FI85242B - HOPTRYCKBAR BEHAOLLARE FRAMSTAELLT AV ETENPROPENKOPOLYMER. - Google Patents
HOPTRYCKBAR BEHAOLLARE FRAMSTAELLT AV ETENPROPENKOPOLYMER. Download PDFInfo
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- FI85242B FI85242B FI854986A FI854986A FI85242B FI 85242 B FI85242 B FI 85242B FI 854986 A FI854986 A FI 854986A FI 854986 A FI854986 A FI 854986A FI 85242 B FI85242 B FI 85242B
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- Finland
- Prior art keywords
- layer
- ethylene
- propylene copolymer
- copolymer
- container
- Prior art date
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- 229920001577 copolymer Polymers 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000011888 foil Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims 2
- 239000002648 laminated material Substances 0.000 claims 2
- 239000010410 layer Substances 0.000 description 44
- 239000000047 product Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000606 toothpaste Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229940034610 toothpaste Drugs 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229920000554 ionomer Polymers 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- 229920003308 DuPont™ Surlyn® 1605 Polymers 0.000 description 2
- 229920003946 DuPont™ Surlyn® 1706 Polymers 0.000 description 2
- 229920003947 DuPont™ Surlyn® 1707 Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001074 Tenite Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/085—Layered products comprising a layer of metal comprising metal 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 comprising polyolefins
-
- 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
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/10—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 paper or cardboard
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/14—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor with linings or inserts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S45/00—Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
- F21S45/40—Cooling of lighting devices
- F21S45/47—Passive cooling, e.g. using fins, thermal conductive elements or openings
- F21S45/48—Passive cooling, e.g. using fins, thermal conductive elements or openings with means for conducting heat from the inside to the outside of the lighting devices, e.g. with fins on the outer surface of the lighting device
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/04—4 layers
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
-
- 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
- B32B2317/00—Animal or vegetable based
- B32B2317/12—Paper, e.g. cardboard
-
- 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
- B32B2323/00—Polyalkenes
-
- 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
- B32B2439/00—Containers; Receptacles
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Laminated Bodies (AREA)
- Tubes (AREA)
- Wrappers (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
Description
1 852421 85242
Kokoonpainuva säiliö, joka on tehty eteenipropeenikopolymeeristä Tämä keksintö koskee yleisesti säiliöalaa ja tarkemmin se koskee kokoonpainuvaa annostelusäiliötä, jonka runko-osalla on laminoitu seinämärakenne, jolla tuotteen läpipääsy ja absorboituminen ja hapen absorboituminen estetään oleellisesti kaikilla sille herkillä säiliön alueilla.This invention relates generally to the container field, and more particularly to a collapsible dispensing container having a laminated wall structure in the body that prevents product passage and absorption and oxygen absorption in substantially all sensitive areas of the container.
Pakkausalalla on jo pitkään tunnettu kokoonpainuvia putkilolta, jotka on muodostettu metalli- ja muovimateriaaleista. Pursote-tut metalliputkilot ovat luontaisesti hauraita ja toistuva käyttö johtaa usein seinämän halkeamiin niin, että tuotetta pursuu muusta kohdasta kuin olennaisesti jäykästä annosteluaukosta.The packaging industry has long known for collapsible tubes made of metal and plastic materials. Extruded metal tubes are inherently brittle and repeated use often results in cracks in the wall so that the product exudes from a location other than a substantially rigid dispensing opening.
Alan aikaisemmista metalliputkiloista alumiiniputkiloilla, vaikka ne todennäköisesti ovat vähiten hauraita, on jonkin verran rajoitetut sovellutuskohteet, sillä tähän saakka ei ole ollut mahdollista levittää niiden sisäpinnoille täysin tyydyttävää päällystettä, kun vaaditaan, että on estettävä alkaalisen ja happaman sisällön metallille aiheuttama korroosio ja sisällön saastuminen reaktiotuotteista. Huolimatta metalliputkilon suhteellisen hauraasta luonteesta mainittu sisäinen päällystysope-raatio vaatii lisäprosessivaiheen, joka välttämättä nostaa lopputuotteen kustannuksia.Of the prior art metal tubes, aluminum tubes, although probably the least brittle, have somewhat limited applications, as it has not hitherto been possible to apply a completely satisfactory coating to their inner surfaces when it is required to prevent alkali and acidic corrosion and contamination of the metal. Despite the relatively fragile nature of the metal tube, said internal coating operation requires an additional process step which necessarily increases the cost of the final product.
