EP3945977A1 - Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene - Google Patents
Process for manufacturing multi-layer substrates comprising sandwich layers and polyethyleneInfo
- Publication number
- EP3945977A1 EP3945977A1 EP20782489.7A EP20782489A EP3945977A1 EP 3945977 A1 EP3945977 A1 EP 3945977A1 EP 20782489 A EP20782489 A EP 20782489A EP 3945977 A1 EP3945977 A1 EP 3945977A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- thermoplastic material
- fibers
- layers
- thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
- A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
- A47L13/16—Cloths; Pads; Sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/06—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/022—Mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0223—Vinyl resin fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/06—Vegetal fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
Definitions
- the present invention relates to methods for manufacturing cleaning wipes, more particularly to pre-moistened cleaning wipes that are formed from multi-layer substrates.
- the present invention relates methods of manufacturing wipes that may typically be pre-moistened during manufacture or use, where the wipe includes a multi layer substrate comprising at least three layers, where the wipe as a whole may include a significant fraction of pulp fibers, and where such can be achieved in a relatively simple, high speed (350 meter per minute (mpm) or more), low capital investment process, where the process does not employ loose pulp fibers within the process, does not require use of process water to aid in maneuvering fibers (pulp or otherwise present in any of the layers) along the plane of the wipe or through the thickness of the wipe, does not require a drying step to remove such process water, does not require use of chemical binders to achieve bonding between the three layers, and which facilitates use of synthetic fibers (e.g., staple or continuous synthetic fibers) having particular properties, for the middle layer of the multi-layer substrate without the fibers of the middle layer protruding through the external surface of either the top or bottom layers.
- synthetic fibers e.g., staple or continuous synthetic fibers
- An embodiment may be directed to a method for manufacturing a multi-layer substrate, including providing both top and bottom surface layers, e.g., both comprised of pulp fibers, providing a thermoplastic material that comprises polyethylene and/or has a tan delta value of 0.2 to 0.4 within the temperature range of 100°F to 350°F, positioning the thermoplastic material so as to be sandwiched between the top and bottom surface layers, and heating the thermoplastic material to a temperature at which the thermoplastic material heat softens. During such heating there may also be application of pressure to the sandwich structure.
- thermoplastic material includes pores therethrough, providing a fluid pathway therethrough such that any liquid loaded into the top surface layer is able to pass through the pathway, into the bottom surface layer.
- the thermoplastic layer may initially have been an initially liquid impervious film layer, prior to the heating and bonding portion of the process.
- the multi-layer substrate can be loaded with a cleaning composition, e.g., by applying the cleaning composition to the top and/or bottom surface layer(s). Because of the fluid pathway, fluid communication is possible from one surface layer to the other, through the fluid pathway in the thermoplastic film layer.
- the multi-layer substrate may be void of any chemical adhesives for holding the plurality of layers together.
- Binders may technically be present in tissue paper or other pulp layers (e.g., in relatively small amounts) because such binders are frequently used as processing aids in processing pulp material layers, although the purpose of such included materials, like kymene, is to impart strength to the pulp fiber structures (better holding such fibers together, in the fixed web), rather than for any purpose of actually adhering a layer of pulp material to a thermoplastic material layer. Instead, the melted thermoplastic material bonds to groups of fibers (e.g., pulp fibers) in the top and bottom layers that were in contact with the thermoplastic material as it melted.
- the referenced tan delta value is defined as the ratio of viscous modulus divided by elastic modulus. It therefore provides information relative to the ratio of a material’s viscous liquid phase stiffness or flow characteristics relative to the material’s solid phase stiffness characteristics. Different polymeric materials exhibit different tan delta characteristics, and this ratio also varies for a given material with temperature. Polyethylene is an exemplary material that exhibits a tan delta value in a range of 0.2 to 0.4 within the temperature range of 100°F to 350°F. Other polymeric materials (e.g., polypropylene) do not necessarily exhibit such characteristics.
- thermoplastic“sandwich” layer that effectively bonds to the exterior nonwoven layers both above and below the thermoplastic inner“sandwich” layer, while at the same time opening up fluid pathways through the thermoplastic layer, allowing liquids (e.g., a cleaning composition) to flow between the top and bottom layers, through the thermoplastic layer.
- Another embodiment is directed to a method of manufacturing a multi-layer substrate, comprising providing top and bottom surface layers in which fibers of each surface layer comprise at least 95% by weight pulp fibers, providing a thermoplastic material that comprises polyethylene or has a tan delta value of 0.2 to 0.4 within the temperature range of 100°F to 350°F, positioning the thermoplastic material so as to be sandwiched between the top and bottom surface layers, creating a sandwich structure having at least 3 layers, and applying a calendaring process to the sandwich structure by heating the sandwich structure to a temperature at which the thermoplastic material melt softens, while applying pressure during such heating.
- thermoplastic material After calendaring, the thermoplastic material includes open pores through the thermoplastic material, providing a fluid pathway therethrough such that any liquid loaded into the top surface layer is able to pass through the pathway to the bottom surface layer.
- the 3-layer multi-layer substrate is loaded with a cleaning composition.
- Figures 1A-1D show schematic views of exemplary multi-layer substrate textures with various dot patterns.
- Figure IE is a photograph showing 4 different exemplary multi-layer substrate textures that were actually formed, each with differently sized unbonded raised texture features (i.e., raised dots).
- Figure 2 is an SEM image of the top surface of an exemplary multi-layer substrate, showing two adjacent unbonded raised regions, with the bonded region extending there-between.
- Figure 3 shows an SEM image of an cross-sectional or edge view through an exemplary multi-layer substrate such as that of Figure 2, showing the top surface layer, the bottom surface layer, and the thermoplastic film layer sandwiched there-between, where there are both bonded regions, and regions in which the thermoplastic layer and the adjacent exterior surface layer are unbonded relative to one another.
- Figure 4 is a chart showing elastic modulus and tan delta values versus temperature for polyethylene, polypropylene, and for a polymer comprised of “bicomponent” core/sheath type fibers, i.e., a (“bico”) polymer.
- Figures 5A-5B illustrate various exemplary wipes packages, showing how the present multi-layer substrate wipes can be pulled through a typical wipe pack orifice, without significant shredding of the exterior layers, even where such layers are pulp fiber layers.
- Figure 6 is an SEM image showing spunbond thermoplastic fibers enveloping adjacent pulp fibers of the adjacent top surface layer.
- Figures 7A-7F illustrate additional exemplary textures and patterns that could be applied during calendaring.
- FIG. 8 schematically illustrates an exemplary calendaring process by which the thermoplastic layer having particular tan delta characteristics is melt softened, bonding it to the adjacent exterior surface layers in multi-layer substrates according to the present invention.
- Figure 9A illustrates images comparing a conventional 1 -sided texture (top of Figure 9A), to a two-sided textured substrate (bottom of Figure 9A).
- Figures 9B-9C illustrate profilometer data for the“bumpy” face and the“other” face of a substrate without two-sided texturing.
- Figures 9D-9E illustrate profilometer data for the first and second faces of a substrate with two-sided texturing (both are“bumpy”).
- Figures 9F-9I illustrate additional profilometer data for the tested comparative one-sided versus two-sided textured samples.
- phrase‘free of or similar phrases if used herein means that the composition or article comprises 0% of the stated component, that is, the component has not been intentionally added. However, it will be appreciated that such components may incidentally form thereafter, under some circumstances, or such component may be incidentally present, e.g., as an incidental contaminant.
- compositions or articles described herein may be free or substantially free from any specific components not mentioned within this specification.
- “disposable” is used in its ordinary' sense to mean an article that is disposed or discarded after a limited number of usage events, preferably less than 25, more preferably less than about 10, and most preferably after a single usage event.
- the wipes disclosed herein are typically disposable.
- the term“substrate” is intended to include any material that is used to clean an article or a surface.
- cleaning substrates include, but are not limited to, wipes, mitts, pads, or a single sheet of material which is used to clean a surface by hand or a sheet of material which can be attached to a cleaning implement, such as a floor mop, handle, or a hand held cleaning tool, such as a toilet cleaning device.
- a cleaning implement such as a floor mop, handle, or a hand held cleaning tool, such as a toilet cleaning device.
- the term “substrate” is also intended to include any material that is used for personal cleansing applications. These substrates can be used for hard surface, soft surface, and personal care applications. Such substrates may typically be in the form of a wipe.
- the substrates contemplated herein are made up of at least 3 individual, distinct layers, which are bonded together in the described calendaring process.
- Each layer of the substrate may be formed from individual fibers which are interlaid, typically in a manner that is not identifiable, similar to a nonwoven. Woven layers are also possible. Films, which may not necessarily be fibrous (e.g., for the middle thermoplastic layer) may also be possible (e.g., a cast or blown film that does not necessarily include fibers)
- the top and bottom surface layers included in the present substrates may be formed by any suitable process, typically through wetlaying, although airlaying may also be possible. Where the exterior surface layers are formed of pulp fibers, wetlaid and airlaid exterior surface layers may be typical.
