EP1001682A1 - A hose film on the basis of polyamides - Google Patents
A hose film on the basis of polyamidesInfo
- Publication number
- EP1001682A1 EP1001682A1 EP98908341A EP98908341A EP1001682A1 EP 1001682 A1 EP1001682 A1 EP 1001682A1 EP 98908341 A EP98908341 A EP 98908341A EP 98908341 A EP98908341 A EP 98908341A EP 1001682 A1 EP1001682 A1 EP 1001682A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- basis
- copolymer
- units
- polyamide
- mixture
- 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.)
- Withdrawn
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 25
- 229920002647 polyamide Polymers 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 31
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000554 ionomer Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 14
- 239000001361 adipic acid Substances 0.000 claims abstract description 14
- 150000007513 acids Chemical class 0.000 claims abstract description 13
- 239000004760 aramid Substances 0.000 claims abstract description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 13
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 13
- 150000001336 alkenes Chemical group 0.000 claims abstract description 8
- -1 aUphatic copolyamide Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 abstract 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 45
- 235000013580 sausages Nutrition 0.000 description 18
- 239000010410 layer Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000010411 cooking Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000014059 processed cheese Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Chemical group 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241001312297 Selar Species 0.000 description 1
- 229920003365 Selar® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C13/0013—Chemical composition of synthetic sausage casings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- A—HUMAN NECESSITIES
- A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
- A22C—PROCESSING MEAT, POULTRY, OR FISH
- A22C13/00—Sausage casings
- A22C2013/0063—Sausage casings containing polyamide, e.g. nylon, aramide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
Definitions
- the invention concerns to hose films on the basis of polyamides and can be used for production of the orientated in two axis hose film to be used in manufacture of paste Uke and viscous products which may be subjected to heat treatment in temperature range 70-125° C.
- the invention concerns in particular, to manufacturing of a hose film for production of sausages, and also of processed cheeses, packed in the form of sausage, which are packing up as a rule, in softened state or viscous-liquid state.
- Composition for reception of a coat for sausages includes polycaprolactone with molecular weight in the range 1000-4000, 1,6- hexamethylenediisocyanate and 1,4-buthanediol in the following ratio of Usted components (weight parts): 24-30, 50-40, 24,84-27,0 (SU, Al, 1034597).
- the components of a composition heat up to 60-50°C with subsequent increase of temperature up to 240°C.
- the received product is poured on potytetrafluorethylene film. After 5 hours the plate poured off is granulated, heated up again and extruded.
- the film has a thickness no less than 0,05 mm and is suitable only for using with special machines.
- Moisture content in the coat is 0,03 %, it is enough for detention of the coat in the process of coating in a stretched and elastic condition, but during cooking the contents of water in the coat increased so, that it negatively influences mechanical characteristics of the coat.
- the coats on the basis polyamide may be better subjected to stretching and shrinkage, they have high durabiUty, and also are suitable not only for machine filUng but also hand-operated filUng.
- polyamides in the known hose film the polycaprolactam, polyaminoenantamide, polyhexamethyleneadipamide and/or polyhexamethylenesebacinamide as separate substances or as a mixture each with other, and also copolymers of above polyamides and of polyaminoundecaneamide or polylaurinelactam are used.
- the thickness of received hose film is about 0,050 mm, that is satisfactory only for machine filUng; permeabiUty for water is in a range 12-28 g/M 3 in a day, and permeabiUty for oxygen is about 15 up to 30 cm 3 / 2 day bar.
- This film is manufactured as foUows: the components are mixed, plasticized at 260° C and moulded, preferable by extrusion of a sleeve with blowing. Then biaxial stretching with multipUcity of the lengthways and across stretching in a range from 1:1,5 up to 1:4 is carried out. Then the sleeve is thermofixed for stabilization of the sizes.
- the closest known technical decision to the claimed one is a hose film on a basis of polyamides, used in manufacture of paste Uke and viscous food products (sausage coat), including polyamide 6, aUphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and terephtaUc acid units, and copolymer including olefin units (EP, Al, 0722664).
- This hose film contains (weight. %): a) polyamide 6 b) aUphatic polyamide (5-50 % of general weight of aU polymers in a layer)
- aUphatic copolyamide is used the copolyamide with units of ⁇ -caprolactam, of hexamethylenediamine and of azelaic acid (polyamide 6/6,9) and/or polyamide 6,12 as copolyamide from hexamethylenediamine and dodecanic acid,
- the hose film may involve dyes and/or pigments in few amounts.