Putkilot, jotka on muodostettu polyeteenistä ja muista muovi-materiaaleista, ovat nauttineet yleistä kaupallista menestystä monien tuotteiden pakkaamisessa; tiettyjen muiden tuotteiden on määrätyn ajan kuluttua havaittu hajaantuvan, kun ne käytetään pakkaukseen. Muovit, joista esimerkkinä on polyeteeni, ovat tietyssä määrin läpäiseviä, kun niitä käytetään seinämänpaksuuksina, joita putkisäiliöissä käytetään ja useimoiin hammastahnoihin maustamis-tarkoituksessa sisältyvien eteeristen öljyjen tilavuusmäärä pienenee säiliön varastoinnin aikana, mikä tekee hammastahnan vähemmän mielyttäväksi. Samoin muovisäiliön seinämä absorboi happea ajan kuluessa ja se voi lopulta hajottaa tuotteen, kuten on todella havaittu tapahtuvan fluoridia sisältävillä hammastahnoilla. Muoviputkilon lisähaitta on siinä, että pinta ei kykene helposti 2 85242 vastaanottamaan painatus- tai koristemateriaalia. Lisäksi muovi-putkiloilla, joista esimerkkinä on polyeteeni, on muistivaiku-tus; ts. ne eivät pysy kokoonpuristettuina niitä puristettaessa, mikä on erityinen haitta hammastahnaputkiloilla.Tubes formed of polyethylene and other plastic materials have enjoyed general commercial success in the packaging of many products; certain other products have been found to disperse after a certain period of time when used for packaging. Plastics, such as polyethylene, are to some extent permeable when used as wall thicknesses used in tubular containers, and the volume of essential oils contained in most toothpastes for seasoning purposes decreases during container storage, making toothpaste less pleasant. Similarly, the wall of the plastic container absorbs oxygen over time and can eventually break down the product, as has actually been observed with fluoride toothpastes. An additional disadvantage of the plastic tube is that the surface is not easily able to receive printing or decorative material. In addition, plastic pipes, such as polyethylene, have a memory effect; i.e., they do not remain compressed when compressed, which is a particular disadvantage of toothpaste tubes.
Yllä esitettyjen ongelmien vastustamiseksi on tästä syystä ehdotettu liitettäväksi metallifoliokerros tuotteen ja polyeteeni-putkilon rungon väliin. Tämä lieventää kokoonpuristuvuusongelmaa siten, että metallikerros antaisi kokoonpuristuvuutensa muoville. Lisäksi metallifoliosulkukerros tuotteen ja polyeteeniputkilon rungon välissä estäisi mainitun eteeristen öljyjen häviön ja hapen absorboitumisen. Metallisulkukerrosta on ehdotettu väli-kerrokseksi vastakkaisten polyeteenikalvojen väliin ja muodostettavaksi laminaatti lämmön avulla käyttäen sopivia liimoja tai ilman niitä. Kuitenkin vaikka yleisluonteeltaan tällainen rakenne on tehokas estämään jonkin verran tuotteen läpipääsyä ja hapen absorboitumista putkilon rungon läpi ja erityisesti kun sisempi kestomuovikerros on kopolymeeriä, jonka muodostavat eteeni ja polaarisen ryhmän sisältävä monomeeri, joka on kopoly-meroituva sen kanssa, jää jäljelle mahdollisuus, että tuote hajoaa, vaikkakin paljon vähäisemmässä määrin.To counter the above problems, it has therefore been proposed to attach a layer of metal foil between the product and the body of the polyethylene tube. This alleviates the compressibility problem so that the metal layer would give its compressibility to the plastic. In addition, a metal foil barrier layer between the product and the body of the polyethylene tube would prevent said loss of essential oils and oxygen absorption. A metal barrier layer has been proposed as an intermediate layer between opposing polyethylene films and to form a laminate by heat with or without suitable adhesives. However, although such a structure is effective in somewhat preventing product passage and oxygen absorption through the tube body, and especially when the inner thermoplastic layer is a copolymer of ethylene and a polar group-containing monomer copolymerizable therewith, the product remains degradable. , although to a much lesser extent.
