CA2668927C - Modeling dough - Google Patents
Modeling dough Download PDFInfo
- Publication number
- CA2668927C CA2668927C CA2668927A CA2668927A CA2668927C CA 2668927 C CA2668927 C CA 2668927C CA 2668927 A CA2668927 A CA 2668927A CA 2668927 A CA2668927 A CA 2668927A CA 2668927 C CA2668927 C CA 2668927C
- Authority
- CA
- Canada
- Prior art keywords
- water
- filler
- dough
- polymeric resin
- modeling
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
- B44C3/04—Modelling plastic materials, e.g. clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
A modeling dough comprising a polar polymeric resin, water, a gellant, and a filler provides a dough resistant to flaking, cracking, and crumbling. In the disclosed invention, the polymeric resin is gelled, thereby providing a water-based resin system that is not sticky yet very ductile. After the dough is air-dried, the components are bound into a solid, durable product. The filler accounts for a large portion of the volume of the dough, so the overall volume is not greatly affected by water loss upon drying. The dough is water-based and easy to wash from skin, carpets, and other surfaces.
Dyes and pigments can be easily incorporated into the formula. The dried product is sandable and paintable.
Dyes and pigments can be easily incorporated into the formula. The dried product is sandable and paintable.
Description
2 MODELING DOUGH
This application is a divisional application of Canadian application serial number 2,160,266 filed October 10, 1995.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improved water-based modeling dough for use by children and artists in general. Specifically, the present invention relates to an improved water-based modeling dough having a gelled polymeric resin and a filler which operate together to form a matrix. The present invention provides an improved water-based modeling dough which forms a solid, lightweight, durable product upon drying.
BACKGROUND OF THE INVENTION
The present invention does not relate to oil-based clays comprising naturally occurring clays that are mined as rocks. Rather, the present invention relates to man-made, water-based modeling doughs.
Non oil-based modeling doughs are normally air-dryable and incorporate starch as the filler. These doughs have a tendency to flake, crack, and crumble in both the wet and dry stages. These doughs also shrink substantially upon drying. In other words, these doughs are characterized by poor plasticity, poor dry strength and substantial drying shrinkage.
Plasticity is the property of a wet dough or clay that permits deformation by application of a relatively slight pressure and retention of the deformed shape after release of the pressure. This property distinguishes the
This application is a divisional application of Canadian application serial number 2,160,266 filed October 10, 1995.
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improved water-based modeling dough for use by children and artists in general. Specifically, the present invention relates to an improved water-based modeling dough having a gelled polymeric resin and a filler which operate together to form a matrix. The present invention provides an improved water-based modeling dough which forms a solid, lightweight, durable product upon drying.
BACKGROUND OF THE INVENTION
The present invention does not relate to oil-based clays comprising naturally occurring clays that are mined as rocks. Rather, the present invention relates to man-made, water-based modeling doughs.
Non oil-based modeling doughs are normally air-dryable and incorporate starch as the filler. These doughs have a tendency to flake, crack, and crumble in both the wet and dry stages. These doughs also shrink substantially upon drying. In other words, these doughs are characterized by poor plasticity, poor dry strength and substantial drying shrinkage.
Plasticity is the property of a wet dough or clay that permits deformation by application of a relatively slight pressure and retention of the deformed shape after release of the pressure. This property distinguishes the
3 dough in its wet stage from its dry stage. When wet, starch-based modeling doughs have a low plasticity and have a tendency to break apart during the molding or manipulating process. These doughs also have a tendency to crack when dry and are not easily shaped in the dry state by sanding or filing. Furthermore, the artist cannot easily add wet dough to the existing dried sculpture. Finally, artists cannot carve dried starch-based doughs.
Another problem inherent with water-based doughs is the loss of volume (shrinkage) upon drying. Because water accounts for a large portion of the volume of the dough in its wet stage, water loss upon drying results in a loss of volume in the resulting molded product.
One attempt to overcome the shrinkage problem has been to incorporate large proportions of filler in the dough mixture, but shrinkage still occurs because the volume of the dough decreases as the filler binds together after drying. One commercially available children's dough, for example, shrinks about 20% upon drying despite its high filler content. In other words, a sculpture made with that dough can lose about 20% of its total volume upon drying. Moreover, the use of large proportions of filler aggravates the flaking, cracking and crumbling problem discussed above, and also tends to decrease the dry strength of the molded sculpture.
Discoloration upon drying is another problem associated with water-based doughs and is compounded by the dry shrinkage discussed above. As the volume decreases, the concentration of the pigment increases and the color darkens.
Yet another problem associated with conventional water-based doughs is that they are heavy and hard to manipulate. Dense, heavy doughs are awkward and the child or artist is limited in the types of shapes that can be created without the dough falling apart.
Another problem inherent with water-based doughs is the loss of volume (shrinkage) upon drying. Because water accounts for a large portion of the volume of the dough in its wet stage, water loss upon drying results in a loss of volume in the resulting molded product.
One attempt to overcome the shrinkage problem has been to incorporate large proportions of filler in the dough mixture, but shrinkage still occurs because the volume of the dough decreases as the filler binds together after drying. One commercially available children's dough, for example, shrinks about 20% upon drying despite its high filler content. In other words, a sculpture made with that dough can lose about 20% of its total volume upon drying. Moreover, the use of large proportions of filler aggravates the flaking, cracking and crumbling problem discussed above, and also tends to decrease the dry strength of the molded sculpture.
Discoloration upon drying is another problem associated with water-based doughs and is compounded by the dry shrinkage discussed above. As the volume decreases, the concentration of the pigment increases and the color darkens.
Yet another problem associated with conventional water-based doughs is that they are heavy and hard to manipulate. Dense, heavy doughs are awkward and the child or artist is limited in the types of shapes that can be created without the dough falling apart.
4 Finally, currently available water-based doughs generally are destructive to textiles, carpeting, furniture and other surfaces. They tend to stain a surface and are not easily removed by washing.
In light of the above problems, the need arises for a water-based, air-drying dough that is easily washed from textiles, carpeting and other'surfaces.
Furthermore, the water-based, air-drying dough should be able to incorporate colorants such as dyes and pigments and not discolor upon drying.
Accordingly, it is a general object of the present invention to provide a water-based modeling dough that overcomes the drawbacks associated with previously known modeling doughs.
The present invention overcomes the drawbacks inherent in known modeling doughs by providing a modeling dough comprising a polar polymeric resin component, water, a gellant, and a filler to form a cohesive polar resin system. The water evaporates to leave a gelled resin-filler matrix that is both lightweight and durable.
In one preferred form, the composition of the invention includes from about 4% to about 15% total polymeric resin, from about 0.05% to about 2% gellant, from about 40% to about 60% water and from about 0.5% to about 30% filler. Optionally, the composition of the invention may include one or more of a buffering agent, a defoamer, a wetting agent, a humectant, a preservative, a colorant and a fragrance.
4a In accordance with a first aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin component, water, a gellant, and a filler, wherein said polar polymeric resin component comprises polyvinyl alcohol and a second polymer selected from the group consisting of alginates, polysaccharide gums, cellulose gums, starches, guars, agars, gum arabic, acrylic acid polymers, copolymers of acrylic acid, silicone polymers, and polyvinylpyrrolidone resins.
In accordance with a second aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is .a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a third aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is a copolymer comprising vinyl alcohol groups and an acid group selected from acrylic acid groups and methacrylic acid groups.
In accordance with a fourth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said filler is selected from the group consisting of plastic microspheres, p-phenylene terephthalamide fiber, cellulose fiber, talc, calcium 4b carbonate, mica, clays, silicates, and mixtures thereof, wherein said polar polymeric resin is a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a fifth aspect of the present invention, there is provided a moldable modeling dough composition a polar polymeric resin, water, a gellant, and a filler, wherein said filler is a wax.
In accordance with a sixth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is selected from the group consisting of cellulose gum and polyvinylpyrrolidone resins.
In accordance with a seventh aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said water-soluble polymeric resin is Gellan gum.
In accordance with an eighth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler comprising a wax, wherein said polar polymeric resin is a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a ninth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler comprising a wax and another filler selected from the group consisting of plastic microspheres, 4c p-phenylene terephthalamide fiber, cellulose fiber, talc, calcium carbonate, mica, clays, silicates, and mixtures thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To achieve the foregoing and other objects in accordance with the purposes of the present invention, as embodied and broadly claimed herein, the modeling dough disclosed in the present invention comprises from about 40% to about 60% water, from about 4% to about 15% total polymeric resin, from about 0.5% to about 30% filler and from about 0.05% to about 2% gellant. A preferred formulation of the dough of the present invention
In light of the above problems, the need arises for a water-based, air-drying dough that is easily washed from textiles, carpeting and other'surfaces.
Furthermore, the water-based, air-drying dough should be able to incorporate colorants such as dyes and pigments and not discolor upon drying.
Accordingly, it is a general object of the present invention to provide a water-based modeling dough that overcomes the drawbacks associated with previously known modeling doughs.
The present invention overcomes the drawbacks inherent in known modeling doughs by providing a modeling dough comprising a polar polymeric resin component, water, a gellant, and a filler to form a cohesive polar resin system. The water evaporates to leave a gelled resin-filler matrix that is both lightweight and durable.
In one preferred form, the composition of the invention includes from about 4% to about 15% total polymeric resin, from about 0.05% to about 2% gellant, from about 40% to about 60% water and from about 0.5% to about 30% filler. Optionally, the composition of the invention may include one or more of a buffering agent, a defoamer, a wetting agent, a humectant, a preservative, a colorant and a fragrance.
4a In accordance with a first aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin component, water, a gellant, and a filler, wherein said polar polymeric resin component comprises polyvinyl alcohol and a second polymer selected from the group consisting of alginates, polysaccharide gums, cellulose gums, starches, guars, agars, gum arabic, acrylic acid polymers, copolymers of acrylic acid, silicone polymers, and polyvinylpyrrolidone resins.
In accordance with a second aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is .a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a third aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is a copolymer comprising vinyl alcohol groups and an acid group selected from acrylic acid groups and methacrylic acid groups.
In accordance with a fourth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said filler is selected from the group consisting of plastic microspheres, p-phenylene terephthalamide fiber, cellulose fiber, talc, calcium 4b carbonate, mica, clays, silicates, and mixtures thereof, wherein said polar polymeric resin is a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a fifth aspect of the present invention, there is provided a moldable modeling dough composition a polar polymeric resin, water, a gellant, and a filler, wherein said filler is a wax.
In accordance with a sixth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is selected from the group consisting of cellulose gum and polyvinylpyrrolidone resins.
