WO2025209771A1

WO2025209771A1 - Toothpaste tube and composition

Info

Publication number: WO2025209771A1
Application number: PCT/EP2025/056369
Authority: WO
Inventors: Saurabh Vinod Acharekar; Sembian CHANDRASEKARAN; Babu Cherian; Susobhan Das; Anil HANKARE; Partha Sarathi MITRA; NV Anil Kumar RAVIPATI; Pavan Basavanahalli SOMASHEKAR
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2024-04-03
Filing date: 2025-03-10
Publication date: 2025-10-09
Anticipated expiration: 2026-10-03

Abstract

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. The present inventors have found that a packaged product having a toothpaste composition including a flavour enclosed in a plastic based laminate tube having a specific multilayer laminate structure provides the toothpaste composition with good chemical and physical stability and desirable consumer-relevant properties (such as desirable viscosity and yield stress) and good flavour performance. It was further found that the toothpaste composition having flavour and packaged in a plastic based laminate tube maintains acceptable cleaning ability and physical stability.

Description

TOOTHPASTE TUBE AND COMPOSITION

Field of the Invention

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.

Background of the Invention

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). The aluminium-based tubes provide good water and gas barrier properties and are preferred for packaging toothpaste composition. Usually, a thin layer of about 5 pm to 12 pm of Aluminium foil is sufficient. Usually, the ABL laminates are made of polyolefins, especially polyethylene, e.g., High Density Polyethylene (HDPE). Tubes of laminates containing aluminium are called ABL tubes.

In recent years to address the recyclability related issues with aluminium based laminates, it is known to provide a plastic based laminates (PBL) with EVOH as the barrier layer.

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.

It is desired to provide a packaged toothpaste composition which is packaged in recyclable and sustainable laminate tube and where the laminate tube provides adequate barrier properties. 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.

Summary of the Invention

The present inventors have found that 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 present inventors have further found that 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.

It was further found that the toothpaste composition having flavour and packaged in a plastic based laminate tubes maintains acceptable cleaning ability and physical stability.

According to a first aspect of the present invention provided is 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/cm³ to 0.99 g/cm³; and wherein the multi-layer laminate structure comprises at least one extrusion lamination layer

Detailed Description of the Invention

According to the first aspect, the present invention provides a toothpaste composition and a laminate tube.

As described herein, a "multilayer structure" means a structure having more than one layer. For example, the multilayer structure (for example, a film) may have two, three, four, five or more layers. 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.

The term "lamination” as used herein 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.

As described herein "polyethylene" or an "ethylene-based polymer" shall mean polymer comprising greater than 50% by mole of units derived from ethylene monomer. This includes ethylene-based homopolymers, ethylene copolymers (meaning units derived from ethylene and an additional monomer), and ethylene interpolymer (meaning units derived from ethylene and at least one additional comonomer). These comonomers may include C3-C12 a-olefin comonomers. 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).

As described herein the term "LDPE" may also be referred to as "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/cm³to 0.940 g/cm³.

Preferably by LDPE it is meant a low-density polyethylene having a density less than or equal to 0.930 g/cm³. Still more preferably the LDPE has a density ranging from 0.91 g/cm³ to 0.930 g/cm³ when measured using ASTM D792 method. Preferably the LDPE has a melt flow index of 0.75 g/10 minutes at 190°C and 2.16 Kg when measured using ASTM 1238 test method.

Suitable commercially available examples of LDPE include ExxonMobil LDPE LD 150BW from the ExxonMobil.

The term "LLDPE", as described herein, may include resins made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bismetallocene catalysts (sometimes referred to as "m-LLDPE"'), phosphinimine, and constrained geometry catalysts; and resin made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers or homopolymers. LLDPE's contain less long chain branching than LDPE's and include the substantially linear ethylene polymers. The LLDPE resins can be made via gasphase, solution-phase or slurry polymerization or any combination thereof; using any type of reactor or reactor configuration known in the art. The LLDPE resins can be made via gasphase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

Preferably by LLDPE it is meant a linear low-density polyethylene having a density less than 0.930 g/cm³. Preferably the multilayer laminate structure includes Linear low-density Polyethylene (LLDPE). Suitable 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 Elite™ 5400 from The Dow Chemical Company.

The term "MDPE" refers to polyethylene having densities from 0.926 g/cm³ to 0.941 g/cm³. "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. The term "HDPE" refers to polyethylene having density of 0.940 g/cm³ or greater, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts, or even metallocene catalysts.

Preferably by HDPE it is meant a high-density polyethylene having a density more than 0.935 g/cm³. Still more preferably the HDPE has a density ranging from 0.941 g/cm³ to 0.969 g/cm³ 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 Elite™ AT 6900 from The Dow Chemical Company.

As used herein, "melt index" (I2) is a measure of melt flow rate of a polymer as measured by ASTM D1238 at a temperature of 190°C and a 2.16 kg load. "Melt index'" may also be referred to herein as "l₂" or "melt flow rate”.

The term “film” as used herein refers to single layer or multilayer structure prepared using a blown film process.

The term “laminate" used herein 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.

Flexible laminate tube

According to the first aspect, the present invention provides a flexible laminate tube. The laminate tube preferably refers to the body of the tube including the shoulder.

Preferably 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/cm³ to 0.97 g/cm³. Preferably 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/cm³ to 0.97 g/cm³. Preferably 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.

Preferably the flexible laminate tube comprises a tube body portion comprising multilayer laminate structure, and a tube shoulder comprising a neck portion.

The tube shoulder may be preferably formed along with the tube body. Preferably the tube shoulder may also be made separately and attached to the tube body portion. Alternately the collapsible tube according to the invention preferably has no shoulder. Preferably the shoulder portion may include 55 wt.% to 100 wt.% polyethylene or an ethylene-based polymer. Preferably the shoulder portion may include ethylene vinyl alcohol copolymer, preferably when present the amount of ethylene vinyl alcohol copolymer is no more than 5 wt.%. More preferably the shoulder portion may include more than 60 wt.%, still more preferably from 50 wt.% to 100 wt.% polyethylene or an ethylene- based polymer. Preferably the polyethylene is HDPE. More preferably the shoulder portion is 100% polyethylene or an ethylene-based polymer.

