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WO2025209771A1 - Composition et tube de dentifrice - Google Patents

Composition et tube de dentifrice

Info

Publication number
WO2025209771A1
WO2025209771A1 PCT/EP2025/056369 EP2025056369W WO2025209771A1 WO 2025209771 A1 WO2025209771 A1 WO 2025209771A1 EP 2025056369 W EP2025056369 W EP 2025056369W WO 2025209771 A1 WO2025209771 A1 WO 2025209771A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
hdpe
polyethylene
sub
laminate structure
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.)
Pending
Application number
PCT/EP2025/056369
Other languages
English (en)
Inventor
Saurabh Vinod Acharekar
Sembian CHANDRASEKARAN
Babu Cherian
Susobhan Das
Anil HANKARE
Partha Sarathi MITRA
NV Anil Kumar RAVIPATI
Pavan Basavanahalli SOMASHEKAR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Conopco Inc
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
Conopco Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever Global IP Ltd, Unilever IP Holdings BV, Conopco Inc filed Critical Unilever Global IP Ltd
Publication of WO2025209771A1 publication Critical patent/WO2025209771A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • 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
    • 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
    • B32B27/08—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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (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
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • 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
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • B32B2439/80—Medical packaging
    • 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
    • B32B2555/00—Personal care

Definitions

  • the present invention relates to a packaged product, particularly the invention relates to a packaged toothpaste composition which is packaged in a recyclable plastic-based laminate tube.
  • Toothpaste compositions are generally packaged in collapsible tubes.
  • the tubes are typically made of laminate i.e., materials that are multilayered and in which the layers are joined to each other, e.g., by coextrusion or adhesive lamination.
  • Plastic laminated tubes typically comprises an inner polyolefin resin layer which is in direct contact with the composition and at least one intermediate barrier layer, including an aluminium foil layer which inhibits loss of flavour from the composition.
  • the outer layers are typically of polyolefin resins, one of which may be coloured white and bears printed indicia with a clear polyolefin laminate overlay to protect the indicia.
  • Laminates containing Aluminium are often called Aluminium based laminates (ABL).
  • ABL Aluminium based laminates
  • the aluminium-based tubes provide good water and gas barrier properties and are preferred for packaging toothpaste composition.
  • a thin layer of about 5 pm to 12 pm of Aluminium foil is sufficient.
  • the ABL laminates are made of polyolefins, especially polyethylene, e.g., High Density Polyethylene (HDPE). Tubes of laminates containing aluminium are called ABL tubes.
  • HDPE High Density Polyethylene
  • EP2155488 B1 discloses collapsible tube containers formed from blown film polymeric material (s) and in particular, collapsible tube containers including a side-seam weld.
  • US2023/405982 A1 discloses a laminated tube comprising of post-industrial and/or postconsumer recycled resin.
  • Toothpaste compositions are formulated with several ingredients such as abrasives, flavouring ingredient, specific pH ranges, antimicrobial agents, sorbitol, various gums, amino acids to provide the desired cleaning performance and benefits like anticaries activity.
  • the flavour impact and the flavour profile in the composition and its stability is heavily influenced by the laminate tube in which it is packaged, and the package needs to be designed to ensure that the flavour profile and flavour impact is not unduly affected during storage. It is desired that while changing the structure and composition of the laminate tube to provide improved recyclability and sustainability, the composition retains its desired properties and is stable during storage.
  • a packaged product having a toothpaste composition comprising a flavour when packaged in a plastic based laminate tube having specific multilayer laminate structure according to the present invention provides for delivering good flavour impact and flavour intensity over extended storage period.
  • the toothpaste composition was surprisingly found to have good chemical and physical stability and desirable consumer-relevant properties (such as desirable viscosity and yield stress).
  • the packaged product having the toothpaste composition comprising flavour when packaged in the laminate tube with the specific multilayered laminate structure according to the present invention provides improved flavour performance over extended storage. It is further found that the toothpaste composition comprising the flavour shows reduced migration and absorption of flavour into the laminate tube with the specific multilayered laminate structure according to the present invention.
  • the toothpaste composition having flavour and packaged in a plastic based laminate tubes maintains acceptable cleaning ability and physical stability.
  • a packaged product comprising: i. a flexible laminate tube comprising a multilayer laminate structure; and, ii. a toothpaste composition enclosed in the flexible tube; wherein the toothpaste composition comprises a flavour; and, wherein the multilayer laminate structure comprising a barrier layer wherein the barrier layer is a multilayered structure having a barrier material sub-layer comprising ethyl vinyl alcohol sandwiched between a first intermediate sub-layer and a second intermediate sub-layer, wherein the first intermediate sub-layer and/or the second intermediate sub-layer comprises high-density polyethylene (HDPE); wherein the multilayer laminate structure comprises 45 wt.% to 90 wt.% of at least one polyethylene having a density ranging from 0.91 g/cm 3 to 0.99 g/cm 3 ; and wherein the multi-layer laminate structure comprises at least one extrusion lamination layer
  • the barrier layer is a multilayered structure having a barrier material sub-layer comprising ethyl vinyl alcohol sandwiched between a first intermediate sub-layer and
  • a "multilayer structure” means a structure having more than one layer.
  • the multilayer structure for example, a film
  • the multilayer laminate structure forms a wall between the packaged toothpaste composition and the surrounding environment and where the multilayer laminate structure comprises at least two films.
  • laminate refers to a process in which two or more films are joined together by an extrusion layer which is extruded in the shape of a film.
  • the extrusion layer thus acts as a bonding agent.
  • the film(s) which are joined together to form the layers of a multilayered laminate structure are preferably produced through a blown film process.
  • the film prepared by a blown film process may be preferably multilayered film.
  • Forms of polyethylene include, but are not limited to, low Density Polyethylene (LDPE); Linear low-density Polyethylene (LLDPE); ultra Low Density Polyethylene (ULDPE); Very Low-Density Polyethylene (VLDPE); single-site catalyzed Linear Low-density Polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).
  • LDPE low Density Polyethylene
  • LLDPE Linear low-density Polyethylene
  • ULDPE ultra Low Density Polyethylene
  • VLDPE Very Low-Density Polyethylene
  • m-LLDPE linear low density Polyethylene
  • MDPE Medium Density Polyethylene
  • HDPE High Density Polyethylene
  • LDPE low density polyethylene polymer
  • high pressure ethylene polymer or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides.
