CA2219662A1 - Marking composition - Google Patents
Marking composition Download PDFInfo
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- CA2219662A1 CA2219662A1 CA 2219662 CA2219662A CA2219662A1 CA 2219662 A1 CA2219662 A1 CA 2219662A1 CA 2219662 CA2219662 CA 2219662 CA 2219662 A CA2219662 A CA 2219662A CA 2219662 A1 CA2219662 A1 CA 2219662A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Disclosed is a marking composition suitable for preparing crayons comprising a fatty acid, a hard wax, an emollient, and a colorant. In some embodiments, the marking composition may also contain a soft wax. In some other embodiments, the marking composition comprises a fatty acid, a hard wax, a soft wax, and a colorant. The marking composition has smooth laydown characteristics when applied on substrates. The composition may also be substantially free of tackiness to the touch. Also disclosed are a writing instrument and a process for making writing instruments from the marking composition.
Description
MARKING COMPOS I TION
ll~CHNICAL FIE~D OF THE INVENTION
The present invention relates to a marking composition and to a writing instrument fabricated from such a marking composition. In particular, this invention relates to a marking composition useful as crayons that have desirable laydown characteristics when applied on substrates such as paper.
BA~KGROUND OF THE INVENTION
Marking compositions are well known in the art that are formulated from combinations of waxes, fatty acids, colorants, color extenders, and other additives. These marking compositions can be used to fabricate crayons, which can be used to draw, write, or coLor on porous and non-porous substrates. Crayons are most often used by children on various types of paper, such as notebook paper, art paper, and posterboard. Furthermore, crayons are available in a wide selection of colors, ranging from primary colors to fluorescent colors.
A variety of crayons and marking compositions have been disclosed in the patent literature. See, for example, U.S. Patents 3,933,708, 4,212,676, 4,990,013, and 3,409,574, the disclosures of which are incorporated in their entirety by reference. Despite this availability, consumers desire crayons with improved properties to obtain better laydown and better drawing qualities. Laydown is a measure of the smoothness qualities with which the writing composition transfers to the writing surface.
Others have proposed that laydown may be improved by the inclusion of increased amounts of emollients, for example, oils such as castor oil in formulating crayons.
Although this approach has had some success in improving laydown, the emollient adversely affects other desirable properties of the marking composLtion. ~or example, the strength of the writing made from such compositions - instrument decreases resulting in manufacturing problems as well as problems in the use of these writing instruments.
For example, writing instruments such as crayons formed from such compositions break or crumble rather easily, especially when used by children.
The above approach also adversely affects the tackiness of the writing instrument. For example, the writing instrument becomes excessively tacky to the touch, especially when held between the fingers during writing.
This excessive tackiness creates an unpleasant feeling for the user. There may also be excessive transfer of some of the components of the writing composition, for example, the pigment, to the user's hands or clothes. The excessive transfer of materials, besides creating an unpleasant feeling to the user, can cause unnecessary stains to the hands and clothes as well as in the areas such as carpets where children play with the crayons.
Thus, there remains a need for a marking composition that has the desirable laydown characteristics. There also remains a need for a marking composition with improved laydown properties that is not overly tacky to the touch.
There further remains a need for a marking composition having improved laydown properties which does not excessively transfer materials to the hands or clothes of the user. There further remains a need for a marking composition having improved laydown characteristics that has the desirable mechanical strength to withstand use by children.
' These and other objects and advantages of the present invention, as well as additional inventive features, will become apparent from the description of the present invention provided herein.
SU*~RY OF THE INVENTION
The foregoing needs are fulfilled to a great extent by the present invention which provides a marking composition that exhibits smooth laydown when applied on substrates.
The marking composition may aLso be substantially free of tackiness to the touch.
The marking composition of the present invention comprises a fatty acid, a hard wax, an emollient, and a colorant in such amounts that the composition has smooth laydown characteristics when applied on substrates. In addition, the composition may be substantially free of tackiness to the touch. In some embodiments, a soft wax also is present and the hard wax is present in the composition in an amount that is substantially equal to or greater than that of the soft wax. The emollient is generally present in an amount less than about 45~ by weight of the composition. In some embodiments, the marking composition of the present invention comprises a fatty acid, a hard wax, a soft wax, and a colorant.
The present invention also provides a method of producing the marking composition which comprises combining and mixing the ingredients at an elevated temperature until a uniform composition is obtained.
The present invention further provides for writing instruments such as crayons prepared from the marking composition of the present invention.
While the invention has been described and disclosed below in connection with certain preferred embodiments and procedures, it is not intended to limit the invention to those specific embodiments. Rather it is intended to cover all such alternative embodiments and modifications as fall within the spirit and scope of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The marking composition of the present invention comprises a fatty acid, a hard wax, an emollient, and a colorant in amounts such that the composition has smooth laydown characteristics when applied on substrates. In certain embodiments, the marking composition of the present invention comprises a fatty acid, a hard wax, a soft wax, an emollient, and a colorant. In some other embodiments, the marking composition comprises a fatty acid, a hard wax, a soft wax, and a colorant. The compositions also have the advantage that they are substantially free of tackiness to the touch.
The present inventive composition is particularly well-suited for use in preparing crayons. A detailed discussion of each of the ingredients that may be used to make the marking composition is set forth below.
The marking composition may contain any suitable fatty acid. The fatty acid may be a saturated fatty acid, an unsaturated fatty acid, or a mixture of fatty acids.
Preferably, the fatty acid is one that adds strength to the composition, especially when the composition is fabricated as a crayon. Also observed is that longer carbon chain fatty acids impart greater hardness and mechanical strength to the composition. The fatty acid generally has from about 12 to about 30 carbon atoms, and preferably from about 16 to about 24 carbon atoms. Suitable fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof. Stearic acid is a preferred fatty acid.
The fatty acid may be present in any suitable amount, for example, it can be present in an amount up to about 60%
by weight of the composition. In certain embodiments, the fatty acid is present in an amount of from about 3% by weight to about 15% by weight of the marking composition, and in certain other embodiments, the fatty acid is present in an amount of from about 15% by weight to about 30% by weight of the marking composition. Some other embodiments include a fatty acid in an amount of from about 30% by weight to about 55~ by weight of the marking composition.
The amount of fatty acid used depends to some extent on the amount of other materials constituting the marking composition, particularly the amount of hard wax employed.
The fatty acid content can be lowered if the hard wax content is suitably increased to provide the desired mechanical strength.
The mar~ing composition of the present invention also comprises at least one hard wax and optionally a soft wax.
The hard wax also imparts desired hardness and mechanical strength to the crayon. Any suitable hard wax can be used.
Preferably a wax having a penetration of about 40 mm or less at 25~C, as determined by the needle penetration method set forth in ASrM D1321 is used. Soft waxes suitable for use have a needle penetration of greater than about 40 mm at 25~C, according to ASTM D1321.
Examples of suitable hard waxes include candelilla wax, carnauba wax, beeswax, microcrystalline wax, fatty acid esters, and alkali and alkaline earth metal and ammonium salts of fatty acids, and combinations thereof.
Any other appropriate hard wax may be used.
Several hard waxes are commercially available.
Examples include the synthetic candelilla wax having a melting point of 72.5-82.5~C, an acid value of 14-25, a saponification value of 44-66, and a needle penetration of 1-4 mm (lOOg, 5 sec, 25~C), and available from Koster Keunen, Inc. in Watertown, Connecticut. This wax has the general composition of 50% hydrocarbons, 40% esters and 10%
acids by weight. Other examples of hard waxes available from Koster Keunen, Inc. are set forth in Table 1 below along with their physical properties.
