CA2090057A1 - Washable dye-containing composition - Google Patents
Washable dye-containing compositionInfo
- Publication number
- CA2090057A1 CA2090057A1 CA 2090057 CA2090057A CA2090057A1 CA 2090057 A1 CA2090057 A1 CA 2090057A1 CA 2090057 CA2090057 CA 2090057 CA 2090057 A CA2090057 A CA 2090057A CA 2090057 A1 CA2090057 A1 CA 2090057A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- dye
- condensation product
- formaldehyde condensation
- sulfonated phenol
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C09D11/00—Inks
- C09D11/16—Writing inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0072—Preparations with anionic dyes or reactive dyes
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A washable dye-containing coloring composition comprising an acid dye, a dye vehicle, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to said composition. The washable dye-containing composition may be in the form of a marker ink, a water-soluble tempera paint, a pan paint or the like commonly used by children.
A washable dye-containing coloring composition comprising an acid dye, a dye vehicle, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to said composition. The washable dye-containing composition may be in the form of a marker ink, a water-soluble tempera paint, a pan paint or the like commonly used by children.
Description
2 0 ~ ~3 0 ~ r7 WA~aBLE DYBoCO~TAINING COMPO~ITION
This invention relates generally to the field of washable coloring materials for drawing, painting, and coloring purposes, such as marker inks and paints. In one particular aspect, the invention relates to tempera 15 paints and it more specifically relates to th~
~ormulation o~ tempera paints that are washable and are especially suitable for use by children. In another aspect the invention relates to writing instruments containing liquid inks, and more specifically to the formulation of inks for use in marking pens or, simply, markers. In one preferred form, the invention relates to improv2ments in tempera paints, and coloring and drawing markers for use by young children.
Tempera paints comprise water soluble binder resin and dyes or pigments as colorants. Such colorants are ordinarily not washable and stain the skin of the user and many fabrics with which the paint may come in contact. In order to overcome this staining problem and to impart washability to the paint, it has been shown that certain colorants used in tempera paint can be 2 ~a~ cl~
chemically modified to improve washability. The chemically modified colorants, however, are expensive, and typically a higher concentration of the chemically modified colorant is needed to provide the desired depth S of color in tempera paints.
It is known that children's coloring markers usually contain inks which are aqueous solutions of dyes known in the trade as "acid dyes." The term ~acid dyes" is actually somewhat of a misnomer in that it does not describe any particular chemical type of dye, but rather refers to the traditional practice of dyeing fabrics from acidified solutions. Not all acid dyes are suitable for use in marker inks, however, and dyes having good chroma and color intensity and good water-solubillty characteristics are typically utilized. However, acid dyes are not washable. Nevertheless, it would be desirable to use acid dyes in tempera paint, marker inks and the like if such dye-containing compositions could be made to be washable.
Marker inks ordinarily also include such ingredients as humectants, biocides, and surfactants. Humectants function to improv~ freeze/thaw stability and to control drying out of the marker tip, while biocides serve the obvious function of preventing spoilage o~ the ink during the expected shelf life of the marker product. In order to limit a grainy appearance of the ink as it is applied andfor to enhance the flow characteristics of the ink, a small amount of surfactant is ordinarily employed. It is I
This invention relates generally to the field of washable coloring materials for drawing, painting, and coloring purposes, such as marker inks and paints. In one particular aspect, the invention relates to tempera 15 paints and it more specifically relates to th~
~ormulation o~ tempera paints that are washable and are especially suitable for use by children. In another aspect the invention relates to writing instruments containing liquid inks, and more specifically to the formulation of inks for use in marking pens or, simply, markers. In one preferred form, the invention relates to improv2ments in tempera paints, and coloring and drawing markers for use by young children.
Tempera paints comprise water soluble binder resin and dyes or pigments as colorants. Such colorants are ordinarily not washable and stain the skin of the user and many fabrics with which the paint may come in contact. In order to overcome this staining problem and to impart washability to the paint, it has been shown that certain colorants used in tempera paint can be 2 ~a~ cl~
chemically modified to improve washability. The chemically modified colorants, however, are expensive, and typically a higher concentration of the chemically modified colorant is needed to provide the desired depth S of color in tempera paints.