  • LDPE resins typically have a density in the range of 0.916 g/cm 3 to 0.940 g/cm 3 .
  • LDPE LD 150BW from the ExxonMobil.
  • LLDPE linear low-density polyethylene having a density less than 0.930 g/cm 3 .
  • the multilayer laminate structure includes Linear low-density Polyethylene (LLDPE).
  • LLDPE includes copolymers of ethylene and a-olefin. a-olefins includes 1 -butene, 1 -hexene, 1 -octene and mixtures thereof.
  • Suitable commercially available examples of LLDPE include EliteTM 5400 from The Dow Chemical Company.
  • MDPE refers to polyethylene having densities from 0.926 g/cm 3 to 0.941 g/cm 3 .
  • MDPE is typically made using chromium or Ziegler-Natta catalysts or using single-site catalysts including but not limited to bis-metallocene catalysts and constrained geometry catalysts.
  • HDPE refers to polyethylene having density of 0.940 g/cm 3 or greater, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts, or even metallocene catalysts.
  • HDPE it is meant a high-density polyethylene having a density more than 0.935 g/cm 3 . Still more preferably the HDPE has a density ranging from 0.941 g/cm 3 to 0.969 g/cm 3 when measured using ASTM D792 method. Preferably the HDPE has a melt flow index lower than 4 g/10 minutes at 190°C and 2.16 Kg when measured using ASTM 1238 test method, still preferably a melt flow index ranging from 0.3 to 2.5 g/10 minutes. Suitable commercially available examples of HDPE include EliteTM AT 6900 from The Dow Chemical Company.
  • film refers to single layer or multilayer structure prepared using a blown film process.
  • laminate refers to a multilayered structure which comprises at least two layers of film and at least an extrusion lamination layer.
  • the laminate surrounds the packaged toothpaste composition and forms a wall between the packaged product and the surrounding environment.
  • the present invention provides a flexible laminate tube.
  • the laminate tube preferably refers to the body of the tube including the shoulder.
  • the laminate tube comprises from 25 wt.% to 90 wt.%, still preferably from 45 wt.% to 90 wt.%, more preferably from 50 wt.% to 90 wt.% still preferably 60 wt.% to 90 wt.%, further preferably from 80 wt.% to 90 wt.% of at least one polyethylene having a density ranging from 0.94 g/cm 3 to 0.97 g/cm 3 .
  • the laminate tube comprises from 45 wt.% to 90 wt.%, more preferably from 50 wt.% to 90 wt.%, still preferably 60 wt.% to 90 wt.%, further preferably from 80 wt.% to 90 wt.% of at least one polyethylene or ethylene-based polymer having a density ranging from 0.94 g/cm 3 to 0.97 g/cm 3 .
  • the at least one polyethylene is HDPE, MDPE or combination thereof.
  • the flexible laminate tube comprises a multilayer laminate structure comprising 45 wt.% to 100 wt.%, more preferably 45 wt.% to 98 wt.%, still preferably from 45 wt.% to 95 wt.%, still more preferably from 45 wt.% to 90 wt.% polyethylene or an ethylene-based polymer and wherein the multilayer laminate structure has a barrier layer.
  • the flexible laminate tube comprises a tube body portion comprising multilayer laminate structure, and a tube shoulder comprising a neck portion.
  • the HDPE has a density ranging from 0.94 g/cm 3 to 0.96 g/cm 3 and a melt flow index in the range from 1 to 3.
  • the tube shoulder may include an inner barrier liner, which is mounted internally in the tube shoulder.
  • the tube shoulder may be molded by a general molding method including extrusion molding, compression molding and injection molding. Further, the prepared tube shoulder is bonded to a separately prepared tube body or to an online formed tube body to complete collapsible laminate tube.
  • the laminate tube includes a neck portion, preferably the shoulder portion comprises the tube neck portion and the neck portion is formed along with the shoulder portion.
  • the neck portion has an external threading portion to releasably engage with the tube cap.
  • the neck portion has an orifice which is in communication with the internal cavity of the tube body.
  • the neck portion may include 55 wt.% to 100 wt.% polyethylene or an ethylene-based polymer, still preferably the neck portion comprises 100% polyethylene or an ethylene-based polymer.
  • the neck portion may include ethylene vinyl alcohol copolymer, when present the ethylene vinyl alcohol is no more than 5 wt.%. More preferably the neck portion is 100% polyethylene or an ethylene-based polymer.
  • the tube shoulder may include an inner barrier liner, which is mounted internally in the tube shoulder.
  • the laminate tube comprises a cylindrical body for storing a packaged product, a shoulder with a neck portion which comprises an outlet for dispensing the packaged product, and a cap or closing off the tube, wherein said body is preferably made of a multilayered laminated structure of the first aspect of the invention.
  • the body may at the outside be provided with a print, which is mostly applied previously.
  • the shoulder portion has a greater rigidity than the tube body portion.
  • ovality of the body portion is in the range of 0 to 6%.
  • the cap could also be optional as it is a separate article that can be made by a standard industrial process. Several processes of making laminate tubes are well known in the art.
  • the films which comprise the outer layer and inner layer of the laminate structure should be capable of being lap-sealed (also called side seam), preferably by application of heat, so that the sides may be sealed off after a product has been filled.
  • the film present in the innermost layer of the multilayer laminate structure should also bond with itself, so that the bottom of the tube may be closed after a product has been filled.
  • the body and the shoulder are manufactured separately or can be manufactured inline, and subsequently welded together.
  • the caps for the tubes are usually manufactured separately.
  • the laminate is cut to size by means of a rotating knife, thus obtaining tubes of the desired length.
  • the obtained tubes are put on a compression mandrel.
  • the upper part of the tube, or tube shoulder is pressed in the right shape and desired dimensions in a separate press and provided with a small quantity of molten multilayer packaging film.
  • the compression mandrels provided with the tube body are introduced into the press in which the shoulder is pressed and welded to the shoulder.
  • the press is cooled, the tubes are removed from the press, and transferred to another device in which each tube is provided with a cap.