Natural hard waxes such as candelilla wax, beeswax, carnauba wax, ceresine wax, and ozokerite wax which are suitable for use in the composition of the present invention can also be obtained from Koster Keunen, Inc.
- Natural candellilla wax contains approximately 50%
hydrocarbons, 28% esters, 12% neutral resins, and 7~
acids. The natural beeswax contains about 70% esters, 13% hydrocarbons, 12% fatty acids, and 4% fatty alcohols.
Natural carnauba wax contains about 70% monoesters, 15%
free alcohols, 5% fatty acids, 5% resins, and 5% other materials. Natural ceresine wax is a blend of hydrocarbon mineral waxes mainly consisting of parafin waxes, and has a melting point of 130-170~F. Ozokerite wax is a blend of hydrocarbon mineral waxes mainly consisting of microcrystalline wax and has a melting point of 160-180~F.
Microcrystalline wax may be a hard wax or a soft wax. A hard microcrystalline wax suitable for use in the present invention can be obtained from Witco in Greenwich, Connecticut, as MULTIWAX W445, having a melting point of 54-102~C. Examples of other commercially available hard waxes include the Polymer Wax AV518 having a drop point of S0-55~C (ASTM D3 954) and a zero acid content is available from ~loechst Celanese, Somerville, New Jersey. Hoechst Wax LP is a hard acid wax having a drop point of 82-89~C (ASTM D 566) and an acid number of 113-130. Hoechst Wax S is also a hard acid wax having a drop point of 81-87~C (ASTM D 566) and'an acid number of 130-150. Hoechst Wax E is an ester derived from Montan wax having a drop point of 79-85~C (ASTM D 566) and an acid number of 15-20. Hoechst Wax F has a drop point of 77-83~C (ASTM D 566) and an acid number of 6-10. Hoechst Wax KSL is a hard ester wax having a drop point of 80-85~C
(ASTM D 566) and an acid number of 28-38. LIPOWAXIM KB2-46-2 is a hard, cream-colored wax produced by Lipo Chemicals, Inc. in Paterson, New Jersey, and has a melting point of approximately 60~C. The composition of LIPOWAX KB2-46-2 is believed to be a trade secret.
Examples of soft waxes include Lanolin Wax having a melting point of 52~C maximum and 0.56~ maximum free fatty ~cid content and available from the Fanning Corporation in Chicago, Illinois. Other examples of suitable soft waxes include hydrogenated lanolin available under the name of FANCOL HLTM which is a mixture of fatty alcohols also available from the Fanning Corporation; hydrogenated castor oil available from Caschem, Inc. in Bayonne, New Jersey, as CASTORWAXTM MP-70, and having a freezing/melting point of 158~F; and LIPOWAX KB2444 produced by Lipo Chemicals which is a cream-colored wax having a melting point of about 90~C. The exact composition of LIPOWAX KB2444 is believed to be a trade secret of Lipo Chemicals.
~nother example of a soft wax is a hydroxypolyester which is 7-hydroxy isohexanol polyester having a melting point of 74-a40c, an acid value of less than 5, an ester value of 50-70, a hydroxyl value of 35-50, a needle penetration of greater than 50 mm at 25~C by ASTM D1321, an average molecular weight of about 1000, an average carbon length of 66, and an iodine value of less than 5, and is available from Koster Keunen, Inc. Certain soft waxes, particularly the hydroxypolyester, help to hold the emollients in place, thereby acting as gelling agents.
These soft waxes help make the marking composition less oily to the touch.
Any suitable amount of the hard wax can be included in the composition of the present invention. The hard wax can be present in an amount of up to about 64~ by weight of the marking composition. In certain embodiments, the hard wax is present in an amount of from about 39% by weight to about 64% by weight of the marking composition, and preferably in an amount of from about 45% by weight to about 55% by weight of the marking composition. Excessive amounts of hard wax can adversely affect the laydown property. In certain other embodiments, for example, where the amount of emollient is low or none, the hard wax can be present in an amount of from about 10% by weight to about 30% by weight of the marking composition, and preferably in an amount of from about 15% by weight to about 25% by weight of the marking composition.
When a soft wax and an emollient are used, the hard wax preferably is used in an amount that is substantiaLly equal to the amount of soft wax, and more preferably in amount greater than that of the soft wax.
Any suitable amount of the soft wax can be used to prepare the marking composition. The soft wax can be present in an amount of up to about 60~ by weight of the marking composition. In certain embodiments, for example, where the amount of emollient is low or none, the soft wax can be present in an amount of from about 20% by weight to about 60% by weight of the marking composition. In certain S other embodiments, for example, where an emollient is present in a significant amount, the soft wax can be present in an amount of up to about 4% by weight of the marking composition.
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The marking composition of the present invention may also contain an emollient. The emollient is desired to enable the marking composition to be more readily and easily transferred to a substrate through normal application of the marking composition to the substrate.
The emollient thus provides a lubricant effect or slipperiness to the mar~ing composition to facilitate the gliding of the marking composition across the surface of a substrate and to ensure a smooth laydown of the marking composition onto the substrate.
The emollient also assists in ensuring the retention of certain other ingredients such as glitter in the marking composition transferred to the substrate. As such, the emollient typically is a liquid or paste at room temperature and is preferably miscible with the other components in the composition, particularly the wax or the fatty acid. In certain embodiments however, the emollient may be a solid such as a flake.
Any suitable emollient may be used in the present inventive marking composition. Emollients such as lanolin oil and its derivatives, mineral oil, fatty esters, fatty acid esters, fatty alcohols, mono- and di-esters of propylene glycols, glycerol di-esters, mono- and di-esters of polyethylene glycols, petrolatum, vegetable shortenings, dimers and trimers of fatty acids, plant oils, silicones, and mixtures thereof are suitable for use in compositions of the invention.
Suitable lanolin derivatives include acetylated lanolin, acetylated lanolin alcohol, hydrogenated lanolin, lanolin alcohol, lanolin acids, isopropyl lanolate, lanolin wax, and hydroxylated lanolin. Suitable fatty esters and fatty acid esters include isopropyl myristate, myristyl myristate, and esterified fatty acid propoxylates such as polyoxypropylene (2) myristyl ether propionate. Suitable fatty alcohols include oleyl alcohol, and suitable vegetable shortenings include KREMIT~ (Armour, Omaha, Nebraska). Suitahle plant oils include castor oil, coconut oil, olive oil, peanut oil, safflower oil, sesame oil, soybean oil, wheat germ oil, corn oil, avocado oil, almond oil, grape seed oil, jojoba oil, apricot kernel oil, palm oil, and sunflower seed oil. Suitable silicones include 5 DOW-CORNING~ 556, 593, and 1107 fluids ~Dow-Corning, Midland, Michigan). Other possible emollients include longer chain hydrocarbons, particularly alkenes, such as polyoxypropylene-polyoxyethylene block copolymers such as PLURONIC~ 25R4 and PLURONIC 25R8 (BASF, Parsippany, New Jersey).
The emollient may be present in any suitable amount, for example, in an amount of up to 45% by weight of the marking composition, and preferably in an amount of from about 5% to about 25% by weight of the marking composition.
Excessive amounts of emollients can increase the tackiness adversely. In certain embodiments, especially the embodiments havinq a large amount of a soft wax, the emollient can be present in a low amount or omitted while still maintaining the desired improved laydown characteristics.