In accordance with a seventh aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said water-soluble polymeric resin is Gellan gum.
In accordance with an eighth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler comprising a wax, wherein said polar polymeric resin is a polyvinyl alcohol having a hydrolysis level of from about 40% to about 80%.
In accordance with a ninth aspect of the present invention, there is provided a moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler comprising a wax and another filler selected from the group consisting of plastic microspheres, 4c p-phenylene terephthalamide fiber, cellulose fiber, talc, calcium carbonate, mica, clays, silicates, and mixtures thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To achieve the foregoing and other objects in accordance with the purposes of the present invention, as embodied and broadly claimed herein, the modeling dough disclosed in the present invention comprises from about 40% to about 60% water, from about 4% to about 15% total polymeric resin, from about 0.5% to about 30% filler and from about 0.05% to about 2% gellant. A preferred formulation of the dough of the present invention
5 comprises from about 43% to 49% water, from about 10% to about 14% total polymeric resin, from about 24% to about 26% filler, from about 0.05% to about 0.2% gellant; from about 1% to about 2% defoamer; from about 0% to about 2%
wetting agent; from about 0% to about 1% buffering agent;
from about 5% to about 15% humectant; from.about 0.5% to about 1% fragrance; from about 0% to about 5% colorant;
and from about 0.15% to about 75% preservative.
Percentages expressed in this application are expressed as percentages by weight unless otherwise indicated.
The polymeric resin binds with the filler upon drying, thereby avoiding the flaking, cracking and crumbling problems associated with prior compositions.
The polymeric resin gives the dough its ductility and plasticity qualities while wet.
However, employing a polymeric resin can result in a dough that is sticky and hard to manipulate. Therefore, a gellant, such as a water soluble borate salt, in an amount of from about 0.05 % to about 2% by weight, should be used to gel the resin substantially, eliminate stickiness, and impart wet ductility to the resulting dough. Preferably, the gellant is used in compositions of the invention in an amount of from about 0.05% to about 0.20% by weight.
Most water soluble borate salts are acceptable.
Sodium tetraborate is the preferred gellant, however, because it also acts as a buffer to maintain the pH of the system at a level high enough to permit gelling of the polymeric resin. Other workable gellants include, but are not limited to gellants such as resorcinol, catechol, gallic acid, 2-4-dihydroxy benzoic acid and congo red dye.
wetting agent; from about 0% to about 1% buffering agent;
from about 5% to about 15% humectant; from.about 0.5% to about 1% fragrance; from about 0% to about 5% colorant;
and from about 0.15% to about 75% preservative.
Percentages expressed in this application are expressed as percentages by weight unless otherwise indicated.
The polymeric resin binds with the filler upon drying, thereby avoiding the flaking, cracking and crumbling problems associated with prior compositions.
The polymeric resin gives the dough its ductility and plasticity qualities while wet.
However, employing a polymeric resin can result in a dough that is sticky and hard to manipulate. Therefore, a gellant, such as a water soluble borate salt, in an amount of from about 0.05 % to about 2% by weight, should be used to gel the resin substantially, eliminate stickiness, and impart wet ductility to the resulting dough. Preferably, the gellant is used in compositions of the invention in an amount of from about 0.05% to about 0.20% by weight.
Most water soluble borate salts are acceptable.
Sodium tetraborate is the preferred gellant, however, because it also acts as a buffer to maintain the pH of the system at a level high enough to permit gelling of the polymeric resin. Other workable gellants include, but are not limited to gellants such as resorcinol, catechol, gallic acid, 2-4-dihydroxy benzoic acid and congo red dye.
6 A variety of polar polymeric resins are useful in the modeling doughs of the present invention. Polymeric resins suitable for use in the modeling doughs of the present invention include, for example, water-soluble resins such as poly(vinyl alcohol), alginate resins, polysaccharide gums, cellulose gums, starches, guars, agars, gum arabic, acrylic acid, Gellan gum, CARBOPOL~
resins, polyvinylpyrrolidone resins, and copolymers of vinyl acetate and methacrylates or acrylates which are then subsequently fully hydrolyzed to yield copolymers of vinyl alcohol and methacrylic or acrylic acid. Examples of the latter resins include ELVANOL 93-01, ELVANOL 75-15, and ELVANOL 85-82. All of these resins are water-soluble either with or without agitation. In general, polymeric resins containing polar groups, such as alcohol, ether, ester, amide, amine, or siloxane groups, may be used as resins in the modeling doughs of the present invention. Non-water-soluble resins containing polar groups may be used.
Poly(vinyl alcohol), as used in the present application, is a cream-colored powder which is soluble in water and insoluble in most organic solvents. It is made by the hydrolysis of poly(vinyl acetate) and, when commercially purchased, may be partially or fully hydrolyzed. It varies in molecular weight according to the length of the resin chain. Both the degree of hydrolyzation and molecular weight independently affect the thermal stability of the dough. Partially hydrolyzed (88 percent), medium weight (85,000 - 146,000) polyvinyl alcohols have proved useful. Molecular weights in this application are defined as weight-average molecular weights except where otherwise indicated. Among the useful polymeric resins are those sold under the tradenames AIRVOe 523 and AIRVOe WS42 by Air Products &
Chemicals, Inc. and ELVANOI~ 52-22 by E.I. du Pont de Nemours and Company.
Trade Mark
resins, polyvinylpyrrolidone resins, and copolymers of vinyl acetate and methacrylates or acrylates which are then subsequently fully hydrolyzed to yield copolymers of vinyl alcohol and methacrylic or acrylic acid. Examples of the latter resins include ELVANOL 93-01, ELVANOL 75-15, and ELVANOL 85-82. All of these resins are water-soluble either with or without agitation. In general, polymeric resins containing polar groups, such as alcohol, ether, ester, amide, amine, or siloxane groups, may be used as resins in the modeling doughs of the present invention. Non-water-soluble resins containing polar groups may be used.
Poly(vinyl alcohol), as used in the present application, is a cream-colored powder which is soluble in water and insoluble in most organic solvents. It is made by the hydrolysis of poly(vinyl acetate) and, when commercially purchased, may be partially or fully hydrolyzed. It varies in molecular weight according to the length of the resin chain. Both the degree of hydrolyzation and molecular weight independently affect the thermal stability of the dough. Partially hydrolyzed (88 percent), medium weight (85,000 - 146,000) polyvinyl alcohols have proved useful. Molecular weights in this application are defined as weight-average molecular weights except where otherwise indicated. Among the useful polymeric resins are those sold under the tradenames AIRVOe 523 and AIRVOe WS42 by Air Products &
Chemicals, Inc. and ELVANOI~ 52-22 by E.I. du Pont de Nemours and Company.
Trade Mark
7 Newly discovered is that poly (vinyl alcohols) having a lower level of hydrolysis also are suitable for use in the modeling doughs of the present invention. For example, poly(vinyl alcohols) having -a level of hydrolysis of from about 40% to about 88% by weight are suitable for use in the modeling doughs of the present invention. These poly(vinyl alcohols) are less brittle than those having a higher level of hydrolysis; thus, a smaller amount of glycerin or other plasticizing agent may be used to soften the mixture to a usable texture.
Examples of such poly(vinyl alcohol) resins include GOHSERAN L-0301 and L-0302, from Nippon Goshei, Ltd., Osaka, Japan, and SP-202W and SP-404W from 3V, Inc., Charlotte, N.C. The listed GOHSERAN resins are hydrolyzed to 50 mol percent max, whereas SP-202W and SP-404W are hydrolyzed to 47 and 55 mol percent respectively. These resins may be used in addition to, or in place of, poly(vinyl alcohol) in the modeling doughs of the present invention.
Another specialized class of polyvinyl alcohols are ELVANOLt93-O1, ELVANOL'75-15, and ELVANOL~85-82, available from E.I. du Pont de Nemours and Company.
These resins are derived from a copolymer of vinyl acetate and an acrylate or methacrylate comonomer. The acrylate or methacrylate comonomer is believed to be present in an amount from about 5 wt. percent to about 50 wt. percent. These resins are fully hydrolyzed to yield copolymers comprising vinyl alcohol groups and methacrylic acid or acrylic acid groups. The acid groups can then further react to form internal esters ( lactones) .
It is believed that these resins are more internally plasticized than are conventional poly(vinyl alcohol) resins. In addition, these grades of ELVANOL also are more stable at high pH than are standard polyvinyl alcohols. Of these grades, ELVANOL 93-01 is the most Trade Mark ' \ \
Examples of such poly(vinyl alcohol) resins include GOHSERAN L-0301 and L-0302, from Nippon Goshei, Ltd., Osaka, Japan, and SP-202W and SP-404W from 3V, Inc., Charlotte, N.C. The listed GOHSERAN resins are hydrolyzed to 50 mol percent max, whereas SP-202W and SP-404W are hydrolyzed to 47 and 55 mol percent respectively. These resins may be used in addition to, or in place of, poly(vinyl alcohol) in the modeling doughs of the present invention.
Another specialized class of polyvinyl alcohols are ELVANOLt93-O1, ELVANOL'75-15, and ELVANOL~85-82, available from E.I. du Pont de Nemours and Company.
These resins are derived from a copolymer of vinyl acetate and an acrylate or methacrylate comonomer. The acrylate or methacrylate comonomer is believed to be present in an amount from about 5 wt. percent to about 50 wt. percent. These resins are fully hydrolyzed to yield copolymers comprising vinyl alcohol groups and methacrylic acid or acrylic acid groups. The acid groups can then further react to form internal esters ( lactones) .
It is believed that these resins are more internally plasticized than are conventional poly(vinyl alcohol) resins. In addition, these grades of ELVANOL also are more stable at high pH than are standard polyvinyl alcohols. Of these grades, ELVANOL 93-01 is the most Trade Mark ' \ \
8 preferred. These resins may be used in addition to, or in place of, poly(vinyl alcohol) in the modeling doughs of the present invention. Preferably, a small amount of a conventional poly(vinyl alcohol), such as AIRVOL 125, is used with the ELVANOL to tailor the rigidity of the modeling dough.
Examples of polysaccharide gums suitable for use as polymeric resins in the modeling doughs of the present invention include Gellan gum, KELSET" KELTOSE; KELZAN, and KELCOGEL; available from Kelco division of Merck, Inc., San Diego, California. Suitable cellulose gums include, for example, carboxymethylcellulose gums, such as AQUALON*cellulose gum, available from AQUALON Co.,-Wilmington, DE., and hydroxyethylcellulose gums, such as that sold under the trademark CELLOCIZE QP40, available from Union Carbide Chemicals & Plastics Co., Inc., Danbury, Conn. These resins may be used in conjunction with poly(vinyl alcohol) in the modeling doughs of the present invention, or may alternatively replace poly(vinyl alcohol).