Preferably the HDPE has a density ranging from 0.94 g/cm³ to 0.96 g/cm³ and a melt flow index in the range from 1 to 3. Preferably the tube shoulder may include an inner barrier liner, which is mounted internally in the tube shoulder. Preferably 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. Preferably 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. Preferably 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. Preferably the tube shoulder may include an inner barrier liner, which is mounted internally in the tube shoulder. Preferably 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. Preferably the shoulder portion has a greater rigidity than the tube body portion.

It is preferred that 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.

When the intended application is to make laminate tube which are collapsible, 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. In such cases, 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.

In a usual process for manufacturing the tubes, 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.

Upon manufacturing the tube body, the multilayer laminate is introduced into a device that is provided with a preform with the shape of body and is provided with expansion hubs for the expansion of the film to the desired dimensions. A guiding ensures that rims of the multilayer laminate overlap. The rims are welded together by means of a fully continuous heat welding system.

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.

Multilayer laminate structure

According to the first aspect, 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/cm³ to 0.99 g/cm³. Preferably, the multilayer laminate structure according to the invention have an overall density in the range from 0.94 g/cm³ to 0.99 g/cm³. Preferably the at least one polyethylene is selected from high-density polyethylene (HDPE), medium density polyethylene (MDPE) and combinations thereof.

Preferably 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.

In a further preferred embodiment, the multilayer laminate structure comprises not more than 70 wt.% of at least one polyethylene having a density ranging from 0.94 g/cm³ to 0.97 g/cm³, more preferably no more than 49 wt.%, even more preferably no more than 37 wt.% by weight of the total multilayer laminate structure.

In a preferred aspect, the total HDPE content in the multilayer laminate structure is not more than 70 wt.%, more preferably not more than 49 wt.%, even more preferably not more than 37 wt.% by weight of the total multilayer laminate structure.

Preferably the total HDPE content in the multilayer laminate structure ranges from 10 wt.% to 70wt.%, more preferably from 15 wt.% to 60wt.%, still preferably 20 wt.% to 49 wt.%, further preferably from 20wt.% to 37 wt.% by weight of the total multilayer laminate structure.

More preferably 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.

Preferably the printable layer is free of MDPE. Preferably the printable layer comprises HDPE.

Still preferably 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.

Printable layer

Preferably the multilayer laminate structure comprises a printable layer.

The term "printable layer" used herein refers to a single layered or multilayered film. Preferably the film is a blown film. As used herein, 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.

Preferably the top printable 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 printable layer and the barrier layer of the multilayer laminate structure. The extrusion layer preferably comprises LDPE.

Preferably 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.

More preferably the printable layer comprises a combination of HDPE and LLDPE. Preferably 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.

It is preferred that 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. Preferably when the printable layer is a single layered structure it comprises HDPE and LLDPE. More preferably the single layered structure has a thickness of 50 micrometers to 95 micrometers, preferably from 85 micrometers to 95 micrometers.

It is preferred that the printable layer, in turn, 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. Preferably 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.

It is preferred that 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. Preferably when 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.

Preferably 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. Preferably the LLDPE is selected from LLDPE, mLLDPE or mixtures thereof. Also, preferred are 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.

Most preferably the middle sub-layer comprises HDPE and at least one of LLDPE or LDPE, preferably LLDPE. Preferably the LLDPE is selected from LLDPE, mLLDPE or mixtures thereof.

Preferably the printable layer comprises an inner sub-layer comprising LLDPE or LDPE, preferably LLDPE. Preferably the inner sub-layer may comprise a mixture of HDPE and LLDPE, LDPE or mixture of LLDPE and LDPE. Most preferably the inner sub-layer LLDPE. Preferably the LLDPE is selected from LLDPE, mLLDPE or mixtures thereof.

Preferably the thickness of the printable layer ranges from 5 pm to 105 pm, preferably from 7 pm to 100 pm. Preferably 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.

Preferably 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.

Barrier layer:

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/mm²/day to 1 g/mm²/day or less, still preferably 0 g/mm²/day to 0.63 g/mm²/day, more preferably 0 g/mm²/day to 0.55 g/mm²/day. The WVTR was measured using ASTM F 1249 method. Preferably the WVTR is in a range from 0.1 g/mm²/day to 1 g/mm²/day, preferably from 0.1 g/mm²/day to 0.8 g/mm²/day, preferably a WVTR value of 0.1 g/mm²/day to 0.63 g/mm²/day or less, still preferably ranging from 0.1 g/mm²/day to 0.55 g/mm²/day.

Preferably the barrier layer provides an oxygen transmission rate (OTR) value of 0 to 0.4, preferably from 0 to 0.3, more preferably from 0 to 0.25 cm³/m²/day/1atm. Preferably the oxygen transmission rate (OTR) is in a range from 0.1 to 0.3 still preferably from 0.25 to 0.3 when measured at 23°C and 0% RH. The OTR was measured using ASTM D 3985 method.

It is preferred that 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 ethyl vinyl alcohol as the barrier material. Preferably the barrier layer may include an additional barrier material selected from the group consisting of ethylene vinyl alcohol derivatives, ceramic coating, and mixtures thereof. More preferably the barrier layer comprises ethylene vinyl alcohol and its derivatives. Also preferred are multilayer structure where the barrier layer comprises a combination of ethylene vinyl alcohol and/or its derivatives and a metal layer, preferably where the metal layer is vacuum deposited.

Preferably the barrier layer comprises less than 5 wt.% ethylene vinyl alcohol, still preferably less than 3 wt.% ethylene vinyl alcohol.

Preferably 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. More preferably 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. Preferably 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.

Preferably the barrier layer comprises less than 10 wt.% by weight of the total multilayer laminate structure, still preferably less 7 wt.% by weight of the total multilayer laminate structure, still preferably 6 wt.% or lesser by weight of the total multilayer laminate structure. Preferably the barrier layer comprises 0.5 wt.% to 10 wt.% by weight of the total multilayer laminate structure, still preferably 0.5 wt.% to 7 wt.% by weight of the total multilayer laminate structure, still preferably 0.5 wt.% to 6 wt.% or lesser by weight of the total multilayer laminate structure.

Preferably 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.

Preferably the barrier layer comprises HDPE. More preferably the barrier layer comprises HDPE and at least one of MDPE and LDPE, more preferably HDPE and at least MDPE, also preferably HDPE and both MDPE and LDPE. Preferably the barrier layer is free of LLDPE. By the term free of it is meant that there is no added LLDPE. Preferably the barrier layer comprises from 50 wt.% to 100 wt.% HDPE and up to 50 wt.% of at least one of MDPE and LDPE or both MDPE and LDPE.

