CN109996444A - Gauffer carries the moisture-proof casing and its manufacturing method of bar form at rigidity certainly - Google Patents

Abstract

The invention discloses a kind of meltings for food, and the moisture-proof casing of tubulose (totally)s extrude, it is converted into rigidity from the form for carrying fold stick, wherein tubulose casing has the layer contacted with food contents, it is characterized in that, the tubulose casing has reduced adhesiveness to the content, and wherein the outer surface of tubulose casing has at most 10g/m²At least one is water-soluble or water dispersible adhesive polymer, it provides adherency contact between fold stick fold, wherein the outer surface of tubulose casing also has the hydrophobic components for reducing adhesive strength, it and include that at least one liquid is organic and/or organic element compound, the compound is substantially non-volatile at room temperature and is substantially insoluble in, wherein total surface concentration of the compound outside casing is greater than adhesive polymer, and is 50 to 500mg/m²；And this fold stick has the feature that after being kept for 24 hours with free state on a smooth surface under 20 DEG C and RH 75%, the longitudinal compression rate under the power of 1N is no more than 0.5%；Fold stick is characterized in that not having macroscopic elastic bending deflection as cantilever support under its own weight；And when bending moment is 60 to 400Nmm irreversible rupture occurs for the fold stick；And fold stick is characterized in that, can make the fold stick de-shirred at 20 DEG C of temperature and RH 60% with the speed not less than 1.5m/sec, and the casing wall will not rupture.

Description

Gauffer carries the moisture-proof casing and its manufacturing method of bar form at rigidity certainly

Invention field

The present invention relates to a kind of moisture-proof casing of tubulose substantially based on synthetic resin, are converted into fold stick (shirred stick) form, and it is suitable for the High-Speed Automatic filling of sausage meat, especially suitable for similar frankfurter Sausage meat gruel is also applied for taking out from processing sausage by automatic stripping device.Fold stick of the invention is characterized in that rigidity And the support of for example special tubular reticulum is not needed to keep its shape and size.In addition, the present invention relates to this fold intestines The manufacturing method of clothing.

Background of invention

The sausage casing foil of compact shredded form is commonly used in production ham and sausage, including frankfurter, dimension It receives during sausage, hot dog or primary gram of sausage and fills meat gruel.Even if to sausage in the form of winding on barrel flat tubular film Manufacturer provides casing, they usually first by the unitary part fold of casing to filling pipe, then only fill intestines with meat gruel Clothing.Casing using the preparatory fold of (also referred to as " tubular type ", " pipe " or " caterpillar ") of compact bar form is more practical, length Degree is about 0.5 meter, the tubulose casing including being up to tens meters.However, if any pith of operating time is wasted in It replaces on fold stick, because usually the stick made of plastic casing cannot keep its shape and size in unsupported situation, Therefore they are packaged in special tubular reticulum to transport and to use.

Those skilled in the art will know that the casing (reinforcement and non-reinforcement) based on viscose glue, can be processed to machinery Stable carrying fold stick certainly.This is as caused by the special characteristic of cellulose membrane, and bending and impression deformation are with irreversible Property.Due to its mechanical stability, automatic filling of the corrugated fiber vegetable sausage casing for manufacturing flange gram good fortune sausage or wienerwurst In the process.The casing of same type can be removed from processing sausage in industrial peeling process by high speed stripper.Due to height Productivity fills the structure feature of automaton, such as Townsend Frank-A-Matic or Townsend SuperMatic RT7, many fold sticks can be admitted to hopper, then they can singly with frankfurter or The meat gruel of wienerwurst is filled.

However, the casing production based on viscose glue is related to disagreeableness " wet " technology of environment, along with including toxic vulcanization The formation of the waste water of object.Moreover, this casing cannot provide satisfactory water vapor barrier, therefore it is packaged in sausage therein It during heat treatment can rapid weight loss.

Previously some trials have been carried out to provide stable carrying pleat certainly from the tubulose casing based on synthetic polymer Wrinkle stick.For example, european patent number 1659868 disclosed on July 1st, 2009 discloses one kind made of essentially synthetic resin Self-supporting carries the manufacturing method of mechanically stable fold tubulose casing.This method is based on by extending the setting of its shape (up to 24 hours) The destruction of casing elasticity in caused fold pleat.It, can be in Folding Process or straight in order to improve its mechanical stability It connects and is sprayed casing with pure water or emulsion oil-in-water before it.For identical purpose, inventor recommends to carry out electricity to casing Dizzy processing.

According to the fold stick of invention manufacture by being bent or when stretcher strain is influenced shows observable shifting Dynamic property.This may cause tight during its transportation, and when it is used as the enteric materials filled automatically in sausage production Weight problem.Further, since forming the spot of monolith polymer material, disclosed side in interface between the fold of fold stick Method can cause the spontaneous adhesion of the casing of fold bar form (alternatively, in other words, obstruction).This is considered as being located at fold difference The result of priceless (non-valent) interaction between the macromolecular on side.Make this fold stick de-shirred as a result, Attempt the multiple fracture for leading to casing；Therefore it cannot be used for filling process.As follows, if casing is wet, and If its outer layer is made of the blend of the hydrophilic polymeric material of such as polyamide or itself and water-soluble polymer, it is this therefore Barrier can more frequently occur.Another factor for increasing obstruction risk is the sided corona treatment on casing surface.

A kind of fold stick is disclosed in U.S. Patent number 7803437 disclosed on September 28th, 2010 comprising in fold Adhesive between the fold of casing.Bonding is realized by water-soluble polymer, such as carboxymethyl cellulose (CMC), It is applied on one or two surface of tubulose casing usually in Folding Process as aqueous solution.This casing include one layer simultaneously It is made of the blend of polyamide and hydrophily especially water-soluble polymer.Similar casing is known in the prior art , and for example disclosed in patent No. RU 2182107 disclosed on May 10th, 2002, wherein they are described as having height Water vapour and smog (smoking property) infiltrative film.The life of this fold stick disclosed in same patent US7803437 Production method can only be realized by the high water vapor permeability of casing.Due to the moisture absorption of the hydrophilic polymer components of casing, There is no the adherency contact formed between fold in the case where force drying.Preferably, by only applying water on the inside pipe surface Soluble polymer realizes cohesive bond.Hydrophobic liquid, such as mineral can also be applied on the inner surface of pipe or outer surface Oil is used as lubricant.In addition, this liquid can be applied on the inner surface of casing, to provide the rippability of enhancing.However, As emphasizing in invention description, their concentration has to be lower than the concentration of water-soluble polymer.

Obviously, it is less likely to be suitable for multilayer moderate penetrability for the production method of fold stick disclosed in the literature (only include the layer based on polyamide) casing or moisture-proof casing (e.g., including impermeable moisture, such as the layer based on polyolefin), Even if they include hydrophilic polymer (further referred to as " moisture absorption layer ") in one layer.Due to the hydrophilic polymer of casing Absorption, remove moisture from adhesive polymer solution and be very limited because compared with single layer casing, external moisture absorption layer Volume reduces；It or is absolutely not since there are damp-proof layers between the tacky surfaces and moisture absorption layer of tubulose casing. At the same time, in the world in many traditional cuisines, the frankfurter of minor diameter is not suitable for smoking.In this case, If the casing for this sausage has certain moisture barrier properties, this is very useful, because it is in sausage through heated place Undesirable weight loss is prevented when reason.

Closest to it is of the invention be patent No. RU 2131670 disclosed on June 20th, 1999, it discloses a kind of fold intestines Clothing is squeezed out by the composition (that is, from moderate moisture-inhibiting and hygroscopic material) based on (total) polyamide and has extra play, outside it It all include water-soluble, film-forming polymers on surface and inner surface.At this point, internal viscosity can not drying layer usually by water-soluble polymeric Object and liquid, substantially hydrophobic material composition, and make casing that there is reduced adhesiveness to sausage meat, while outer layer is used as The mechanical protection agent of aramid layer.The document is taught that these coatings can be applied on casing in Folding Process, and institute Obtained fold stick is automatic filling that is stable and being suitable for casing.

However, since the outer layer of water-soluble polymer is continuous, between the casing fold of fold stick bonding Intensity is too high.This causes this casing wall in high productivity filling process to occur sporadicly to rupture with high de-shirred rate.This The behavior of kind fold casing is heavily dependent on the environmental condition in the operating room for completing filling；Firstly, it depends on sky Gas relative humidity and air humidity is lower, the average frequency of rupture is higher.In addition, the layer of internal substantial liquid has hindered The fold of wrinkle is sufficiently densely stacked and makes that the fold stick with high compression degree cannot be manufactured.In addition, for certain The meat gruel of type cannot be provided especially for rich in those of collagen or polysaccharide, such as starch, the internal layer of this casing Required rippability (or sufficiently low meat adhesion strength).