Suitable polyvinylpyrrolidones include PVP K-15 and K-60, available from GAF Chemicals Corp., Wayne, N.J.
Another suitable class of resins are the CARBOPOL resins.
available from B.F. Goodrich Co., Cleveland, Ohio.
CARBOPOL resins are crosslinked copolymers of acrylic acid. For example, CARBOPOL 961 may be used in the modeling dough of the present invention. These resins may be used in conjunction with poly(vinyl alcohol) in the modeling doughs of the present invention or, alternatively may replace poly(vinyl alcohol) altogether.
In addition, CARBOPOL resins allow for pH-sensitive thickening of the modeling dough. As the pH of the dough is increased over a range of about 7= to about 9, the acrylic acid in the polymeric resin is neutralized, and becomes ionic. This will result in a stiffer, less tacky modeling dough.
Trade Mark
Examples of polysaccharide gums suitable for use as polymeric resins in the modeling doughs of the present invention include Gellan gum, KELSET" KELTOSE; KELZAN, and KELCOGEL; available from Kelco division of Merck, Inc., San Diego, California. Suitable cellulose gums include, for example, carboxymethylcellulose gums, such as AQUALON*cellulose gum, available from AQUALON Co.,-Wilmington, DE., and hydroxyethylcellulose gums, such as that sold under the trademark CELLOCIZE QP40, available from Union Carbide Chemicals & Plastics Co., Inc., Danbury, Conn. These resins may be used in conjunction with poly(vinyl alcohol) in the modeling doughs of the present invention, or may alternatively replace poly(vinyl alcohol).
Suitable polyvinylpyrrolidones include PVP K-15 and K-60, available from GAF Chemicals Corp., Wayne, N.J.
Another suitable class of resins are the CARBOPOL resins.
available from B.F. Goodrich Co., Cleveland, Ohio.
CARBOPOL resins are crosslinked copolymers of acrylic acid. For example, CARBOPOL 961 may be used in the modeling dough of the present invention. These resins may be used in conjunction with poly(vinyl alcohol) in the modeling doughs of the present invention or, alternatively may replace poly(vinyl alcohol) altogether.
In addition, CARBOPOL resins allow for pH-sensitive thickening of the modeling dough. As the pH of the dough is increased over a range of about 7= to about 9, the acrylic acid in the polymeric resin is neutralized, and becomes ionic. This will result in a stiffer, less tacky modeling dough.
Trade Mark
9 In addition, a number of other suitable materials have been found suitable for use in the modeling doughs of the present invention in conjunction with poly(vinyl alcohol). For example, starches, such as wheat, corn, and potato starch may be used. In addition, other plant sources, such as guar, agars, and gum arabic may be used.
Examples of such materials include SUPERCOI guar gum, available from Aqualon Co., Wilmington, De., and AMAIZO~
710 corn starch, available from American Maize Products Co., Hammond, Ind.
Further, non-water-soluble resins, such as silicone polymers, may be used with poly(vinyl alcohol) as the polar resin in the modeling doughs of the present invention. An example of such a silicone polymer is DOW
CORNING Q2-3233.
The polymeric resin is preferably present in compositions of the invention in an amount of from about 4% to about 15% by weight of the composition. The polymeric resin is more preferably present in compositions of the invention in an amount of from about
Examples of such materials include SUPERCOI guar gum, available from Aqualon Co., Wilmington, De., and AMAIZO~
710 corn starch, available from American Maize Products Co., Hammond, Ind.
Further, non-water-soluble resins, such as silicone polymers, may be used with poly(vinyl alcohol) as the polar resin in the modeling doughs of the present invention. An example of such a silicone polymer is DOW
CORNING Q2-3233.
The polymeric resin is preferably present in compositions of the invention in an amount of from about 4% to about 15% by weight of the composition. The polymeric resin is more preferably present in compositions of the invention in an amount of from about
10% to about 14% by weight of the composition.
If bounceability of the dough is a requisite feature of the product, then a lower molecular weight, partially hydrolyzed polymeric resin such as Airvol * 203 or Airvol~
205 should be used. This resin grade also produces doughs that are especially resistant to cracking.
However, doughs made with this resin grade have reduced thermal stability and will have a shorter shelf-life.
The average molecular weights of Airvol 203 and Airvol 205 are each about 31,000 - 50,000. Alternatively, polyvinyl alcohois with lower levels of hydrolysis or copolymers of vinyl alcohol and methacrylic acid or acrylic acid can be used to achieve bounceability.
Dry shrinkage is another problem inherent in water-based doughs disclosed in the prior art and overcome by the present invention. The present invention overcomes A'Trade Mark . ,, 10 this problem by incorporating a filler that bonds with the gelled polymeric resin to form an adequate matrix.
The water evaporates upon drying without substantial shrinkage to the sculpture or other molded object.
Workable fillers, included in the amount of 10 to 30 weight percent, include, for example, hollow composite microspheres, inert talc, calcium carbonate, mica, clay or ceramic particles and combinations thereof. Most preferred in compositions of the invention is a concentration of filler in an amount of from about 24% to about 26% by weight.
Hollow composite microspheres are the preferred filler primarily because of the low cost. They are functionally desirable because they are lightweight (having density of about 0.13 g/cc) and lower the density of the modeling dough.
The hollow composite microsphere filler incorporated in the modeling dough disclosed by the present invention is especially helpful in preventing the molded object or sculpture from shrinking upon drying. While the weight percent of water in the present invention can be high (40% to 60%), the actual partial volume of water is relatively low due to the relatively high density of water (1.0 g/cc) and low density of the microspheres. An even more preferred range of water content in compositions of the inventions is from about 43% to about 49% by weight.
As a result of these relative weights, the hollow microspheres constitute the majority of the volume of the dough. The polymeric resin and the microspheres bind together to give a sufficient structural integrity for molding. Thus, when the water evaporates, the dough does not lose a large percentage of its total volume.
The preferred filler consists essentially of hollow composite microspheres of.about 50 micron diameter and having a wettable particulate coating. Microspheres with
If bounceability of the dough is a requisite feature of the product, then a lower molecular weight, partially hydrolyzed polymeric resin such as Airvol * 203 or Airvol~
205 should be used. This resin grade also produces doughs that are especially resistant to cracking.
However, doughs made with this resin grade have reduced thermal stability and will have a shorter shelf-life.
The average molecular weights of Airvol 203 and Airvol 205 are each about 31,000 - 50,000. Alternatively, polyvinyl alcohois with lower levels of hydrolysis or copolymers of vinyl alcohol and methacrylic acid or acrylic acid can be used to achieve bounceability.
Dry shrinkage is another problem inherent in water-based doughs disclosed in the prior art and overcome by the present invention. The present invention overcomes A'Trade Mark . ,, 10 this problem by incorporating a filler that bonds with the gelled polymeric resin to form an adequate matrix.
The water evaporates upon drying without substantial shrinkage to the sculpture or other molded object.
Workable fillers, included in the amount of 10 to 30 weight percent, include, for example, hollow composite microspheres, inert talc, calcium carbonate, mica, clay or ceramic particles and combinations thereof. Most preferred in compositions of the invention is a concentration of filler in an amount of from about 24% to about 26% by weight.
Hollow composite microspheres are the preferred filler primarily because of the low cost. They are functionally desirable because they are lightweight (having density of about 0.13 g/cc) and lower the density of the modeling dough.
The hollow composite microsphere filler incorporated in the modeling dough disclosed by the present invention is especially helpful in preventing the molded object or sculpture from shrinking upon drying. While the weight percent of water in the present invention can be high (40% to 60%), the actual partial volume of water is relatively low due to the relatively high density of water (1.0 g/cc) and low density of the microspheres. An even more preferred range of water content in compositions of the inventions is from about 43% to about 49% by weight.
As a result of these relative weights, the hollow microspheres constitute the majority of the volume of the dough. The polymeric resin and the microspheres bind together to give a sufficient structural integrity for molding. Thus, when the water evaporates, the dough does not lose a large percentage of its total volume.
The preferred filler consists essentially of hollow composite microspheres of.about 50 micron diameter and having a wettable particulate coating. Microspheres with
11 a larger diameter, such as up to about 150 microns, are workable, but may give the dough a grainy texture. This may be desired for certain applications. Microspheres with a smaller diameter may result in a heavier dough but result in a smoother texture. Thus, the choice of a particular size is determined by the desired end properties.
The microsphere coating facilitates the wetting of the microspheres by the liquid ingredients of the dough.
The coating also contributes to the smooth feel and inhibits stickiness in the final product, thereby allowing for easy manipulation. The preferred coating is calcium carbonate. Other coatings include talc, alumina trihydrate, and titanium dioxide, as well as functional components such as pigments and dyes.
One preferred coated microsphere is sold under the tradename DUALITE"' M6001AE by Pierce & Stevens. M6001AE
is an ultra-low density, resilient, polymeric microsphere coated with calcium carbonate. It is a lightweight filler that reduces density of the dough and occupies the volume not attributable to water and resin. The resilient polymeric microspheres are shear stable and impact resistant, thus remaining intact under formulation conditions. Other hollow composite microsphere fillers useful in the composition of the invention have densities ranging from 0.10 to 0.75 g/cc, and include the wettable particulate coatings discussed above.
Other workable microspheres are available in various sizes and densities. Ceramic microspheres range in diameter from 15 to 40 microns and have a density of about 0.7 g/cc. However, the ceramic microspheres give the dough a grainier texture and a brownish coloring.
Silica alumina alloy microspheres range in diameter from 1 to 100 microns and have densities ranging from 2.1 to 2.5 g/cc, depending upon the wall thickness. Plastic microspheres made from a variety of materials are
The microsphere coating facilitates the wetting of the microspheres by the liquid ingredients of the dough.
The coating also contributes to the smooth feel and inhibits stickiness in the final product, thereby allowing for easy manipulation. The preferred coating is calcium carbonate. Other coatings include talc, alumina trihydrate, and titanium dioxide, as well as functional components such as pigments and dyes.
One preferred coated microsphere is sold under the tradename DUALITE"' M6001AE by Pierce & Stevens. M6001AE
is an ultra-low density, resilient, polymeric microsphere coated with calcium carbonate. It is a lightweight filler that reduces density of the dough and occupies the volume not attributable to water and resin. The resilient polymeric microspheres are shear stable and impact resistant, thus remaining intact under formulation conditions. Other hollow composite microsphere fillers useful in the composition of the invention have densities ranging from 0.10 to 0.75 g/cc, and include the wettable particulate coatings discussed above.