The marking composition preferably contains a colorant which can be a pigment or dye. The pigment may be an inorganic pigment, an organic pigment, or a mixture thereof. The inorganic pigment is preferably iron blue, iron oxide, zinc oxide, ultramarine blue, titanium dioxide, or a mixture thereof. The organic pigment is preferably an azo, a naphthol, or a phthalo pigment. Dyes, either acidic or basic, can be used in the present inventive marking composition.
The pigment can have any suitable particle size, however, a preferable particle size is from about 0.1 micron to about 25 microns. More preferably, the pigment has a particle size of about 0.3 micron to about 20 microns, and, even more preferably, the pigment particle size is in the range of about 0.5 micron to about 15 microns.
Examples of suitable dyes include the polymeric colorants REACTINT~ brand Blue x 3LV, Orange x 38, and Violet x 80LT, available from the Milliken Chemical Co. in Inman, South Carolina. These are dark viscous liquids containing the dyes Blue x 3LV, Orange x 38, and Violet x 80LT.
The colorant may be present in any suitable amount.
The present inventive marking composition preferably contains pigment in an amount of from about 0.5% to about 20% by weight of the marking composition, more preferably from about 2% to about 15% by weight of the marking composition. Where a dye colorant is used, it may be included in an amount of from about 1% by weight to about 3% by weight of the marking composition.
The marking composition of the present invention can contain additional ingredients such as glitter.
The glitter may be of any suitable material and will generally comprise a metallic material, a nonmetallic material, or, more commonly, a reflective material coating, such as a metal coating, on a suitable substrate such as a polymer or other solid organic substrate. Suitable metallic glitters include particles or flakes of aluminum, copper, silver, gold, brass, or other metals. Suitable non-metallic glitters incLude particles or flakes of cellulose acetate, poly(ethylene terephthalate), polymethacrylate, poly(vinylbutyral), and the like.
Suitable metallized glitters include coated metallized materials such as coated aluminum metallized cellulose acetate, poly(ethylene terephthalate), polymethacrylate, poly~vinylbutyral), and the like. Coated aluminum metallized poly(ethylene terephthalate) is the preferred glitter for use in the context of the present invention.
The glitter may be of any color (e.g., silver, gold, blue, red, etc.) or even a mixture of colors. If pigment is present in the marking composition, the glitter may be the same color as the pigment or a different color from the pigment.
The glitter also may be of any dimensions that are suitable for use in such a composition. The glitter is preferably less than about 0.05 x 0.05 x O.OOS cm (0.02 x 0.02 x 0.002 inches) in size, more preferably less than aboutO.03 x 0.03 x 0.003 cm (0.01 x 0.01 x 0.001 inches) in size, and most preferably about 0.02 x 0.02 x 0.003 cm (0.008 x 0.008 x 0.001 inches) to about 0.02 x 0.02 x 0.001 cm (0.008 x 0.008 x 0.0005 inches), or even about 0.01 x 0.01 x 0.001 cm (0.004 x 0.004 x 0.005 inches) or less, in size, although glitter which is too small in size may not exhibit a desirable glitter effect.
The glitter may be present in any suitable amount, preferably less than about 15% by weight of the marking composition, more preferably in an amount fro~ about 3% to about 10% by weight of the marking composition, and even more preferably in an amount from about 4% to about 8% by weight of the marking composition. For additional details, see, e.g., U.S. Patents 5,261,952 and 5,383,954.
The marking composition may additionally include a filler. The filler preferably functions as a pigment dispersant or extender, if pigment is added to the marking composition. Any suitable filler may be utilized, such as calcium carbonate, titanium dioxide, talc, silica, clay (e.g., kaolin clay), feldspar, corn starch, mica, and mixtures thereof. Examples of preferred fillers include talc and kaolin clay. The particle size of the filler is preferably 50 microns or less, more preferably 25 microns or less, although if mica is used, the particle size is preferably about 25-75 microns. Talc of about 3-6 microns average diameter particle size is preferred for use in certain embodiments of the present invention. An example of a talc is NYTALrM 400, which is available from The Vanderbilt Co. in Norwalk, Connecticut.
In certain embodiments, the filler acts to provide a shimmering effect to the composition. Filler can also be included in compositions of the invention when a pigment is not used. In cerain embodiments, the filler improves the CA 022l9662 l997-l0-28 strength of the marking composition and the marking instrument.
Two or more fillers can be combined for use in compositions of the invention. For example, the mica S particles can be coated with titanium dioxide. Such a coated mica is available as MAGNAPEARL~ from The Mearl Corporation in Charleston, SC. MAGNAPE~RL can provide smooth laydown as well as a shimmer effect to the marking composition. MAGNAPEARL can also provide added strength to the marking composition and the writing instrument.
The filler may be present in any suitable amount.
Preferably filler is used in an amount up to about 20~ by weight of the marking composition, and more preferably in an amount of from about 5% to about 15~ by weight of the marking composition.
A cleanability additive can also be included in the marking composition of the present invention to aid in the removal of the composition, preferably with mild soap and water, from non-porous surfaces, such as table tops, counter tops, etc. Suitable cleanability additives include polyoxypropylene-polyoxyethylene block copolymers, polyoxyethylene alcohols, polyoxyethylene esters, polyoxyethylene ethers, and derivatives and mixtures thereof.
The marking composition of the present invention preferably contains a cleanability agent such as polyoxyethylene (12) tridecyl ether or alcohol, polyoxyethylene (10) alkyl aryl ether, polyoxyethylene (40) stearate, or polyoxyethylene (20) stearyl alcohol. The marking composition more preferably contains polyoxyethylene (40) stearate (available as LIPOPEG~ 39S
(Lipo Chemicals, Patterson, New Jersey)) or polyoxyethylene (12) tridecyl ether alcohol (available as RENEX~ 30 (ICI
America, Wilmington, Delaware)), most preferably a mixture of the two. Certain emollients may also act as cleanability additives or aid in cleanability, such as polyoxypropylene-polyoxyethylene block copolymers, e.g., PLURONIC~ 25R4 or 25R8.
The cleanability additive may be present in any suitable amount. Preferably it is present in an amount up to about 5~ by weight of the marking composition, and more preferably in an amount from about 1% to about 4~ by weight of the marking composition.
Other additives may be incorporated into the marking compositions of the present invention in minor amounts.
For example, processing aids such as foam inhibitors and mold release agents, as well as oxidation and W
stabilizers may be added. These additives are typically used in an amount of from about 0.01% to about 5% by weight of the marking composition, and preferably in an amount of from about 0.1~ to about 1~ by weight of the marking composition.
Examples of suitable foam inhibitors include petroleum hydrocarbons such as FOAMKILL~ 614 (Crucible Chemical Co., Greenville, South Carolina). Examples of suitable mold release agents include the Group IIA metal salts of fatty acids, particularly calcium stearate. Examples of suitable oxidation stabilizers include sterically hindered phenols.
Examples of suitable W stabilizers include hindered amine light stabilizers and benzotriazoles.
The marking composition of the present invention may be prepared by heating the components to a semisolid, or preferably, liquid, state and mixing them together.
Generally, a portion of the waxes and fatty acid, is heated above its melting temperature, e.g., to about 104-116~C
(220-240~F). Then, the remainder of the waxes and the fatty acid is added to the liquified waxy material, while stirring the composition with suitable stirring means, such as, for example, a disperser head mixer. The filler and colorant are then added in sequence to the composition under continued stirring of the composition. The emollient, along with any other additives such as cleanability agents and the like, are added to the liquified material, while continuing to stir the composition. The composition is then appropriately molded, such as by pouring the composition into flatbed molds. The mold is cooled and the composition is shaped into suitable forms such as crayons.