Therefore, there is still a need for food contents are had reduced adhesiveness by a kind of moisture-proof casing of fold, it is suitable for using Sausage meat carries out High-Speed Automatic filling and automatically moves out hot worked sausage by industrial stripper.

According to foregoing teachings, the object of the present invention is to provide a kind of moisture-proof casing of single-layer or multi-layer, to food, especially For the sausage meat and meat gruel of frankfurter, there is reduced adhesiveness, moisture-proof casing is corrugated into rigidity from carrying stick Formula, on the one hand the fold stick with balance strength can keep the integrality of fold stick in its transport and filling process, another Aspect, it can pass through high speed de-shirred process in the case where no rupture.

Hereinafter, it is understood to mean that applied to the term " rigidity " (rigid) of fold stick significantly beyond its weight Bending or stretcher strain power under, the ability being irreversibly broken that stick has.Hereinafter " certainly applied to the term of fold stick Carrying " (self bearing) is interpreted as under the load moderately applied, such as occur in its transport and treatment process Under inertia force, without additional shape fixed mechanism such as outer tubular net or the bar with plug, stick keeps it The ability of integrality and shape.

It is a further object to provide the methods for this fold casing of high efficiency manufacture.

Invention description

Term and definition

Hereinafter, including specification and claims when describing composition or preparation, accord with unless otherwise indicated Number " % " indicates the weight percent of the total weight based on composition or mixture (blend).

In addition, hereinafter, the word including parenthesized prefix and/or ending is for indicating while including by the word The concept with or without these prefixes and/or ending indicated.For example, word (total) polyamide means a kind of polyamides simultaneously The blend of amine (homopolymer) or copolyamide or some polyamide and/or copolyamide.

In addition, in copolymer description, unless otherwise stated, the monomer being firstly mentioned is calculated as with its molar percentage Major part, for example, ethylene unit is dominant in the copolymer of ethylene and alpha-olefin, in the copolymer of propylene and ethylene, Propylene units are dominant.

Term " polymer " " and " polymer " and their molecule fragment are (for example, in context " polymer chain In (polymeric chain) " or " polymer segment (polymeric segment) "), (it can make on its limited significance For word relevant to homopolymer) and be clearly used as in its broad sense (as usual word relevant with high Middle Molecular Substance) Hereafter,.

Brief description of the invention

After further investigation, surprisingly, it was found that the purpose of the present invention can pass through a kind of pleat for food The casing that wrinkles realizes, is rigidity from carrying bar form and is the moisture-proof casing of tubulose that (totally)s extrude of melting, has and the food The layer of condition contact, this layer reduce the adhesion strength of this food, and wherein the outer surface of fold tubulose casing has at least 10g/ m²At least one it is water-soluble or water dispersible bonds (co) polymer, adherency contact is provided between the fold of fold stick, Wherein

Fold casing outer surface also has the hydrophobic components for reducing adhesion strength, at least one liquid it is organic and/ Or organic element (organoelement) compound, it is substantially non-volatile at room temperature and be substantially insoluble in, and should The total surface concentration of compound is greater than the surface concentration of adhesive polymer, and the total surface concentration is 50 to 500mg/m², Wherein fold stick is characterized in that following characteristics:

Under 20 DEG C and relative humidity (referred to hereinafter as RH) 75%, after keeping 24 hours on a smooth surface with free state, Its longitudinal compression rate under the power of 1N is no more than 0.5%；

When fold stick is as cantilever support, the elastic bending deflection that is visible by naked eyes under its own weight；With

When bending moment is 60 to 400Nmm, irreversible rupture occurs for fold stick；With

Fold stick can at 20 DEG C of temperature and RH 60% with the speed not less than 1.5m/sec by de-shirred, and intestines Clothing wall will not rupture.

In general, the average wall thickness of casing is 15 to 45 μm.The thickness range of casing wall is based on the fact that if thickness is small In 15 μm, then the mechanicalness of casing is too weak；If thickness is higher than 45 μm, it can only be changed into too long of fold stick, and in addition, Since the stability of the warped regions between independent sausage is poor, the linkage section of this casing manufacturing flange gram good fortune sausage is used Process be hindered.

In general, casing is characterized in that, measured under 23 DEG C and RH 85% according to DIN 53 122, moisture-vapor transmission (water vapor diffusion current density) is no more than 40 preferably smaller than 20, and more preferably less than 10g/m²/ day.

The adhesive strength of fold stick fold can estimate by fold stick bending strength, and if bending moment value Less than 60Nmm, this often means that fold stick will be difficult to transport and can be broken in the hopper of filling machine, if bending force The value of square is greater than 400Nmm, this often means that the adherency contact between the fold of fold stick is too strong, or can occur " blocking " between the fold of casing；Under any circumstance, fold stick cannot all carry out de-shirred in the case where rupturing, It is such case at least in for the automatic filling process with high productivity.

If after keeping in 20 DEG C and RH 75% of smooth flat without restrained condition about one day, the feature of fold stick It is, the longitudinal compression rate under the power of 1N is greater than 0.5%, this often means that (substantially right under above-mentioned environmental condition Should be in those of heating room), fold stick tends to spontaneous de-shirred, therefore is not sufficiently stable under condition of storage.

Due to the high surface concentration of component, reduced adhesion strength (hereinafter referred to as CDAS), which is divided into liquid, in room temperature Under it is substantially non-volatile and be substantially insoluble in, the adherency contact between the fold of fold casing according to the present invention seems With discrete features and adhesive polymer is likely distributed between the different location of tubulose casing outer surface.This distribution allows real Its existing desirable balance for being used for the mechanical strength of fold stick needed for the automatic filling process of high productivity.

Another object of the present invention is related to the manufacturing method of moisture-proof casing, which is rigidity carrying fold stick certainly The fold of form, the purpose realize that this method includes the life of the tubulose casing based on essentially synthetic resin by a kind of method Production stage, the synthetic resin provide the internal layer of the casing and pipe that have low-permeability relative to vapor in addition to other features There is reduced adhesiveness to food contents, this method includes that tubulose casing (totally)s extrude, and is optionally then taken to it To stretching, and heat setting can be can be carried out, the subsequent fold rigidity that is converted into is from carrying stick, and wherein conversion process includes following Operation:

(i) Aquo System comprising adhesive polymer and CDAS is applied on the outer surface of moisture-proof casing, so that CDAS Total surface concentration be higher than adhesive polymer surface concentration, and be 50 to 500mg/m²；

(ii) after Folding Process, shape is directly carried out to fold stick by shape setting tool and is fixed；

(iii) force drying fold stick 0.5-20 minutes in the stationary state, the wherein preferred surface temperature of the fold stick Reach 45-75 DEG C,

(iv) it is cooled to room temperature, and；

(v) shape setting tool is removed, obtains rigidity from carrying fold stick.

In general, the Aquo System for the certain volume being applied on tubulose casing surface is (that is, water and be dissolved or dispersed in wherein Adhesive component) be more than CDAS.However, the adhesive polymer concentration in the Aquo System is selected, so that its surface concentration is less than The surface concentration of CDAS.In fact, Aquo System and CDAS can be used as oil-in-water or water-in-oil emulsion is administered to casing table On face, or passes through two individual sprayers and be sprayed both individual liquid.

Detailed description of the invention

The moisture-proof casing of tubulose that basically synthetic resin (totally)s extrude is suitable for producing fold intestines according to the present invention Clothing, this is known in the prior art.Usually they may include 1 to 9 layer (totally) extrude.This casing can be non-directional , uniaxial orientation, but preferably they are biaxially oriented and heat setting.

In general, the moisture-proof casing of tubulose for being suitable for fold has at least one damp-proof layer, which includes at least one tool There are the resin of moisture barrier properties, such as the alkene (co) polymer of vinylidene chloride (co) polymer, nonfunctionalized, or in other words It says, (total) polyolefin；And (total) polyolefin also by group functionalization, the group are generally selected from anhydride group, acidic group Group or epoxy group.(total) polyolefin of nonfunctionalized may include that Noblen, propylene and at least one have 2 to 12 carbon (co) polymer, Alathon, ethylene and at least one alpha-olefin with 3 to 12 carbon atoms of the alpha-olefin of atom The copolymer of copolymer, ethylene and at least one ethylenically unsaturated monomers, the ethylenically unsaturated monomers are selected from vinyl esters (methyl) alkyl acrylate.Functionalized (total) polyolefin may include copolymer, and it includes ethylene and at least one ethylene linkage The unit of formula unsaturated monomer, the ethylenically unsaturated monomers such as ethylenic unsaturated carboxylic acid, ethylenic unsaturated carboxylic acid Salt, the cyclic acid anhydride of ethylenic unsaturated carboxylic acid, the ethylene oxidic ester of ethylenic unsaturated carboxylic acid and optionally, it is one or more Ethylenically unsaturated monomers selected from vinyl esters He (methyl) alkyl acrylate.In addition, functionalized (total) polyolefin can Including any of above at least one ethylenically unsaturated monomers, such as ethylenic unsaturated carboxylic acid, ethylenic unsaturated carboxylic acid Ethylene oxidic ester and ethylenic bond unsaturated dicarboxylic cyclic acid anhydride grafting nonfunctionalized (total) polyolefin.