Preferably the barrier layer includes at least 3 sub-layers. More preferably the barrier layer includes 3, 5, or 7 sub-layers. Preferably in the barrier layer, the barrier material is sandwiched between the sub-layers, preferably sandwiched between at least two sub-layers. Preferably the barrier layer has a barrier material sub-layer which is sandwiched on at least one side by a sublayer comprising HDPE, still preferably the barrier layer has a barrier material which is sandwiched on both side by a sub-layer comprising HDPE. Preferably the HDPE sub-layer comprises 75% or more HDPE by weight of the sub-layer, still preferably 80 wt.% HDPE, still more preferably 85 wt.% HDPE, still further preferably 90 wt.% HDPE, furthermore preferably 95 wt.% HDPE and most preferably 100 wt.% HDPE.

Preferably the barrier layer is a blown film. Preferably when the barrier layer is a multilayered structure with 3, 5, 7, or more sub-layers it is formed by a blown film process. Preferably the barrier layer has at least one sub-layer comprising HDPE. Preferably the barrier layer has at least one or more layers comprising MDPE.

Preferably, 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.

More preferably the barrier layer is a 7 layered structure. Preferably 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. As may be understood by person skilled, the term ‘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.

Preferably the top sub-layer of the barrier layer comprises MDPE. Preferably 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. Preferably the copolymer has an ethylene monomer which is higher than or equal to 75 wt.%. Also preferred are interpolymer which is a terpolymer of ethylene, acrylic acid, or methacrylic acid and alkyl acrylate. Preferably the interpolymer comprises from 50 wt.% to 98 wt.% ethylene. Preferably the copolymer of ethylene and acrylic acid has a density of more than or equal to 0.925 g/cm³.

Preferably 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. Preferably the barrier material sublayer is sandwiched between two sub-layers. Preferably 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.

More preferably the barrier material sub-layer is sandwiched between a sub-layer comprising HDPE and at least one further sub-layer comprising MDPE or LDPE, more preferably at least MDPE, also preferably both MDPE and LDPE. Preferably the barrier material is sandwiched between two sub-layers comprising HDPE, and two further sub-layers comprising at least one of MDPE and LDPE, more preferably at least MDPE. Preferably the barrier material layer comprises a sub-layer comprising LLDPE. Preferably the barrier material layer is free of LLDPE.

The term ‘sandwiched between’ as used in context of the current invention is not limited to embodiments where sub-layers comprising HDPE should be immediately adjacent to barrier material layer. The term ‘sandwiched between’ in context of the invention is used to imply that the barrier material sub-layer is surrounded by at least one sub-layer comprising HDPE within the barrier layer. For example, the term ‘sandwiched between’ does not necessarily mean that the first intermediate sub-layer and/or second intermediate sub-layer is immediately adjacent the EVOH comprising sub-layer. The first intermediate sub-layer and/or second intermediate sublayer may or may not be immediately adjacent to the EVOH comprising sub-layer. As may be understood by skilled person, 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. Preferably when the barrier layer has a 7 layered structure, preferably the first intermediate sublayer comprises HDPE. Preferably the first tie layer between the first intermediate sub layer and the barrier material sub-layer comprises LDPE and a tie material. Preferably second tie sublayer which lies between the barrier material sub-layer and the second intermediate sub-layer comprises LDPE and tie material. Preferably the second intermediate sub-layer comprises HDPE. Preferably the inner sub-layer comprises MDPE.

Preferably when the barrier layer includes 3 sub-layers, it comprises a primary lamination layer, a middle barrier layer with barrier properties and a secondary lamination layer. Preferably the lamination layers comprise HDPE or MDPE.

Preferably when the multilayered laminate structure may have a single layer which acts as both a barrier layer and the sealant layer. Preferably the structure has an inner layer on the product side and an outer layer facing the external environment and a tie layer there between wherein the inner layer acts as both a barrier layer and sealant layer. Preferably in such a multilayered laminate structure the barrier material may be the innermost sub-layer of the inner layer, preferably the barrier material is a layer of EVOH. The inner layer may include further sublayers comprising HDPE, LLDPE, LDPE, MDPE and mixtures thereof. Preferably the inner layer has a sub-layer of HDPE, LLDPE, LDPE, MDPE where the MDPE sub-layer is in proximity to the EVOH sub-layer. Preferably the tie layer comprises LDPE and preferably the outer layer is printable and preferably comprises HDPE, more preferably a combination of HDPE and LLDPE.

Metallized layer

Preferably the barrier layer may be metalized. Preferably the multilayer laminate structure comprises a metal layer applied to the top sub-layer of the barrier layer. Preferably where 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. Preferably 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. In some embodiments, the metallized layer is formed from aluminum or aluminum oxide (AI2O3). The metallized layer may also include the metalloid silicon or oxides thereof. According to some embodiments, 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.

While various thicknesses are contemplated, 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.

Preferably 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.

When present, the metalized layer may be sandwiched between two layers comprising a copolymer or an interpolymer. Preferably the copolymer includes those comprises a combination of ethylene, and acrylic acid, alkyl acrylate or methacrylic acid. Preferably the copolymer has an ethylene monomer which is higher than or equal to 75 wt.%. Also preferred are interpolymer which is a terpolymer of ethylene, acrylic acid, or methacrylic acid and alkyl acrylate. Preferably the interpolymer comprises from 50 wt.% to 98 wt.% ethylene. Preferably the copolymer of ethylene and acrylic acid has a density of more than or equal to 0.925 g/cm³.

Preferably 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. Preferably the barrier material sub-layer has a thickness ranging from 10 to 13 micrometers.

Preferably the barrier material sub-layer has a thickness ranging from 10 to 11 micrometers.

Preferably 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.

Sealant layer

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. The term "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.

Preferably 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.

Preferably the sealant layer is a blown film. Preferably when the sealant layer is a multilayered structure with 3, 5, 7, or more sub-layers it is formed by a blown film process.

Preferably 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. For example, 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.

Preferably 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.