- the layer(s) could be meltblown, spunbond, spunlaid, SMS (spunbond-meltblown-spunbond), coformed, carded webs, thermal bonded, thermoformed, spunlace, hydroentangled, needled, or chemically bonded.
- SMS spunbond-meltblown-spunbond
- Pulp fibers may generally be ribbon-shaped, rather than the generally circular cross section seen with synthetic fibers.
- Examples of synthetic fibers often used in forming nonwoven layers and that could be used in multi-layer wipes (e.g., as exterior surface layers) include, but are not limited to, polypropylene, PLA, PET, PVC, polyacrylics, polyvinyl acetates, polyvinyl alcohols, polyamides, polystyrenes, or the like.
- Polyethylene or other thermoplastic polymers having the desired tan delta characteristics may be useful as the interior thermoplastic material layer.
- PLA e.g., a spunbond PLA nonwoven layer, a PLA film, etc.
- PLA is an example of another material that may also be suitable for use in one or more of the layers, including as a thermoplastic layer having the desired tan delta properties.
- thermoplastic interior layer may be provided as a synthetic nonwoven, formed according to any desired process.
- the thermoplastic layer may also be a“cast” film, e.g., rather than being comprised of fibers.
- Such layer could alternatively comprise loose fibers of a material having the desired tan delta characteristics, where a layer of such loose fibers are placed on one of the exterior layers, covered with the other exterior layer, and then processed as described herein. Structured nonwoven fixed fiber forms that do not involve use of loose fibers may be preferred. Avoiding the use of loose pulp fibers in the exterior surface layers (using structured fixed fiber forms) is particularly beneficial.
- the basis weight of any of the layers of the substrate may be expressed in grams per square meter (gsm). Basis weight may sometimes also be expressed in“pounds” (e.g., referring to lbs/3000 ft 2 of the sheet material).
- the substrates as a whole may have basis weight values from 30-80 gsm.
- wiping refers to any shearing action that the wipe undergoes while in contact with a target surface. This includes hand or body motion, substrate- implement motion over a surface, or any perturbation of the substrate via energy sources such as ultrasound, mechanical vibration, electromagnetism, and so forth.
- the cleaning compositions dosed onto the substrate as described herein may provide sanitization, disinfection, or sterilization, other cleaning, or other treatment.
- sanitize shall mean the reduction of“target” contaminants in the inanimate environment to levels considered safe according to public health ordinance, or that reduces a“target” bacterial population by significant numbers where public health requirements have not been established.
- an at least 99% reduction in bacterial population within a 24 hour time period is deemed “significant.” Greater levels of reduction (e.g., 99.9%, 99.99%, etc.) are possible, as are faster treatment times (e.g., within 10 minutes, within 5 minutes, within 4 minutes, within 3 minutes, within 2 minutes, or within 1 minute), when sanitizing or disinfecting.
- the term "disinfect” shall mean the elimination of many or all “target” pathogenic microorganisms on surfaces with the exception of bacterial endospores.
- the term "sterilize” shall mean the complete elimination or destruction of all forms of “target” microbial life and which is authorized under the applicable regulatory laws to make legal claims as a "sterilant” or to have sterilizing properties or qualities.
- Some embodiments may provide for at least a 2 or more log reduction (e.g., 3 -log reduction, or 6-log reduction) in a bacterial population within a designated time period (e.g., 10 minutes, 5 minutes, 4 minutes, 3 minutes, 1 minute, 30 seconds, 10 seconds or the like).
- a 2-log reduction is equivalent to a 99% reduction
- a 3- log reduction is equivalent to at least a 99.9% reduction
- a 4-log reduction is equivalent to at least a 99.99% reduction
- a 5-log reduction is equivalent to at least a 99.999% reduction, etc.
- An example of a target microbe may be Staphylococcus aureus. It will be appreciated that microefficacy can also be achieved against other target microbes, numerous examples of which will be apparent to those of skill in the art. It will also be appreciated that the present cleaning compositions need not include an antimicrobial agent, where sanitization or disinfection is not necessarily desired.
- “texture” refers to the character or appearance of a substrate as determined by the arrangement and thickness of its constituent fibers.
- texture can be quantified using imaging techniques and/or caliper measurements at the local and macro scales, as described in Applicant’s Application Serial No. 16/042,690, filed July 23, 2018 (Docket No. 510.174), herein incorporated by reference in its entirety .
- “patterns” are typically visual, with areas of discernable contrast.
- “Texture” is typically tactile, and relates to variations relative to the normal plane of the substrate (i.e., 3 -dimensional texture in the substrate). Visual pattern and tactile texture interact in a complex manner with a user’s visual/tactile sense of sight and touch to produce a given aesthetic perception for a given substrate, in addition to other quantifiable technical characteristics associated with such.
- the present invention is directed to methods for manufacturing multi-layer substrates including at least 3 layers.
- the exterior faces of the wipe are provided by structured plant based fibers (fixed fibers, rather than loose fibers), such as structured, fixed wood pulp fibers (e.g., tissue paper).
- structured plant based fibers fixed fibers, rather than loose fibers
- structured, fixed wood pulp fibers e.g., tissue paper
- tissue paper e.g., tissue paper
- Synthetic exterior layers such as meltblown, spunbond, spunlaid, SMS (spunbond-meltblown-spunbond), coform, carded webs, thermal bonded, thermoformed, spunlace, hydroentangled, needled, or chemically bonded fibers may also be suitable for processing according to the present methods, e.g., as described in Applicant’s Application bearing Clorox Docket No. 510.186. Configurations based on tissue exterior layers re described in Applicant’s Application bearing Clorox Docket No. 510.188, each of which is herein incorporated by reference in its entirety.
- An interior “sandwich” layer comprising a thermoplastic material (e.g., different from the exterior layers) is provided, between the tissue or other pulp layers (or other top and bottom exterior layers), which adheres the entire multi-layer substrate together in a single mass, with low risk of delamination, while providing desired characteristics relative to hand-feel, stiffness, and absorbency (ability to load the substrate to a desired loading ratio with a cleaning composition), while also providing a fluid pathway through the thermoplastic layer through which the cleaning composition can migrate from the top surface layer, to the bottom surface layer, or vice versa.
- a thermoplastic material e.g., different from the exterior layers
- the melt softened thermoplastic material encapsulates, envelops, wraps, or otherwise coats individual adjacent fibers of the exterior surface layer, providing a strong bond between the two adjacent layers, such that delamination does not readily occur. Even if a synthetic fiber were used in the exterior layers, the fibers of the exterior surface layers may provide differing characteristics, such that they do not melt soften in the same way the interior sandwich layer does, at the given processing conditions.
- thermoplastic sandwich“cheese” layer typically does not penetrate through the exterior“bread” surface layers, so that none of the melt softened thermoplastic material with specific tan delta characteristics is on the exposed exterior faces of the wipe.
- relatively softer (e.g., pulp) fibers are used for wiping and cleaning versus contact with harder more abrasive synthetic melt softened fibers.
- the wipe may thus be less harsh on the surfaces being treated so as to reduce risk of undesirable mechanical scratching, abrasion, or erosion.
- Such multi-layer substrates may be formed through a thermal and pressure calendaring process in which the top and bottom layers are provided preformed (e.g., the tissue or other layers are provided preformed, with the fibers already in a structure, fixed form, as a structured sheet, such as a nonwoven), and a thermoplastic material comprising polyethylene or another polymer having suitable tan delta values is also provided.
- the thermoplastic material may also be in the form of a structured sheet (e.g., also a nonwoven, as a cast film, etc.), or may even be provided as loose fibers that are positioned onto a face of the bottom exterior layer, covered by the top exterior layer, and then calendared.
- the layers may be assembled, e.g., with the tissue or other exterior layers as “bread” sandwiching the thermoplastic film layer (as“cheese”) therebetween, followed by subjecting the assembly to heat (and typically pressure) at a temperature and time period that melt softens the thermoplastic material.
- This heating may open up pores through the thermoplastic material, even if it was provided as a liquid impervious film layer prior to the treatment.
- Heat softening of the thermoplastic material also causes it to wrap around or otherwise coat and envelop the adjacent fibers of the top and bottom surface layers, effectively tying the adjacent layers to one another, without any chemical adhesive to prevent the layers from delaminating or pulling apart from one another.
- thermoplastic film layer As mentioned, at the same time that this layer bonding occurs, any liquid impervious film characteristics that may have previously existed with respect to the interior thermoplastic layer are broken, so that a fluid pathway is created through the thermoplastic layer, through which a cleaning composition or other liquids applied to either the top or bottom layer can penetrate from one surface layer to the other surface layer, through the thermoplastic film layer.
- a desired cleaning composition may be loaded onto the multi-layer substrate. Because of the presence of the fluid pathway, even if the cleaning composition is loaded as a liquid into only one of the top or bottom layers, it will flow through the substrate to the other exterior layer through the broken thermoplastic layer.