From the prior art as can be seen that any of above material at least about 2 μm of thickness that layer (totally)s extrude is usual It can provide no more than 40g/m²The moisture-vapor transmission value in/day.

It reduces and the condition of the adhesiveness of food (for example, sausage meat) the also composition to the enteric layers that can be contacted with the food Apply certain limitation.

From the prior art it is well known that the polar substances of such as protein are difficult to adhere to the material with low-surface-energy (hereinafter referred to " ζ "), for example, above-mentioned (total) polyolefin (functionalized and nonfunctionalized polyolefin) and organosilicon (co) polymer and fluorine-containing (co) polymer, the free energy on the surface surface Neng Ji, normalize to surface area, and numerically Equal to surface tension coefficient.In this case, it is characterized in that by the casing comprising internal layer that the (co) polymer squeezes out, The ζ of its inner surface is measured according to DIN 53364, typically no more than 35 dynes/cm.

Since polyolefin is simultaneously Moisture barrier resins, this internal layer can be the sole layer of casing.If it is such Words, for its stress-strain property and heat resistance, the most suitable material for squeezing out single layer casing be propylene homopolymer or The crystallizable copolymer of its blend.

In addition, there is its inner surface the tubulose casing of low ζ value can be multilayer.In this variant of casing, at least One or more layers is not contacted with food (especially meat gruel), and at least one layer or multilayer are preferably from the material for being different from polyolefin It squeezes out, for example, being based on the material of (total) polyamide, (total) polyester or vinylidene chloride (co) polymer.Therefore, casing may include Two layers, three layers or more.Preferably, the outer layer of this multilayer tubular casing is squeezed out by non-polyolefin resin, and and the former The layer directly contacted includes above-mentioned functionalized (total) polyolefin.For example, casing may include the internal layer and outer layer of tubular structure, it should Internal layer is made of the blend of functionalized (total) polyolefin and (total) polyolefin of nonfunctionalized, which directly connects with the former It touches and is mainly the material based on polyamide.Alternatively, casing may include two instead of the layer of the single composition based on polyolefin Adjacent layer, one of them includes functionalized polyolefin and it is adjacent with aramid layer, and second includes nonfunctionalized Polyolefin and it be tubular structure internal layer.

Layer based on polyamide is usually mainly comprising aliphatic (total) polyamide.This (total) polyamide wraps in its macromolecular Unit containing monomer (i) as at least one: γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, ι-amino-undecanoic Acid, κ-aminolauric acid, tetra-methylenedimine, hexamethylene diamine, dodecamethylene diamine, adipic acid, azelaic acid, decanedioic acid and ten Two docosandioic acids；And comprising optionally, no more than at least one monomer selected from group (ii) of 15wt.%: it is M-phthalic acid, right Phthalic acid, m-xylene diamine and paraxylene diamines.Aliphatic series (total) polyamide substantially most preferably be product such as PA 6,PA 66,PA 6/66.In addition, (total) polyamide of composition casing may include partially aromatic (total) polyamide, by extremely The polycondensation reaction preparation of a kind of few aliphatic diamine and at least one aromatic dicarboxylic acid, or vice versa, at least one aromatic diamine and extremely The polycondensation reaction preparation of few a kind of aromatic dicarboxylic acid such as PA 6I/6T or PA MXD6.

Any layer based on polyamide hereinafter mentioned, no matter casing layer structure and layer arrangement are (relative to tubulose knot Outer layer, internal layer or the sandwich layer of structure), it all may include identical (total) polyamide.

The layer based on polyamide of said external in addition to (total) polyamide also may include at least one no more than 40% Kind (co) polymer, is selected from half aromatics (total) polyester and alkene (co) polymer.

It particularly, may include two layers to the casing of fold, wherein the outer layer of tubular structure or exterior layer mainly include polyamides Amine, and the internal layer of tubular structure include optionally with functionalized (total) polyene of (total) polyolefin blend of nonfunctionalized Hydrocarbon.Another variant of its layer structure can imply that following arrangement: wherein outer layer mainly includes polyamide, and sandwich layer includes function Change (total) polyolefin, optionally with (total) polyolefin blend of nonfunctionalized；Internal layer mainly includes at least one thermoplasticity (co) polymer, such as the alkene (co) polymer of nonfunctionalized；Alkene (co) polymer (uses such as anhydride group, acid groups Or epoxy group is functionalized)；And organosilicon (co) polymer or fluorine-containing (co) polymer.

Additionally, it has been found that having the internal layer of reduced adhesiveness can be special by resin extruded its food contents Sign is there is sufficiently high ζ value according to the measurement of DIN 53364, such as higher than 35 dynes/cm, i.e., the resin can be determined as Hydrophilic resin.Surface before with such high ζ is typically considered to the adsorption capacity for having enhancing to polar substances.In general, This resin is the blend polymer based on (total) polyamide.As at least one blend other than (total) polyamide Component, total content are usually 2-45%, and can be selected from (total) polyolefin of nonfunctionalized, functionalized (total) polyolefin, Half aromatics (total) polyester and water-soluble polymer, such as polyvinyl alcohol (referred to hereinafter as PVA).In general, the alkene in these blends (co) polymer and/or the content of half aromatics (total) polyester are 2 to 25%, and the content of water-soluble (co) polymer be 25 to 45%.

Suitable polyvinyl alcohol preferably has the saponification degree not higher than 88mol%, and half aromatics (total) polyester is selected from poly- (to benzene Naphthalate), it is poly- (terephthalic acid (TPA) 1,4- butanediol ester) and poly- (terephthalic acid (TPA) 1,3- propylene glycol ester).

It is obvious that this casing with ζ > 35 dyne/cm inner surface must be multilayer, and furthermore should have At least one damp-proof layer, the damp-proof layer are not the internal layers of tubular structure.This layer or multilayer mainly include above-mentioned nonfunctionalized and/ Or functionalized (total) polyolefin or PVdC (co) polymer, and one of these layers can be the outer layer of tubular structure.Example Such as, casing may include two layers, and wherein the outer layer of tubular structure mainly includes functionalized (total) polyolefin, optionally with non-official (total) polyolefin blend of energyization.As variant, it may include three layers, and wherein the outer layer of tubular structure mainly includes non-functional (total) polyolefin changed, and sandwich layer includes functionalized (total) polyolefin, it is optionally total with nonfunctionalized (total) polyolefin It is mixed.

It is, however, most preferred that if casing substantially has the internal layer (ζ > 35 dyne/cm) based on polyamide, at least One damp-proof layer between above-mentioned internal layer and outer layer also mainly includes polyamide.In this case, external to be based on polyamides The layer of amine can additionally comprise polyester, such as poly- (ethylene glycol terephthalate) (PET) or poly- (mutual-phenenyl two acid bromide two alcohol ester) (PBT) and (total) polyolefin, concentration are typically not greater than 40%.Particularly, casing may include three layers, and wherein tubular structure is outer Layer of the layer choosing from said external based on polyamide, and sandwich layer include functionalized (total) polyolefin, optionally with nonfunctionalized (total) polyolefin blend.

Any layer of casing can be also comprising at least one component no more than 10%, selected from pigment, colorant, thin or thick The filler of dispersion, lubricant, stretches auxiliary agent, foaming agent and its any mixture at plasticizer.

According to the present invention, any of above tubulose casing may be converted into fold stick.

In a preferred embodiment of the invention, the bonding (co) polymerization that the fold of fold stick is bonded together is selected Object, so that their weight average molecular weight is not less than about 15kDa.Under normal circumstances, the expectation strength institute of adherency contact is provided The polymer molecular weight needed depends on the chemical property of polymer.For example, weight average molecular weight is preferably at least the N- ethylene of 15kDa The polymer of base pyrrolidones is suitable as adhesive.On the other hand, ethylene oxide (ethylene glycol) polymer obtain bonding and Adhesive property, while their molecular weight is to be greater than about 40kDa, preferably greater than 100kDa.

The water-soluble polymer that bonding polymer materials may include (either alone or in any combination), including PVA, polyvinyl pyrrole Ethylene oxide (polyethylene oxide or the PEO) of alkanone (referred to hereinafter as PVP), polyacrylamide, average molecular weight higher than 40kDa consolidates Body polymer, cellulose ether, starch, modified starch, natural gum, carrageenan, alginate, agar.

The molecular weight of suitable polyethylene oxide is special provision, since it is known that this molecular weight at room temperature It is moderately viscous liquid (molecular weight ranges 0.2-0.6kDa) below about the polymer of 40kDa, or fragile waxy substance (molecular weight ranges 0.7-40kDa)；And in intermediate molecular weight range, they have the consistency of thickened lubricant, therefore, They cannot act as adhesive when used alone.However, this ethylene oxide polymer (for example, PEG grades, it can be from Clariant AG is obtained) it can be used as the plasticizer for example, adhesive polymer listed above, including high molecular weight PEO (for example,Mw is about 600-4000kDa, can be obtained from Dow Chemical Co.).

Further it is provided that the polymer of fold stick fold bonding may include aqueous dispersion polymers, such as polyvinyl acetate, Butadiene rubber, Afpol and its any mixture.

Above-mentioned CDAS is preferably selected from non-volatile and water-insoluble liquid, such as paraffin oil, silicone oil, liquid vegetable oil, liquid Substantially nonvolatile fatty acid or its any mixture.

Other than above-mentioned adhesive polymer and CDAS, the outer surface of fold tubulose casing can have reduction adhesion strength Water-soluble component (hereinafter referred to as WSCDAS), including water-soluble or aqueous dispersion polymers water-soluble plasticizer, for example, sweet Oil, 1,3- propylene glycol, liquid polyethylene glycol (molecular weight ranges are about 0.2 to 15kDa), triethanolamine, monoethanolamine, it is mono-, Two-or glyceryl triacetate and other water soluble salt, for example, the chloride of alkali or alkaline earth metal or ammonium, phosphate, Sulfate or acetate and its mixture, and total surface concentration is 2 to 200mg/m².For soluble or dispersibility The plasticizer of polymer can soften adherency contact, and soluble-salt reduces water in applied solution or dispersion Activity, to prevent the fold " obstruction " in fold casing.

The surface of the moisture-proof tubulose casing of fold can also have functional additive, such as antimicrobial, prevent from applying Solution and adherency contact by microbial spoilage.

The length ratio (degree of compression) of preferred initial tubular casing and generated fold stick is at least 100.

The moisture-proof casing precursor of tubulose based on essentially synthetic resin can be by extrusion blow molding processes or three bubble method preparations, should Method includes the stage that molding (totally)s extrude, is oriented either uniaxially or biaxially stretching and heat setting.In above-mentioned two situations, it is producing The final stage of process, tubulose casing should be cooled down, be folded and be wound into a roll.Therefore, casing precursor is in roll form.

If the production process of tubulose casing includes the orientation stretching stage, following heat is preferably carried out in this way Setting: preparation orientation casing, it is characterised in that the moisture-induced minimum level measured at room temperature and at high temperature is shunk.This Kind Shrinkage behavior makes it possible to dry fold stick at high temperature, and without the risk of its geometry variation, this permits again in turn Perhaps the production cycle is reduced.

Reel casing before carrying out fold can be by some rotogravure methods (for example, passing through flexographic plate The art of printing) apply printing image.In addition, if casing has the resin layer of the single or external coextrusion of low ζ value, such as poly- third Alkene can then reinforce the adherency contact between the fold of fold stick with Corona discharge Treatment in advance.

In general, CDAS and adhesive polymer solution or dispersion (for example, latex) comprising or not comprising WSCDAS can be with The form of previously prepared oil-in-water or water-in-oil emulsion is administered on the outer surface of casing, then carries out fold processing.

However, in a preferred embodiment of the present methods, two kinds of liquid pass through is applied directly to swaging machine by spraying In device.In such a case, it is possible to which the component of such as WSCDAS and functional additive are added to these solution in advance or divided In granular media.

Folding Process itself (fold of tubulose casing) is commonly known in the art.The fold side industrially used In method, so-called " screw thread method " is most preferred.The technology and corresponding machine allow the fold of fold stick with most compact side Formula is overlapped and is packed.

Then, fold stick is fixed in the tool, pressure limits its geometry.Such tool can be selected from:

It is furnished with the tubular plastic or cotton net of clip, diameter is approximately equal to the outer diameter of fold stick, or；

The combination of this net and smooth shaft, diameter are less than fold stick internal diameter (stick opening diameter)；

Rigid wire rod cylinder, internal geometry correspond to the fold stick of required shape and equipped with fixable Top and bottom part, or；

Threaded rod, in the end opposite with screw thread equipped with the disc-shaped stop of welding, wherein the retainer is limited Fold stick；Dish type retainer can be moved as another along the free-moving washer of bar；With a nut, it is screwed in screw thread Above and by movable washer it is pressed on fold stick.

Casing is transformed into the fold stick fixed with tool, is further dried by one of known method, including right Stream is dry, stream of hot air is dry, be dried in vacuo, radiant heat (IR) is dry and induction drying.No matter which kind of method is used, in fold During stick is dry, the maximum temperature on surface is typically not greater than 75 DEG C.

According to the method for application, the drying process of fixed fold stick is usually required 0.5 to 20 minute.

Drying steps are extremely important for the ideal relaxation of fold stick and mechanical property.Particularly, due to the step, pass through The shape of rigidity and dimensionally stable that the shape and size of the inner space of shape setting tool determine is endowed fold stick.This is outstanding It is related to its constant length, actually with the distance between the limiter of the shape setting tool (top of online clip, cylinder The retainer in portion and bottom part, bar tool) it is consistent.

After drying, fold stick can be cooled down substantially in still air nonactively；Or with pressure side Formula, such as cool down in the air stream.Cooling fold stick is pulled out from shape setting tool and is packed then to transport.

Following embodiment is merely to illustrate the present invention, and does not limit the range being defined by the claims, these implementations Example discloses the most preferred embodiment of the present invention.

Embodiment

Test method

The determination of the inner surface type (hydrophobic or hydrophilic) of tubulose casing

Nominally tubulose casing inner surface type is determined according to surface energy (ζ) value, therefore has ζ≤35mN/m (mN/m= Dyne/cm) nominally surface be considered hydrophobic, and be nominally hydrophilic with the surface of ζ > 35mN/m.

The de-shirred casing that one segment length is about 200mm is carefully routed up or longitudinally cutting.If in extrusion or/and pleat During wrinkle, casing inside and lubricant contact, then by the inner surface of test by being carried out with the filler of hexane or ethanol wet Degreasing, it is hydrocarbon or siloxanes that this, which depends on lubricant,.Then, casing is dried at room temperature at least 3 hours.It is entire along it Width by will comprising 35vol% formamide and 65vol% cellosolvo (ethyl cellosolve) liquid composition It is applied to and lays flat on the test surfaces with smooth specimen and observe the liquid behavior to determine surface type.If during 3 seconds There is no spreading liquid (liquid rests on initial boundary or resolves into individual drop, then according to DIN 53364, ζ≤ 35mN/m, nominally the surface is considered hydrophobic；In case of spreading liquid, then ζ > 35mN/m, the surface are considered Nominally being hydrophilic.

The measurement of CDAS surface concentration on tubulose casing outside

The equipment and chemicals used when measurement is: scale spacing is the scale of 1mm, and precision is the analysis day of 0.01mg It puts down, the round-bottomed flask of 500ml, rotary evaporator, drying oven and solvent (hexane or ethyl alcohol).From the pleat with the known degree of compression The preparatory measuring section that the de-shirred casing including about 2m is cut on wrinkle stick, it then carefully routed up.This section one end is beaten Knot；The certain distance of measurement distance knot about 1.5-1.7m, with ink markings and records.Later, the solvent of about 200ml (is used for Extract hexane, liquid vegetable oil, substantially nonvolatile liquid fat acid and the ethyl alcohol and liquid for extracting silicone oil of paraffin oil State polyethylene glycol) it is put into tubulose casing, the other end of this section knots at ink markings.Then filling is shaken in 2-3 minutes Tubulose casing (bubble) and overturn repeatedly, clean its inner surface with solvent.A knot is cut later, and bubble content is set It changes in the round-bottomed flask weighed in advance, accuracy 0.1mg.Flask with content is put into rotary evaporator To remove the major part of solvent.Then, flask is transferred in drying oven, is heated to 105 DEG C of temperature, is done herein It is dry to be cooled down in the drying atmosphere of drier to constant weight, and weighed again with the accuracy of 0.1mg.On casing outer surface CDAS surface concentration (C_CDAS) with mg/m²It indicates, calculating formula is as follows:

C_CDAS=M/HL=(M₂–M₁)/HL,

Wherein M is CDAS weight, is equal to M₂–M₁, wherein M₂And M₁It is the weight of flask, wherein content and empty flask phase It is indicated with mg with answering.H is the width of the flat tube indicated as unit of rice, the length of tube as unit of rice of L- measurement.