Preferably the sealant layer may be a multilayered structure. Preferably where the sealant layer comprises a top sealant sub-layer, an intermediate sealant sub-layer and an inner sealant sublayer. The sealant layer may preferably include from about 12% to 55% MDPE based on the total thickness of the sealant layer. The sealant layer may preferably include from 10% to 45% of a HDPE based on the total thickness of the sealant layer. The sealant layer may preferably include from 5% to 22% of a LLDPE based on the total thickness of the sealant layer. The sealant layer may preferably include from 0% to 35% of a LDPE based on the total thickness of the sealant layer.

Preferably the sealant layer is multilayered having 3 to 7 layers. Preferably the sealant layer has a thickness ranging from 40 to 80 micrometers, still preferably from 50 to 60 micrometers.

Tie layer:

Preferably the barrier layer may include one or more tie layer. The term "tie layer” refers to a layer which binds any two layers having dissimilar polarity. Preferably the tie layer may comprise a tie material.

Preferably the tie material comprises modified polyolefin. Preferably the modified polyolefin is based on ethylene polymer or propylene polymers. Preferably the tie material comprises modified polyolefins selected from the group consisting of maleated polyethylene, ethyleneacrylic acid copolymer, ethylene-meth acrylic acid copolymer, anhydride grafted ethylene/1 - butene copolymer, anhydride grafted ethylene/1 -hexene copolymer, polyethylene vinyl acetate copolymer, ethylene methyl acrylate copolymer, anhydride grafted ethylene/1 -octene copolymer maleated polyethylene and maleic anhydride grafted polyethylene. Preferably the tie-material comprises those selected from maleated polyethylene and polyethylene grafted maleic anhydride, still preferably polyethylene grafted maleic anhydride.

Preferably the tie material is selected from the group consisting of maleated polyethylene, a copolymer of ethylene and carboxylic acid or a combination thereof. As used herein, a 'maleated" substance is one which comprises a salt or ester of maleic acid. More preferably the tie layer is a polyethylene grafted maleic anhydride, preferably a maleic anhydride-grafted linear low-density polyethylene. Suitable commercially available examples of polyethylene grafted maleic anhydride include Bynel™ 41E687B from Dow. Preferably the tie layer comprises a tie material and LDPE.

Preferably the tie layer comprises 3 wt.% or less of the polyethylene grafted maleic anhydride.

Extrusion layer:

The term "extrusion layer" refers to a layer through which the blown film are joined together by a molten resin extruded in film shape between two films to form the layers of the multilayer laminate structure. The molten resin acts as a bonding agent. For example, the sealant layer and the barrier layer are attached/laminated through an extrusion layer. Preferably the extrusion layer comprises a polyolefin, a polyolefin copolymer, or combination thereof. Preferably the copolymer is selected from ethylene-acrylic acid polymer. Preferably the extrusion layer comprises a polymer of ethylene or copolymer of ethylene with carboxylic acid, preferably acrylic acid.

Preferably 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. Preferably 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).

Preferably 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.

Preferably 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.

Preferably the extrusion layer has a thickness ranging from 10 micrometers to 30 micrometers, more preferably 15 micrometers to 25 micrometers.

Recycled Polyethylene:

Preferably the flexible laminate tube according to the present invention may include recycled polyethylene. The recyclable tube may preferably comprise at least 50 wt.% HDPE.

Preferably the flexible laminate tube comprises from 15 wt.% to 70 wt.% post-consumer recycled (PCR) polyethylene. Preferably the flexible laminate tube comprises from 30 wt.% to 85 wt.% virgin (PCR) polyethylene.

Preferably 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. Preferably 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.

Preferably the recycled HDPE is added in the middle layer of the barrier layer which is not in direct contact with other layers. Preferably the first intermediate sub-layer and/or the second intermediate sub-layer of the barrier layer comprises recycled HDPE.

It is preferred that 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.

In a preferred embodiment of the present invention, provided is a multi-layered laminate structure comprising:

(i) at least one printable layer;

(ii) a first extrusion layer;

(iii) at least one barrier layer;

(iv) a second extrusion layer; and,

(v) at least one sealant layer.

In a preferred embodiment of the present invention, provided is a 3 layered multilayer laminate structure comprising:

(i) at least one printable layer;

(ii) an extrusion layer; and,

(iii) at least one barrier layer preferably comprising a sealant sub-layer.

Preferably in the multilayer laminate structure according to the first aspect of the present invention an adhesive system is absent. Preferably in the multilayer laminate structure according to the first aspect of the present invention an adhesive system is absent between the top printable layer and the barrier layer. Preferably in the multilayer laminate structure according to the first aspect of the present invention an adhesive system is absent between the barrier layer and the sealant layer.

Preferably the multilayer laminate structure according to the first aspect of the present invention has a thickness ranging from 170 micrometers to 220 micrometers. In yet another preferred embodiment of the present invention 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.

Preferably the top printable layer comprises HDPE and at least one of LDPE or LLDPE, where HDPE content in said layer is 10 to 60 wt.%. Preferably the top printable layer comprises LDPE and LLDPE. Preferably the top printable layer comprises 40 wt.% to 80 wt.% LDPE and 10 wt.% to 30 wt.% LLDPE. Preferably the top printable layer accounts for 10 wt.% to 35 wt.% of total thickness of said laminate. Preferably the top printable layer is free of MDPE. More preferably, the HDPE content in printable layer is 25 wt.% to 60 wt.%.

Preferably 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. Preferably the sealant layer accounts for 10 wt.% to 35 wt.% of total thickness of said laminate.

In one aspect, the sealant layer comprises HDPE wherein the HDPE content in said layer is 5 wt.% to 80 wt.%, preferably 5. to 20 wt.%, more preferably 5 to 15 wt.%, even more preferably 8 wt.% to 12 wt.%.

Preferably the barrier layer comprises HDPE and at least one of MDPE or LDPE, more preferably HDPE and MDPE, still preferably HDPE, MDPE and LDPE. Preferably the barrier layer accounts for 20 wt.% to 60 wt.% of total thickness of said laminate. Preferably 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.

Optional ingredients present in the multilayer laminate structure:

Preferably the multilayered laminated structure may include suitable additives, for example stabilizers, neutralizers, lubricants, or antioxidants. In principle, additives used for polyolefins, such as polyethylene or polypropylene, are also suitable for cycloolefin polymer films. Examples of UV stabilizers which can be used are absorbers, such as hydroxyphenyl benzotriazoles, hydroxy benzophenones, formamidine or benzylidene camphor; quenchers, such as cinnamic esters or nickel chelates; free- radical scavengers, such as sterically hindered phenols, hydroperoxide scavengers, such as nickel or zinc complexes of sulfur-containing compounds, or light stabilizers and mixtures thereof. Examples of suitable lubricants include fatty acids and esters, amides, and salts thereof; silicones or waxes, such as polypropylene or polyethylene waxes. Examples of antioxidants which can be added are free-radical scavengers, such as substituted phenols and aromatic amines, and/or peroxide scavengers, such as phosphites, phosphates and thio compounds.

