container

Abstract

A rigid container, wherein the container comprises a rigid shell (1), based on cellulose fibre pulp, provided at its inside with a barrier laminate comprising a first barrier layer (2) and a second barrier layer (3) in the form of parylene layer.

Description

[0001] CONTAINER

[0002] The present invention relates to a rigid paper-based container. The Invention further relates to a method to manufacture said container.

[0003] Background of the invention

[0004] Pulp-based rigid packaging containers are an attractive alternative for petroleum-based containers such as plastic bottles and jars, for example to package consumer goods. Pulpbased containers are based on paper pulp, possibly derived from recycling programs. Paper and cardboard material is transformed into pulp, typically using water, and the pulp is compressed and dried to form a rigid shell. A typical problem observed in the art is that liquid content quickly affects the stability of the pulp-based container, since the liquid swells the cellulose fibers within the pulp, thereby reducing the consistency of the container, and its capacity to hold the liquid content, leading to increased water loss by evaporation and leakage, if not collapse of the container.

[0005] T o overcome this disadvantage, the inner surface of the pulp-based bottles are typically coated. Coating is for example carried out using petroleum-sourced polymers, such as plastics. The use of traditional plastics is increasingly less desired for environmental reasons, because recyclability of the bottles becomes cumbersome, if not impossible, as the coating typically requires a minimum thickness to provide the required protection of the pulp, while recyclability demands a layer that is as thin as possible to meet technical recyclability and to meet legal requirements to qualify as recyclable product.

[0006] US 2022 / 0275165 A1 relates to repulpable and recyclable packaging materials and / or finished packaging structures.

[0007] There is a continuous need to optimize packaging containers, in particular to reduce the use of conventional plastics in pulp-based containers. At the same time, it is desired to increase the barrier properties of the pulp-based containers, to protect the cellulose pulp against moisture from the container content, in particular against aggressive content such as surfactantcontaining materials. It is furthermore desired, that the coating laminate is easily separated from the pulp bottle, to allow the recycling of the pulp and possibly the coating material. Summary of the invention.

[0008] It was surprisingly found that with a container according to the present invention, an improved rigid cellulose pulp-based container could be provided. Accordingly, in a first aspect, the present invention relates to a rigid container, wherein the container comprises a rigid shell (1), based on cellulose fibre pulp, provided at its inside with a barrier laminate comprising:

[0009] • A first barrier layer (2),

[0010] • A second barrier layer (3) in the form of parylene layer.

[0011] In a second aspect, the invention relates to a method for providing a container according to the invention, the method comprising the steps of: a. Providing a rigid cellulose pulp fiber-based container shell (1), b. Providing a barrier laminate at the inside wall of the shell, wherein the barrier laminate comprises

[0012] - a first barrier layer (2) and

[0013] - a second barrier layer (3) in the form of a parylene layer, to result in a container according to the invention.

[0014] In a third aspect, the present invention relates to the use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to improve the barrier property against liquid water.

[0015] In a fourth aspect, the present invention relates to the use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to improve the barrier property against a surfactant, preferably a surfactant comprising product.

[0016] In a fifth aspect, the present invention relates to the use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to enhance recyclability of the pulp based shell, preferably to provide smooth release of part of a barrier laminate comprising the parylene layer (2) from an underlying substrate, more preferably to provide smooth release from an underlying part of the barrier laminate. Detailed description of the invention

[0017] The present invention relates to a rigid packaging container that is based on cellulose fibercomprising pulp, such as paper pulp or cardboard pulp. The cellulose fiber pulp-based container typically is a rigid material. It can typically not be easily bent without damaging the integrity. The container is therefore typically not a flexible product. It accordingly preferably does not comprise a sealing layer, as is often used in flexible laminates, such as in sachets. The rigid container typically has a three-dimensional shape.

[0018] Shell (1)

[0019] The rigid container comprises preferably a total of one, or a total of two, but preferably a total of one layer of cellulose pulp, preferably paper-pulp or cardboard pulp. Paper typically comprises cellulose fibers. The pulp layer forms the pulp-based shell (1) of the container.

[0020] The cellulose fiber pulp-based shell preferably has a grammage of between 200 and 1200 gram / m2(gsm), preferably of between 300 and 800 gram / m2. This provides suitable rigidity to the final container product to comprise a consumer product (5), such as for example a bottle or jar, whereas the container can be suitably transported during manufacturing, filling, and to points of sale. The cellulose fibre pulp-based shell preferably has a thickness of between 0.5 and 5 mm, more preferably of from 0.5 to 3 mm, even more preferably from 0.6 to 2 mm and even more preferably from 0.7 to 1.7 mm. As the skilled person understands, a higher thickness results typically in higher grammage (g / m2).

[0021] In view of the aim of providing a container with less impact on the environment, cellulose fibre pulp, is preferably present in an amount of more than 50 wt%, more preferably more than 70 wt%, even more preferably more than 80 wt% and even more preferably more than 90 wt%, and most preferably more than 95 wt%, based on the weight of the container. Preferably, cellulose fibers constitute more than 50 wt%, more preferably more than 70 wt%, even more preferably more than 80 wt%, even more preferably more than 85 wt%, even more preferably more than 90 wt%, and most preferably more than 95 wt% of the weight of the container. The amount of total non-fibrous material, for example the amount of plastic, is preferably below 20 wt%, preferably below 10 wt%, and more preferably below 5 wt%, based on the weight of the container. It can be for example from 1 to 20 wt%, more preferred from 2 to 10 wt%, or more preferred from 3 to 5 wt%, based on the weight of the container. The total amount of petroleum derived material, for example the amount of petroleum-derived plastic, is preferably below 20 wt%, preferably below 10 wt%, and more preferably below 5 wt%, based on the weight of the container. It can be for example from 1 to 20 wt%, more preferred from 2 to 10 wt%, or more preferred from 3 to 5 wt%, based on the weight of the container.