  • Devices to manufacture such tubes are available from a variety of suppliers, example AISA and PSG.
  • the tubes are brought to a filling device and filled with the desired cosmetic product through the bottom which subsequently is heat sealed.
  • the present invention provides a laminate tube comprising a multilayer laminate structure.
  • the laminate tube is preferably a collapsible flexible tube.
  • the multilayer laminate structure comprises 45 wt.% to 90 wt.% of at least one polyethylene.
  • the multilayer laminate structure comprises at least one polyethylene having a density ranging from 0.91 g/cm 3 to 0.99 g/cm 3 .
  • the multilayer laminate structure according to the invention have an overall density in the range from 0.94 g/cm 3 to 0.99 g/cm 3 .
  • the at least one polyethylene is selected from high-density polyethylene (HDPE), medium density polyethylene (MDPE) and combinations thereof.
  • the multilayer laminate structure comprises at least a layer of HDPE surrounding the barrier layer. More preferably the multilayer laminate structure comprises a layer of HDPE on either side of the barrier layer.
  • the multilayer laminate structure comprises not more than 70 wt.% of at least one polyethylene having a density ranging from 0.94 g/cm 3 to 0.97 g/cm 3 , more preferably no more than 49 wt.%, even more preferably no more than 37 wt.% by weight of the total multilayer laminate structure.
  • the multilayer laminate structure comprises: i) a printable layer comprising HDPE and preferably at least one of LDPE or LLDPE; ii) a sealant layer comprises polyethylene wherein the polyethylene comprises HDPE; iii) a barrier layer therebetween; and, iv) a first extrusion layer for laminating the barrier layer to the printable layer and preferably a second extrusion layer for laminating the barrier layer to the sealant layer.
  • the printable layer is free of MDPE.
  • the printable layer comprises HDPE.
  • the printable layer comprises HDPE and at least one of LDPE or LLDPE. Still more preferably the printable layer is free of MDPE and comprises HDPE. Still further preferably the printable layer is free of MDPE and comprises HDPE and at least one of LDPE or LLDPE.
  • the multilayer laminate structure comprises a first extrusion layer between the printable layer and the barrier layer, wherein the extrusion layer is formed by extruding a polymer into a film for extrusion laminating the printable layer and the barrier layer.
  • the multilayer laminate structure comprises a second extrusion layer between the sealant layer and the barrier layer, wherein the extrusion layer is formed by extruding a polymer into a film for extrusion laminating the sealant layer and the barrier layer.
  • the multilayer laminate structure comprises a printable layer.
  • printable layer refers to a single layered or multilayered film.
  • the film is a blown film.
  • top printable layer refers to the layer farthest away from a product, such as toothpaste, when packaged in a packaging, e.g., tube, made from the multilayer laminated structure. This layer is preferably printed.
  • the printable layer comprises HDPE. It is preferred that the printable layer comprises HDPE and at least one of LDPE or LLDPE.
  • the top printable layer is preferably free of MDPE, meaning thereby that the printable layer comprises less than 3 wt.% MDPE, still preferably less than 1 wt.% MDPE, most preferably 0 wt.% MDPE. It is preferred that the printable layer comprises HDPE and at least one of LDPE or LLDPE, wherein the amount of HDPE in the printable layer ranges from 10 wt.% to 60 wt.% by weight of the printable layer. It is particularly preferred that the printable layer comprises LDPE and LLDPE. In such a case it is preferred that the top printable layer comprises 40 wt.% to 80 wt.% LDPE and preferably from 10 wt.% to 30 wt.% LLDPE.
  • the printable layer comprises a combination of HDPE and LLDPE.
  • the LLDPE may be selected from LLDPE, metallocene LLDPE or combinations thereof. Processing agents and masterbatch may also be added and usually are comprised in said top printable layer.
  • thickness of the printable layer accounts for 10% to 35% of total thickness of said multilayered laminate structure.
  • the printable layer may have sub-layers or a single layered structure.
  • the printable layer is a single layered structure it comprises HDPE and LLDPE.
  • the single layered structure has a thickness of 50 micrometers to 95 micrometers, preferably from 85 micrometers to 95 micrometers.
  • the printable layer comprises sub-layers.
  • the sub-layer of the printable layer is composed of a sub-layer of HDPE and at least one sub-layer of LDPE or LLDPE. It is further preferred that the printable layer comprises a sub-layer of HDPE, a sublayer of LDPE and a sub-layer of LLDPE.
  • the printable layer may comprise at least a sub-layer of LLDPE, at least a sub-layer of HDPE and LLDPE and at least a sub-layer of HDPE, LLDPE and mLLDPE.
  • the printable layer has a structure which preferably comprises at least 3 sublayers.
  • the printable layer with a 3-layer structure comprises a top sub-layer, a middle sublayer, and an inner sub-layer.
  • the printable layer is a multilayered structure, the printable layer is a blown film wherein the sub-layer is formed by known extrusion process and then blown to form the film.
  • a top sub-layer comprises HDPE, still preferably a top sub-layer which comprises HDPE and at least one of LLDPE and LDPE, preferably the top sub-layer comprises HDPE and LLDPE.
  • the LLDPE is selected from LLDPE, mLLDPE or mixtures thereof.
  • printable layer which comprises a top sub-layer comprising LLDPE or LDPE, preferably LLDPE. It is preferred that when the multilayer laminate structure includes a metallization layer, the top sub-layer comprises LLDPE and LDPE.
  • the printable layer when comprising at least a 3-layered structure may include a middle sublayer comprising HDPE, still preferably HDPE and at least one of LLDPE or LDPE, preferably LLDPE. Also, preferred are printable layer which comprises a middle sub-layer comprising LLDPE or LDPE, preferably LLDPE.
  • the middle sub-layer comprises HDPE and at least one of LLDPE or LDPE, preferably LLDPE.
  • LLDPE is selected from LLDPE, mLLDPE or mixtures thereof.
  • the printable layer comprises an inner sub-layer comprising LLDPE or LDPE, preferably LLDPE.
  • the inner sub-layer may comprise a mixture of HDPE and LLDPE, LDPE or mixture of LLDPE and LDPE.
  • the inner sub-layer LLDPE is selected from LLDPE, mLLDPE or mixtures thereof.