It is known that children's coloring markers usually contain inks which are aqueous solutions of dyes known in the trade as "acid dyes." The term ~acid dyes" is actually somewhat of a misnomer in that it does not describe any particular chemical type of dye, but rather refers to the traditional practice of dyeing fabrics from acidified solutions. Not all acid dyes are suitable for use in marker inks, however, and dyes having good chroma and color intensity and good water-solubillty characteristics are typically utilized. However, acid dyes are not washable. Nevertheless, it would be desirable to use acid dyes in tempera paint, marker inks and the like if such dye-containing compositions could be made to be washable.
Marker inks ordinarily also include such ingredients as humectants, biocides, and surfactants. Humectants function to improv~ freeze/thaw stability and to control drying out of the marker tip, while biocides serve the obvious function of preventing spoilage o~ the ink during the expected shelf life of the marker product. In order to limit a grainy appearance of the ink as it is applied andfor to enhance the flow characteristics of the ink, a small amount of surfactant is ordinarily employed. It is I
3 2~ 3 important to note ~hak surfactants, when used at all, are included in very low concentrations in marker inks in order to preven~ the phenomenon known as "strike-throuqh," where the ink soaks through the paper to which it is applied instead of remaining on the surface.
It is well known that a major deficiency of children's coloring markers is their propensity to leave enduring stains on both skin and clothing. While permanence is a desirable characteristic of the so-called "permanent~ markers, it is one of the most objectionable of properties for coloring instruments used by young children. Accordingly, much e~fort has ~een expended over many years by producers of these instruments to reduce or eliminate staining. This is attested by the rather numerous offerings of so-called "washable"
markers, many of which on close examination, are found to remove very poorly from fabrics that are typically used in children's clothing. Most such markers achieve their limited washability by utilizing dyes which have good fugivity from fabrics and by utilizing lowered dye concentrations in an effort to minimize skin staining.
In most cases, these l'washable" products leave objectionable stains on the skin. The inks used in such marXers therefore lack fugivity from skin.
In a more recant approach, the tints or dyes used in these "washable" markers are produced by the chemical grafting of a chromophore onto a water soluble polymer, 4 ~3 such as poly (ethylene glycol), in an effort to impart improved fugivity properties to the chromophore. While this approach is a workable one for enhancing washability from skin and launderability from fabric, it is relatively expensive.
It is therefore one general object of ~he invention to provide a method of washability from skin of a dye-containing composition.
Another object is to provide a water-soluble dye-containing composition which, in addition to being washable from skin, exhibits enhanced launderability from fabrics.
A related object is to provide non-toxic washable dye-containing compositions, such as paints and inks, which are suitable for use by young children who may make marks on themselves and their clothing.' -Another related object is to improve washability from skin and/or launderability from fabrics of dye-containing compositions without the necessity for chemical or other alteration of the dyestuff itself.
A further object is to improve washability from skin of dye-containing compositions which otherwise have good launderability from textiles, but quite limited washability from skin.
Yet another object is to provide a non-toxic washable acid dye-containing composition that is washable from skin and launderable from fabrics.
2 ~ Q, ~ 7 These and other objects and advan~ages of the invention will be apparent to those skilled in this art from the following description o~ the invention and the appended claims.
The discovery of the present invention is that one may incorporate into a washable acid dye-containing composition an additive which will impart to the composition washability from skin. At the same time, it has been discovered that, in many instances, the additive will noticeably enhance launderability from fabrics ordinarily used in children's clothing. Thus, in accordance with the present invention, one may produce a washable acid dye-containing composition which has unexpectedly good washability from skin and, in many instances, enhanced launderability from textiles without the need for chemically altering the desired dye.
It has been discovered that sulfonated phenol-formaldehyde condensation products are e~fective in imparting washability from skin. The sulfonated phenol-formaldehyde condensation products may also enhance the launderability from fabrics of an acid dye-containing composition.
In one of its most general aspects, the invention includes acid dye-containing coloring compositions that include a sulfonated phenol-formaldehyde condensation product, which are easily washed from the skin, and, laundered from textiles. In another general aspect, the 6 ~ao~ri present invention includes a m~thod of imparting skin washability and fabric launderability to an acid dye-containing composition by adding to the composition an effective amount of a sulfonated phenol formaldehyde condensation product.
Thus, in one form, the invention is a washable dye-containing coloring composition comprising an acid dye, a dye vehicle, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition. As used herein, the term washable (or washability) includes washability from skin and/or launderability from textiles or fabrics.
Washability from skin means that the stain or color imparted by the dye-containing composition to skin will not be visible to the naked eye after the skin is washed according to the procedure set forth hereinafter.
Correspondingly, launderability from textiles or fabric means that the stain or color imparted by the dye-containing composition to fabric will not be visib;e to the naked eye after the fa~ric is laundered according to the procedures set forth hereinafter. The condensation products desirable for use in the dye containing composition of the present invention do not impair the stability of the composition. In one embodiment, the invention is a washable tempera paint, comprising an acid dye, water and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition. Such a tempera paint may 2 ~ 7 include binders, extenders, thickeners, and de~oamers, and, preferably, preservatives. Additionally, as is known, freeze/thaw additives may also be included. In another embodiment, the invention is a washable marker ink, comprising an acid dye, water, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability. Such a marker ink, which is especially suitable for use by children, may also advantageously include humectants, surfactants, and, preferably, preservatives, all of which are well known in the art.
The additive which has now b~en discovered to impart skin washability and, in some instances, enhance fabric launderability of washable acid dye-containing compositions is a sulfonated phenol-formaldehyde condensation product. The sulfonated phenol-formaldehyde condensation products useful in the practice of the present invention desirably do not impair the stability of the dye-containing composition. By stability, it is meant that the dye-containing composition,~ which includes the condensation product additive, must not precipitate when maintained at a temperature of 140F for two weeks.
In addition, it is preferred to use sulfonated phenol-formaldehyde condensation products which, in addition to imparting washability from skin, also enhance launderability from textiles.
8 2 ~ o~3 ~ f~ '~, 7 A sulfonated phenol-formaldehyde condensation product useful in the practice of the present invention is Intratex~N, commercially available ~rom Crompton and Knowles Corporation. Sulfonated phenol-formaldehyde condensation products useful in the practice of the invention ar~, as described in U.S. Patent No. 4,501,5gl, preferably linear, low molecular weight condensation products, that is, products having an average molecular weight of less than about 1000, for example, in the range of 250 to 700. Such products are water-soluble and may be prepared by conventional art-recognized techniques, for example, by condensation of formaldehyde with one or more phenols in a mole ratio of about 1.0 to 0.8, phenol(s) to formaldehyde, at a pH of less than 7 using an acid catalyst such as HC1, wherein at least one of the phenols is a phenolsulfonic acid or alkali metal salt thereof. Preferably, the phenols comprise, in addition to the sulfonic acid or salt thereof, a sulfone, for example, dihydroxy aromatic diphenol sulfone. Such condensation products contain, in addition to sulfonic acid groups or alkali metal salts thereof, sulfone groups. Other sulfonated phenol-formaldehyde condensation products are described in U.S. Paten~ Re.
33,365, and U.S. Patent Nos. 4,592,940 and 4,680,212.
The sulfonated phenol-formaldehyde condensation product, Intratex N is preferred. Intratex N exhibited the effect of imparting skin washability and enhancing fabric launderability. Other sulfonated phenol-formaldehyde 9 2 ~3 9 f~ 7 condensation products may produce equivalent, or even better results and all are within the scope of the invention.
The specific mechanism by which the sulfonated phenol-formaldehyde condensation product5 impart skin washability and enhance fabric launderability is not known. However, it is postulated that the condensation products may adhere to the skin and to the fabric faster than the dye and tie up the reactive sites of these substrates, such that the dye has a reduced ability to physically or chemically associate with skin or fabric.
The sulfonated phenol-formaldehyde condensation product, Intratex N, was tested in numerous water-based acid-dye compositions comprising, water, defoamer, acid dyes, ~inders, extenders, thickeners, freeze-thaw additives and preservatives. In general, it has been found that the beneficial effect of the sulfonated phenol-formaldehyde condensation product is dependent on the type and amount of dye that is present in the composition. Further, there must be a sufficient amount of the sulfonated phenol-formaldehyde condensation product in the composition to impart washability.
To impart washability, the amount of sulfonated phenol-formaldehyde condensation product present in the composition generally must exceed the amount of dye in the composition. Preferably, the weight ratio of sulfonated phenol-formaldehyde condensation product to dye in the dye-containing composition should be at least lo 2~
about 3:1. The upper limit of the weight ratio of sulfonated phenol-formaldehyde condensation product to dye is not critical, however, and may be as high as about 20:1 or so. The upper limit of the additive concentration i5 imposed only by the constraints on the viscosity and the long term stability of the composition.
For tempera paints, the concentration of dye in the composition is desirably in the range of from about 0.25%
to about 1.5% by weight, and the concentration of the sulfonated phenol-formaldehyde condensation product is desirably in the range of from about 2.5% to about 6.0%
by weiqht. For marker inks, the concentration of dye in the composition is desirably in the range of from about 0.5% to about 8 to 10% by weight and the concentration of the sulfonated phenol-formaldehyde condensation product is desirably in the range of from about 18% to about 40%
by weight.
It has been found that the addition of a sulfonated phenol-formaldehyde condensation product additive produces skin washability and may enhance fabric launderability when included in acid dye-containing composition~. In the practice of this invention, it is also preferable to select acid dyes which otherwise are known to have good launderability from fabrics in the absence of the additive. When used in the composition of the invention, such acid dyes not only have washability from skin, but enhanced launderability from fabric as well. By way of illustration, and not in limitation, 11 2 ~ ~! Q .~
acid dyes that have been found suitable for use in this invention are Acid Violet 17, Acid Blue 9, Acid Yellow 17, and Acid Red 388. Yellow F . D . & C #6 may also be used.
In addition to the acid dye, water and the sulfonated phenol-for~aldehyde condensation product, the compositions of the invention may, when in the ~orm of a tempera paint, also advantageously include defoamers, binders, extenders, thic~eners, freeze-thaw additives and preservatives~ These materials and their functions are well known, and their mention here is by way of illustration only.
For example, it is desirable to include a de~oamer in the tempera paint to reduce foaming of the composition during preparation. A small amount of defoamer may be used, for example, less then one percent.
A binder may also be included in the composition to promote adhesion o~ the paint to the substrate and to assist in the film forming character of the paint after the water evaporates. Suitable binders include starches, such as dextrin, for example. A generally useful concentration range for the binder is ~rom about 5% to about 20% by weight.
A thickener may be advantageously included in th~
composition in order to impart thic~ness and body to the paint. Suitable thickeners include, for example, water soluble cellulosics. Generally the concentration range 12 2 0 ~ O ~ ~ ~
for the thickeners is from about 0.5~ to about 5% by weight.
Extenders may also be included in the paint composition in order to impart body to the paint and to assist in the brushability of the paint. Illustrative of suitable extenders are magnesium silicate hydrate (talc), microcrystalline silica, sodium aluminosilicate, calcium carbonate, clays and mi~tures thereof. A generally useful concentration range for the extenders is from about 15% to about 40% by weight.
A freeze-thaw additive may be advantageously included in thc tempera paint composition in order to prevent coagulation of the paint after a freeze-thaw cycle. The preferred freeze-thaw additive i5 sodium acetate. The concentration of this additive in the composition may be from about 2% to about 5% by weight.
In addition to the acid dye, water, and the sulfonated phenol-formaldehyde condensation praduct, the compositions of the invention may, when in the form of a marker ink, also advantageously include a humectant, a surfactant, and a preservative. These materials and their functions are well known, and their mention here is by way of illustration only.
For example, it is desirable to include a humectant in a marker ink to retard the evaporation of water from the ink solution. This avoids unduly rapid drying of the ink in the marker nib which can cause clogging of the ni~
and impaix the function of the marker. Typical 13 2~ ;7 humectants include polyhydric alcohols such as glycerine, propylene glycol, ethylene glycol, and diethylene glycol, hydroxylated starches, low molecular weight (m.w. =
200-400) poly(ethylene glycols)~ and mixtures of these materials. A generally useful concentration range for these humectants is from about 5% up to about 30% by weight.
Small amounts of surfactant (up to about 0.1% by weight) are also useful in marker ink compositions for the purpose of adjusting such properties as viscosity (for proper dispensing of ink through thP nib), and surface tension (for good flow properties without creating "strike-through"~. Nonionic surfactants, such as poly (ethylene glycol) ether, alkylaryl polyether alcohol, fluorinated alkyl esters, and mixtures of such materials are preferred for use in marker inks.
Preservatives of conventional types are also advantageously employed in marker inks and tempera paints in order to extend the shelf life of the composition.
Some typical preservatives useful in the present invention include methyl p-hydroxybenzoate, glutaraldehyde, hydroxybenzoic acid esters, 3-iodo-2-propynyl butyl carbamate, bicyclic ox~zolidones, and a biocide comprising as the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and, 2-methyl-4-isothiazolin-3-one. Preservatives are usually effective when present in an amount of from about 0.1% up to about 0.8% by weight.