Other workable microspheres are available in various sizes and densities. Ceramic microspheres range in diameter from 15 to 40 microns and have a density of about 0.7 g/cc. However, the ceramic microspheres give the dough a grainier texture and a brownish coloring.
Silica alumina alloy microspheres range in diameter from 1 to 100 microns and have densities ranging from 2.1 to 2.5 g/cc, depending upon the wall thickness. Plastic microspheres made from a variety of materials are
12 available in sizes ranging from 10 to 1000 micron diameter and densities ranging from 0.13 to 0.95 g/cc.
Any of these materials, or combinations of such materials, may be employed for the purpose of achieving particular combinations of properties.
In addition to microspheres, other fillers may be used with the modeling doughs of the present invention.
For example, polymeric fillers, having plate-like, fibrous, or other shapes.may be used, as may non-polymeric fillers. These materials may replace the microspheres in whole or in part. For example, KEVLARe and KAYOCEL synthetic and natural polymers, available from American Fillers and Abrasives, Inc., Bangor, Michigan, may be used in the modeling doughs of the present invention. Alternatively, compounds such as mica, silicates, and clays may be used. Examples of suitable mica are those available from KMG Minerals, Inc., Kings Mountain, N.C. When used, the mica is preferably 325 mesh mica. Suitable silicates include sodium potassium aluminum silicate, available from Nord Perlite, Dayton, Ohio. Suitable clays include, for example, clays available from Southern Clay Products, Gonzales, Texas, under the names LAPONITE RDS'and LAPOMER~
40, and POLARGEL T*1 available from American Colloid Co., Arlington Heights, Ill. Although clay may be used as a filler in the modeling doughs of the present invention, the modeling doughs of the present invention preferably are formulated without clay. Wheat flour, available from ConAgra, Inc., Omaha, Ne., may also be used as a.filler, and may further act as a water-soluble polymeric resin.
Non-fibrous fillers may have a particle size ranging up to about 150 microns. Preferably, the fillers have a particle size less than about 50 microns. Fibrous fillers may have a size of about 30 microns to 0.5 mm depending on the desired texture of the finished product.
Also newly discovered is that waxes may be used in A-Trade Mark
Any of these materials, or combinations of such materials, may be employed for the purpose of achieving particular combinations of properties.
In addition to microspheres, other fillers may be used with the modeling doughs of the present invention.
For example, polymeric fillers, having plate-like, fibrous, or other shapes.may be used, as may non-polymeric fillers. These materials may replace the microspheres in whole or in part. For example, KEVLARe and KAYOCEL synthetic and natural polymers, available from American Fillers and Abrasives, Inc., Bangor, Michigan, may be used in the modeling doughs of the present invention. Alternatively, compounds such as mica, silicates, and clays may be used. Examples of suitable mica are those available from KMG Minerals, Inc., Kings Mountain, N.C. When used, the mica is preferably 325 mesh mica. Suitable silicates include sodium potassium aluminum silicate, available from Nord Perlite, Dayton, Ohio. Suitable clays include, for example, clays available from Southern Clay Products, Gonzales, Texas, under the names LAPONITE RDS'and LAPOMER~
40, and POLARGEL T*1 available from American Colloid Co., Arlington Heights, Ill. Although clay may be used as a filler in the modeling doughs of the present invention, the modeling doughs of the present invention preferably are formulated without clay. Wheat flour, available from ConAgra, Inc., Omaha, Ne., may also be used as a.filler, and may further act as a water-soluble polymeric resin.
Non-fibrous fillers may have a particle size ranging up to about 150 microns. Preferably, the fillers have a particle size less than about 50 microns. Fibrous fillers may have a size of about 30 microns to 0.5 mm depending on the desired texture of the finished product.
Also newly discovered is that waxes may be used in A-Trade Mark
13 the modeling doughs of the present invention in conjunction with other fillers. Any compatible natural or synthetic wax may be used, including water-soluble waxes and non-water-soluble waxes. Non-water-soluble waxes are immiscible with water and are especially suitable as fillers.
Waxes, defined as those waxes that are solid at room temperature, can be powdered to add to the other solid ingredients during the preparation of the modeling dough.
Preferably, DUALITE~ microspheres are used in conjunction with a wax when a wax is used. When used, the wax preferably has a molecular weight ranging from about 150 to about 4,000. Examples of suitable waxes include sodium stearate, such as that available from Witco Oleochemicals / Surfactants Group, Houston, Texas;
AQUAWAX*114, a micronized wax available from Micro Powders, Inc., Tarrytown, N.Y.; DOW CORNING 290, available from Dow Corning, and those CARBOWAXt polyethylene glycols available from Union Carbide that are solid at room temperature. Carbowaxes and other water-soluble, low molecular weight waxes that are liquid at room temperature may properly be classified as humectants.
The preferred composition of the modeling dough disclosed by the present invention incorporates any one or more of the following optional components: (1) a defoamer; (2) a wetting agent or dispersant; (3) a humectant; (4) a preservative; (5) a colorant; (6) a buffering agent; and (7) a scent or fragrance.
A defoamer is used to eliminate air bubbles upon mixing of the components. Such additives are readily available from numerous sources. The amount of defoamer is not critical, though such materials are typically used in amounts of from about 1 to 2% by weight. Balab Bubblebreaker~ 748, an aliphatic oil and surfactant Trade Mark ..,
Waxes, defined as those waxes that are solid at room temperature, can be powdered to add to the other solid ingredients during the preparation of the modeling dough.
Preferably, DUALITE~ microspheres are used in conjunction with a wax when a wax is used. When used, the wax preferably has a molecular weight ranging from about 150 to about 4,000. Examples of suitable waxes include sodium stearate, such as that available from Witco Oleochemicals / Surfactants Group, Houston, Texas;
AQUAWAX*114, a micronized wax available from Micro Powders, Inc., Tarrytown, N.Y.; DOW CORNING 290, available from Dow Corning, and those CARBOWAXt polyethylene glycols available from Union Carbide that are solid at room temperature. Carbowaxes and other water-soluble, low molecular weight waxes that are liquid at room temperature may properly be classified as humectants.
The preferred composition of the modeling dough disclosed by the present invention incorporates any one or more of the following optional components: (1) a defoamer; (2) a wetting agent or dispersant; (3) a humectant; (4) a preservative; (5) a colorant; (6) a buffering agent; and (7) a scent or fragrance.
A defoamer is used to eliminate air bubbles upon mixing of the components. Such additives are readily available from numerous sources. The amount of defoamer is not critical, though such materials are typically used in amounts of from about 1 to 2% by weight. Balab Bubblebreaker~ 748, an aliphatic oil and surfactant Trade Mark ..,
14 mixture or any other of the commercially available defoamers are equally suitable.
The wetting agent promotes dispersion of the microspheres and of any particulate colorant during the mixing of the disclosed modeling dough, and such materials are well known. One preferred wetting agent is sold under the tradename NOPCOSPERSE 44 by Henkel, a nonionic polyelectrolyte. The preferred weight percent of wetting agent is from about 0 to about 2%.
The humectant is not an essential component, but it is preferably added to help plasticize the polymeric resin. Without the humectant, the disclosed modeling dough may be more brittle. If too much humectant is added, however, the surface of the dough may become tacky, and paint applied to the dried dough may not dry completely as a result of the moisture affinity of the dough. The preferred humectants are triglycerol and glycerin because they are superior plasticizers in this system and produce a dough with a smooth texture.
Alternative, yet satisfactory, humectants are propylene glycols, liquid poly(ethylene glycols) (such as Carbowax 200) and diethylene glycol. The humectant may be present in an amount of from about 0 to about 20% by weight, and preferably about 5% to about 15% by weight. Where the polymeric resin is a poly(vinyl alcohol) having a level of hydrolysis of from about 40% to about 80%, the humectant preferably is present in an amount up to about
The wetting agent promotes dispersion of the microspheres and of any particulate colorant during the mixing of the disclosed modeling dough, and such materials are well known. One preferred wetting agent is sold under the tradename NOPCOSPERSE 44 by Henkel, a nonionic polyelectrolyte. The preferred weight percent of wetting agent is from about 0 to about 2%.
The humectant is not an essential component, but it is preferably added to help plasticize the polymeric resin. Without the humectant, the disclosed modeling dough may be more brittle. If too much humectant is added, however, the surface of the dough may become tacky, and paint applied to the dried dough may not dry completely as a result of the moisture affinity of the dough. The preferred humectants are triglycerol and glycerin because they are superior plasticizers in this system and produce a dough with a smooth texture.
Alternative, yet satisfactory, humectants are propylene glycols, liquid poly(ethylene glycols) (such as Carbowax 200) and diethylene glycol. The humectant may be present in an amount of from about 0 to about 20% by weight, and preferably about 5% to about 15% by weight. Where the polymeric resin is a poly(vinyl alcohol) having a level of hydrolysis of from about 40% to about 80%, the humectant preferably is present in an amount up to about
15% by weight.
A desirable additive that increases shelf-life is a preservative, and a wide variety of such materials are available commercially. One preferred preservative is Kathon~ LX1.5, a 1.5% solution of isothiazolines. Another preferred preservative is Nuosep95. The preferred weight percent of preservative is from about 0.15% to about 0.75%.
Trade Mark A colorant further may be used in the modeling dough. If no colorant is used, the resulting dough generally is white. A white dough has many applications because it can be easily painted with water-based paints.
5 Also, white is an attractive color in itself and has many applications without the need for painting. If a colored dough is desired, a variety of pigments and dyes may be used. Fluorescent doughs are especially attractive to children. Fluorescent pigments that work especially well 10 include those sold under the trade names Aurora Pink Z-11-3, Saturn Yellow Z-17N and Signal Green Z-18-3, by Day Glo Color Corp., Cleveland, OH. The colorant may be present in an amount up to about 15% by weight.
Preferably, the colorant is present in an amount up to 15 about 5% by weight.
A buffer may also be added to raise the pH in some formulations. The buffer comprises a buffering agent included with the aqueous phase of the modeling dough.
When the pH is below 7.0, the polymeric resin may not gel properly, and pH levels above pH 7 are thus preferred.
The pH of the modeling dough preferably ranges from about 8 to about 8.5 before drying. If boric acid is used as the gellant, the pH tends to drift and creates the need for a buffer. Also, for formulations using low molecular weight, partially hydrolyzed polymeric resins are acidic and may require a buffer. However, one appropriate buffering agent is sodium tetraborate, which is also the preferred gellant.