The marking composition of the present invention is hard enough for children to handle and resists easily breaking, yet is soft enough to allow for the laydown of the composition on a substrate in the course of the normal marking of a substrate with the composition. Particularly, - the laydown characteristics of compositions of the present invention are improved over such characteristics of previously available compositions.
The marking composition of the present invention is suitable for use in writing instruments, in particular, crayons, and may be applied to a variety of porous and non-porous writing surfaces or substrates.
The following examples serve to further illustrate the present invention and are not intended to limit the scope of the invention.
Example 1 This example illustrates the preferred amounts of the ingredients by class that can be used to prepare an embodiment of the marking composition of the present invention that includes a hard wax, a soft wax and an emollient.
Component preferred range, wt%
Fatty acid about 30-about 55 Hard wax about 12-about 34 Soft wax about 1-about 4 Emollient about 10-about 40 Filler about 0-about 20 Colorant about 0-about 15%
Example 2 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition invention set forth in Example 1.
Component Preferred Range, wt~
Stearic acid about 30-about 55 Paraffin wax about 3-about 10 Syn. Carnauba wax about 8-about 20 KESTER WAX K80D22 about l-about 4 Hydroxypolyester about 1-about 4 LIPONATE MM about 2-about 5 LIPONATE TDTM about 3-about 10 Castor oil about 5-about 25 MAGNAPEARL 2000 about 0-about 20 Colorant about 2-about 15 Example 3 This Example illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 2. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic acid 41.8 Paraffin wax 6.8 Syn. Carnauba wax 13.6 KESTER WAX 80D22 1.7 Hydroxypolyester 1.7 LIPONATE MM 3.4 LIPONATE TDTM 5.4 Castor oil 8.2 MAGNAPEARL 2000 6.8 Ultramarine Blue 10.6 1 0 0 . O
CA 022l9662 l997-l0-28 Example 4 This Example illustrates the preferred amounts of the ingredients by class that can be used to prepare another embodiment of the marking composition of the present invention comprising a fatty acid, a hard wax, soft wax, and an emollient.
Component preferred range, wt%
Fatty acid about 3-about 15 Hard wax about 39-about 64 Soft wax about 1-about 4 Emollient about 5-about 15 Filler about l-about 15 Dye about l-about 3 Example 5 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition present invention set forth in Example 4..
Component preferred range, wt%
Stearic acid about 3-about 15 Paraffin wax about 30-about 45 Syn. Carnauba wax about 8-about 15 KESTER WAX K80D22 about 1-about 4 Hydroxypolyester about l-about 4 Castor Oil about 5-about 15 MAGNAPEARL 2000 about l-about 15 Colorant about l-about. 3 Example 6 This Example illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 5. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic acid 22.2 Paraffin wax 37.5 Syn. Carnauba wax 12.1 KESTER WAX K80D22 1.5 Hydroxypo.lyester 1.5 Castor oil 12.6 MAGNAPEARL 2000 12.6 Liquid Dye (Milliken Color) 1.5 100.O
Example 7 This Example illustrates the preferred amounts of the ingredients by class that can be used to prepare yet another embodiment of the marking composition of the present invention which comprises a fatty acid, a hard wax, and a soft wax.
Component preferred range, wt~
Fatty acid about 15-about 30 Hard wax about 10-about 30 Soft wax about 20-about 60 Filler about 5-about 20 Colorant about 1-about 5 Example 8 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition of the present invention set forth in Example 7..
Component preferred range, wt%
Stearic Acid about 15-about 30 LIPOWAX KB2444 about 20-ab,out 60 LIPOWAX KB2462 about 5-about 15 Paraffin wax ' about 5 about 15 FOAMKILL 614 about 0.1-about 1 NYTAL 400 (talc) ' about 5-about 20 Colorant about l-about 5 Example 9 This ExampLe illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 8. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic Acid 19.6 LIPOWAX KB2444 43.2 LIPOWAX KB2462 9.8 Paraffin wax 9.8 FOAMKILL 614 0.3 NYTAL 400 14.4 Phthalo green pigment 2.9 While this invention has been described with emphasis upon a preferred embodiment, it will be obvious to those of ordinary skill in the art that the preferred composition may be varied. It is intended that the invention may be practiced otherwise than as specifically described herein.
Accordlngly, this invention includes all modifications encompassed within the spirit and scope of the following claims.
ll~CHNICAL FIE~D OF THE INVENTION
The present invention relates to a marking composition and to a writing instrument fabricated from such a marking composition. In particular, this invention relates to a marking composition useful as crayons that have desirable laydown characteristics when applied on substrates such as paper.
BA~KGROUND OF THE INVENTION
Marking compositions are well known in the art that are formulated from combinations of waxes, fatty acids, colorants, color extenders, and other additives. These marking compositions can be used to fabricate crayons, which can be used to draw, write, or coLor on porous and non-porous substrates. Crayons are most often used by children on various types of paper, such as notebook paper, art paper, and posterboard. Furthermore, crayons are available in a wide selection of colors, ranging from primary colors to fluorescent colors.
A variety of crayons and marking compositions have been disclosed in the patent literature. See, for example, U.S. Patents 3,933,708, 4,212,676, 4,990,013, and 3,409,574, the disclosures of which are incorporated in their entirety by reference. Despite this availability, consumers desire crayons with improved properties to obtain better laydown and better drawing qualities. Laydown is a measure of the smoothness qualities with which the writing composition transfers to the writing surface.
Others have proposed that laydown may be improved by the inclusion of increased amounts of emollients, for example, oils such as castor oil in formulating crayons.
Although this approach has had some success in improving laydown, the emollient adversely affects other desirable properties of the marking composLtion. ~or example, the strength of the writing made from such compositions - instrument decreases resulting in manufacturing problems as well as problems in the use of these writing instruments.
For example, writing instruments such as crayons formed from such compositions break or crumble rather easily, especially when used by children.
The above approach also adversely affects the tackiness of the writing instrument. For example, the writing instrument becomes excessively tacky to the touch, especially when held between the fingers during writing.
This excessive tackiness creates an unpleasant feeling for the user. There may also be excessive transfer of some of the components of the writing composition, for example, the pigment, to the user's hands or clothes. The excessive transfer of materials, besides creating an unpleasant feeling to the user, can cause unnecessary stains to the hands and clothes as well as in the areas such as carpets where children play with the crayons.
Thus, there remains a need for a marking composition that has the desirable laydown characteristics. There also remains a need for a marking composition with improved laydown properties that is not overly tacky to the touch.
There further remains a need for a marking composition having improved laydown properties which does not excessively transfer materials to the hands or clothes of the user. There further remains a need for a marking composition having improved laydown characteristics that has the desirable mechanical strength to withstand use by children.
' These and other objects and advantages of the present invention, as well as additional inventive features, will become apparent from the description of the present invention provided herein.
SU*~RY OF THE INVENTION
The foregoing needs are fulfilled to a great extent by the present invention which provides a marking composition that exhibits smooth laydown when applied on substrates.
The marking composition may aLso be substantially free of tackiness to the touch.
The marking composition of the present invention comprises a fatty acid, a hard wax, an emollient, and a colorant in such amounts that the composition has smooth laydown characteristics when applied on substrates. In addition, the composition may be substantially free of tackiness to the touch. In some embodiments, a soft wax also is present and the hard wax is present in the composition in an amount that is substantially equal to or greater than that of the soft wax. The emollient is generally present in an amount less than about 45~ by weight of the composition. In some embodiments, the marking composition of the present invention comprises a fatty acid, a hard wax, a soft wax, and a colorant.
The present invention also provides a method of producing the marking composition which comprises combining and mixing the ingredients at an elevated temperature until a uniform composition is obtained.