Additives:

Preferably the multilayer laminate structure according to the present invention includes an additive. Preferably the additive can be selected from a colouring agent, a coloured masterbatch, a TiC>2 masterbatch, a slip agent, an anti-blocking agent, an antifogging agent, a UV barrier additive, and mixtures thereof. Preferably the total amount of the additive ranges from 1 to 20 wt.% of the sublayer.

Preferably the multilayered laminate structure may include a colorant masterbatch. The colorant masterbatch refers to a mixture in which pigments are dispersed or dyes are dissolved, at high concentration, in a carrier material. The colorant masterbatch is used to impart color to the final product. The carrier material may be a polyethylene, more preferably HDPE, LDPE, LLDPE and mixtures thereof. The pigment may preferably be selected from an inorganic pigment, an organic pigment or dye, a polymeric resin, and mixtures thereof. Nonlimiting examples of pigments include titanium dioxide (e.g., rutile, anatase), copper phthalocyanine, antimony oxide, zinc oxide, calcium carbonate, fumed silica, phthalocyamine (e.g., phthalocyamine blue), ultramarine blue, cobalt blue, monoazo pigments, diazo pigments, acid dye, base dye, quinacridone, and/or a mixture thereof.

Process for preparing the multilayer laminate structure:

The process for preparing the multilayered laminate structure as described herein comprises the steps of:

(i) obtaining at least one film by the process comprising: a. melting the at least one polyethylene to obtain a polyethylene melt stream; b. extruding the polyethylene melt in upward stream or downward stream from an annular die to obtain an extruded material; c. inflating the extruded material to obtain blown film bubble; and d. quenching the blown film bubble with chilled water to obtain the film; (ii) obtaining at least one extrusion lamination polymer; and

(iii) laminating at least two films by extruding the extrusion lamination polymer between the at least two films to obtain a multilayered laminate structure.

Extrusion process is one of the processes most widely used to make polyethylene into films, and tubes. For making films, 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.

According to the first aspect of the present invention, provided is a toothpaste composition comprising a flavour.

The term "toothpaste" 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. Flavour:

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. Also preferred are 1-menthyl acetate, ethyl vanillin, heliotropine, 4-cis-heptenal, diacetyl, methyl-para-tert-butyl phenyl acetate and mixtures thereof. Preferably the flavour is in the adsorbed form, encapsulated form, or mixtures thereof.

Also encompassed within flavour herein are 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. 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.

Bicarbonate salt:

Preferably the toothpaste composition comprises 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. Sodium salt

Preferably the toothpaste composition comprises a sodium salt. Preferably the sodium salt is selected from the group consisting of sodium chloride, sodium carbonate and mixtures thereof.

Water

Preferably the toothpaste composition comprises from 15 wt.% to 34.5 wt.% water based on the weight of the toothpaste composition.

In some embodiments 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.

More preferably the toothpaste composition has 5 wt.% to 60 wt.% abrasive. More preferably the toothpaste composition includes a surfactant.

A composition according to the invention will generally contain further ingredients to enhance performance and/or consumer acceptability, in addition to the ingredients specified above.

Abrasive:

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.

Preferably the composition according to the inventio may include one or more particulate abrasive materials selected from but not limited to silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates, hydroxyapatites, trimetaphosphates, insoluble hexametaphosphates, including agglomerated particulate abrasive materials, usually in amounts ranging from 3 wt.% and 60 wt.% by weight of the toothpaste composition.

Preferred toothpaste compositions comprises 10 wt.% to 60 wt.% abrasive, more preferably 30 wt.% to 50 wt.% and most preferably 30 wt.% to 45 wt.% abrasive preferably where the abrasive is a calcium-based abrasive. Preferred toothpaste composition includes a calcium-based abrasive. A particularly preferred abrasive is fine ground natural chalk (FGNC). It is obtained from limestone or marble. FGNC may also be modified chemically or physically by coating during or after milling by heat treatment. Typical coating materials include magnesium stearate and oleate. The morphology of FGNC may also be modified during the milling process by using different milling techniques, for example, ball milling, air-classifier milling or spiral jet milling. FGNC can be used as the sole calcium containing abrasive. However, FGNC can also be used with other calcium containing abrasives to balance the abrasion.

Other preferred calcium-based abrasives include dicalcium phosphate (DCP), calcium pyrophosphate and precipitated calcium carbonate (PCC).

When a combination of calcium-based abrasives is used, it is preferred that FGNC is 35 to 100 %, more preferably 75 to 100 % and especially from 95 to 100 % of the total content of calcium based-abrasive. In such cases, the balance, most preferably, is PCC.

Other 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. Typical examples of suitable low refractive index abrasive silicas (e.g., having an R.l. of between 1.435 and 1.445) are Tixosil 63 and 73 ex Rhone Poulenc; Sident 10 ex Degussa; Zeodent 113 ex Zeofinn; Zeodent 124 ex Huber, Sorbosil AC 77 ex Crosfield Chemicals (having an R.l. of approximately 1.440). The amount of these silicas in the total composition generally ranges from 5 to 60% by weight, usually 5 wt.% to 20 wt.%.

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.%.

In some embodiments, the toothpaste composition may have silica-based abrasive as the only abrasive. Such composition are generally in the gel format.

Surfactant:

Preferably 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. Preferably the surfactant may be selected from the group consisting of anionic surfactant, amphoteric surfactant, nonionic surfactant, or mixtures thereof.

Preferably 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. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl isethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate are examples of anionic surfactant of this type.

Preferred compositions contain 0.25 wt.% to 12 wt.%, more preferably from 0.5 wt.% to 8 wt.%, and most preferably from 1 wt.% to about 6 wt.% anionic surfactants.

Some 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.

Other surfactants like nonionic, amphoteric or zwitterionic surfactants may also be included.