[0022] It may be preferred, that the cellulose fibre pulp-based shell comprises microfibri Hated cellulose (MFC), for example in an amount of from 0.1 and 10 wt%, preferably from 0.5 to 3 wt%. The use of MFC in the pulp-based shell may contribute to an easier discharge of the product from the container, and more complete discharge of the consumer product from the container, thereby reducing waste. Without willing to be bound to theory, it is believed that the use of MFC in the paper pulp, which was observed to result in a very smooth inner surface (product-facing surface) of the subsequent barrier laminate, may contribute to this effect.

[0023] Barrier laminate

[0024] At the inside wall of the container of the invention, a barrier laminate is provided. The barrier laminate comprises a first barrier layer (2) and a parylene barrier layer (3). It is preferred, that the first barrier layer (2) is positioned ‘upstream’ of the parylene layer (3), i.e. closer to the pulpbased shell, preferably between the shell (1) and the parylene layer (3), and most preferably the first barrier layer (2) is in contact with the shell (1). (The first barrier layer (2) is not a layer of parylene, as is clear from this context). In this way, the first barrier layer (2) effectively may function as a pre-coat. The parylene layer (3) is preferably in contact with and deposited on the first barrier layer (2). The layer on which the parylene is deposited, typically the first barrier layer (2), is preferably not plasma treated. This constellation, wherein the parylene layer (3) is not deposited on the shell (1) but preferably is deposited on an underlying layer, preferably the first barrier layer (2), provided the unexpected advantage that part of the barrier laminate, i.e. the part including and downstream of the parylene layer (3), could be removed relatively easily from the remaining part, e.g. including the first barrier layer (2), of the barrier layer and the shell (1). This is advantageous in recycling processes, wherein part of the barrier laminate is removed from the pulp-based shell, thereby reducing total amount of non-fibrous material in the recycling slurry, and improving the recycling process and resulting recycled pulp material.

[0025] Alternatively, the parylene layer (3) may be positioned upstream of the first barrier layer (2), i.e. closer to the shell (1), and may be applied to be in direct contact with the shell (1). In this case, the first barrier layer (2) may be positioned adjacent to the parylene layer (3). In the context of the present invention, adhesive is less suitable to connect a barrier layer to the shell and preferably is absent from the container of the present invention, preferably absent between the shell (1) and the parylene layer (3) or absent between the shell (1) and the first barrier layer (2). It is a preferred situation that the barrier laminate does not comprise a further layer apart from the first barrier layer (2) and the parylene layer (3).

[0026] The thickness of the barrier laminate, including the first barrier layer (2) and the parylene layer (3) preferably is from 10gsm to 180gsm, more preferably from 30gsm to 120gsm, or 10pm to 150pm, more preferably 30pm to 100pm, or, 1wt% to 40wt%, more preferably, 5wt% to 25wt%

[0027] Parylene layer (3)

[0028] The container of the invention comprises a second barrier in the form of a layer of parylene (3), as part of the barrier laminate provided at the inside of the container.

[0029] Parylene is known in the art. Parylene is the common name of a class of polymers whose backbone consists of para-benzenediyl rings -CeH4- connected by 1 ,2-ethanediyl bridges - CH2-CH2-. Parylenes are obtain through polymerization of vaporized monomers, for instance parylene N can be obtained by polymerization of para-xylylene H2C=C6H4=CH2. Another name for parylene N is poly-(para-xylol).

[0030] Reaction scheme showing pyrolysis of dimer starting reagent to form the para-xylylene monomer which polymerises to form parylene N polymer.

[0031] Repeating unit of parylene N.

[0032] In traditional applications, parylene coatings are applied to electronic circuits and other equipment. They are used in medicine to prevent adverse reactions to implanted devices. Parylene coatings are typically applied by chemical vapor deposition in an atmosphere of the monomer such as para-xylylene.

[0033] Several varieties of parylene can be used in the context of the present invention. Derivatives of parylene can be obtained by replacing hydrogen atoms on the phenyl ring or the aliphatic bridge by other functional groups. Parylene N is the unsubstituted polymer that is obtained by polymerization of the para-xylylene intermediate. Parylene C has one hydrogen atom in the aryl ring replaced by chlorine. Parylene D has two chlorine substitutions on the ring with chorine at the meta position, as known in the art.

[0034] Repeating unit of parylene C

[0035] Parylene AF-4 has the four hydrogen atoms on the aliphatic chain replaced by fluorine atoms. Parylene VT-4 (also called parylene F) has fluorine substituted for the four hydrogens on the aryl ring.

[0036] Specifically, replacement of one hydrogen on the phenyl ring by a methyl group or an ethyl group yields parylene M and parylene E, respectively.

[0037] Another common variant is parylene D, with two such substitutions on the ring.

[0038] Substitution may occur by alkyl groups on either the phenyl ring or the ethylene bridge, or both. Replacement of one hydrogen on the phenyl ring by a methyl group yields parylene M, substitution or an ethyl group yields and parylene E, respectively.