- the manufacturing of monolayer and multilayer sausage coat includes mixturing and melting at the temperature about 240° C of components of the mixture in special extruder until producing of a homogeneous melted mixture, extrusion of the latter through ring injectors with blowing, moulding of an integral sleeve, which stretched then in longitudinal and cross directions under air pressure. A received film is fixed by additional heat treatment.
- the hose film received according to the known technology gives shrinkage from 5 up to 25 % (at 80° C) in share and cross directions, it has thickness of 0,033-0,056 mm, can be manufactured as multilayer.
- Water permeabiUty of the sausage coat changes from 11,5 up to 13, 1 g/m a day, and oxygen permeabiUty varies from 13,6 up to 18,5 cm 3 /m 2 day bar.
- Multilayer hose film contains as a minimum one layer of the mentioned above polyamide mixture.
- Other layers consist mainly from polyamides (for example, polyamide 6), polyamide mixtures, polyolei ⁇ ns (for example, polyethylene or polypropylene), also from polyolefins, containing binding functional groups.
- the layers can be manufactured from copolymers with units of ethylenenonsaturated monomers (for example, vinylacetate, vinyl alcohol, acryUc and methacryUc acid), and also of vinyUdenchloride or acrylonitrile copolymers, of ionomer resins or of mixtures of above named polymers.
- a coat usually consists of 3- 5 layers. Such coat may be manufactured by coextrusion through ring injectors, which are speciaUy designed according to quantity of layers. Multilayer coats being compared with monolayer show higher water and vapour permeabiUty and permeabiUty for oxygen.
- the problem to be solved by the invention consists in creation of a hose film to be used in manufacture of paste Uke and viscous food products, having lower water and vapour permeabiUty and permeabiUty for oxygen, and also having increased strength characteristics under heat treatment.
- the problem is solved by the claimed invention.
- Aromatic polyamide containing hexamethylenediamine and terephthaUc acid units 3-7
- Ionomer resin 3-6 Mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids 0 1-5
- the hose film may contain zinc salt of copolymer of ethylenemethacryUc acid as ionomer resin.
- the copolymer of polycaprolactam and of polyhexamethylendiamine and of adipic acid may be used (polyamide 6/6,6 with elements of the formulas -N-(CH 2 ) 5 -CO-, -N-(CH 2 ) 6 -NH-, -CO-(CH 2 ) 4 -
- the hose film may contain as a mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids the mixture with the contents of graft units from 0,3 up to 0,9 weight %
- the hose film may be carried out as multilayer, and at least one layer has the foUowing composition: (weight parts):
- hose film can contain if necessary, additional dyes, pigments and/or auxiUary substances of processing. The share of these components rather smaU, so the basic characteristics of the film remain constant. Below the components of the hose film are designated as foUows:
- graft copolymers for example, acrylic polymer with graft units of maleic anhydride, Unear polyethylene of low density with graft units of maleic anhydride and ethylenepropylene rubber with graft groups of maleic anhydride are used.
- the properties are reached which have not both separate components of the film and known structures of hose films, namely: higher water and vapour permeabiUty and permeabiUty for oxygen, and besides, the film is thermostable up to 125° C and is not subjected to breaks at thermal processing (cooking).
- Components 1-5 in the above specified quantities are carefully mixed and loaded into the bunker of an extruder where the mixture of granules is homogenized at 255° C up to receiving of homogeneous melt.
- the melt is submited on the ring head of extruder, on passage through which a primary sleeve is produced. Leaving from the extruder a primary sleeve is sharply cooled and then is heated up for plastification. Then it undergo to biaxial stretching which is carried out by compressed air. Then the moulded sleeve is directed to the furnace for thermofixation where there is the process of its stabilization. Then a sleeve is cooled, then it is submitted on the receiver, where it is reeled up on a fiber drum in a combined form.
- Example 2 To receive a multilayer hose the foUowing polymeric mixtures are appUed. Mixture 1; 1) 80 weight parts of usual granulated polycaprolactam (polyamide 6) (as in the example 1) 2) 10 weight parts of copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid (polyamide 6/6,6) (according to example 1)
- the mixture III is prepared similarly to mixture 1.
