Therefore, according to the present invention, can provide a kind of 1, the 1-vinylidene chloride resin film, it is formed by following resin combination, described resin combination contains the fatty acid component and the formed ester of Polyglycerine composition of the carbonatoms 19～25 of 0.05～1.5 weight part with respect to 100 weight part vinylidene chloride resinoids.
In addition, according to the present invention, can provide a kind of by the film formed casing for meat paste product of above-mentioned vinylidene chloride resinoid.
And then, according to the present invention, can provide a kind of in above-mentioned casing for meat paste product packing the packed meat paste product of meat emulsion product is arranged.
Embodiment
1.1, the 1-vinylidene chloride resin
Use among the present invention 1,1-vinylidene chloride resin (following be called sometimes " PVDC resinoid "), be the vinylidene chloride of 60～98 weight % and 2～40 weight % can with the formed multipolymer of other monomers (comonomer) of vinylidene chloride copolymerization.
As comonomer, for example can list vinylchlorid; The alkyl acrylate (carbonatoms of alkyl is 1～18) of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl etc.; The alkyl methacrylate (carbonatoms of alkyl is 1～18) of methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, methacrylic acid stearyl etc.; The vinyl cyanide class of vinyl cyanide, methacrylonitrile etc.; The aromatic vinyl of vinylbenzene etc.; The carbonatoms of vinyl-acetic ester etc. is the vinyl ester of 1～18 aliphatic carboxylic acid; Carbonatoms is 1～18 alkyl vinyl ether; The vinyl polymerized unsaturated carboxylic acid of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid etc.; The alkyl ester (carbonatoms that contains part ester, alkyl is 1～18) of the vinyl polymerized unsaturated carboxylic acid of toxilic acid, fumaric acid, methylene-succinic acid etc.; The dienes monomer; The monomer that contains functional group; Polyfunctional monomer.
These comonomers can be distinguished use separately, also can or be used in combination more than it 2 kinds.In these comonomers, preferred vinylchlorid, methyl acrylate and dodecylacrylate, preferred especially vinylchlorid.
If the copolymerization ratio of comonomer is too small, then the resinoid internal plasticiztion of vinylidene chloride becomes insufficient, and melt processable descends.If the copolymerization ratio of comonomer is excessive, then the resinoid barrier properties for gases of vinylidene chloride descends.The copolymerization ratio of comonomer is preferably 3～35 weight %, more preferably 8～25 weight %.
The viewpoint of the processibility when being shaped to film, Autofillingpackagingmachine suitability, winter hardiness, the resinoid reduced viscosity of vinylidene chloride [η sp/C] is preferably 0.035～0.070, more preferably 0.040～0.065, is preferably 0.045～0.063 especially.If the resinoid reduced viscosity of vinylidene chloride is low excessively, then processibility descends, if too high, then shows painted tendency, and is therefore not preferred.2 kinds or its above vinylidene chloride resinoid using reduced viscosity different can be merged, thus, processibility and tone height balance can be made.Merging under 2 kinds of uses or the resinoid situation of vinylidene chloride more than it, the reduced viscosity that is preferably each resin is all in above-mentioned scope.
The vinylidene chloride resinoid is according to required, can with other resin alloys.As other resins, for example can list vinyl-vinyl acetate copolymer, (methyl) acrylate (being total to) polymkeric substance, MBS.As (methyl) acrylate (being total to) polymkeric substance, be preferably the homopolymer or the multipolymer [for example, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer] of (methyl) alkyl acrylate of the carbonatoms 1～18 of alkyl.Other resins use with the ratio smaller or equal to 20 weight parts usually with respect to 100 weight part vinylidene chloride resinoids.
The vinylidene chloride resinoid that uses among the present invention can with suspension polymerization, letex polymerization, solution polymerization etc. arbitrarily polymerization synthesize, wherein, preferably utilize suspension polymerization to synthesize.The vinylidene chloride resinoid generally with the form of powdered resin, mixes with additive component, forms the powder shaped mixture.As the formed material of film, can use this powder shaped mixture.If utilize suspension polymerization, do not need the pulverizing process after the polymerization, can synthesize the vinylidene chloride resinoid with the form of powdered resin with the granularity about 40～600 μ m.
2. polyglycerol fatty acid glyceryl ester
In the present invention, in order to improve the meat separability of vinylidene chloride resin film, can use specific polyglycerol fatty acid glyceryl ester.That is, the polyglycerol fatty acid glyceryl ester that uses among the present invention is the fatty acid component of carbonatoms 19～25 and the ester that the Polyglycerine composition forms.
As the fatty acid component of carbonatoms 19～25, representational example has: methylene-succinic acid, docosoic acid etc. wherein, are preferably docosoic acid [CH
3(CH
2)
20COOH].Fatty acid component can be in the state of free acid when esterification, also can be the form of salt, alkyl ester etc.
As the Polyglycerine composition, can use the Polyglycerine of the various polymerization degree, but from the meat separability.The viewpoint of intermiscibility etc. is set out, and is preferably Glycerol dimer, triglycerin and four glycerine.Polyglycerol fatty acid glyceryl ester can be monoesters, diester, three esters etc. any one, also can be their mixture.
If the carbonatoms of the fatty acid component of polyglycerol fatty acid glyceryl ester is smaller or equal to 18 (for example, stearic acid), then increase relatively the cooperation ratio except needing in order to obtain sufficient meat separability, the suitability of reply such as the sliding of vinylidene chloride resin film Autofillingpackagingmachine is also not necessarily abundant.On the other hand, if for example anhydrosorbitol docosane acid esters of the carbonatoms that uses fatty acid component in 19～25 scope, beyond the polyglycerol fatty acid glyceryl ester, then the meat separability is insufficient, even increase the cooperation ratio relatively, also is difficult to obtain sufficient meat separability.
As polyglycerol fatty acid glyceryl ester, preferably poly-docosane acid glyceride.As poly-docosane acid glyceride, be preferably at least a Polyglycerine docosane acid esters that is selected from Glycerol dimer list docosane acid esters, the two docosane acid esters of Glycerol dimer, triglycerin list docosane acid esters and the two docosane acid esters of triglycerin.In addition, can use the mixed ester of Glycerol dimer list diester (mixture of diglycerol monoester and Glycerol dimer diester), triglycerin list diester (mixture of triglycerin monoesters and triglycerin diester) etc.Monoesters in the mixed ester, diester components in proportions are arbitrarily.
Because the chemical structure of polyglycerol fatty acid glyceryl ester has a lot of hydroxyls, therefore differing fully is specific surely.Polyglycerol fatty acid glyceryl ester obtains with the form of mixed ester under many circumstances.Concrete example as the polyglycerol fatty acid glyceryl ester that uses among the present invention can list, the two docosane acid esters of following Glycerol dimer list docosane acid esters, Glycerol dimer list docosane acid esters, triglycerin list docosane acid esters and triglycerin.
As Glycerol dimer list docosane acid esters, for example can list the ester shown in the following formula (1).
As the two docosane acid esters of Glycerol dimer, for example can list the ester shown in the following formula (2).
As triglycerin list docosane acid esters, for example can list the ester shown in the following formula (3).
As the two docosane acid esters of triglycerin, for example can list the ester shown in the following formula (4).
In the present invention, use the meat stripper of above-mentioned polyglycerol fatty acid glyceryl ester as the vinylidene chloride resin film, but its cooperation ratio is 0.05～1.5 weight part with respect to 100 weight part vinylidene chloride resinoids, be preferably 0.1～1.3 weight part, more preferably 0.2～1.0 weight part.Under many circumstances, polyglycerol fatty acid glyceryl ester is with respect to 1 of 100 weight parts, the cooperation ratio of 1-vinylidene chloride resin is in the scope of 0.4～0.8 weight part, can obtain the balance excellence between meat separability and the Autofillingpackagingmachine suitability, and the vinylidene chloride resin film that the membrane property of the transparency etc. is also good.
3. various additives
1, during the polymerization of 1-vinylidene chloride resin, when forming mixture, can make it contain various additives such as softening agent, thermo-stabilizer, antioxidant, lubricant, weighting agent, polishing finishing composition, tinting material, UV light absorber, tensio-active agent, pH regulator agent.
As softening agent; can list with the polyester softening agent is the softening agent of representative; for example; dioctyl phthalate (DOP), Tributyl O-acetylcitrate are (promptly; acetyl tributyl citrate), dibutyl sebate, dioctyl sebate, ethanoyl direactive glyceride, ethanoyl double glyceride, ethanoyl Witepsol W-S 55 and contain 2～3 ethanoyl glyceride type in them; hexanodioic acid and 1; the ester of 3-butyleneglycol, hexanodioic acid and 1, the ester of 4-butyleneglycol, their 2 kinds or its above mixture etc.Softening agent uses with the ratio of 0.05～10 weight part usually with respect to 100 weight part vinylidene chloride resinoids.If the cooperation ratio of softening agent is excessive, then softening agent oozes out easily.
As thermo-stabilizer, for example can use epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, epoxy prepolymer, contain (methyl) acrylic resin of glycidyl etc.Epoxidized vegetable oil and epoxidation animal oil, so long as all the time as 1, the material that the thermo-stabilizer of 1-vinylidene chloride resin uses gets final product, there is no particular limitation, can use following substances, that is, by making natural animal-plant oil ring oxidation with hydrogen peroxide, peracetic acid etc., thereby two keys are modified as the material of oxyethane ring with unsaturated link(age).As preferred epoxidized vegetable oil, epoxidised soybean oil, epoxidation linseed oil wet goods are arranged.
As epoxidized fatty acid ester, the epoxide of the unsaturated fatty acid ester of epoxidized fatty acid monooctyl ester etc. is arranged.As epoxy prepolymer, the dihydroxyphenyl propane glycidyl ether is for example arranged.(methyl) acrylic resin as containing glycidyl can list, contain can with the glycidyl ester of the unsaturated organic acid of vinyl polymerization (methyl) acrylic acid esters co-polymer as copolymer composition.In these epoxy compoundss, preferably at the widely used epoxidized vegetable oil in food product pack field.
Thermo-stabilizer is with respect to 100 weight part vinylidene chloride resinoids, usually with 0.1～5 weight part, preferably with 0.5～4 weight part, more preferably use with the ratio of 1～3 weight part.If excessively increase the cooperation ratio of thermo-stabilizer, then ooze out on vinylidene chloride resin film surface, perhaps lump easily, barrier properties for gases becomes and reduces easily.
As antioxidant, for example can list, 2,6-di-t-butyl-4-methyl-phenol (BHT), triglycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester (チ バ ガ イ ギ one society's system, Irganox 245), 2,4-dimethyl-6S-alkylphenol, 2, the such phenol antioxidant of 4-dimethyl-6-(1-methyl five decyls) phenol and their mixture (the system Irganox 1141 of チ バ ガ イ ギ one society); Thio-2 acid, the such thioether class antioxidant of two octadecyl thiodipropionate; Three nonyl phenyl phosphate ester, the such phosphate-based antioxidants of two octadecyl pentaerythritol diphosphate.Antioxidant uses with the ratio of 0.0001～0.05 weight part usually with respect to 100 weight part vinylidene chloride resinoids.
As lubricant, for example can list oxidized polyethlene wax, paraffin, Ployethylene Wax, montanic acid ester type waxes, the such wax class of montanic acid calcium; The fatty acid ester of monoglyceride etc.In addition, the material as the secondary processing of melt-processed that is fit to the PVDC based resin composition and film for example can list the list of the lipid acid of stearylamide etc. or bisamide.These lubricants with respect to 100 weight part vinylidene chloride resinoids, use with the ratio of 0.001～2 weight part usually.
As weighting agent, for example can list silicon-dioxide, lime carbonate.Silicon-dioxide, lime carbonate can also be given (wrapping mechanism suitability) agent etc. and work as polishing finishing composition, film lubrication.In addition, silicon-dioxide can also work as inorganic lubricant.Weighting agent and polishing finishing composition with respect to 100 weight part vinylidene chloride resinoids, usually with smaller or equal to 1 weight part, preferably use in smaller or equal to the scope of 0.5 weight part respectively in right amount.Under the situation of using weighting agent, its lower value with respect to 100 weight part vinylidene chloride resinoids, is generally 0.001 weight part.
As UV light absorber, for example can list 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole.Come an amount of the use as required.Under the situation of using UV light absorber,, use with the ratio of 0.0001～1 weight part usually with respect to 100 weight part vinylidene chloride resinoids.
As tensio-active agent, for example the such nonionic class tensio-active agent of sorbitan fatty(acid)ester, other polyglycerol fatty acid glyceryl ester, polyoxyethylene sorbitan fatty acid ester etc. can come an amount of the use as required.These tensio-active agents also work as the meat stripper of film for packaging, therefore can be as required, and merge with meat stripper of the present invention and to use.But these tensio-active agents reduce oilness sometimes, cause layering, are clamminess etc., and therefore under situation about using, its usage ratio is preferably the usage ratio less than the polyglycerol fatty acid glyceryl ester that uses among the present invention.Under the situation of using these tensio-active agents, with respect to 100 weight part vinylidene chloride resinoid, the more preferably ratios of 0.001～0.1 weight part.
As other stablizers, also can use for example magnesium hydroxide, magnesium oxide, the such inorganic base of secondary calcium phosphate suitably, in right amount; Citric acid, the such organic monoacid salt of alkali metal citrates; The edetate class.
As the pH regulator agent, can list for example trisodium phosphate, Sodium Acid Pyrophosphate.The pH regulator agent is used in smaller or equal to the scope of 0.5 weight part in right amount with respect to the vinylidene chloride resinoid of 100 weight parts.Under the situation of adding the pH regulator agent, its lower value is generally 0.0001 weight part with respect to 100 weight part vinylidene chloride resinoids.
As tinting material, for example can use azo class pigment, phthalocyanine pigment, the such pigment dyestuff of quinacridine ketone pigment; Titanium oxide, aluminium class, mica, the such mineral dye of carbon black; Lime carbonate, the such pigment extender of magnesium oxide.Wherein, the film for packaging field at the meat emulsion product of fish sausage etc. is extensive use of the such such yellow ultramarine of red pigment, Pigment Yellow 73 of Pigment red.Tinting material can be distinguished separately and to use, and perhaps merges to use 2 kinds or more than it.
Tinting material is with respect to 100 weight part vinylidene chloride resinoids, usually to use in right amount smaller or equal to 1 weight part.But, under the situation of titanium oxide pigments, be mixed to sometimes till 10 weight parts.Under the situation of using tinting material, its lower value is generally about 0.001 weight part with respect to 100 weight part vinylidene chloride resinoids.
4.1, the 1-vinylidene chloride resin film
Generally contain under the situation of resin combination of vinylidene chloride resinoid and various additives,, make powder shaped mixture (compound) by making resinoid powdered resin of vinylidene chloride and various additive blend in modulation.By blend, the additive of the liquid of epoxidized vegetable oil, softening agent etc. is absorbed by the resinoid powdered resin of vinylidene chloride.The additive of powder is attached to around the resinoid powdered resin of vinylidene chloride.As required, can use by following 1, the powdered resin that 1-vinylidene chloride resin (composition) forms, described vinylidene chloride resinoid (composition) be when polymerization begins or the polymer fabrication processes of polymerization when finishing in added part or all liquid softening agent or stablizer forms.
Can use arm mixer, ribbon blender, the such mixing tank of Henschel mixing tank to mix each composition.In this mixed processes, additive component is easy to generate cohesion.If there are a large amount of condensation products in the vinylidene chloride based resin composition, then aspects such as processibility, extrudability, film-forming properties, stretchiness are impaired, and then film occurred because the bad order that the generation flake causes.Therefore, for the dispersiveness that improves additive component, the generation that suppresses condensation product, preferably use dispersing auxiliary or adjust order by merging.Even under the situation that can not avoid condensation product to generate like this, remove condensation product by screening.
The vinylidene chloride based resin composition (mixture) of powder shaped can be shaped to unstretching film or thin slice or stretched film by melt extruding.Preferred forming method as film for example can list, and utilizes the inflation method of circular mold.In inflation method, at least can be, preferably stretch along biaxially oriented along the single shaft direction.Biaxial stretch-formed alignment films has heat-shrinkable, in addition, is suitable as and can carries out distillatory thermotolerance film.Stretching ratio, preferably making vertically is 2～5 times, laterally is 2～5 times.
The thickness of film as unitary film, is generally 5～50 μ m, is preferably 10～30 μ m.The tubular membrane that preferred use will utilize inflation method to obtain folds, shears the duplicature that is processed into desirable width and obtains.The thickness of duplicature is 2 times of unitary film.The percent thermal shrinkage of stretched film is preferably, when dipping was measured after 3 minutes in 120 ℃ glycerol bath, vertical and horizontal all are about 30～60%.
Using 1, under the situation of 1-vinylidene chloride resin film as the meat emulsion product film for packaging, at first after utilizing inflation method to make biaxially-stretched film, folding is flat, form 2 eclipsed duplicatures (double compression film), then, portion shears on the limit at film two ends, be rolled onto then on the core of paper tube etc., form raw material film cylindraceous.The raw material film that this duplicature is constituted supplies in the automatic packing equipment, makes the cross direction two ends be overlapped into the bonding shape of envelope, carries out clinkering (heat-sealing) when forming tubulose (comprising cylindric).As the clinkering method, generally use high-frequency electrode.The pipe of operation formation is delivered in the filling part of identical Autofillingpackagingmachine usually continuously like this, after filling content, by the metal clip ligation.Like this, obtain to be filled with such content of meat emulsion product and two ends by the wrapping body of ligation.
More particularly, in Autofillingpackagingmachine, the pipe of double-deck vinylidene chloride resin film system by continuously from above below delivering to during, be filled in this pipe from nozzle tip through stream by the quantitative meat emulsion product raw material of volume pump.Smooth out with the fingers with some cycles and get the pipe that is filled with raw material by a pair of roller of smoothing out with the fingers.The raw material of filling simultaneously carries out ligation by 2 metal clips in 2 places through smoothing out with the fingers the part that only becomes pipe after getting.Downside metal clip in 2 metal clips forms the upper end ligation portion of first filling part, and the upside metal clip forms the lower end ligation portion of back filling part.Part between 2 ligation portions is downcut, can obtain one packed meat paste product.
Vinylidene chloride resin film of the present invention has excellent meat separability, even the cooperation ratio of polyglycerol fatty acid glyceryl ester reduces relatively, also can show very high meat separability.In addition, vinylidene chloride resin film of the present invention, its Autofillingpackagingmachine suitability excellence, sliding, anti-laminarity excellence, be not clamminess in the surface.Vinylidene chloride resin film of the present invention, the packaging casing of the meat emulsion product of the breaded fish stick that preferred especially conduct is principal constituent with the flesh of fish, sausage etc.
Vinylidene chloride resin film of the present invention carries out the packed meat paste product that packing forms as casing, the distillation sterilising treatment under can high pressure resistant high temperature.Carried out the packed meat paste product of such heat sterilization, in general, cohesiveness between content and the casing is strong, when peeling off casing, demonstrate the meat thing in a large number attached to the tendency on the release surface of packing film, but the meat separability of casing of the present invention is very excellent, can solve such problem.In addition, the meat separability is not only carrying out excellence under the rapid refrigerative situation behind the heat sterilization, and also is excellent under slow refrigerative situation.
Embodiment
Below, enumerate embodiment and comparative example, be described more specifically the present invention.
The evaluation method of various characteristics is as follows.
(1) meat separability
Carry out high frequency sealing and fill the breaded fish stick raw material in the pipe that forms or the sausage raw material is made meat packing body to the vinylidene chloride resin film, as sample, utilize following method to estimate the meat separability with wherein 10 (n=10).Meat packing body is cut off at two ends, and making length is 10cm.Use cutting machine along the high frequency potted line of pipe, form otch along its length, along the circumferential direction peel film with certain speed and power.After carrying out this strip operation, be determined at the ratio of the area that is attached with meat on the film, estimate with reference to following judgement criteria value.The sample that the numerical value of judgement criteria is more little shows good meat separability more.
0: there is not meat to adhere to (peeling off) comprehensively,
1: the area that is attached with meat was 1～5% (adhering to very slightly),
2: the area that is attached with meat was 6～25% (adhering to slightly),
3: the area that is attached with meat was 26～50% (adhering to quite in large quantities),
4: the area that is attached with meat was 51～75% (adhering in a large number),
5: the area that is attached with meat was 76～100% (comprehensively adhering to).
(2) Autofillingpackagingmachine suitability:
＜sliding 〉
Utilize Autofillingpackagingmachine (Wu Yu KAP) to make two ends overlapping by profiled sheeting the film of the 2 overlapping thickness that forms 20 μ m, wide 72mm, and then, on the filler nozzle, utilize high frequency to seal, make the pipe of the wide 30mm of folding.Make this pipe by the tension detection roller, under pulling speed 30m/ minute condition, draw, measure the suffered tension force of mensuration roller of this moment.The sliding of film is estimated by following standard.
A: slip tension goes for automatic packing smaller or equal to 3kg;
B: slip tension is 3～4kg, needs to adjust the condition of automatic packing;
C: slip tension, can not be suitable for even adjust the such condition of load more than or equal to 4kg.
Peeling off of＜duplicature; Layering 〉
A: even after passing through profiled sheeting, duplicature is not peeled off yet,
B: behind profiled sheeting, duplicature is partly peeled off,
C: behind profiled sheeting, pipe is peeled off continuously comprehensively and is duplicature.
Being clamminess property of＜film 〉
A: the sense of touch smoother,
B: sense of touch is clamminess.
The cooperation prescription of the meat raw material (breaded fish stick raw material and sausage raw material) that test is used eventually is as shown in table 1.
Table 1
| Breaded fish stick | Sausage | ||
| 1 | 1 | 2 | |
| The wall pollack walleye pollack ground flesh of fish | 55.0 | 55.0 | 50.0 |
| Frozen water | 31.2 | 25.2 | 30.0 |
| Vegetables oil | 0.0 | 6.0 | 5.0 |
| Salt | 1.7 | 1.7 | 1.8 |
| Tripoly phosphate sodium STPP | 0.1 | 0.1 | 0.2 |
| Soybean protein | 3.0 | 3.0 | 2.0 |
| W-Gum | 9.0 | 9.0 | - |
| Dry egg white | - | - | 3.0 |
| Pigskin gelatin | - | - | 3.0 |
| Yam starch | - | - | 5.0 |
Embodiment 1
1.
Engineering 1
Utilize ribbon blender, mixed following substances 30 minutes 70 ℃ of heating, described material is: 100 weight parts are by 1 of the suspension polymerization acquisition, 1-Ethylene Dichloride-vinyl chloride copolymer [1 of 89 weight %, the vinylchlorid of 1-Ethylene Dichloride/11 weight %, reduced viscosity (η sp/C) 0.060], as the Uniflex DBS and the 3 weight part acetyl tributyl citrates of 4 weight parts of softening agent, epoxidation linseed oil as 1.5 weight parts of thermo-stabilizer, the silicon-dioxide of 0.12 weight part as the polishing finishing composition, stearylamide as 0.05 weight part of lubricant, as the Pigment Yellow 73-95 (Pigment Yellow 95) of 0.3 weight part of tinting material and the Pigment red-166 (Pigment Red 166) of 0.08 weight part, and (promptly as the two docosane acid esters of the triglycerin list of 0.5 weight part of meat stripper, the list of docosoic acid and triglycerin/two ester mixtures; Below brief note is " TGMDB ").Then, cooling mixture with the screening of perforate 30 purpose wire nettings, is removed condensation product.The extrusion moulding mixture (compund) of powder shaped is modulated in operation like this.
2.
Engineering 2
Using the machine that melt extrudes of bore 90mm is under 185 ℃ at resin temperature, and synthetic mixture in the engineering 1 is melt extruded into tubulose.The tubular body arranged inside that will melt extrude is quick cooling in 6 ℃ body lotion, forms noncrystalline state.After the tubular body arranged inside with noncrystalline state elevates the temperature by 20 ℃ of pre-heating baths, utilization during passing through between 2 pairs of different pinch rolls of speed, in tubular body arranged inside, be blown into the inflation method of air, carry out biaxial stretch-formedly, make length direction stretch 2.72 times, cross direction stretches 3.63 times.The pinch roll that the biaxially-stretched film utilization that is obtained is batched side folds, and obtains the duplicature (double compression film) of the flat length of wide 1200mm, thick 40 μ m.
3.
Engineering 3
The double compression film that obtains in the engineering 2 is cut into the wide 72mm that is, shearing that then will long 1500m double compression film volume be stacked in and form stratiform on the paper tube, make Autofillingpackagingmachine raw material film.This raw material film is suspended on the Autofillingpackagingmachine (Wu Yu chemical industry system KAP), by profiled sheeting, make the two ends of film cross direction be overlapped into the bonding shape of envelope (folding width 30mm), utilization is configured in meat and fills with the high-frequency electrode on the nozzle, make overlapping the clinkering in these two ends, be shaped to pipe.With a side's of this pipe end aluminum steel ligation, fill breaded fish stick raw material from the opposing party's end, then with the aluminum steel ligation of this end according to the cooperation prescription of " breaded fish stick 1 " shown in the table 1.Operation like this, the meat packing body that to modulate 100 62g gap lengths heavy, the ligation of two places be 235mm.With these wrapping bodies gauge pressure 2.5kg/cm in jar
2Down, 120 ℃ of distillation sterilising treatment of carrying out 15 minutes, then with about 20 minutes, with being water-cooled to normal temperature, acquisition meat packing body sample.The results are shown in table 2.
Embodiment 2
In the engineering 3 of embodiment 1, " breaded fish stick 1 " replaced to " sausage 1 " shown in the table 1, in addition, operation similarly to Example 1.The results are shown in table 2.
Embodiment 3
In the engineering 1 of embodiment 1, the meat stripper is replaced to the two docosane acid esters of the Glycerol dimer list (mixture of the two docosane acid esters of Glycerol dimer list docosane acid esters and Glycerol dimer by TGMDB, below brief note is " DGMDB "), in addition, operation similarly to Example 1.The results are shown in table 2.
Embodiment 4
In the engineering 1 of embodiment 1, the meat stripper is replaced to DGMDB by TGMDB, and in engineering 3, " breaded fish stick 1 " replaced to " sausage 1 " shown in the table 1, in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 1
In the engineering 1 of embodiment 1, the meat stripper is replaced to triglycerin list SUNSOFT Q-182S (mixture of triglycerin monostearate and triglycerin SUNSOFT Q-182S, below brief note is " TGMDS ") by TGMDB, in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 2
In the engineering 1 of embodiment 1, the meat stripper is replaced to TGMDS by TGMDB, and in engineering 3, " breaded fish stick 1 " replaced to " sausage 1 " shown in the table 1, in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 3
In the engineering 1 of embodiment 1, the meat stripper is replaced to Glycerol dimer list SUNSOFT Q-182S (mixture of Glycerol dimer monostearate and Glycerol dimer SUNSOFT Q-182S, below brief note is " DGMDS ") by TGMDB, in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 4
In the engineering 1 of embodiment 1, the meat stripper is replaced to DGMDS by TGMDB, and in engineering 3, " breaded fish stick 1 " replaced to " sausage 1 " shown in the table 1, in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 5
In the engineering 1 of embodiment 1, the meat stripper is replaced to the two docosane acid esters of the anhydrosorbitol list (mixture of the two docosane acid esters of anhydrosorbitol list docosane acid esters and anhydrosorbitol by TGMDB, below brief note is " SBMDB "), in addition, operation similarly to Example 1.The results are shown in table 2.
Comparative example 6
In the engineering 1 of embodiment 1, the meat stripper is replaced to SBMDB by TGMDB, and in engineering 3, " breaded fish stick 1 " replaced to " sausage 1 " shown in the table 1, in addition, operation similarly to Example 1.The results are shown in table 2.
Table 2
| Meat stripper (weight part) | Meat cooperates prescription (with reference to table 1) | The meat separability | The Autofillingpackagingmachine suitability | ||||||||
| TGMDB | DGMDB | TGMDS | DGMDS | SBMDB | The breaded fish stick prescription | The sausage prescription | Sliding | Layering | Film is clamminess | ||
| Embodiment 1 | 0.5 | - | - | - | - | 1 | - | 0 | A | A | A |
| Embodiment 2 | 0.5 | - | - | - | - | - | 1 | 0 | A | A | A |
| Embodiment 3 | - | 0.5 | - | - | - | 1 | - | 1 | A | A | A |
| Embodiment 4 | - | 0.5 | - | - | - | - | 1 | 0-1 | A | A | A |
| Comparative example 1 | - | - | 0.5 | - | - | 1 | - | 3 | B | B | B |
| Comparative example 2 | - | - | 0.5 | - | - | - | 1 | 2-3 | B | B | B |
| Comparative example 3 | - | - | - | 0.5 | - | 1 | - | 4 | B | B | B |
| Comparative example 4 | - | - | - | 0.5 | - | - | 1 | 3 | B | B | B |
| Comparative example 5 | - | - | - | - | 0.5 | 1 | - | 5 | A | B | A |
| Comparative example 6 | - | - | - | - | 0.5 | - | 1 | 5 | A | B | A |
(remarks)
(1) TGMDB: the two docosane acid esters of triglycerin list
(2) DGMDB: the two docosane acid esters of Glycerol dimer list
(3) TGMDS: triglycerin list SUNSOFT Q-182S
(4) DGMDS: Glycerol dimer list SUNSOFT Q-182S
(5) SBMDB: the two docosane acid esters of anhydrosorbitol list
Embodiment 5
1.
Engineering 1
Utilize ribbon blender; mixed following substances 30 minutes 70 ℃ of heating; described material is: 100 weight parts are by 1 of the suspension polymerization acquisition; 1-Ethylene Dichloride-vinyl chloride copolymer [1 of 89 weight %; the vinylchlorid of 1-Ethylene Dichloride/11 weight %; reduced viscosity (η sp/C) 0.060], as the Uniflex DBS and the 2.5 weight part acetyl tributyl citrates of 3 weight parts of softening agent; epoxidation linseed oil as 1.5 weight parts of thermo-stabilizer; the lime carbonate of 0.15 weight part as the polishing finishing composition; stearylamide as 0.05 weight part of lubricant; and as the two docosane acid esters (TGMDB) of the triglycerin list of 0.3 weight part of meat stripper.Then, cooling mixture with the screening of perforate 30 purpose wire nettings, is removed condensation product.The extrusion moulding mixture is modulated in operation like this.
2.
Engineering 2
Using the machine that melt extrudes of bore 90mm is under 185 ℃ at resin temperature, and synthetic mixture in the engineering 1 is melt extruded into tubulose.The tubular body arranged inside that will melt extrude is quick cooling in 6 ℃ body lotion, forms noncrystalline state.After the pre-heating bath by 20 ℃ of the tubular body arranged inside of noncrystalline state is elevated the temperature, utilization during passing through between 2 pairs of different pinch rolls of speed, in tubular body arranged inside, be blown into the inflation method of air, carry out biaxial stretch-formedly, make length direction stretch 2.72 times, cross direction stretches 3.63 times.The pinch roll that the biaxially-stretched film utilization that is obtained is batched side folds, and obtains the double compression film of the flat length of wide 1200mm, thick 40 μ m.
3.
Engineering 3
The double compression film that obtains in the engineering 2 is cut into the wide 72mm that is, the double compression film volume of shearing that then will long 1500m is stacked in and forms stratiform on the paper tube, makes Autofillingpackagingmachine raw material film.This raw material film is suspended on the Autofillingpackagingmachine (Wu Yu chemical industry system KAP), by profiled sheeting, make the two ends of film cross direction be overlapped into the bonding shape of envelope (folding width 30mm), utilization is configured in meat and fills with the high-frequency electrode on the nozzle, make overlapping the clinkering in these two ends, be shaped to pipe.With a side's of this pipe end aluminum steel ligation, fill sausage raw material from the opposing party's end, then with the aluminum steel ligation of this end according to the cooperation prescription of " sausage 2 " shown in the table 1.Operation like this, the meat packing body that to modulate 100 62g gap lengths heavy, the ligation of two places be 235mm.With these wrapping bodies gauge pressure 2.5kg/cm in jar
2Descend, handle, cool off with operating similarly to Example 1 then, obtain meat packing body sample 120 ℃ of distillations of carrying out 15 minutes.The results are shown in table 3.
Embodiment 6
In the engineering 1 of embodiment 5, the cooperation ratio of meat stripper TGMDB is replaced with 0.4 weight part by 0.3 weight part, in addition, operation similarly to Example 5.The results are shown in table 3.
Embodiment 7
In the engineering 1 of embodiment 5, the cooperation ratio of meat stripper TGMDB is replaced with 0.6 weight part by 0.3 weight part, in addition, operation similarly to Example 5.The results are shown in table 3.
Embodiment 8
In the engineering 1 of embodiment 5, the cooperation ratio of meat stripper TGMDB is replaced with 0.8 weight part by 0.3 weight part, in addition, operation similarly to Example 5.The results are shown in table 3.
Comparative example 7
In the engineering 1 of embodiment 5, the meat stripper is replaced with triglycerin list SUNSOFT Q-182S (TGMDS) by TGMDB, in addition, operation similarly to Example 5.The results are shown in table 3.
Comparative example 8
The cooperation ratio of TGMDS is replaced with 0.4 weight part by 0.3 weight part, in addition, operate equally with comparative example 7.The results are shown in table 3.
Comparative example 9
The cooperation ratio of TGMDS is replaced with 0.6 weight part by 0.3 weight part, in addition, operate equally with comparative example 7.The results are shown in table 3.
Comparative example 10
The cooperation ratio of TGMDS is replaced with 0.8 weight part by 0.3 weight part, in addition, operate equally with comparative example 7.The results are shown in table 3.
Comparative example 11
In the engineering 1 of embodiment 5, the meat stripper is replaced with the two docosane acid esters (SBMDB) of anhydrosorbitol list by TGMDB, in addition, operation similarly to Example 5.The results are shown in table 3.
Comparative example 12
The cooperation ratio of SBMDB is replaced with 0.4 weight part by 0.3 weight part, in addition, operate equally with comparative example 11.The results are shown in table 3.
Comparative example 13
The cooperation ratio of SBMDB is replaced with 0.6 weight part by 0.3 weight part, in addition, operate equally with comparative example 11.The results are shown in table 3.
Comparative example 14
The cooperation ratio of SBMDB is replaced with 0.8 weight part by 0.3 weight part, in addition, operate equally with comparative example 11.The results are shown in table 3.
Table 3
| Meat stripper (weight part) | The sausage prescription | The meat separability | |||
| TGMDB | TGMDS | SBMDB | |||
| Embodiment 5 | 0.3 | - | - | 2 | 2 |
| Embodiment 6 | 0.4 | - | - | 2 | 1-2 |
| Embodiment 7 | 0.6 | - | - | 2 | 1 |
| Embodiment 8 | 0.8 | - | - | 2 | 0 |
| Comparative example 7 | - | 0.3 | - | 2 | 5 |
| Comparative example 8 | - | 0.4 | - | 2 | 4 |
| Comparative example 9 | - | 0.6 | - | 2 | 3 |
| Comparative example 10 | - | 0.8 | - | 2 | 2-3 |
| Comparative example 11 | - | - | 0.3 | 2 | 5 |
| Comparative example 12 | - | - | 0.4 | 2 | 5 |
| Comparative example 13 | - | - | 0.6 | 2 | 4 |
| Comparative example 14 | - | - | 0.8 | 2 | 3 |
(remarks)
(1) TGMDB: the two docosane acid esters of triglycerin list
(2) TGMDS: triglycerin list SUNSOFT Q-182S
(3) SBMDB: the two docosane acid esters of anhydrosorbitol list
The industry utilizability
Vinylidene chloride resin film of the present invention has excellent meat fissility and automatic filling packing applicability, is suitable as the packaging material of the meat emulsion product of breaded fish stick, sausage etc. Of the present invention 1, the 1-vinylidene chloride resin film, sliding is good, is difficult to produce layering, surfaces of tacky also do not occur. Vinylidene chloride resin film of the present invention, the excellences such as the transparency, heat sealability (such as, high frequency clinkering).
If use by the film formed casing of vinylidene chloride resinoid of the present invention, the meat emulsion product when then peeling off casing is suppressed to adhering to of the release surface of packaging film, can improve the commodity value of packed meat paste product.
Like this, vinylidene chloride resin film of the present invention has excellent meat fissility and automatic filling packing applicability, can be suitable for oppressing the packing casing of meat emulsion product of the breaded fish stick, sausage etc. that are principal component. In addition, vinylidene chloride resin film of the present invention can be used for requiring the highly field of the packaging material of meat fissility.
Claims (20)
1. one kind 1, the 1-vinylidene chloride resin film is formed by following resin combination, and described resin combination is, with respect to the vinylidene chloride resinoid of 100 weight parts, contain the fatty acid component and the formed ester of Polyglycerine composition of the carbonatoms 19～25 of 0.05～1.5 weight part.
2. vinylidene chloride based resin composition film as claimed in claim 1, fatty acid component is a docosoic acid.
3. vinylidene chloride resin film as claimed in claim 1, Polyglycerine composition are to be selected from least a in Glycerol dimer, triglycerin and four glycerine.
4. vinylidene chloride resin film as claimed in claim 1, ester is poly-docosane acid glyceride.
5. as claimed in claim 41,1-vinylidene chloride resin film, poly-docosane acid glyceride are at least a Polyglycerine docosane acid esters that is selected from Glycerol dimer list docosane acid esters, the two docosane acid esters of Glycerol dimer, triglycerin list docosane acid esters and the two docosane acid esters of triglycerin.
6. vinylidene chloride resin film as claimed in claim 1, vinylidene chloride resinoid be the vinylidene chloride of 60～98 weight % and 2～40 weight % can with other monomeric multipolymers of vinylidene chloride copolymerization.
7. vinylidene chloride resin film as claimed in claim 6 can be vinylchlorid with other monomers of vinylidene chloride copolymerization.
8. vinylidene chloride resin film as claimed in claim 1, the resinoid reduced viscosity of vinylidene chloride (η sp/C) is 0.035～0.070.
9. vinylidene chloride resin film as claimed in claim 1, resin combination further contains softening agent to be the ratio of 0.05～10 weight part with respect to 100 weight part vinylidene chloride resinoids.
10. vinylidene chloride resin film as claimed in claim 1, resin combination further contains thermo-stabilizer to be the ratio of 0.1～5 weight part with respect to 100 weight part vinylidene chloride resinoids.
11. vinylidene chloride resin film as claimed in claim 1, resin combination further contains lubricant to be the ratio of 0.001～2 weight part with respect to 100 weight part vinylidene chloride resinoids.
12. vinylidene chloride resin film as claimed in claim 1, resin combination further contains weighting agent to be the ratio of 0.001～1 weight part with respect to 100 weight part vinylidene chloride resinoids.
13. vinylidene chloride resin film as claimed in claim 1, resin combination further contains tinting material to be 10 weight parts or the ratio below it with respect to 100 weight part vinylidene chloride resinoids.
14. vinylidene chloride resin film as claimed in claim 1, resin combination are the mixture that is mixed with the powder shaped of resinoid powdered resin of vinylidene chloride and additive component.
15. vinylidene chloride resin film as claimed in claim 1 is biaxially-stretched film.
16. vinylidene chloride resin film as claimed in claim 15 is that stretching ratio is 2～5 times longitudinally, horizontal stretching ratio is 2～5 times a biaxially-stretched film.
17. a casing for meat paste product is film formed by each described vinylidene chloride resinoid of claim 1～16.
18. casing for meat paste product as claimed in claim 17 is to make double-deck film be overlapped into envelope at the cross direction two ends to paste the pipe that shape seals, moulding forms.
19. a packed meat paste product, packing meat emulsion product in claim 17 or 18 described casing for meat paste product and forming.
20. packed meat paste product as claimed in claim 19, be as the meat emulsion product packing be that the breaded fish stick of principal constituent or sausage fall into the goods that form with the flesh of fish.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP283162/2003 | 2003-07-30 | ||
| JP2003283162A JP4634701B2 (en) | 2003-07-30 | 2003-07-30 | Vinylidene chloride resin film, casing for meat paste products, and packaged meat paste products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1829768A true CN1829768A (en) | 2006-09-06 |
| CN100465224C CN100465224C (en) | 2009-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800219672A Active CN100465224C (en) | 2003-07-30 | 2004-07-08 | 1,1-vinylidene chloride resin film, casing for meat paste product, and packed meat paste product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4634701B2 (en) |
| KR (1) | KR101100499B1 (en) |
| CN (1) | CN100465224C (en) |
| WO (1) | WO2005012422A1 (en) |
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| JP6913506B2 (en) * | 2017-05-16 | 2021-08-04 | 株式会社クレハ | Vinylidene chloride-based resin film and vinylidene chloride-based resin composition |
| WO2019161884A1 (en) * | 2018-02-20 | 2019-08-29 | Emery Oleochemicals Gmbh | Lubricant for processing chlorinated polyvinylchloride |
| CN117813349A (en) | 2021-08-30 | 2024-04-02 | 株式会社吴羽 | Vinylidene chloride resin composition, stretched film, and filled package |
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| JPS5261261A (en) * | 1975-11-10 | 1977-05-20 | Kureha Chemical Ind Co Ltd | Method of producing packed boiled fish paste |
| US4481324A (en) * | 1983-02-25 | 1984-11-06 | Glyco Inc. | Polyglycerol plastic lubricants |
| JPS649260A (en) * | 1987-07-02 | 1989-01-12 | Asahi Chemical Ind | Wrapping film of vinylidene chloride resin |
| JP3512831B2 (en) * | 1993-05-07 | 2004-03-31 | 旭化成ライフ＆リビング株式会社 | Vinylidene chloride resin film |
| US6291565B1 (en) * | 1994-05-19 | 2001-09-18 | The Dow Chemical Company | Food packaging film |
| JPH09151290A (en) * | 1995-09-27 | 1997-06-10 | Kureha Chem Ind Co Ltd | Vinylidene chloride polymer composition and its molded item |
| KR20010043523A (en) * | 1998-05-13 | 2001-05-25 | 그래햄 이. 테일러 | Extrudable vinylidene chloride polymer compositions |
| JP3802304B2 (en) * | 2000-01-31 | 2006-07-26 | 理研ビタミン株式会社 | Resin film for food packaging and slippery improver composition used therefor |
| JP3967173B2 (en) * | 2001-05-09 | 2007-08-29 | 株式会社クレハ | Polyvinylidene chloride resin composition and method for producing the same |
-
2003
- 2003-07-30 JP JP2003283162A patent/JP4634701B2/en not_active Expired - Lifetime
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2004
- 2004-07-08 CN CNB2004800219672A patent/CN100465224C/en active Active
- 2004-07-08 KR KR1020067001601A patent/KR101100499B1/en not_active IP Right Cessation
- 2004-07-08 WO PCT/JP2004/010074 patent/WO2005012422A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102666697A (en) * | 2009-09-30 | 2012-09-12 | 陶氏环球技术有限责任公司 | Acetylated polyglycerine fatty acid ester and a pvc insulator plasticised therewith |
| US9481633B2 (en) | 2009-09-30 | 2016-11-01 | Dow Global Technologies Llc | Acetylated polyglycerine fatty acid ester and a PVC insulator plasticised therewith |
| CN102051009A (en) * | 2009-10-29 | 2011-05-11 | 株式会社吴羽 | Poly1,1-dichloroethylene resin composition, producing method thereof and molding formed by the same |
| CN102051009B (en) * | 2009-10-29 | 2013-03-20 | 株式会社吴羽 | Poly1,1-dichloroethylene resin composition, producing method thereof and molding formed by the same |
| CN105273340A (en) * | 2014-07-23 | 2016-01-27 | 旭化成化学株式会社 | Vinylidene chloride resin cling film |
| CN107846925A (en) * | 2015-07-17 | 2018-03-27 | Wm.雷格利 Jr.公司 | Chewing gum and matrix containing the elastomer from edible oil sources |
| CN111547384A (en) * | 2019-02-08 | 2020-08-18 | 玛鲁哈日鲁株式会社 | Meat processed food package |
| CN111547384B (en) * | 2019-02-08 | 2021-10-29 | 玛鲁哈日鲁株式会社 | Meat processed food package |
| CN115087703A (en) * | 2020-03-27 | 2022-09-20 | 旭化成株式会社 | Aqueous dispersion of vinyl halide polymer, multilayer film, and blister package for pharmaceutical products |
| CN116003937A (en) * | 2023-02-20 | 2023-04-25 | 河南双汇投资发展股份有限公司 | Film for improving peeling effect of high-temperature ham sausage and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20060090794A (en) | 2006-08-16 |
| CN100465224C (en) | 2009-03-04 |
| KR101100499B1 (en) | 2011-12-29 |
| WO2005012422A1 (en) | 2005-02-10 |
| JP4634701B2 (en) | 2011-02-16 |
| JP2005048109A (en) | 2005-02-24 |
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