  • the thickness of the printable layer ranges from 5 pm to 105 pm, preferably from 7 pm to 100 pm.
  • the thickness is at least 15 pm, still preferably at least 17 pm, further preferably at least 25 pm, still more preferably at least 30 pm, but preferably the thickness is not more than 95 pm, still preferably not more than 80 pm and still further preferably not more than 70 pm.
  • the ink layer is coated on the printable layer can be deposited through any printing technology suitable for polyolefin and well known to the person skilled in the art and not limited to rotogravure technology, flexographic technology, offset UV or EB, digital printing.
  • the multilayer laminate structure according to the first aspect of the present invention includes a barrier layer.
  • the barrier layer is preferably an intermediate layer and is preferably sandwiched between two layers of the multilayer laminate structure.
  • the barrier layer is more preferably sandwiched between the printable layer and the sealant layer.
  • the barrier layer preferably provides a water vapor transmission rate (WVTR) value ranging from 0 g/mm 2 /day to 1 g/mm 2 /day or less, still preferably 0 g/mm 2 /day to 0.63 g/mm 2 /day, more preferably 0 g/mm 2 /day to 0.55 g/mm 2 /day.
  • WVTR water vapor transmission rate
  • the WVTR is in a range from 0.1 g/mm 2 /day to 1 g/mm 2 /day, preferably from 0.1 g/mm 2 /day to 0.8 g/mm 2 /day, preferably a WVTR value of 0.1 g/mm 2 /day to 0.63 g/mm 2 /day or less, still preferably ranging from 0.1 g/mm 2 /day to 0.55 g/mm 2 /day.
  • the thickness of the barrier layer accounts for 4% to 60% of total thickness of said laminate, still preferably 4% to 20% of the total thickness of the laminate.
  • the barrier layer comprises ethylene vinyl alcohol with at least 20 mol% ethylene, still preferably at least 25 mol% ethylene, furthermore preferably at least 29 mol% ethylene.
  • the ethylene vinyl alcohol comprises from 20 mol% ethylene to less than 38 mol% ethylene, more preferably from 20 mol% ethylene to less than 35 mol% ethylene, still more preferably from 25 mol% ethylene to less than 35 mol% ethylene, still more preferably from 29 mol% ethylene to less than 35 mol% ethylene.
  • the presence of ethylene vinyl alcohol having from 29 mol% ethylene to less than 35 mol% ethylene provides good oxygen barrier properties to the multilayer laminate structure.
  • the barrier layer still preferably the EVOH sub-layer has a thickness ranging from 6 micrometers to 15 micrometers, still preferably from 8 micrometers to 15 micrometers still more preferably from 11 micrometers to 13 micrometers.
  • the barrier layer comprises at least 5 layered structure, comprising a first intermediate sub-layer, a first tie sub-layer, a barrier material sub-layer comprising EVOH, a second tie sub-layer, and a second intermediate sub-layer.
  • the barrier layer is a 7 layered structure.
  • the 7 layered structure comprises a top sub-layer, a first intermediate sub-layer, a first tie sub-layer, a barrier material sub-layer, a second tie sub-layer, a second intermediate sub-layer, an inner sub-layer.
  • intermediate sub-layer is intended to mean a sublayer in the barrier layer.
  • Such an intermediate sub-layer may be present on either side or both sides of EVOH comprising sub-layer of the barrier layer.
  • the top sub-layer of the barrier layer comprises MDPE.
  • the top-sub layer of the barrier layer comprises a copolymer of ethylene and a carboxylic acid selected from the group consisting of acrylic acid, alkyl acrylate, methacrylic acid.
  • the copolymer has an ethylene monomer which is higher than or equal to 75 wt.%.
  • interpolymer which is a terpolymer of ethylene, acrylic acid, or methacrylic acid and alkyl acrylate.
  • the interpolymer comprises from 50 wt.% to 98 wt.% ethylene.
  • the copolymer of ethylene and acrylic acid has a density of more than or equal to 0.925 g/cm 3 .
  • the barrier layer has a barrier material which is sandwiched on at least one side by a sub-layer comprising HDPE, still preferably the barrier layer has a barrier material which is sandwiched on both side by a sub-layer comprising HDPE.
  • the barrier material sublayer is sandwiched between two sub-layers.
  • the barrier layer comprises at least two sub-layers comprising HDPE and a sub-layer of barrier material, where the barrier material sublayer is sandwiched between the two sub-layers comprising HDPE.
  • EVOH comprising sub-layer may comprise to its immediately adjacent one or two tie sub-layer on one or both sides, followed by which HDPE comprised sub- layer may be present. In other embodiments, there may even be more than two sub-layers between the EVOH comprised sub-layer and the HDPE comprised sub-layers in the barrier layer.
  • the first intermediate sublayer comprises HDPE.
  • the first tie layer between the first intermediate sub layer and the barrier material sub-layer comprises LDPE and a tie material.
  • second tie sublayer which lies between the barrier material sub-layer and the second intermediate sub-layer comprises LDPE and tie material.
  • the second intermediate sub-layer comprises HDPE.
  • the inner sub-layer comprises MDPE.
  • the barrier layer comprises 3 sub-layers, it comprises a primary lamination layer, a middle barrier layer with barrier properties and a secondary lamination layer.
  • the lamination layers comprise HDPE or MDPE.
  • the barrier layer may be metalized.
  • the multilayer laminate structure comprises a metal layer applied to the top sub-layer of the barrier layer.
  • the top sub-layer of the barrier material comprises MDPE, more preferably MDPE and a copolymer of ethylene and a carboxylic acid selected from the group consisting of acrylic acid, alkyl acrylate, methacrylic acid.
  • the copolymer has an ethylene monomer which is higher than or equal to 75 wt.%.
  • the metals that can be deposited to form the metallized layer include Al, Zn, Au, Ag, Cu, Ni, Cr, Ge, Se, Ti, Sn, or oxides thereof.
  • the metallized layer is formed from aluminum or aluminum oxide (AI2O3).
  • the metallized layer may also include the metalloid silicon or oxides thereof.
  • the metallized layer may comprise aluminum, silicon, or oxides thereof. More preferably the metallized layer is a Al metal layer.
  • the skilled person would be familiar with multiple applicable metallization techniques.