Nonionic surfactants can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkyl- aromatic in nature. Examples of suitable nonionic surfactants include but is not limited to alkyl polyglucoside, poloxamers (sold under trade name PLURONIC®), polyoxyethylene, polyoxyethylene sorbitan esters (sold under trade name TWEENS®), POLYOXYL® 40 hydrogenated castor oil, fatty alcohol ethoxylates, polyethylene oxide condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, ethylene oxide condensates of aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides, and mixtures of such materials. Preferably the alkyl polyglucoside includes those characterized by the formula C_nH2n+iO(C6HioOs)xH wherein n has a value ranging from 12 to 22, more preferably from 12 to 16 and the degree of polymerization (x) ranges from 1 to 20, still preferably from 1 to 10, more preferably from 1 to 2, still more preferably from 1 to 1.4. Preferably the alkyl polyglucoside is incorporated in the toothpaste composition in an amount ranging from 0.1 wt.% to 2 wt.%.

Useful amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical is a straight chain or branched and wherein one of the aliphatic substituent contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxylate, sulfonate, sulfate, phosphate, or phosphonate. Other suitable amphoteric surfactants are betaines, specifically cocam idopropyl betaine. Mixtures of amphoteric surfactants can also be used. Betaines may also be used, a suitable example of which is cocoamidopropyl betaine.

One or more surfactants are optionally present in a total amount of about 0.01 wt.% to about 10 wt. %, more preferably present in an amount ranging from 0.05 wt. % to about 5 wt. %, or from 0.1 wt. % to about 3 wt. % by total weight of the composition.

Foam modulator:

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. 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.%.

Bipolar antimicrobial particle:

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.

Thickening silica:

Preferably the toothpaste composition comprises an inorganic thickening agent. Preferably the inorganic thickening agent includes a thickening silica. Preferably the dentifrice composition comprises from 1 to 6 wt. %; still preferably from 2 to 5 wt. %; still more preferably from furthermore preferably 3 to 5 wt. % thickening silica, based on the total weight of the composition. Examples of thickening silicas which may be used are Zeodent 165, Zeodent 163 and Zeodent 153 (from Huber); Aerosil® 200 and Sident® 22S (from Evonik); Sylodent® 15 and Perkasil® SM 660 (from W.R. Grace & Co.); and Tixocil 43B (From Rhodia).

Preferably 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.

When present, 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. Other preferred 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.

Humectant:

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

70 wt.% humectant. Further preferred compositions have 10 wt.% to 40 wt.%, more particularly

10 wt.% to 20 wt.% humectant by weight of the toothpaste composition.

Preferably when the toothpaste composition is a silica-based gel composition the amount of humectant ranges from 40 wt.% to 70 wt.%, more preferably 40 wt.% to 66 wt.% by weight of the toothpaste composition.

Preferably when the toothpaste composition is a chalk-based composition the amount of humectant ranged from 5 wt.% to 30 wt.%, more preferably 10 wt.% to 25 wt.%, still preferably 10 wt.% to 20 wt.% by weight of the toothpaste composition.

A particularly preferred humectant is sorbitol, generally available as 70% aqueous solution. When the humectant is supplied as a solution in water, for example sorbitol as a 70 weight % solution in water, the amount of humectant is calculated as the active weight of the humectant, e.g. for a composition comprising 25 weight % sorbitol (as 70 weight% aqueous solution), the concentration of humectant is 17.5 weight %.

Other preferred humectants include glycerine, maltitol and xylitol. More preferred toothpastes contain glycerine and sorbitol for a lubricated mouth feel, but their cumulative levels should not exceed the disclosed upper limit.

Binder:

Toothpaste composition preferably includes a binder. Preferred toothpaste compositions have a binder, which lends a good structure to the paste. Cellulosic binders are especially preferred. Preferred cellulosic binders include cellulose ethers, which include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), ethyl hydroxyethyl cellulose (EHEC), carboxymethyl cellulose (CMC), carboxymethylhydroxyethyl cellulose (CMHEC), hydroxypropylhydroxyethyl cellulose (HPHEC), methyl cellulose (MC), methylhydroxypropyl cellulose (MHPC), methylhydroxyethyl cellulose (MHEC), carboxym ethyl methyl cellulose (CMMC), hydrophobically modified carboxymethyl cellulose (HMCMC), hydrophobically modified hydroxyethyl cellulose (HMHEC), hydrophobically modified hydroxypropyl cellulose (HMHPC), hydrophobically modified ethylhydroxyethyl cellulose (HMEHEC), hydrophobically modified carboxymethylhydroxyethyl cellulose (HMCMHEC), hydrophobically modified hydroxypropylhydroxyethyl cellulose (HMHPHEC), hydrophobically modified methyl cellulose (HMMC), hydrophobically modified methylhydroxypropyl cellulose (HMMHPC), hydrophobically modified methylhydroxyethyl cellulose (HMMHEC), and hydrophobically modified carboxymethylmethyl cellulose (HMCMMC).

Other cellulosic binders include cationic hydroxyethyl cellulose (cationic HEC), cationic hydrophobically modified hydroxyethyl cellulose (cationic HMHEC) and microcrystalline cellulose.

A highly preferred binder is Sodium carboxymethyl cellulose (SCMC). Particularly preferred sodium carboxymethyl celluloses include those with degree of substitution of from 0.6 to 1.2, (i.e. for every 10 anhydroglucose units, 6 to 12 hydroxy groups will be substituted with carboxymethyl groups), 0.6 to 0.99, preferably from 0.7 to 0.95.

In addition to, or as a replacement of cellulosic binder, guar gum or its derivatives could be used, however, such binders are less preferred to the cellulosic ones. Such derivatives include carboxymethyl guar (CM guar), hydroxyethyl guar (HE guar), hydroxypropyl guar (HP guar), carboxymethylhydroxypropyl guar (CMHP guar), cationic guar, hydrophobically modified guar (HM guar), hydrophobically modified carboxymethyl guar (HMCM guar), hydrophobically modified hydroxyethyl guar (HMHE guar), hydrophobically modified hydroxypropyl guar (HMHP guar), cationic hydrophobically modified hydroxypropyl guar (cationic HMHP guar), hydrophobically modified carboxymethylhydroxypropyl guar (HMCMHP guar) and hydrophobically modified cationic guar (HM cationic guar).

Other less preferred gums include xanthan gum, carrageenan and derivatives, 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.