Huomio kiinnitetään seuraavaan aikaisempaan tekniikkaan: US-patentissa 3 295 725 esitetään putkilo, jossa yhdistyvät yllä mainitut alumiiniputkilon ja muoviputkilon edut. Tämä on . .·. laminoitu, kokoonpainuva annostelusäiliö, joka sisältää sekä - - metallisulun että polyeteenisisäseinämän. Kestomuovikerrosta kuvataan yleisesti polyolefiiniksi ja kopolymeeriksi, jonka ovat muodostaneet olefiini ja polaarisen ryhmän sisältävä monomeeri, joka on kopolymeroitavissa sen kanssa. Tällä laminaatilla vältetään yllä kuvatut rajoitukset lukuunottamatta eteeristen öljyjen absorboitumista hammastahnasta.Attention is drawn to the following prior art: U.S. Patent 3,295,725 discloses a tube which combines the above advantages of an aluminum tube and a plastic tube. This is . . ·. laminated, collapsible dispensing container containing both a metal barrier and a polyethylene inner wall. The thermoplastic layer is generally described as a polyolefin and a copolymer formed by an olefin and a polar group-containing monomer copolymerizable therewith. This laminate avoids the limitations described above except for the absorption of essential oils from toothpaste.
CA-patentissa 728 525 esitetään laminoitu putkilo, joka sisältää polyeteeniä olevan sisäkerroksen. Tässä tiedostetaan ongelma, että kestomuovinen seinämä absorboi mausteöljyjä.CA Patent 728,525 discloses a laminated tube containing an inner layer of polyethylene. Here we are aware of the problem that the thermoplastic wall absorbs spice oils.
3 85242 US-patentissa 4 096 946 esitetään laminoitu pakkaus, jossa käytetään vinylideenikloridia sisäkerroksena ja eteenin ja propee-nin kopolymeeria ulkokerroksena. Tämä ei kuitenkaan ole putkilo; se ei sisällä metallia; eikä tässä US-patentissa mainittu mitään kopolymeerin aromisulkuominaisuuksista.U.S. Pat. No. 3,854,242 to U.S. Pat. No. 4,096,946 discloses a laminated package using vinylidene chloride as the inner layer and a copolymer of ethylene and propylene as the outer layer. However, this is not a tube; it does not contain metal; and none of the aroma barrier properties of the copolymer were mentioned in this U.S. patent.
US-patentissa 4 207 363 esitetään laminaattikalvo, jota käytetään lihan pakkaamiseen ja joka sisältää propeenieteenikopolymeeriä ulkokerroksena. Tämä ei myöskään ole putkilo; se ei sisällä metallia; eikä tässä US-patentissa mainita mitään kopolymeerin aromisulkuominaisuuksista.U.S. Patent 4,207,363 discloses a laminate film used to package meat and containing a propylene-ethylene copolymer as an outer layer. This is also not a tube; it does not contain metal; and this U.S. patent does not mention any of the aroma barrier properties of the copolymer.
Lisäksi US-patenteissa 4 405 667, 4 308 084 ja 4 279 344 esitetään laminoituja pakkaustuotteita, jotka sisältävät eteenipropeeni-kopolymeeriä. Mikään näistä tuotteista ei kuitenkaan ollut putkilo eikä mitään mainintaa kopolymeerin aromisulkuominaisuuk-sista tehty.In addition, U.S. Patents 4,405,667, 4,308,084 and 4,279,344 disclose laminated packaging products containing an ethylene-propylene copolymer. However, none of these products were a tube and no mention was made of the aroma barrier properties of the copolymer.
Tämän vuoksi tämän keksinnön tärkeänä pyrkimyksenä on saada aikaan kokoonpainuva annostelusäiliö, jonka runko-osalla on laminoitu seinämärakenne.Therefore, it is an important object of the present invention to provide a collapsible dispensing container having a body portion with a laminated wall structure.