The present invention further provides for writing instruments such as crayons prepared from the marking composition of the present invention.
While the invention has been described and disclosed below in connection with certain preferred embodiments and procedures, it is not intended to limit the invention to those specific embodiments. Rather it is intended to cover all such alternative embodiments and modifications as fall within the spirit and scope of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The marking composition of the present invention comprises a fatty acid, a hard wax, an emollient, and a colorant in amounts such that the composition has smooth laydown characteristics when applied on substrates. In certain embodiments, the marking composition of the present invention comprises a fatty acid, a hard wax, a soft wax, an emollient, and a colorant. In some other embodiments, the marking composition comprises a fatty acid, a hard wax, a soft wax, and a colorant. The compositions also have the advantage that they are substantially free of tackiness to the touch.
The present inventive composition is particularly well-suited for use in preparing crayons. A detailed discussion of each of the ingredients that may be used to make the marking composition is set forth below.
The marking composition may contain any suitable fatty acid. The fatty acid may be a saturated fatty acid, an unsaturated fatty acid, or a mixture of fatty acids.
Preferably, the fatty acid is one that adds strength to the composition, especially when the composition is fabricated as a crayon. Also observed is that longer carbon chain fatty acids impart greater hardness and mechanical strength to the composition. The fatty acid generally has from about 12 to about 30 carbon atoms, and preferably from about 16 to about 24 carbon atoms. Suitable fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, and mixtures thereof. Stearic acid is a preferred fatty acid.
The fatty acid may be present in any suitable amount, for example, it can be present in an amount up to about 60%
by weight of the composition. In certain embodiments, the fatty acid is present in an amount of from about 3% by weight to about 15% by weight of the marking composition, and in certain other embodiments, the fatty acid is present in an amount of from about 15% by weight to about 30% by weight of the marking composition. Some other embodiments include a fatty acid in an amount of from about 30% by weight to about 55~ by weight of the marking composition.
The amount of fatty acid used depends to some extent on the amount of other materials constituting the marking composition, particularly the amount of hard wax employed.
The fatty acid content can be lowered if the hard wax content is suitably increased to provide the desired mechanical strength.
The mar~ing composition of the present invention also comprises at least one hard wax and optionally a soft wax.
The hard wax also imparts desired hardness and mechanical strength to the crayon. Any suitable hard wax can be used.
Preferably a wax having a penetration of about 40 mm or less at 25~C, as determined by the needle penetration method set forth in ASrM D1321 is used. Soft waxes suitable for use have a needle penetration of greater than about 40 mm at 25~C, according to ASTM D1321.
Examples of suitable hard waxes include candelilla wax, carnauba wax, beeswax, microcrystalline wax, fatty acid esters, and alkali and alkaline earth metal and ammonium salts of fatty acids, and combinations thereof.
Any other appropriate hard wax may be used.
Several hard waxes are commercially available.
Examples include the synthetic candelilla wax having a melting point of 72.5-82.5~C, an acid value of 14-25, a saponification value of 44-66, and a needle penetration of 1-4 mm (lOOg, 5 sec, 25~C), and available from Koster Keunen, Inc. in Watertown, Connecticut. This wax has the general composition of 50% hydrocarbons, 40% esters and 10%
acids by weight. Other examples of hard waxes available from Koster Keunen, Inc. are set forth in Table 1 below along with their physical properties.
Natural hard waxes such as candelilla wax, beeswax, carnauba wax, ceresine wax, and ozokerite wax which are suitable for use in the composition of the present invention can also be obtained from Koster Keunen, Inc.
- Natural candellilla wax contains approximately 50%
hydrocarbons, 28% esters, 12% neutral resins, and 7~
acids. The natural beeswax contains about 70% esters, 13% hydrocarbons, 12% fatty acids, and 4% fatty alcohols.
Natural carnauba wax contains about 70% monoesters, 15%
free alcohols, 5% fatty acids, 5% resins, and 5% other materials. Natural ceresine wax is a blend of hydrocarbon mineral waxes mainly consisting of parafin waxes, and has a melting point of 130-170~F. Ozokerite wax is a blend of hydrocarbon mineral waxes mainly consisting of microcrystalline wax and has a melting point of 160-180~F.
Microcrystalline wax may be a hard wax or a soft wax. A hard microcrystalline wax suitable for use in the present invention can be obtained from Witco in Greenwich, Connecticut, as MULTIWAX W445, having a melting point of 54-102~C. Examples of other commercially available hard waxes include the Polymer Wax AV518 having a drop point of S0-55~C (ASTM D3 954) and a zero acid content is available from ~loechst Celanese, Somerville, New Jersey. Hoechst Wax LP is a hard acid wax having a drop point of 82-89~C (ASTM D 566) and an acid number of 113-130. Hoechst Wax S is also a hard acid wax having a drop point of 81-87~C (ASTM D 566) and'an acid number of 130-150. Hoechst Wax E is an ester derived from Montan wax having a drop point of 79-85~C (ASTM D 566) and an acid number of 15-20. Hoechst Wax F has a drop point of 77-83~C (ASTM D 566) and an acid number of 6-10. Hoechst Wax KSL is a hard ester wax having a drop point of 80-85~C
(ASTM D 566) and an acid number of 28-38. LIPOWAXIM KB2-46-2 is a hard, cream-colored wax produced by Lipo Chemicals, Inc. in Paterson, New Jersey, and has a melting point of approximately 60~C. The composition of LIPOWAX KB2-46-2 is believed to be a trade secret.
Examples of soft waxes include Lanolin Wax having a melting point of 52~C maximum and 0.56~ maximum free fatty ~cid content and available from the Fanning Corporation in Chicago, Illinois. Other examples of suitable soft waxes include hydrogenated lanolin available under the name of FANCOL HLTM which is a mixture of fatty alcohols also available from the Fanning Corporation; hydrogenated castor oil available from Caschem, Inc. in Bayonne, New Jersey, as CASTORWAXTM MP-70, and having a freezing/melting point of 158~F; and LIPOWAX KB2444 produced by Lipo Chemicals which is a cream-colored wax having a melting point of about 90~C. The exact composition of LIPOWAX KB2444 is believed to be a trade secret of Lipo Chemicals.
~nother example of a soft wax is a hydroxypolyester which is 7-hydroxy isohexanol polyester having a melting point of 74-a40c, an acid value of less than 5, an ester value of 50-70, a hydroxyl value of 35-50, a needle penetration of greater than 50 mm at 25~C by ASTM D1321, an average molecular weight of about 1000, an average carbon length of 66, and an iodine value of less than 5, and is available from Koster Keunen, Inc. Certain soft waxes, particularly the hydroxypolyester, help to hold the emollients in place, thereby acting as gelling agents.
These soft waxes help make the marking composition less oily to the touch.
Any suitable amount of the hard wax can be included in the composition of the present invention. The hard wax can be present in an amount of up to about 64~ by weight of the marking composition. In certain embodiments, the hard wax is present in an amount of from about 39% by weight to about 64% by weight of the marking composition, and preferably in an amount of from about 45% by weight to about 55% by weight of the marking composition. Excessive amounts of hard wax can adversely affect the laydown property. In certain other embodiments, for example, where the amount of emollient is low or none, the hard wax can be present in an amount of from about 10% by weight to about 30% by weight of the marking composition, and preferably in an amount of from about 15% by weight to about 25% by weight of the marking composition.
When a soft wax and an emollient are used, the hard wax preferably is used in an amount that is substantiaLly equal to the amount of soft wax, and more preferably in amount greater than that of the soft wax.