Other thickening agents:

Preferred toothpaste compositions may also include one or more other thickening agents such as carboxyvinyl polymers which include carbomers which are commercially available from B. F. Goodrich as the CARBOPOL® series, including CARBOPOL® 934, 940, 941 and 956.

Other preferred grades include acrylates/C -30 alkyl acrylate crosspolymer which are commercially available as ULTREZ® 21 , PEMULEN® TR-1 , and PEMULEN®TR-2, from Noveon Corporation. Preferred compositions can include 0.05 to 10 wt.%, more preferably 0.1 to

5 wt.%, and even more preferably 0.25 to about 4 wt.% of other thickening agents.

Preferably the toothpaste composition may further comprise a preservative agent, such as benzyl alcohol or parabens such as methylparaben and propylparaben. In some embodiments, the preservative is benzyl alcohol. The preservative agent may be present in the composition in an amount of from 0.1 to 1 weight %; 0.2 to 0.5 weight %; or about 0.3 weight %, based on the total weight of the composition.

De-sensitizing agents:

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.%.

Silicate:

Preferred toothpaste compositions can have alkali metal silicate. The alkali metal is sodium or potassium, preferably sodium. Sodium silicate is generally available as 10 to 40 % aqueous solution, most common being 30 % solution. Sodium silicate is available as neutral sodium silicate or alkaline sodium silicate. Preferred toothpastes have neutral sodium silicate. Sodium silicate is available with varying ratios of Na2O: SiC>2.

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.%.

Anti-caries agent:

Preferred compositions can include one or more anti-caries agent. Such agents are typically fluorides.

When used herein, the term “fluoride source” means a source of free fluoride ions and/or monofluorophosphate ions. Non-liming examples of fluoride ion source includes sodium monofluorophosphate, ammonium monofluorophosphate, stannous fluoride, sodium fluoride and ammonium fluoride. Other preferred anti-caries agents include aminefluorides, sodium trimetaphosphate and casein. It is highly preferred that the source of fluoride is an alkali-metal salt of monofluorophosphoric acid, preferably sodium monofluorophosphate (SMFP).

SMFP is the fluoride source of choice when it comes to toothpaste compositions having Calcium based abrasives, especially chalk as sodium fluoride reacts with the calcium carbonate to form insoluble calcium fluoride which has limited anti-caries activity. Preferred compositions include 0.01 wt.% to 2 wt.%, more preferably 0.15 wt.% to 1 wt.% and especially preferably 0.2 wt.% to 0.5 wt.% anti-caries agent. It is preferable to maintain the free fluoride ion concentration from 100 to 2000 ppm, preferably from 900 to 1500 ppm. Other preferred anticaries agents include sodium fluoride and stannous fluoride, aminefluorides, sodium trimetaphosphate and casein and mixtures thereof. Most preferably the source of fluoride is sodium fluoride and sodium monofluorophosphate (SMFP).

Fluoride source may be added to the composition preferably at a level of about 0.001 wt.% percent to about 10 wt.%, e.g., from about 0.003 wt.% to about 5 wt.%, 0.01 wt.% to about 1 wt.%, or about 0.05 wt.%. In some embodiment, the stannous fluoride is present in an amount of 0.1wt.% to 2 wt.% (0.1 wt.% to 0.6 wt.%) of the total composition weight. However, it is to be understood that 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. In some embodiment, 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.%).

Other antibacterial agents:

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).

Preservative:

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.%.

Antioxidant:

Preferred antioxidants are those which are compatible with other components and are not hazardous to health. These include ascorbic acid, ascorbyl palmitate, thiodipropionic acid, calcium ascorbate, dilauryldithiopropionate, gum guaiac, sodium ascorbate, butylated hydroxyl toluene, butylated hydroxyl anisole, and tocopherols. Mixture of antioxidants can be used. When present, the antioxidant is added in a level effective to reduce or mitigate discoloration that would otherwise result from oxidation of the components of the toothpastes. Preferred levels are from 0.01 to 1 wt.%.

Sweetening agent:

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.%.

Bleaching agent:

Preferred toothpastes can include one or more bleaching agents such as peroxy compounds e.g., potassium peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, colour change systems, and chelating agents from 0.001 to 6 wt.%, preferably at from 0.5 to 4 wt.%, which include alkali metal salts of citric acid, alanine, glycine, and serine.

The most preferred are the alkali metal salts of citric acid, especially potassium citrate and most preferably tri-potassium citrate.

Preferred compositions may also include one or more of breath strips, sparkles, large silica particles, granules, beads, and flavour encapsulates for enhanced sensory benefits or for visual appeal.

Colorant:

The composition according to the present invention may comprise at least one colorant.

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.

Titanium dioxide can also be added to the composition for opacity. Titanium dioxide is generally included from 0.25 to 5 wt.%.

Preferably 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.

Preferably the pH of the toothpaste composition when it is silica-abrasive based gel toothpaste composition the pH ranges from 5.5 to 7. Preferably the pH of the toothpaste composition when it is a chalk-base composition the pH ranges from 8.5 to 10 when measured using a 1 wt.% aqueous solution of the toothpaste composition in distilled water and as measured at 25°C using conventional pH sensitive electrodes.

The composition according to the invention may preferably include further ingredients which are common in the art, such as:

• antimicrobial agents, e.g. chlorhexidine, sanguinarine extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; cetylpyridium chloride clay complex bis-guanides, such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2' methylenebis-(4-chloro- 6-bromophenol);

• anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.;

• 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;

• vitamins such as Vitamins A, C, D, B (preferably B3) and E;

• plant extracts; • plant-derivable antioxidants such as flavonoid, catechin, polyphenol, and tannin compounds and mixtures thereof;

• desensitising agents, e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;

• anti-calculus agents, e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and phosphocitrates etc.;

• biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.;

• proteinaceous materials such as collagen;

• preservatives;

• opacifying agents;

• hyaluronic acid;

• amino acids such as arginine;

• colouring agents;

• pH-adjusting agents;

• sweetening agents;

• mouth feel agents

• pharmaceutically acceptable carriers, e.g. starch, sucrose, water, or water/alcohol systems etc.;

• surfactants, such as anionic, nonionic, cationic and zwitterionic or amphoteric surfactants;

• Humectants such as glycerol, sorbitol, propylene glycol, xylitol, lactitol etc.;

• polymeric compounds which can enhance the delivery of active ingredients such as antimicrobial agents can also be included;

• buffers and salts to buffer the pH and ionic strength of the oral care composition; and

• other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium peroxydiphosphate,

• effervescing systems such as sodium bicarbonate/citric acid systems,

• colour change systems, and so on.