- Figures 1A-1D illustrate exemplary wipes lOOa-lOOd, each with a different applied surface texture and bonding pattern, but where each is configured as a multi-layer substrate including a melted thermoplastic layer sandwiched between top and bottom pulp fiber or other exterior surface layers. While shown with various textures, it will be appreciated that numerous other textures could be provided, or perhaps no texture at all. Additional exemplary textures are shown in Figures 7A-7F.
- Figure IE shows photographs of 4 exemplary multi-layer wipes lOOa-lOOd that were actually manufactured for evaluation.
- Figure 2 shows a close up of one of the raised ridges 102 of an exemplary wipe, showing how the raised circular ridge 102 (a“dot”) is unbonded to the thermoplastic film layer disposed therebelow, such that there is actually a gap there-between, at the ridge 102.
- the region 104 surrounding the raised ridge 102 is bonded (and is so labeled) to the underlying thermoplastic film layer disposed therebelow.
- the bonded region 104 may be contiguous, as shown (i.e., there is a single contiguous bonded region, rather than multiple bonded regions that are fully separated from one another).
- the bonded region 104 may thus be contiguous, even though it does not cover the entire top exterior face (or bottom exterior face) of the wipe, because there are spaced apart unbonded regions 102.
- the unbonded regions may be configured as“islands” in a“sea” of the bonded region. It will be appreciated that other configurations are of course possible.
- the texture may be an embossed texture that is applied during the thermal calendaring or other manufacturing operation that laminates the 3 layers of the “sandwich” structure together.
- the texture could have been introduced into the substrate structure as a result of the geometry used in the forming screen used during the tissue making process, when depositing the pulp fibers that make up the tissue or other exterior surface layer(s).
- FIG. 3 is an SEM image of an end or cross-section through an exemplary multi-layer substrate, such as that of Figure 2, showing the thermoplastic film layer 106 (labeled“Bico”) sandwiched between a through-air-dried (“TAD”) pulp fiber top surface layer 108a, and a TAD pulp fiber bottom surface layer 108b.
- TAD through-air-dried
- thermoplastic layer 106 may (or may not be) bonded to the top pulp fiber layer 108a.
- unbonded characteristic may apply to one or both faces of the thermoplastic layer.
- the fibrous portion of the top and bottom surface layers of the multi-layer substrates may be formed predominantly, and in an embodiment entirely, from pulp fibers, e.g., wood pulp or other plant fibers.
- pulp fibers e.g., wood pulp or other plant fibers.
- the thermoplastic layer is clearly not comprised of such pulp fibers (as it is instead a synthetic thermoplastic polymeric material, (e.g., having particular tan delta value characteristics)
- the substrate as a whole is one in which a majority of the fiber weight of the substrate may be pulp. For example, greater than 70% (by weight) of the fibers of the substrate may be pulp fibers. In an embodiment 75% to 90%, 75% to 85%, or 75% to 80% of the fibers in the substrate may be pulp fibers, by weight.
- synthetic fibers may account for less than 30%, such as 10% to 25%, 15% to 25%, or 20% to 25% by weight of the fibers.
- the thermoplastic interior layer is a fibrous film (e.g., a thin spunbond film).
- the thermoplastic film may not necessarily be fibrous, e.g., such as in the case of a cast or“bubble” blown film that is not made up of numerous fibers, but is simply a continuous thin (e.g., cast) sheet.
- the thermoplastic material may still account for less than 30%, 10% to 25%, 15% to 25%, or 20% to 25% of the dry substrate, but may simply be in non-fibrous form (e.g., a cast or blown sheet). In such a case, technically, 100% of the fibers of the substrate may be pulp fibers.
- all fibers of the top surface layer and bottom surface layer may consist of or consist essentially of pulp fibers.
- these layers may not include any synthetic fibers, or any synthetic structural components (e.g., no synthetic fillers).
- the substrates may be more sustainably sourced, e.g., where a higher fraction of the components used are derived from sustainable sources as compared to, e.g., existing wipes formed from a blend of pulp and synthetic fibers.
- the location of pulp versus synthetic materials in the wipe may differ in that all pulp may be in the exterior surface layers, rather than having pulp fibers intermixed (e.g., homogenously) through a given (e.g., interior) layer.
- the pulp fibers may typically be obtained from wood, although other possible sources of pulp are also possible, e.g., from Lac, Esparto grass, bagasse, hemp, flax, jute or the like. Combinations of more than one material may be used.
- Various exemplary pulp fibers may include, but are not limited to, thermomechanical pulp fibers, chemimechanical pulp fibers, chemithermomechanical pulp fibers, refiner mechanical pulp fibers, stone ground wood pulp fibers, peroxide mechanical pulp fibers, and the like.
- the fibers of the pulp substrate may generally comprise cellulosic fibers, which are typically hydrophilic. Such hydrophibcity differs from many synthetic fibers, which are typically hydrophobic, absent special treatment.
- the top and botom surface layers may alternatively be formed from a material that comprises synthetic fibers, or a blend of pulp and synthetic fibers. Any of various nonwoven materials may be used, which are widely available from various commercial sources. Such layers and fibers may be meltblown, spunbond, spunlaid, SMS (spunbond- meltblown-spunbond), coform, carded webs, thermal bonded, thermoformed, spunlace, hydroentangled, needled, or chemically bonded. In an embodiment, such surface layers may also incorporate a fraction of pulp fibers therein (e.g., as a homogenous blend of randomly distributed synthetic and pulp fibers, or where the pulp fibers are positioned non-randomly, e.g., at an exterior, or at an interior surface).
- a fraction of pulp fibers therein e.g., as a homogenous blend of randomly distributed synthetic and pulp fibers, or where the pulp fibers are positioned non-randomly, e.g., at an exterior, or at an interior surface).
- the fraction of synthetic fibers within the top and botom exterior surface layers may be at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%, by weight, of the fibers present in a given layer.
- 100% of the fibers in a given exterior surface layer may be synthetic fibers.
- a wide variety of synthetic materials that can be formed into fibers, and laid into a nonwoven substrate layer are appropriate for use in the contemplated multi-layer substrates.
- polymeric synthetic materials include, but are not limited to polyethylene, polypropylene, PET, PVC, poly aery lies, polyvinyl acetates, polyvinyl alcohols, polyamides, polystyrenes, or the like.
- the external surface layers may comprise a material other than polyethylene, and/or a material that does not have the tan delta characteristics possessed by the internal thermoplastic layer, which is configured to be melt-softened, bonding the 3 layers together.
- the top and bottom layers of the multi-layer substrate may have a basis weight of no more than 50 lbs, no more than 40 lbs, no more than 30 lbs, or no more than 20 lbs, at least 3 lbs, at least 5 lbs, or at least 10 lbs, such as from 7 lbs to 20 lbs, or 8 lbs to 15 lbs.
- Such“lbs” values refer to the weight per /3000ft 2 , as will be appreciated by those of skill in the art.
- the multilayer substrate as a whole may have a basis weight of 30-80 gsm.
- the top and bottom layers comprise pulp fibers, and do not include any added synthetic fibers, e.g., such as various polyolefins or other fibers formed from synthetic polymers, e.g., polyethylene, polypropylene, PET, PVC, polyacrylics, polyvinyl acetates, polyvinyl alcohols, polyamides, polystyrenes, or the like. While such synthetic fibers are widely used in the manufacture of nonwoven substrates, such embodiments may seek to reduce the use of such non-sustainable materials. Furthermore, by limiting or eliminating their use in the top and bottom exterior surface layers, additional benefits can be provided.
- synthetic fibers e.g., such as various polyolefins or other fibers formed from synthetic polymers, e.g., polyethylene, polypropylene, PET, PVC, polyacrylics, polyvinyl acetates, polyvinyl alcohols, polyamides, polystyrenes, or the like. While such synthetic fibers are widely used in the manufacture of
- the present wipes can provide functional parity, and sometimes advantages, over conventional nonwoven wipes in durability, safety for use on all surfaces, ease and convenience, ability to clean and absorb light liquid spills, ability to clean large areas effectively, and microefficacy in the case of sanitization or disinfection.
- the use of significant quantities of synthetic resins in existing pre-moistened nonwoven wipes represents a significant expense, such that cost savings, renewability and sustainability benefits, and biodegradability benefits can be achieved using pulp substrates, as described herein.
- the individual layers of the top and bottom (e.g., pulp fiber) layers that are used in manufacturing the multi-layer substrate can be formed by any of a number of different techniques, e.g., such as any of those suitable for use in forming tissue layers. Examples include, but are not limited to wet-laying and air-laying, as well as conventional press-drying, and through-air drying techniques. Methods of making such substrate layers will be apparent to those of skill in the art. Wet-laying processes are described in U.S. Patent Nos. 5,246,772 and 5,238,534 to Manning. Air-laying processes are described in U.S. Patent Publication No. 2003/0036741 to Abba et al. and U.S. Patent Publication No.
- top and bottom tissue layers are formed by through-air-drying.