Any suitable amount of the soft wax can be used to prepare the marking composition. The soft wax can be present in an amount of up to about 60~ by weight of the marking composition. In certain embodiments, for example, where the amount of emollient is low or none, the soft wax can be present in an amount of from about 20% by weight to about 60% by weight of the marking composition. In certain S other embodiments, for example, where an emollient is present in a significant amount, the soft wax can be present in an amount of up to about 4% by weight of the marking composition.
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The marking composition of the present invention may also contain an emollient. The emollient is desired to enable the marking composition to be more readily and easily transferred to a substrate through normal application of the marking composition to the substrate.
The emollient thus provides a lubricant effect or slipperiness to the mar~ing composition to facilitate the gliding of the marking composition across the surface of a substrate and to ensure a smooth laydown of the marking composition onto the substrate.
The emollient also assists in ensuring the retention of certain other ingredients such as glitter in the marking composition transferred to the substrate. As such, the emollient typically is a liquid or paste at room temperature and is preferably miscible with the other components in the composition, particularly the wax or the fatty acid. In certain embodiments however, the emollient may be a solid such as a flake.
Any suitable emollient may be used in the present inventive marking composition. Emollients such as lanolin oil and its derivatives, mineral oil, fatty esters, fatty acid esters, fatty alcohols, mono- and di-esters of propylene glycols, glycerol di-esters, mono- and di-esters of polyethylene glycols, petrolatum, vegetable shortenings, dimers and trimers of fatty acids, plant oils, silicones, and mixtures thereof are suitable for use in compositions of the invention.
Suitable lanolin derivatives include acetylated lanolin, acetylated lanolin alcohol, hydrogenated lanolin, lanolin alcohol, lanolin acids, isopropyl lanolate, lanolin wax, and hydroxylated lanolin. Suitable fatty esters and fatty acid esters include isopropyl myristate, myristyl myristate, and esterified fatty acid propoxylates such as polyoxypropylene (2) myristyl ether propionate. Suitable fatty alcohols include oleyl alcohol, and suitable vegetable shortenings include KREMIT~ (Armour, Omaha, Nebraska). Suitahle plant oils include castor oil, coconut oil, olive oil, peanut oil, safflower oil, sesame oil, soybean oil, wheat germ oil, corn oil, avocado oil, almond oil, grape seed oil, jojoba oil, apricot kernel oil, palm oil, and sunflower seed oil. Suitable silicones include 5 DOW-CORNING~ 556, 593, and 1107 fluids ~Dow-Corning, Midland, Michigan). Other possible emollients include longer chain hydrocarbons, particularly alkenes, such as polyoxypropylene-polyoxyethylene block copolymers such as PLURONIC~ 25R4 and PLURONIC 25R8 (BASF, Parsippany, New Jersey).
The emollient may be present in any suitable amount, for example, in an amount of up to 45% by weight of the marking composition, and preferably in an amount of from about 5% to about 25% by weight of the marking composition.
Excessive amounts of emollients can increase the tackiness adversely. In certain embodiments, especially the embodiments havinq a large amount of a soft wax, the emollient can be present in a low amount or omitted while still maintaining the desired improved laydown characteristics.
The marking composition preferably contains a colorant which can be a pigment or dye. The pigment may be an inorganic pigment, an organic pigment, or a mixture thereof. The inorganic pigment is preferably iron blue, iron oxide, zinc oxide, ultramarine blue, titanium dioxide, or a mixture thereof. The organic pigment is preferably an azo, a naphthol, or a phthalo pigment. Dyes, either acidic or basic, can be used in the present inventive marking composition.
The pigment can have any suitable particle size, however, a preferable particle size is from about 0.1 micron to about 25 microns. More preferably, the pigment has a particle size of about 0.3 micron to about 20 microns, and, even more preferably, the pigment particle size is in the range of about 0.5 micron to about 15 microns.
Examples of suitable dyes include the polymeric colorants REACTINT~ brand Blue x 3LV, Orange x 38, and Violet x 80LT, available from the Milliken Chemical Co. in Inman, South Carolina. These are dark viscous liquids containing the dyes Blue x 3LV, Orange x 38, and Violet x 80LT.
The colorant may be present in any suitable amount.
The present inventive marking composition preferably contains pigment in an amount of from about 0.5% to about 20% by weight of the marking composition, more preferably from about 2% to about 15% by weight of the marking composition. Where a dye colorant is used, it may be included in an amount of from about 1% by weight to about 3% by weight of the marking composition.
The marking composition of the present invention can contain additional ingredients such as glitter.
The glitter may be of any suitable material and will generally comprise a metallic material, a nonmetallic material, or, more commonly, a reflective material coating, such as a metal coating, on a suitable substrate such as a polymer or other solid organic substrate. Suitable metallic glitters include particles or flakes of aluminum, copper, silver, gold, brass, or other metals. Suitable non-metallic glitters incLude particles or flakes of cellulose acetate, poly(ethylene terephthalate), polymethacrylate, poly(vinylbutyral), and the like.
Suitable metallized glitters include coated metallized materials such as coated aluminum metallized cellulose acetate, poly(ethylene terephthalate), polymethacrylate, poly~vinylbutyral), and the like. Coated aluminum metallized poly(ethylene terephthalate) is the preferred glitter for use in the context of the present invention.
The glitter may be of any color (e.g., silver, gold, blue, red, etc.) or even a mixture of colors. If pigment is present in the marking composition, the glitter may be the same color as the pigment or a different color from the pigment.
The glitter also may be of any dimensions that are suitable for use in such a composition. The glitter is preferably less than about 0.05 x 0.05 x O.OOS cm (0.02 x 0.02 x 0.002 inches) in size, more preferably less than aboutO.03 x 0.03 x 0.003 cm (0.01 x 0.01 x 0.001 inches) in size, and most preferably about 0.02 x 0.02 x 0.003 cm (0.008 x 0.008 x 0.001 inches) to about 0.02 x 0.02 x 0.001 cm (0.008 x 0.008 x 0.0005 inches), or even about 0.01 x 0.01 x 0.001 cm (0.004 x 0.004 x 0.005 inches) or less, in size, although glitter which is too small in size may not exhibit a desirable glitter effect.
The glitter may be present in any suitable amount, preferably less than about 15% by weight of the marking composition, more preferably in an amount fro~ about 3% to about 10% by weight of the marking composition, and even more preferably in an amount from about 4% to about 8% by weight of the marking composition. For additional details, see, e.g., U.S. Patents 5,261,952 and 5,383,954.
The marking composition may additionally include a filler. The filler preferably functions as a pigment dispersant or extender, if pigment is added to the marking composition. Any suitable filler may be utilized, such as calcium carbonate, titanium dioxide, talc, silica, clay (e.g., kaolin clay), feldspar, corn starch, mica, and mixtures thereof. Examples of preferred fillers include talc and kaolin clay. The particle size of the filler is preferably 50 microns or less, more preferably 25 microns or less, although if mica is used, the particle size is preferably about 25-75 microns. Talc of about 3-6 microns average diameter particle size is preferred for use in certain embodiments of the present invention. An example of a talc is NYTALrM 400, which is available from The Vanderbilt Co. in Norwalk, Connecticut.
In certain embodiments, the filler acts to provide a shimmering effect to the composition. Filler can also be included in compositions of the invention when a pigment is not used. In cerain embodiments, the filler improves the CA 022l9662 l997-l0-28 strength of the marking composition and the marking instrument.