2 ~ ~ ~ t~ ",; jl ~E8? PROC~D~RB~
The washability from skin of the compositions of the invention was measured by the following test:
1. Wash hands with soap and warm water. The pre-stain cleansing re~oves excess oil and dirt from the skin and provides a more consistent skin surface for testing. Allow the skin to dry for 30 seconds.
2. In the case of a composition of the invention used in a marker, draw a stripe on the palm of the hand with the flat side of the nib. In the usual case, a 1/4 inch wide by 1 inch long stripe works well. Apply enough pressure and/or multiple passes to develop a stripe with good color intensity. If it is desired to make a comparison among two or more compositions, more than one stripe may be drawn. Let stripes dry for fifteen minutes.
3. In the case of a composition of the invention used in a tempera paint, apply a stripe of paint with a pain~ brush and allow to dry for fifteen minutes.
4. In the case of a marker, place hand under tap and briefly rinse off excess inX with warm water.
20~005~
It is well known that a major deficiency of children's coloring markers is their propensity to leave enduring stains on both skin and clothing. While permanence is a desirable characteristic of the so-called "permanent~ markers, it is one of the most objectionable of properties for coloring instruments used by young children. Accordingly, much e~fort has ~een expended over many years by producers of these instruments to reduce or eliminate staining. This is attested by the rather numerous offerings of so-called "washable"
markers, many of which on close examination, are found to remove very poorly from fabrics that are typically used in children's clothing. Most such markers achieve their limited washability by utilizing dyes which have good fugivity from fabrics and by utilizing lowered dye concentrations in an effort to minimize skin staining.
In most cases, these l'washable" products leave objectionable stains on the skin. The inks used in such marXers therefore lack fugivity from skin.
In a more recant approach, the tints or dyes used in these "washable" markers are produced by the chemical grafting of a chromophore onto a water soluble polymer, 4 ~3 such as poly (ethylene glycol), in an effort to impart improved fugivity properties to the chromophore. While this approach is a workable one for enhancing washability from skin and launderability from fabric, it is relatively expensive.
It is therefore one general object of ~he invention to provide a method of washability from skin of a dye-containing composition.
Another object is to provide a water-soluble dye-containing composition which, in addition to being washable from skin, exhibits enhanced launderability from fabrics.
A related object is to provide non-toxic washable dye-containing compositions, such as paints and inks, which are suitable for use by young children who may make marks on themselves and their clothing.' -Another related object is to improve washability from skin and/or launderability from fabrics of dye-containing compositions without the necessity for chemical or other alteration of the dyestuff itself.
A further object is to improve washability from skin of dye-containing compositions which otherwise have good launderability from textiles, but quite limited washability from skin.
Yet another object is to provide a non-toxic washable acid dye-containing composition that is washable from skin and launderable from fabrics.
2 ~ Q, ~ 7 These and other objects and advan~ages of the invention will be apparent to those skilled in this art from the following description o~ the invention and the appended claims.
The discovery of the present invention is that one may incorporate into a washable acid dye-containing composition an additive which will impart to the composition washability from skin. At the same time, it has been discovered that, in many instances, the additive will noticeably enhance launderability from fabrics ordinarily used in children's clothing. Thus, in accordance with the present invention, one may produce a washable acid dye-containing composition which has unexpectedly good washability from skin and, in many instances, enhanced launderability from textiles without the need for chemically altering the desired dye.
It has been discovered that sulfonated phenol-formaldehyde condensation products are e~fective in imparting washability from skin. The sulfonated phenol-formaldehyde condensation products may also enhance the launderability from fabrics of an acid dye-containing composition.
In one of its most general aspects, the invention includes acid dye-containing coloring compositions that include a sulfonated phenol-formaldehyde condensation product, which are easily washed from the skin, and, laundered from textiles. In another general aspect, the 6 ~ao~ri present invention includes a m~thod of imparting skin washability and fabric launderability to an acid dye-containing composition by adding to the composition an effective amount of a sulfonated phenol formaldehyde condensation product.
Thus, in one form, the invention is a washable dye-containing coloring composition comprising an acid dye, a dye vehicle, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition. As used herein, the term washable (or washability) includes washability from skin and/or launderability from textiles or fabrics.
Washability from skin means that the stain or color imparted by the dye-containing composition to skin will not be visible to the naked eye after the skin is washed according to the procedure set forth hereinafter.