According to another aspect of the present invention provided is a use of a packaged product for providing improved flavour impact and/or flavour intensity wherein the toothpaste composition comprises a bicarbonate salt and wherein the toothpaste composition is enclosed in a flexible tube comprising a multilayer laminate structure and wherein the multilayer laminate structure comprises a barrier layer comprising ethyl vinyl alcohol; and, wherein the multilayer laminate structure comprises 45 wt.% to 90 wt.% of at least one polyethylene having a density ranging from 0.91 g/cm³ to 0.99 g/cm³. In accordance with yet another aspect, the present invention provides 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 flavor; wherein the multilayer laminate structure comprises a) a printable layer comprising polyethylene wherein the polyethylene comprises HDPE; b) a sealant layer comprising polyethylene wherein the polyethylene comprises HDPE; c) a barrier layer; d) a first extrusion layer for laminating the barrier layer to the printable layer; and e) a second extrusion layer for laminating the barrier layer to the sealant 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 HDPE.

The invention is further illustrated with reference to the following, non-limiting Examples.

Examples

In the laminate, the abbreviated component identifications have the following meaning.

Example 1 : Evaluation of the flavour performance and stability of a toothpaste composition enclosed in a plastic based laminate tube. Different multilayered laminate structure according to the invention were prepared as provided in table 1 below. The multilayered laminate structure as provided below has a printable layer, a barrier layer, and a sealant layer. Blown film of the printable layer, the barrier layer, and the sealant layer having a structure as provided in table 1 below were taken. In Structure 4, the barrier layer after the blow film process is subjected to a metallization step. In the metallization step, a coating of Al is deposited by vapour deposition. The metallization coating has a thickness of 60 nanometers. The barrier layer and the printable layer were laminated by extruding a film of LDPE between the printable layer and the barrier layer. The sealant layer and the barrier layer were laminated by extruding a film of LDPE between the barrier layer and the sealant layer.

Table 1

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/cm³ to 0.99 g/cm³ and has an ethyl vinyl alcohol barrier layer.

A chalk-based toothpaste composition and a silica-based composition were prepared as provided in table 2 Table 2

The above formulations provided in table 2 were then packaged in two different laminate tube prepared from the multilayer laminate structure 1 (given in table 1 above) and the tubes were stored at 45°C for 3 months, and the flavour impact and profile study and the product stability was studied at regular intervals of 1 month and the data was recorded and provided in table 3 below.

Table 3

The data provided in table 3 shows that when a toothpaste composition is packaged in a flexible tube comprising a multilayered laminate structure with an EVOH barrier layer according to the present invention, the flavour impact and profile is maintained even under adverse storage conditions. The laminate structure according to the present invention shows good flavour impact and profile along with storage stability across different toothpaste composition having silica- based abrasive (Ex 1) and chalk-based abrasive (Ex 2). 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

As seen from table 4 above, the toothpaste compositions when stored in PBL laminate tubes made according to the invention had better stability and lower flavor absorption onto the laminate tubes.

Claims

1. 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, said 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/cm³ to 0.99 g/cm³; and wherein the multi-layer laminate structure comprises at least one extrusion lamination layer.

2. A packaged product according to claim 1 wherein the at least one polyethylene is selected from high-density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and combinations thereof.

3. A packaged product according to claim 1 wherein the multilayer laminate structure comprises a printable layer comprising polyethylene wherein the polyethylene comprises HDPE.

4. A packaged product according to any one of the claims 1 to 3 wherein the multilayer laminate structure comprises a sealant layer comprising polyethylene wherein the polyethylene comprises HDPE.

5. A packaged product according to claim 4 wherein the sealant layer comprises a further polyethylene selected from MDPE, LDPE or LLDPE, more preferably the sealant layer comprises HDPE and MDPE in combination with either LLDPE or LDPE.

6. A packaged product according to any one of claims 1 to 5, wherein the barrier layer is at least a 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.

7. A packaged product according to any one of claims 1 to 6 wherein the first intermediate sub-layer and/or the second intermediate sub-layer comprising HDPE comprises 75% or more HDPE by weight of the sub-layer, more preferably 100 % HDPE by weight of the sub-layer.

8. A packaged product according to any one of the preceding claims wherein the multilayer laminate structure has a thickness ranging from 50 micrometers to 300 micrometers, preferably 60 to 250 micrometers.

9. A packaged product according to any one of the preceding claims wherein the ethylene vinyl alcohol has 20 mol% to less than 38 mol% ethylene, still preferably from 25 mol% to less than 38 mol% ethylene, further preferably from 25 mol% to less than 35 mol% ethylene, still preferably from 29 mol% to less than 35 mol% ethylene.

10. A packaged product according to any one of the preceding claims wherein the barrier material sub-layer comprising ethylene vinyl alcohol has a thickness ranging from 5 micrometers to 15 micrometers, more preferably 6 micrometers to 15 micrometers, 10 to 13 micrometers, more preferably from 10 micrometers to 11 micrometers.

11. A packaged product according to any one of the preceding claims wherein the barrier layer comprises a metal layer, preferably wherein the metal layer has a thickness not more than 100 nanometers.

12. A packaged product according to any one of the preceding claims, wherein total HDPE content in the multilayer laminate structure is not more than 70 wt.%, more preferably not more than 49 wt.%, still preferably not more than 37 wt.% by weight of the total multilayer laminate structure.

13. A packaged product according to any one of the preceding claims wherein the polyethylene comprises a recycled polyethylene, more preferably post-consumer recycled polyethylene, more preferably the recycled polyethylene is HDPE.

14. A packaged product according to any one of the preceding claims wherein the toothpaste composition comprises from 0.1 to 5 wt.%, still preferably from 0.1 to 1.5 wt.% flavour.

15. 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; wherein the multilayer laminate structure comprises a) a printable layer comprising polyethylene wherein the polyethylene comprises HDPE; b) a sealant layer comprising polyethylene wherein the polyethylene comprises HDPE; c) a barrier layer; d) a first extrusion layer for laminating the barrier layer to the printable layer; and e) a second extrusion layer for laminating the barrier layer to the sealant 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 HDPE.