WO2000044982A1 - Process and chemical formulation for making rigid, biodegradable articles - Google Patents

Process and chemical formulation for making rigid, biodegradable articles Download PDF

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Publication number
WO2000044982A1
WO2000044982A1 PCT/US2000/002209 US0002209W WO0044982A1 WO 2000044982 A1 WO2000044982 A1 WO 2000044982A1 US 0002209 W US0002209 W US 0002209W WO 0044982 A1 WO0044982 A1 WO 0044982A1
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WO
WIPO (PCT)
Prior art keywords
rigidifying
solution
paper
cellulosic
water
Prior art date
Application number
PCT/US2000/002209
Other languages
French (fr)
Other versions
WO2000044982A8 (en
Inventor
L. Keough Gene
Original Assignee
G Enterprises, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by G Enterprises, Inc. filed Critical G Enterprises, Inc.
Priority to AU32177/00A priority Critical patent/AU3217700A/en
Publication of WO2000044982A1 publication Critical patent/WO2000044982A1/en
Publication of WO2000044982A8 publication Critical patent/WO2000044982A8/en

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Classifications

    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B3/00Footwear characterised by the shape or the use
    • A43B3/16Overshoes
    • A43B3/163Overshoes specially adapted for health or hygienic purposes, e.g. comprising electrically conductive material allowing the discharge of electrostatic charges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65HHANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H75/00Storing webs, tapes, or filamentary material, e.g. on reels
    • B65H75/02Cores, formers, supports, or holders for coiled, wound, or folded material, e.g. reels, spindles, bobbins, cop tubes, cans, mandrels or chucks
    • B65H75/04Kinds or types
    • B65H75/08Kinds or types of circular or polygonal cross-section
    • B65H75/10Kinds or types of circular or polygonal cross-section without flanges, e.g. cop tubes
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18Reinforcing agents