  • the metal layer may be applied but are not limited to using physical vapor deposition such as the vacuum vapor deposition, or chemical vapor deposition method such as photochemical vapor deposition.
  • Vacuum metallization is a well-known technique for depositing metals in which a metal source is evaporated in a vacuum environment, and the metal vapor condenses on the surface of the film to form a thin layer as the film passes through the vacuum chamber.
  • the metallized layer may in one or more embodiments have a thickness of not more than 100 nanometers, or preferably from 10 to 80 nanometers, or still preferably from 20 nanometers to 60 nanometers.
  • the metallized layer may advantageously provide a good barrier to oxygen and water vapor.
  • the combination of barrier material sub-layer with the metallized layer deposited on the specified outer surface can provide a synergistic combination of both mechanical and barrier properties.
  • the metal layer according to the present invention is not a foil layer adhered to the rest of the barrier with a tie layer, wherein by the term metal foil layer it is meant that the layer has a thickness ranging from 6 micrometers to 15 micrometers, from 6 micrometers to 12 micrometers, from 10 micrometers to 15 micrometers.
  • barrier layer has a thickness ranging from 40 micrometers to 80 micrometers, more preferably the barrier layer has a thickness ranging from 40 micrometers to 60 micrometers.
  • barrier material sub-layer has a thickness ranging from 10 to 13 micrometers.
  • the barrier layer may additionally comprise at least one sub-layer to provide heat sealability.
  • the heat-sealable sub-layer comprises any one of those selected from HDPE, MDPE, LDPE and combinations thereof.
  • the multilayer structure preferably comprises a sealant layer.
  • the sealant layer may generally be heated and pressed to seal two multilayer structures or portions of the multilayer structure to one another by their sealant layers.
  • sealant layer used herein refers to a multilayer polyolefin and refers to a layer generally present on the inside of a packaging film to heat seal and moisture seal the contents of the packaged product.
  • the sealant film is laminated to the barrier film by an extrusion layer which is extruded in the shape of a film.
  • the extrusion layer thus acts as a bonding agent to form the top sealant layer and the barrier layer of the multilayer laminate structure.
  • the extrusion layer preferably comprises LDPE.
  • the sealant layer is a blown film.
  • the sealant layer is a multilayered structure with 3, 5, 7, or more sub-layers it is formed by a blown film process.
  • the sealant layer forms the innermost layer of laminate tube and is in contact with product, toothpaste composition.
  • the sealant layer preferably comprises a polyethylene having a heat seal initiation temperature of 95°C or less.
  • the sealant layer may comprise a polyethylene having a heat seal initiation temperature of 92.5°C or less, 90°C or less, 87.5°C or less, 85°C or less, 82.5°C or less, 80°C or less, 75°C or less, or even 70°C or less.
  • the sealant layer comprises HDPE. Still preferably the sealant layer comprises HDPE and at least one of MDPE, LDPE or LLDPE. Still more preferably the sealant layer comprises HDPE, MDPE and LLDPE.
  • the sealant layer is multilayered having 3 to 7 layers.
  • the sealant layer has a thickness ranging from 40 to 80 micrometers, still preferably from 50 to 60 micrometers.
  • the tie layer comprises 3 wt.% or less of the polyethylene grafted maleic anhydride.
  • the extrusion layer comprises from 50 wt.% to 100 wt.% LDPE, more preferably the 80 wt.% to 100 wt.% LDPE, still preferably 100 wt.% LDPE.
  • the extrusion layer comprises LDPE and ethylene acrylic acetate (EAA), more preferably when the barrier layer comprises a metalized coating, the extrusion layer between the top printable layer and the barrier layer comprises a mixture LDPE and ethylene acrylic acetate (EAA).
  • the extrusion layer between the barrier layer and the sealant layer comprises from 50 wt.% to 100 wt.% LDPE, more preferably the 80 wt.% to 100 wt.% LDPE, still preferably 100 wt.% LDPE.
  • the extrusion layer is a monolayer of polyethylene or polyethylene blended with the copolymer or a coextruded layer of ethylene acrylic acid copolymer and polyethylene.
  • the extrusion layer has a thickness ranging from 10 micrometers to 30 micrometers, more preferably 15 micrometers to 25 micrometers.
  • the flexible laminate tube according to the present invention may include recycled polyethylene.
  • the recyclable tube may preferably comprise at least 50 wt.% HDPE.
  • the shoulder portion of the flexible laminate tube comprises at least 50 wt.% HDPE.
  • the HDPE in the shoulder portion of the flexible laminate tube may be virgin HPDE, recycled HDPE or a mixture thereof.
  • the shoulder portion of the flexible laminate tube comprises from 50 wt.% to 100 wt.% HDPE, more preferably from 70 wt.% to 100 wt.% HDPE, still more preferably from 85 wt.% to 100 wt.% HDPE.
  • Suitable recycled HDPE has a melt flow rate less than 1 g/minute.
  • total thickness of the laminate ranges from 50 pm to 350 pm, more preferably from 175 pm to 350 pm, also preferably the total thickness of the laminate ranges from 50 pm to 300 pm. More preferably it is 60 pm to 250 pm, further preferably 70 pm to 150 pm.
  • the range 50 pm to 300 pm generally applies to laminates useful for making collapsible tubes.
  • a 3 layered multilayer laminate structure comprising:
  • the multilayer laminate structure according to the first aspect of the present invention has a thickness ranging from 170 micrometers to 220 micrometers.
  • the multilayer laminated structure comprising a top printable layer, a sealant layer at the bottom and an intermediate barrier layer therebetween, where said i) top printable layer comprises HDPE and preferably at least one of LDPE or LLDPE; ii) said sealant layer comprises polyethylene wherein the polyethylene comprises HDPE; and, iii) said intermediate barrier layer is extrusion laminated to the printable layer and sealant layer.
  • the sealant layer comprises HDPE and at least one of LDPE, LLDPE or MDPE, more preferably the sealant layer comprises HDPE, LLDPE and MDPE or HDPE, LDPE and MDPE.
  • the sealant layer accounts for 10 wt.% to 35 wt.% of total thickness of said laminate.
  • the barrier layer comprises HDPE and at least one of MDPE or LDPE, more preferably HDPE and MDPE, still preferably HDPE, MDPE and LDPE.