[0039] Parylene M

[0040] Parylene AM2

[0041] Suitably, the parylene used for a layer in the container of the invention is selected from the group consisting of parylene N (poly(p-xylene) or a derivative thereof. Accordingly, the layer is preferably selected from the group consisting of parylene N, parylene C (poly(2-chloro-p- xylene), parylene D, parylene F, parylene AF4, parylene E, parylene M, parylene A, parylene AM2 and mixtures thereof. More preferably, the parylene is selected from the group consisting of parylene N, parylene D or parylene C and mixtures thereof. Even more preferably, the parylene is selected from the group consisting of parylene N or parylene C and mixtures thereof. Most preferably, the parylene is parylene C. It was observed, that in the context of the present invention, parylene N and C showed a particular good resistance to moisture and impact of chemicals when used in cellulose fibre pulp-based rigid container for packaging consumer products.

[0042] The parylene layer (3) has preferably a thickness of between 1 and 100 microns, preferably between 2 and 50 microns, preferably of between 2.5 and 30 microns, most preferably of between 3 and 25 microns, and can for example preferably be from 4 to 20 microns.

[0043] Preferably, the parylene layer (3) has a thickness of between 1 and 100 gsm (grams per square meter), more preferably of between 2 and 80 gsm, even more preferably between 3 and 60 gsm, even more preferably between 5 and 50 gsm, more preferably between 5 and 40 gsm. The thickness may preferably be from 5 to 25 gsm. The latter weight ranges (expressed as gsm) correspond typically with the respective thickness ranges indicated earlier (microns). It is desired, that the grammage of the parylene layer (3) is less than 30 wt%, preferably less than 20 wt%, even more preferably less than15wt%, even more preferably less than 10wt%, even more preferably less than 3wt%, of the total weight of the rigid container. In this manner optimal recyclability of the container is achieved. The grammage of the parylene layer (3) is preferably from 0.5 to 30wt%, more preferably from 1 to 15wt%, even more preferably from 2 to 20wt%, even more preferably from 3 to 15 wt% and even more preferably from 4 to 10wt%, based on the total weight of the container. The amount of polymer other than parylene may be from 1 to 20 wt%, preferably from 1.5 to 10 wt%, more preferably from 2 to 8 wt%, based on the weight of the container. It can be for example from 1 to 20 wt%, more preferred from 1.5 to 10 wt%, or more preferred from 2 to 8 wt%, based on the weight of the container. The barrier laminate, as present at the inside of the container, preferably comprises a total of one parylene layer.

[0044] First barrier layer (2)

[0045] The laminate deposited at the inner wall of the shell (1) comprises a first barrier layer (2). The first barrier layer (2) contributes to provide a consistent surface, which is beneficial in the context of cellulose pulp fiber-based shell. The first barrier layer (2) may, for example, be one or more layers, either with or without a mineral filler, selected from the group consisting of acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), cellulose nitrate, ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), microfibri Hated cellulose (MFC), nanocrystalline cellulose (NCC), native and chemically modified starches, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyisobutylene, poly(butylene succinate-co-adipate) (PBSA), polyesters, polyhydroxyalkanoates (PHA) and their copolymers, polylactic acid (PLA), polyolefins, polyurethanes (Pll), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl dichloride, silanes, styrene acrylate, styrene- butadiene, waxes, or xylan and chemically modified xylan, preferably acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), polyesters, styrene acrylate, styrene-butadiene, and combinations thereof. It is preferably not a parylene layer, as is clear from the above. It is preferred that the barrier laminate, as present at the inside of the container, comprises a total of one first barrier layer.

[0046] The first barrier layer (2) has preferably a grammage of between 5 and 150 gsm, more preferably from 5 to 120 gsm, even more preferably from 5 to 100 gsm and even more preferably from 10 to 50 gsm and even more preferably from 10 to 40 gsm, and even more preferably from 15 to 30 gsm. The first barrier layer is preferably deposited using dispersion coating and can suitably be applied using flow coating or spray coating, as known to the skilled person. It was observed in the present invention, that both a first barrier layer (2) and a parylene barrier layer (3) are relatively poor barrier barriers against water, and show insufficient barrier properties against water, when applied as a barrier layer in a cellulose fiber pulp-based rigid container, especially when used in relatively thin layers e.g. to allow recyclability. Surprisingly, a combination of these materials resulted in excellent barrier properties against water during long-term storage, while allowing recyclability in view of their thickness. This combination of a first barrier layer (2) and a parylene barrier layer (3) preferably has a thickness from 10gsm to 180gsm, more preferably from 30gsm to 120gsm, or 10pm to 150pm, more preferably 30pm to 100pm, or, 1wt% to 40wt%, more preferably, 5wt% to 25wt%.

[0047] It was furthermore observed that typical barrier layers used in combination with rigid cellulose fibre pulp-based shells especially at a thickness that allows for recyclability of the container, showed very poor resistance to surfactant. It was surprisingly observed that the combination of a parylene layer (3) and a first barrier layer (2) resulted in a barrier laminate for a cellulose fibre pulp-based shell (1) that showed sufficiently resistant against surfactant. In this manner, a cellulose fiber pulp-based container can be provided that can comprise a surfactant-comprising consumer product, preferably a liquid surfactant-comprising consumer good, wherein the barrier laminate is as thin as possible and preferably wherein the container still meets requirements for recyclability.

[0048] Third barrier layer (4)

[0049] The barrier laminate may further comprise an additional barrier layer (4), i.e. in addition to a first barrier layer (2) and a parylene layer (3). A third barrier layer (4) is preferably in contact with the parylene layer (3). The third barrier layer (4) is preferably located between the parylene layer (3) and the shell (1), more preferably between the first barrier layer (20) and the parylene layer (3). A third barrier layer (4) is preferably directly adjacent to the parylene layer (3).

[0050] The third barrier layer (4) may comprise a metal or metal oxide layer. The third barrier layer (4) preferably comprises one or more materials selected from the group consisting of aluminum metal, aluminum oxide, zinc oxide, titanium oxide, silicon oxide and combined layers of these. More preferably, the third barrier layer (4) comprises aluminum metal or aluminum oxide, and most preferably is an aluminum oxide layer. It may be preferred that the third barrier layer (4) is aluminum metal or aluminum oxide, preferably in combination with zinc oxide or titanium oxide. The third barrier layer (4), such as preferably the metal or metal oxide layer, may be deposited on the first barrier layer (2) that preferably directly coats the cellulose pulp fiber-based shell (1). The third barrier layer may be deposited using techniques used in the art, such as physical or chemical vapor deposition. In case the third barrier layer (4) comprises multiple materials, such as for example a combination of a metal and a metal oxide or two metal oxides, the layers are deposited on top of each other in layers. The parylene layer may be treated with plasma, preferably at least at the side facing the third barrier layer, if the third barrier layer, such as preferably the metal or metal oxide layer, is deposited adjacent to the parylene layer and not between the parylene layer and the first barrier layer. If it is deposited between the parylene layer and the first barrier layer, a plasma treatment is not required and preferably is absent in that situation. If a metal layer or metal oxide layer is present as third barrier layer (4), it may be preferred, that a further pre-coat layer is present on which the metal or metal oxide is deposited. It is preferred that a total of one third barrier layer (4) is present. In such a case, a single third barrier layer may consist of layers of metal, metal oxide or both. Alternatively, it can be preferred that the single third barrier layer consists only of a single type of metal or a single type of metal oxide.

[0051] The additional barrier layer, i.e. the third barrier layer (4), preferably comprising a metal layer or metal oxide layer, and more preferably being an aluminum layer or an aluminum oxide layer, preferably has a thickness of between 0.01 and 1 micron.

[0052] In a preferred situation, the container of the invention comprises a first barrier layer (2), a metal or metal oxide layer (4), and a parylene layer (3), wherein the parylene layer is parylene N or parylene C. Especially if the parylene layer is parylene N, it may be preferred that a third barrier layer (4), preferably comprising metal or metal oxide, more preferably comprising aluminum or aluminum oxide, is present.

[0053] It can be preferred that no additional barrier layer, i.e. third barrier layer (4) is present, preferably, that no metal or metal oxide layer is present in the barrier laminate provided in the container. It can be preferred that no additional, i.e. third barrier layer, (4) comprising polypropylene, polyethylene, polyethylene terephthalate, with or without metalisation is present. An advantage of the present invention, in the context of the use of a rigid cellulose fiber pulp-based container, is that no third barrier layer, such as a metal layer or metal oxide layer, is needed. The barrier laminate may preferably consist of the first barrier layer (2) and the parylene layer (3).

[0054] It is preferred, that no plasma treated material is present in the container, except for the parylene layer if a third barrier layer comprising metal or metal oxide is deposited on it, more preferably. More preferred, the container does not comprise plasma-treated material. It may be preferred that the shell (1) is not plasma treated. It may be preferred that the parylene layer is not plasma treated. In particularly it may be preferred that the layer on which the parylene is deposited is not plasma-treated. Preferably the second barrier layer (3) is not plasma-treated.

[0055] Ink layer

[0056] The packaging container of the invention is used to protect a consumer product (5). In this respect, it also provides a communication function to the consumers who will buy the consumer products, typically via information printed on the surface of the container facing the consumer, including information regarding ingredients, appealing artwork and advertisement etc. The container therefore preferably comprises a layer of ink (6). This layer of ink is preferably connected to the pulp-based shell (1). It may be preferred that there is a primer applied between the pulp-based shell and the ink layer. Appropriate primers are known to the person skilled in the art, and may, for example, be a polyurethane primer. The layer of ink is preferably in direct connection with the cellulose-pulp-based shell (1) and typically faces the outside of the container, i.e. the site opposite to the site of the container that will be in contact with the consumer product to be packaged.

[0057] Protection layer

[0058] For example, to protect the ink layer (6), the container preferably comprises a protection layer (7) on top of the ink layer. The protection layer is typically facing the outside world. It is typically located opposite to the product-facing site of the container. The protection layer (7) may be an over-print varnish (OPV), OPVs are well-known to the person skilled in the art and the chosen varnish depends on the intended use of the container of the present invention. For example, the OPV may be selected from the group consisting of conventional offset letterpress varnishes, acrylic varnishes, UV varnishes, and gravure varnishes. OPVs can be water-based polymer formulations or solvent-based polymer formulations.

[0059] The protection layer may also be a layer comprising parylene, preferably being parylene C or parylene N. In the latter case, the container comprises more than one layer of parylene and preferably comprises a total of two layers of parylene. A second parylene layer (7) could be preferred, as it provides an additional protection layer to outside influences.

[0060] It might be preferred that a further barrier layer is applied at the outside of the container. This further barrier layer (protection layer) may function as a protection of an ink layer (6). This further barrier layer may preferably comprise a parylene or one or more from the list consisting of acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), cellulose nitrate, ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), microfibri Hated cellulose (MFC), nanocrystalline cellulose (NCC), native and chemically modified starches, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyisobutylene, poly(butylene succinate-co-adipate) (PBSA), polyesters, polyhydroxyalkanoates (PHA) and their copolymers, polylactic acid (PLA), polyolefins, polyurethanes (Pll), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl dichloride, silanes, styrene acrylate, styrenebutadiene, waxes, or xylan and chemically modified xylan, preferably acrylic acid, ethyleneacrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), polyesters, styrene acrylate, styrene-butadiene, and combinations thereof.

[0061] The protection layer (7) typically is deposited directly on the ink layer (6), it is preferably in direct contact with the ink layer. The protection layer, e.g. a second parylene layer, faces the outside of the container, typically the site opposite to the site that is intended to face or faces the consumer product to be packaged.

[0062] The thickness of the protection layer (7), preferably of the second parylene layer, is preferably between 1 and 30 microns, preferably of between 5 and 15 microns.

[0063] Preferred product

[0064] A preferred product according to the invention is a rigid container, wherein the container comprises a rigid shell (1), based on cellulose fibre pulp, having a thickness of from 500 to 5000 microns, and a grammage of between 200 and 1200 gs,m and provided at its inside with a barrier laminate comprising:

[0065] • A first barrier layer (2), having a grammage of between 5 and 150 gsm, wherein the first barrier layer (2) comprises one or more from the list consisting of acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), cellulose nitrate, ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), microfibri Hated cellulose (MFC), nanocrystalline cellulose (NCC), native and chemically modified starches, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyisobutylene, poly(butylene succinate-co-adipate) (PBSA), polyesters, polyhydroxyalkanoates (PHA) and their copolymers, polylactic acid (PLA), polyolefins, polyurethanes (Pll), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl dichloride, silanes, styrene acrylate, styrene-butadiene, waxes, or xylan and chemically modified xylan, preferably acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), polyesters, styrene acrylate, styrene-butadiene, and combinations thereof; • A second barrier layer (3) in the form of parylene layer, having a thickness of between 1 and 100 microns, wherein the parylene layer comprises parylene which is selected from the group consisting of parylene N, parylene C (poly(2-chloro-p-xylene), parylene D, parylene F, parylene AF4, parylene E, parylene M, parylene A, parylene AM2 and mixtures thereof, More preferably, the parylene is selected from the group consisting of parylene N, parylene D or parylene C and mixtures thereof and more preferably wherein the parylene layer comprises parylene N, parylene C, or a mixture thereof; wherein the first barrier layer is positioned between the shell (1) and the second barrier layer (3).

[0066] Packaged consumer product

[0067] In a further aspect, the invention relates to the container of the invention containing a consumer product. The container may be in the form of a bottle, jar, box, tray, refill pod, pot, tube, preferably in the form of a bottle or jar. Typical consumer products that can be packaged in the container of the invention are preferably selected from the group consisting of frozen confectionary, bouillon, soup, sauces, coffee, tea, supplements, vitamins, electrolyte powders, laundry detergents, home cleaning products, skin cleansing products, skin care products, personal care products (e.g. deodorant or body lotion) and haircare products. In particular it is preferred if the consumer product comprises a surfactant, such as for example if the consumer product is a detergent product, such as a liquid laundry detergent, or a skin cleansing product, such as a shower gel or soap bar, a skin or personal care product, such as a body lotion, shampoo or toothpaste. The surfactant is preferably selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof. Most preferably the consumer product comprises an anionic surfactant.

[0068] Process

[0069] In a further aspect, the present invention relates to a process to provide the rigid container according to the invention. The process comprises the steps of: a. Providing a rigid cellulose pulp fiber-based container shell (1), b. Providing a barrier laminate at the inside wall of the shell, wherein the barrier laminate comprises

[0070] - a first barrier layer (2) and

[0071] - a second barrier layer (3) in the form of a parylene layer, to result in a container according to the invention. In step a) a rigid shell based on cellulose pulp (1) is provided. Cellulose pulp shells can be produced via wet or dry moulding processes and are commercially available.

[0072] In step b) a barrier laminate is provided at the inside of the shell (1).

[0073] Deposition of first barrier layer (2)

[0074] The provision of the barrier layer comprises the application of a first barrier layer (2). The first barrier layer typically is provided to the pulp-based shell. The first barrier layer is suitably applied by coating techniques known in the art, such as e.g. dispersion coating, and by using different coaters as known in the art. Various coating methods can be used, such as flow and spray coating, which are commonly used to apply a thin layer of material to which the solvent is evaporated. Evaporation of solvent can be effectuated by several methods, such as infra-red dryers, air float dryers and impingement dryers. Coating is carried out to preferably obtain a first barrier layer (2) of preferably between 1 and 130 micron, more preferably 5 and 100 micron, and most preferably 10 and 50 micron. In gsm this is represented as preferably from 5 to 150 gsm, more preferably, 5 to 100 gsm, and most preferably 10 to 50 gsm.

[0075] Deposition of the parylene layer (3)

[0076] The shell is positioned into a deposition chamber, also called coating chamber. The process is essentially illustrated in Figure 1. The shell (1) can be coated with one or more other layers before it is brought into the coating chamber, and preferably has been coated with the first barrier layer (2).

[0077] Once in the deposition chamber, typically an atmosphere is created of a parylene monomer. The parylene monomer is preferably selected from the group consisting of para-xylylene (i.e, the monomer for parylene N), the monomer of parylene C, the monomer of parylene D, the monomer of parylene E, the monomer of parylene F, the monomer of parylene AF-4, the monomer of parylene M, or the monomer of parylene AM-2. It is preferred, that the parylene monomer is selected from the group consisting of para-xylylene (i.e, the monomer for parylene N), the monomer of parylene C, the monomer of parylene D, even more preferably from the group consisting of para-xylylene (i.e, the monomer for parylene N) and the monomer of parylene C, and most preferably the monomer is the monomer for parylene C. This atmosphere is typically created by vaporizing a raw material, i.e. a dimer molecule, for example dichloro[2,2]paracyclophane for parylene C, 2,2-paracyclophane for parylene N, octafluor[2.2]paracyclophane for parylene F (AF-4), as the skilled person is aware. This is typically done in a sublimation process at a temperature typically of between 150 and 175 °C and typically in a vaporizer, that may be connected to the coating chamber. The dimer vapour is heated high enough to trigger pyrolysis, typically at a temperature between 650 and 690 °C, typically in a pyrolysis furnace that is connected to the coating chamber. In this respect, for example, the vaporizer feeds into the pyrolysis furnace, and the latter feeds into the coating chamber. During pyrolysis the dimer splits to form two monomer molecules, each with two, highly reactive, carbon-centered free radicals. This reactive monomer vapour then enters the coating chamber, which is held at room temperature, typically at a pressure of 30-50 Torr (39999.7 - 6666.1 Pa).

[0078] Accordingly, the step of applying a parylene layer, preferably comprises the steps of:

[0079] - providing an atmosphere comprising parylene monomer in vapour form, preferably para-xylylene, i.e, the monomer for parylene N, or a monomer of parylene C, a monomer of parylene D, a monomer of parylene E, a monomer of parylene F, a monomer of parylene AF-4, a monomer of parylene M, or a monomer of parylene AM-2, and allowing monomer of parylene to deposit on a substrate, preferably on the first barrier layer (2) or shell (1), more preferably on the first barrier layer (20, and to polymerize, to form a second barrier layer in the form of a parylene layer (3).

[0080] In these steps, the parylene monomer in vapour form is allowed to deposit on the shell (1) or on the first barrier layer (2), wherein the latter is preferred. This is typically achieved by decreasing the temperature below the deposition temperature of the respective monomers. Deposition typically occurs by reducing the temperature below 60°C. Preferably, the temperature is above the polymerization temperature of the parylene, and the temperature is preferably brought to between -30 and 60 °C, preferably between 0 and 30 °C, most preferably between 5 and 25 °C. If a third barrier layer (4) is present, it can be preferred that the parylene layer (3) is deposited on the third barrier layer (4).

[0081] The pressure during polymerization is preferably of from 0.3 to 0.5 Torr, which translates to a pressure of from 40.0 - 66.6 Pa.

[0082] Excess parylene is typically captured in a cold trap. A pump, such as a vacuum pump, connected to the coating chamber, typically removes the air and other gasses from the coating chamber, and thereby allows parylene deposition, preferably on the first barrier layer (2). The parylene coating process may include masking part of the container, e.g. the outside, to prevent the parylene coating all surfaces, for example, masking the outside of the container to get an inside deposition.

[0083] The thickness of the parylene layer can be controlled by the deposition time, wherein longer deposition results in a thicker coating. Typically, a deposition time is used of from 12 to 48 hours, more preferably of from 12 to 17 hours, to achieve for example parylene layers of between 0.5 and 100 microns, preferably 1 and 100, more preferably between 2 and 80 microns, preferably of between 2 and 50 micron, most preferably of between 5 and 40 micron. Or the thickness could preferably be from 2.5 to 30 micron, more preferably from 3 to 20 micron.

[0084] The parylene layer preferably is from 1 to 100, preferably from 2 to 80 more preferably from 3 to 70 even more preferably from 5 to 50, even more preferably from 5 to 40 gsm, even more preferably from 5 to 25, or even more preferably from 5 to 20 gsm.

[0085] Plasma treatment

[0086] If plasma treatment is carried out, it may be preferred to apply an Ar / C>2 plasma. Suitably, the charge of the plasma treatment is from 15 to 100 seem of Argon and Oxygen. The power is preferably from 150 to 500 Watts. The exposure time is preferably of from 1 to 4 minutes. It is preferred that the process does not comprise a step of plasma treatment.

[0087] Deposition of an additional barrier layer

[0088] An additional, third barrier layer (4) may be applied by deposition techniques as known in the art, such as for example physical vapour deposition (PVD), chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD). It may be preferred that the process does not comprise the step of applying a third barrier layer (4).

[0089] Use

[0090] Using a parylene layer enables a much thinner / lighter cellulose pulp-based barrier system, when compared to traditional plastic coated systems (e.g. PE), that still provides a water vapour transmission rate measured at 23°C and 50% RH that is preferably below 25, more preferably below 10 and optimally below 1 g / m2 / day. The barrier laminate preferably has an oxygen transmission rate at 23 °C and at 50 RH of below 25, preferably 10, more preferably below 5 and more preferably of below 1 and most preferably of below 0.5 cc / m2 / day. The relatively higher fiber content, compared to existing containers not according to the present invention, enhances their recyclability. Accordingly, the present invention relates to the use of parylene in a rigid cellulose pulp--based container to provide barrier property. Preferably, the barrier property is against influence from one or more of moisture (such as liquid water, or water vapor), oxygen, fat, salt, alkaloid, acid, fragrance, flavours, and mixtures of these, preferably of liquid water or oxygen. It may be preferred that the barrier property is protection against moisture wherein the water vapour transmission rate measured at 23°C and 50% RH is below 40, preferably below 30 and optimally below 10 g / m2 / day, or the WVTR is measured at 25 °C and at 50 RH below and is below 15, preferably below 10 and most preferably below 5, or wherein both apply. It can be preferred that the barrier property is protection against oxygen, wherein the barrier laminate has an oxygen transmission rate at 25 °C and at 50 RH of below 25, preferably 10, more preferably below 5 and more preferably of below 1 and most preferably of below 0.5 cc / m2 / day.

[0091] It was surprisingly observed, that parylene was suitable to enhance the barrier property of a barrier laminate applied inside a cellulose fiber pulp-based shell (1) against liquid water. In particular, it was observed, that barrier properties against surfactants-comprising products, e.g. surfactant -comprising liquid products was enhanced.

[0092] The invention accordingly relates in a further aspect to the use of a parylene layer (3) in a barrier laminate comprising a first barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell of a rigid container, to improve the barrier property against liquid water.

[0093] The invention relates in a further aspect to the use of a parylene layer (3) in a barrier laminate comprising a first barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell of a rigid container, to improve the barrier property against a surfactant, preferably a surfactant comprising product, more preferably a surfactant comprising liquid product. The surfactant preferably comprises one or more of an anionic, a non-ionic, or a zwitterionic or amphoteric or cationic surfactant, preferably an anionic surfactant.

[0094] It was furthermore observed, that the parylene layer (3) could be removed from the underlying layer, e.g. a first barrier layer (2), with relative ease. The invention therefore further relates to the use of a parylene layer (3) in a barrier laminate comprising a first barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell of a rigid container, to enhance recyclability of the pulp based shell, more in particular to provide smooth release of part of a barrier laminate comprising the parylene layer (3) from an underlying substrate, preferably from an underlying part of the barrier laminate. The presence of a first barrier layer (2) provided easy removal of the parylene layer in the context of a barrier laminate provided at the inside of a rigid cellulose pulp-based shell of a container.

[0095] The invention is now exemplified by the following, non-limiting examples:

[0096] Examples

[0097] Example 1

[0098] Wet-molded bottle shells manufactured from cellulose-pulp were used with a thickness of the wall of 1000-micron. The shells were coated at the inside surface using flow coating technique. In some bottles a coating (first barrier layer) of 20 micron of REEF™1 from Cellucomp was applied (comparative example A), which is an acrylic polymer with curran (an MFC). In other shells, a parylene C coating (second barrier layer) was applied with a thickness of the coating of 50 micron (comparative example B). In other shells first a pre-coat (20 gsm) Cellucomp REEF™ 1 (first barrier layer) was applied followed by a 40 micron parylene C coating (second barrier layer).

[0099] The bottles were filled with water. The bottles then were subjected to a storage test at 23 °C at a humidity of 50% RH. After 12 weeks the weight decrease of the bottles was measured, which reflects the migration of water from the bottle content through the shell.

[0100] Results were as follows:

[0101] Table 1 . Loss of water after 12 weeks storage for shells coated with different barrier layers.

[0102] The test indicates that a (pre-)coating of Cellucomp REEF™ resulted in a weight decrease of 3.5wt%, indicating that a Cellucomp REEF™ 1 coating on its own is not sufficient to block water (liquid and vapour) migration, thereby weakening the pulp texture of the shell. A parylene coating C did not result in proper barrier properties as well, resulting in even higher water (liquid and vapour) migration levels (7.4%). A combination of both a precoat layer and parylene C proved to provide optimal barrier properties to the water. It was surprising that the barrier property against water could be restored by combination with a parylene layer, which itself showed very poor barrier properties against liquid water when applied to a pulp shell, since the behaviour and barrier properties of combinations of barrier layers typically is unpredictable.

[0103] Example 2

[0104] Jars prepared from paper-pulp (wet moulded) were provided with different barrier coating layers (first barrier layer) known from the art, using flow coating, as depicted in the table 2. The coatings were applied to produce a smooth barrier coating, at minimum thickness to achieve full coverage of the jar fibre surface, as dictated by the coating viscosity.

[0105] Samples were tested under the following conditions: ambient: 23°C and 50%RH and elevated 37°C and 70% RH to resemble ambient and extreme conditions across Europe, North America, etc.

[0106] The jars were filled with body lotion (Vaseline Advanced Repair Body Lotion, Unilever) containing surfactants (Stearic acid, glycol stearate, PEG-100 stearate, glyceryl stearate, cetyle alcohol) and water, amongst other ingredients. The jars were stored for 12 weeks at 23°C / 50%RH and 37°C / 70%RH °.

[0107] Table 2. Content reduction from pulp-based jars coated with different barrier layers.

[0108] As is clear from table 2, a parylene coating is the only coating that shows acceptable barrier properties against surfactant, even in the presence of water. It is found that a barrier laminate applied to the inner surface of a cellulose fiber pulp-based shell, wherein the barrier laminate comprises parylene and another barrier layer (first barrier layer (2)) provides good barrier properties against surfactant-comprising products. Example 3

[0109] The bottles used in example 1 were filled with a surfactant-comprising (15-30% anionic surfactant. 5-15% Nonionic surfactants), laundry detergent (Persil non-Bio™, from Unilever). The bottles were subject to 12 weeks of storage at @ 23°C / 50RH. Results are depicted in Table 3.

[0110] Table 3. Weight reduction in bottles filled with water (Example 1) and filled with laundry detergent upon 12 weeks storage.

[0111] The test shows a surprising resistance of parylene against surfactant and a combination of parylene with a first barrier layer provides optimal resistance against water and surfactantcomprising products contained in the pulp-based bottle.

[0112] Example 4

[0113] The pulp-based bottles from example 1 , coated with a pre-coat of a dispersion coating (Reef™ 1) and a parylene layer on top of it, were tested to remove part of the barrier laminate. The bottles were cut in half and the parylene was removed by pulling out the layer. The parylene layer (3) easily separated from the pre-coat (first barrier layer (2)). This exemplifies that a barrier laminate comprising a layer of parylene and possibly any subsequent downstream layers is easily removed from the barrier layer on which the parylene is applied. This leaves a pulp-based shell with only one barrier layer behind that is easily recycled. A bottle without the first barrier layer (2), did not result in easy separation of the parylene layer from the shell. Example 5

[0114] A container according to the present invention, can for example be built up from the following layers:

Claims

Claims1. A rigid container, wherein the container comprises a rigid shell (1), based on cellulose fibre pulp, having a thickness of from 500 to 5000 microns, and provided at its inside with a barrier laminate comprising:• A first barrier layer (2), having a grammage of between 5 and 150 gsm;* A second barrier layer (3) in the form of parylene layer, having a thickness of between 1 and 100 microns; wherein the first barrier layer is positioned between the shell (1) and the second barrier layer (3).

2. The container according to claim 1, wherein the shell (1) has a thickness of from 500 to 3000 microns, preferably from 600 to 2000 microns and more preferably from 600 and 1700 micron.

3. The container according to any one of the preceding claims, wherein the shell (1) has a grammage of between 200 and 1200 gsm, preferably between 300 and 800 gsm.

4. The container according to any one of the preceding claims, wherein the parylene layer comprises parylene which is selected from the group consisting of parylene N, parylene C (poly(2-chloro-p-xylene), parylene D, parylene F, parylene AF4, parylene E, parylene M, parylene A, parylene AM2 and mixtures thereof.

5. The container according to any one of the preceding claims, wherein the parylene layer comprises parylene N, parylene C, or a mixture thereof.

6. The container according to any one of the preceding claims, wherein the parylene layer has a thickness of between 2 and 50 microns.

7. The container according to anyone of the preceding claims, wherein the first barrier layer (2) comprises one or more from the list consisting of acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), cellulose nitrate, ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), microfibri Hated cellulose (MFC), nanocrystalline cellulose (NCC), native and chemically modified starches, polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polyisobutylene, poly(butylene succinate-co-adipate) (PBSA), polyesters, polyhydroxyalkanoates (PHA) and their copolymers, polylactic acid (PLA), polyolefins,polyurethanes (Pll), polyvinyl acetate (PVAc), polyvinyl alcohol (PVOH), polyvinyl dichloride, silanes, styrene acrylate, styrene-butadiene, waxes, or xylan and chemically modified xylan, preferably acrylic acid, ethylene-acrylic or methacrylic acid copolymers, butenediol vinyl alcohol copolymers (BVOH), ethyl-vinyl acetates, ethylene vinyl alcohol (EVOH), polyesters, styrene acrylate, styrene-butadiene, and combinations thereof.

8. The container according to anyone of the preceding claims, wherein the first barrier layer has a grammage of 10 to 50 gsm, more preferably from 15 to 30 gsm.

9. The container according to anyone of the preceding claims, wherein the grammage of the parylene layer (3) is less than 30 wt% preferably less than 20 wt%, preferably less than 15wt%, preferably less than 10w%, more preferably less than 3wt% of the total grammage of the container.

10. The container according to anyone of the preceding claims, wherein the container further comprises a further barrier layer applied at the outside of the container, preferably in the form of a parylene layer.

11. A combination of a container and a consumer product, wherein the combination comprises a container according to anyone of the preceding claims, and the consumer product is a liquid surfactant-comprising consumer product (5), preferably a liquid laundry detergent product or a liquid personal care product, and wherein the consumer product is contained in the container.

12. A method for providing a container according to the invention, the method comprising the steps of: a. Providing a rigid cellulose pulp fiber-based container shell (1), having a thickness of from 500 to 5000 microns, b. Providing a barrier laminate at the inside wall of the shell, wherein the barrier laminate comprises- a first barrier layer (2) having a grammage of between 5 and 150 gsm; and- a second barrier layer (3) in the form of a parylene layer, having a thickness of between 1 and 100 microns; wherein the first barrier layer is positioned between the shell (1) and the second barrier layer (3); to result in a container according to the invention.

13. Use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to improve the barrier property against liquid water.

14. Use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to improve the barrier property against a surfactant comprising product, preferably an aqueous surfactant comprising consumer product.

15. Use of a parylene layer (3) in a barrier laminate comprising a further barrier layer (2), wherein the barrier laminate is provided on the inside of a cellulose fiber pulp-based shell (1) of a rigid container, to enhance recyclability of the pulp based shell, preferably to provide smooth release of part of a barrier laminate comprising the parylene layer (3) from an underlying substrate, more preferably to provide smooth release form from an underlying part of the barrier laminate.

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