- Mixtures 1, II, III are plasticizated in three single-screw extruders at 240°C until producing of homogeneous alloys, then they are fed to 3-layer ring injectors and are coextruded in a sleeve.
- the sleeve is processed in oriented in two axis and thermofixed hose film.
- the hose film produced according to the invention meets the requirements, necessary for use, in particular in manufacture of cooked sausages and of processed cheeses.
- the thickness of a film for machine filUng of sausage forcemeat is 0,037-0,040 mm, for hand-operated filUng it is 0,030-0,033 mm.
- the hose film remains rather strong, also at high temperatures about up to 125°C it has large elasticity and it is soft to the touch, adjoins to contents even after complete cooUng, wiU not practicaUy lead to precipitation of jeUy and of fat between sausage forcemeat and coat; its durabiUty at filUng and accuracy of caUbre of sausages, made in such environments, does not decrease. There is no adhesion of food products to the hose film.
- Distinctive feature of invented hose film is its low water- vapor- and oxygen permeabiUty, that defines a high degree of safety of a ready product (abihty to oxidize and loss of weight), and also it thermostabiUty.
- the durabiUty of the coat is kept during heat treatment, percent of sausage sticks spoiled at cooking is no more than 1 % on 1000 ready sticks.
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Food Science & Technology (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Polymers & Plastics (AREA)
- Mechanical Engineering (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Processing Of Meat And Fish (AREA)
- Polyamides (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention concerns hose films on the basis of polyamides which can be used for production of hose films orientated in two axes usable in manufacture of paste-like and viscous products which may be subjected to heat treatment in temperature range 70-125 °C. A hose film on the basis of polyamides, including polyamide 6, aliphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and teraphthalic acid units and a copolymer, including olefin units, is claimed which additionally contains a ionomer resin. As aliphatic copolyamide, it contains a copolymer of polycaprolactam, polyhexamethylenediamine and adipic acid. As copolymer including olefin units, it contains a mixture of graft copolymers on the basis of derivatives of carboxylic and polycarboxylic acids. The components are present in following amounts (weight parts): Polyamide 6: 77-83; copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid: 7-13; aromatic polyamide, containing hexamethylenediamine and terephthalic acid units: 3-7; ionomer resin: 3-6; mixture of graft copolymers on the basis of derivatives of carboxylic and polycarboxylic acids: 0.1-5.
Description
A HOSE FILM ON THE BASIS OF POLYAMIDES Branch of the invention
The invention concerns to hose films on the basis of polyamides and can be used for production of the orientated in two axis hose film to be used in manufacture of paste Uke and viscous products which may be subjected to heat treatment in temperature range 70-125° C. The invention concerns in particular, to manufacturing of a hose film for production of sausages, and also of processed cheeses, packed in the form of sausage, which are packing up as a rule, in softened state or viscous-liquid state. Background of the invention
There is the plenty of kinds of a polymeric film, used in manufacture of paste like or of packed up processed products.
Composition for reception of a coat for sausages includes polycaprolactone with molecular weight in the range 1000-4000, 1,6- hexamethylenediisocyanate and 1,4-buthanediol in the following ratio of Usted components (weight parts): 24-30, 50-40, 24,84-27,0 (SU, Al, 1034597).
For production of the coat the components of a composition heat up to 60-50°C with subsequent increase of temperature up to 240°C. The received product is poured on potytetrafluorethylene film. After 5 hours the plate poured off is granulated, heated up again and extruded.
Nevertheless it is necessary to carry out a previous treatment of a known composition before extrusion, which require a lot of time. Besides the film has a thickness no less than 0,05 mm and is suitable only for using with special machines. Moisture content in the coat is 0,03 %, it is enough for detention of the coat in the process of coating in a stretched and elastic condition, but during cooking the contents of water in the coat increased so, that it negatively influences mechanical characteristics of the coat.
The coats on the basis polyamide may be better subjected to stretching and shrinkage, they have high durabiUty, and also are suitable not only for machine filUng but also hand-operated filUng.
It is known a film, used in manufacture of paste Uke food products, in particular of sausages and cheese, containing at least one aUphatic polyamide
and at least one ionomer resin and/or at least one modified copolymer of ethylene and of vinylacetate (DE, Al, 2850181).
As polyamides in the known hose film the polycaprolactam, polyaminoenantamide, polyhexamethyleneadipamide and/or polyhexamethylenesebacinamide as separate substances or as a mixture each with other, and also copolymers of above polyamides and of polyaminoundecaneamide or polylaurinelactam are used.
The thickness of received hose film is about 0,050 mm, that is satisfactory only for machine filUng; permeabiUty for water is in a range 12-28 g/M3 in a day, and permeabiUty for oxygen is about 15 up to 30 cm3/ 2 day bar.
This film is manufactured as foUows: the components are mixed, plasticized at 260° C and moulded, preferable by extrusion of a sleeve with blowing. Then biaxial stretching with multipUcity of the lengthways and across stretching in a range from 1:1,5 up to 1:4 is carried out. Then the sleeve is thermofixed for stabilization of the sizes.
However the known technical decision does not allow to receive more thin films for hand-operated filUng and to provide strength of the film necessary at cooking. On cutting of the coat its propensity to breaks was indicated. For preparation of cooked sausages a forcemeat should fiUed in this coat under significant pressure about 0,3-0,6 bars. For hand-operated filUng of sausage forcemeat, during which pressure of the fiUing is insignificant, such coat hardly can be used, as after terminating of the working cycle of preparation of sausages folds or fractures wiU be formed
The closest known technical decision to the claimed one is a hose film on a basis of polyamides, used in manufacture of paste Uke and viscous food products (sausage coat), including polyamide 6, aUphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and terephtaUc acid units, and copolymer including olefin units (EP, Al, 0722664).
This hose film contains (weight. %): a) polyamide 6 b) aUphatic polyamide (5-50 % of general weight of aU polymers in a layer) As the aUphatic copolyamide is used the copolyamide with units of ε-caprolactam,
of hexamethylenediamine and of azelaic acid (polyamide 6/6,9) and/or polyamide 6,12 as copolyamide from hexamethylenediamine and dodecanic acid,
B) up to 20% of aromatic polyamide, partiaUy aromatized by hexamethylenediamine and terephtaUc or isophtaUc acids units (PA 6-T or PA
6-T), c) up to 20 % of copolymer having olefin units of polyolefin, modified by carboxy groups, in particular of copolymer of ethylene and of methacryUc acid.
The hose film may involve dyes and/or pigments in few amounts. The manufacturing of monolayer and multilayer sausage coat includes mixturing and melting at the temperature about 240° C of components of the mixture in special extruder until producing of a homogeneous melted mixture, extrusion of the latter through ring injectors with blowing, moulding of an integral sleeve, which stretched then in longitudinal and cross directions under air pressure. A received film is fixed by additional heat treatment.
The hose film received according to the known technology (prototype) gives shrinkage from 5 up to 25 % (at 80° C) in share and cross directions, it has thickness of 0,033-0,056 mm, can be manufactured as multilayer. Water permeabiUty of the sausage coat changes from 11,5 up to 13, 1 g/m a day, and oxygen permeabiUty varies from 13,6 up to 18,5 cm3/m2 day bar.
Multilayer hose film contains as a minimum one layer of the mentioned above polyamide mixture. Other layers consist mainly from polyamides (for example, polyamide 6), polyamide mixtures, polyoleiϊns (for example, polyethylene or polypropylene), also from polyolefins, containing binding functional groups. Besides the layers can be manufactured from copolymers with units of ethylenenonsaturated monomers (for example, vinylacetate, vinyl alcohol, acryUc and methacryUc acid), and also of vinyUdenchloride or acrylonitrile copolymers, of ionomer resins or of mixtures of above named polymers. A coat usually consists of 3- 5 layers. Such coat may be manufactured by coextrusion through ring injectors, which are speciaUy designed according to quantity of layers.
Multilayer coats being compared with monolayer show higher water and vapour permeabiUty and permeabiUty for oxygen.