The measurement of water-soluble polymer surface concentration outside tubulose casing

The equipment and chemicals used when measurement is:

Scale spacing is the scale of 1mm, and precision is the assay balance of 0.01mg, the reality equipped with 15kDa weight shutoff film Test the ultrafiltration apparatus (can obtain from Sartorius AG, Germany) of the grade Vivacell 250 of room scale, 500ml round bottom Flask, rotary evaporator, drying oven, double distilled water.

Tubulose casing is handled with mode solvent identical with previous test method, the difference is that using double distilled water As solvent.The casing section for being washed till the pipe without CDAS and also being used as smaller length obtained by above-mentioned test.At with solvent After managing the section, the content of this section is replaced into the pond 250ml of ultrafiltration apparatus.After first time filters, with 5 times of solution bodies Product is reduced, and double distilled water is added in pond until reaching about initial volume.To filter-circulating repetition 10 times diluted, and Ultrafiltrate is collected in a separate container.Then, solution replacement without low-molecular weight polymer will be washed till to weighing in advance In round-bottomed flask.With 3 to 80ml double distilled water flushing tank；Rinse water is poured into the same flask.It is burnt by being concentrated by evaporation Bottle content is simultaneously dried as afore-mentioned test, the difference is that drying temperature is maintained at 120 DEG C of level.Then, will have There is the flask of content to cool down in the drying atmosphere of drier and weighs again, accuracy 0.1mg.By subtracting sky flask Weight can acquire the weight of water-soluble polymer from measured value.

Identical previous test formula can be used in water-soluble polymer surface concentration, by subtracting corresponding weight and length Value calculates.

Above-mentioned test method be it is unrelated with its chemical property have > water-soluble polymer of 15kDa molecular weight it is general Method.Meanwhile bubble content can be tested by analyzing program for any other of previously known polymer design (bubble content).For example, certain polymer can selectively be extracted by suitable nonaqueous solvents (for example, PVP can selectively be dissolved by chloroform or acetone), concentration weight point is then carried out by evaporation and dry extract Analysis.For this or some other polymer, the photometric analysis of coloured complex be also it is applicable, PVP- can be used for example Congo red (patent No. SU 1599727 disclosed in October 15 nineteen ninety) and PVA-I₂Compound.In a kind of finally situation, no Need ultrafiltration program.

The test of fold stick compressibility

Equipment used in test is:

Scale spacing is the vernier caliper of 0.1mm；Drier is more than the removable of fold stick length at least 1cm equipped with diameter Moving platform, and at the space that slightly wet sodium chloride is placed under platform, keep RH ≈ 75%；Air thermometer；Diameter The distiller bracket with stainless steel vertical rod no more than 10mm；Polyethylene washer, internal diameter are more than stick diameter about 1mm, outer diameter Correspond roughly to the outer diameter of fold stick；A set of diameter is identical and gross mass is the steel washer of about 102g (weight is about 1N).

Fold stick is placed on platform, and it is small to conserve 24 in an atmosphere on the wet salt in drier with cover at room temperature When.Then, it pulls it and by the distance between its both ends of vernier caliper measurement (short section for omitting non-pleated casing).It Afterwards, it inserts a rod into the chamber of fold stick, the end for protruding it upward, then makes stick fall, until its female end and bracket base Rigid contact.The polyethylene washer and steel washer that total weight is about 102g are successively fallen in upright wand.The component made is kept Motionless about 10 minutes, later with identical vernier caliper measurement by the distance between the fold stick end of gravity compressed of 1N.

Compressibility (χ) is taken as

Wherein L₁It is free fold stick length, L₂It is the fold stick length of compression.

The test of fold stick bending strength

The equipment used in testing is:

One group analysis balance weights；For the lightweight basket of weighing weighed in advance, with the screw thread of knot attachment in its handle On；One group of smooth cylindrical metal bar has through-hole in one of its end, as the attachment point of screw thread and notch or apart from it The ink markings of his end 50-100mm；Scale, scale interval 1mm；One has the distiller bracket of marmon clamp.

Smooth cylinder bar of the selection for test from described group, so that its diameter is less than fold stick internal diameter 1-5mm, and And the distance of notch or ink markings apart from the end with hole is approximately equal to the half length of tested fold stick.It surveys Measure and record the exact value of the distance.Bar is attached at the other end of screw thread, and basket is for weighing.It wears the free end of selected bar The opening for crossing fold stick, for testing, until the end is overlapped with notch or ink markings since its female end, therefore screw thread Partly also pass through the opening.Then, secured the shaft on bracket by marmon clamp, the edge of marmon clamp close to the notch/ The female end of label and bar.Later, carefully gently counterweight is placed in basket with 10 grams of step-lengths, until the fracture of fold stick, then Record the gross mass of counterweight in basket.

Fracture moment of flexure (the M indicated with Newton millimetre (Nmm)_Fracture) calculated by following formula:

M_Fracture=0.0098 (L_Stick–L_Label) M,

Wherein corresponding L_StickIt is fold stick length, L_LabelIt is from rod end with hole to notch or to mark (being indicated with millimeter) Distance, the gross mass of counterweight when M is with the fracture of gram basket indicated, 0.0098 is the conversion factor from gram force to newton (unit of power).

Assess de-shirred ability of fold stick in the case where no rupture under given de-shirred rate

Used test device is located at interior, wherein keeping about 20 DEG C of steady temperature and about 60% RH；The device It is that a kind of half industry is gathered materials, comprising:

It is used for the electric industrial up- coiler equipped with linear speed adjuster of casing, and

It is securely fixed in the hollow metal cylinder shape bracket of suitable bracket and horizontal orientation, internal diameter is greater than fold A rear base of rod outside diameter about 1mm, cylindrical body fully open, and another pedestal (towards take-up roll) has opening with one heart, It has a diameter larger than fold stick internal diameter and is less than its outer diameter.Holder device exceeds bracket rolling wire.The nearest pedestal of cylindrical stent The distance between up- coiler volume is about 400mm.This bracket has to be filled with the machine for filling frankfurter automatically The almost the same structure feature of the fold rod bracket set,

The long plastics bath of length, is made of, therefore its highest part is located under cold tap small slope.The length of bath Maximum length of the degree slightly larger than the de-shirred casing removed from stick.

All fold sticks to be tested are always held in room air about one day.

With hand by casing section de-shirred that length is about 0.5m.Its free end passes through the opening of bracket and is fixed on a roll of volume It is put into bracket on machine, while by fold stick itself.1 for each stick, one of following linear speed angle value is preset: 0.5, 1.5,2 and 2.5m/sec (or correspondingly, 30,60,90,120 and 150m/min).Then start to wind and continue complete to stick De-shirred.If the process is not accompanied by the visible rupture of tubulose casing, the roller with winding casing is taken out simultaneously from the device It moves into bath.Its free end is placed on the contact for the funnel being fixed below tap, and fixed with marmon clamp.Then, By casing completely wound in bath, and its second end is distorted and is squeezed with aluminum wire clamp.Then, by not having bladdery laminar flow Casing is full of water.When casing is filled (including its vertical component), stops the supply of water and check that casing is complete for the first time The damage of whole property, i.e., the point for the leakage visually seen.If not finding to leak, casing and funnel disconnect and pass through marmon clamp It is connected to leading contact, is present in this way to avoid bubble in the pipe of filling water.Then, water is added under low pressure, makes Casing starts inflation.(the usual drawing for synthesizing casing usually filled by sausage meat when its diameter increases by 10% than initial diameter Stretch), stop supplying water.After this, the rechecking of blowing casing is executed to find to leak.

Since maximum rolls revolving speed (linear velocity 2.5m/sec), until completing test.

Inspection result is to show that fold stick can or cannot be gone in non-cracked situation under given de-shirred rate The conclusion of fold is laid a good foundation.If casing does not pass through test, all processes are repeated with lower convoluting speed.If The reason of rupture be it is suspicious, then carry out the control leakage test with initial (without fold) tubulose casing.

Fold casing is tested for the property by the industrial equipment of sausage manufactory

Filling test

For embodiment according to an embodiment of the present invention preparation fold stick, and according to comparative example preparation can The stable fold stick of receiving carries out vacuum packaging and in commercially available anti-gas and moisture-proof bag immediately after being cooled to room temperature Middle sealing is then transported to sausage manufactory.Sack is opened in the factory and provides fold stick to Handtmann VF In the hopper of the filling machine of 616 grades (Albert Handtmann Holding GmbH&Co.KG, Germany), the filling equipment There is the maximum productivity for producing 3600kg meat gruel per hour, equipped with the chain for representing chain sausage Handtmann PLH 216. Fill casing with the meat gruel of frankfurter, machine productivity from low value (1000kg/h) to medium level (2000kg/h) to High level (3500kg/h) continuously rises.According to test result, have recorded fold stick filling behavior (fold stick it is mechanically stable Property/unstability and casing integrality holding).

Peel test

The frankfurter being filled into test casing is subjected to the cooking process of standard, then cooling with the cold shower； Later, casing is removed from sausage by automatic high speed machine (stripper) Townsend SP 2600.It is tied by reference to test Fruit has recorded the peeling behavior (holding of sausage surface integrity, the availability of maximum detachment rate) of frankfurter.

The material and its shorthand notation referred in embodiment and table

Random copolymer based on propylene, grade Moplen RP210G (about 135 DEG C of Vicat softening point), is purchased from Lyondell-Basell Co.–PP。

The terpolymer of propylene, ethylene and butylene, grade Adsyl 7BC 39F are purchased from Lyondell Basell Industries N.V.-TP。

High pressure (low-density, branching) polyethylene, grade PVD15803 are purchased from PJSC KazanOrgSintez-PE.

The maleinization copolymer of propylene, grade50E561 is purchased from E.I.duPont de Nemours and Co.–Ad1。

Maleinization low density polyethylene (LDPE), grade4200, it is purchased from E.I.duPont de Nemours and Co.–Ad2。

Polyamide 6, gradeB33 is purchased from BASF SE-PA.

Copolyamide 6/66, gradeC33 is purchased from BASF SE-CPA.

Aromatic copolyamides 6I/6T, gradePA3426 is purchased from E.I.duPont de Nemours and Co.–APA。

Poly- (mutual-phenenyl two acid bromide two alcohol ester), gradeB4500 is purchased from BASF SE-PBT.

Polyvinyl alcohol, grade BC-5 are purchased from Chang Chun Petrochemical Co., Ltd-PVA.

Polyvinylpyrrolidone, weight average molecular weight 28000-34000, grade25, it is purchased from BASF SE- PVP。

The sanlose for being 10P with medium degree of etherification falling and 2% solution viscosity value, grade C 10000P2 is purchased from Clariant AG-CMC.

Pharmaceutical grade white paraffin wax oil82, it is purchased from ExxonMobil Fuels&Lubricants-POi.

The pure oleic acid of chemistry, is purchased from Sigma-Aldrich Co.LLC-OA.

The pure glycerol of chemistry, is purchased from Sigma-Aldrich Co.LLC-Gl.

It abridges used in table

N.O.- non-directional casing；

The box of cart.- rod failure；

C- convection current (drying)；

IR-infra-red radiation (drying)；

A- aging at room temperature；

'+'-is；

'-'-is no.

Embodiment 1

Fold stick is prepared using single layer non-directional tubulose casing, the average wall thickness of the casing is about 30 μm, and diameter is about 20mm has zero shrinkage value after impregnating in water at 85 DEG C, is made up of PP of extrusion-blown modling technology and air cooling.

It is operated first two hours in fold, makes the appearance of casing by sided corona treatment by the discharger of setting on the printer Face activation, the surface energy until reaching 42 dynes/cm.However, not applying print image.

Using 9 type of G-6PA (Zden ě kCo., Czech Republic) swaging machine, be equipped with fold spiral shell Bar and single spraying system.By means of the spraying system before fold itself, pass through the outside with emulsion spray casing, the lotion It is to be prepared by mixing and stirring 1% aqueous solution (volume ratio 15:1) of PVP and POi.It is 16ml/ in emulsion feed rate When min, which is moved to inside machine with the speed of 100m/min, is then transformed into fold stick, each includes the pipe of 25m Shape casing.Obtained wet and loose fold stick is moved in shape setting tool, the shape setting tool is with upper The form for stating the box of threaded rod is made, and there are two washer and nuts for each equipment.After tightening nut, the length of each fold stick Degree is reduced by about 1.5 times and becomes equal to about 250mm.Later, the box with fold stick is placed in air drying baking oven, temperature It is 60 DEG C, air circulation speed 8m/sec, and is kept for 5 minutes wherein.The surface temperature of the stick just taken out is about 58 DEG C.So Fold stick is cooled down 45 minutes at room temperature afterwards, takes out from shape setting tool, after being sampled test, they is packed It is good, it is transported to sausage manufactory and is tested for the property, including above-mentioned filling and peel test.Fold is shown in Tables 1 and 2 All important parameters and its feature of the production process of casing.

Comparing embodiment 1

Wet fold stick will be processed into according to embodiment 1 with the tubulose casing used in embodiment 1 of Corona discharge Treatment And it is dry, the difference is that replacing above-mentioned emulsion using tap water.The production process of fold casing is shown in Tables 1 and 2 Parameter and its feature.

Embodiment 2

The tubulose casing for being processed into fold stick is:

The double-deck biaxial orientation casing, average wall thickness are about 20 μm, and diameter about 20mm soaks at 85 DEG C with vertical and horizontal Entering after-contraction value in water is 1%, wherein the layer has internal layer (A) He Yuhuan as shown below being in contact with food contents The outer layer (B) of border contact and the layer percentage thickness of the total wall thickness based on casing in bracket as shown below:

A (30%): TP-40% and Ad1-60%；

B (70%): PA-95%, APA-3%, PBT-2%；The layer is expressed as (PA) in table 2.

Fold stick is not machined to by fold by corona discharge pretreated casing, which is equipped with fold Screw and two spraying systems, and before fold itself, by the two spraying systems, the outer surface of casing is sprayed respectively 1% aqueous solution of mist PVP and paraffin oil are correspondingly supplied with the volume flow rate of 15 and 1ml/min, and the speed of casing with Embodiment 1 it is identical.Then the resulting wet and loose fold stick of approximately equal length with embodiment 1 shape is put into fix In tool, which once includes tubular plastic net, and when each fold stick has been compacted about 1.6 times, end is by clip Extruding is about 234mm up to length, and the stick of dry compacting under the same conditions as example 1.It is shown in Tables 1 and 2 The parameter and its feature of the production process of fold casing.

Comparing embodiment 2

Use the tubulose casing of embodiment 2.Two hours before its fold, corona is carried out to it using identical printing machine Discharge treatment prints image without applying, and then fold stick is processed into according to embodiment 2, the difference is that using tap water Instead of above-mentioned PVP solution.The fixation and drying of fold stick are also carried out in mode in the same manner as in Example 2.In Tables 1 and 2 Show the parameter and its feature of the production process of fold casing.

Embodiment 3

The casing precursor of fold stick is provided by three layers of biaxially oriented tubulose casing, wall thickness, diameter and shrinkage character with Embodiment 2 is identical.The casing has a layer of following presentation: the internal layer (A) that is in contact with food contents and contacting with environment The layer percentage thickness of the total wall thickness based on casing in outer layer (C) and bracket as shown below:

A (20%): TP；

B (10%): Ad1；

C (70%): PA-95% and APA-3%, PBT-2%；The layer is expressed as (PA) in table 2.

After being pre-processed with corona discharge, casing flexographic printing techniques application to printed image.

Then it is processed into fold stick in the same way as in example 2, the difference is that using paraffin oil and oil The mixture of sour (volume ratio 1:1) is as CDAS, correspondingly for PVP aqueous solution and paraffin-oleic acid mixture volume flow rate For 15ml/min and 1.5ml/min.

As described in example 1 above, the fold stick being fixed in box passes through infra-red furnace tunnel drying 5 minutes, maximum surface Temperature is 68 DEG C, then that they are 10 minutes cooling by room temperature air-flow.The next embodiment 1 operated according to this specification It carries out.The parameter and its feature of the production process of fold casing are shown in Tables 1 and 2.

Comparing embodiment 3

Tubulose casing used in embodiment 3 is located in the case where image is printed in no application with corona discharge in advance Reason is processed into wet fold stick and is dried according to embodiment 3, the difference is that the charging of PVP solution has inactivated.1 He of table The parameter and its feature of the production process of fold casing are shown in table 2.

Embodiment 4

The casing precursor of fold stick is provided by three layers of biaxially oriented tubulose casing, wall thickness, diameter and shrinkage character with Embodiment 2 is identical.The casing has a layer of following presentation: the internal layer (A) that is in contact with food contents and contacting with environment The layer percentage thickness of the total wall thickness based on casing in outer layer (C) and bracket as shown below:

A (20%): CPA -65% and PE -35%；

B (10%): Ad2；

C (70%): PA-95% and APA-3%, PBT-2%；The layer is expressed as (PA) in table 2.

The casing is processed into fold stick, and is further dried in the same way as in example 2.It is shown in Tables 1 and 2 The parameter and its feature of the production process of fold casing.

Comparing embodiment 4a

According to patent No. RU 2131670, by equipment used in embodiment 2 by tubulose casing used in embodiment 4 It is transformed into fold stick.Directly with 4%PVP aqueous solution with the volume flow rate spraying treatment pipe of 15ml/min before fold step itself Shape casing outer surface, and CDAS is not added, and handled with emulsion spray of 10.0% oleic acid in the aqueous solution of 2.0%PVP Inner surface.Wet fold stick can only be compressed 1.3 times.Following behaviour is realized in a manner of identical in the embodiment 1 with this specification Make.The parameter and its feature of the production process of fold casing are shown in Tables 1 and 2.

Comparing embodiment 4b

Tubulose casing used in embodiment 4 is transformed into fold stick, difference in mode in the same manner as in Example 2 It is that the PVP concentration in water-based system increases to 4%, and the volume flow rate of oil is reduced to 0.5ml/min.

Embodiment 5

The casing precursor of fold stick is provided by three layers of biaxially oriented tubulose casing, wall thickness, diameter and shrinkage character with Embodiment 2 is identical.The casing has a layer of following presentation: the internal layer (A) that is in contact with food contents and contacting with environment The layer percentage thickness of the total wall thickness based on casing in outer layer (C) and bracket as shown below:

A (20%): CPA-60%, PVA-34% and G1-6%；The layer is expressed as (CPA+PVA) in table 2.

B (10%): Ad2；

C (70%): PA-95%, APA-3%, PBT-2%；The layer is expressed as (PA) in table 2.

The casing is subjected to fold and drying in mode in the same manner as in Example 3, the difference is that Aquo System is Solution comprising 1%CMC.The parameter and its feature of the production process of fold casing are shown in Tables 1 and 2.

Comparing embodiment 5

Fold stick will be converted into mode same as Example 5 according to the casing of embodiment 5, the difference is that aqueous CMC concentration in system increases to 5%, and CDAS volume flow rate is reduced to 0.5ml/min；And it is different from force drying, Fold stick is maintained in shape fixed bin 15 minutes at room temperature.The production process of fold casing is shown in Tables 1 and 2 Parameter and its feature.1. casing layered structure of table and its processing parameter

Its midrange corresponds to following presentation:

I- Example No. or comparing embodiment number, the latter are expressed as No. C.

II- casing layered structure (layer is shown from internal to external).

III- Corona discharge Treatment.

IV- is directly used in pretreated liquid before fold step.

IV₁Water (H₂) or aqueous solutions of polymers O；Concentration (wt.%)；Volume flow rate (ml/min).

IV₂- CDAS, component, concentration (vol.%.)；Volume flow rate (ml/min).

V-shaped shape setting tool.

VI- dry (fixation carries out aging in the tool).

VI₁Dry type.

VI₂The maximum surface temperature of fold stick, DEG C.

VI₃Time, minute.

The feature of 2. fold stick of table

Its midrange, which corresponds to, to be indicated:

I- Example No. or comparing embodiment number, the latter are expressed as No. C.

II- casing inner surface type (nominally to be expressed as NPb- hydrophobic for ζ≤35 c；ζ > 35 c are expressed as NP1- name On be hydrophilic).

The length of the degree of compression of the casing of III- fold bar form-initial tubular casing and generated fold stick (in box) Degree ratio.

The surface concentration of IV- component, mg/m²。

IV₁Polymer.

IV₂-CDAS。

V- compressibility, %.

VI- is broken moment of flexure, Nmm.

VII- stable de-shirred rate, m/sec.

VIII- casing filling behavior.

^aIt is stranded that fold stick does not occur.

^bApparent round point shape " obstruction " occurs for fold stick, and with relatively low intensity.

After its boiling (scalding) and cooling, according to peel test as described above, all Frankfort type sausages (have been demonstrate,proved Its bright casing can be subjected to filling test) it is all successfully detached from from casing under the maximum operation rate of stripper, and sausage The integrity intact on surface is bad.Therefore, all casing tested all have food contents the adhesiveness of reduction.

The comparison of the embodiment above embodiment and comparing embodiment only can be derived that clear conclusion below:

The invention discloses a kind of moisture-proof casing of the single-layer or multi-layer of fold, have reduced adhesion strength to food, should Casing is converted into the mechanically stable rigid fold stick of self-supporting, can be transported and be able to use efficient automatic filling equipment It is filled by sausage meat, and there is no technical problems, the damage including its integrality and shape.

The essential prerequisite for realizing these features of fold stick is disclosed before fold step itself The combination of the mass ratio of the component and component that are applied on casing outer surface can be provided with balance adhesion strength The bonding of fold stick fold.In this regard, another prerequisite is using method of the invention.Component and its amount and by before this Other selections of the production method of fold stick made of body casing cause the mechanicalness of generated stick too weak, so that they are several It is not construed as self-supporting；Or they bond too strong, prevent they are not from having the case where casing breadage Under with sufficiently high rate carry out de-shirred.

The method of the moisture-proof casing for being used to prepare fold bar form of the invention, which allows to manufacture, has required combining properties Product, and its operational cycle time is considerably shorter than method well known in the prior art.

Claims (36)

1. a kind of rigidity for food is from the fold casing for carrying bar form, the fold casing is the pipe that melting (totally)s extrude Shape moisture-proof casing, the casing with food contents with being in contact and have reduced adhesiveness to the food contents Layer, the casing outer surface have at least 10g/m²At least one is water-soluble or water dispersible adhesive polymer, it is described water-soluble Property or water dispersible adhesive polymer provided between the fold of the fold bar form adherency contact, in which:

The outer surface of the fold casing also has the hydrophobic components for reducing adhesion strength；The hydrophobic components are at least A kind of liquid is organic and/or organic element compound, substantially non-volatile at room temperature and be substantially insoluble in；And institute State surface concentration of organic and/or total organic element compound surface concentration greater than the adhesive polymer and total table Face concentration is 50 to 500mg/m², and wherein the fold stick has the feature that

After being kept for 24 hours with free state on a smooth surface under 20 DEG C and RH 75%, the feature of the fold stick exists In under the power of 1N, longitudinal compression rate is no more than 0.5%；

The fold stick is characterized in that, as cantilever support, is become under its own weight without macroscopic elastic bending Shape；Simultaneously when bending moment reaches 60 to 400Nmm, the fold stick generation irreversibly ruptures；With

The fold stick is characterized in that, can be in the speed for being not less than 1.5m/sec at 20 DEG C of temperature and RH 60% Degree is lower to carry out de-shirred, and the casing wall will not rupture.

2. fold casing according to claim 1, wherein according to DIN 53 122 at 23 DEG C and under relative humidity 85% The moisture-vapor transmission value of measurement is no more than 40 preferably smaller than 20, and more preferably less than 10g/m²/ day.

3. fold casing according to claim 1, wherein the weight average molecular weight of bonding (co) polymer is preferably not less than About 15kDa.

4. fold casing according to claim 3, wherein water soluble adhesive polymer is selected from the group including the following terms: poly- The polyethylene oxide of vinyl alcohol, polyvinylpyrrolidone, polyacrylamide, average molecular weight higher than 40kDa, cellulose ether, shallow lake Powder, modified starch, natural gum, carrageenan, alginate, agar or its any mixture.

5. fold casing according to claim 3, wherein water dispersible adhesive polymer is selected from the group including the following terms: Polyvinyl acetate, butadiene rubber, Afpol or its any mixture.

6. fold casing according to claim 1, wherein substantially non-volatile at room temperature and be substantially insoluble in Organic and/or organic element compound be selected from including the following terms group: paraffin oil, silicone oil, liquid vegetable oil, liquid base Nonvolatile acid or its any mixture in sheet.

7. fold casing according to claim 1, wherein fold casing outer surface, which also has, reduces adhesion strength Water-soluble component and include selected from least one of the group compound including the following terms: the bonding of water-soluble or water dispersible is poly- Close water-soluble plasticizer, the water soluble salt of object；And the water-soluble component surface concentration is 2 to 200mg/m²In the range of.

8. fold casing according to claim 7, wherein the water-soluble plasticizer is selected from the group including the following terms: sweet Oil；1,3- propylene glycol；The polyethylene glycol that molecular weight is 0.2 to 15kDa；Triethanolamine；Monoethanolamine；Mono-, two- or triacetic acid Glyceride.

9. fold casing according to claim 7, wherein water soluble salt is selected from the group including the following terms: alkali metal or alkali The chloride of earth metal or ammonium, phosphate, sulfate or acetate.

10. fold casing according to claim 1, wherein the fold casing, which has 1 to 9, (totally)s extrude layer.

11. fold casing according to claim 1, wherein the casing is non-directional, or preferably uniaxial or double It is axis orientation and heat setting.

12. fold casing according to claim 1, wherein it mainly includes the anti-of polymer that the casing, which includes at least one, Damp layer, the polymer are selected from the group including the following terms: vinylidene chloride (co) polymer；The alkene of nonfunctionalized is (total) poly- Close object；By the (co) polymer of the alkene of group functionalization, the group is generally selected from anhydride group, acid groups or epoxy group Group.

13. fold casing according to claim 1, wherein being measured according to DIN 53364, the surface of tubulose casing inner surface It can value at most 35 dynes/cm.

14. fold casing according to claim 13, wherein the layer contacted with food contents generally comprises at least one Thermoplasticity (co) polymer, the thermoplasticity (co) polymer are selected from the group including the following terms: the alkene (total) of nonfunctionalized Polymer；By the alkene (co) polymer of group functionalization, the group is generally selected from anhydride group, acid groups or epoxy group Group；Organosilicon (co) polymer；Fluorine-containing (co) polymer；Or mixtures thereof.

15. fold casing described in 2 and 14 according to claim 1, wherein the alkene (co) polymer of nonfunctionalized, which is selected from, includes The group of the following terms: Noblen；The copolymer of propylene and at least one alpha-olefin with 2 to 12 carbon atoms；Ethylene Homopolymer；The copolymer of ethylene and at least one alpha-olefin with 3 to 12 carbon atoms；Ethylene and at least one ethylenic bond are not It is saturated the (co) polymer of monomer, the ethylenically unsaturated monomers are selected from vinyl esters and (methyl) alkyl acrylate.

16. fold casing described in 2 and 14 according to claim 1, wherein functionalized alkene (co) polymer be selected from include with Under group: (i) copolymer, the copolymer include ethylene and at least one functionalized ethylenically unsaturated monomers unit, The ethylenically unsaturated monomers are selected from ethylenic unsaturated carboxylic acid, the salt of ethylenic unsaturated carboxylic acid, ethylenic bond unsaturation carboxylic The ethylene oxidic ester of sour cyclic acid anhydride, ethylenic unsaturated carboxylic acid；It include optional one or more alkene with, the copolymer Keyed unsaturated monomer, the ethylenically unsaturated monomers are selected from vinyl esters and (methyl) alkyl acrylate；There are also (ii) (total) polyolefin of any nonfunctionalized is grafted at least one functionalized ethylenically unsaturated monomers, the official The ethylenically unsaturated monomers of energyization are selected from ethylenic unsaturated carboxylic acid, the ethylene oxidic ester of ethylenic unsaturated carboxylic acid and ethylene linkage The cyclic acid anhydride of formula unsaturated dicarboxylic.

17. fold casing described in 2 and 14 according to claim 1, wherein the casing has a single layer, the single layer is usually by can The propylene (co) polymer of crystallization is made.

18. fold casing described in 2-14 according to claim 1, wherein at least one damp-proof layer is not the interior of the tubulose casing Layer.

19. fold casing according to claim 13, wherein at least one layer of the casing is not connect with food contents The layer of touching, and mainly include at least one substantially aliphatic (total) polyamide.

20. fold casing according to claim 19, wherein substantially aliphatic (total) polyamide wraps in its macromolecular Containing at least one selected from the unit of the monomer in the following group (i): γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, ι-ammonia Base hendecanoic acid, κ-aminolauric acid, tetra-methylenedimine, hexamethylene diamine, dodecamethylene diamine, adipic acid, azelaic acid, the last of the ten Heavenly stems Diacid and dodecanedioic acid；And comprising optionally, at least one no more than 15wt% is selected from the following group in its macromolecular (ii) monomer in: M-phthalic acid, terephthalic acid (TPA), m-xylene diamine and paraxylene diamines.

21. fold casing according to claim 19, wherein at least one layer mainly comprising at least one substantially aliphatic series (total) polyamide is also selected from (total) of half aromatics (total) polyester and alkene (co) polymer comprising at least one no more than 40% Polymer.

22. fold casing described in 9-21 according to claim 1, wherein the casing includes two layers, wherein the tubular structure Outer layer mainly include polyamide, and the internal layer of the tubular structure is optionally to mix with (total) polyolefin of nonfunctionalized Functionalized (total) polyolefin.

23. fold casing described in 9-21 according to claim 1, wherein the casing includes three layers, wherein the tubulose casing It is functionalized (total) polyene optionally mixed with (total) polyolefin of nonfunctionalized that outer layer, which mainly includes polyamide, sandwich layer, Hydrocarbon；And the internal layer of the tubular structure mainly includes at least one thermoplasticity (co) polymer, the thermoplasticity (co) polymer Selected from the group including the following terms: the alkene (co) polymer of nonfunctionalized；Pass through the alkene (co) polymer of group functionalization； Organosilicon (co) polymer and fluorine-containing (co) polymer；The group is selected from anhydride group, acid groups or epoxy group.

24. fold casing according to claim 1, wherein being measured according to DIN 53364, tubulose casing inner surface surface energy Value is greater than 35 dynes/cm.

25. fold casing according to claim 24, wherein the tubulose casing internal layer includes mixture, the mixture At least one (co) polymer comprising at least one thermoplastic substantially aliphatic (total) polyamide and 2 to 45%, it is described (co) polymer is selected from polyvinyl alcohol, half aromatics (total) polyester and alkene (co) polymer.

26. fold casing according to claim 25, wherein substantially aliphatic (total) polyamide wraps in its macromolecular Containing at least one selected from the monomeric unit of the following group (i): γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, ι-amino ten One alkanoic acid, κ-aminolauric acid, tetra-methylenedimine, hexamethylene diamine, dodecamethylene diamine, adipic acid, azelaic acid, decanedioic acid And dodecanedioic acid；And optionally, also it is selected from comprising at least one no more than 15wt% with the monomer of the following group (ii): isophthalic Dioctyl phthalate, terephthalic acid (TPA), m-xylene diamine and paraxylene diamines.

27. fold casing according to claim 25, wherein the saponification degree of polyvinyl alcohol is at most 88mol%.

28. fold casing according to claim 25, wherein it includes following every group that half aromatics (total) polyester, which is selected from: poly- (ethylene glycol terephthalate), poly- (terephthalic acid (TPA) 1,4- butanediol ester) and poly- (terephthalic acid (TPA) 1,3- propylene glycol ester).

29. according to fold casing described in claim 25-28, wherein the casing includes two layers, wherein the tubular structure Outer layer mainly include functionalized (total) polyolefin optionally mixed with (total) polyolefin of nonfunctionalized.

30. according to fold casing described in claim 25-28, wherein the casing includes three layers, wherein the tubular structure Outer layer mainly include nonfunctionalized (total) polyolefin；And sandwich layer includes optionally mixed with (total) polyolefin of nonfunctionalized Functionalized (total) polyolefin closed.

31. according to fold casing described in claim 25-28, wherein the casing includes three layers, wherein the tubular structure Outer layer mainly include at least one polyamide；Optionally, at least one (co) polymer no more than 40%, it is described (total) poly- It closes object and is selected from half aromatics (total) polyester and alkene (co) polymer；And sandwich layer, the sandwich layer include optionally with nonfunctionalized Functionalized (total) polyolefin of (total) polyolefin mixing.

32. fold casing according to claim 1, wherein any one of the layer that (totally)s extrude of tubulose casing includes not At least one component greater than 10%, described group is selected from the group including the following terms: pigment, colorant, thin or rough segmentation dissipate Filler, lubricant, stretches auxiliary agent, foaming agent or its any mixture at plasticizer.

33. a kind of method for manufacturing casing comprising be converted to just fold casing described in any one of claim 1-32 Property from carrying fold stick, the method includes be substantially based on the tubulose casing of synthetic resin, and the stage (totally)s extrude；Optionally, Orientation stretching and heat setting stage；And on the outer surface that Aquo System is applied to casing after the fold stage, it is described Aquo System includes adhesive polymer, wherein

Apply the hydrophobic components for reducing adhesion strength also on the outer surface of casing, and includes at least one base at room temperature Liquid that is non-volatile and being substantially insoluble in is organic in sheet and/or organic element compound, so that the compound is outside casing The total surface concentration in portion is greater than adhesive polymer, and the total surface concentration is 50 to 500mg/m²；

The method includes the fold rod shape fixed stages by means of shape setting tool；

The method includes the 0.5-20 minutes stages of force drying fold stick under shape stationary state, wherein the fold stick Preferred surface temperature be 45 to 75 DEG C；

The method includes being cooled to room temperature the fold stick and release the fold stick from the shape setting tool It puts, to obtain the rigidity from the stage for carrying fold stick.

34. according to the method for claim 33, wherein the hydrophobic components of adhesion strength will be reduced in the Aquo System In emulsified.

35. according to the method for claim 33, wherein by the hydrophobic components for reducing adhesion strength with liquid, in room The substantially non-volatile and mixing of organic and/or organic element compound or these compounds that is substantially insoluble under temperature The form of object is separately applied on the casing.

36. according to the method for claim 33, wherein Aquo System also includes the water-soluble component for reducing adhesion strength.