Definitions

  • the present invention relates generally to biodegradable materials, and more
  • a common example of a biodegradable material is paper. As is well known in
  • paper is typically formed from cellulose fibers derived from trees and other
  • Certain cellulose-digesting bacteria are capable of consuming the fibers and
  • wastewater treatment systems such as sewage plants and septic
  • wastewater streams including bathroom tissue, facial tissue, etc.
  • the present invention provides a chemical solution and a method of
  • the chemical solution includes a rigidifying agent dissolved in an
  • aqueous solvent that functions as a carrier to saturate the rigidifying agent into the
  • the material is dried so that a residue remains to form a substantially rigid structure
  • a sugar such as sucrose is dissolved in a solvent
  • sucrose including water and isopropyl alcohol to form the rigidifying solution.
  • the sucrose including water and isopropyl alcohol to form the rigidifying solution.
  • tissue paper The tissue
  • the rigidified material may be used to make a wide range of disposable
  • Fig. 1 is an isometric view of a roll of bathroom tissue having a core made in
  • FIG. 2 is an isometric view showing the core of Fig. 1 partially immersed in
  • Fig. 3 is an isometric view of a sheet of corrugated material made in
  • Fig. 4 is an isometric view of a container made in accordance with the present
  • Fig. 5 is an isometric view of a tampon applicator made in accordance with the
  • Fig. 6 is a front elevation of disposable clothing made in accordance with the
  • Fig. 7 is a side elevation of a disposable shoe cover made in accordance with
  • the material is formed from a biodegradable
  • the material provides a new composition of matter having the structural rigidity
  • a non-toxic, rigidifying agent is
  • the material can be any material that forms a substantially rigid material with the fibers.
  • the material can be any material that forms a substantially rigid material with the fibers.
  • tissue paper writing paper, parchment, cardboard, corrugated paper, and etc.
  • Variations in paper types are produced, for example, by changing one or more
  • variables in the paper-making process such as pulping method, fiber size, degree of pulping
  • Household tissue paper commonly used for facial tissue and bathroom tissue
  • This type of paper is typically formed from thin, relatively
  • septic systems typically contain bacteria or other biological materials which readily
  • tissue paper is relatively highly absorbent and, therefore, the
  • biodegradable material includes incorporating a rigidifying agent into the cellulosic
  • the rigidifying agent which is capable of combining with the cellulose fibers to form a substantially rigid structure.
  • the group of substances which is capable of combining with the cellulose fibers to form a substantially rigid structure.
  • sugar refers inclusively to all types of sugars including
  • monosaccharides e.g., fructose, glucose, dextrose, etc.
  • disaccharides e.g., sucrose
  • Sugars are typically commercially available in a crystallized form (e.g., table
  • sugar EQUAL sweetener, NUTRASWEET sweetener, etc.
  • EQUAL sweetener EQUAL sweetener
  • NUTRASWEET sweetener NUTRASWEET sweetener
  • raw sugar starch available in other forms such as raw sugar starch, sugar beets, and liquids/syrups (e.g.,
  • cellulosic material is incorporated in and/or around the cellulose fibers to impart a
  • any number or combination of sugars may be used as the rigidifying agent, for the
  • sucrose is used as the rigidifying agent.
  • Sucrose is commonly available in crystal form as ordinary table sugar.
  • sucrose when dissolved in a suitable aqueous solvent, the sucrose loses its crystal
  • the rigidifying solution is then applied to household tissue paper so as to saturate the tissue with the solution.
  • tissue paper When allowed to dry, most or all of the solvent is evaporated,
  • sucrose does not re-crystallize when the solvent is evaporated, but forms a relatively
  • a relatively small amount of an alcohol is added to the water.
  • the solvent acts as a carrier liquid to fully
  • the solvent preferably does
  • the rigidifying solution includes table sugar dissolved in an aqueous solution of
  • water/alcohol solvent is preferably heated to approximately 120°-200° Fahrenheit to
  • tissue including, for example, spraying, brushing, or rolling the solution onto the
  • tissue Other techniques for applying a liquid to a material are also suitable.
  • the application process is effective to
  • now saturated material may be formed into any desired shape prior to drying.
  • the material may first be formed as desired, and then saturated with the
  • sucrose rigidifying agent provides sufficient stiffness to the cellulosic material so that
  • the rigidified material is usually
  • the sugar/cellulose structure is at least somewhat elastic and, therefore, capable of
  • the rigidifying process is completed by drying the saturated cellulosic
  • drying process may vary depending on the
  • solvent is capable of drying "naturally" under ordinary room conditions.
  • drying process may be assisted or shortened by heating the material
  • Heat may be any substance that decreases decreasing the ambient pressure, and/or moving air across the material. Heat may be any substance that decreases.
  • sucrose which is incorporated, the resulting material is remarkably strong, having a
  • sucrose solvent such as
  • the rigidified tissue may be formed with a desired color by adding
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • the coloring agent is any coloring agent to the rigidifying solution.
  • coloring agents are suitable and therefore within the scope of the invention, one
  • preferred coloring agent is conventional food color because it is inexpensive, readily
  • rigidifying solution results in a rigidified material with a moderately intense color.
  • a scenting agent may be added to the rigidifying
  • the material is dried. While various concentrations of scenting agent may be used, in
  • potpourri is added to the sugar/water/isopropyl alcohol rigidifying solution, it has been found that approximately 10-milliliters of potpourri
  • rigidifying solution may typically be added in any order.
  • the coloring or scenting agent may be added to the sugar, and the
  • the rigidified material may be further processed after drying
  • material may be ornamented with indicia or decoration using ink, paint, etc.
  • Exemplary indicia include trademarks, use or disposal instructions, and etc.
  • rigidified material may be cut to a desired shape, punctured, folded, bent, or otherwise
  • present invention may be applied, it is possible to at least illustrate a few of such uses.
  • the rigidified material is obviously well suited to replace ordinary
  • articles formed of paper and other cellulosic material may be made using
  • cellulose fibers may be applied to the cellulose fibers during the paper-making process.
  • the cellulose fibers may be applied to the cellulose fibers during the paper-making process.
  • the solution may be added to the cellulosic material before it is formed into a pulp, or
  • the rigidifying agent provides a structural
  • Figs. 1 and 2 show one
  • inner core 10 may be constructed from the
  • core 10 may
  • tissue 12 when formed of a different cellulosic material than tissue 12.
  • core 10 may be disposed of in the toilet.
  • inner core 10 is substantially cylindrical in shape
  • Inner core 10 may be formed in any size and shape but is typically formed to the
  • the length of inner core 10 is approximately 4 7 /i6 inches, the outer
  • Inner core 10 is usually formed from one or more sheets of bathroom tissue. It
  • tissue employed is a multi-ply material or a single-ply material.
  • the rigidifying solution is applied to the sheets such as by spraying.
  • a suitable rigidifying solution is the sugar/water/isopropyl alcohol solution
  • the solution may contain a coloring and/or scenting
  • the sheets may be placed over a form of the desired
  • the form is usually constructed of glass, metal, or some other
  • tissue is then rewound onto heated mandrels.
  • mandrels are heated to ensure that the inner layers of tissue, which have been
  • a mandrel may be configured for heating.
  • the mandrel may be heated to a desired temperature
  • element may be powered by 120 VAC wall current using either manual or automatic
  • thermocouples mounted to the mandrel.
  • the mandrel temperature may be measured using a non-thermal thermocouples
  • thermometer focused on a portion of the mandrel which is free of
  • Fig. 1 The inner layers of tissue, although integral with the outer layers, have been
  • Fig. 3 shows another example of a biodegradable, environmentally-friendly
  • first outer layer 18 includes a relatively flat first outer layer 18, a ribbed inner layer 20, and a relatively flat first outer layer 22.
  • ribbed layers may be added for increased strength, thickness, etc.
  • at least one of layers 18, 20, and 22 is formed
  • the other layer(s) may be
  • sheet 16 formed of rigidified material. In the latter case, all of sheet 16 will be biodegradable.
  • a further example of an article formed from rigidified cellulosic material is the
  • Container 24 illustrated in Fig. 4.
  • Container 24 may be formed from corrugated
  • material such as illustrated in Fig. 3, or it may be formed of non-corrugated material.
  • the elasticity of the rigidified material allows the creation of a living hinge 26 to
  • the container walls are preferably made from
  • the walls may be formed by gluing separate pieces of
  • container 24 may optionally be
  • interior of the container may be lined, for example, by wax paper or plastic, for
  • applicator 30 is formed from rigidified material coated with a perforated layer of plastic, wax, or etc.
  • plastic coating may or may not fully
  • Fig. 6 shows a biodegradable garment 32 made in accordance with the
  • garment 32 is depicted as a pair of coveralls, it will be appreciated
  • garment 32 may be made in any suitable shape or style of clothing including a
  • garment 32 may
  • portion, and preferably most of the garment is made of rigidified material so that the
  • Garment 32 is substantially biodegradable. Garment 32 may be useful for any activity
  • a few exemplary applications include medical or surgical garments, garments
  • Fig. 7 shows a disposable shoe cover 34 which can be worn over a shoe 36 to
  • disposable shoe cover 34 may be
  • the experiment was measured at 100 ml in a glass beaker.
  • Table 1 Summary Findings - Before & After - iron, pH, grains hardness

Abstract

A rigidifying chemical solution and method of incorporating it into a cellulosic material to form a substantially rigid material is disclosed. The rigid material is dissolvable in water and biodegradable in conventional wastewater treatment systems. The chemical solution includes a rigidifying agent, such as sugar, dissolved in an aqueous solvent. When the rigidifying solution is applied to a cellulosic material such as paper, the solvent functions to incorporate the rigidifying agent into the cellulosic material. When the material dries, a rigidifying residue remains to form a substantially rigid structure with the cellulosic material. The rigidified material may be used to make a wide range of disposable articles.