A preferred buffering system contains tris (hydroxymethyl) aminomethane and HC1 as the buffering agents. The buffer would therefore comprise tris (hydroxymethyl) aminomethane, 0.1M HC1, and water, as set forth in Example 14. Alternative buffering agents, when needed due to a pH below 7.0, include 2-amino-2-methyl-l-propanol, such as AMP 95, sold by IMC Chemical Group, Inc., and sodium bicarbonate. The preferred _ r ~16 amount of buffering agent is from about 0 to about 1% by weight of the total modeling dough composition, in addition to the gellant.
A scent may be added to the dough. The term "scent"
is hereby defined to include any scent or fragrance suitable for use in the modeling doughs of the present invention. If a scent or fragrance is added, it is preferred to include a scent or fragrance that corresponds to the color of the dough. For example, orange-colored dough may include an orange fragrance.
The dough may then be molded into the shape of an orange, and the resulting model will smell like an orange.
Similarly, black dough may include a licorice scent or fragrance; purple dough may include a grape scent or fragrance, and so for-Ch.
The particular choice of scent is not subject to any particular limitation. Oil-based scents may be used, although it is preferred to use water-based scents.
Timed-release scents may be used where it is desired to retain the scent after the modeling dough has dried.
Examples of suitable scents include: floral, foods, fruits, spices, and woods. For example, floral scent F-340-F, WS, available from Shaw Mudge & Co., Stamford, CT;
or artificial grape fragrance, available from International Flavors & Fragrances, Dayton, NJ, may be used. When used, the scent may be present in an amount ranging from about 0.05% to about 5% by weight.
Preferably, the scent is present in an amount ranging from about 0.5% to about 1.0% by weight.
The following examples further illustrate the present invention but, of course, should not be construed as in any way limiting its scope. Percentages in the following examples are defined as percentages by weight.
Example 1 This example illustrates a preferred modeling dough made with poly (vinyl alcohol).
The modeling dough is formulated in two steps.
First, a poly(vinyl alcohol) premix is made. Second, this premix is blended with the remaining components.
remis Percent Deionized water 57.41 Glycerin 24.80 Poly(vinyl alcohol) 14.17 Defoamer --Balab Bubblebreaker 748 2.13 Wetting Agent --NOPCOSPERSE*44 1.06 Preservative --RATHOOLX1.5 0.10 --NUOSEPTt95 0.33 Total 100.00 Modeling Doucth Percent Premix 60.38 Filler --DUALITE*microspheres 25.58 Deionized water 13.76 Gellant --Sodium Tetraborate 0.28 Total 100.00 Example 2 This example illustrates the use of a filler other than plastic microspheres in the modeling dough of the present invention.
*Trade Mark Example 1 is repeated, except that mica (325 mesh) is used as the filler. The dough thus is formulated as follows:
remix Percent Deionized water 57.41 Glycerin 24.80 poly(vinyl alcohol) 14.17 Defoamer ,f---Balab Bubblebreakez=748 2.13 Wetting Agent --NOPCOSPERSe44 1.06 Preserva ive ~
--KATHON~LX1.5 0.10 --NUOSEPTk95 0.33 Total 100.00 Modelina Dough Percent Premix 60.38 Filler --mica 25.58 Deionized water 13.76 Gellant --Sodium Tetraborate 0.28 Total 100.00 Example 3 Example 3 illustrates the use of a wax in combination with plastic microspheres as a filler in the modeling dough of the present invention.
Comvonent Percent Airvol 107 (20 percent aqueous solution) 61.95 Glycerin 2.00 Preservative --NTJOSEPTX-9 5 0.20 --KATHON*LX1.5 0.15 *"I'rade Mark Wax --Aquawax 114 2.00 Calcium carbonate 2.00 Filler --DUALITE6001AE microspheres 2.00 2 percent aqueous borate solution 29.70 Total 100.00 The dough of Example 3 was prepared by blending the foregoing ingredients. The dough exhibited satisfactory extrusion properties and was cuttable with a cookie cutter.
Examples 4 - 6 These examples illustrate the use of a wax in combination with plastic microspheres as a filler.
Further, these examples illustrate the process of preparation of the modeling doughs of the present invention.
Example Example Example Component Percent Deionized water 47.9 47.5 46.8 Resin --AIRVOL~ 523 8.5 8.5 8.5 Glycerin 14.4 14.4 14.4 Defoamer --Balab Bubblebreaker 2.1 2.1 2.1 Wetting Agent --NOPCOSPERSE*44 0.6 0.6 0.6 Preserva~ive --KATHON15 0.15 0.15 0.15 --NUOSEP 95 0.2 0.2 0.2 Filler --DUALITE*6001 AE 25.6 25.6 25.6 ~ Trade Mark Borate solution (2%) 0.28 0.28 0.28 Wax --Dow Corning 290 0.28 0.69 1.38 Total 100.0 100.0 100.0 5 The modeling doughs of Examples 4-6 were prepared by first blending the deionized water, AIRVOe 523, glycerin, Balab Bubblebreakef7; NOPCOSPERS244, and IiATHON*LX15 to form a premix. After this premix was formed, additional deionized water was added, and the remaining ingredients 10 incorporated into the blend to form a modeling dough.
All of the doughs of Examples 4-6 were satisfactory modeling doughs_.
Examples 7 - 8 Examples 7 and 8 illustrate the use of sodium 15 stearate, a wax, in the modeling doughs of the present invention. The polyvinyl premix wax a mixture.of 14.2%
AIRVOL 523, 57.3% water, and 24.8% glycerin.
Example Example 20 Component Percent Polyvin~l alcohol premix 60.40 60.40 DUALITE 6001AE 23.56 21.56 Borate solution (2%) 0.28 0.28 Deionized water 13.76 . 13.76 Sodium stearate 2.00 4.00 Total 100.00 100.00 Example 9 Example 9 illustrates the use of a polymeric resin other than unmodified poly(vinyl alcohol) in the modeling doughs of the present invention.
Trade Mark Component Percent Aqueous PVA/whejt flour solution 77.7 (17.5% Elvanol 75-15, 15% wheat flour) Glycerin 2.1 2% borate solution 20.2 Total 100.00 The dough of Example 9 was sticky, but otherwise acceptable as a modeling dough. The wheat flour in this example serves as a filler rather than as a polymeric resin.
Example 10 Example 10 illustrates the use of a plastic filler other than plastic microspheres. In addition, Example 10 illustrates the use of a polymeric resin other than poly(vinyl alcohol) in the modeling doughs of the present invention.
Component Percent Aqueous solution 73.3 (10% ELVANOe52-22, 10% AMAIZO'710) Glycerin 3.0 Preservative --NUOSEPT*95 0.25 --KATHONICLX 1.5 percent 0.15 Filler --KAYOCEL 2W100 7.0 2% borate solution 16.3 Total 100.00 The dough prepared according to Example 10 was stiff, but otherwise satisfactory as a modeling dough.
Trade Mark = ` .
Example 11 Example 11 illustrates the use of a polymeric resin other than poly(vinyl alcohol) in the modeling doughs of the present invention.
The modeling dough of Example 1 is prepared using GAF PVP K-15 as the polymeric resin.
Examples 12 - 13 These examples illustrate the use of a scent in the modeling doughs of the present invention.
Example 12 Example 13 Components Percent Percent DUALITe6001 AE 26.0 26.0 Premix 60.3 60.45 DI Water 13.0 13.0 Sodium Tetraborate 0.31 0.31 Fragrance 0.5 0.25 --water-soluble 100.0 100.0 blueberry fragrance The polyvinyl premix was a mixture of 14.2% AIRVOL-*
523, 57.3% water, and 24.8% glycerin. The blueberry fragrance is that available from Thornley Chemical, Wilmington, DE.
Example 14 This example illustrates'the use of a buffer in the preparation of the modeling dough. It also illustrates the use of two polyvinyl alcohols.
The buffer of example 14 comprises 60.57 grams of tris(hydroxymethyl)aminomethane, 57.0 ml of 0.1M HC1, and 943.0 ml of deionized water.
Modeling Dough Component Amount (g) ELVANOL*93-01 23.96 AIRVOL*125 1.20 Buffer 81.49 Glycerine 7.20 'rf Trade Mark NOPCOSPERSEA44 1.55 BALAB*748 3.24 Preservative --KATHON* LX 1.5 0.12 --NUOSEPT;*95 0.40 AMP 95% 0.96 Filler --Dualite 6001AE 48.0 --Water 26.0 While particular embodiments of the invention have been shown, it will of course be understood that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the foregoing teachings. It is, therefore, contemplated by the appended claims to cover any such modifications as incorporate those features which constitute the essential features of these improvements within the true spirit and scope of the invention.
*-Trade Mark
A desirable additive that increases shelf-life is a preservative, and a wide variety of such materials are available commercially. One preferred preservative is Kathon~ LX1.5, a 1.5% solution of isothiazolines. Another preferred preservative is Nuosep95. The preferred weight percent of preservative is from about 0.15% to about 0.75%.
Trade Mark A colorant further may be used in the modeling dough. If no colorant is used, the resulting dough generally is white. A white dough has many applications because it can be easily painted with water-based paints.
5 Also, white is an attractive color in itself and has many applications without the need for painting. If a colored dough is desired, a variety of pigments and dyes may be used. Fluorescent doughs are especially attractive to children. Fluorescent pigments that work especially well 10 include those sold under the trade names Aurora Pink Z-11-3, Saturn Yellow Z-17N and Signal Green Z-18-3, by Day Glo Color Corp., Cleveland, OH. The colorant may be present in an amount up to about 15% by weight.
Preferably, the colorant is present in an amount up to 15 about 5% by weight.
A buffer may also be added to raise the pH in some formulations. The buffer comprises a buffering agent included with the aqueous phase of the modeling dough.
When the pH is below 7.0, the polymeric resin may not gel properly, and pH levels above pH 7 are thus preferred.
The pH of the modeling dough preferably ranges from about 8 to about 8.5 before drying. If boric acid is used as the gellant, the pH tends to drift and creates the need for a buffer. Also, for formulations using low molecular weight, partially hydrolyzed polymeric resins are acidic and may require a buffer. However, one appropriate buffering agent is sodium tetraborate, which is also the preferred gellant.
A preferred buffering system contains tris (hydroxymethyl) aminomethane and HC1 as the buffering agents. The buffer would therefore comprise tris (hydroxymethyl) aminomethane, 0.1M HC1, and water, as set forth in Example 14. Alternative buffering agents, when needed due to a pH below 7.0, include 2-amino-2-methyl-l-propanol, such as AMP 95, sold by IMC Chemical Group, Inc., and sodium bicarbonate. The preferred _ r ~16 amount of buffering agent is from about 0 to about 1% by weight of the total modeling dough composition, in addition to the gellant.