  • the barrier layer accounts for 20 wt.% to 60 wt.% of total thickness of said laminate.
  • the barrier layer is a multilayered structure comprising at least two sub-layers comprising HDPE and a barrier material sub-layer, where the barrier material sub-layer is sandwiched between the two sub-layers comprising HDPE.
  • the process for preparing the multilayered laminate structure as described herein comprises the steps of:
  • Extrusion process is one of the processes most widely used to make polyethylene into films, and tubes.
  • blown film process is used and it starts from feeding a plastic material from a hopper into an extruder wherein the plastic material is heated to form a melt.
  • This melt form of plastic is forced to pass through a circular-shaped die that yields a semi-solid tube whose diameter is expanded by blowing air through the die.
  • the film is cooled using either air or water to crystallize it. Further, several nip rollers flatten it to form rolls of sheeting.
  • the film can be extruded in upward, downward, and horizontal directions and the rate of extrusion and blowing can be controlled to achieve desired properties of the extruded film.
  • teethpaste denotes an oral composition which is used to clean the surfaces of the oral cavity. Such a composition is not intentionally swallowed for purposes of systemic administration of therapeutic agents, but is applied to the oral cavity, used to treat the oral cavity, and then expectorated. Typically, such a composition is used in conjunction with a cleaning implement such as a toothbrush, usually by applying it to the bristles of the toothbrush and then brushing the accessible surfaces of the oral cavity.
  • the toothpaste composition may be in the form of a viscous material, preferably the toothpaste is in the form of an extrudable semi-solid. Still preferably the toothpaste composition may in the form of a cream product, gel product or a paste product (or mixture thereof).
  • the term “toothpaste composition” according to the invention more preferably encompasses a gel format or a paste format.
  • the toothpaste composition may be single-phase composition or may be a combination of two or more separate toothpaste compositions.
  • the toothpaste composition may be in any desired form, such as deep striped, surface striped, multilayered, having a gel format surrounding a paste format, or any combination thereof.
  • Each toothpaste composition comprising two or more separate toothpaste compositions may be contained in a physically separated compartment of a dispenser and dispensed side-by-side.
  • the toothpaste composition according to the first aspect of the invention includes a flavour.
  • Flavour preferably enhance the taste of the composition.
  • Any orally acceptable natural or synthetic flavour can be used, including without limitation tea flavour, vanillin, sage, marjoram, parsley oil, spearmint oil, cinnamon oil, oil of Wintergreen (methylsalicylate), peppermint oil, clove oil, bay oil, anise oil, eucalyptus oil, citrus oils, fruit oils and essences including those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, pineapple, etc., bean and nut-derived flavors such as coffee, cocoa, cola, peanut, almond, etc.
  • flavour is in the adsorbed form, encapsulated form, or mixtures thereof.
  • ingredients that provide fragrance and/or other sensory effect in the mouth, including cooling or warming effects.
  • Such ingredients illustratively include menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, methyl salicylate, oxanone, a-irisone, propenyl guaiethol, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine, N,2,3-trimethyl-2- isopropylbutanamide, 3-(1-menthoxy)-propane-1 ,2-diol, cinnamaldehyde glycerol acetal (CGA), menthone glycerol acetal (MGA) and the like.
  • CGA menthone glycerol
  • One or more flavour are optionally present in a total amount of from about 0.01 wt. % to about 5 wt. %, more preferably in an amount ranging from 0.03 wt. % to 2.5 wt.%, still preferably from 0.05 wt.% to 1.5 wt.%, further preferably from 0.1 wt.% to about 0.3 wt.% by total weight of the composition.
  • Preferred coolants are the paramenthane carboxyamide agents such as N-ethyl-p-menthan-3-carboxamide (known commercially as "WS-3®”), menthane carboxamidoethyl acetate (known commercially as “WS-5®” and mixtures thereof.
  • the flavour is generally present in an amount ranging from 0.001 to 5 wt.%, more preferably from 0.1 to 5 wt.%, still more preferably from 0.1 to 3 wt.%, furthermore preferably from 0.1 to 2.5 wt.%, still preferably from 0.1 to 1.5 wt.% flavour by weight of the composition.
  • the toothpaste composition comprises a bicarbonate salt.
  • a bicarbonate salt Any orally acceptable bicarbonate can be used, including without limitation, alkali metal bicarbonate such as sodium and potassium bicarbonate, ammonium bicarbonate and the like.
  • the bicarbonate salt is present in a total amount ranging from 0.1 wt. % to 50 wt. %, preferably from 0.1 to 20 wt.%, more preferably from 0.1 wt. % to 5 wt. %, by total weight of the composition.
  • the toothpaste composition comprises a sodium salt.
  • the sodium salt is selected from the group consisting of sodium chloride, sodium carbonate and mixtures thereof.
  • the toothpaste composition comprises from 15 wt.% to 34.5 wt.% water based on the weight of the toothpaste composition.
  • the water content is at least 35 wt.%, still preferably from 35 wt.% to 55 wt.%, more preferably from 35 wt.% to 50 wt.%, still preferably from 35 wt.% to 45 wt.% and more preferably from 38 wt.% to 45 wt.%, based on the total weight of the composition.
  • the toothpaste composition has 5 wt.% to 60 wt.% abrasive. More preferably the toothpaste composition includes a surfactant.
  • composition according to the invention will generally contain further ingredients to enhance performance and/or consumer acceptability, in addition to the ingredients specified above.
  • a toothpaste generally contains an abrasive, preferably the abrasive is a silica-based abrasive, calcium-based abrasive, or a mixture thereof.
  • Toothpaste composition in the form of gel usually comprises silica-based abrasive, whereas opaque paste generally contain calcium-based abrasives, especially chalk.
  • the quantity of the abrasive needs some control because excess abrasive causes more abrasion. Further, uncontrolled amounts of abrasives will also adversely affect viscosity of the toothpaste.
  • DCP dicalcium phosphate
  • PCC precipitated calcium carbonate
  • FGNC is 35 to 100 %, more preferably 75 to 100 % and especially from 95 to 100 % of the total content of calcium based-abrasive.
  • the balance most preferably, is PCC.