- Such processes are typically carried out prior to the positioning and calendaring processes described herein, e.g., where the inputs to the presently described process are nonwovens or similar structured sheet or web materials, already processed into such structured sheets, so that the present processes do not require use of loose fibers (particularly loose pulp fibers), do not require use of process water to maneuver fibers along the plane or through a thickness of the given sheet or web (as the sheet or web is already formed in the material used as an input to the present process), do not require drying or another mechanism for removing process water, and do not require use of chemical binders to adhere the various layers to one another (as this is achieved through melt softening the interior thermoplastic layer).
- tissue layers are used as the exterior surface layers
- one or both of the tissue layers may comprise more than a single ply, or each may comprise only a single ply.
- multiple plies are provided, they may be adhered together, so as to have adequate peel strength, e.g., as described in Applicant’s Application Serial No. 16/042,690, filed July 23, 2018 (Docket No. 510.174), already incorporated by reference.
- no chemical adhesive may be present anywhere in the multi-layer substrates.
- a chemical adhesive may be present in the tissue layers (i.e., between plies), but may not be present between the thermoplastic layer and the adjacent top and bottom tissue layers
- the present multi-layer wipes include a sandwich structure in which a thermoplastic layer is provided, on the inside of the wipe, sandwiched between the top and bottom surface layers (e.g., pulp layers). While in an embodiment, the surface layers could also be thermoplastic, these exterior layers may include different tan delta characteristics than the sandwiched thermoplastic layer. Where no chemical adhesive is used to adhere the 3 layers into an integral, single structure that does not readily delaminate between layers, but in which the thermoplastic sandwich“cheese” layer itself is used for this purpose, the Applicant has found that not just any thermoplastic polymer will be suitable for such a purpose.
- the multi-layer substrates have sufficient adhesion between the layers that they do not delaminate even when wet (e.g., allowed to soak for weeks, in storage) or when used for cleaning hard surfaces.
- the interior thermoplastic layer not only binds the multi-layer substrate together as it melts, but it also may impart additional strength to the exterior layers, where these layers may be relatively weak.
- Tan delta value is an engineering characteristic that can be evaluated for thermoplastic polymeric materials, and gives information relative to how much “liquid” viscous phase characteristics dominate versus“solid” elastic phase characteristics, in a given material, at a given temperature. Tan delta is simply calculated as the ratio of viscous modulus divided by elastic modulus for a given material, at a given temperature.
- Figure 4 charts both tan delta and elastic modulus values for 3 tested thermoplastic materials - polyethylene, polypropylene, and a bicomponent material that comprises polyethylene.
- the bicomponent material tested is believed to be comprised of bicomponent fibers, with a fiber core (that is not polyethylene), and an exterior coating or sheath on the core, that is polyethylene.
- Figure 4 charts both elastic modulus and the tan delta value for these 3 materials over the temperature range of about 100°F to 350°F.
- Figure 4 shows how the elastic modulus (i.e., stiffness) of the polypropylene is the highest, followed by the“bico”, followed by the polyethylene, and that the stiffness of each decreases with increasing temperature.
- the tan delta value for the polypropylene is very low, less than 0.2, and remains less than 0.15 at temperatures from 100°F to over 300°F. It isn’t until nearly 350°F that the tan delta value increases somewhat, but only slightly, up to a value of about 0.15, and certainly still less than 0.2.
- the polyethylene tan delta value is quite different, being about 0.2 at a temperature of 100°F, and increasing to about 0.25 to 0.3 at about 175°F-190°F. After peaking at around this temperature, the tan delta value begins to decrease, to 0.2 at about 250°F, and dropping somewhat below 0.2 (e.g., about 0.18) at about 260°-270°F.
- Tan delta for the“bico” is between that of the polypropylene and the polyethylene for much of the temperature range, until about 250°F where it is higher than the polyethylene.
- Both the polyethylene and the “bico” material (which comprises polyethylene) include points along the temperature range of 100°F to 350°F where tan delta is at least 0.2 (e.g., greater than 0.2 to 0.4, or greater than 0.2 to 0.3), meeting the stated requirement.
- the polypropylene tan delta never reaches 0.2 over this temperature range of 100°F to 350°F.
- the selected thermoplastic material for the interior“sandwich” layer has a tan delta value that is at least 0.2 (e.g., from 0.2 to 0.4, or from 0.2 to 0.3) somewhere within the temperature range of 100°F to 350°F.
- the selected thermoplastic material may have such a tan delta value at the particular temperature at which the thermal calendaring step is performed (e.g., 150°F, 175°F, 200°F, 225°F, 250°F, 275°F, 300°F, 325°F, etc.) or at any narrower range within the temperature range of 100°F to 350°F.
- the selected thermoplastic material may advantageously have a melting temperature that is less than 400°F, less than 375°F, less than 350°F, less than 325°F, less than 300°F, at least 150°F, at least 175°F, at least 200°F, or at least 225°F. Having a relatively lower melting temperature of course reduces energy requirements needed in the calendaring process, but may also be important depending on what materials are used in the top and bottom surface layers, to ensure they do not decompose, ignite, or melt.
- any pulp fiber content is included in the exterior surface layers, it can be important to ensure the temperature is low enough that such pulp fibers do not ignite, or become embrittled or discolored due to“burning”, which may occur even below the paper ignition temperature of 451°F. As such, selection of lower melting temperature thermoplastic materials may be preferred, so long as they can provide a good bond to the exterior top and bottom layers.
- the interior thermoplastic layer may comprise, e.g., at least 25%, at least 30%, at least 35%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, from 25% to 100%, from 30% to 100%, or from 50% to 100% of a material having the desired tan delta characteristics.
- some portion or component of the thermoplastic material may not have the stated tan delta characteristics, so long as the thermoplastic material as a whole includes such characteristics.
- the bico fiber is believed to include a polypropylene core, which does not have the stated tan delta characteristics, although the sheath portion of the fiber is believed to be polyethylene, which does have the stated tan delta characteristics.
- the bico fibers as a whole do meet the stated tan delta characteristics.
- the thermoplastic material is a bicomponent fiber or other bicomponent (or other multicomponent) structure, e.g., such as a layered film or the like
- the polyethylene or other material having the stated tan delta characteristics may be positioned on the exterior of the thermoplastic material, so as to easily contact the adjacent exterior surface layers during the calendaring process.
- Figures 5A-5B show how the present multi-layer substrates may be packaged within any of various exemplary flex packs (Figure 5A), cylinders ( Figure 5B) or other containers for storage and dispensing.
- the wipes 100 may be pulled through an orifice such as typically provided with such containers, without fear of shredding or delamination of the various layers.
- Applicant tested prototype wipes such as shown in Figure IE by pulling them through orifices (e.g., as seen in Figures 5A-5B), and there was no significant shredding of the exterior tissue layers, or delamination of the layers from one another. Rather, each wipe was able to be pulled through the orifice, remaining fully intact, time after time.
- Figure 6 shows an SEM image at the interface between a spunbond fibrous thermoplastic layer 106 and an adjacent exterior tissue layer (e.g., 108a) showing how the pulp fibers at the interface are wrapped around, enveloped, or coated by the melt-softened thermoplastic material, that occurs during the thermal calendaring process.
- This strong connection between the pulp fiber layer and the thermoplastic layer provides a strong bond, so that shredding or delamination does not occur when pulling the wipe through a typical wipe pack orifice.
- Figure 5B further shows how such wipes may be packaged as a“donut”, e.g., in a cylindrical container.
- the ability to package the wipes in such a donut configuration is somewhat surprising when the exterior surface layers are pulp, given the high pulp content (e.g., 75-80% pulp) of the substrate. For example, it is difficult to package pre dosed 100% pulp substrates in such a configuration without the donut collapsing or creasing vertically, due to insufficient wet stiffness of the substrate.
- thermoplastic film layer is not required to be particularly thick.
- the thermoplastic film layer may have a thickness of 0.01 mm to 0.1 mm, or 0.01 mm to 0.05 mm. It may be so thin as to be transparent or translucent, prior to assembly into the sandwich structure. That said, it will be apparent that if desired, the thermoplastic middle sandwich layer may be thicker.
- the thermoplastic middle sandwich layer may thus have a thickness ranging from 0.01 mm to 5 mm, from 0.01 mm to 3 mm, from 0.01 mm to 2 mm, from 0.01 mm to 1 mm, from 0.01 mm to 0.5 mm, or the like.
- Strength and/or stiffness characteristics of the wipe may be dictated at least in part by the characteristics of the middle thermoplastic layer of the present substrate.
- strength and stiffness of the substrate as a whole may progressively increase as one uses, respectively, fibers, a film, a yam, a nonwoven (e.g., a bico nonwoven), or a woven structured material for the middle sandwich layer.
- Such materials are listed generally in order of increasing resiliency, where strength and/or stiffness of the overall substrate increase with increasing resiliency of the middle layer.
- thickness of the middle layer will also affect the strength and/or stiffness of the finished substrate.
- thermoplastic middle sandwich layer may provide the greatest strength and/or stiffness to the substrate, while a nonwoven thermoplastic middle sandwich layer would typically provide somewhat lower strength and/or stiffness.
- a yam e.g., where multiple fibers are twisted or otherwise arranged together, providing a yam diameter significantly greater than that of the individual fibers making up the yam may provide somewhat lower stiffness and strength, and a film or simple deposition of individual, loose fibers onto either of the exterior surface layers to form the thermoplastic middle sandwich layer may provide even lower stiffness and/or strength.
- thermoplastic middle sandwich layer It will be apparent that numerous possible configurations are possible as to the structure of the thermoplastic middle sandwich layer, and that numerous possible methods are possible for providing such (e.g., providing preformed layers, for example, as a film, nonwoven, or woven) that are simply placed between the exterior layers, or by providing one of the exterior surface layers, and then depositing individual loose fibers, yam or the like onto the interior surface of such exterior layer, followed by positioning the other exterior surface layer there over, after which the 3-layer structure is then subjected to heat and/or pressure, to adhere the layers to one another, and cause the formation of cracks, fissures and the like through the thermoplastic middle sandwich layer, through which a cleaning lotion that eventually becomes loaded into the substrate can pass from one exterior surface layer, through the thermoplastic middle sandwich layer, to the other exterior surface layer.
- providing preformed layers for example, as a film, nonwoven, or woven
- individual loose fibers, yam or the like onto the interior surface of such exterior layer, followed by positioning the other exterior surface layer there
- thermoplastic middle sandwich layer of any suitable material (e.g., pulp), which serves as a carrier to lay down loose fibers (or fibers formed into a yam) of the thermoplastic material onto the pulp or other suitable exterior surface layer.
- a nonwoven exterior surface layer of any suitable material (e.g., pulp), which serves as a carrier to lay down loose fibers (or fibers formed into a yam) of the thermoplastic material onto the pulp or other suitable exterior surface layer.
- the opposite exterior surface layer e.g., another pulp nonwoven layer
- the 3-layer structure may be processed with appropriate heat and/or pressure to melt soften the thermoplastic middle sandwich layer, as described herein.
- the resulting substrate exhibits lofted characteristics due to the“fuzzy”, loose bulk structure of the nonwoven randomly laid pulp fibers in the exterior layers.
- synthetic exterior layers it may be desirable to provide the substrate with a lofted structure, so as to increase the bulk and thickness of the substrate, where such lofted characteristics may not otherwise be provided with synthetic exterior layers.
- lofting may be provided through overfeeding one or more of the layers (e.g., exterior layers) into the rollers which heat and press the layered substrate.
- the feed rate of one or both exterior surface layers may be greater than a pick up rate on the other side of such rollers, which causes the material of the overfed layers to bunch up or create pleats as it enters the rollers (e.g., the heated nip and the opposite roller) where the melt softening of the middle layer occurs.
- This causes a bunched up, pleated, or similar lofted configuration including air gaps to be locked in to the exterior layer as the middle layer melt softens, and bonds to the exterior overfed layer.
- Such a lofted configuration gives more cloth-like hand feel characteristics, and may provide“reservoirs” within which the cleaning lotion may be stored.
- This lofted configuration is durable after dosing and during use, akin to what may be provided with a fuzzy, lofted pulp containing (non-synthetic) layer.
- Other techniques for providing a lofted layer may also be used.
- a pin roller could be used to pull portions of the exterior surface layer laterally outward from the substrate plane, creating a fuzzy, lofted texture with decreased density and increased volume and thickness to such layer.
- Various other techniques will be apparent to those of skill in the art, in light of the present disclosure.
- any synthetic substrate layers or materials could be selected to be biodegradable and/or compostable (e.g., meeting the standard of ASTM D6400 or other applicable standard). Of course, pulp layers easily meet such criteria.
- FIG 8 schematically illustrates an exemplary calendaring process 200 that may be used to form the substrates including 3 or more distinctly identifiable layers.
- Figure 8 shows use of a rolled web of the 3 starting sheet materials, although it will be appreciated that they could be provided as distinct, separate sheets of material, or that the middle thermoplastic layer could be laid down as loose fibers, before calendaring.
- Process 200 is shown as including a mechanism 202 for feeding thermoplastic material 204, as well as mechanisms 206a, 206b for providing top and bottom exterior surface layers 208a, 208b.
- the thermoplastic material 204 is sandwiched between exterior surface layers 208a, 208b as it is fed into calendaring portion of process 100, e.g., along an optional conveyor belt 210.
- a 4 th optional layer 207 is shown in Figure 8.
- Sandwiched structure 212 may pass under a roller 214 and then to rollers 216a, 216b.
- rollers 216a, 216b are rubber, while the other is metal.
- the rollers may heat the sandwich structure 212 to the desired temperature, for a desired period of time, so as to melt soften the interior layer 204, causing it to bond to the surface exterior layers 208a, 208b.
- the pressure applied may be e.g., at about 10 bars, at least about 15 bars, or at least about 25 bars. More generally, such pressure may be less than 300 bars, less than 200 bars, less than 100 bars or less than 50 bars, from 1 to 500 bars, from 5 to 500 bars, from 10 to 300 bars, or from 25 to 200 bars pressure.
- the thickness and weight of the constituent layers may have an effect on the required pressure and temperature, and contact time in order to achieve good bonding, as described herein.
- the presently described process is far simpler, in that it uses pulp layers that are already provided in structured form, where the fibers are already fixed relative to the pulp layer, and adhering two such pulp layers so as to form the exterior surface layers, sandwiching therebetween a thermoplastic layer having particular characteristics that permit bonding of the distinct 3 layers without use of any chemical adhesives that would require curing, etc.
- rollers to perform the heating and pressing
- heated plates could alternatively be used (e.g., introducing the sandwich structure between platen plates and pressing the sandwich), although the rollers configuration may be preferred as allowing for far higher production volumes.
- the cleaning composition is an aqueous composition, including at least 70%, at least 80%, or at least 90% water by weight (e.g., 90% to 99% water).
- the composition may include 0.05% to 5% by weight of a quaternary ammonium compound, and/or 0.1% to 5% by weight of a glycol ether solvent.
- the quaternary ammonium compound may be included from 0.05%, from 0.1%, up to 5%, up to 4%, up to 3%, up to 2%, or up to 1% by weight of the cleaning composition.
- the glycol ether solvent may be included from 0.1%, from 0.25%, up to 5%, up to 4%, up to 3%, up to 2%, or up to 1% by weight of the cleaning composition.
- Other solvents, surfactants, and various other adjuvants often included in cleaning compositions may optionally be present. While some embodiments may include lower alcohol solvents (e.g., C 1 -C 4 alcohols), the amount of such volatile solvents may be limited, e.g., to less than 10%, less than 5%, less than 3%, less than 2%, or less than 1% by weight.
- the composition may be free of, or substantially free of, such lower alcohol or other highly volatile solvents.
- Quaternary ammonium compounds or other cationic biocides can have broad spectrum antimicrobial properties.
- a variety of different quaternary ammonium compounds can be used in the cleaning composition.
- Non-limiting examples of quaternary ammonium compounds are typically halides (e.g., a chloride) of alkyldimethylbenzylammonium, alkyldimethylethylbenzylammonium, alkyldimethylammonium, or the like.
- the alkyl groups of such quaternary ammonium compounds may typically range from C 12 to Cie.
- Quaternary ammonium compounds are described in more detail in U.S. Patent No. 6,825,158, incorporated by reference herein, and will already be familiar to those of skill in the art.
- Organic acids can also be used to provide antimicrobial properties.
- such an organic acid may be included in an amount of at least 0.1%, or at least 0.5%, up to 5%, up to 4%, up to 3%, up to 2%, or up to 1% by weight of the cleaning composition.
- the cleaning composition may include a glycol ether solvent.
- exemplary glycol ether solvents include, but are not limited to alkyl ethers of alkylene glycols and alkylene glycol ethers, such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, diethylene glycol monoethyl or monopropyl or monobutyl ether, di- or tri-polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and/or propionate esters of glycol ethers.
- any among a wide variety of surfactants may be included in the cleaning composition, as desired.
- a surfactant may be present from 0.05%, from 0.1%, up to 10%, up to 5%, up to 4%, up to 3%, up to 2%, or up to 1% by weight of the cleaning composition.
- Various surfactants and other optional adjuvants are disclosed in U.S. Pat. No. 3,929,678 to Laughlin and Heuring, U.S. Pat. No. 4,259,217 to Murphy, U.S. Pat. No.
- liquids include, but is not limited to, solutions, emulsions, suspensions and so forth.
- liquids may comprise and/or contain one or more of the following: disinfectants; antiseptics; diluents; surfactants, such as nonionic, anionic, cationic; waxes; antimicrobial agents; sterilants; sporicides; germicides; bactericides; fungicides; virucides; protozoacides; algicides; bacteriostats; fungistats; virustats; sanitizers; antibiotics; pesticides; and so forth. Examples of some such components and exemplary compositions are disclosed in U.S.
- Patent Nos. 6,825,158; 8,648,027; 9,006,165; 9,234,165, 9,988,594 and U.S. Publication Nos. 2008/003906 and 2018/0216044 each of which is herein incorporated by reference in its entirety.
- a selected amount of liquid may be added to the container or wipes during manufacture such that the cleaning substrates contain the desired amount of liquid.
- the substrates are not necessarily loaded to their saturation point, but are typically loaded with the cleaning composition to some ratio less than full saturation. For example, many substrates are capable of holding about 8 to 14 times their weight in liquid.
- the substrates may be loaded at a loading ratio less than saturation, e.g., less than 6: 1, less than 5: 1, less than 4: 1, such as from 1 : 1 to 4: 1, from 2: 1 to 4: 1, from 2.5: 1 to 3.5: 1, from 2.5: 1 to 3: 1 or from 2.5: 1 to 3.75: 1.
- the substrate may be configured so as to be all synthetic (e.g., without pulp in the exterior surface layers)
- this may offer additional flexibility in the chemistries that may be dosed (e.g., during manufacture) onto such substrate for use, while minimizing or eliminating risk of undesired incompatibility that may result between components of such compositions and substrates that may include pulp, other natural fibers, or other natural components.
- a wide variety of bleaching agents e.g., chlorine-based and otherwise, including peroxides, hypochlorites, etc.
- Compositions which achieve disinfection based on acids e.g., acetic acid
- acids e.g., acetic acid
- Such acid disinfectants and bleaches are often incompatible with non-synthetic substrate materials.
- Non-limiting examples of such compositions are disclosed in U.S. Patent Nos. 5,460,833 to Andrews et al.; 6,221,823 to Crisanti; 6,346,279 to Rochon et al; 6,551,980 to Wisniewski et al.; 6,699,825 to Rees et al.; 6,803,057 to Ramirez et al.; 6,812,196 to Rees et al.; 6,936,597 to Urban; 7,008,600 to Katsigras et al; 7,070,737 to Bains et al.; 7,354,604 to Ramirez et al.; 7,598,214 to Cusack et al; 7,605,096 to Tamarchio et al; 7,658,953 to Bobbert; 7,696,143 to McCue et al.; 7,915,207 to Chopski
- the size and shape of the wipe can vary with respect to the intended application and/or end use of the same.
- the cleaning substrate can have a substantially rectangular shape of a size that allows it to readily engage standard cleaning equipment or tools such as, for example, mop heads, duster heads, brush heads, mitten shaped tools for wiping or cleaning, and so forth.
- standard cleaning equipment or tools such as, for example, mop heads, duster heads, brush heads, mitten shaped tools for wiping or cleaning, and so forth.
- another shape e.g., circular, oval, or the like may be provided.
- the wipes or other cleaning substrates may be provided pre-moistened with a cleaning composition.
- the wet cleaning substrates can be maintained over time in a sealable container such as, for example, within a bucket or tub with an attachable lid, sealable plastic pouches or bags, canisters, jars, and so forth.
- a sealable container such as, for example, within a bucket or tub with an attachable lid, sealable plastic pouches or bags, canisters, jars, and so forth.
- the wet, stacked cleaning substrates are maintained in a re-sealable container.
- the use of a re-sealable container is particularly desirable when using aqueous volatile liquid compositions since substantial amounts of liquid can evaporate while using the first sheets thereby leaving the remaining sheets with little or no liquid.
- Exemplary re-sealable containers and dispensers include, but are not limited to, those described in U.S. Pat. No.
- the cleaning substrates are stacked and placed in the container and the liquid subsequently added thereto, all during mass manufacturing. It is advantageous that the thermoplastic layer at the center of each wipe not be liquid impervious, to facilitate easier loading of the wipes. As described herein, even if the thermoplastic film as initially provided before lamination of the 3 layers together is liquid impervious, Applicant has found that cracks or other fluid pathways are opened up within the film during thermal calendaring, as contemplated herein. While this may not necessarily occur with any and all thermal calendaring operations, it does occur under the conditions contemplated herein.
- the presence of such cracks or other fluid pathways that are opened up during manufacture of the multi-layer substrate advantageously allow liquid cleaning composition dosed on either face of the substrate to migrate through the wipe, to the opposite exterior face, through the thermoplastic film layer.
- a given volume or weight of the cleaning composition may simply be dosed into the bottom of the container, allowing it to wick into the stack of wipes.
- thermoplastic film layer were“broken” to include the described fluid pathways or not (i.e., if it remained impervious), as both the top and bottom surface layers will contact the cleaning composition at the bottom of the container simultaneously.
- any initially liquid impervious characteristics of the film are “broken” by the thermal calendaring process, this may further aid the cleaning composition in wicking upwards throughout the full height of each wipe, and the donut as a whole.
- the substrate can subsequently be used to wipe a surface.
- the moistened cleaning substrates can be used to treat various surfaces.
- “treating” surfaces is used in the broad sense and includes, but is not limited to, wiping, polishing, swabbing, cleaning, washing, disinfecting, scrubbing, scouring, sanitizing, and/or applying active agents thereto.
- the wipes or other cleaning substrates of the present invention can be provided in a kit form, wherein a plurality of cleaning substrates and a cleaning tool are provided in a single package.
- substrate dimensions are from about 5 1 ⁇ 2 inches to about 11 inches in length, and from about 5 1 ⁇ 2 inches to about 11 inches in width to comfortably fit in a hand.
- the substrate can have dimensions such that the length and width differ by no more than about 2 inches. Larger substrates may be provided that can be used and then folded, either once or twice, so as to contain dirt within the inside of the fold and then the wipe can be re-used. Such larger substrates may have a length from about 51 ⁇ 2 inches to about 13 inches and a width from about 10 inches to about 13 inches. Such substrates can be folded once or twice and still fit comfortably in the hand.
- the present multi-layer substrates may exhibit values in each direction that result in a ratio of MD/CD that is relatively close to 1, e.g., such as 0.5 to 1.5, 0.75 to 1.25, or 0.8 to 1.2.
- the substrates may be substantially isotropic with respect to their tensile strength. Such substantially isotropic characteristics reduce the likelihood of there being problems when folding substrates into stacks for packaging, or forming donuts for packaging.
- Exemplary multi-layer substrates were tested for their ability to effectively deliver an antimicrobial quaternary ammonium compound to a surface during simulated cleaning. Applicant notes that the generally anionic characteristics of typical pulp substrates lead to a tendency of the substrate to bind or otherwise retain the cationic quaternary ammonium compound, even when squeezing an aqueous cleaning composition including such a quat from the substrate. In other words, typically, the concentration of quaternary ammonium compound in the “squeezate” (the cleaning composition as squeezed from the pre-loaded wipe) is less than the concentration of quaternary ammonium compound in the cleaning composition before it was loaded into the wipe.
- the multi-layer substrates of the present invention may be loaded with cleaning compositions including from 0.1% to 3%, such as 0.1% to 2% by weight of quat.
- the wipes may release at least 40%, at least 50%, at least 55%, at least 60%, or at least 65% of the quaternary ammonium compound (i.e., quaternary ammonium compound in the squeezate as compared to the cleaning composition before loading).
- the wipes may exhibit at least a 3 -log reduction in a target microbe, such as Staphylococcus aureus, within a given time frame (e.g., such as 5 minutes, 4 minutes, 3 minutes, 1 minute, 30 seconds, 10 seconds, etc.) ⁇
- the dot patterns and textures shown in Figure IE included smallest dots (100b), small dots (100c), medium dots (100a), and large dots (lOOd).
- the wet thickness of the resulting substrates is affected by the dot pattern or texture.
- a flat sample (not shown) had a wet thickness of 0.3 mm
- the sample 100a (smallest dots) had a wet thickness of 0.39 mm
- the sample 100b (small dots) had a wet thickness of 0.65 mm
- the sample 100c (medium dots) had a wet thickness of 0.66 mm
- sample lOOd large dots
- the forgoing values are for substrates with only one tissue layer textured. Two sided samples include somewhat higher wet thickness values.
- the dosed exemplary multi-layer substrate was tested for microefficacy against Staphylococcus aureus at a loading ratio of 3.75: 1, using an existing quat cleaning composition, at a contact time of 3 min 30 sec.
- the control population of 6.1 log was reduced to 0 in each of 60 replicates. Testing was performed under 5% soil load conditions. Such results indicated excellent efficacy against Staphylococcus aureus at a 3:30 contact time.
- the small increase in cycles for 75% removal may be due to the absence of synthetic fibers on the exterior surface and reduced tendency of the present wipes to “dump” cleaning composition, as compared to the comparative example blended wipe.
- the reported values represent averages for two sides of the wipes.
- the conventional wipe “dumps” or releases more liquid from the first side, thereby requiring few cycles to clean, but also reducing mileage.
- This“dumping” characteristic is described in Applicant’s Application Serial No. 16/042,690, filed July 23, 2018 (Docket No. 510.174), previously incorporated by reference.
- the present wipes do not include any synthetic fibers exposed at the exterior faces of the wipe, but any synthetic fibers are rather located only within the interior of the wipe (and potentially incidentally exposed at the edges).
- the exterior surface may be soft, rather than abrasive.
- Applicant did prepare some prototype substrates that did include synthetic fibers on the exterior surfaces (i.e., using a blend of pulp and synthetic fibers to form the exterior“tissue layers”, the resulting wipes did not provide the same desired hand-feel characteristics as were provided where the exterior pulp fiber or tissue layers did not include exposed synthetic fibers. While 100% pulp fibers on the exterior faces may thus be preferred, it will be appreciated that some small fraction of synthetic fibers (e.g., less than 10%, less than 5%, less than 3%, or less than 1%) may be included in some embodiments.
- the exterior tissue layers may be of a through-air dried configuration. While conventional press-dried tissue was also tried in this exterior layer, this also resulted in less desirable hand-feel characteristics. Such conventional (not through-air-dried) tissue also undesirably presses out any initially included texture, while through-air-dried processing preserves such pre-existing texture. While these alternatives may not be preferred, they may still be suitable, for some uses.
- tissue or nonwoven manufacturing techniques e.g., dry crepe technique (DCT), structured tissue or new tissue technology (NTT), and others that will be apparent to those of skill in the art
- DCT dry crepe technique
- NTT new tissue technology
- thermoplastic polymer having the described tan delta characteristics eliminates any need for a chemical adhesive to adhere the top and bottom surface layer to the thermoplastic layer, it will be appreciated that in other embodiments, e.g., even using polypropylene or another material having poor tan delta characteristics, it may be possible to achieve a multi-layer substrate that does not delaminate, e.g., by using a chemical adhesive to provide the needed bonding.
- the degree of lamination and strength of the bond between adjacent layers typically depends on the temperature, pressing or contact time, and applied pressure associated with the calendaring operation. Temperature may be a primary variable responsible for bond strength achieved, although pressure and time may also have an effect, and may also affect the resulting texture that is“embossed” into the pulp fiber surface layer, and the resulting bond pattern. Where the pulp fiber or other layers provided on both exterior faces are embossed with a texture, the resulting multi-layer substrate exhibits a more“cloth-like” feel that is drapable and less stiff, as compared to where only one of the two faces is embossed with a texture.
- FIGS. 7A-7F illustrate various possible embossing patterns that can be applied by the calendar rollers. It will be apparent that the possibilities are nearly limitless.
- Temperatures applied during calendaring may be at least 150°F, at least 175°F, at least 200°F, from 200°F to 400°F, or from 200°F to 350°F.
- Applied pressure may be at least 50 psi, at least 100 psi, at least 150 psi, at least 200 psi, from 100 psi to 1000 psi, or from 300 psi to 600 psi.
- Contact time (time at the given pressure and/or temperature) may be at least 100 ms, at least 200 ms, from 100 ms to 5 s, from 200 ms to 1 s, or from 200 ms to 500 ms.
- Such a manufacturing process may be attractive, e.g., as compared to traditional non-woven substrate manufacture, as it may not require any processing of individual fibers not already provided in a nonwoven layer, water usage, water filtration, drying steps, loss of fibers during processing, and the like.
- the present calendaring process may allow for greater production line speeds (e.g., up to 900 m/min, typically from 50 m/min to 600 m/min) as compared to SPINLACE manufacturing conventional blended substrates (that are not multi-layer), which are at significantly lower line production speeds.
- Increased line speed results in decreased contact time (all else being equal).
- higher line speed may be accommodated by increasing web surface temperature (so shorter contact time is needed), increasing the roller diameter (thus increasing contact time), or increasing applied pressure (nip pressure).
- temperature can be increased by about 5% (in °C) to maintain bonding level).
- the present substrates also provide for the ability to modulate the substrate stiffness by changing the pattern applied during calendaring (e.g., see the various patterns of Figure IE or 7A-7F), as well as the ability to modulate stiffness and tensile strength characteristics by providing texturing on one or both of the substrate faces, the ability to provide for relatively higher quat release even at higher pulp fractions, and more uniform lotion release, with better mileage, as described in Applicant’s Application Serial No. 16/042,690, filed July 23, 2018 (Docket No. 510.174), due to the high pulp content.
- Table 4 below shows the results of additional testing conducted on exemplary formed multi-layer wipes including exterior pulp layers and an interior thermoplastic layer, relative to dry stiffness characteristics.
- the stiffness characteristics of wipes that are formed to include exterior pulp layers exhibit significantly higher stiffness than conventional, currently available wipes, even those that are blended substrates, which may include, e.g., up to 60% pulp fibers.
- Stiffness values were measured using ASTM D-1388-96.
- the exemplary 3-layer substrate materials include approximately at least double the dry stiffness of wipes produced using current wipes technologies. Such increased stiffness is believed to be due at least in part to the use of fixed pulp fibers, where the pulp layers used in forming the substrates are already in structured form (e.g., as non woven sheets, similar to a paper towel).
- two steel rollers e.g., 216a, 216b
- both include the texture to be applied to the substrate which can result in two- sided texturing.
- Figure 9A illustrates images comparing a conventional 1 -sided texture (top of Figure 9A), to a two-sided textured substrate, where the“bumps” can be provided in both faces, where the textured“bumps” are axially aligned with one another through the substrate thickness.
- Such may be important in providing a user of the wipe with the same hand feel and other characteristics no matter which face of the wipe is oriented towards the hand, and which face is oriented towards the surface being cleaned (both have the same tactile characteristics, rather than differing from one another).
- conventional wipes are not the same on one face as compared to the other, while the present processes can be implemented in a way to provide the same user tactile experience no matter the orientation of the wipe in the user’s hands, where two-sided texturing is provided.
- Figures 9B-9C illustrate profilometer data for the“bumpy” face and the “other” face of a substrate without two-sided texturing
- Figures 9D-9E illustrate profilometer data for the first and second faces of a substrate with two-sided texturing (both are“bumpy”).
- Figures 9F-9I illustrate additional profilometer data for the tested comparative one-sided versus two-sided textured samples.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201962828301P | 2019-04-02 | 2019-04-02 | |
US201962860655P | 2019-06-12 | 2019-06-12 | |
PCT/US2020/024675 WO2020205360A1 (en) | 2019-04-02 | 2020-03-25 | Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3945977A1 true EP3945977A1 (en) | 2022-02-09 |
EP3945977A4 EP3945977A4 (en) | 2022-10-12 |
Family
ID=72667477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20782489.7A Pending EP3945977A4 (en) | 2019-04-02 | 2020-03-25 | Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP3945977A4 (en) |
CN (1) | CN113518573B (en) |
CA (1) | CA3128040A1 (en) |
CL (1) | CL2021002497A1 (en) |
MX (1) | MX2021011796A (en) |
WO (1) | WO2020205360A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11273625B2 (en) * | 2018-12-21 | 2022-03-15 | The Clorox Company | Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene |
WO2022020115A1 (en) * | 2020-07-24 | 2022-01-27 | The Clorox Company | Compostable nonwoven with low extensibility |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2897108A (en) * | 1953-05-11 | 1959-07-28 | Kimberly Clark Co | Disposable absorbent pad |
US3929678A (en) | 1974-08-01 | 1975-12-30 | Procter & Gamble | Detergent composition having enhanced particulate soil removal performance |
US4171047A (en) | 1975-10-03 | 1979-10-16 | Sterling Drug Inc. | Package including a container and a longitudinally folded pre-moistened web therein |
US4259217A (en) | 1978-03-07 | 1981-03-31 | The Procter & Gamble Company | Laundry detergent compositions having enhanced greasy and oily soil removal performance |
US4353480A (en) | 1979-06-11 | 1982-10-12 | Lever Brothers Company | Closure for a dispenser container |
US4565647B1 (en) | 1982-04-26 | 1994-04-05 | Procter & Gamble | Foaming surfactant compositions |
US4574021A (en) * | 1983-03-03 | 1986-03-04 | Kimberly-Clark Corporation | Soft moisture resistant tissue product |
US4741944A (en) | 1986-07-30 | 1988-05-03 | Kimberly-Clark Corporation | Wet wipe and wipe dispensing arrangement |
US4778048A (en) | 1987-12-28 | 1988-10-18 | Kimberly-Clark Corporation | Product containing a tilted stack of wet wipes |
US5246772A (en) | 1990-10-12 | 1993-09-21 | James River Corporation Of Virginia | Wetlaid biocomponent web reinforcement of airlaid nonwovens |
US5238534A (en) | 1992-01-24 | 1993-08-24 | James River Corporation Of Virginia | Wetlaid nonwovens on high speed machines |
US5776872A (en) | 1992-03-25 | 1998-07-07 | The Procter & Gamble Company | Cleansing compositions technical field |
US5883062A (en) | 1993-09-14 | 1999-03-16 | The Procter & Gamble Company | Manual dishwashing compositions |
CA2169559C (en) | 1993-09-14 | 2004-11-30 | Jeffrey F. Andrews | Disinfectant composition |
EP0802786B1 (en) | 1995-01-09 | 2000-12-13 | The Procter & Gamble Company | Three in one ultra mild lathering antibacterial liquid personal cleansing composition |
DE19504192A1 (en) | 1995-02-09 | 1996-08-14 | Henkel Ecolab Gmbh & Co Ohg | Thickening aqueous cleaning agents for hard surfaces |
US5595786A (en) | 1995-06-07 | 1997-01-21 | Contec, Inc. Of Spartanburg | Method of preparing surface for receiving a coating and apparatus therefor |
US6221823B1 (en) | 1995-10-25 | 2001-04-24 | Reckitt Benckiser Inc. | Germicidal, acidic hard surface cleaning compositions |
WO1998055295A1 (en) | 1997-06-05 | 1998-12-10 | Bba Nonwovens Simpsonville, Inc. | High strength baby wipe composite |
EP0906950A1 (en) | 1997-10-03 | 1999-04-07 | The Procter & Gamble Company | Peroxygen bleach-containing compositions comprising a particular chelating agent system |
US6270875B1 (en) * | 1998-01-26 | 2001-08-07 | The Procter & Gamble Company | Multiple layer wipe |
EP0949325A1 (en) | 1998-04-08 | 1999-10-13 | The Procter & Gamble Company | Carpet cleaning compositions and method for cleaning carpets |
US6346279B1 (en) | 1998-12-14 | 2002-02-12 | Virox Technologies, Inc. | Hydrogen peroxide disinfectant with increased activity |
US20030036741A1 (en) | 1999-10-14 | 2003-02-20 | Kimberly-Clark Worldwide, Inc. | Textured airlaid materials |
NZ522970A (en) | 2000-06-05 | 2004-05-28 | S | Biocidal cleaner composition |
EP1167510A1 (en) | 2000-06-23 | 2002-01-02 | The Procter & Gamble Company | Flushable hard surface cleaning wet wipe |
US20030220048A1 (en) * | 2000-10-16 | 2003-11-27 | The Procter & Gamble Company | Breast pads |
US20020183233A1 (en) | 2000-12-14 | 2002-12-05 | The Clorox Company, Delaware Corporation | Bactericidal cleaning wipe |
US6699825B2 (en) | 2001-01-12 | 2004-03-02 | S.C. Johnson & Son, Inc. | Acidic hard-surface antimicrobial cleaner |
DK1379257T3 (en) | 2001-03-23 | 2009-12-14 | Enzon Inc | Anticancer prophylaxis using substituted aromatic acids |
US6551980B1 (en) | 2001-11-13 | 2003-04-22 | Colgate-Palmolive Company | Cleaning wipe |
US20030119394A1 (en) | 2001-12-21 | 2003-06-26 | Sridhar Ranganathan | Nonwoven web with coated superabsorbent |
GB2391810A (en) | 2002-08-14 | 2004-02-18 | Reckitt Benckiser Inc | Disinfectant with residual antimicrobial activity |
GB2392167A (en) | 2002-08-22 | 2004-02-25 | Reckitt Benckiser Inc | Composition containing an acid with anionic and nonionic surfactants |
ATE438304T1 (en) | 2002-11-15 | 2009-08-15 | Virox Technologies Inc | A HYDROGEN PEROXIDE DISINFECTANT CONTAINING ACID AND/OR ALCOHOL |
GB2397823A (en) | 2003-01-31 | 2004-08-04 | Reckitt Benckiser Nv | Aqueous cleaning compositions |
GB2401875A (en) | 2003-05-22 | 2004-11-24 | Reckitt Benckiser Nv | Aqueous cleaning compositions |
US7070737B2 (en) | 2003-08-01 | 2006-07-04 | The Clorox Company | Disinfecting article with extended efficacy |
US7008600B2 (en) | 2003-08-01 | 2006-03-07 | The Clorox Company | Disinfecting article and cleaning composition with extended stability |
US20050159063A1 (en) * | 2004-01-16 | 2005-07-21 | Bernard Hill | Disposable cleaning substrate |
US20050266229A1 (en) | 2004-05-26 | 2005-12-01 | Richard Porticos | Nonwoven with attached foam particles |
JP2006020830A (en) * | 2004-07-08 | 2006-01-26 | Matsushita Electric Ind Co Ltd | Self-propelled vacuum cleaner, and program of the same |
US20070037721A1 (en) * | 2004-09-01 | 2007-02-15 | The Procter & Gamble Company | Moistened disposable wipe for controlling allergens |
EP1906773A1 (en) | 2005-07-25 | 2008-04-09 | Ecolab, Inc. | Antimicrobial compositions for use on food products |
US7658953B2 (en) | 2006-01-13 | 2010-02-09 | Aseptix Research B.V. | Enhanced activity biocidal hydrogen peroxide composition |
US20070190172A1 (en) | 2006-01-13 | 2007-08-16 | Aseptix Technologies B.V. | Enhanced activity biocidal hydrogen peroxide composition |
US7696109B2 (en) | 2006-02-24 | 2010-04-13 | The Clorox Company | Low-density cleaning substrate |
US20100062671A1 (en) * | 2008-09-05 | 2010-03-11 | Nutek Disposables, Inc. | Composite wipe |
US8287755B2 (en) | 2008-12-09 | 2012-10-16 | The Clorox Company | Solid-layered bleach compositions |
CN102218866B (en) * | 2010-04-02 | 2014-12-24 | 株式会社广谷 | Manufacturing method of vehicular interior decorating material |
US8575084B2 (en) | 2010-11-12 | 2013-11-05 | Jelmar, Llc | Hard surface cleaning composition for personal contact areas |
US8569220B2 (en) | 2010-11-12 | 2013-10-29 | Jelmar, Llc | Hard surface cleaning composition |
JP5871538B2 (en) * | 2011-09-28 | 2016-03-01 | ユニ・チャーム株式会社 | Manufacturing method of fiber sheet |
US8648027B2 (en) | 2012-07-06 | 2014-02-11 | The Clorox Company | Low-VOC cleaning substrates and compositions comprising a cationic biocide |
US10064409B2 (en) | 2013-05-03 | 2018-09-04 | Basf Se | Synergistic antimicrobial formulation |
DE102013217325A1 (en) | 2013-08-30 | 2015-03-05 | Werner & Mertz Gmbh | Detergent with descaling effect |
US10076115B2 (en) | 2014-10-09 | 2018-09-18 | ProNatural Brands, LLC | Naturally-derived surface sanitizer and disinfectant |
WO2017174959A1 (en) | 2016-04-08 | 2017-10-12 | Reckitt Benckiser Llc | Sprayable thickened aqueous acidic compositions |
-
2020
- 2020-03-25 CA CA3128040A patent/CA3128040A1/en active Pending
- 2020-03-25 EP EP20782489.7A patent/EP3945977A4/en active Pending
- 2020-03-25 WO PCT/US2020/024675 patent/WO2020205360A1/en unknown
- 2020-03-25 MX MX2021011796A patent/MX2021011796A/en unknown
- 2020-03-25 CN CN202080018329.4A patent/CN113518573B/en active Active
-
2021
- 2021-09-27 CL CL2021002497A patent/CL2021002497A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
MX2021011796A (en) | 2021-10-13 |
EP3945977A4 (en) | 2022-10-12 |
CA3128040A1 (en) | 2020-10-08 |
CL2021002497A1 (en) | 2022-07-01 |
CN113518573B (en) | 2023-04-04 |
CN113518573A (en) | 2021-10-19 |
WO2020205360A1 (en) | 2020-10-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11858238B2 (en) | Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene | |
KR20060105805A (en) | Wet wipe with low liquid add-on | |
AU2018331271B2 (en) | Cleaning wipes with particular lotion retention and efficacy characteristics | |
US20200080031A1 (en) | Multi-layer cleaning and disinfecting wipes having optimal delamination behavior with cleaning lotion | |
EP3945977A1 (en) | Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene | |
US10973385B2 (en) | Cleaning wipes having particular pore volume distribution characteristics | |
US20190105869A1 (en) | Melamine wipes | |
US11365496B2 (en) | Melamine wipes and methods of manufacture | |
WO2022020115A1 (en) | Compostable nonwoven with low extensibility | |
WO2004098369A1 (en) | Multi-layered cleaning swab and methods for manufacturing same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210723 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20220912 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 7/05 20190101ALI20220906BHEP Ipc: B32B 7/022 20190101ALI20220906BHEP Ipc: B32B 3/26 20060101ALI20220906BHEP Ipc: D04H 3/007 20120101ALI20220906BHEP Ipc: C11D 1/62 20060101ALI20220906BHEP Ipc: B32B 5/26 20060101ALI20220906BHEP Ipc: B32B 5/06 20060101ALI20220906BHEP Ipc: A47L 13/17 20060101ALI20220906BHEP Ipc: A47L 13/16 20060101AFI20220906BHEP |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230503 |