A scent may be added to the dough. The term "scent"
is hereby defined to include any scent or fragrance suitable for use in the modeling doughs of the present invention. If a scent or fragrance is added, it is preferred to include a scent or fragrance that corresponds to the color of the dough. For example, orange-colored dough may include an orange fragrance.
The dough may then be molded into the shape of an orange, and the resulting model will smell like an orange.
Similarly, black dough may include a licorice scent or fragrance; purple dough may include a grape scent or fragrance, and so for-Ch.
The particular choice of scent is not subject to any particular limitation. Oil-based scents may be used, although it is preferred to use water-based scents.
Timed-release scents may be used where it is desired to retain the scent after the modeling dough has dried.
Examples of suitable scents include: floral, foods, fruits, spices, and woods. For example, floral scent F-340-F, WS, available from Shaw Mudge & Co., Stamford, CT;
or artificial grape fragrance, available from International Flavors & Fragrances, Dayton, NJ, may be used. When used, the scent may be present in an amount ranging from about 0.05% to about 5% by weight.
Preferably, the scent is present in an amount ranging from about 0.5% to about 1.0% by weight.
The following examples further illustrate the present invention but, of course, should not be construed as in any way limiting its scope. Percentages in the following examples are defined as percentages by weight.
Example 1 This example illustrates a preferred modeling dough made with poly (vinyl alcohol).
The modeling dough is formulated in two steps.
First, a poly(vinyl alcohol) premix is made. Second, this premix is blended with the remaining components.
remis Percent Deionized water 57.41 Glycerin 24.80 Poly(vinyl alcohol) 14.17 Defoamer --Balab Bubblebreaker 748 2.13 Wetting Agent --NOPCOSPERSE*44 1.06 Preservative --RATHOOLX1.5 0.10 --NUOSEPTt95 0.33 Total 100.00 Modeling Doucth Percent Premix 60.38 Filler --DUALITE*microspheres 25.58 Deionized water 13.76 Gellant --Sodium Tetraborate 0.28 Total 100.00 Example 2 This example illustrates the use of a filler other than plastic microspheres in the modeling dough of the present invention.
*Trade Mark Example 1 is repeated, except that mica (325 mesh) is used as the filler. The dough thus is formulated as follows:
remix Percent Deionized water 57.41 Glycerin 24.80 poly(vinyl alcohol) 14.17 Defoamer ,f---Balab Bubblebreakez=748 2.13 Wetting Agent --NOPCOSPERSe44 1.06 Preserva ive ~
--KATHON~LX1.5 0.10 --NUOSEPTk95 0.33 Total 100.00 Modelina Dough Percent Premix 60.38 Filler --mica 25.58 Deionized water 13.76 Gellant --Sodium Tetraborate 0.28 Total 100.00 Example 3 Example 3 illustrates the use of a wax in combination with plastic microspheres as a filler in the modeling dough of the present invention.
Comvonent Percent Airvol 107 (20 percent aqueous solution) 61.95 Glycerin 2.00 Preservative --NTJOSEPTX-9 5 0.20 --KATHON*LX1.5 0.15 *"I'rade Mark Wax --Aquawax 114 2.00 Calcium carbonate 2.00 Filler --DUALITE6001AE microspheres 2.00 2 percent aqueous borate solution 29.70 Total 100.00 The dough of Example 3 was prepared by blending the foregoing ingredients. The dough exhibited satisfactory extrusion properties and was cuttable with a cookie cutter.
Examples 4 - 6 These examples illustrate the use of a wax in combination with plastic microspheres as a filler.
Further, these examples illustrate the process of preparation of the modeling doughs of the present invention.
Example Example Example Component Percent Deionized water 47.9 47.5 46.8 Resin --AIRVOL~ 523 8.5 8.5 8.5 Glycerin 14.4 14.4 14.4 Defoamer --Balab Bubblebreaker 2.1 2.1 2.1 Wetting Agent --NOPCOSPERSE*44 0.6 0.6 0.6 Preserva~ive --KATHON15 0.15 0.15 0.15 --NUOSEP 95 0.2 0.2 0.2 Filler --DUALITE*6001 AE 25.6 25.6 25.6 ~ Trade Mark Borate solution (2%) 0.28 0.28 0.28 Wax --Dow Corning 290 0.28 0.69 1.38 Total 100.0 100.0 100.0 5 The modeling doughs of Examples 4-6 were prepared by first blending the deionized water, AIRVOe 523, glycerin, Balab Bubblebreakef7; NOPCOSPERS244, and IiATHON*LX15 to form a premix. After this premix was formed, additional deionized water was added, and the remaining ingredients 10 incorporated into the blend to form a modeling dough.
All of the doughs of Examples 4-6 were satisfactory modeling doughs_.
Examples 7 - 8 Examples 7 and 8 illustrate the use of sodium 15 stearate, a wax, in the modeling doughs of the present invention. The polyvinyl premix wax a mixture.of 14.2%
AIRVOL 523, 57.3% water, and 24.8% glycerin.
Example Example 20 Component Percent Polyvin~l alcohol premix 60.40 60.40 DUALITE 6001AE 23.56 21.56 Borate solution (2%) 0.28 0.28 Deionized water 13.76 . 13.76 Sodium stearate 2.00 4.00 Total 100.00 100.00 Example 9 Example 9 illustrates the use of a polymeric resin other than unmodified poly(vinyl alcohol) in the modeling doughs of the present invention.
Trade Mark Component Percent Aqueous PVA/whejt flour solution 77.7 (17.5% Elvanol 75-15, 15% wheat flour) Glycerin 2.1 2% borate solution 20.2 Total 100.00 The dough of Example 9 was sticky, but otherwise acceptable as a modeling dough. The wheat flour in this example serves as a filler rather than as a polymeric resin.
Example 10 Example 10 illustrates the use of a plastic filler other than plastic microspheres. In addition, Example 10 illustrates the use of a polymeric resin other than poly(vinyl alcohol) in the modeling doughs of the present invention.
Component Percent Aqueous solution 73.3 (10% ELVANOe52-22, 10% AMAIZO'710) Glycerin 3.0 Preservative --NUOSEPT*95 0.25 --KATHONICLX 1.5 percent 0.15 Filler --KAYOCEL 2W100 7.0 2% borate solution 16.3 Total 100.00 The dough prepared according to Example 10 was stiff, but otherwise satisfactory as a modeling dough.
Trade Mark = ` .
Example 11 Example 11 illustrates the use of a polymeric resin other than poly(vinyl alcohol) in the modeling doughs of the present invention.
The modeling dough of Example 1 is prepared using GAF PVP K-15 as the polymeric resin.
Examples 12 - 13 These examples illustrate the use of a scent in the modeling doughs of the present invention.
Example 12 Example 13 Components Percent Percent DUALITe6001 AE 26.0 26.0 Premix 60.3 60.45 DI Water 13.0 13.0 Sodium Tetraborate 0.31 0.31 Fragrance 0.5 0.25 --water-soluble 100.0 100.0 blueberry fragrance The polyvinyl premix was a mixture of 14.2% AIRVOL-*
523, 57.3% water, and 24.8% glycerin. The blueberry fragrance is that available from Thornley Chemical, Wilmington, DE.
Example 14 This example illustrates'the use of a buffer in the preparation of the modeling dough. It also illustrates the use of two polyvinyl alcohols.
The buffer of example 14 comprises 60.57 grams of tris(hydroxymethyl)aminomethane, 57.0 ml of 0.1M HC1, and 943.0 ml of deionized water.
Modeling Dough Component Amount (g) ELVANOL*93-01 23.96 AIRVOL*125 1.20 Buffer 81.49 Glycerine 7.20 'rf Trade Mark NOPCOSPERSEA44 1.55 BALAB*748 3.24 Preservative --KATHON* LX 1.5 0.12 --NUOSEPT;*95 0.40 AMP 95% 0.96 Filler --Dualite 6001AE 48.0 --Water 26.0 While particular embodiments of the invention have been shown, it will of course be understood that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the foregoing teachings. It is, therefore, contemplated by the appended claims to cover any such modifications as incorporate those features which constitute the essential features of these improvements within the true spirit and scope of the invention.
*-Trade Mark
Claims (13)
1. A moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is a copolymer comprising vinyl alcohol groups and an acid group selected from acrylic acid groups and methacrylic acid groups.
2. The moldable modeling dough composition according to claim 1, wherein said filler comprises a wax.
3. The moldable modeling dough composition according to claim 1, comprising from 40% to about 60%
water, from about 4% to about 15% total polymeric resin, from about 0.5% to about 30% filler, and from about 0.2%
to about 2% gellant.
water, from about 4% to about 15% total polymeric resin, from about 0.5% to about 30% filler, and from about 0.2%
to about 2% gellant.
4. The moldable modeling dough composition according to claim 1, comprising from about 43% to 49%
water, from about 10% to about 14% total polymeric resin, from about 24% to about 26% filler, and from about 0.05%
to about 0.2% gellant.
water, from about 10% to about 14% total polymeric resin, from about 24% to about 26% filler, and from about 0.05%
to about 0.2% gellant.
5. The moldable modeling dough composition according to claim 4, further comprising from about 5% to about 15% of a humectant.
6. The moldable modeling dough composition according to claim 4, further comprising from 0% to about 1% of a buffering agent.
7. The moldable modeling dough composition according to claim 1, further comprising a scent.
8. The moldable modeling dough composition according to claim 1, further comprising from 0% to about 1% of a buffering agent.
9. A moldable modeling dough composition a polar polymeric resin, water, a gellant, and a filler, wherein said filler is a wax.
10. A moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said polar polymeric resin is selected from the group consisting of cellulose gum and polyvinylpyrrolidone resins.
11. The moldable modeling dough composition according to claim 10, wherein said filler is a wax.
12. A moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler, wherein said water-soluble polymeric resin is Gellan gum.
13. A moldable modeling dough composition comprising a polar polymeric resin, water, a gellant, and a filler comprising a wax and another filler selected from the group consisting of plastic microspheres, p-phenylene terephthalamide fiber, cellulose fiber, talc, calcium carbonate, mica, clays, silicates, and mixtures thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2696896A CA2696896C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2668927A CA2668927C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/320,880 | 1994-10-11 | ||
| US08/320,880 US5498645A (en) | 1991-07-24 | 1994-10-11 | Modeling dough |
| CA002160266A CA2160266C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2668927A CA2668927C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002160266A Division CA2160266C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2696896A Division CA2696896C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2668927A1 CA2668927A1 (en) | 1996-04-12 |
| CA2668927C true CA2668927C (en) | 2010-08-17 |
Family
ID=23248215
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2727797A Expired - Lifetime CA2727797C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA002160266A Expired - Lifetime CA2160266C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2668927A Expired - Lifetime CA2668927C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2668924A Expired - Lifetime CA2668924C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2696896A Expired - Lifetime CA2696896C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2727797A Expired - Lifetime CA2727797C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA002160266A Expired - Lifetime CA2160266C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2668924A Expired - Lifetime CA2668924C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
| CA2696896A Expired - Lifetime CA2696896C (en) | 1994-10-11 | 1995-10-10 | Modeling dough |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5498645A (en) |
| AU (1) | AU694261B2 (en) |
| CA (5) | CA2727797C (en) |
| DE (1) | DE19537723A1 (en) |
| ES (1) | ES2127077B1 (en) |
| FR (4) | FR2726000B1 (en) |
| GB (2) | GB2294053B (en) |
Families Citing this family (51)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716675A (en) | 1992-11-25 | 1998-02-10 | E. Khashoggi Industries | Methods for treating the surface of starch-based articles with glycerin |
| US5990205A (en) * | 1997-08-18 | 1999-11-23 | Mattel, Inc. | Polyvinyl-based kneading and molding play composition |
| US5886083A (en) * | 1997-08-18 | 1999-03-23 | Mattel, Inc. | Artificial snow and method of making the same |
| US5916949A (en) | 1997-08-18 | 1999-06-29 | Mattel, Inc. | Moldable compositions and method of making the same |
| DE29720344U1 (en) * | 1997-11-17 | 1998-02-19 | Franz Kolb Nachf Fa | Industrial plasticine for design model making |
| US5972092A (en) * | 1998-08-07 | 1999-10-26 | Mattel, Inc. | Lightweight modeling play composition |
| US20010005699A1 (en) | 1999-02-03 | 2001-06-28 | Morgan William E. | Multi-layer golf ball |
| JP2001131329A (en) * | 1999-11-08 | 2001-05-15 | Pajiko:Kk | Light-weight clay |
| US6359057B1 (en) | 2000-02-10 | 2002-03-19 | Binney & Smith, Inc. | Modeling dough and method of making the same |
| US6387169B1 (en) * | 2000-02-11 | 2002-05-14 | Mattel, Inc. | Guar gum based flowing gel play composition |
| US6299374B1 (en) | 2000-03-09 | 2001-10-09 | David Naor | Instruments for producing edible colored indicia on food substrates and medicaments |
| US6348534B1 (en) | 2000-06-16 | 2002-02-19 | Michael Bianco | Gel toy |
| US6545066B1 (en) * | 2000-11-28 | 2003-04-08 | United States Gypsum Company | Lightweight ready-mix joint compound |
| KR100567684B1 (en) * | 2001-05-02 | 2006-04-05 | 김성만 | Novel modeling material |
| US6767938B1 (en) | 2003-02-18 | 2004-07-27 | Mattel, Inc. | Modeling dough and a surface active drying agent coating composition for same |
| DE10359135B4 (en) * | 2003-11-24 | 2008-02-21 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Shaped bodies, process for their preparation and use |
| US20050113471A1 (en) * | 2003-11-25 | 2005-05-26 | Jorge Sanchez | Modeling compound and method of making a modeling compound |
| DE102005011692A1 (en) * | 2004-03-11 | 2005-09-29 | Henkel Kgaa | Plastically deformable mass |
| FR2879503B1 (en) * | 2004-12-21 | 2007-02-23 | Christophe Hermet | METHOD FOR MANUFACTURING DECORATING ELEMENTS |
| KR100619840B1 (en) | 2005-02-23 | 2006-09-13 | 주식회사 엑스티아이 | Composition of light weight modeling material with low viscosity |
| NL1029514C2 (en) * | 2005-07-13 | 2007-01-16 | If Products | Ornament preparation method, used for preparing baby hand or foot casts, comprises making impression in curable polyorganosiloxane material in mold |
| US20070238815A1 (en) * | 2006-04-11 | 2007-10-11 | Lai On Products Industrial, Ltd. | Sponge-like sculpturing compound |
| US7544765B2 (en) * | 2006-10-12 | 2009-06-09 | University Of Florida Research Foundation, Inc. | Methods for producing thermoplastic fluoropolymers |
| KR100757790B1 (en) * | 2006-11-17 | 2007-09-11 | 주식회사 만지락 | Modeling material having no sulfur and the manufacturing method |
| WO2008060055A1 (en) * | 2006-11-17 | 2008-05-22 | Manjirak Co., Ltd | Non-sulfurous statuary material and method of manufacturing the same |
| US7988106B2 (en) | 2007-02-23 | 2011-08-02 | Carnevali Jeffrey D | Adaptive mounting structure |
| US20080287575A1 (en) * | 2007-05-16 | 2008-11-20 | Lai On Products (Industrial ), Ltd. | Light-weight sculpturing compound without borax |
| DE202008014446U1 (en) * | 2008-10-06 | 2010-02-25 | Trends2Com Bvba | modeling clay |
| US7897659B2 (en) * | 2009-01-23 | 2011-03-01 | Huizhou Seasoar Art Supplies Co., Ltd. | Water-based moldable modeling dough and method preparing therefor |
| CN102442798A (en) * | 2010-10-12 | 2012-05-09 | 惠州海翔文教用品有限公司 | Bamboo clay and preparation method thereof |
| CA2819828A1 (en) | 2010-12-01 | 2012-06-07 | Mattel, Inc. | Play modeling dough |
| US8603236B2 (en) | 2010-12-01 | 2013-12-10 | Mattel, Inc. | Play composition including crosslinkable binder |
| US8871017B2 (en) | 2012-04-13 | 2014-10-28 | Hasbro, Inc. | Modeling compound |
| NZ700933A (en) * | 2012-04-13 | 2017-05-26 | Hasbro Inc | Modeling compounds and methods of making and using the same |
| US8915996B2 (en) * | 2012-06-26 | 2014-12-23 | Arizona Cultured Stone Products, Inc. | Low dust, light weight filler composition |
| US20140243437A1 (en) * | 2013-02-28 | 2014-08-28 | Eun Sung Lee | Paint Composition For Forming Three-Dimensional Film |
| RU2559448C2 (en) * | 2013-10-18 | 2015-08-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ярославский государственный технический университет" (ФГБОУВПО "ЯГТУ") | Polymer clay for artistic modelling |
| CN105691081B (en) * | 2014-11-28 | 2018-08-24 | 天津市艺缘彩金科技发展有限公司 | A kind of colored drawing sand draws materials and method for drafting |
| CA2996524C (en) | 2015-08-27 | 2023-08-29 | Crayola Llc | Moldable compositions and methods of using the same |
| CN109312109B (en) * | 2016-04-15 | 2022-10-28 | 瑞典德尔塔公司 | Composition comprising a fatty acid ester and a fatty acid ester |
| US11008438B2 (en) | 2016-12-02 | 2021-05-18 | Composite Technologies International, Llc | Composition and method to form a composite core material |
| CA3060387A1 (en) * | 2017-04-18 | 2018-10-25 | WeCool Toys Inc. | Apparatus and a method for the preparation of a play, craft and/or toy compound |
| GB201706076D0 (en) | 2017-04-18 | 2017-05-31 | Wecool Toys Inc | Apparatus and a method for the preparation of a play, craft and/or toy compound |
| US11084924B2 (en) | 2017-07-17 | 2021-08-10 | Crayola Llc | Moldable compositions and methods of using thereof |
| CN109354887A (en) * | 2018-09-27 | 2019-02-19 | 漯河市罗弗文具制造有限公司 | A kind of plastic rubber and preparation method thereof |
| US10612237B1 (en) | 2018-12-18 | 2020-04-07 | Composite Technologies International, Llc | Composite panel |
| US11396197B2 (en) | 2019-06-19 | 2022-07-26 | Crayola Llc | Marking system for moldable substrates |
| US10895104B1 (en) | 2020-02-11 | 2021-01-19 | Diana L. Hertel | Device for forming a temporary seal for flood protection |
| JP2023060727A (en) * | 2021-10-18 | 2023-04-28 | 株式会社エポック社 | Creamy object |
| CN113956594B (en) * | 2021-10-21 | 2023-07-14 | 上海晨光文具股份有限公司 | Water-based boron-free ultra-light clay formula and preparation method thereof |
| WO2024017974A1 (en) | 2022-07-19 | 2024-01-25 | Delta Of Sweden Ab | Mouldable compositions |
Family Cites Families (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3061572A (en) * | 1959-01-28 | 1962-10-30 | Packer Marvin | Polyvinyl acetate and a mixture of a compatible and incompatible plasticizer and method of preparation |
| US3167440A (en) * | 1960-05-17 | 1965-01-26 | Rainbow Crafts Inc | Plastic modeling composition of a soft, pliable working consistency |
| US3213051A (en) * | 1961-06-21 | 1965-10-19 | Borden Co | Polyvinyl acetate and polyvinyl alcohol adhesives |
| US3135648A (en) * | 1961-07-13 | 1964-06-02 | Air Reduction | Polyvinyl alcohol adhesive containing a boron compound and cellulosic articles laminated therewith |
| US3353981A (en) * | 1963-01-28 | 1967-11-21 | Michael S Striker | Plastic articles of manufacture and methods of preparing the same |