There ia a lack both of monolayer and of multilayer hose films, claimed in EP 0722664. It is their rather high water and vapor permeability and peπneabiUty for oxygen of air, these parameters are of priority for ready sausage products, as they define a safety of ready product and loss of its weight. Moreover, the durabiUty of a coat for viscous products and steriUzed sausages, requiring stabiUty under the technological rules on the temperature up to 125° C, is insufficient high. Summary of the invention
The problem to be solved by the invention consists in creation of a hose film to be used in manufacture of paste Uke and viscous food products, having lower water and vapour permeabiUty and permeabiUty for oxygen, and also having increased strength characteristics under heat treatment. The problem is solved by the claimed invention.
A hose film on the basis of polyamides, including polyamide 6, aUphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units and copolymer, including olefin units, according to the invention, additionally contains ionomer resin, as aUphatic copolyamide it contains copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid, and as a copolymer including olefin units it contains a mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids with the following ratio of components (weight parts): Polyamide 6 77- 83 Copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid 7-13
Aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units 3-7
Ionomer resin 3-6 Mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids 0 1-5
The hose film may contain zinc salt of copolymer of ethylenemethacryUc acid as ionomer resin.
In the claimed film hose the copolymer of polycaprolactam and of polyhexamethylendiamine and of adipic acid may be used (polyamide 6/6,6 with elements of the formulas -N-(CH2)5-CO-, -N-(CH2)6-NH-, -CO-(CH2)4-
CO-) with quantity of parts of monomers accordingly 85, 7,5 and 7,5 weight %. The hose film may contain as a mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids the mixture with the contents of graft units from 0,3 up to 0,9 weight % The hose film may be carried out as multilayer, and at least one layer has the foUowing composition: (weight parts):
Polyamide 6 77- 83
Copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid 7-13 Aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units 3-7
Ionomer resin 3-6
Mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids 0,1-5 In such embodiment of the invention in the hose film other layers of multilayer hose film are carried out from polyamides, or of polyamide mixtures, or of polyolefins, or of polyolefins containing connecting functional groups, or of copolymers with units of ethylenenonsaturated monomers, or of copolymers of vinyUdenchloride or acrylonitrile or of ionomer resins or of mixtures of these polymers.
Detailed description of the invention The hose film can contain if necessary, additional dyes, pigments and/or auxiUary substances of processing. The share of these components rather smaU, so the basic characteristics of the film remain constant. Below the components of the hose film are designated as foUows:
1) - polyamide 6,
2) - copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid,
3) - aromatic polyamide, containing units of hexamethylenediamine and of tereftaUc acid, 4) - ionomer resin
5) - mixture of graft copolymers on the base of derivatives of carboxyUc and of polycarboxyUc acids.
As graft copolymers for example, acrylic polymer with graft units of maleic anhydride, Unear polyethylene of low density with graft units of maleic anhydride and ethylenepropylene rubber with graft groups of maleic anhydride are used.
Mixture of graft copolymers on the basis of derivatives of carboxyUc and of polycarboxyUc acids aUows to enter into structure of the hose film some other, more easier processed and more accessible copolymers, for example, copolymer of polycaprolactam and of polyhexamethylendiamine and of adipic acid instead of copolymer of polycaprolactam and polyhexamethylendiamine and azelaic acid used at manufacturing of known hose films
Due to preferable use of set of components of the hose fimi in the ratio: from 79 to 81 % of total weight of a component 1), from 9 up to 11 % of a component 2), from 4 up to 6 of % of a component 3), from 4 up to 5% of a component 4), from 0,5 up to 1,5 % of a component 5), the properties are reached which have not both separate components of the film and known structures of hose films, namely: higher water and vapour permeabiUty and permeabiUty for oxygen, and besides, the film is thermostable up to 125° C and is not subjected to breaks at thermal processing (cooking).
Example 1. A mixture from
1) 80 weight parts of usual granulated polycaprolactam (polyamide 6) with relative viscosity 4 (measured for 1 g of granulated polycaprolactam in 100 ml of 96 % sulfuric acid at 20° C)
2) 10 weight parts of copolymer of polycaprolactam and of polyhexamethylendiamine and of adipic acid (polyamide 6/6,6) with relative
viscosity 3,32 (measured for 1 g of granulated polycaprolactam in 100 ml of 96
% sulfuric acid at 20°C).
3) 5 weight parts of aromatic polyamide with units of hexamethylenediamine and of terephthaUc acid (Selar PA 3426, Du Pont de Nemour Inc.) (melting index 90 g for 10 mines at 275°C and loading of 10 kg).
4) 4 weight parts of ionomer resin - copolymer of ethylene and of methacryl acid with 2-20 % of methacryl acid having melting index 2,5 g for 10 min at 190° C and 2,16 kgs of a loading and with kind of an ion - Zn (SerUn -N 1652, DuPont). 5a) 0,5 weight parts of acryUc polymer with graft units of maleic anhydride (Fuzabond A, DuPont) (melting index 3,5 g for 10 min at 280°C and 2,16 kgs of loading).
5b) 0,5 weight parts of Unear polyethylene of low density with graft units of maleic anhydride (Fuzabond E, DuPont) (melting index 3,0 g at 280° C for 10 min. and 2,16 kgs of a loading).
Components 1-5 in the above specified quantities are carefully mixed and loaded into the bunker of an extruder where the mixture of granules is homogenized at 255° C up to receiving of homogeneous melt. The melt is submited on the ring head of extruder, on passage through which a primary sleeve is produced. Leaving from the extruder a primary sleeve is sharply cooled and then is heated up for plastification. Then it undergo to biaxial stretching which is carried out by compressed air. Then the moulded sleeve is directed to the furnace for thermofixation where there is the process of its stabilization. Then a sleeve is cooled, then it is submitted on the receiver, where it is reeled up on a fiber drum in a combined form.
Example 2. To receive a multilayer hose the foUowing polymeric mixtures are appUed. Mixture 1; 1) 80 weight parts of usual granulated polycaprolactam (polyamide 6) (as in the example 1)
2) 10 weight parts of copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid (polyamide 6/6,6) (according to example 1)
3) 5 weight parts of aromatic polyamide with units of hexamethylenediamine and of terephthaUc acid (according to example 1)
4) 4 weight parts of ionomer resin - copolymer of ethylenemethacryUc acid with 2-20 % of methacryUc acid (according to example 1)
5a) 0,5 weight parts of acryUc polymer with graft units of maleic anhydride (according to example 1). 56) 0,5 weight parts of Unear polyethylene of low density with graft units of maleic anhydride (according to example 1)
Mixture II:
70 weight parts of polyethylene of low density with melting index 0,2 g for 10 min at 190° C and 2,16 kgs of a loading and 30 weight parts of Unear polyethylene of low density modified by maleic anhydride with melting index 3 g for 10 min at 190°C and loading of 2,16 kgs.
Mixture III:
The mixture III is prepared similarly to mixture 1. Mixtures 1, II, III are plasticizated in three single-screw extruders at 240°C until producing of homogeneous alloys, then they are fed to 3-layer ring injectors and are coextruded in a sleeve. The sleeve is processed in oriented in two axis and thermofixed hose film.
At general thickness of the film of 0,055 mm the layers have the foUowing thickness: External layer (mixture 1): 0,030 mm Average layer (mixture II): 0,015 mm Internal layer (mixture III): 0,010 mm.
Examples 3-10 of compositions of the hose film are brought in Table 1.
Table 1.
Properties of claimed hose films according to used compositions of examples 1-10 are submitted in table 2.
Table 2
Technological Examples properties of the coat
(unit of measurements)
1 2 3 4 5 6 7 8 9 10
DurabiUty on break, mPa
Lengthways 60 70 40 40 50 50 60 60 55 45
Across 120 120 100 100 105 105 110 110 115 100
Relative lengthening at break, %
Lengthways 160 180 200 200 190 190 170 160 160 200
Across 60 70 80 80 80 80 70 60 65 90
Water and vapor 10 2,8 28 30 28 24 18 14 16 34 permeabiUty g/M2atm
PermeabiUty on O2 12 5,6 34 30 30 26 20 14 18 38 cm3/m2 atm
TheπnostabiUty °C 125 125 95 95 95 95 125 125 120 90
DurabiUty on cooking
80° C 0,1 0, 1 0,5 0,4 0,3 0,3 0,1 0,1 0, 15 0,5
125° C 0,15 0,15 0,7 0,5 0,4 0,4 0,2 0,3 0,2 0,7
Note:
The data are brought for a film by thickness of 0,04 mm. Conditions at tests: On items 1,2 V = 50 mm/min, V - speed of stretching, on items 3,4 during 24 hours at 23°C and relative humidity of air 80 %; on item 5 during 4 hours, on item 6 in water at 80°C with and 125° C, percent on 1000 sausage sticks.
The hose film produced according to the invention meets the requirements, necessary for use, in particular in manufacture of cooked sausages and of processed cheeses. The thickness of a film for machine filUng of sausage forcemeat is 0,037-0,040 mm, for hand-operated filUng it is 0,030-0,033 mm.
The hose film remains rather strong, also at high temperatures about up to 125°C it has large elasticity and it is soft to the touch, adjoins to contents even after complete cooUng, wiU not practicaUy lead to precipitation of jeUy and of fat between sausage forcemeat and coat; its durabiUty at filUng and accuracy of caUbre of sausages, made in such environments, does not decrease. There is no adhesion of food products to the hose film.
Distinctive feature of invented hose film is its low water- vapor- and oxygen permeabiUty, that defines a high degree of safety of a ready product (abihty to oxidize and loss of weight), and also it thermostabiUty.
The durabiUty of the coat is kept during heat treatment, percent of sausage sticks spoiled at cooking is no more than 1 % on 1000 ready sticks.
Industrial application
This invention may be used most effectively in the industry of production Uary materials for food industry
Claims
1. A hose film on the basis of polyamides, including polyamide 6, aUphatic copolyamide, aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units and copolymer, including olefin units, characterized in that it additionaUy contains ionomer resin, as aUphatic copolyamide it contains copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid, and as a copolymer including olefin units it contains a mixture of graft copolymers on the basis of derivatives of carboxylic and polycarboxyUc acids with the foUowing ratio of components (weight parts): Polyamide 6 77-83
Copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid 7-13
Aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units 3-7 Ionomer resin 3-6
Mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids 0,1-5
2. The hose film on the basis of polyamides according to claim 1, characterized in that as ionomer resin it contains zinc salt of copolymer of ethylenemethacryUc acid.
3. The hose film on the basis of polyamides according to claim 1, characterized in that as a copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid it contain the copolymer with quantity of parts of monomers units accordingly 85, 7,5 and 7,5 weight. %.
4. The hose film on the basis of polyamides according to claim 1, characterized in that as a mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids it contain the mixture with the contents of graft units from 0,3 up to 0,9 weight %
5. The hose film on the basis of polyamides according to claim 1 characterized in that it is carried out as multilayer, and at least one layer has the foUowirig composition: (weight parts): Polyamide 6 77-83 Copolymer of polycaprolactam and of polyhexamethylenediamine and of adipic acid 7-13
Aromatic polyamide, containing hexamethylenediamine and terephthaUc acid units 3-7 Ionomer resin 3-6
Mixture of graft copolymers on the basis of derivatives of carboxyUc and polycarboxyUc acids 0,1-5
6.The hose film on the basis of polyamides according to claim 5, characterized in that other layers of multilayer hose film are carried out of polyamides, or of polyamide mixtures, or of polyolefins, or of polyolefins containing binding functional groups, or of copolymers with units of ethylenenonsaturated monomers, or of copolymers of vinyUdenchloride or of acrylonitrile, or of ionomer resins or of mixtures of these polymers.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU97112750A RU2113125C1 (en) | 1997-08-06 | 1997-08-06 | Polyamide-based tubular film |
| RU97112750 | 1997-08-06 | ||
| PCT/RU1998/000028 WO1999007227A1 (en) | 1997-08-06 | 1998-02-10 | A hose film on the basis of polyamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1001682A1 true EP1001682A1 (en) | 2000-05-24 |
Family
ID=20195682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98908341A Withdrawn EP1001682A1 (en) | 1997-08-06 | 1998-02-10 | A hose film on the basis of polyamides |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1001682A1 (en) |
| CN (1) | CN1067330C (en) |
| AU (1) | AU6639998A (en) |
| BR (1) | BR9811065A (en) |
| CZ (1) | CZ247398A3 (en) |
| PL (1) | PL325775A1 (en) |
| RU (1) | RU2113125C1 (en) |
| TR (1) | TR199800790A3 (en) |
| UA (1) | UA26187C2 (en) |
| WO (1) | WO1999007227A1 (en) |
| YU (1) | YU32998A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092007A2 (en) * | 2000-05-30 | 2001-12-06 | Dow Global Technologies Inc. | Improved barrier compositions for multilayer extrusion and barrier performance |
| RU2182107C1 (en) * | 2001-03-30 | 2002-05-10 | Общество С Ограниченной Ответственностью Производственно-Коммерческая Фирма "Атлантис-Пак" | Polymer film for packing foodstuff and package made from such film |
| DE10208858A1 (en) * | 2002-03-01 | 2003-09-11 | Kalle Gmbh & Co Kg | Smoke and water vapor permeable food casing made of a thermoplastic mixture |
| US7507150B2 (en) * | 2004-08-23 | 2009-03-24 | Visko Teepak Belgium Nv | Shirred casing |
| US20060093772A1 (en) * | 2004-10-27 | 2006-05-04 | Fish Robert B Jr | Multilayered pipes comprising hydrolysis resistant polyamides |
| CZ299888B6 (en) * | 2005-05-06 | 2008-12-17 | Cutisin, S. R. O. | Smokable flat or tubular food package or film with low water-vapor permeability for packaging foodstuffs |
| DE102005037275A1 (en) * | 2005-08-08 | 2007-02-22 | Kalle Gmbh | Multilayer food casing with at least one layer based on a polyester / polyamide mixture |
| CN100344692C (en) * | 2005-12-27 | 2007-10-24 | 上海大学 | Method for preparing aqueous nano SiO2 acrylic acid composite emulsion |
| CN102574387B (en) * | 2009-10-20 | 2015-03-25 | 株式会社细川洋行 | Plastic film and infusion bag |
| FR2974028B1 (en) * | 2011-04-14 | 2013-04-19 | Arkema France | MULTILAYER STRUCTURE COMPRISING A LAYER OF A PARTICULAR COPOLYAMIDE AND A BARRIER LAYER |
| TWI725066B (en) * | 2015-10-30 | 2021-04-21 | 日商宇部興產股份有限公司 | Film laminates and packaging materials or containers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2850181C2 (en) * | 1978-11-18 | 1991-04-18 | Naturin-Werk Becker & Co, 6940 Weinheim | Tubular film for packaging and wrapping pasty foods |
| DE9007334U1 (en) * | 1990-05-26 | 1991-03-14 | Hoechst Ag, 65929 Frankfurt | Multilayer tubular packaging sleeve |
| DE19501834A1 (en) * | 1995-01-21 | 1996-07-25 | Hoechst Ag | Sausage casing based on polyamide |
| DE19529603A1 (en) * | 1995-08-11 | 1997-02-13 | Wolff Walsrode Ag | Polyamide sausage casing with improved peeling characteristics |
-
1997
- 1997-08-06 RU RU97112750A patent/RU2113125C1/en active
-
1998
- 1998-02-10 WO PCT/RU1998/000028 patent/WO1999007227A1/en not_active Application Discontinuation
- 1998-02-10 EP EP98908341A patent/EP1001682A1/en not_active Withdrawn
- 1998-02-10 BR BR9811065-9A patent/BR9811065A/en unknown
- 1998-02-10 AU AU66399/98A patent/AU6639998A/en not_active Abandoned
- 1998-04-06 CN CN98108830A patent/CN1067330C/en not_active Expired - Fee Related
- 1998-04-10 PL PL98325775A patent/PL325775A1/en unknown
- 1998-05-04 TR TR1998/00790A patent/TR199800790A3/en unknown
- 1998-08-03 UA UA98084208A patent/UA26187C2/en unknown
- 1998-08-04 YU YU32998A patent/YU32998A/en unknown
- 1998-08-06 CZ CZ982473A patent/CZ247398A3/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9907227A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2113125C1 (en) | 1998-06-20 |
| WO1999007227A1 (en) | 1999-02-18 |
| TR199800790A2 (en) | 1999-10-21 |
| CZ247398A3 (en) | 1999-02-17 |
| CN1067330C (en) | 2001-06-20 |
| PL325775A1 (en) | 1999-02-15 |
| BR9811065A (en) | 2000-09-19 |
| YU32998A (en) | 1999-12-27 |
| UA26187C2 (en) | 1999-06-07 |
| CN1207341A (en) | 1999-02-10 |
| AU6639998A (en) | 1999-03-01 |
| TR199800790A3 (en) | 1999-10-21 |
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