Muuna tämän keksinnön tarkoituksena on saada aikaan putkimainen säiliö, jonka runko-osassa on useita tarttuvia kerroksia, joista yksi saa aikaan sulun tuotteen vaeltamiselle ja hapen absorboi-' : ' tumiselle, kuten metallifolio, ja toinen sanotuista kerroksista on eteenipropeenikopolymeeria tai sen seosta, jonka tiheys ja kiteisyys vaihtelevat. Viimemainittu kerros on sisin ja edullisesti uloin kerros ja eri lisälamellit on kerrostettu niiden väliin.Another object of the present invention is to provide a tubular container having a plurality of adhesive layers in the body, one of which provides a barrier to product migration and oxygen absorption, such as a metal foil, and the other of said layers is an ethylene-propylene copolymer or a mixture thereof. and crystallinity vary. The latter layer is the innermost and preferably the outermost layer and various additional lamellae are sandwiched between them.
- - Tällaisia lisäkerroksia ovat paperi ja sopivat liima- ja sidos-aineet, kuten eteenin ja akryylihapon kopolymeeri. Tämän kek-: : sinnön kokoonpainuva annostelusäiliö voidaan muodostaa tämän : keksinnön laminoidusta alustasta tavanomaisilla ja tunnetuilla laitteilla. Esimerkki tällaisesta laitteesta ja menetelmästä : on löydettävissä US-patentista 3 832 964, joka liitetään viit teenä tähän esitykseen.- - Such additional layers include paper and suitable adhesives and binders, such as a copolymer of ethylene and acrylic acid. The collapsible dispensing container of the present invention can be formed from the laminated substrate of the present invention by conventional and known devices. An example of such an apparatus and method can be found in U.S. Patent 3,832,964, which is incorporated herein by reference.
4 85242 Tämän keksinnön lisätarkoituksena on saada aikaan menetelmä laminoitujen putkiloiden valmistamiseksi, jossa putkimainen runko muodostetaan sulkukerroksesta ja eteenipropeenikopoly-meeri laminoidaan siihen; laminoitu putkilon runko asetetaan sitten muodostuselimeen vasten sulkukerroselintä, joka on myös asetettu sen päälle.It is a further object of the present invention to provide a method of making laminated tubes in which a tubular body is formed from a barrier layer and an ethylene-propylene copolymer is laminated thereto; the laminated tube body is then placed against the forming member against a barrier layer member which is also placed thereon.
Muut tämän keksinnön tarkoitukset ja edut käyvät paremmin ilmi kuvauksen edistyessä.Other objects and advantages of the present invention will become more apparent as the description proceeds.
Piirroksissa, joissa samoja numeroita käytetään tarkoittamaan samoja osia molemmissa: kuva 1 on poikkileikkauskuvanto tämän keksinnön laminoidun alustan pienestä osasta; kuva 2 on sivupystykuvanto kokoonoainuvasta annostelusäilöstä, joka pitää sisällään tämän keksinnön uudet ajatukset, osien runqon seinämistä ollessa leikattu auki laminoidun rakenteen esittämiseksi tarkemmin.In the drawings, in which the same numerals are used to refer to the same parts in both: Figure 1 is a cross-sectional view of a small portion of the laminated substrate of the present invention; Figure 2 is a side elevational view of a collapsible dispensing container incorporating the novel ideas of the present invention, with portions of the runqo walls of the portions cut open to show the laminated structure in more detail.
Tämän keksinnön kestomuovi on eteenipropeenikopolymeeri.The thermoplastic of the present invention is an ethylene-propylene copolymer.
Viitaten ensin piirrosten kuvaan 1 siinä esitetään alusta 10 poikkileikkauteena, joka paljastaa kerrosrakenteen komponentit, joita tarvitaan laminoidun rakenteen muodostamiseen.Referring first to Figure 1 of the drawings, there is shown a cross-section of the substrate 10 revealing the components of the layer structure required to form the laminated structure.
- - Havaitaan, että pohjimmaisin kerros 11 on eteenipropeenikopoly-!.! meeriä. Toinen kerros 12 sen päällä on liimakerros, joka yhdistää eteenipropeenikopolymeerikerroksen 11 kolmanteen kerrokseen 13, joka on metallifolio, kuten alumiinifolio. Neljäs kerros 14 on toinen liima, joka kiinnittää metallifoliokerroksen 13 toisen pinnan lujasti Daperikerrokseen 15. Ylimmäinen kerros 16 on eteeni-propeenikopolymeeriä.- - It is observed that the bottom layer 11 is an ethylene-propylene copoly -!.! mers. The second layer 12 on it is an adhesive layer connecting the ethylene-propylene copolymer layer 11 to a third layer 13, which is a metal foil, such as an aluminum foil. The fourth layer 14 is a second adhesive that firmly adheres the second surface of the metal foil layer 13 to the Daper layer 15. The top layer 16 is an ethylene-propylene copolymer.
-”· Eteenipropeenikopolymeeri on erityisen hyödyllinen, koska sillä on hyvin pienet aromin absorboimisominaisuudet, kuten voidaan nähdä seuraavista taulukoista, joissa eteenipropeenikopolymeeriä on verrattu polyeteeniin, kun päällyste-kerrosten paksuudet ovat samat: 5 85242- ”· Ethylene-propylene copolymer is particularly useful because it has very low aroma absorption properties, as can be seen from the following tables comparing ethylene-propylene copolymer to polyethylene when the thickness of the coating layers is the same: 5 85242
Taulukko ITable I
Laimentamattoman mausteöljyn absorboituminen polymeeriin (2 viikon kosketus)Absorption of undiluted spice oil into the polymer (2 weeks contact)
Polymeeri Painonlisays (%)Polymer Weight Gain (%)
Alumiini 0Aluminum 0
Eteenipropeenikopolymeeri Rigidex 40 (British Petroleum) 4,8Ethylene-propylene copolymer Rigidex 40 (British Petroleum) 4.8
Matalatiheyksinen polyeteeni Tenite 154 (Eastman ) 5,5Low density polyethylene Tenite 154 (Eastman) 5.5
Matalatiheyksinen polyeteeniLow density polyethylene
Lupolen 1804 H (BASF) 5,6 + 0,14Lupolen 1804 H (BASF) 5.6 + 0.14
Suurtiheyksinen polyeteeni LR (USI) 5,9High density polyethylene LR (USI) 5.9
Ionomeeri Surlyn 1707 (DuPont) 15,7Ionomer Surlyn 1707 (DuPont) 15.7
Ionomeeri Surlyn 1605 (DuPont) 19,0Ionomer Surlyn 1605 (DuPont) 19.0
Ionomeeri Surlyn 1706 (DuPont) 24,3Ionomer Surlyn 1706 (DuPont) 24.3
Taulukko IITable II
Aromiaineen suhteellinen absorboituminen polymeereihin X ) 3 kuukauden kosketusajan jälkeen hammastahnan kanssa . X X )Relative absorption of the flavoring substance into the polymers X) after a contact time of 3 months with toothpaste. X X)
Polymeeri Aromiainetta absorboitunutPolymer Flavor absorbed
Eteenipropeenikopolymeeriethylene-propylene copolymer
Rigidex 40 (British Petroleum) 59Rigidex 40 (British Petroleum) 59
Suurtiheyksinen polyeteeni LR (USI) 84High density polyethylene LR (USI) 84
Matalatiheyksinen polyeteeni NA (USI) 100 + 13Low density polyethylene NA (USI) 100 + 13
Ionomeeri Surlyn 1706 893Ionomer Surlyn 1706 893
Ionomeeri Surlyn 1707 1557Ionomer Surlyn 1707 1557
Ionomeeri Surlyn 1605 1672 x ^ 32,2°C:ssa X X ) ____ Suhteessa matalatiheyksiseen polyeteeniin, joka asetettiin mielivaltaisesti arvoon 100; mitä pienempi luku, sitä vähemmän aromiainetta on absorboitunut.Ionomer Surlyn 1605 at 1672 x ^ 32.2 ° C X X) ____ Relative to low density polyethylene arbitrarily set at 100; the lower the number, the less flavor is absorbed.
6 852426 85242
Tarkoituksena on, että tämän keksinnön puitteissa liimat voivat olla eteenin ja akryylihapon ja metakryylihaDon tai niiden natrium- tai sinkkisuolojen kopolymeeriä laimenninsysteemissä.It is contemplated that within the scope of this invention, the adhesives may be a copolymer of ethylene and acrylic acid and methacrylic acid or their sodium or zinc salts in a diluent system.
Metallifolio voi edullisesti olla alumiinifolio.The metal foil may preferably be an aluminum foil.
Paperikerros on edullisesti voimapaperia.The paper layer is preferably kraft paper.
Kunkin kerroksen paksuusalue on seuraava:The thickness range of each layer is as follows:
Eteenipropeenikopolymeerikerros 11 0,013-0,076 mm, edullisesti 0,025 mm.Ethylene propylene copolymer layer 11 0.013-0.076 mm, preferably 0.025 mm.
Liimakerros 12 - riittävä tarttuvuuden takaamiseksi.Adhesive layer 12 - sufficient to ensure adhesion.
Metallifoliokerros 13 - 0,013 - 0,051 mm, edullisesti 0,025 mm. Liimakerros 14 - riittävä tarttuvuuden takaamiseksi.Metal foil layer 13 to 0.013 to 0.051 mm, preferably 0.025 mm. Adhesive layer 14 - sufficient to ensure adhesion.
Paperikerros 15 - 0,038 - 0,064 mm, edullisesti 0,051 mm. Eteenipropeenikopolymeerikerros 16 - 0,089 - 0,127 mm, edullisesti 0,103 mm.Paper layer 15 to 0.038 to 0.064 mm, preferably 0.051 mm. Ethylene propylene copolymer layer 16 to 0.089 to 0.127 mm, preferably 0.103 mm.
Ylin eteenipropeenikopolymeerikerros 16 tarttuu paperikerrokseen 15 kohdistamalla alustaan riittävästi lämpöä ja painetta. Tapauksessa, jossa lämmön ja paineen käyttö ei ole asianmukaista, on käytettävä sopivaa liimaa.The top ethylene-propylene copolymer layer 16 adheres to the paper layer 15 by applying sufficient heat and pressure to the substrate. In the event that the use of heat and pressure is not appropriate, a suitable adhesive must be used.
Kuva 2 on esimerkki kokoonpainuvan säiliön laminoidusta rakenteesta, jossa kerrokset on esitetty kuten kuvassa 1 kerroksen 11 ollessa sisin ja muiden kerrosten ollessa samoja materiaaleja ja samassa järjestyksessä kuin siinä esitettiin.Figure 2 is an example of a laminated structure of a collapsible container, in which the layers are shown as in Figure 1 with the layer 11 being inner and the other layers being of the same materials and in the same order as shown therein.
. 1 Edellä olevasta arvellaan ilmenevän, että tässä keksinnössä on saatu aikaan kokoonpainuva säiliörakenne, joka vähentää oleellisesti ongelmia, joita aikaisemmalla tekniikalla ei tähän saakka ole ratkaistu. Laminoitu alusta ja laminoitu uloke-kappale 20 eliminoivat oleellisesti tuotteen läpipääsyn ja hapen absorboitumisen.. It is believed from the foregoing that the present invention provides a collapsible container structure that substantially reduces problems not previously solved by the prior art. The laminated substrate and laminated protrusion 20 substantially eliminate product permeation and oxygen absorption.
Eteenipropeenikopolymeeriä oleva ulkokerros on kestomuovi, joka kykenee sulamaan yhteen sivusaumausvaiheen aikana ja takaa riittävän suojan paperi- ja metallifoliovälikerrokselle. Tässä paljastettua yleistä tyyppiä olevan kokoonpainuvan hammastahnaputkilon saumaustekniikka on löydettävissä U5-paten-tista 3 295 725, joka liitetään viitteenä tähän esitykseen.The outer layer of ethylene-propylene copolymer is a thermoplastic that is able to fuse together during the side sealing step and provides adequate protection for the paper and metal foil interlayer. The sealing technique for a collapsible toothpaste tube of the general type disclosed herein can be found in U5 Patent 3,295,725, which is incorporated herein by reference.
7 852427 85242
Eteenipropeenikopolymeeriä ja paperia oleva ulkokerros voidaan kuitenkin eliminoida, jos folioulkokerroksella on riittävä paksuus niin, että se vastustaa vahingoittumista, ja valuttamalla kestomuovimateriaalia limisivusaumaan sen sulkemisen aikana, kun tällaista systeemiä käytetään.However, the outer layer of ethylene-propylene copolymer and paper can be eliminated if the outer layer of foil is thick enough to resist damage, and by draining the thermoplastic material into the adhesive side seam during sealing when such a system is used.
Edelleen ulkokerros voi olla paperia kolmikerroslaminaatissa, joka on muodostettu paperista, foliosta ja eteenipropeenikopoly-meeristä kuvatulla tavalla. Koska uloin ja sisin kerros ovat edullisesti samoja, alustasta muodostetun putkilon taivutetut reunat on helppo lämpösaumata. Sopivaa liimaa voidaan käyttää, kun lämpösaumaus ei ole mahdollinen. Tämä muunnos on lisäys edellä mainittuun nelikerroslaminaattiin, joka koostuu ulkoa sisälle eteenipropeenikopolymeeristä, paperista, foliosta ja eteenipropeenikopolymeeristä. Tarkoituksena on, että sopivia liimoja käytetään aina tarvittaessa lamellien välissä.Further, the outer layer may be paper in a three-layer laminate formed of paper, foil and ethylene-propylene copolymer as described. Since the outer and inner layers are preferably the same, the bent edges of the tube formed of the substrate are easy to heat seal. A suitable adhesive can be used when heat sealing is not possible. This modification is an addition to the above-mentioned four-layer laminate consisting externally to internally of ethylene-propylene copolymer, paper, foil and ethylene-propylene copolymer. It is intended that suitable adhesives be used between the lamellae whenever necessary.
Eteenipropeenikopolymeerejä voidaan myös käyttää ulokekappa-leeseen, korkkiin, kaulaosaan, mäntään ja muihin hammastahna-annostelijoihin tarkoitettujen annosteluventtiilien muodostamisessa, erityisesti silloin, kun sisäosat ovat alttiina niiden sisältämälle hammastahnalle ja jälleen vaadittaessa käytettäisiin luonnollisesti yhteensopivia liimoja.Ethylene-propylene copolymers can also be used to form dispensing valves for the cantilever, cap, neck, plunger and other toothpaste dispensers, especially when the interiors are exposed to the toothpaste they contain and, again, naturally compatible adhesives are used when required.
Lisäksi kun materiaalia valetaan kalvoksi kuitumassatynnyrien sisäpinnoille, joita tynnyreitä käytetään maustetun hammas-tahnan varastointiin, se hidastaa aromiaineen häviötä tynnyreihin, mikä pidentää varastointi-ikää.In addition, when the material is cast as a film on the inner surfaces of the pulp barrels used to store the flavored toothpaste, it slows down the loss of flavor to the barrels, which extends the shelf life.
Tässä on esitetty erilaisia keksinnön muunnoksia ja nämä ja muita muutoksia voidaan luonnollisesti tehdä poikkeamatta tämän esityksen uusista ajatuksista.Various modifications of the invention are set forth herein, and these and other modifications may, of course, be made without departing from the novel ideas of this disclosure.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68728184A | 1984-12-28 | 1984-12-28 | |
| US68728184 | 1984-12-28 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| FI854986A0 FI854986A0 (en) | 1985-12-16 |
| FI854986A FI854986A (en) | 1986-06-29 |
| FI85242B true FI85242B (en) | 1991-12-13 |
| FI85242C FI85242C (en) | 1992-03-25 |
Family
ID=24759813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI854986A FI85242C (en) | 1984-12-28 | 1985-12-16 | Compressible container made of ethylene propylene copolymer |
Country Status (26)
| Country | Link |
|---|---|
| JP (1) | JPS61158442A (en) |
| AT (1) | AT395559B (en) |
| AU (1) | AU583329B2 (en) |
| BE (1) | BE903960A (en) |
| BR (1) | BR8506516A (en) |
| CA (1) | CA1272437A (en) |
| CH (1) | CH669562A5 (en) |
| DE (1) | DE3544029A1 (en) |
| DK (1) | DK598885A (en) |
| ES (1) | ES8701045A1 (en) |
| FI (1) | FI85242C (en) |
| FR (1) | FR2575409B1 (en) |
| GB (2) | GB2168926B (en) |
| GR (1) | GR853105B (en) |
| IN (1) | IN164709B (en) |
| IT (1) | IT1182105B (en) |
| LU (1) | LU86231A1 (en) |
| MY (1) | MY101671A (en) |
| NL (1) | NL8503549A (en) |
| NO (1) | NO170522C (en) |
| NZ (1) | NZ214515A (en) |
| PH (1) | PH23516A (en) |
| PT (1) | PT81717B (en) |
| SE (1) | SE466393B (en) |
| ZA (1) | ZA859498B (en) |
| ZM (1) | ZM10185A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113885A (en) * | 1998-12-18 | 2000-09-05 | Colgate Palmolive Company | Polyolefin packaged dentifrice having reduced flavor loss |
| KR20220149559A (en) * | 2020-03-10 | 2022-11-08 | 도판 인사츠 가부시키가이샤 | tube container |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3505143A (en) * | 1966-03-10 | 1970-04-07 | American Can Co | Method of laminating sheet material by coating metal foil with a copolymer of ethylene and an ethylenically unsaturated carboxylic acid |
| JPS5034472A (en) * | 1973-07-30 | 1975-04-02 | ||
| JPS5422770U (en) * | 1977-07-19 | 1979-02-14 | ||
| JPS5725949A (en) * | 1980-07-22 | 1982-02-10 | Toyo Ink Mfg Co | Manufacture of laminate |
| JPS5733223A (en) * | 1980-08-08 | 1982-02-23 | Toshiba Corp | Bearing bracket made of steel plate |
| US4418841A (en) * | 1982-11-23 | 1983-12-06 | American Can Company | Multiple layer flexible sheet structure |
| IN165840B (en) * | 1984-12-28 | 1990-01-20 | Colgate Palmolive Co | |
| IN164974B (en) * | 1984-12-28 | 1989-07-15 | Colgate Palmolive Co | |
| US4951841A (en) * | 1984-12-28 | 1990-08-28 | Colgate-Palmolive Company | Dispensing container made from an ethylene vinyl alcohol containing laminated material and the material therefor |
-
1985
- 1985-12-09 IN IN1037/DEL/85A patent/IN164709B/en unknown
- 1985-12-10 NZ NZ214515A patent/NZ214515A/en unknown
- 1985-12-11 ZA ZA859498A patent/ZA859498B/en unknown
- 1985-12-12 AU AU51148/85A patent/AU583329B2/en not_active Ceased
- 1985-12-13 DE DE19853544029 patent/DE3544029A1/en not_active Withdrawn
- 1985-12-16 FI FI854986A patent/FI85242C/en not_active IP Right Cessation
- 1985-12-16 PH PH33177A patent/PH23516A/en unknown
- 1985-12-18 AT AT0365985A patent/AT395559B/en not_active IP Right Cessation
- 1985-12-19 PT PT81717A patent/PT81717B/en not_active IP Right Cessation
- 1985-12-20 DK DK598885A patent/DK598885A/en not_active Application Discontinuation
- 1985-12-20 SE SE8506041A patent/SE466393B/en not_active IP Right Cessation
- 1985-12-20 IT IT48971/85A patent/IT1182105B/en active
- 1985-12-20 GR GR853105A patent/GR853105B/el unknown
- 1985-12-20 GB GB8531359A patent/GB2168926B/en not_active Expired
- 1985-12-20 FR FR8518994A patent/FR2575409B1/en not_active Expired
- 1985-12-23 NL NL8503549A patent/NL8503549A/en not_active Application Discontinuation
- 1985-12-24 CH CH5538/85A patent/CH669562A5/de not_active IP Right Cessation
- 1985-12-24 CA CA000498577A patent/CA1272437A/en not_active Expired - Lifetime
- 1985-12-26 BR BR8506516A patent/BR8506516A/en unknown
- 1985-12-27 JP JP60299744A patent/JPS61158442A/en active Granted
- 1985-12-27 ES ES550472A patent/ES8701045A1/en not_active Expired
- 1985-12-27 ZM ZM101/85A patent/ZM10185A1/en unknown
- 1985-12-27 NO NO855319A patent/NO170522C/en unknown
- 1985-12-30 LU LU86231A patent/LU86231A1/en unknown
- 1985-12-30 BE BE0/216078A patent/BE903960A/en not_active IP Right Cessation
-
1987
- 1987-09-30 MY MYPI87002436A patent/MY101671A/en unknown
-
1988
- 1988-07-05 GB GB8815959A patent/GB2206531B/en not_active Expired
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Owner name: COLGATE-PALMOLIVE COMPANY |