| US3143518A (en) * | 1963-06-21 | 1964-08-04 | United Resin Products Inc | Hot melt polyvinyl alcohol adhesive plasticized with propylene glycol |
| DE1696193B2 (en) * | 1966-04-07 | 1974-07-04 | Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt | Satin white coating slips with good viscosity stability |
| US3558340A (en) * | 1967-01-20 | 1971-01-26 | Herman Spector | Process for coating modelling clay and product produced thereby |
| US3607332A (en) * | 1968-03-20 | 1971-09-21 | Minnesota Mining & Mfg | Modeling composition |
| US3632786A (en) * | 1968-11-12 | 1972-01-04 | Monsanto Co | Polyvinyl alcohol adhesive composition with high wet tack containing a boron compound and a cis 1 2 polyol compound |
| US3853797A (en) * | 1969-11-14 | 1974-12-10 | J Pelzig | Polyvinyl acetate /dextrin/ c to c polyhydric alcohols material for novelty items and arts and crafts applications |
| US3784391A (en) * | 1971-12-27 | 1974-01-08 | Nl Industries Inc | Finely divided hollow microcapsules of polymeric resins |
| US4005033A (en) * | 1973-05-17 | 1977-01-25 | Champion International Corporation | Resilient organic microspheres in mastic adhesives, sealants, caulks, coating compounds and related products, and methods of manufacture |
| US3959197A (en) * | 1973-10-16 | 1976-05-25 | Monsanto Research Corporation | Use of solvent mixtures in making foamable compositions |
| US3886112A (en) * | 1973-12-17 | 1975-05-27 | Polymer Films Inc | Polyvinyl alcohol based composition and articles made therefrom |
| US3873485A (en) * | 1974-04-01 | 1975-03-25 | A Thomas Fichera | Moldable aqueous plastic mass of polyethylene oxide fumed silica and polyglycol |
| US3961967A (en) * | 1974-04-10 | 1976-06-08 | Deere & Company | Foundry facing sand composition |
| JPS5141748A (en) * | 1974-10-08 | 1976-04-08 | Nisshin Flour Milling Co | NENDOYOGANGUSOZAI |
| JPS51125446A (en) * | 1975-04-08 | 1976-11-01 | Kuraray Co Ltd | Powder composition for use in molding |
| US4095008A (en) * | 1975-08-13 | 1978-06-13 | Rogers Corporation | Syntactic foam matrix board |
| JPS5913554B2 (en) * | 1975-10-17 | 1984-03-30 | 日本ゼオン （株） | adhesive composition |
| CA1080870A (en) * | 1976-03-24 | 1980-07-01 | William J. Long | Water-resistant gypsum composition and products and process of making same |
| JPS52143122A (en) * | 1976-05-25 | 1977-11-29 | Nippon Flour Mills | Handicraft plastic material and method of producing same |
| US4076547A (en) * | 1976-06-10 | 1978-02-28 | Polymerics, Inc. | Polymeric molding composition |
| JPS54154411A (en) * | 1978-05-26 | 1979-12-05 | Nippon Synthetic Chem Ind | Composition for clay work |
| JPS5552086A (en) * | 1978-10-13 | 1980-04-16 | Kuraray Co | Fluid gel for toys and handmaking study |
| AU528141B2 (en) * | 1979-03-13 | 1983-04-14 | Verve Enterprises P/L. | Modelling compound |
| US4303603A (en) * | 1979-07-20 | 1981-12-01 | Torobin Leonard B | Method and apparatus for producing hollow plastic microspheres |
| DE2937843C2 (en) * | 1979-09-19 | 1981-02-05 | Fa. J.S. Staedtler, 8500 Nuernberg | Modeling clay and their use |
| JPS5670074A (en) * | 1979-11-13 | 1981-06-11 | Unitika Ltd | Cold-curing adhesive for polyvinyl alcohol parer |
| DE3115746C2 (en) * | 1981-04-18 | 1985-06-27 | Eberhard Faber Gmbh, 8430 Neumarkt | Air-drying modeling or molding compounds and their use |
| DE3238232A1 (en) * | 1981-04-18 | 1984-04-19 | Eberhard Faber Gmbh, 8430 Neumarkt | Air-drying modelling or moulding composition |
| SU1060636A1 (en) * | 1981-07-15 | 1983-12-15 | Владимирский политехнический институт | Process for producing carbonized foamed plastic |
| DE3270781D1 (en) * | 1981-09-30 | 1986-05-28 | Kiyoharu Kawashima | Clay capable of changing colour and method for its production |
| IT1140254B (en) * | 1981-10-30 | 1986-09-24 | Pietro Cattaneo | THERMOPLASTIC COMPOSITION BASED ON POLYVINYL ALCOHOL SUITABLE TO BE SUBJECTED AS SUCH TO THE COMMON HOT FORMING METHODS OF THERMOPLASTIC MATERIALS, SUCH AS MOLDING AND EXTRUSION, FOR THE PRODUCTION OF MANUFACTURED, AND MANUFACTURED SUCH PRODUCTS |
| JPS5936278A (en) * | 1982-08-25 | 1984-02-28 | 深沢 克正 | Chemical clay |
| US4731389A (en) * | 1982-09-03 | 1988-03-15 | Air Krete, Inc. | Foam insulation and process for producing the same |
| ES538081A0 (en) * | 1984-11-29 | 1985-11-16 | Jarrett Luisa | PROCEDURE TO OBTAIN A SPECIAL PASTA TO MODEL |
| DE3641761A1 (en) * | 1986-12-06 | 1988-06-16 | Henkel Kgaa | Lightweight knifing fillers with a long shelf life |
| US4980005A (en) * | 1987-03-13 | 1990-12-25 | The Boeing Company | Method for producing an aerospace structure having a cast-in-place noncompressible void filler |
| JPH0684835B2 (en) * | 1987-08-07 | 1994-10-26 | ダイキン工業株式会社 | Defroster for air conditioner |
| GB2214186A (en) * | 1988-01-05 | 1989-08-31 | Wiggins Teape Group Ltd | Release coatings |
| US4956404A (en) * | 1989-01-10 | 1990-09-11 | Josef Pelzig | Plastic composition for toys, novelty items and arts and crafts |
| ES2023549A6 (en) * | 1990-05-22 | 1992-01-16 | Pastor Manzano Jose | Method for the manufacture of coloured pastes suitable for use by children |
| JPH085285B2 (en) * | 1990-10-18 | 1996-01-24 | 住友ゴム工業株式会社 | Safety tire |
| FR2673634B1 (en) * | 1991-03-08 | 1994-06-17 | Mizoule Henri | PLAYING PASTE BASED ON POLYVINYL ALCOHOL. |
| US5171766A (en) * | 1991-07-24 | 1992-12-15 | Binney & Smith Inc. | Modeling dough |
| US5157063A (en) * | 1991-11-21 | 1992-10-20 | Wetherell Joseph J | Elastic modeling paste |
| DE4225665C2 (en) * | 1992-08-04 | 1995-11-23 | Gerda Burgard | Use of a mass as a modeling mass for artistic purposes |
| CA2076328C (en) * | 1992-08-18 | 2000-10-10 | Micheline Desbiens | Modeling paste composition and preparation process of same |
-
1994
- 1994-10-11 US US08/320,880 patent/US5498645A/en not_active Expired - Lifetime
-
1995
- 1995-10-04 GB GB9520276A patent/GB2294053B/en not_active Expired - Lifetime
- 1995-10-06 ES ES009501938A patent/ES2127077B1/en not_active Expired - Fee Related
- 1995-10-10 FR FR9511899A patent/FR2726000B1/en not_active Expired - Lifetime
- 1995-10-10 CA CA2727797A patent/CA2727797C/en not_active Expired - Lifetime
- 1995-10-10 CA CA002160266A patent/CA2160266C/en not_active Expired - Lifetime
- 1995-10-10 CA CA2668927A patent/CA2668927C/en not_active Expired - Lifetime
- 1995-10-10 CA CA2668924A patent/CA2668924C/en not_active Expired - Lifetime
- 1995-10-10 DE DE19537723A patent/DE19537723A1/en not_active Ceased
- 1995-10-10 CA CA2696896A patent/CA2696896C/en not_active Expired - Lifetime
- 1995-10-11 AU AU33183/95A patent/AU694261B2/en not_active Expired
-
1998
- 1998-10-22 GB GBGB9822978.4A patent/GB9822978D0/en active Pending
-
1999
- 1999-01-11 FR FR9900190A patent/FR2771742B1/en not_active Expired - Lifetime
- 1999-01-11 FR FR9900192A patent/FR2771743B1/en not_active Expired - Lifetime
- 1999-01-11 FR FR9900191A patent/FR2772039B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2772039A1 (en) | 1999-06-11 |
| FR2771743B1 (en) | 2003-05-02 |
| GB2294053A (en) | 1996-04-17 |
| US5498645A (en) | 1996-03-12 |
| ES2127077A1 (en) | 1999-04-01 |
| CA2668927A1 (en) | 1996-04-12 |
| DE19537723A1 (en) | 1996-04-18 |
| GB2294053B (en) | 1999-04-21 |
| CA2668924C (en) | 2011-07-12 |
| FR2726000B1 (en) | 1999-07-16 |
| FR2771742A1 (en) | 1999-06-04 |
| AU694261B2 (en) | 1998-07-16 |
| GB9822978D0 (en) | 1998-12-16 |
| CA2727797A1 (en) | 1996-04-12 |
| CA2668924A1 (en) | 1996-04-12 |
| CA2160266A1 (en) | 1996-04-12 |
| CA2696896A1 (en) | 1996-04-12 |
| CA2696896C (en) | 2011-04-19 |
| AU3318395A (en) | 1996-04-26 |
| FR2772039B1 (en) | 2002-07-19 |
| FR2771742B1 (en) | 2001-09-07 |
| GB9520276D0 (en) | 1995-12-06 |
| CA2160266C (en) | 2009-09-08 |
| ES2127077B1 (en) | 2000-01-16 |
| FR2726000A1 (en) | 1996-04-26 |
| FR2771743A1 (en) | 1999-06-04 |
| CA2727797C (en) | 2011-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2668927C (en) | Modeling dough | |
| CA2073490C (en) | Modeling dough | |
| US4956404A (en) | Plastic composition for toys, novelty items and arts and crafts | |
| US6359057B1 (en) | Modeling dough and method of making the same | |
| US5276075A (en) | Washable acrylic paint | |
| US5506290A (en) | Plastic moldable composition | |
| US5916949A (en) | Moldable compositions and method of making the same | |
| US5157063A (en) | Elastic modeling paste | |
| CA2996524C (en) | Moldable compositions and methods of using the same | |
| US5972092A (en) | Lightweight modeling play composition | |
| US6767938B1 (en) | Modeling dough and a surface active drying agent coating composition for same | |
| US8603236B2 (en) | Play composition including crosslinkable binder | |
| KR100619840B1 (en) | Composition of light weight modeling material with low viscosity | |
| AU2018204799B2 (en) | Moldable compositions and methods of using thereof | |
| EP2196498A1 (en) | Lightweight modeling composition | |
| GB2327086A (en) | Modeling dough composition | |
| WO1996039470A1 (en) | Moldable sculpting medium | |
| GB2346149A (en) | A Washable Marking Composition | |
| JP5241589B2 (en) | Composition of lightweight clay and production method thereof | |
| JPS61266478A (en) | Coating material | |
| JPH0562914B2 (en) | ||
| JP2013148922A (en) | Blending composition of lightweight clay, and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20151013 |