EP3753856B1 - Childproof package unit - Google Patents

Childproof package unit Download PDF

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Publication number
EP3753856B1
EP3753856B1 EP19181379.9A EP19181379A EP3753856B1 EP 3753856 B1 EP3753856 B1 EP 3753856B1 EP 19181379 A EP19181379 A EP 19181379A EP 3753856 B1 EP3753856 B1 EP 3753856B1
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EP
European Patent Office
Prior art keywords
container
acid
cardboard
closure
top surface
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP19181379.9A
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German (de)
English (en)
French (fr)
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EP3753856A1 (en
Inventor
Christine KÖLB
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalli Werke GmbH and Co KG
Original Assignee
Dalli Werke GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalli Werke GmbH and Co KG filed Critical Dalli Werke GmbH and Co KG
Priority to EP19181379.9A priority Critical patent/EP3753856B1/en
Priority to HRP20240021TT priority patent/HRP20240021T1/hr
Priority to PL19181379.9T priority patent/PL3753856T3/pl
Priority to DK19181379.9T priority patent/DK3753856T3/da
Priority to ES19181379T priority patent/ES2968645T3/es
Priority to PT191813799T priority patent/PT3753856T/pt
Publication of EP3753856A1 publication Critical patent/EP3753856A1/en
Application granted granted Critical
Publication of EP3753856B1 publication Critical patent/EP3753856B1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D5/00—Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/42—Details of containers or of foldable or erectable container blanks
    • B65D5/72—Contents-dispensing means
    • B65D5/721—Contents-dispensing means consisting of mobile elements forming part of the containers or attached to the containers
    • B65D5/723—Sliding elements for covering and uncovering discharge openings of containers, e.g. slide-closures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2215/00—Child-proof means
    • B65D2215/02—Child-proof means requiring the combination of simultaneous actions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2215/00—Child-proof means
    • B65D2215/06—Child-proof means based on the difference in size between children's and adults' hands

Definitions

  • the present invention refers to a package unit comprising shaped or granular item(s) and a cardboard container having a childproof closure to avoid that children have undesired access to said item(s).
  • Detergent compositions or water softener compositions commonly comprise a variety of components which are to be avoided to have contact with human skin, eyes or mucosa.
  • pre-portioned quantities of consumer products like e.g. detergent or cleaning compositions to avoid incorrect dosing or unneeded high amounts of said product.
  • pre-dosed portions of detergent compositions commonly are offered in form of a tablet, a pouch, a sachet or similar, wherein said portions may comprise one, but also two, three or more different partial compositions provided as separate layers or regions of a tablet or in separate chambers of a pouch or sachet.
  • FR 1 276 701 A describes a cardboard container wherein one of its faces is pierced with an opening, an independent drawer also pierced with an opening being slidably mounted against the interior side of said face. Thus, by moving the drawer, the container can be opened or closed.
  • DE 89 07 662 U1 describes a container according to the preamble of claim 1.
  • a package unit in accordance with appended claim 1 comprising (i) a cardboard container having an upper top surface (1), a bottom (2) and at least three side surfaces (3), and an upper surface (11), wherein on one of said top (1) or side surfaces (3) a childproof closure (4) is provided, wherein said closure (4) is made of cardboard and is slidely movable between a position closing the container and a position providing an opening (O) allowing the removal, discharge, pouring or taking out of the content of said container, and (ii) shaped or granular items, comprising (a) a detergent or cleaning composition, or (b) a water softener composition.
  • the package container is prepared essentially as a whole from cardboard, paperboard and/or paper.
  • the container is prepared from corrugated cardboard, e.g. single wall double faced corrugated cardboard; or a double wall corrugated cardboard or triple wall corrugated cardboard having paper sheets at least on both outer surfaces ("faced cardboard"), wherein the use of a single wall double faced corrugated cardboard is preferred.
  • face cardboard a double wall corrugated cardboard or triple wall corrugated cardboard having paper sheets at least on both outer surfaces
  • Said cardboard preferably comprises a vapor or moisture barrier layer, preferably "inside” the cardboard, which means that said barrier layer is provided between the both outer surface layers.
  • Said vapor or moisture barrier layer may be a layer provided attached to or applied to one of the surfaces of the paper sheets used for preparation of the corrugated cardboard, wherein said layered surface is then faced to the inner side of the cardboard, or said barrier layer is provided as a separate film, sheet or layer, which is included into the corrugated cardboard during its preparation.
  • a "solid" cardboard may be used, e.g.
  • a cardboard laminate including a vapor or moisture barrier layer sandwiched between two cardboard sheets, between a cardboard and a paper sheet or between two paper sheets, or a cardboard laminate comprising only a cardboard sheet and a barrier layer, however due to the weight, rigidity and comfort the use of corrugated cardboard panels is preferred.
  • the vapor or moisture barrier layer can be provided in form of a film, e.g. a film of a material known in the art for such barrier layers.
  • suitable materials are polyethylene (PE), like high density polyethylene or low density polyethylene; polyethylene terephthalate (PET); polyvinyl alcohol (PVOH); polyvinyl acetate (PVA); polypropylene (PP), polylactic acid (PLA) and/or polyamide (PA), which can be used as single polymers, mixture of polymers or copolymers of the mentioned, wherein PE films are particularly preferred.
  • PE polyethylene
  • PET polyethylene terephthalate
  • PVOH polyvinyl alcohol
  • PVA polyvinyl acetate
  • PP polypropylene
  • PLA polylactic acid
  • PA polyamide
  • an oiled paper may be used as a vapor or moisture barrier sheet.
  • the moisture barrier layer can be provided as a coating on at least one surface of a sheet used for preparation of the cardboard or the package container of the present invention.
  • Such coatings may comprise at least one of: (i) a wax compound, (ii) a surfactant, in particular a surfactant solid 20°C (iii) a polymer, (iv) a triazine-containing compound; (v) a nano-cellulose material; (vi) a nanoclay material; and/or (vii) an inorganic oxide material. Presence of at least one of compounds (i), (ii) or (iii) is preferred
  • the thickness of the barrier film or layer typically ranges from about 5 nanometers to about 100 ⁇ m, preferably from 10 nm to 50 ⁇ m, 20 nm to 25 ⁇ m, 30 nm to 10 ⁇ m, 40 nm to 5 ⁇ m or 50 nm to1 ⁇ m.
  • wax compounds (i) are natural waxes, in particular wax esters or wax alcohols.
  • waxes are lanolin, paraffine, carnauba wax, candelilla wax or bees wax
  • wax alcohols may be represented by cetyl alcohol, carnaubyl alcohol, ceryl alcohol and myricyl alcohol
  • examples of waxy acids are myristinic acid, palmic acid, stearic acid, laurinic acid, lignoceric acid, cerotinic acid, montanic acid and melissic acid, without being restricted to the mentioned.
  • Suitable surfactants (ii) are nonionic or anionic surfactants which are solid at room temperature (defined being 20°C), preferably which are solid up to a temperature of 35°C. Due to their characteristics nonionic surfactants are preferred, in particular fatty alcohols or esters, optionally comprising EO or PO groups. Such surfactants are disclosed in detail below as part of the detergent composition.
  • Suitable polymers (iii) are those as mentioned above for the barrier film and further copolymers including styrene butadiene copolymers, modified styrene butadiene copolymers, styrene/acrylate copolymers, carboxylated polystyrene, acrylic/polyacrylic polymers, polyvinylacetate-ethylene, polyvinyl acrylic polymer, soy protein polymer; corn zein (protein), starch, a polyolefin dispersion (e.g., modified propylene-based dispersion), polyvinylidene chloride, polylactic acid, polyhydroxyalkanoate polymers, polybutylene succinate, plasticized cellulose acetate, and mixtures thereof.
  • styrene butadiene copolymers modified styrene butadiene copolymers, styrene/acrylate copolymers, carboxylated polystyrene, acrylic/polyacrylic poly
  • Triazine compounds (iv) that can be included are 1,3,5-triazines such as melamine, ammeline, ammelide, cyanuric acid, 2-ureidomelamine, melam, melem, melon, melamine salts such as, for example, melamine cyanurate, melamine phosphate, dimelamine pyrophosphate or melamine polyphosphate and functionalized melamines, such as for instance hexamethoxymethyl melamine or acrylate-functionalized melamine.
  • 1,3,5-triazines such as melamine, ammeline, ammelide, cyanuric acid, 2-ureidomelamine, melam, melem, melon, melamine salts such as, for example, melamine cyanurate, melamine phosphate, dimelamine pyrophosphate or melamine polyphosphate and functionalized melamines, such as for instance hexamethoxymethyl melamine or acrylate-
  • the barrier layer may comprise nanocrystalline cellulose which is a uniform, redispersible natural nanoparticle obtained from the crystalline regions of cellulose fibers.
  • the cellulose can be derived from natural cellulose such as wood or wheat straw. Alternatively, the cellulose can be derived from a regenerated source such as rayon or viscose.
  • Exemplary nanocrystalline cellulose is available from CELLUFORCE TM of Montreal, Quebec, Canada.Nanocrystalline cellulose is typically about 100 nm to 200 nm long and is typically about 5 nm to 10 nm in diameter.
  • cellulose is milled and hydrolyzed to remove amorphous regions. The resulting nanocrystalline cellulose is then separated and concentrated before being modified for coating applications.
  • Nanocrystalline cellulose is light weight, biodegradable, non-toxic, cost-efficient, and recyclable.
  • Suitable nanoclay materials include platey kaolins, nanoclays, clay nanocomposite, and polymer-clay nanocomposite structures including hyper-platey, nano-dimensional thickness crystals. Nanoclay materials as described herein can be e.g. dispersed within a polymer-based or water-based matrix.
  • Suitable inorganic oxide materials (vii) that perform as a barrier layer or coating include aluminum oxide (AlOx), silicon oxide (SiOx), and magnesium oxide (MgOx).
  • AlOx aluminum oxide
  • SiOx silicon oxide
  • MgOx magnesium oxide
  • x is a suitable number or fraction for the stoichiometric amount of oxygen (e.g., Al 2 O 3 , SiO 2 , MgO).
  • Such oxide coatings may be prepared using plasma-assisted deposition on a substrate.
  • the thickness of the cardboard (laminate) including the (preferably corrugated) cardboard and the optional vapor/moisture barrier layer preferably should be in the range from 0,5 mm to 3 mm to provide suitable stability to said container, more preferred 0,8 mm to 2,5 mm, even more preferred 1 mm to 2 mm.
  • the cardboard container comprises a top surface (1), a bottom (2) and at least three, preferably at least four side surfaces (3) and a closure (4) slidely movable between a position closing the container and a position providing an opening (O), see FIG. 1 and Fig. 2 .
  • the cardboard container comprises a main container body which is preferably folded from one continuous piece of a cardboard panel, cut in a form allowing the folding into the container main body of the present invention.
  • Said container main body has at least three, preferably four side surfaces (3) an upper surface (11) and a bottom (2).
  • said upper surface (11) comprises a perforation or pre-cut for an opening (O1), which can be removed by pushing it so that opening (O1) is obtained.
  • FIG. 3a an embodiment is shown wherein said container main body has only one flap representing upper surface (11).
  • the main body may have two overlapping flaps (11a, 11b) providing together surface (11), wherein one of it (11a) has said perforation or pre-cut for said opening (O1) and the other one (11b) has a punched hole (12) corresponding in size and position to openings (O) and (O1) ( FIG. 3b ), or is shorter in length ( FIG 4a ) or width ( FIG. 4b ), so that the area below the perforation or pre-cut for said opening (O1) is kept free from container material.
  • Said perforation or pre-cut for opening (O1) serves as a proof for non-use of the package, thus, the consumer can be sure that the package comprises all of and only those items originally filled in by the producer.
  • said main body of the container comprises only one flap representing an upper surface (11) which is not fully spanning the length of the container, so that the area below punched hole (8) / opening (O) of the top surface (1) is free of cardboard material.
  • said main body of the container comprises an upper surface (11) which is not fully spanning the width of the container, so that the area below punched hole (8) / opening (O) of the top surface (1) is free of cardboard material, e.g. surface (11) is provided by two small flaps supporting the closure (4) / top surface (1), however, leaving the area below punched hole (8) / opening (O) free of cardboard material.
  • a "non-use proof" may be realized e.g. by applying a paper strip on top surface (1) spanning at least embossment (6) and punched hole (8).
  • the cardboard container further comprises a top surface (1) having at least two punched holes (8, 9) and further preferably a passage (10) allowing a terminal end (E) of the flat panel (5) of closure (4) to move through said passage (10) in an outward direction to allow movement of the closure (4) ( FIG, 5 ).
  • the punched holes (8, 9) are lying "in-line” in a direction of movement of closure (4), i.e. both punched holes (8, 9) are positioned in the plane area of top surface (1), not on the edges.
  • the cardboard container comprises a closure (4), comprising a flat panel (5) having on one surface at least two embossments (6, 7) which are shaped in a form so that they fit into the punched holes (8, 9) of the top surface (1) to close the container.
  • said flat panel (5) has a front end (F) which is close to embossment (6) and an opposing terminal end (E), which is the end farest away from embossment (6)
  • Said closure is mounted slidably movable below said top surface (1), or "sandwiched" between the upper surface (11) of the main body and top surface (1) in an orientation so that in the "closed " position the embossments (6, 7) fill the punched holes (8, 9).
  • the flat panel (5) preferably includes a stop element (S), e.g. a shoulder, avoiding that said closure (4) is moved / pulled out too far from the container.
  • a stop element e.g. a shoulder
  • the top surface (1) may be an integral part of the continuous panel cut in form of the container main body, however, preferably is an independent panel cut in a suitable shape to fit on top of the container main body and to be fastened in its position. Said top surface panel is preferably applied to the main body in a distance allowing to "sandwich" the closure (4) between surface (11) of the main body and said top surface (1), so that closure (4) after pushing the embossments (6, 7) is slidely movable between said surfaces.
  • At least one of the side surfaces (3) provides at the edge between the upper surface (11) and said side surface (3) at least one suitable small bulge (B) ensuring said distance between said upper surface (11) and said top surface (1) when it is placed and combined with said container main body by means of an adhesive, fixing material or fixing device.
  • all parts of the container of the present invention i.e. said main body, said independent top surface (1) and said closure (4), are made from the same cardboard material. It is, however, also possible to prepare the main body of the container from a cardboard material comprising said moisture barrier, wherein said independent top surface (1) and/or said closure (4) are made of a cardboard panel (having preferably similar thickness and construction), having no moisture barrier included. Due to environment protection and cost advantages the last embodiment might be preferred.
  • the cardboard container punched hole (8) is closed by embossment (6) when the closure (4) is fully inserted into the container, thus lying with its full length directly below surface (1), or between surface (1) and surface (11). This is described as the "closed” position. If the closure (4) is moved laterally in an outward direction, so that its terminal end (E) leaves the container, e.g. by passing through passage (10), said punched hole (8) represents opening (O), which allows the removal, discharge, pouring or taking out of the content comprised in said container.
  • opening (O1) or the perforation / precut for opening (O1) is placed in accordance with opening (O), thus, any content removed, discharged, poured or taken out from the container is passing both openings placed at the similar position.
  • the position where embossment (6) of closure (4) is not engaging with punched hole (8), but leaves said hole open to provide opening (O), is defined as the "open" position.
  • top surface (1) also can be positioned accordingly at any of the “side surfaces (3)", meaning that the closure (4) is not placed on top of the container, but at one of the side surfaces, however, has the equivalent construction.
  • top surface a surface is meant being at the uppermost end of the container when said container is placed (stored) as usual for using it.
  • side surface a surface is meant which is positioned either in front, in back, on the left or on the right side, when the package / container is placed (e.g. for storage) on a surface.
  • the punched holes (8, 9) are spaced apart from each other by a distance (D) of at least 1 cm, preferably at least 1,5 cm, more preferred at least 2 cm, even more preferred at least 2,5 cm, said distance (D) is measured from one border of punched hole (8) to the closest boarder of punched hole (9). Accordingly, embossments (6, 7) are also spaced apart from each other by distance (D).
  • punched hole (8) providing opening (O) in the "open" position of closure (4), has a form and diameter suitably adapted to the size and or form of the content of the package container.
  • the form and diameter of punched hole (8) / opening (O) can be selected either to allow the content, e.g. a shaped item, to fall out unhindered, if the container is turned accordingly, or it might be selected in a way allowing the shaped item to enter opening (O), but not to fall out without some help by the consumer.
  • the punched hole (8) / opening (O) can be formed in a shape so that said pouch has to be turned and/or compressed a little bit to get it out of the opening. This can be a further hurdle for children to have access to the container content.
  • the diameter at the smallest site of punched hole (8) / opening (O) preferably is at least 2 cm, more preferred at least 2,5 cm, even more preferred at least 3 cm, even more preferred at least 3,5 cm or even at least 4 cm or at least 5 cm, in particular if the content of the container is/are shaped item/s). It is, however, preferred according to the invention that punched hole (8) / opening (O) leaves a remainder of the cardboard material between the border of the hole (8) and the edge of top surface (1), said remainder may be represented by at least 0,3 cm, at least 0,5 cm, at least 0,8 cm, at least 1 cm, or at least 1,5 cm of cardboard material between the border of the hole and the edge of top surface (1).
  • the second punched hole (9) may have any form and size allowing to provide pressure on the engaging embossment (7) with at least one finder of a human hand, e.g. 2 to 4 cm at its smallest site.
  • punched hole (8) and embossment (6), or punched hole (9) and embossment (7) independently from each other have a form which can be easily cut by punching tools, thus, a circular, rectangular (optional with rounded corners), square (optional with rounded corners), oval, elliptic or any combination of these forms are preferred.
  • both punched holes (8, 9) are provided in the flat area of top surface (1) leaving a remainder of the cardboard material between the hole and the edge of top surface (1). This means that preferably both punched holes (8, 9) are not positioned at the edge of said surface (1).
  • the container can be opened by a consumer by applying simultaneously pressure to both embossments (6, 7) engaging into punched holes (8, 9) in the "closed” position, and by lateral movement of the closure (4) to one side.
  • the full length of the closure (4) is similar to the length of the top surface (4), one edge between top surface (4) and one side surface (3) preferably should provide a passage (10) allowing the terminal end (E) of the flat panel (5) to leave the container.
  • the terminal end (E) of flat panel (5) protruding from the container when embossments (6, 7) are pressed down and closure (4) is moved laterally can further be used to pull the closure further out to open said opening (O) fully.
  • said closure preferably comprise a shoulder serving as a stop (S).
  • the container may comprise in at least one, preferably in at least two of its bottom flaps positioned at the inner side of the container (2a, 2c, as exemplified in FIG. 8 ) forming said bottom (2) punched holes (13) having any suitable size and form, which (i) don't destabilize said flap (2a or 2c) or bottom (2), (ii) allow to fix said flap (2a) / (2c) to at least one of the other bottom flaps (2b, 2d) and (iii) to provide some space for collecting optionally some fluid or liquid tickling out from any liquid-filled content, e.g. liquid-filled detergent pouches, comprised in the container of the invention.
  • said punched holes (13) each have a length of 50% to 85%, preferably 60% to 80% of the length of the respective flap comprising said hole (13), and a width of 5 to 15% of the width of the respective flap.
  • the package container comprises shaped or granular item(s), selected from (a) detergent or cleaning agents or (b) water softeners.
  • shaped item is meant that the composition is provided in form of a body, e.g. a tablet, capsule, sphere, pellets, beads, or as a pouch or sachet comprising a packaging film and a liquid, gelly, pasty or solid (e.g. in form of a powder, particles, granulate, pressed or sintered) detergent or cleaning composition.
  • Said pouch or sachet can be provided with one compartment or with more than one compartment, wherein each of the compartments independent from each other can comprise a composition in a form as defined above.
  • said pouch or sachet can comprise e.g.
  • a tablet, capsule, sphere, pellet or bead may also comprise different layers or areas, providing optionally different ingredients, e.g. a multi-layer body, a tablet having a mould filled with a solid, gelly or pasty composition or any of the embodiments known in the art commonly used for providing such detergent / cleaning compositions in form of shaped bodies.
  • the content of the package container may be in "granulate form", that means that the composition can be provided as particles having a particle size in the range of from 0,1 mm to 2 mm, e.g. 0,2 to 1,5 mm, but having an "irregular shape", which means that not all the granules have the same size or shape.
  • the detergent or cleaning composition is preferably a laundry cleaning composition or a dishwashing composition, more preferably a laundry or an automatic dishwashing composition.
  • the cleaning composition can be provided in form a pouch comprising a liquid, a gel, a paste a, powder, granulates, particles, including pouches with different compartments comprising combinations of the mentioned, or as a mono-layer tablet, a multi-layer or multiphase (e.g. tab in tab) tablet, a bar or any other suitable form or combinations thereof.
  • the cleaning composition is provided in form of a pouch or a sachet comprising said composition in form a liquid, a gel, a paste a, powder, granulates, particles or combinations thereof or in form of a tablet, a sphere, a pressed, sintered or shaped body or in granulate form.
  • the detergent or cleaning composition is provided in form of a pouch or sachet, it might be provided as a pouch having one compartment, two compartments, three compartments or four compartments, or even having more than four compartments, e.g. five, six, seven or more compartments, without any restriction. It is, however, preferred that said pouch or sachet comprises one to four, preferably two, three or four compartments.
  • Such type of pouches or sachets are known in the art and commonly are prepared by usage of a water-soluble film material, forming the compartment(s) which is/are filled with detergent compositions in liquid, gelly or solid (e.g. particulate, powder or granular) form.
  • the compartments may comprise compositions having differing ingredients, providing together the "whole" detergent composition. Examples of suitable ingredients of the detergent composition are described below.
  • Suitable water-soluble film materials for forming the pouches are well known in the art and include commonly polyvinylalcohol polymer or a polyvinylalcohol copolymer.
  • the preferred material for making the pouch or sachet comprises water-soluble polyvinyl alcohol (including co-polymers thereof), wherein preferably the polymer present in the film is from 60 to 100%, more preferably 80% to 98%, and most preferably 80% to 95% hydrolysed, to improve the dissolution of the material.
  • Suitable co-polymers include monomers of carboxylates, sulphonates and ethoxylates. Itaconic acid, acrylic acid, methacrylic acid are examples of suitable carboxylic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS) is an example of a preferred sulphonic acid.
  • AMPS 2-acrylamido-2-methyl-1-propane sulphonic acid
  • the water-soluble film herein may comprise furter additive ingredients.
  • plasticisers for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, propane diol, sorbitol and mixtures thereof, additional water, disintegrating aids, fillers, anti-foaming agents, emulsifying/dispersing agents, and/or antiblocking agents.
  • the pouch or water-soluble film itself comprises a detergent additive to be delivered to the wash water, for example organic polymeric soil release agents, dispersants or dye transfer inhibitors.
  • the surface of the film of the pouch may be dusted with fine powder to reduce the coefficient of friction.
  • Sodium aluminosilicate, silica, talc and amylose are examples of suitable fine powders.
  • Highly preferred for preparation of the pouches / sachets are polyvinyl alcohol films formed by extrusion, blow-extrusion, blow-molding, extrusion casting or solution casting into a thin film. Such a film is preferably 10 to 200 micrometers thick, more preferably from 40 to 100 micrometers thick.
  • Particularly suitable commercially available films are provided under the tradename MonoSol ® by MonoSol (Kuraray) company.
  • the cleaning composition(s) may comprise any of the ingredients known in the art as common ingredients in cleaning compositions, particularly in laundry or automatic dishwashing compositions.
  • Such ingredients are selected from the group consisting of e.g. builders, surfactants, preferably non-ionic and/or anionic surfactants, polymers/cobuilders, enzymes, complexing agents, bleaching agents, dispersing agents, optical brighteners, stabilizers, colorants, odorants, anti-redeposition agents, anti-corrosion agents, tableting agents, desintegrants, silver protecting agents, dyes, and perfume, without any restriction.
  • the cleaning composition comprises preferably at least one type of a surfactant, preferably non-ionic and/or anionic surfactants, and an alkaline or acid compound and further preferably at least one type of a builder and/or at least one enzyme.
  • ingredients represent examples of ingredients which can be included in a cleaning composition of the present invention, however should not be considered as limited to the mentioned.
  • the cleaning composition comprises one or more surfactants.
  • Said surfactants may be selected from anionic, non-ionic, cationic or amphoteric surfactants, however, are preferably anionic and/or non-ionic.
  • surfactants are changing the surface tension, dispersing, foam controlling and surface modification.
  • Examples of possible surfactant as at least one ingredient can be selected from the group consisting of anionic, cationic, non-ionic as well as amphoteric surfactants, and preferably may be selected from the group consisting of anionic or non-ionic surfactants or mixtures thereof. More preferably, the composition of the present invention comprises a mixture of anionic and non-ionic surfactants.
  • surfactants are present in the composition of the present invention, their total amount preferably may be in the range of from 0,1 to 50 wt.-%, more preferably of from 1 to 30 wt.-%, even more preferably of from 1,5 to 25 wt.-%, even more preferably of from 1,5 to 20 wt.-%, and most preferably of from 1,5 to 15 wt.-%, based on the whole composition.
  • the composition comprises at least one nonionic surfactant and optionally at least one anionic surfactant.
  • Anionic surfactants suitable to be used in cleaning compositions, in particular in combination with enzymes are well known in the state of the art and include for example alkylbenzenesulfonic acids or salts thereof and alkylsulfonic acids or salts thereof.
  • Suitable anionic alkylbenzene sulfonic or alkylsulfonic surfactants include in particular C 5 -C 20 , preferably C 10 -C 16 , even more preferably C 11 -C 13 alkylbenzenesulfonates, in particular linear alkylbenzene sulfonates (LAS), alkylestersulfonates, primary or secondary alkenesulfonates, sulfonated polycarboxylic acids and any mixtures thereof.
  • Alkylethersulfates may be used as well.
  • Non-ionic surfactants are non-ionic, in particular low foaming non-ionic surfactants.
  • Washing or cleaning agents particularly laundry cleaning agents or dishwashing and among this preferably automatic dishwashing compositions, are especially preferred when they comprise non-ionic surfactants from the group of the alkoxylated alcohols.
  • Preferred non-ionic surfactants are alkoxylated, advantageously ethoxylated, particularly primary alcohols preferably containing 8 to 18 carbon atoms and, on average, 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol group may be linear or, preferably, methyl-branched in the 2-position or may contain e.g.
  • EO ethylene oxide
  • alcohol ethoxylates with linear groups from alcohols of natural origin with 6 to 22 carbon atoms, e.g. from coco-, palm-, tallow- or oleyl alcohol, and an average of 2 to 8 EO per mole alcohol.
  • Exemplary preferred ethoxylated alcohols include C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO or 7 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohols with 3 EO and C 12-18 alcohols with 5 EO.
  • the cited degrees of ethoxylation constitute statistically average values that can be a whole or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 100 EO.
  • ethoxylated non-ionic surfactant(s) prepared from C 6-20 monohydroxy alkanols or C 6-20 alkylphenols or C 12-20 fatty alcohols and more than 12 mole, preferably more than 12 mole and especially more than 20 mole ethylene oxide per mole alcohol, are used with particular preference.
  • a particularly preferred non-ionic surfactant is obtained from a straight-chain fatty alcohol containing 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol, and at least 12 moles, preferably at least 15 moles and more preferably at least 20 moles of ethylene oxide.
  • the so-called narrow range ethoxylates are particularly preferred.
  • surfactant(s) that comprise one or more tallow fat alcohols with 20 to 30 EO may be used in combination with a silicone defoamer.
  • a special type of surfactants used in automatic dishwasher cleaning compositions is a 'carry-over' surfactant.
  • a 'carry-over' surfactant has the property that some amount of the surfactant used remains in the machine after the rinsing cycles to give a performance during the final rinsing cycle and the (optional) drying phase of the whole washing cycle of the dishwashing machine. This type of surfactant is described in EP 1 524 313 in more detail.
  • alkoxylated nonionic surfactants and Gemini surfactants are commonly used.
  • the alkoxy groups mostly consist of ethyleneoxide, propyleneoxide and butyleneoxide or combinations thereof.
  • amphoteric surfactants are known to be used in cleaning compositions.
  • alkylpolyglucoside surfactants can also be used, preferably in a low foaming form.
  • surfactants are selected from a group consisting of gemini surfactants with a short C-Chain (C8-C12) as spacer and two times 5-40EO groups as hydrophilic headgroups (e.g. Dehypon GRA, Dehypon E 127, Genapol EC 50, Genapol EC 65) and Long Chain (C12-22) high ethoxylateted (20-100EO) carry over surfactant Lutensol AT Types.
  • surfactants commonly known to be used in cleaning compositions can be part of the composition, this includes all anionic, non-ionic, cationic and amphoteric surfactants known in the art.
  • the present invention is not limited by any of the surfactants commonly used in cleaning compositions.
  • composition of the present invention preferably comprises one or more builder(s).
  • the main functions of the builders are to soften the washing water, to provide alkalinity and a buffering capacity to the washing liquid and to have an anti-redeposition or dispersing function in the cleaning composition.
  • the physical properties of the cleaning composition are also depending on the builders that are used.
  • inorganic as well as organic builders may be incorporated into the composition.
  • these builders may assist in the removal of particulate soil.
  • the builder or the mixture of builders preferably will be present in an amount of from 0,1 to 90 wt.-%, preferably in an amount of from 5 - 80 wt.-%, more preferably in an amount of 8 - 70 wt.-%, and even more preferably in an amount of from 10 - 50 wt.-%, based on the whole composition.
  • the builders in this context are, in particular, the silicates, aluminosilicates, carbonates, sulfates, organic co-builders, and - in cases where no environmental prejudices against their use exist - also the phosphates, which, however, are not preferred.
  • Phosphate builders include alkaline, ammonium or alkanolammonium salts of polyphosphates, including tripolyphosphates, pyrophosphates and polymeric meta-phosphates.
  • the composition of the present invention comprises less than 5 wt.-% of a polyphosphate builder, based on the whole composition.
  • the alkali metal phosphates have the highest importance for the agents according to the present invention, with particular preference for pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) resp. pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the weight proportion of the phosphate in terms of the total weight of the cleaning composition is preferably from 1 to 70 wt.-%, more preferably from 10 to 60 wt.-%, and most preferred from 20 to 50 wt.-%.
  • composition of the present invention may as well comprise an organic builder, including polycarboxylate builders in the form of their acid or a salt, including alkali metal salts such as potassium, sodium and lithium salts.
  • organic builder including polycarboxylate builders in the form of their acid or a salt, including alkali metal salts such as potassium, sodium and lithium salts.
  • the group of preferred builders includes in particular the citrates as well as the carbonates and the organic co-builders.
  • citrate hereby includes both citric acid as well as its salts, in particular its alkali metal salts. These builders are acid or alkaline and thus further can be used for adapting the pH of the composition.
  • Polycarboxylates/polycarboxylic acids and phosphonates may be particularly mentioned as the organic co-builders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, polycarboxylic acids in this context being understood to be carboxylic acids that carry more than one acid function. These include, for example, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA) and mixtures thereof. Besides their building effect, the free acids also typically have the property of an acidifying component and hence also serve to establish a relatively low and mild pH of the inventive agents. Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof are particularly to be mentioned in this regard.
  • Usable organic builder substances are, for example, the polycarboxylic acids usable in the form of the free acid and/or sodium salts thereof, "polycarboxylic acids” being understood as those carboxylic acids that carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, as well as mixtures thereof.
  • the free acids typically also possess, besides their builder effect, the property of an acidifying component, and thus also serve to establish a lower and milder pH for washing or cleaning agents. To be recited in this context are, in particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.
  • Citric acid or salts of citric acid are used with particular preference as a builder substance.
  • a further particularly preferred builder substance is methylglycinediacetic acid (MGDA). According to the invention it is particularly preferred to add MGDA as at least one builder / complexing agent into the composition.
  • MGDA methylglycinediacetic acid
  • Ethylenediamine-N,N'-disuccinate (EDDS might be used, preferably in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • liquid cleaning agents may contain at least one hydrophobically modified polymer, preferably a hydrophobically modified polymer containing carboxylic acid groups, the weight amount of the hydrophobically modified polymer in terms of the total weight of the cleaning agent being preferably 0,1 to 10 wt.-%, preferably between 0,2 and 8,0 wt.-%, and in particular 0,4 to 6,0 wt.-%.
  • polymers having cleaning activity can be contained in the cleaning agent.
  • the weight proportion of the polymers having cleaning activity in terms of the total weight of automatic cleaning agents according to the present invention is preferably from 0,1 to 20 wt.-%, preferably 1,0 to 15 wt.-%, and in particular 2,0 to 12 wt.-%.
  • Suitable polymers are known to those skilled in the art and comprise e.g. polymeric polycarboxylates; these are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight from 500 to 70.000 g/mol or derivatives thereof.
  • the molecular weight indicated for polymeric polycarboxylates are herein weight-average molecular weights Mw of the respective acid form that were determined in principle by means of gel permeation chromatography (GPC), a UV detector having been used. The measurement was performed against an external polyacrylic acid standard that yields realistic molecular weight values because of its structural affinity with the polymers being investigated.
  • GPC gel permeation chromatography
  • Suitable polymers are, in particular, polyacrylates that preferably have a molecular weight from 2.000 to 20.000 g/mol.
  • the short-chain polyacrylates which have molecular weights from 2.000 to 10.000 g/mol and particularly preferably from 3.000 to 5.000 g/mol, may be preferred because of their superior solubility.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid that contain 50 to 90 wt.-% acrylic acid and 50 to 10 wt.-% maleic acid have been found particularly suitable.
  • Their relative molecular weight, based on free acids is equal to in general 2.000 to 70.000 g/mol, preferably 20.000 to 50.000 g/mol, and in particular 30.000 to 40.000 g/mol.
  • Sulfonic acid group-containing polymers in particular those from the group of the copolymeric polysulfonates, are used preferably as polymers having cleaning activity.
  • These copolymeric polysulfonates contain, besides sulfonic acid group-containing monomer(s), at least one monomer from the group of the unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic acid anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof.
  • the unsaturated dicarboxylic acids are of course also usable.
  • Particularly preferred sulfonic acid group-containing monomers in this context are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropylacrylate, 3-sulfopropylmethacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and mixtures of the a
  • the copolymers can also encompass, besides carboxyl group-containing monomers and sulfonic acid group-containing monomers, at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers allows to improve, in particular, the rinsing performance of automatic dishwashing agents.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methlypentene-1, 3-methlypentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3 -dimethylhexene-1,2,4-dimethylhexene-1, 2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as, for example, 1-decene, 1-dodecene, 1-hexadecene, 1-oct
  • the weight proportion of the sulfonic acid group-containing copolymers in terms of the total weight of cleaning agents according to the present invention is preferably from 0,1 to 15 wt.-%, preferably from 1,0 to 12 wt.-%, and in particular from 2,0 to 10 wt.-%.
  • Organic co-builders that may be recited are in particular polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins or further organic co-builders.
  • composition further comprises at least one enzyme
  • enzymes are often used to aid the removal of stains. In most cases enzymes react with the soiling and break it down into pieces that have increased water solubility or are better dispersible in the washing liquid.
  • the enzymes that can be used in cleaning compositions include, but are not limited to, proteases, amylases, lipases, cellulases, mannanase, peroxidase, oxidase, xylanase, pullulanase, glucanase, pectinase, cutinase, hemicellulases, glucoamylases, phospholipases, esterases, keratanases, reductases, phenoloxidases, lipoxygenases, ligninases, tannases, pentosanases, malanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. These enzymes are known to the skilled artisans.
  • Particularly preferred enzymes are selected from a group consisting of amylases, lipases, proteases, cellulases or mixtures thereof, most preferred at least one enzyme is a protease.
  • Each of said enzymes can be added to the composition in an amount of 0,001 to 10 wt.% (referring to pure enzyme), preferably from 0,005 to 5 wt.%, more preferred from 0,01 to 2 wt.%, even more preferred from 0,1 to 1 wt.% of pure enzyme (meaning the active enzyme).
  • the enzyme(s) can be added to the composition in form of granules, e.g. as granulates comprising a binder and the enzyme or the enzyme and any further suitable detergent ingredient.
  • granules at least 2 wt.-% of a granule is represented by the enzyme(s).
  • the enzyme(s) are provided in form of such granules, wherein at least 5 wt.-% of a granule is represented by the enzyme(s), preferably at least 10 wt.-%, more preferred at least 20 wt.-%, even more preferred at least 40 wt.-%.
  • the core of the granules may consist of the enzyme(s) or up to 90 wt.-%, up to 80 wt.-% or up to 70 wt.-% are represented by the enzyme(s).
  • a further preferred ingredient of cleaning compositions is at least one complexing agent.
  • the cleaning composition of the present invention may optionally comprise one or more complexing agent(s) as at least one further ingredient.
  • Complexing agents are commonly used as co-builders to support the performance of the builders.
  • a function of complexing agents is to capture trace metal ions like, Cu(ll), Fe(II), Fe(lll), Mn(ll), Cd(ll), Co(II), Cr(lll), Hg(II), Ni(ll), Pb(ll), Pd(II), Zn(II), Ca(II), Mg(ll)
  • trace metal ions like, Cu(ll), Fe(II), Fe(lll), Mn(ll), Cd(ll), Co(II), Cr(lll), Hg(II), Ni(ll), Pb(ll), Pd(II), Zn(II), Ca(II), Mg(ll)
  • the complexing agent(s) that are known to be used in cleaning compositions include, but are not limited to S,S-ethylenediamine-N,N'-disuccinic acid (S,S-EDDS), ethylenediaminetetraacetic acid (EDTA), diethylene triamine penta(methylene phosphonate) (DETPMP), nitrilotriacetic acid (NTA), ethanol diglycine (EDG), imino disuccinic acid (IDS), methylglycine diacetic acid (MGDA), diethylene triamine pentaacetic acid (DTPA), ethylene diamine dihydroxyphenyl acetic acid (EDDHA), N-(hydroxyethyl) ethylenediamine triacetic acid (HEDTA), hydroxyethylidene-1,1-diphosphonic acid (HEDP), phytic acid, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), aminoethyl ethanol
  • phosphonates are preferred complexing agents.
  • Useful phosphonates encompass, besides 1-hydroxyethane-1,1-diphosphonic acid, a number of different compounds such as, for example, diethylenetriaminepenta(methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • Hydroxyalkane-or aminoalkanephosphonates are preferred in this Application.
  • 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is used preferably as a sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in alkaline fashion (pH 9).
  • Suitable aminoalkanephosphonates are, e.g.
  • EDTMP ethylenediaminetetramethylenephosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • They are used preferably in the form of the neutrally reacting sodium salts, e.g. as a hexasodium salt of EDTMP resp. as a hepta- and octasodium salt of DTPMP.
  • HEDP is preferably used as a builder.
  • the aminoalkanephosphonates moreover possess a pronounced ability to bind heavy metals. It may accordingly be preferred, in particular if the agents also contain bleaches, to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the aforesaid phosphonates.
  • washing- or cleaning compositions that contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates are particularly preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • the cleaning compositions can of course contain two or more different phosphonates.
  • Preferred cleaning compositions may contain at least one complexing agent from the group above in terms of the total weight of the cleaning agent in a range from 0,01 to 8,0 wt.-%, preferably 0,02 to 5,0 wt.-%, and in particular 0,05 to 3,0 wt.-%.
  • Builders and co-builders can generally be added to the composition in acid form, neutralized or in a partly neutralized form.
  • alkali metal salts are preferred, like sodium, potassium and lithium or ammonium salts.
  • composition may comprise a bleaching system
  • Bleaching agents can be used in a cleaning composition either alone or in combination with a bleach activator and/or a bleach catalyst.
  • the function of the bleaching agent is the removal of bleachable stains and to achieve an antibacterial effect on the load and inside of the laundry or the dish washing machine.
  • Bleaching agents that can be used in cleaning compositions include, but are not limited to, active chlorine compounds, inorganic peroxygen compounds and organic peracids. Examples are sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, hydrogen peroxide, hydrogen peroxide-based compounds, persulfates, peroxymonosulphate, peroxodisulphate, ⁇ -phthalimido-perox-caproic acid, benzoyl peroxide, sodium hypochlorite, sodium dichloroisocyanurate, etc. as well as mixtures thereof.
  • at least one bleaching agent is selected from inorganic bleaching agents, preferably from sodium perborate or sodium percarbonate or a mixture thereof.
  • the weight proportion of the bleaching agent in terms of the total weight of the cleaning composition is preferably from 1 to 40 wt.-%, more preferably from 2 to 30 wt.-%, and most preferred from 3 to 20 wt.-%.
  • the composition may further comprise at least one bleach catalyst, preferably a meta containing bleach catalyst that is selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
  • bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-ammine complexes may also be employed as the bleach catalysts.
  • Such catalysts are broadly described in the state of the art and well known by skilled artisans.
  • one type of metal-containing bleach catalyst is disclosed which is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminete
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594 .
  • Preferred examples of theses catalysts include Mn IV 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(PF 6 ) 2 ("MnTACN"), Mn III 2 ( ⁇ O) 1 ( ⁇ -OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 ( ⁇ O) 6 (1,4,7-triazacyclo nonane) 4 -(ClO 4 ) 2 , Mn III Mn IV 4 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 3 , and mixtures thereof.
  • ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, and mixtures thereof and mixtures of pentaamineacetate cobalt (iii) nitrate and MnTACN.
  • Complexes of manganese in the valence state II, III, IV or V which preferably comprise one or a plurality of macrocyclic ligands with the donor functions N, NR, PR, O and/or S are particularly preferably employed.
  • Ligands having nitrogen donor functions are preferably employed.
  • the at least one bleach catalyst from such having a group 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) 1,2,4,7,-tetramethyl-1,4,7-triazacyclo nonane and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN) as the macromolecular ligands.
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Preferred manganese complexes are for example [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV 4( ⁇ -O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -0) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ](PF 6 ) 2 (MnTACN), [Mn IV 2 ( ⁇ -O) 3 (Me/Me-TACN) 2 ](PF 6 ) 2 (OAc
  • At least one metal containing bleach catalyst is MnTACN.
  • the composition may comprise a bleach activator.
  • bleach activator any compound is meant providing the possibility to use a comparatively low temperature to achieve the desired bleaching performance when inorganic peroxygen based bleaching agents are applied.
  • Such a bleach activator reacts with the peroxygen to form an organic peracid.
  • these peracids can have a hydrophobic or a hydrophilic character.
  • bleach activators agents commonly used in cleaning compositions include, but are not limited to, tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzene sulfonate (NOBS), acetyl caprolactone, N-methyl morpholinium acetonitrile and salts thereof, sodium 4-(2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS) and salts thereof, lauryloxybenzylsulfonate (LOBS), iso-lauryloxybenzylsulfonate (I-LOBS), N-methylmorpholinum-acetonitril (MMA), Pentaacetylglucose, Nitrilquats, Benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-clorobenzoylcaprolactam, benzoyloxybenzylsulfonate (BOBS), phenylbenzoate (Ph
  • the composition may optionally comprise one or more dyes as at least one further ingredient.
  • the dye is used to colour the cleaning composition, parts of the composition or speckles in the composition. This might render the product more attractive to the consumer.
  • Dyes that can be used in cleaning compositions include, but are not limited to, Nylosan yellow N-7GL, Sanolin brilliant flavine 8GZ, Sanolin yellow BG, Vitasyn quinoline yellow 70, Vitasyn tartrazine X90, Puricolor yellow AYE23, Basacid yellow 232, Vibracolor yellow AYE17, Simacid Eosine Y, Puricolor red ARE27, Puricolor red ARE14, Vibracolor red ARE18, Vibracolor red ARE52, Vibracolor red SRE3, Basacid red 316, Ponceau SX, Iragon blue DBL86, Sanolin blue EHRL, Sanolin turquoise blue FBL, Basacid blue 750, Iragon blue ABL80, Vitasyn blue AE90, Basacid blue755, Vitasyn patentblue V 8501, Vibracolor green AGR25. These dyes are available at the firms Clariant or BASF.
  • composition of the present invention may optionally comprise one or more perfumes as at least one further ingredient.
  • the perfume is added to the cleaning composition to improve the sensorial properties of the product or of the machine load after cleaning.
  • the perfume can be added to the cleaning composition as a liquid, paste or as a co-granulate with a carrier material for the perfume.
  • a carrier material for the perfume for example, a perfume-cyclodextrine complex.
  • perfumes that have a deodorizing effect can be applied.
  • Such perfumes or raw materials encapsulate malodours by binding to their sulphur groups.
  • the detergent/cleaning composition comprises at least an anionic and/or nonionic surfactant as defined above and an alkaline and/or acid compound, preferably one or more of the builder compounds as cited above, more preferred sodium carbonate and/or sodium bicarbonate as an alkalic compound and/or citric acid or citrate as an acid compound.
  • Typical water softener compositions comprise at least one of the compounds described above as builders, co-builders or complexing agents.
  • the water softener comprisesin addition to optional adjuvants and additives at least one of (a) one or more polycarboxylic acid homopolymer(s) or salt(s) thereof in an amount of 1 to 90 wt.-%, (b) one or more low molecular polycarboxylic acid(s) or salt(s) thereof in an amount of 1 to 90 wt.-%, and/or (c) one or more copolymer(s) based on maleic acid or (meth)acrylic acid or salt(s) thereof in an amount of 0.1 to 25 wt.-%.
  • the one or more comonomer(s) may be selected from the group comprising
  • hydrophobic monomers examples include styrene, methyl styrene, 2-ethylhexyl acrylate, octylacrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl methacrylate, octylmethacrylate, lauryl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl acrylamide, octylacrylamide, lauryl acrylamide, stearyl acrylamide, behenyl acrylamide, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 1-vinyl naphthalene, 2-vinyl naphthalene, 3-methyl styrene, 4-propyl styrene, t-butyl styrene, 4-cyclohe
  • hydrophilic group(s) of the monomer(s) of the maleic acid or (meth)acrylic acid based copolymers give the monomer where it is attached to an increased hydrophilic character.
  • the hydrophilic group(s) is/are typically one or more selected from the group comprising hydroxyl, carboxamide, amine, carboxylate, carboxyl, phosphate, phosphono, phosphino, phosphonate, sulfonyl or sulfo group and the like.
  • hydrophilic monomers with hydrophilic groups are (meth)allyl sulphonic acid, vinyl sulphonic acid, vinyl phosphonic acid, dimethylacrylamide, dimethylaminopropylmethacrylate, diethylaminopropylmethacrylate, vinyl formamide, vinyl acetamide, vinyl pyrrolidone, vinyl imidazole, phenyl (meth)allyl ether sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS), sulphonated styrene, allyloxybenzene sulfonic acid, allyloxy-2-hydroxy propyl sulfonic acid, 2-acryloxypropionic acid or (meth)allyl phosphonic acid, and the like or salts thereof.
  • AMPS 2-acrylamido-2-methyl propane sulfonic acid

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EP19181379.9A 2019-06-19 2019-06-19 Childproof package unit Active EP3753856B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP19181379.9A EP3753856B1 (en) 2019-06-19 2019-06-19 Childproof package unit
HRP20240021TT HRP20240021T1 (hr) 2019-06-19 2019-06-19 Jedinica pakiranja za zaštitu od djece
PL19181379.9T PL3753856T3 (pl) 2019-06-19 2019-06-19 Jednostka opakowania zabezpieczona przed dziećmi
DK19181379.9T DK3753856T3 (da) 2019-06-19 2019-06-19 Børnesikker emballageenhed
ES19181379T ES2968645T3 (es) 2019-06-19 2019-06-19 Unidad de envase a prueba de niños
PT191813799T PT3753856T (pt) 2019-06-19 2019-06-19 Unidade de embalagem de segurança para crianças

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19181379.9A EP3753856B1 (en) 2019-06-19 2019-06-19 Childproof package unit

Publications (2)

Publication Number Publication Date
EP3753856A1 EP3753856A1 (en) 2020-12-23
EP3753856B1 true EP3753856B1 (en) 2023-10-11

Family

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Family Applications (1)

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EP19181379.9A Active EP3753856B1 (en) 2019-06-19 2019-06-19 Childproof package unit

Country Status (6)

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EP (1) EP3753856B1 (da)
DK (1) DK3753856T3 (da)
ES (1) ES2968645T3 (da)
HR (1) HRP20240021T1 (da)
PL (1) PL3753856T3 (da)
PT (1) PT3753856T (da)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112019012235B1 (pt) 2016-12-16 2022-10-18 Nutrition & Biosciences Usa 4, Inc Composição e método para o tratamento de um substrato
PL3907149T3 (pl) 2020-05-08 2022-12-19 The Procter & Gamble Company Pojemnik na produkt detergentowy z blokadą
EP4165154B1 (en) 2020-06-10 2024-05-08 The Procter & Gamble Company A laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative
EP4165156A1 (en) 2020-06-10 2023-04-19 The Procter & Gamble Company A laundry care or dish care composition comprising a poly alpha-1,6-glucan derivative
IT202000014083A1 (it) * 2020-06-12 2021-12-12 Massimo Zafferri Confezione per il contenimento e l’erogazione di prodotti
DE102020005504A1 (de) 2020-06-30 2021-12-30 Brohl Wellpappe Gmbh & Co. Kg Verpackung mit einem Behälter
EP3936450A1 (en) 2020-07-09 2022-01-12 The Procter & Gamble Company Cardboard support element
EP3936451A1 (en) 2020-07-09 2022-01-12 The Procter & Gamble Company Detergent product container
GB2607442A (en) * 2021-05-14 2022-12-07 Unilever Global Ip Ltd Package containing water-soluble capsules
EP4238876A1 (en) 2022-01-14 2023-09-06 The Procter & Gamble Company Process for forming a hood for a tray

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1276701A (fr) * 1960-10-10 1961-11-24 Parisienne Impression Boîte à orifice restreint distributeur
DE8907662U1 (de) * 1989-06-23 1990-10-25 Weidenhammer Packungen KG GmbH & Co, 6832 Hockenheim Verpackungsbehälter
DE4015602A1 (de) * 1990-05-15 1991-11-21 Weidenhammer Packungen Behaelter fuer rieselfaehige produkte, insbesondere haushaltsgrosspackung fuer waschmittel
DE10261535A1 (de) * 2002-12-23 2004-07-15 Henkel Kgaa Verpackungssystem
EP1520908A1 (de) * 2003-10-01 2005-04-06 Dalli-Werke GmbH & Co. KG Maschinengeschirrreiniger mit verbesserten Spüleigenschaften
WO2009000562A1 (de) * 2007-06-22 2008-12-31 Henkel Ag & Co. Kgaa Faltkarton mit verbesserter wasserdampfbarriere

Also Published As

Publication number Publication date
PT3753856T (pt) 2024-01-15
DK3753856T3 (da) 2024-01-08
HRP20240021T1 (hr) 2024-03-29
ES2968645T3 (es) 2024-05-13
EP3753856A1 (en) 2020-12-23
PL3753856T3 (pl) 2024-03-11

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