Two or more fillers can be combined for use in compositions of the invention. For example, the mica S particles can be coated with titanium dioxide. Such a coated mica is available as MAGNAPEARL~ from The Mearl Corporation in Charleston, SC. MAGNAPE~RL can provide smooth laydown as well as a shimmer effect to the marking composition. MAGNAPEARL can also provide added strength to the marking composition and the writing instrument.
The filler may be present in any suitable amount.
Preferably filler is used in an amount up to about 20~ by weight of the marking composition, and more preferably in an amount of from about 5% to about 15~ by weight of the marking composition.
A cleanability additive can also be included in the marking composition of the present invention to aid in the removal of the composition, preferably with mild soap and water, from non-porous surfaces, such as table tops, counter tops, etc. Suitable cleanability additives include polyoxypropylene-polyoxyethylene block copolymers, polyoxyethylene alcohols, polyoxyethylene esters, polyoxyethylene ethers, and derivatives and mixtures thereof.
The marking composition of the present invention preferably contains a cleanability agent such as polyoxyethylene (12) tridecyl ether or alcohol, polyoxyethylene (10) alkyl aryl ether, polyoxyethylene (40) stearate, or polyoxyethylene (20) stearyl alcohol. The marking composition more preferably contains polyoxyethylene (40) stearate (available as LIPOPEG~ 39S
(Lipo Chemicals, Patterson, New Jersey)) or polyoxyethylene (12) tridecyl ether alcohol (available as RENEX~ 30 (ICI
America, Wilmington, Delaware)), most preferably a mixture of the two. Certain emollients may also act as cleanability additives or aid in cleanability, such as polyoxypropylene-polyoxyethylene block copolymers, e.g., PLURONIC~ 25R4 or 25R8.
The cleanability additive may be present in any suitable amount. Preferably it is present in an amount up to about 5~ by weight of the marking composition, and more preferably in an amount from about 1% to about 4~ by weight of the marking composition.
Other additives may be incorporated into the marking compositions of the present invention in minor amounts.
For example, processing aids such as foam inhibitors and mold release agents, as well as oxidation and W
stabilizers may be added. These additives are typically used in an amount of from about 0.01% to about 5% by weight of the marking composition, and preferably in an amount of from about 0.1~ to about 1~ by weight of the marking composition.
Examples of suitable foam inhibitors include petroleum hydrocarbons such as FOAMKILL~ 614 (Crucible Chemical Co., Greenville, South Carolina). Examples of suitable mold release agents include the Group IIA metal salts of fatty acids, particularly calcium stearate. Examples of suitable oxidation stabilizers include sterically hindered phenols.
Examples of suitable W stabilizers include hindered amine light stabilizers and benzotriazoles.
The marking composition of the present invention may be prepared by heating the components to a semisolid, or preferably, liquid, state and mixing them together.
Generally, a portion of the waxes and fatty acid, is heated above its melting temperature, e.g., to about 104-116~C
(220-240~F). Then, the remainder of the waxes and the fatty acid is added to the liquified waxy material, while stirring the composition with suitable stirring means, such as, for example, a disperser head mixer. The filler and colorant are then added in sequence to the composition under continued stirring of the composition. The emollient, along with any other additives such as cleanability agents and the like, are added to the liquified material, while continuing to stir the composition. The composition is then appropriately molded, such as by pouring the composition into flatbed molds. The mold is cooled and the composition is shaped into suitable forms such as crayons.
The marking composition of the present invention is hard enough for children to handle and resists easily breaking, yet is soft enough to allow for the laydown of the composition on a substrate in the course of the normal marking of a substrate with the composition. Particularly, - the laydown characteristics of compositions of the present invention are improved over such characteristics of previously available compositions.
The marking composition of the present invention is suitable for use in writing instruments, in particular, crayons, and may be applied to a variety of porous and non-porous writing surfaces or substrates.
The following examples serve to further illustrate the present invention and are not intended to limit the scope of the invention.
Example 1 This example illustrates the preferred amounts of the ingredients by class that can be used to prepare an embodiment of the marking composition of the present invention that includes a hard wax, a soft wax and an emollient.
Component preferred range, wt%
Fatty acid about 30-about 55 Hard wax about 12-about 34 Soft wax about 1-about 4 Emollient about 10-about 40 Filler about 0-about 20 Colorant about 0-about 15%
Example 2 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition invention set forth in Example 1.
Component Preferred Range, wt~
Stearic acid about 30-about 55 Paraffin wax about 3-about 10 Syn. Carnauba wax about 8-about 20 KESTER WAX K80D22 about l-about 4 Hydroxypolyester about 1-about 4 LIPONATE MM about 2-about 5 LIPONATE TDTM about 3-about 10 Castor oil about 5-about 25 MAGNAPEARL 2000 about 0-about 20 Colorant about 2-about 15 Example 3 This Example illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 2. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic acid 41.8 Paraffin wax 6.8 Syn. Carnauba wax 13.6 KESTER WAX 80D22 1.7 Hydroxypolyester 1.7 LIPONATE MM 3.4 LIPONATE TDTM 5.4 Castor oil 8.2 MAGNAPEARL 2000 6.8 Ultramarine Blue 10.6 1 0 0 . O
CA 022l9662 l997-l0-28 Example 4 This Example illustrates the preferred amounts of the ingredients by class that can be used to prepare another embodiment of the marking composition of the present invention comprising a fatty acid, a hard wax, soft wax, and an emollient.
Component preferred range, wt%
Fatty acid about 3-about 15 Hard wax about 39-about 64 Soft wax about 1-about 4 Emollient about 5-about 15 Filler about l-about 15 Dye about l-about 3 Example 5 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition present invention set forth in Example 4..
Component preferred range, wt%
Stearic acid about 3-about 15 Paraffin wax about 30-about 45 Syn. Carnauba wax about 8-about 15 KESTER WAX K80D22 about 1-about 4 Hydroxypolyester about l-about 4 Castor Oil about 5-about 15 MAGNAPEARL 2000 about l-about 15 Colorant about l-about. 3 Example 6 This Example illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 5. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic acid 22.2 Paraffin wax 37.5 Syn. Carnauba wax 12.1 KESTER WAX K80D22 1.5 Hydroxypo.lyester 1.5 Castor oil 12.6 MAGNAPEARL 2000 12.6 Liquid Dye (Milliken Color) 1.5 100.O
Example 7 This Example illustrates the preferred amounts of the ingredients by class that can be used to prepare yet another embodiment of the marking composition of the present invention which comprises a fatty acid, a hard wax, and a soft wax.
Component preferred range, wt~
Fatty acid about 15-about 30 Hard wax about 10-about 30 Soft wax about 20-about 60 Filler about 5-about 20 Colorant about 1-about 5 Example 8 This Example illustrates the specific ingredients that can be used to prepare the embodiment of the marking composition of the present invention set forth in Example 7..
Component preferred range, wt%
Stearic Acid about 15-about 30 LIPOWAX KB2444 about 20-ab,out 60 LIPOWAX KB2462 about 5-about 15 Paraffin wax ' about 5 about 15 FOAMKILL 614 about 0.1-about 1 NYTAL 400 (talc) ' about 5-about 20 Colorant about l-about 5 Example 9 This ExampLe illustrates the preparation of an embodiment of the marking composition of the present invention according to Example 8. The following ingredients were combined and melt mixed to obtain a marking composition having smooth laydown characteristics.
Component wt~
Stearic Acid 19.6 LIPOWAX KB2444 43.2 LIPOWAX KB2462 9.8 Paraffin wax 9.8 FOAMKILL 614 0.3 NYTAL 400 14.4 Phthalo green pigment 2.9 While this invention has been described with emphasis upon a preferred embodiment, it will be obvious to those of ordinary skill in the art that the preferred composition may be varied. It is intended that the invention may be practiced otherwise than as specifically described herein.