  • abrasives can also be used depending upon the intended degree of abrasion and the composition of the toothpaste. These include synthetic abrasive polishing agents such as amorphous precipitated silica and silica gels. Other abrasives include magnesium carbonate, sodium metaphosphate, potassium metaphosphate, zirconium silicate, potassium metaphosphate, magnesium orthophosphate, tricalcium phosphate, magnesium orthophosphate, tri-magnesium phosphate, aluminum silicate, zirconium silicate and perlite.
  • the toothpaste composition may preferably comprise a silica-based abrasive.
  • the preferred abrasive silicas used in the present invention is a silica with a low refractive index. It may be used as the sole abrasive silica, or in conjunction with a low level of other abrasive silicas, e.g., those according to EP 236070.
  • suitable low refractive index abrasive silicas e.g., having an R.l.
  • Preferred silica abrasive-based toothpaste compositions comprises 3 wt.% to 20 wt.% abrasive, more preferably 5 wt.% to 18 wt.% and most preferably 5 wt.% to 15 wt.% abrasive, preferably Also preferred are low-abrasive toothpaste composition which have lowered levels of the silica- based abrasive, in these composition the silica-based abrasive is present in an amount ranging from 4 to 10 wt.%, still preferably 4 wt.% to 9 wt.%, still further preferably from 4 wt.% to 8 wt.%.
  • the toothpaste composition may have silica-based abrasive as the only abrasive. Such composition are generally in the gel format.
  • the toothpaste composition includes a surfactant, also commonly referred to as sudsing agent.
  • Suitable surfactants are those which are reasonably stable and provide foam throughout a wider pH range.
  • the surfactant may be selected from the group consisting of anionic surfactant, amphoteric surfactant, nonionic surfactant, or mixtures thereof.
  • the surfactant is anionic.
  • Anionic surfactants useful herein include the water-soluble salts of alkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical (e.g., sodium alkyl sulfate) and the water-soluble salts of sulfonated monoglycerides of fatty acids having from 8 to 20 carbon atoms, sarcosinate, taurate and mixtures thereof.
  • anionic surfactants in particular, sodium lauryl sulphate has antibacterial effect. Such action provides some degree of instant antibacterial effect. However, this effect is generally very short-lived.
  • surfactants like nonionic, amphoteric or zwitterionic surfactants may also be included.
  • Toothpaste composition according to the present invention may preferably include at least one foam modulator, useful for example to increase amount, thickness or stability of foam generated by the composition upon agitation.
  • Any orally acceptable foam modulator can be used, including without limitation, polyethylene glycols (PEGs), also known as polyoxyethylene.
  • PEGs polyethylene glycols
  • High molecular weight PEGs are suitable, including those having an average molecular weight of 200,000 to 7,000,000, for example 500,000 to 5,000,000, or 1,000,000 to 2,500,000.
  • One or more PEGs are optionally present in a total amount of about 0.1 wt. % to about 10 wt. %, for example from about 0.2 wt. % to about 5 wt. %, or from about 0.25 wt. % to 5 wt.%.
  • Preferred toothpaste compositions comprise bipolar antimicrobial particle in an amount ranging from 0.1 wt.% to 10 wt.%, more preferably 0.5 wt.% to 5 wt.% particles. It is further preferred that such particle contains 1 wt.% to 60 wt.% loading of the quaternary ammonium antimicrobial agent.
  • a particularly preferred quaternary ammonium antibacterial agent is cetylpyridinium chloride.
  • the thickening silica may also be present in a lower amount ranging from 0 to 2 wt.% thickening silica by weight of the toothpaste composition
  • Conventional gel toothpastes generally contain up to 8.5 wt.% thickening silica whereas opaque toothpastes typically contain 4 wt.% to 10 wt.% thickening silica.
  • the toothpaste composition preferably can include up to 2 wt.% thickening silica.
  • Preferred compositions have 1.5 wt.%, or even less than 1 wt.% thickening silica.
  • Optimal compositions have less than 0.5 wt.% thickening silica. Highly preferred compositions do not contain thickening silica.
  • preferred thickening silicas include AEROSIL® T series from Degussa or the CAB-O-SIL® series from Cabot Corporation, silica gels such as the SYLODENT® or SYLOX® series from W. R. Grace & Co or precipitated silica such as ZEOTHIX® 265 from J. M. Huber Corporation.
  • Useful silica thickeners also include ZEODENT® 165, ZEODENT® 163 and/or 167 and ZEOFREE® 153, 177, and/or 265 silicas, all available from J. M. Huber Corporation.
  • thickening silicas include MFIL®, MFIL®-P (From Madhu Silica), SIDENT® 22 S and AEROSIL® 200 (Ex. Evonik Industries), SYLODENT® and PERKASIL® thickening silicas from WR Grace & Company and Tixosil® 43 and 331 from Rhodia, synthetic finely divided pyrogenic silica such as those sold under the trademarks SYLOID® 244, SYLOID® 266 and AEROSIL® D-200.
  • Toothpaste composition preferably includes a humectant.
  • Humectants are generally included in toothpastes for a soft and supple mouth feel. Humectants also reduce the tendency of toothpastes to lose moisture. Toothpaste composition preferably include from 0 wt.% to 70 wt.% humectant, 3.5 wt.% to
  • compositions have 10 wt.% to 40 wt.%, more particularly
  • xanthan gum such as Irish moss and viscarin, gellan gum, sclerotium gum and derivatives, pullulan, rhamsan gum, welan gum, konjac, curdlan, algin, alginic acid, alginates and derivatives, starch phosphate derivatives, agar and derivatives, gum arabic and derivatives, pectin and derivatives, chitosan and derivatives, karaya gum, locust bean gum, natto gum, tragacanth gum, chitin derivatives, gelatin, betaglucan, dextrin, dextran, cyclodextrin and polyquaterniums, furcellaren gum, ghatti gum, psyllium gum, quince gum, tamarind gum, larch gum, and tara gum.
  • xanthan gum such as Irish moss and viscarin, gellan gum, sclerotium gum and derivatives, pullulan, rhamsan gum, welan gum
  • compositions can include 0.05 to 10 wt.%, more preferably 0.1 to
  • a de-sensitizing agent is a potassium salt selected from potassium nitrate, potassium chloride, potassium citrate, potassium tartarate and potassium acetate used preferably from 0.5 to 3 wt.%, more preferably from 1 to 2.5 wt.% and especially from 1.7 to 2.2 wt.%.
  • Sodium silicate with Na2O: SiC>2 ratio in the range of 3.0 to 3.8 is preferred, more highly preferred range being 3.25 to 3.5.
  • Preferred toothpastes include 0.1 to 5 wt.% silicate (on dry weight basis). Thus, a 30 % solution of sodium silicate is added to the composition in an amount in the range of 0.3 wt.% to 3 wt.%.
  • compositions can include one or more anti-caries agent.
  • agents are typically fluorides.
  • the weights of fluoride salts to provide the appropriate level of fluoride ion will obviously vary based on the weight of the counter ion in the salt, and one of skill in the art may readily determine such amounts.
  • the fluoride source is a fluoride salt present in an amount of 0.1 wt.% to 2 wt.% (0.1 wt.% to 0.6 wt.%) of the total composition weight (e.g., sodium fluoride (e.g., about 0.32 wt.%).
  • Additional anti-bacterial agents can be present in the composition, though not strictly necessary.
  • examples include triclosan and other halogenated bisphenolic compounds such as 2,2' methylenebis-(4-chloro-6-bromophenol).
  • Toothpastes with calcium containing abrasives especially chalk are prone to bacterial growth.
  • Certain preservatives e.g., methyl, ethyl, butyl, propyl, and isopropyl esters of parahydroxybenzoic acid may be particularly useful against bacterial growth.
  • a mixture of methyl, ethyl, butyl, and propyl esters of parahydroxybenzoic acid is particularly preferred. The activity of this mixture can be enhanced by adding phenoxyethanol.
  • Formaldehyde and dimethyl hydantoin are other preferred preservatives.
  • Preservatives are generally included at 0.05 wt.% to 0.8 wt.%.
  • Toothpaste composition may preferably include a sweetening agent.
  • Preferred sweetening agents include sodium saccharin, aspartame, sucralose, thaumatin, acesulfame potassium, stevioside, stevia extract, paramethoxy cinnamic aldehyde, neohesperidyl dihydrochalcone and perillartine. Typical levels are from 0.005 wt.% to 5 wt.%, more preferably from 0.01 wt.% to 1 wt.%.
  • Colorants herein include pigments, dyes, lakes, and agents imparting a particular luster or reflectivity such as pearling agents.
  • Any orally acceptable colorant can be used, including without limitation titanium dioxide, zinc oxide, red, yellow, brown, and black iron oxides, ferric ammonium ferrocyanide, manganese violet, ultramarine, titaniated mica, bismuth oxychloride, and mixture thereof.
  • One or more colorants are optionally present in a total amount of from 0.001 wt.% to 20 wt.%, more preferably from 0.01 wt.% to 10 wt. %, still preferably in an amount ranging from 0.1 wt. % to about 5 wt.%, by total weight of the composition.
  • the pH of the toothpaste composition when measured using a 1wt.% aqueous solution of the toothpaste composition in distilled water and as measured at 25°C using conventional pH sensitive electrodes is from 5.5 to 10.5, still preferably from 6.0 to 10.0, preferably from 6.5 to 9.5, more preferably 6.5 to 9.0, even more preferably from 7.0 to 8.0.
  • anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta phosphate and casein;
  • plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates
  • desensitising agents e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;
  • biomolecules e.g. bacteriocins, antibodies, enzymes, etc.
  • Flexible PBL laminate tube were prepared from the multilayered laminate structure (Structure 1 to 4) as described under Example 1 where the structure includes at least one polyethylene with a density ranging from 0.91 g/cm 3 to 0.99 g/cm 3 and has an ethyl vinyl alcohol barrier layer.
  • Example 3 Evaluation of the flavor and stability of a toothpaste composition enclosed in a PBL tube according to the invention when compared with a packaged product in a commercially available PBL and ABL tube.
  • the toothpaste composition as in Example 2 was tested in three different tubes as shown below under different temperature and humidity conditions. Samples were stored for 3 months at different temperature points, post-which tubes were washed, and flavour loss from toothpaste (extractable from laminate) (in % of flavour added) was determined. Table 4

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Abstract

La présente invention se rapporte à un produit emballé, en particulier l'invention se rapporte à une composition de dentifrice emballée qui est emballée dans un tube stratifié à base de plastique recyclable. Les présents inventeurs ont découvert qu'un produit emballé contenant une composition de dentifrice aromatisé renfermée dans un tube stratifié à base de plastique ayant une structure stratifiée multicouche spécifique conférait à la composition de dentifrice une bonne stabilité chimique et physique et des propriétés souhaitables pour le consommateur (telles qu'une viscosité et une limite d'élasticité souhaitables) et de bonnes performances aromatiques. Il a en outre été découvert que la composition de dentifrice aromatisée et emballée dans un tube stratifié à base de plastique conservait une capacité de nettoyage et une stabilité physique acceptables.
PCT/EP2025/056369 2024-04-03 2025-03-10 Composition et tube de dentifrice Pending WO2025209771A1 (fr)

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EP24168239.2 2024-04-03

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0236070A2 (fr) 1986-02-28 1987-09-09 Unilever Plc Silices
EP2155488B1 (fr) 2007-05-02 2011-01-26 Boddington IP Limited Réceptacles pour tubes souples
US20120205267A1 (en) * 2011-02-16 2012-08-16 Alcan Packaging Beauty Services Laminated Material Suitable for Forming Containers
US20230405982A1 (en) 2021-04-05 2023-12-21 Kim Pack Co., Ltd. Recycled and recyclable barrier laminate tube

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0236070A2 (fr) 1986-02-28 1987-09-09 Unilever Plc Silices
EP2155488B1 (fr) 2007-05-02 2011-01-26 Boddington IP Limited Réceptacles pour tubes souples
US20120205267A1 (en) * 2011-02-16 2012-08-16 Alcan Packaging Beauty Services Laminated Material Suitable for Forming Containers
US20230405982A1 (en) 2021-04-05 2023-12-21 Kim Pack Co., Ltd. Recycled and recyclable barrier laminate tube

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