Description

PROCESS AND CHEMICAL FORMULATION FOR MAKING RIGID,
BIODEGRADABLE ARTICLES
Cross-Reference to Related Applications
This application is a continuation of U.S. Provisional Patent Application Serial
No. 60/117,800 entitled "SYSTEM AND CHEMICAL FORMULATION FOR
MAKING RIGID/READILY DISSOLVABLE MATERIAL" filed on January 29,
1999.
Field of the Invention
The present invention relates generally to biodegradable materials, and more
particularly to a process for treating cellulosic materials, such as paper, to reversibly
impart a substantial rigidity to the material without destroying the biodegradability of
the material.
Background
It is well known that the escalating human population has placed a significant
strain on the capacities of local, national, and global waste disposal and landfill
resources. This situation is exacerbated by particular trends such as the reliance on
pre-packaged, individual meals, single-use disposable items, and etc. As a result,
there has been an increasing focus, in recent years, on reducing the amount of waste
disposed of in landfills.
One important approach to waste reduction involves recycling used materials
such as paper, cardboard, plastics, glass, etc. However, many materials cannot be
recycled either due to their nature or the way in which the materials are used.
Additionally, recycling may be inconvenient or unavailable in many communities so that used materials, which are capable of recycling, are nevertheless disposed of in
landfills.
An alternative approach to waste reduction involves manufacturing products
from materials which are capable of disintegration or biodegradation. Such products
either partially or fully decompose under the influence of natural environmental
conditions or biological processes. As a result, the use of biodegradable products
significantly reduces the volume of waste matter accumulated in landfills.
A common example of a biodegradable material is paper. As is well known in
the art, paper is typically formed from cellulose fibers derived from trees and other
plants. Certain cellulose-digesting bacteria are capable of consuming the fibers and
converting them to naturally occurring compounds which are reincorporated into the
environment. Indeed, wastewater treatment systems such as sewage plants and septic
tanks typically employ such bacteria to decompose the cellulosic material found in
wastewater streams including bathroom tissue, facial tissue, etc. Considering the
enormous amount of tissue paper consumed each day, it is obvious that the ability of
wastewater treatment systems to biodegrade tissue paper saves a substantial amount of
landfill space. Thus, it would be desirable to make a variety of products from tissue
paper since the used products could be disposed of without burdening overcrowded
landfills.
Unfortunately, while paper, and especially tissue paper, is well suited for
biodegradation in sewage lines, it has a limited number of uses given its naturally
weak structural characteristics. Furthermore, techniques developed to increase the
strength of paper typically also reduce its biodegradability. Summary of the Invention
The present invention provides a chemical solution and a method of
incorporating the solution into a cellulosic material to form a substantially rigid
material that is dissolvable in water and biodegradable in conventional wastewater
treatment systems. The chemical solution includes a rigidifying agent dissolved in an
aqueous solvent that functions as a carrier to saturate the rigidifying agent into the
cellulosic material. After the rigidifying solution is applied to the cellulosic material,
the material is dried so that a residue remains to form a substantially rigid structure
with the cellulosic material.
In one exemplary embodiment, a sugar such as sucrose is dissolved in a solvent
including water and isopropyl alcohol to form the rigidifying solution. The sucrose
solution is sprayed onto one or more layers of household tissue paper. The tissue
paper is then heated to evaporate the solvent, leaving the sucrose incorporated into the
tissue paper and imparting a substantial rigidity to the paper without destroying the
inherent tendency of the paper to disintegrate in water. When disposed of in
conventional sewage lines, the rigidified tissue paper loses its rigidity, disintegrates,
and biodegrades.
The rigidified material may be used to make a wide range of disposable
articles.
Brief Description of the Drawings
Fig. 1 is an isometric view of a roll of bathroom tissue having a core made in
accordance with the present invention. Fig. 2 is an isometric view showing the core of Fig. 1 partially immersed in
water and beginning to lose its structural rigidity and to disintegrate.
Fig. 3 is an isometric view of a sheet of corrugated material made in
accordance with the present invention.
Fig. 4 is an isometric view of a container made in accordance with the present
invention.
Fig. 5 is an isometric view of a tampon applicator made in accordance with the
present invention.
Fig. 6 is a front elevation of disposable clothing made in accordance with the
present invention.
Fig. 7 is a side elevation of a disposable shoe cover made in accordance with
the present invention.
Detailed Description
One example of a substantially rigid, readily-dissolvable material in accordance
with the present invention is depicted in the form of a bathroom tissue core, indicated
generally at 10, in Figs. 1 and 2. The material is formed from a biodegradable,
relatively pliant cellulosic substance that is strengthened and stiffened by applying a
rigidifying solution to the substance and then drying it in a desired shape. However,
the rigidifying residue that remains after drying is re-dissolvable upon exposure to
water. As a result, the material can safely be disposed of in the sewage system. Thus,
the material provides a new composition of matter having the structural rigidity
necessary for a variety of applications, while retaining the inherent biodegradability of
a cellulosic substance. The invented process for treating the cellulosic material to reversibly impart a
structural rigidity is surprisingly easy and inexpensive to implement in either single-
unit construction or mass production. In essence, a non-toxic, rigidifying agent is
dissolved in a solvent to form a rigidifying solution. The rigidifying solution is then
applied to an accumulation of cellulosic fibers. When the solvent dries and/or
evaporates from the fibers, at least a portion of the rigidifying agent remains as a
residue that forms a substantially rigid material with the fibers. The material can
easily be formed into any desired shape prior to drying so that the material will retain
the desired shape until disposed of in water. It will be appreciated that the invention is
susceptible to an almost unlimited number of uses, a few of which will be specifically
mentioned below.
As is well known to those of skill in the art, there are many cellulosic
substances which are suitable for making paper and paper-like products. A few of the
most common of such substances include wood, hemp, and cotton. In addition, there
are a wide variety of paper types and configurations well known in the art including
tissue paper, writing paper, parchment, cardboard, corrugated paper, and etc.
Variations in paper types are produced, for example, by changing one or more
variables in the paper-making process such as pulping method, fiber size, degree of
compression, additives, etc. For the sake of clarity, the invention is herein described
in the context of only one such substance and configuration, i.e., household tissue
paper. Nevertheless, it will be understood that the invention is in no way limited by
such description as the invention may be effectively practiced with any of the known
cellulosic materials, or combinations thereof, and in any desired configuration. Household tissue paper, commonly used for facial tissue and bathroom tissue,
is manufactured by a variety of sources and is available in virtually any retail store
that sells food or sundries. This type of paper is typically formed from thin, relatively
lightly compressed layers of wood pulp fiber according to conventional paper-making
processes well known in the art. Upon immersion in water, household tissue paper
loses virtually all structural rigidity and will begin to tear and/or disintegrate when
exposed to even slight forces. Due to its pliant and fragile nature in water, tissue
paper is well-suited for disposal in ordinary sewage systems because it is unlikely to
form obstructions in waste lines. In addition, modern sewage treatment facilities and
septic systems typically contain bacteria or other biological materials which readily
breakdown or decompose the tissue paper, returning naturally occurring byproducts to
the environment. Thus, its low cost, ready availability, and biodegradability make
household tissue paper well suited for use as the source of cellulosic material.
In addition, tissue paper is relatively highly absorbent and, therefore, the
rigidifying solution is easily incorporated into the cellulosic material. Some less
absorbent cellulosic materials, while still being suitable for use in the rigidifying
process, may be less efficient in incorporating the rigidifying solution. Consequently,
the increase in rigidity for these materials may not be as dramatic as is the case with
tissue paper.
As mentioned briefly above, the process of forming the substantially rigid,
biodegradable material includes incorporating a rigidifying agent into the cellulosic
materials to provide structural stiffness to the cellulose fibers. Any substance may be
employed as the rigidifying agent, which is capable of combining with the cellulose fibers to form a substantially rigid structure. For example, the group of substances
commonly referred to as sugars have been found to provide an inexpensive, readily
available rigidifying agent for use with cellulosic materials such as tissue paper. As
used herein, the term sugar refers inclusively to all types of sugars including
monosaccharides (e.g., fructose, glucose, dextrose, etc.), disaccharides (e.g., sucrose,
etc.), and trisaccharides (e.g., raffinose, etc.), as well as sugar substitutes such as
aspartame.
Sugars are typically commercially available in a crystallized form (e.g., table
sugar, EQUAL sweetener, NUTRASWEET sweetener, etc.), but may also be
available in other forms such as raw sugar starch, sugar beets, and liquids/syrups (e.g.,
KARO corn syrup, etc.). In any event, it is believed that the sugar, when introduced
to cellulosic material, is incorporated in and/or around the cellulose fibers to impart a
substantial rigidity to the fibrous web. Subsequently, upon exposure of the rigidified
material to a solvent, the sugar is dissolved into the solvent and unincorporated from
the cellulosic material, thereby returning the material to its pre-rigidified state. While
any number or combination of sugars may be used as the rigidifying agent, for the
sake of clarity, the description below will focus on an exemplary embodiment in
which sucrose is used as the rigidifying agent.
Sucrose is commonly available in crystal form as ordinary table sugar.
However, when dissolved in a suitable aqueous solvent, the sucrose loses its crystal
structure and forms a homogenous rigidifying solution with the solvent. In
accordance with one preferred embodiment of the invention, a sufficient quantity of
the rigidifying solution is then applied to household tissue paper so as to saturate the tissue with the solution. When allowed to dry, most or all of the solvent is evaporated,
leaving a sucrose residue incorporated into the fibrous structure of the tissue. The
sucrose does not re-crystallize when the solvent is evaporated, but forms a relatively
uniform, continuous matrix with the tissue fibers.
It will be appreciated that the choice of solvent will vary depending on the
rigidifying agent selected. Water has been found to be a preferred solvent for use with
sugar. Preferably, a relatively small amount of an alcohol is added to the water.
While many different alcohols can be used, a non-toxic alcohol such as isopropyl
alcohol may be preferred for many applications. In addition to breaking down the
crystallized structure of the sugar, the solvent acts as a carrier liquid to fully
incorporate the sugar into the cellulosic material. Further, the solvent preferably does
not adversely affect the cellulosic material, and may be easily removed by drying the
material.
As will be understood by those of skill in the art, the volume ratios of the sugar
and solvent will vary depending on the particular sugar and solvent used.
Additionally, it may be desirable to heat the solvent when dissolving the sugar to
reduce the time needed to dissolve the sugar and/or increase the amount of sugar
dissolved in the solvent. In the exemplary preferred embodiment discussed above, in
which the rigidifying solution includes table sugar dissolved in an aqueous solution of
water and isopropyl alcohol, the following volume ratios have been found to be
suitable: 6: 1: 12 (water:alcohol:sugar) (where sugar is measured by dry volume). The
water/alcohol solvent is preferably heated to approximately 120°-200° Fahrenheit to
ensure that the sugar is completely dissolved. However, other ratios and temperatures may also be used depending on the application and desired characteristics of the
resulting rigidified material.
Various techniques may be employed to apply the rigidifying solution to the
tissue including, for example, spraying, brushing, or rolling the solution onto the
tissue. Other techniques for applying a liquid to a material are also suitable.
Typically, though not necessarily, the particular method used will be selected for
compatibility with the manufacturing process and equipment of the particular rigid,
biodegradable article in question. In any event, the application process is effective to
introduce the rigidifying agent to the cellulosic material so that the agent combines
with the cellulose fibers to form a substantially rigid structure. In general, it is usually
desirable to saturate the cellulosic material with the rigidifying solution to ensure full
incorporation of the rigidifying agent.
Once the rigidifying solution has been applied to the cellulosic material, the
now saturated material may be formed into any desired shape prior to drying.
Alternatively, the material may first be formed as desired, and then saturated with the
rigidifying solution. In any event, depending on the characteristics of the cellulosic
material used, it may be necessary to support the saturated material in the desired
shape until the drying process has at least partially been completed. For example, in
the exemplary embodiment in which tissue paper is used, physical support is usually
necessary due to the relative pliability of wet tissue paper. However, once dry, the
sucrose rigidifying agent provides sufficient stiffness to the cellulosic material so that
further support is typically unnecessary. Indeed, the rigidified material is usually
sufficiently rigid to successfully resist moderate deforming forces. Further, the sugar/cellulose structure is at least somewhat elastic and, therefore, capable of
deforming under relatively heavier forces without cracking, tearing, etc.
The rigidifying process is completed by drying the saturated cellulosic
material. It will be appreciated that the drying process may vary depending on the
rigidifying agent and aqueous solvent solution being used. In the
sucrose/water/isopropyl alcohol formulation described above, the water/alcohol
solvent is capable of drying "naturally" under ordinary room conditions.
Alternatively, the drying process may be assisted or shortened by heating the material,
decreasing the ambient pressure, and/or moving air across the material. Heat may be
applied through any conventional means including microwave energy. Care should be
taken, however, to avoid igniting any components of the rigidifying solution that may
be flammable, such as isopropyl alcohol. As will be expected, the necessary drying
time will generally decrease with increasing temperature, decreasing pressure,
increased air flow, etc.
In the process just described, a dramatically increased rigidity is imparted to
household tissue paper by incorporating sucrose in and/or around the cellulose fibers
of the paper. Depending on the number of layers of tissue paper used and the quantity
of sucrose which is incorporated, the resulting material is amazingly strong, having a
rigidity equal to a much greater thickness of cardboard. However, the rigidity is
completely reversible by simply immersing the material in a sucrose solvent such as
water. Thus, unlike prior paper rigidifying processes, the invented process does not
destroy the inherent tendency of the tissue to disintegrate in water, or the
biodegradability of the tissue in standard wastewater treatment systems. In addition to a dramatically increased rigidity, other characteristics may be
imparted to the tissue paper by adding optional substances to the rigidifying solution.
For example, the rigidified tissue may be formed with a desired color by adding
selected coloring agents to the rigidifying solution. Preferably, the coloring agent is
selected so as not to interfere with the rigidifying process. While a number of
coloring agents are suitable and therefore within the scope of the invention, one
preferred coloring agent is conventional food color because it is inexpensive, readily
available in a variety of colors, and is non-toxic. Other coloring agents may also be
used.
It will be appreciated that the intensity of color imparted to the rigidified
material will be at least somewhat proportional to the concentration of coloring agent
in the solution. Thus, the amount of coloring agent added to the rigidifying solution
can be varied to adjust the color of the material. In the embodiment where food
coloring is used in the sugar/water/isopropyl alcohol solution, it has been found that
adding approximately 16-drops of food coloring to approximately 187-milliliters of
rigidifying solution results in a rigidified material with a moderately intense color.
Other factors potentially effecting the final color of the rigidified material will include
the absorbency and initial color of the cellulosic material.
Additionally, or alternatively, a scenting agent may be added to the rigidifying
solution to impart a desired scent to the rigidified tissue paper. For example, potpourri
or any other scented material may be added which will leave a scented residue when
the material is dried. While various concentrations of scenting agent may be used, in
the embodiment where potpourri is added to the sugar/water/isopropyl alcohol rigidifying solution, it has been found that approximately 10-milliliters of potpourri
added to approximately 187-milliliters of solution results in a rigidified material with
a moderate scent. As a further option, selected enzymes, which are capable of
disintegrating other materials in holding tanks, septic tanks, etc., may be incorporated
into the rigidifying solution to enhance the utility of the rigidified material.
While the coloring and scenting agents have been described as being added to
the rigidifying solution, it will be appreciated that the various constituents of the
rigidifying solution may typically be added in any order. Thus, reference herein to
adding a coloring or scenting agent to the rigidifying solution will be understood to
include adding such agent to the solvent either before or after the sugar is added.
Alternatively, the coloring or scenting agent may be added to the sugar, and the
combination dissolved in the solvent. As a further alternative, one or more of the
various rigidifying, coloring, and/or scenting agents may be added to either the water
or the alcohol before the other solvent component is added. In short, there is generally
no required sequence for mixing the rigidifying solution.
As another option, the rigidified material may be further processed after drying
to impart other characteristics desirable for a particular application. For example, a
particular coating such as wax (or wax paper), plastic, or etc., may be applied to
selected regions of the rigidified material to provide a water-insoluble surface. This
may be desirable, for example in food containers, etc. Additionally, the rigidified
material may be ornamented with indicia or decoration using ink, paint, etc.
Exemplary indicia include trademarks, use or disposal instructions, and etc. Although the invented process imparts a substantial rigidity to the cellulosic
material, additional post-process shaping remains possible. For example, the
rigidified material may be cut to a desired shape, punctured, folded, bent, or otherwise
reshaped. In some cases, it may be desirable to slightly moisten the material to
increase its pliability.
While it is impractical to describe with any detail the myriad uses to which the
present invention may be applied, it is possible to at least illustrate a few of such uses.
For example, the rigidified material is obviously well suited to replace ordinary
cardboard in virtually any application in which cardboard is currently used. Not only
is the material much easier to dispose of than cardboard, it also requires much less
cellulosic material than cardboard to produce a structure having a given degree of
strength and rigidity.
This latter point illustrates a further advantage of the present invention.
Specifically, articles formed of paper and other cellulosic material may be made using
less cellulosic material without sacrificing rigidity. Indeed, the rigidifying solution
may be applied to the cellulose fibers during the paper-making process. For example,
the solution may be added to the cellulosic material before it is formed into a pulp, or
alternatively, before the pulp is formed into a continuous sheet, or alternatively, before
the sheet is finally dried. In any event, the rigidifying agent provides a structural
stiffness that otherwise must be supplied by a greater thickness of cellulose fibers.
Thus, in addition to producing materials and articles which are easily biodegradable,
the invention also reduces the consumption of natural resources such as trees. Focusing now more closely on the drawings, Figs. 1 and 2 show one
application in which the rigidified material is used to replace the cardboard ordinarily
found in a consumer article. Specifically, in place of a cardboard inner core for a roll
of paper such as bathroom tissue paper, inner core 10 may be constructed from the
same bathroom tissue 12 which is wound around the core. Alternatively, core 10 may
be formed of a different cellulosic material than tissue 12. In any event, when
bathroom tissue 12 is exhausted, core 10 may be disposed of in the toilet. In view of
the large number of bathroom tissue rolls consumed by the average household, the
elimination of the non-biodegradable cardboard core achieves an enormous reduction
of landfill waste .
As depicted in Figs. 1 and 2, inner core 10 is substantially cylindrical in shape
with a hollow center bore adapted to fit over standard bathroom tissue dispensers.
Inner core 10 may be formed in any size and shape but is typically formed to the
dimensions of a standard cardboard inner core for a bathroom tissue roll.
Accordingly, the length of inner core 10 is approximately 47/i6 inches, the outer
diameter is approximately Pλ inches, and the inner diameter is approximately 1 45/β4
inches. In alternative embodiments, such as a paper towel core, the dimensions of the
core will preferably be compatible with standard paper towel cores made of
cardboard.
Inner core 10 is usually formed from one or more sheets of bathroom tissue. It
will be understood that the number of tissue layers used will depend on whether the
tissue employed is a multi-ply material or a single-ply material. In accordance with
the present invention, the rigidifying solution is applied to the sheets such as by spraying. A suitable rigidifying solution is the sugar/water/isopropyl alcohol solution
described above. Optionally, the solution may contain a coloring and/or scenting
agent. Once saturated with rigidifying solution, the sheets are then formed into a roll
of the desired size. Alternatively, the sheets may be placed over a form of the desired
size and shape. The form is usually constructed of glass, metal, or some other
material adapted for easy release of the sheets after drying.
In a typical mass production application, the rigidifying process is incorporated
into the existing tissue manufacturing process. Thus, once the tissue is formed into
large, core-less rolls, the first several sheets of the outer edge of the tissue is sprayed
with rigidifying solution. The tissue is then rewound onto heated mandrels. The
mandrels are heated to ensure that the inner layers of tissue, which have been
saturated with rigidifying solution, are dried quickly. Typical mandrel temperatures
may be in the range of approximately 250° to 300° Fahrenheit. It has been found that
these temperatures achieve sufficient diying within approximately 25-30 seconds. A
slight amount of force may be applied to the wetted layers of tissue (e.g., by rollers,
etc.) to adhere the adhere the solution and layers together.
There are a variety of ways in which a mandrel may be configured for heating.
In tests involving a non-rotated section of a standard stainless steel 316 industrial roll
paper mandrel, it has been found that the mandrel may be heated to a desired
temperature by placing a resistive electrical heating element (approximately 1/4"
diam.) in the inside diameter (approximately 1" diam.) of the mandrel. The heating
element may be powered by 120 VAC wall current using either manual or automatic
control to achieve the desired temperature. Various devices may be used for detecting the mandrel temperature including one or more thermocouples mounted to the mandrel. Alternatively, the mandrel temperature may be measured using a non-
contact infra-red thermometer focused on a portion of the mandrel which is free of
tissue paper and painted black. It is calculated that a full-size heated mandrel such as
described above would require approximately two kilowatts of power to initially heat
the mandrel to approximately 300° Fahrenheit, and approximately 0.6 kilowatts/hour
to maintain the mandrel at the target temperature.
When the tissue has been completely wound onto the mandrels, the tissue
forms a long roll which can be cut into individual rolls of standard size as shown in
Fig. 1. The inner layers of tissue, although integral with the outer layers, have been
rigidified and thus provide a structurally sound core to replace the standard cardboard
core. Nevertheless, upon immersion in water 14, the inner layers lose their rigidity
and become essentially indistinguishable from the non-rigidified layers. Thus, the
core can be safely disposed of in standard sewage systems.
Fig. 3 shows another example of a biodegradable, environmentally-friendly
article formed according to the present invention. Indicated generally at 16 is a sheet
of corrugated material, at least a portion of which is formed from substantially rigid,
biodegradable material. In the embodiment depicted in Fig. 3, corrugated sheet 16
includes a relatively flat first outer layer 18, a ribbed inner layer 20, and a relatively
flat second outer layer 22. Ribbed inner layer 20 is sandwiched between outer layers
18 and 22 to form an extremely strong composite structure. While sheet 16 is
depicted as consisting of three layers, it will be appreciated that additional flat and/or
ribbed layers may be added for increased strength, thickness, etc. In accordance with the invention, at least one of layers 18, 20, and 22 is formed
from rigidified cellulosic material as described above. The other layer(s) may be
formed from conventional material such as paperboard, cardboard, etc. However,
preferably more than one of the layers, and most preferably all of the layers, are
formed of rigidified material. In the latter case, all of sheet 16 will be biodegradable.
In any event, at least a portion of sheet 16 will disintegrate upon immersion in water,
and will biodegrade when exposed to cellulose-consuming micro-organisms.
A further example of an article formed from rigidified cellulosic material is the
container 24 illustrated in Fig. 4. Container 24 may be formed from corrugated
material, such as illustrated in Fig. 3, or it may be formed of non-corrugated material.
The elasticity of the rigidified material allows the creation of a living hinge 26 to
connect a lid 28 to the container. The container walls are preferably made from
continuous sheets of tissue paper which are formed into a box and then rigidified as
described above. Alternatively, the walls may be formed by gluing separate pieces of
rigidified material together. As with the other articles, container 24 may optionally be
formed of colored or scented rigidified material as described above. In addition, the
interior of the container may be lined, for example, by wax paper or plastic, for
storage of food, liquid, or etc.
As an additional example, a sewer-disposable tampon applicator is indicated
generally at 30 in Fig. 5. As is well known in the art, conventional tampon applicators
are formed from plastic and/or cardboard coated with plastic. Unfortunately, these
materials are often disposed of in sewer lines where they cause blockages because
they retain their rigidity after immersion in water. In contrast, applicator 30 is formed from rigidified material coated with a perforated layer of plastic, wax, or etc.
Consequently, when applicator 30 is disposed of in the sewer lines, the rigidified
material quickly loses its rigidity and begins to disintegrate, thus preventing any
blockages of the sewer lines. While the plastic coating may or may not fully
biodegrade, the main bulk of applicator 30 will biodegrade, thereby substantially
reducing the solid wastes processed by wastewater treatment systems.
Fig. 6 shows a biodegradable garment 32 made in accordance with the
invention. While garment 32 is depicted as a pair of coveralls, it will be appreciated
that garment 32 may be made in any suitable shape or style of clothing including a
gown, poncho, shirt, shorts, pants, hood, etc. In addition, although garment 32 may
include conventional non-biodegradable items such as zippers, buttons, etc., at least a
portion, and preferably most of the garment is made of rigidified material so that the
garment is substantially biodegradable. Garment 32 may be useful for any activity
where it is desired to protect underlying clothing or to prevent transmission of bodily
fluids. A few exemplary applications include medical or surgical garments, garments
for handling hazardous wastes or asbestos removal, garments or tarpaulins for
painting, and etc.
Fig. 7 shows a disposable shoe cover 34 which can be worn over a shoe 36 to
protect the shoe from a dirty environment and/or to protect a clean or delicate flooring
from foot traffic. As with conventional shoe covers, disposable shoe cover 34 may be
made in any size or shape as desired, and may include optional elements such as an
elastic opening 38 or a non-skid sole (not shown). It will be understood that the examples described above and illustrated in the
drawings are just a few of the virtually unlimited uses to which the present invention
may be applied. Those of skill in the art will appreciate that any application or article
requiring a structurally rigid, disposable material may be suitable for employing the
rigidified material described above. Thus, the invention is not limited to the specific
examples illustrated herein, but includes all such applications and articles.
Experimental results on the degradability of the rigidified material are
summarized below:
EXPERIMENTAL RESULTS
Rigidified material samples were dimensioned as: 1 V* inch diameter x 4 VΛ
inches long, i.e., an inner core 10. For testing purposes, a lΔ x Yi inch sample was
removed from the outer edge of one end of the core. The measured values of ambient
air temperature and relative humidity during the experiment were 72° Fahrenheit, and
57%. The measured value of the sample water was 70° Fahrenheit. Water volume for
the experiment was measured at 100 ml in a glass beaker.
Physical Properties
Wall thickness of rigidified material sample - .016 inch
Color - pink
Procedures:
Using the measured water sample, the standing pH value, iron level, and water
grain hardness values were tested (see Table 1). Following the initial measurements of
baseline data for iron, pH, and grain hardness a l x V-. inch square sample of the rigidified was placed in the 100 ml water solution. A timer stop watch was activated
when the sample square was placed in the water.
Timed interval observations were completed as follows:
(Note: a gentle swirling action kept the sample in motion)
1 minute - color changes began to appear at all four edges of the
sample
2 minutes - ply separation began
3 minutes - ply separation section began to go clear. Remained
opaque.
5 minutes wall thickness of ply section are noticeably thinner
10 minutes breakup of ply sections- wall thickness measured at .006
inch
13 minutes suspension of ply sections in water sample
15 minutes continued degradation of ply section samples
Post Testing Readings:
Water Sampling
A repeated test series for measurements of iron, pH, and grain hardness were
conducted on the water sample taken from the 100 ml volume used to observe/test the
rigidified material sample. The following table includes data summarizing the results
of the iron, pH, and grain hardness before and after the test series. Table 1 : Summary Findings - Before & After - iron, pH, grains hardness
Figure imgf000023_0001
Comparison Testing of Standard Household Tissue Core (Cardboard)
Using a standard cardboard inner core of similar diameter and length with a
measured wall thickness of .021 inch, a lA x V2 section was placed into a 100 ml water
volume sample of comparable temperature under exact conditions of ambient air and
relative humidity values. For the purposes of the test, the primary consideration was
the ability of the core sample to dissolve into the water volume sample. Using a timer
stop watch, the sample was observed over a 30 minute period and the only observable
result was ply separation after approximately 15 minutes with no further degradation
of wall thickness through the entire observation period. At the end of the 30 minute
observation period the wall thickness measured .021 inch, the thickness measured at
the beginning of the test.
Conclusion
The timed observations demonstrate that the rigidified material sample is able
to reduce its mass beginning within the first minute of contact with water. Further,
with turbulent conditions associated with conventional water disposal systems, the
entire rigidified material mass would degrade as a solute into the water.
While the invention has been disclosed in its prefened form, the specific
embodiments thereof as disclosed and illustiated herein are not to be considered in a limiting sense as numerous variations are possible. Applicant regards the subject
matter of the invention to include all novel and non-obvious combinations and
subcombinations of the various elements, features, functions and or properties
disclosed herein. No single feature, function, element or property of the disclosed
embodiments is essential. The following claims define certain combinations and
subcombinations which are regarded as novel and non-obvious. Other combinations
and subcombinations of features, functions, elements and/or properties may be
claimed through amendment of the present claims or presentation of new claims in
this or a related application. Such claims, whether they are broader, narrower or equal
in scope to the original claims, are also regarded as included within the subject matter
of applicant's invention.

Claims

I CLAIM:
1. A process for imparting a substantial rigidity to a cellulosic material
without destroying an inherent tendency of the material to at least partially
disintegrate in water, the process comprising:
dissolving one or more sugars in an aqueous solvent to form a rigidifying
solution;
applying the rigidifying solution to the material; and
drying the material.
2. The process of claim 1, wherein the aqueous solution includes water.
3. The process of claim 2, wherein the aqueous solution includes an
alcohol.
The process of claim 3, wherein the material includes tissue paper.
The process of claim 1, wherein the material includes paper.
6. The process of claim 2, wherein the material includes tissue paper.
7. The process of claim 1, further comprising the step of adding a coloring
agent to the rigidifying solution to impart a selected color to the material.
8. The process of claim 1, further comprising the step of adding a scenting
agent to the rigidifying solution to impart a selected scent to the material.
9. The process of claim 1, wherein the step of drying includes heating the
material.
10. The process of claim 1, further comprising the step of forming the
material into a desired shape.
11. The process of claim 10, wherein the step of forming is carried out
before the step of drying.
12. A process for reversibly imparting a substantial rigidity to a material
formed from cellulosic fibers, comprising:
dissolving a rigidifying agent in a carrier liquid, where the rigidifying agent is
in the form of a plurality of crystals; and
incorporating the rigidifying agent into the material by
applying the carrier liquid to the material, and
evaporating the carrier liquid such that at least a portion of the
rigidifying agent remains as a non-crystal residue to form a substantially rigid
structure with the cellulosic fibers;
where the non-crystal residue is dissolvable upon exposure of the rigid
structure to water.
13. The process of claim 12, wherein the rigidifying agent includes a sugar.
14. The process of claim 12, wherein the carrier liquid includes water and an
alcohol.
15. The process of claim 12, wherein the step of evaporating includes
heating the material.
16. The process of claim 12, wherein the cellulosic fibers include wood
pulp.
17. An aqueous chemical solution combinable with cellulosic fibers and
effective to reversibly form a substantially rigid material with the fibers upon drying,
the chemical solution comprising:
an aqueous solvent; and
a selected amount of one or more sugars dissolved in the aqueous solvent.
18. The chemical solution of claim 17, wherein the aqueous solvent includes
water and an alcohol.
19. The chemical solution of claim 17, further comprising a coloring agent.
20. The chemical solution of claim 17, further comprising a scenting agent.
21. The chemical solution of claim 17, wherein the one or more sugars
includes sucrose in the form of food-grade table sugar.
22. A roll of bathroom tissue, comprising:
a substantially rigid inner core; and
a selected quantity of bathroom tissue wound around the inner core;
where the inner core is formed from one or more layers of cellulosic material
and a rigidifying residue that remains after applying a solution including a sugar and
water to the cellulosic material, and then diying the cellulosic material.
23. The claim of 22, wherein the cellulosic material includes paper.
24. The claim of 23, wherein the paper includes tissue paper.
25. The claim of 22, wherein the solution further includes an alcohol.
26. A composition of matter comprising cellulose fibers and one or more
sugars, the composition being formed by dissolving the one or more sugars in a
solvent to form a solution, applying the solution to the fibers, and drying the fibers.
27. The composition of claim 26, wherein the solvent includes water and an
alcohol.
28. The composition of claim 26, wherein the cellulose fibers include wood
pulp.
29. The composition of claim 26, wherein the cellulose fibers are in the
form of paper.
30. An environmentally-friendly article, comprising:
at least one substantially rigid, biodegradable portion formed from
one or more layers of tissue paper, and
a rigidifying residue remaining after a solution including a sugar, water,
and an alcohol is applied to the tissue paper and then dried.
31. The article of claim 30, wherein the biodegradable portion is in the form
of a core for a paper roll.
32. The article of claim 30, wherein the biodegradable portion forms at least
a part of an applicator for a tampon.
33. The article of claim 30, wherein the biodegradable portion forms at least
a part of a garment.
34. The article of claim 30, wherein the biodegradable portion forms at least
a part of a container.
35. The article of claim 30, wherein the biodegradable portion forms at least
a part of a corrugated material.
36. The article of claim 30, wherein the biodegradable portion forms at least
a part of a shoe cover.
37. In a process for making paper, where a cellulosic material is formed into
a pulp and then dried as a substantially continuous sheet, the improvement
comprising:
adding a sugar to the cellulosic material to stiffen the paper.
38. The process of claim 37, wherein the sugar is added to the cellulosic
material before it is dried.
PCT/US2000/002209 1999-01-29 2000-01-28 Process and chemical formulation for making rigid, biodegradable articles WO2000044982A1 (en)

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US60/117,800 1999-01-29

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GB2401870A (en) * 2003-04-04 2004-11-24 Malcolm Hatton Water soluble core for kitchen or toilet paper
EP1675716A1 (en) * 2003-09-26 2006-07-05 US Ingenuity, LLC Dispensing paper-roll core systems
WO2007030749A1 (en) * 2005-09-09 2007-03-15 The Procter & Gamble Company Dispensing paper-roll core systems
US7638475B2 (en) 2006-03-24 2009-12-29 Georgia-Pacific Consumer Products Lp Space saving toilet cleaning system
US20140246161A1 (en) * 2008-12-18 2014-09-04 Sca Tissue France Water-degradable paper sheet, and tube for a paper roll consisting of such a sheet
US9139957B2 (en) 2009-08-03 2015-09-22 Sca Tissue France Fibrous sheet disintegrating in water, process for manufacturing said fibrous sheet, use of said fibrous sheet for the manufacture of a core
WO2019125312A1 (en) * 2017-12-22 2019-06-27 Hayat Kimya Sanayi Anonim Sirketi A water disintegrable core
US10350850B2 (en) * 2008-12-12 2019-07-16 Essity Operations France Core forming support of a paper reel

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Cited By (15)

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GB2401870A (en) * 2003-04-04 2004-11-24 Malcolm Hatton Water soluble core for kitchen or toilet paper
US7951440B2 (en) 2003-09-26 2011-05-31 The Procter & Gamble Company Dispensing paper-roll core systems
EP1675716A1 (en) * 2003-09-26 2006-07-05 US Ingenuity, LLC Dispensing paper-roll core systems
EP1675716A4 (en) * 2003-09-26 2007-02-21 Procter & Gamble Dispensing paper-roll core systems
US8075699B2 (en) 2003-09-26 2011-12-13 The Procter & Gamble Company Dispensing paper-roll core systems
WO2007030749A1 (en) * 2005-09-09 2007-03-15 The Procter & Gamble Company Dispensing paper-roll core systems
US7638475B2 (en) 2006-03-24 2009-12-29 Georgia-Pacific Consumer Products Lp Space saving toilet cleaning system
US10350850B2 (en) * 2008-12-12 2019-07-16 Essity Operations France Core forming support of a paper reel
US20140246161A1 (en) * 2008-12-18 2014-09-04 Sca Tissue France Water-degradable paper sheet, and tube for a paper roll consisting of such a sheet
US9353482B2 (en) * 2008-12-18 2016-05-31 Sca Tissue France Water-degradable paper sheet, and tube for a paper roll consisting of such a sheet
US9139957B2 (en) 2009-08-03 2015-09-22 Sca Tissue France Fibrous sheet disintegrating in water, process for manufacturing said fibrous sheet, use of said fibrous sheet for the manufacture of a core
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US9896803B2 (en) 2009-08-03 2018-02-20 Sca Tissue France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
US10626557B2 (en) 2009-08-03 2020-04-21 Essity Operations France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
WO2019125312A1 (en) * 2017-12-22 2019-06-27 Hayat Kimya Sanayi Anonim Sirketi A water disintegrable core

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