Accordlngly, this invention includes all modifications encompassed within the spirit and scope of the following claims.
Claims (23)
1. A marking composition comprising a fatty acid, a hard wax, an emollient, and a pigment, wherein said composition has smooth laydown characteristics when applied on substrates.
2. The marking composition of claim 1, wherein said emollient is present in an amount less than about 45% by weight of the composition.
3. The marking composition of claim 2, wherein said fatty acid has from about 16 to about 30 carbon atoms.
4. The marking composition of claim 3, wherein said fatty acid is stearic acid.
5. The marking composition of claim 3, wherein said hard wax has a needle penetration of less than about 40 mm at 25°C by ASTM D1321.
6. The marking composition of claim 5, wherein said hard wax is selected from the group consisting of candelilla wax, carnauba wax, beeswax, microcrystalline wax, fatty acid esters, and alkali and alkaline earth metal and ammonium salts of fatty acids, and combinations thereof.
7. The marking composition of claim 5, which further comprises a soft wax having a needle penetration of greater than about 40 mm at 25°C by ASTM D1321.
8. The marking composition of claim 7, wherein said soft wax is selected from the group consisting of microcrystalline wax, vegetable fats, animal fats, fatty acid esters, and alkali and alkaline earth metal and ammonium salts of fatty acids, and hydroxypolyesters, and combinations thereof.
9. The marking composition of claim 7, wherein said hard wax is present in an amount of from about 10%
by weight to about 25% by weight of the composition and said soft wax is present in an amount of from about 5% by weight to about 15% by weight of the composition.
by weight to about 25% by weight of the composition and said soft wax is present in an amount of from about 5% by weight to about 15% by weight of the composition.
10. The marking composition of claim 6, wherein said emollient is selected from the group consisting of consisting of lanolin oil and its derivatives, mineral oil, fatty esters, fatty acid esters, fatty alcohols, mono- and di-esters of propylene glycols, glycerol di-esters, mono- and di-esters of polyethylene glycols, petrolatum, vegetable shortening, dimers and trimers of fatty acids, plant oils, silicones, and combinations thereof.
11. The marking composition of claim 6, wherein said emollient is selected from the group consisting of castor oil, tridecyl trimellitate, myristyl myristate, and combinations thereof.
12. The marking composition of claim 11, wherein said pigment is present in an amount of from about 2% by weight to about 15% by weight of the composition.
13. The marking composition of claim 12, which additionally comprises a filler.
14. The marking composition of claim 13, wherein said filler is selected from the group consisting of calcium carbonate, talc, titanium dioxide, silica, clay, feldspar, corn starch, mica, and combinations thereof.
15. A writing instrument made from the marking composition of claim 1.
16. A marking composition comprising a fatty acid having from about 16 to about 30 carbon atoms in an amount of from about 30% by weight to about 55% by weight of the composition, a hard wax in an amount of from about 12% by weight to about 34% by weight of the composition, a soft wax in an amount of from about 1% by weight to about 4% by weight of the composition, an emollient in an amount of from about 10% by weight to about 40% by weight of the composition a filler in an amount of up to about 20% by weight of the composition, and a pigment in an amount of up to about 15% by weight of the composition, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
17. A marking composition comprising a fatty acid, a hard wax, a soft wax, and a pigment, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
18. The marking composition of claim 17, wherein said fatty acid is present in an amount of from about 15%
by weight to about 30% by weight of the composition, said hard wax in an amount of from about 10% by weight to about 30% by weight of the composition, said soft wax in an amount of from about 20% by weight to about 60% by weight of the composition, and said pigment in an amount of from about 1% by weight to about 5% by weight of the composition, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
by weight to about 30% by weight of the composition, said hard wax in an amount of from about 10% by weight to about 30% by weight of the composition, said soft wax in an amount of from about 20% by weight to about 60% by weight of the composition, and said pigment in an amount of from about 1% by weight to about 5% by weight of the composition, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
19. A marking composition comprising a fatty acid having from about 16 to about 30 carbon atoms in an amount of from about 3% by weight to about 15% by weight of the composition, a hard wax in an amount of from about 39% to about 64% by weight of the composition, a soft wax in an amount of from about 1% by weight to about 4% by weight of the composition, an emollient in an amount of from about 5% by weight to about 15% by weight of the composition, a filler in an amount of from about 1% by weight to about 15% by weight of the composition, and a dye in an amount of from about 1% by weight to about 3%
by weight of the composition, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
by weight of the composition, wherein said composition is substantially free of tackiness to the touch and has smooth laydown characteristics when applied on substrates.
20. A method of making the marking composition of claim 1, comprising combining and mixing said fatty acid, said hard wax, said soft wax, and said emollient at an elevated temperature to obtain a melt mix, and combining and mixing said melt mix and said pigment.
21. The composition of claim 16, wherein said composition is in the form of a crayon.
22. The composition of claim 18, wherein said composition is in the form of a crayon.
23. The composition of claim 19, wherein said composition is in the form of a crayon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76415196A | 1996-12-12 | 1996-12-12 | |
| US08/764,151 | 1996-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2219662A1 true CA2219662A1 (en) | 1998-06-12 |
Family
ID=25069830
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2219662 Abandoned CA2219662A1 (en) | 1996-12-12 | 1997-10-28 | Marking composition |
| CA002275204A Abandoned CA2275204A1 (en) | 1996-12-12 | 1997-12-12 | Marking composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002275204A Abandoned CA2275204A1 (en) | 1996-12-12 | 1997-12-12 | Marking composition |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU5898198A (en) |
| CA (2) | CA2219662A1 (en) |
| WO (1) | WO1998026017A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1093494A1 (en) * | 1998-06-17 | 2001-04-25 | Binney & Smith Inc. | Crayons containing ester waxes |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1146098A1 (en) * | 2000-04-14 | 2001-10-17 | Sicpa Holding S.A. | Solid marking composition as writing means, a writing instrument, an optically variable marking layer and use of a plurality of optically variable pigments |
| CN110003721A (en) * | 2019-04-03 | 2019-07-12 | 安硕文教用品（上海）股份有限公司 | It is a kind of to write smooth color pencil lead and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933708A (en) * | 1973-05-24 | 1976-01-20 | Sun Oil Company Of Pennsylvania | Crayon wax composition |
| US4990013A (en) * | 1988-10-20 | 1991-02-05 | Hejmanowski Conrad L | Glitter crayon |
| US4978390A (en) * | 1988-10-27 | 1990-12-18 | Binney & Smith Inc. | Washable solid marking composition |
| US5261952A (en) * | 1992-03-31 | 1993-11-16 | Binney & Smith Inc. | Solid marking composition containing glitter |
-
1997
- 1997-10-28 CA CA 2219662 patent/CA2219662A1/en not_active Abandoned
- 1997-12-12 CA CA002275204A patent/CA2275204A1/en not_active Abandoned
- 1997-12-12 AU AU58981/98A patent/AU5898198A/en not_active Abandoned
- 1997-12-12 WO PCT/US1997/022930 patent/WO1998026017A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1093494A1 (en) * | 1998-06-17 | 2001-04-25 | Binney & Smith Inc. | Crayons containing ester waxes |
| EP1093494A4 (en) * | 1998-06-17 | 2002-03-20 | Binney & Smith Inc | Crayons containing ester waxes |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2275204A1 (en) | 1998-06-18 |
| AU5898198A (en) | 1998-07-03 |
| WO1998026017A1 (en) | 1998-06-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |