CN105733138A - Cylindrical packaging body - Google Patents

Cylindrical packaging body Download PDF

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Publication number
CN105733138A
CN105733138A CN201510931628.8A CN201510931628A CN105733138A CN 105733138 A CN105733138 A CN 105733138A CN 201510931628 A CN201510931628 A CN 201510931628A CN 105733138 A CN105733138 A CN 105733138A
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CN
China
Prior art keywords
precursor film
sealing
side direction
boundling
tubular package
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510931628.8A
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Chinese (zh)
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CN105733138B (en
Inventor
持丸智英
石井雄三
上山隆久
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Kureha Corp
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Kureha Corp
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Publication of CN105733138A publication Critical patent/CN105733138A/en
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Publication of CN105733138B publication Critical patent/CN105733138B/en
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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
    • 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
    • B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
    • B65D77/22—Details
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Abstract

The invention provides a cylindrical packaging body which has a clamping part with excellent sealing performance. The cylindrical packaging body is provided with: (A) a filling material; (B) a cylindrical base metal thin film filled with the filling material and configured by a polyvinylidene chloride resin thin film, through conducting bunching packaging on the two end parts in a long edge direction; (C) a reinforcing belt which is welded to the base material thin film so as to wind and cover the part of the base material thin film that is subject to bunching packaging and is made of a polyvinylidene chloride resin thin film, characterized in that: a short edge of the base material thin film prior to the bunching packaging has a hot shrinkage rate RB-TD below 100 DEG C put between the range of 10.0-18.9 percent, the extraction rate of acetone is less than 9.0 %, and thorn energy is more than 2.1mJ under 120 DEG C.

Description

Tubular package
Technical field
The present invention relates to the tubular package using processed foods such as cheese, sausage, breaded fish stick, Petasos as implant.
Background technology
Seal as the tubular film that will be filled with the processed food such as cheese, sausage, breaded fish stick, Petaso, thus obtain encapsulating method during each package body, it is known to the method that the end of tubular film is carried out boundling sealing.But the tubular package adopting this method by the end boundling sealing of tubular film and obtaining, exists on its closure part or sealing side, it is easy to problem pin hole occur.Therefore, in order to solve this problem, adopt the both ends to the long side direction of the precursor film of tubular to carry out boundling sealing, the method that band is reinforced in welding in the boundling closure part have been carried out described precursor film.But, adopt welding in the part that the boundling of precursor film seal to reinforce the method being with and the tubular package obtained, pin hole on tubular film and not necessarily sufficient in the sealing of package body.
For this, Japanese Patent Laid-Open 2009-46148 publication and patent documentation 1 describe a kind of tubular package, it possesses implant；By the both ends of long side direction are carried out boundling sealing, make the precursor film of the tubular that described implant is filled；Welding is on described precursor film, thus the reinforcing being wound around and covering the part that described precursor film is sealed by boundling is with, wherein, by by the percent thermal shrinkage before the described welding reinforcing band and stretching secant spring rate, it is set in particular range, can be adequately suppressed on tubular film and pin hole occurs, improve sealing.
But, precursor film, to study reinforcing band, is left the leeway of research by these.The sealing reinforcing band by welding and obtain, particularly improves welding and reinforces the part of band, and the sealing hereinafter referred to as " clamping section " is limited, accordingly, it would be desirable to be developed to improve further the new method of the sealing of tubular package.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2009-46148 publication
Summary of the invention
The problem that invention to solve
The present invention is in view of the problem existed in above-mentioned conventional art, it is therefore intended that provide the tubular package that the sealing of a kind of clamping section is good.
Technical scheme
The inventors of the present invention, for reaching above-mentioned purpose, are repeatedly performed that study with keen determination found that a kind of tubular package, and it possesses: (A) implant；(B) by the both ends of long side direction are carried out boundling sealing, tubular precursor film that described implant is filled, that be made up of is made polyvinylidene chloride based resin film；(C) welding is on described precursor film, thus be wound around and cover part that described precursor film sealed by boundling, the reinforcing that is made up of polyvinylidene chloride based resin film is with, wherein, by as described precursor film, use acetone extraction rate, thorn energy, the percent thermal shrinkage polyvinylidene chloride based resin film in particular range, the sealing of tubular package clamping section is improved, thus completing the present invention.
That is, tubular package involved in the present invention, possesses: (A) implant；(B) by the both ends of long side direction are carried out boundling sealing, tubular precursor film that described implant is filled, that be made up of is made polyvinylidene chloride based resin film；(C) welding is on described precursor film, thus be wound around and cover part that described precursor film sealed by boundling, the reinforcing that is made up of polyvinylidene chloride based resin film be with,
It is characterized in that, the short side direction of the described precursor film before boundling sealing percent thermal shrinkage R at 100 DEG CB-TDIn the scope of 10.0～18.9%, acetone extraction rate is below 9.0%, and the thorn energy at 120 DEG C is at more than 2.1mJ.
The tubular package of the present invention, the short side direction of the described precursor film before the sealing of its boundling percent thermal shrinkage R at 100 DEG CB-TDWith the described long side direction percent thermal shrinkage R at 100 DEG C reinforcing band before weldingC-MD, it is preferred to meet following formula (F1):
-8%≤RB-TD-RC-MD≤ 9% (F1)
Shown in condition, more preferably meet following formula (F1a):
4.5%≤RB-TD-RC-MD≤ 6.5% (F1a)
Shown in condition.
And, the tubular package of the present invention, the thorn energy at 120 DEG C of the described precursor film before the sealing of its boundling, it is preferred to more than 2.5mJ, additionally, the stretching secant spring rate E of the long side direction of the described precursor film before boundling sealingB-MD, it is also preferred that in the scope of 332～450MPa.
In addition, the tubular package of the present invention, as described precursor film, preferably it is made up of the polyvinylidene chloride based resin film containing vinylidene Yu the copolymer of Vinyl Chloride Monomer, in addition, band is reinforced, it is preferable that be made up of the polyvinylidene chloride based resin film containing vinylidene Yu the copolymer of Vinyl Chloride Monomer as described.
Beneficial effect
According to the present invention, the tubular package that the sealing of clamping section is good can be obtained.
Detailed description of the invention
Hereinafter, it is appropriately carried out mode according to the present invention, is specifically described.
Tubular package involved in the present invention, possesses: (A) implant；(B) by the both ends of long side direction are carried out boundling sealing, tubular precursor film that described implant is filled, that be made up of is made polyvinylidene chloride based resin film；(C) welding is on described precursor film, thus be wound around and cover part that described precursor film sealed by boundling, the reinforcing that is made up of polyvinylidene chloride based resin film be with,
It is characterized in that, the short side direction of the described precursor film before boundling sealing percent thermal shrinkage R at 100 DEG CB-TDIn the scope of 10.0～18.9%, acetone extraction rate is below 9.0%, and the thorn energy at 120 DEG C is at more than 2.1mJ.
As (A) implant involved in the present invention, there is no particular restriction, for instance can enumerate the processed foods such as cheese, sausage, breaded fish stick, Petaso.
(precursor film)
Precursor film involved in the present invention is by the both ends of long side direction being carried out boundling sealing, making the tubular film that described implant is filled.And, precursor film involved in the present invention, it is necessary to be the thin film being made up of polyvinylidene chloride based resin film.In this manual, polyvinylidene chloride resinoid refers to hereinafter referred to as PVDC resinoid, the copolymer resin being main component with vinylidene chloride.This PVDC resinoid, has good barrier to oxygen and water vapour, when using accordingly, as precursor film, can suppress the appearance of the degradation phenomena such as oxidation or decrement of implant, keep commodity value.In addition, this PVDC resinoid, its heat fills adaptability, to boiling or the adaptability of the high-temperature sterilization treatment such as distillation is also very excellent, therefore, it is suitable especially for the precursor film material of the tubular package of implant to it can be used as with processed foods such as cheese, sausage, breaded fish stick, Petasos.
In precursor film involved in the present invention, the percent thermal shrinkage R at 100 DEG C of the short side direction (TD) before boundling sealingB-TD, it is necessary in the scope of 10.0～18.9%.Percent thermal shrinkage RB-TDLess than 10.0%, contraction during distillation will be not enough, so will produce gauffer on tubular package, and on the contrary, more than 18.9%, the sealing of clamping section will decline.Additionally, fully shrink from when passing through and distill, thus become to be difficult to that this viewpoint of gauffer occurs on tubular package, as described percent thermal shrinkage RB-TD, it is preferred to 15.0～18.9%.Additionally, the percent thermal shrinkage of the described precursor film before the sealing of this boundling, can pass through to control to manufacture the stretching ratio etc. during thin film, be properly carried out adjusting.
Additionally, in precursor film involved in the present invention, the acetone extraction rate before boundling sealing needs below 9.0%.The acetone extraction rate of the precursor film words more than 9.0%, precursor film material involved in the present invention and PVDC is resinoid melt after the decline of melt viscosity bigger, when using reinforcing band that precursor film is carried out pack and to seal, it is impossible to welding securely, the sealing of clamping section declines.Additionally, the viewpoint of the sealing from further raising clamping section, the acetone extraction rate before the boundling sealing of this precursor film, it is preferred to less than 6.0%, more preferably less than 4.0%, it is particularly preferred to be less than 3.0%.Additionally, as the lower limit of acetone extraction rate, be not particularly limited, but from the extrudability viewpoint of thin film, it is preferred to more than 1.0%.Additionally, the acetone extraction rate of described precursor film before the sealing of this boundling, temperature when can pass through to control to be polymerized precursor film material involved in the present invention and PVDC resinoid, response time, it is properly carried out adjusting.
And, in precursor film involved in the present invention, the thorn energy demand before boundling sealing is at more than 2.1mJ.The thorn energy of precursor film is less than 2.1mJ, and precursor film will bear film shrunk stress during incessantly distillation, it is possible to can occur pin hole on clamping section, and the sealing of clamping section declines.Additionally, from the viewpoint of the sealing improving clamping section further, this precursor film thorn energy before boundling seals is preferably more than 2.5mJ, more preferably more than 2.8mJ, more preferably more than 3.2mJ, it is particularly preferred to for more than 3.5mJ.Additionally, the thorn energy of the described precursor film before the sealing of this boundling, can pass through to control the copolymerization ratio etc. of precursor film material involved in the present invention and the resinoid molecular weight of PVDC, vinylidene chloride and vinyl chloride, be properly carried out adjusting.
Additionally, in precursor film involved in the present invention, the stretching secant spring rate E of the long side direction (MD) before boundling sealingB-MD, it is preferable that in the scope of 332～450MPa, additionally, the stretching secant spring rate E of short side direction (TD)B-TD, it is preferable that in the scope of 220～370MPa.The stretching secant spring rate E of long side directionB-MDOr the stretching secant spring rate E of short side directionB-TDThe words of not enough described lower limit, cause that precursor film lacks enough intensity, therefore, in the part sealed by boundling, pin hole will occur, on the contrary, exceeding the described upper limit, namely the installation of reinforcing band is mated (fit) property and will be declined, reinforcing band can not with precursor film welding, and the sealing of the tubular package obtained declines.Additionally, the stretching secant spring rate of the described precursor film before the sealing of this boundling, can pass through to control the addition of the additives such as vinylidene chloride and the copolymerization ratio of vinyl chloride, plasticizer, be properly carried out adjusting.
Thickness before the boundling sealing of precursor film involved in the present invention, there is no particular restriction, it is preferable that in the scope of 20～80 μm, more preferably in the scopes of 30～60 μm.The words of the thickness described lower limit of deficiency, because the tendency of pin hole easily occurs from outside impact and friction when the tubular package obtained has transport, on the other hand, exceed the words of the described upper limit, then cause that the boundling of precursor film end is insufficient, include reinforcing band and there will be the part not having welding, and the insufficient tendency of sealing of the tubular package obtained to some extent.
The material of precursor film involved in the present invention and PVDC resinoid, can obtain by making the monomer beyond vinylidene chloride and vinylidene chloride carry out copolymerization.As the monomer beyond this vinylidene chloride, it is not particularly limited, for instance vinyl chloride, acrylonitrile, methacrylate can be enumerated.
In addition, this PVDC resinoid is preferably the resin containing following copolymer, this copolymer is 78～84 mass %, is more preferably 79～83 mass %, is particularly preferably the vinylidene chloride of 80～82 mass %, with 22～16 mass %, be more preferably 21～17 mass %, it is particularly preferred to be the copolymer of the described vinyl chloride of 20～18 mass %.The words of the addition described lower limit of deficiency of vinylidene chloride, have when carrying out melt extruded and stretching masking, can not tendency crystallization fully, cause the tendency being difficult to stably be filmed, in addition, because the precursor film thermostability obtained is not enough, the tendency of problems with will be occurred, namely the problem that breaking occurs in the tubular package obtained by high-temperature heating treatment such as retort sterilisation process, on the contrary, exceed the described upper limit, because the fusing point of the increase of accompanying crystallization rises, have the tendency that the load change of melt extruded is big.
To precursor film material involved in the present invention and PVDC resinoid, as required, it is possible to add other resins.As other resins this, include, for example vinyl-vinyl acetate copolymer, methacrylate, MBS etc., wherein this methacrylate is preferably the copolymer of the alkyl methacrylate that carbon number is 1～18 of alkyl, such as, methyl methacrylate-butyl methacrylate copolymer.Other resins this, can add in PVDC resinoid as PVDC resin composition, it is possible to by one part or whole, add in advance in the painted resin combination containing pigment, and by this painted resin combination, add in PVDC resinoid.Additionally, from the viewpoint such as gas barrier property and thermostability, other resins this, it is preferable that adding into the content ratio with the vinylidene chloride composition in the resinoid mixture of PVDC is more than 50 mass %.
And, precursor film material involved in the present invention and PVDC resinoid, in order to give the characteristic of the fissility etc. between melt extruding property, heat stability, draftability, flexibility, painted and implant to it, the additives such as plasticizer, stabilizer, lubricant, coloring agent, surfactant, mercerising polishing agent can be added.Additionally, in PVDC resinoid, hybrid shaping the formed scrap etc. of PVDC resin composition that man-hour produces, that recycling can be circulated can be added.
As described additive, well-known plasticizer, stabilizer, binding agent, viscosifier, pigment, lubricant, auxiliary agent, filler, surfactant etc. can be enumerated.As aqueous plasticizer, citroflex A-4 (ATBC), diacetyl glycerol monolaurate (GDAML), dibutyl sebacate (DBS), di-n-octyl sebacate and diacetyl monoglyceride (DALG) etc. can be enumerated.As stabilizer, the such as epoxidized vegetable oil such as epoxidised soybean oil (ESBO), epoxidized linseed (ELO), the amide derivatives of Arrcostab, magnesium hydroxide, tetrasodium pyrophosphate etc. can be enumerated.As binding agent, the poly-multivalence alcohol etc. such as polyisobutylene (PIB), polybutene (PB), polybutadiene, Polyethylene Glycol, polyglycerol, polypropylene glycol can be enumerated.As viscosifier, the glycerol fatty acid ester such as interfacial agent, such as naphthenic processing oil, hard paraffin, liquid paraffin and mineral wet goods paraffin class or the aqueous saturated hydrocarbons of naphthenic etc. such as sorbitan carboxylic esters, methyl glycol fatty acid ester, such as sorbitol list trioleate, glycerol list trioleate can be enumerated.As lubricant, the such as paraffin class such as oxidic polyethylene, hard paraffin can be enumerated；The unsaturated fatty acid amide such as such as butyramide, valeric acid amide, hexanoic acid amide, sad (Caprylicacid) amide, capric acid (Capricacid) amide, lauric amide, myristic acid amide, palm fibre acid amide, stearic amide, arachidamide, behenamide (Docosanamide)；The such as unsaturated fatty acid such as oleamide, erucyl amide amide；Span；Polyglyceryl fatty acid ester；The substituted amides such as such as N-oleyl palmitamide, N-stearyl stearoyl amide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide；The methylol amides such as such as hydroxymethylstearic acid amide；The such as satisfied fatty acid bisamide such as di-2-ethylhexylphosphine oxide stearic amide, vinyl di-hydroxy stearic acid amide；The unsaturated fatty acid bisamides such as the such as double; two erucyl amides of vinyl；The fragrance such as xyxylene di-hydroxy stearic acid amide same clan bisamide etc. between such as.As auxiliary agent, can enumerate: ethylene-vinyl acetate copolymer；Such as 2,6-di-t-butyl-4-methyl-phenol (BHT), triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxyphenyl) propionic ester], 2,4-dimethyl-6-S-alkyl phenol, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, and the phenol antioxidant such as these mixture；The such as thioether antioxidants such as thiodipropionic acid, thiodipropionic acid diester；The such as phosphite antioxidant such as trisnonyl phenyl phosphite, distearyl pentaerythrityl diphosphite etc..As inserts, silicon dioxide, calcium carbonate, zeolite etc. can be enumerated.As interfacial agent, sorbitan carboxylic esters class etc. can be enumerated.
Manufacture method as precursor film involved in the present invention, for instance can adopt following methods, namely adds described PVDC resinoid heat fusing with melt extruder, and extrudes from tubular nozzle, carry out biaxial stretch-formed method by methods such as blow molding methods after chilling.The stretching ratio of the longitudinal direction (MD) time biaxial stretch-formed, it is preferred to 2～5 times, more preferably 2.2～3.5 times.Additionally, the stretching ratio of horizontal (TD), it is preferred to 2～5 times, more preferably 3.5～4.5 times.Draft temperature, it is preferred to about 15～40 DEG C, more preferably about 15～30 DEG C.
Additionally, in the manufacture method of precursor film involved in the present invention, in order to improve the dimensional stability of precursor film, the thin film after stretching can be made, to longitudinal direction (MD) and laterally (TD) mitigation or contraction.The longitudinally mitigation rate of (MD), it is preferred to about 1～20%, more preferably about 5～9%.Additionally, the mitigation rate of horizontal (TD), it is preferred to about 1～20%, more preferably about 5～10%.Relax temperature, it is preferred to about 40～80 DEG C, more preferably about 50～70 DEG C.
(reinforcing band)
(C) involved in the present invention reinforces band, and welding is on described precursor film, thus being wound around and covering the part that described precursor film is sealed by boundling.And, reinforcing band involved in the present invention, it is necessary to be the thin film being made up of polyvinylidene chloride based resin film.As reinforcing band, by using the reinforcing band being made up of polyvinylidene chloride based resin film, thus increasing the weldability reinforced between band and described precursor film.
Reinforcing band involved in the present invention, the percent thermal shrinkage R at 100 DEG C of the long side direction (MD) before weldingC-MD, it is preferable that in the scope of 10～27%, more preferably in the scope of 12～25%, it is particularly preferred in the scope of 13～24%.Percent thermal shrinkage RC-MDIn described scope, the sealing of the tubular package obtained is balanced with as what reinforce between the change in size etc. of band, will become good.On the other hand, percent thermal shrinkage RC-MDThe words of not enough described lower limit, on the both ends of the tubular package obtained, just cannot being adequately suppressed pin hole to occur, the sealing of the tubular package obtained to some extent becomes insufficient tendency, on the contrary, exceed the words of the described upper limit, will produce as reinforce with use before change in size or excess shrinkage cause wrinkling, additionally, have reinforce with shrink hardening part, contact with the package body being positioned at periphery and impaired, thus bringing out the tendency of pin hole.Additionally, the percent thermal shrinkage R that the short side direction (TD) of the described reinforcing band before welding is at 100 DEG CC-TD, from the viewpoint of the shape defect of the clamping section suppressing the excess shrinkage shrinking the poor clamping section poor sealing caused and reinforcing band between precursor film to cause, it is preferable that in the scope of 8～35%.Additionally, the described percent thermal shrinkage reinforcing band before this welding, can pass through to control to manufacture the stretching ratio etc. during thin film, be properly carried out adjusting.
Additionally, reinforcing band involved in the present invention, the stretching secant spring rate E of the long side direction (MD) before weldingC-MD, it is preferable that in the scope of 250～450MPa, more preferably in the scope of 260～420MPa, it is particularly preferred in the scope of 270～400MPa, additionally, the stretching secant spring rate E of short side direction (TD)C-TD, it is preferable that in the scope of 220～370MPa.The stretching secant spring rate E of long side directionC-MDStretching secant spring rate E with short side directionC-TDIn described scope, balanced between the sealing of the tubular package obtained with the hardness etc. reinforcing band will become good.On the other hand, the stretching secant spring rate E of long side directionC-MDOr the stretching secant spring rate E of short side directionC-TD, the words of not enough described lower limit, reinforce band and will there is no enough hardness, therefore, in the part sealed by boundling of precursor film, when adding reinforcing band, it is easy to occur adding the place reinforcing band uneven, for this, on the both ends of the tubular package obtained, just cannot be adequately suppressed pin hole to occur, the tendency that the sealing of the tubular package obtained to some extent declines, on the contrary, exceed the words of the described upper limit, installation from the part that band is sealed by boundling to precursor film and the matching of reinforcing will decline, reinforcing band can not with precursor film welding, the tendency that the sealing of the tubular package obtained to some extent declines.Additionally, the described stretching secant spring rate reinforcing band before this welding, can pass through to control the addition of the additives such as plasticizer, be properly carried out adjusting.
Involved in the present invention reinforces band thickness before welding, it is preferable that in the scope of 10～150 μm, more preferably in the scopes of 30～120 μm, it is particularly preferred in the scope of 40～100 μm.The thickness described lower limit of deficiency, in the manufacturing process of tubular package, causes being difficult to be wrapped on both ends, and has the tendency not enough as the intensity reinforcing band.On the other hand, thickness exceedes the described upper limit, can not with the part welding sealed by boundling of precursor film, the tendency that the sealing of the tubular package obtained to some extent declines.
The involved in the present invention material reinforcing band and PVDC resinoid, can obtain by making the monomer beyond vinylidene chloride and vinylidene chloride carry out copolymerization.As the monomer beyond this vinylidene chloride, it is not particularly limited, for instance vinyl chloride, acrylonitrile, methacrylate can be enumerated.In these materials, reactive good between vinylidene chloride, and the control of the physical property of the copolymer obtained becomes to be easy to viewpoint, it is preferred to use vinyl chloride.
In addition, this PVDC resinoid is preferably the resin containing following copolymer, this copolymer is 78～84 mass %, is more preferably 79～83 mass %, is particularly preferably the vinylidene chloride of 80～82 mass %, with 22～16 mass %, be more preferably 21～17 mass %, it is particularly preferred to be the copolymer of the described vinyl chloride of 20～18 mass %.The words of the addition described lower limit of deficiency of vinylidene chloride, have when carrying out melt extruded and stretching masking, can not crystallization fully, become the tendency being difficult to stably be filmed, in addition, because the reinforcing band thermostability obtained is not enough, the tendency of problems with will be occurred, namely the problem that breaking occurs in the tubular package obtained by high-temperature heating treatment such as retort sterilisation process, on the contrary, exceeding the described upper limit, because the fusing point of the increase of accompanying crystallization rises, the load of melt extruded just has the tendency becoming big.
The involved in the present invention material reinforcing band and PVDC resinoid, in order to control the percent thermal shrinkage reinforcing band and the stretching secant spring rate that obtain, such as, the mercerising such as lubricant, the calcium carbonate polishing agent such as the plasticizers such as dibutyl sebacate, epoxidised vegetable wet goods stabilizer, fatty acid ester can be added.
Reinforcing band involved in the present invention, such as, can manufacture by the following method, namely with melt extruder, described PVDC resinoid is added heat fusing, and extrude from tubular nozzle, undertaken biaxial stretch-formed by methods such as blow molding methods after chilling, and the reinforcing band thin film that will obtain, cut into suitably sized.The stretching ratio of the longitudinal direction (MD) time biaxial stretch-formed, it is preferred to 2～5 times, more preferably 2.2～3.5 times.Additionally, the stretching ratio of horizontal (TD), it is preferred to 2～5 times, more preferably 3.5～4.5 times.Draft temperature, it is preferred to about 15～40 DEG C, more preferably about 15～30 DEG C.
Additionally, in the involved in the present invention manufacture method reinforcing band, in order to improve the dimensional stability reinforcing band, the thin film after stretching can be made, relax to longitudinal direction (MD) and horizontal (TD) or shrink.The longitudinally mitigation rate of (MD), it is preferred to about 1～20%, more preferably about 5～9%.Additionally, the mitigation rate of horizontal (TD), it is preferred to about 1～20%, more preferably about 5～15%.Relax temperature, it is preferred to about 40～80 DEG C, more preferably about 50～70 DEG C.
In addition, the PVDC resinoid used in the present invention, any one polymerization that can be through in suspension polymerisation, emulsion polymerization, polymerisation in solution synthesizes, but, in order to form mixture as powdered resin, preferably with the granularity with about 40～600 μm, it is not necessary to the suspension polymerization of pulverizing process obtains.Additionally, PVDC resinoid is when it is polymerized, it can be made to contain antioxidant, plasticizer, epoxide etc..The resinoid powdered resin of PVDC, in general has the mean diameter of about 40～600 μm.In the present invention, the powdered resin containing the additive such as epoxide and plasticizer during polymerization, can be used.Certainly, without the powdered resin of the additive such as epoxide and plasticizer, could be used that in the present invention.The resinoid powdered resin of PVDC containing the additive such as epoxide and plasticizer during polymerization is, before polymerization, or in the course of the polymerization process, on at least any one time point again or after polymerisation, these additives are added in polyreaction system, it is made to cover in generation PVDC resinoid, as the resin that powdered resin reclaims.
Additionally, in the present invention, the percent thermal shrinkage of precursor film or reinforcing band is using precursor film or reinforces band thin film as sample film, and the method described in JIS:Z1709 is measured.Namely, on the long side direction (MD) or short side direction (TD) of sample film, the distance between 2 is made to be 100mm and mark, after soaking 3 minutes in the boiling water of 100 DEG C, tap water cools down, then, measure the distance d between described 2, the distance of the point to point after being namely immersed in boiling water, unit is mm, and calculate reduced value (100-d) mm of distance between 2 after soaking in boiling water, percentage ratio relative to the distance 100mm being immersed between 2 before boiling water, it can be used as precursor film or reinforce band percent thermal shrinkage at 100 DEG C, unit is %.
The stretching secant spring rate of precursor film or reinforcing band is using precursor film or reinforces band thin film as sample film, uses the tensilon cupping machine that A&D company produces, and the method described in JIS:K7113 item 8.5 is measured.Namely, cut from precursor film or reinforcing band thin film, the width making long side direction (MD) measurement sample thin film or short side direction (TD) measurement sample thin film respectively becomes 20mm, then sample film is arranged on cupping machine, condition determination is 23 DEG C, 50%RH, make the long side direction of this sample film or the test length of short side direction and chuck spacing become 100mm, and carry out tension test by the 10mm/ speed divided.And, deformation will be specified: ε is set to 0.025, read the deformation quantity of sample film until arriving stress required till 0.025: F, unit is N, and area of section according to sample film further: S, unit is mm2, use relationship below:
(stretching secant spring rate: E)=(F/ (ε × S))
Calculating precursor film or reinforce the stretching secant spring rate of band, unit is MPa.
The acetone extraction rate of precursor film is measured according to following methods.That is, as sample, precursor film 5g is immersed in oxolane (THF) 100ml of 60 DEG C, so as to dissolve.And the THF solution obtained is stirred, meanwhile, carrying out every time a small amount of for methanol to be dripped, drippage total amount is 500ml, after sample carries out precipitation again, is dried by mixed solvent at 90 DEG C.Afterwards, add methanol 50ml, include the sample precipitated again, solution is poured in apparatus,Soxhlet's, put absorbent cotton at an upper portion thereof.Then, methanol 70ml is poured into and has dried in advance, and determine in the boiling flask of 150ml of quality, and be arranged on apparatus,Soxhlet's, extract 24 hours at 85 DEG C.By the sample after extraction, put in apparatus,Soxhlet's, and put absorbent cotton on top.Then, acetone 120ml is poured into and has dried in advance, and determine in the boiling flask of quality, be then fitted on apparatus,Soxhlet's, extract 24 hours at 75 DEG C.Use filter paper No.5A, namely based on the filter paper of the standard of " JISP3801-1995 filter paper (chemical analysis with) ", 100ml extracting solution is filled in graduated cylinder, and put into and dried in advance, and determine in the 150ml boiling flask of quality.Clean used graduated cylinder with carbon tetrachloride, and cleanout fluid is joined in boiling flask.In being adjusted to the thermostatic water tank of 80 DEG C, use apparatus,Soxhlet's dry acetone.Afterwards, using the drying machine being adjusted to 105 DEG C to dry 1 hour, stand cooling 1 hour, obtain the quality of the boiling flask equipped with extract, and according to following formula, obtain the acetone extraction rate of precursor film in exsiccator, unit is %.
Acetone extraction amount %={ (A-B) × E/ (C × D) } × 100%
A: equipped with the quality (g) of the boiling flask of extract.
B: the quality (g) of the boiling flask dried in advance.
C: the quality (g) of sample.
D: the amount (100ml) of the extracting solution after filter paper NO.5A filters.
E: the amount (120ml) of the acetone for extracting.
The thorn energy of precursor film is measured by the following method.That is, on the reinforcing ring that internal diameter is 45mm, install precursor film, at the temperature of 120C, at temperature when namely distilling, with sting speed 50mm/ divide byBe needled into precursor film, by the load on from extensibility 0% to breakaway poing, with displacement principal value of integral, as precursor film thorn energy under 120C, unit is mJ.
(tubular package)
Tubular package involved in the present invention is a kind of package body possessing implant described above, precursor film and reinforcing band.The tubular package of the present invention, the long side direction of the short side direction of the described precursor film before the sealing of its boundling percent thermal shrinkage RB-TD under 100C and the described reinforcing band before welding percent thermal shrinkage RC-MD under 100C, it is preferred to meet following formula (F1):
-8%≤RB-TD-RC-MD≤ 9% (F1)
Shown in condition, more preferably meet following formula (F1a):
4.5%≤RB-TD-RC-MD≤ 6.5% (F1a)
Shown in condition.As it has been described above, by controlling precursor film and reinforcing the difference of the respective percent thermal shrinkage being with, the tendency that the sealing of the clamping section of the tubular package obtained is improved.On the other hand, RB-TD-RC-MDValue, not enough described lower limit, when carrying out the high-temperature heating treatment such as retort sterilisation process, reinforce band can excess shrinkage, therefore, have the portion on the shoulders being positioned at the tubular package obtained reinforce band end on, the tendency rolled easily occurs.On the other hand, RB-TD-RC-MDValue, exceed the described upper limit, cause reinforcing band the tightness of the part sealed by boundling of precursor film is insufficient, therefore, the tendency that the sealing of the clamping section of the tubular package obtained to some extent is insufficient, and have and reinforce the tendency that band easily departs from from tubular package.
Additionally, the tubular package of the present invention, the stretching secant spring rate E of the short side direction of the described precursor film before the sealing of its boundlingB-TDStretching secant spring rate E with the described long side direction reinforcing band before weldingB-MD, it is preferred to meet following formula (F2):
-140MPa≤EB-TD-EC-MD≤80MPa(F2)
Shown in condition, more preferably meet following formula (F2a):
-135MPa≤EB-TD-EC-MD≤-50MPa(F2a)
Shown in condition.As it has been described above, by controlling precursor film and reinforcing the difference of the respective stretching secant spring rate being with, the tendency that the sealing of the clamping section of the tubular package obtained is improved.On the other hand, EB-TD-EC-MDThe words of the not enough described lower limit of value, reinforce band and become result relatively really up to the mark relative to precursor film, make to reinforce the installation of part that band seals by from boundling to precursor film and matching declines, reinforcing band can not with precursor film welding, the tendency that the sealing of the tubular package obtained to some extent declines.On the contrary, EB-TD-EC-MDValue, exceed the described upper limit, reinforce band excessively soft result relative to precursor film so that reinforce band and the tightness of the part sealed by boundling of precursor film is become insufficient, therefore, the sealing of the clamping section of the tubular package obtained has the tendency of minimizing.
Manufacture method as the tubular package of this present invention, such as can come with following methods, it is shaped to tubular by precursor film, fill implant simultaneously, afterwards by the mode of ultrasonic sealing, the end of precursor film is carried out boundling, meanwhile, bring plus reinforcing and carry out sealing sealing, the method thus obtaining tubular package.And, as the device for this method, for instance, the auto-filling-packing machine that trade name is KAP that KUREHA company produces can be used.Embodiment
Hereinafter, according to embodiment and comparative example, the present invention is carried out more specific description, but the present invention is not limited in following example.
(embodiment 1)
First; monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts in the copolymer A that mass ratio (VD/VC) is 81/19; add and amount to the citroflex A-4 (ATBC) of 9 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil; add further and amount to the surfactant of 0.2 mass parts, lubricant and mercerising polishing agent, it is thus achieved that polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
In addition; monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts in the copolymer A that mass ratio (VD/VC) is 81/19; add and amount to the citroflex A-4 (ATBC) of 8 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil; add further and amount to the surfactant of 0.1 mass parts, lubricant and mercerising polishing agent, it is thus achieved that polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that reinforce band thin film.Use the reinforcing band thin film that obtains, determine the stretching secant spring rate reinforcing the thickness of band, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction.Its result is as shown in table 1.
Then, use and cut into precursor film that width is 82mm and cut into the reinforcing band that width is 16mm, implant is packed in the auto-filling-packing machine that trade name is KAP3000 type that KUREHA company produces, obtain tubular package, the paste that above-mentioned implant is made up of 50 mass % flesh of fish meat pastes, 28.6 mass % frozen water, 10 mass % vegetable oil, 8 mass % corn starchs, 2 mass % soybean proteins, 1.4 mass % Sal.That is, precursor film is shaped to tubular, fills implant simultaneously, and by the mode that ultrasound seals, the end of precursor film is carried out boundling, meanwhile, add that reinforcing brings and carry out melted sealing sealing, and obtain tubular package.In addition, in the precursor film of tubular, condition is adjusted to the length of folding length and circumference half to be 36mm, Cutting Length be 225mm, quality is 75g, above-mentioned Cutting Length refers to implant of choosing from tubular package, and the precursor film of remaining tubular is shakeout, the length then measured along long side direction.Additionally, the operating condition of auto-filling-packing machine is as follows.
Filling speed: 150/point.
Beckiron gap: 0.1mm.
Sealing pressure: 450kPa.
Amplitude amount scale: 69 (being equivalent to 16 μm).
Sealing design: flat 6.5mm seal widths.
Thickness before the distillation of the weld portion that precursor film is with reinforcing: 80～160 μm.
Longitudinal closed condition: be provided with the processed goods of annular knurl stricture of vagina.
Boundling degree: diameter 2mm.
Thin film cutter: the commercially available cutter that olfa company produces.
(embodiment 2)
Monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts in the copolymer A that mass ratio (VD/VC) is 81/19; add and amount to the citroflex A-4 (ATBC) of 8 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil; add further and amount to the surfactant of 0.4 mass parts, lubricant and mercerising polishing agent, it is thus achieved that polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
Then, except the precursor film that replacement obtains in embodiment 1, and use beyond this precursor film, in the same manner as in Example 1, it is thus achieved that tubular package.
(embodiment 3)
It is the copolymer A of 81/19 that monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts into mass ratio (VD/VC), monomer when being polymerized with vinyl chloride (VC) with vinylidene chloride (VD) puts in the mixture of copolymer B that mass ratio (VD/VC) is 71/29, wherein A/B (mass ratio)=75/25, add the citroflex A-4 (ATBC) amounting to 6 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil, add the surfactant amounting to 0.25 mass parts further, lubricant and mercerising polishing agent, obtain polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
Then, except the precursor film that replacement obtains in embodiment 1, and use beyond this precursor film, in the same manner as in Example 1, it is thus achieved that tubular package.
(comparative example 1)
Monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts into the copolymer C that mass ratio (VD/VC) is 80/20, monomer when being polymerized with vinyl chloride (VC) with vinylidene chloride (VD) puts in the mixture of copolymer B that mass ratio (VD/VC) is 71/29, wherein C/B (mass ratio)=75/25, add the citroflex A-4 (ATBC) amounting to 8 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil, add the surfactant amounting to 0.2 mass parts further, lubricant and mercerising polishing agent, obtain polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
Then, except the precursor film that replacement obtains in embodiment 1, and use beyond this precursor film, in the same manner as in Example 1, it is thus achieved that tubular package.
(comparative example 2)
It is the copolymer A of 81/19 that monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts into mass ratio (VD/VC), monomer when being polymerized with vinyl chloride (VC) with vinylidene chloride (VD) puts in the mixture of copolymer B that mass ratio (VD/VC) is 71/29, wherein A/B (mass ratio)=85/15, add the citroflex A-4 (ATBC) amounting to 6.5 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil, add the surfactant amounting to 0.4 mass parts further, lubricant and mercerising polishing agent, obtain polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
Then, except the precursor film that replacement obtains in embodiment 1, and use beyond this precursor film, in the same manner as in Example 1, it is thus achieved that tubular package.
(comparative example 3)
Monomer when the vinylidene chloride (VD) of 100 mass parts is polymerized with vinyl chloride (VC) puts in the copolymer D that mass ratio (VD/VC) is 82/18; add and amount to the citroflex A-4 (ATBC) of 6 mass parts, dibutyl sebacate (DBS) and epoxidized vegetable oil; add further and amount to the surfactant of 0.4 mass parts, lubricant and mercerising polishing agent, it is thus achieved that polyvinylidene chloride resinoid.And, using diameter is the extruder screw of 90mm, the polyvinylidene chloride resinoid obtained is carried out melt extruded, the thin film that will obtain, draft temperature and stretching ratio according to table 1 carry out biaxial stretch-formed, after mitigation temperature according to table 1 and mitigation rate relax further, it is thus achieved that precursor film.Determine the thickness of the precursor film obtained, acetone extraction rate, thorn energy at 120 DEG C, long side direction at 100 DEG C and the percent thermal shrinkage of short side direction, long side direction and short side direction and stretch secant spring rate.Its result is as shown in table 1.
Then, except the precursor film that replacement obtains in embodiment 1, and use beyond this precursor film, in the same manner as in Example 1, it is thus achieved that tubular package.
<assessment of tubular package sealing>
Being evaluated as that the sealing of the tubular package obtained in embodiment and comparative example is carried out is as follows.That is, heat accumulation ability of swimming retort sterilisation device (Ban manufacturing company produces, trade name is FlavorAce) is used, at temperature 120 DEG C, setting pressure 2.5kg/cm2When, tubular package has been carried out to time the distillation of 15 minutes process, and it can be used as sample.Carried out distillation process second day, 100 samples are extracted randomly, and these samples are immersed in No. 1 pigment solution of cyan of 0.4 mass %, and when temperature 5～10 DEG C, stood 5 days.Afterwards, being taken out by sample from pigment solution, after outer surface is washed, sealed off by thin film, whether the implant of investigation the inside has painted, in this way sealing has been assessed.In addition, to find because pigment solution permeates, and cause that the implant of the inside has painted clamping section, namely the part of band is reinforced in welding, it is judged to poor sealing clamping section, obtain the ratio (percentage ratio) of poor sealing clamping section in 200 clamping sections of 100 samples, as the sealing disqualification rate of clamping section.Its result is as shown in table 1.
Table 1
From the result shown in table 1 it can be seen that the tubular package of the present invention, i.e. embodiment 1～3, the sealing of the clamping section of its tubular package is excellent.
Industrial utilizability
As it has been described above, according to the present invention, the tubular package that the sealing of clamping section is good can be obtained.
Therefore, the present invention tubular package, as useful for the tubular package of implant with the processed food such as cheese, sausage, breaded fish stick, Petaso.

Claims (7)

1. a tubular package, possesses: (A) implant；(B) by the both ends of long side direction are carried out boundling sealing, tubular precursor film that described implant is filled, that be made up of is made polyvinylidene chloride based resin film；(C) welding is on described precursor film, thus be wound around and cover part that described precursor film sealed by boundling, the reinforcing that is made up of polyvinylidene chloride based resin film be with,
It is characterized in that, the short side direction of the described precursor film before boundling sealing percent thermal shrinkage R at 100 DEG CB-TDIn the scope of 10.0～18.9%, acetone extraction rate is below 9.0%, and the thorn energy at 120 DEG C is at more than 2.1mJ.
2. tubular package according to claim 1, it is characterised in that the short side direction of the described precursor film before boundling sealing percent thermal shrinkage R at 100 DEG CB-TDWith the described long side direction percent thermal shrinkage R at 100 DEG C reinforcing band before weldingC-MD, meet following formula (F1):
-8%≤RB-TD-RC-MD≤ 9% (F1)
Shown in condition.
3. tubular package according to claim 2, it is characterised in that the short side direction of the described precursor film before boundling sealing percent thermal shrinkage R at 100 DEG CB-TDWith the described long side direction percent thermal shrinkage R at 100 DEG C reinforcing band before weldingC-MD, meet following formula (F1a):
4.5%≤RB-TD-RC-MD≤ 6.5% (F1a)
Shown in condition.
4. tubular package according to any one of claim 1 to 3, it is characterised in that the thorn energy at 120 DEG C of the described precursor film before boundling sealing is more than 2.5mJ.
5. tubular package according to any one of claim 1 to 4, it is characterised in that the stretching secant spring rate E of the long side direction of the described precursor film before boundling sealingB-MD, in the scope of 332～450MPa.
6. tubular package according to any one of claim 1 to 5, it is characterised in that described precursor film, is made up of the polyvinylidene chloride based resin film containing vinylidene Yu the copolymer of Vinyl Chloride Monomer.
7. tubular package according to any one of claim 1 to 6, it is characterised in that described reinforcing band, is made up of the polyvinylidene chloride based resin film containing vinylidene Yu the copolymer of Vinyl Chloride Monomer.
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CN111474076A (en) * 2020-03-25 2020-07-31 山东省医疗器械产品质量检验中心 Method for separating polyvinylidene chloride coating in medicinal composite material and application

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