Correspondingly, launderability from textiles or fabric means that the stain or color imparted by the dye-containing composition to fabric will not be visib;e to the naked eye after the fa~ric is laundered according to the procedures set forth hereinafter. The condensation products desirable for use in the dye containing composition of the present invention do not impair the stability of the composition. In one embodiment, the invention is a washable tempera paint, comprising an acid dye, water and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition. Such a tempera paint may 2 ~ 7 include binders, extenders, thickeners, and de~oamers, and, preferably, preservatives. Additionally, as is known, freeze/thaw additives may also be included. In another embodiment, the invention is a washable marker ink, comprising an acid dye, water, and a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability. Such a marker ink, which is especially suitable for use by children, may also advantageously include humectants, surfactants, and, preferably, preservatives, all of which are well known in the art.
The additive which has now b~en discovered to impart skin washability and, in some instances, enhance fabric launderability of washable acid dye-containing compositions is a sulfonated phenol-formaldehyde condensation product. The sulfonated phenol-formaldehyde condensation products useful in the practice of the present invention desirably do not impair the stability of the dye-containing composition. By stability, it is meant that the dye-containing composition,~ which includes the condensation product additive, must not precipitate when maintained at a temperature of 140F for two weeks.
In addition, it is preferred to use sulfonated phenol-formaldehyde condensation products which, in addition to imparting washability from skin, also enhance launderability from textiles.
8 2 ~ o~3 ~ f~ '~, 7 A sulfonated phenol-formaldehyde condensation product useful in the practice of the present invention is Intratex~N, commercially available ~rom Crompton and Knowles Corporation. Sulfonated phenol-formaldehyde condensation products useful in the practice of the invention ar~, as described in U.S. Patent No. 4,501,5gl, preferably linear, low molecular weight condensation products, that is, products having an average molecular weight of less than about 1000, for example, in the range of 250 to 700. Such products are water-soluble and may be prepared by conventional art-recognized techniques, for example, by condensation of formaldehyde with one or more phenols in a mole ratio of about 1.0 to 0.8, phenol(s) to formaldehyde, at a pH of less than 7 using an acid catalyst such as HC1, wherein at least one of the phenols is a phenolsulfonic acid or alkali metal salt thereof. Preferably, the phenols comprise, in addition to the sulfonic acid or salt thereof, a sulfone, for example, dihydroxy aromatic diphenol sulfone. Such condensation products contain, in addition to sulfonic acid groups or alkali metal salts thereof, sulfone groups. Other sulfonated phenol-formaldehyde condensation products are described in U.S. Paten~ Re.
33,365, and U.S. Patent Nos. 4,592,940 and 4,680,212.
The sulfonated phenol-formaldehyde condensation product, Intratex N is preferred. Intratex N exhibited the effect of imparting skin washability and enhancing fabric launderability. Other sulfonated phenol-formaldehyde 9 2 ~3 9 f~ 7 condensation products may produce equivalent, or even better results and all are within the scope of the invention.
The specific mechanism by which the sulfonated phenol-formaldehyde condensation product5 impart skin washability and enhance fabric launderability is not known. However, it is postulated that the condensation products may adhere to the skin and to the fabric faster than the dye and tie up the reactive sites of these substrates, such that the dye has a reduced ability to physically or chemically associate with skin or fabric.
The sulfonated phenol-formaldehyde condensation product, Intratex N, was tested in numerous water-based acid-dye compositions comprising, water, defoamer, acid dyes, ~inders, extenders, thickeners, freeze-thaw additives and preservatives. In general, it has been found that the beneficial effect of the sulfonated phenol-formaldehyde condensation product is dependent on the type and amount of dye that is present in the composition. Further, there must be a sufficient amount of the sulfonated phenol-formaldehyde condensation product in the composition to impart washability.
To impart washability, the amount of sulfonated phenol-formaldehyde condensation product present in the composition generally must exceed the amount of dye in the composition. Preferably, the weight ratio of sulfonated phenol-formaldehyde condensation product to dye in the dye-containing composition should be at least lo 2~
about 3:1. The upper limit of the weight ratio of sulfonated phenol-formaldehyde condensation product to dye is not critical, however, and may be as high as about 20:1 or so. The upper limit of the additive concentration i5 imposed only by the constraints on the viscosity and the long term stability of the composition.
For tempera paints, the concentration of dye in the composition is desirably in the range of from about 0.25%
to about 1.5% by weight, and the concentration of the sulfonated phenol-formaldehyde condensation product is desirably in the range of from about 2.5% to about 6.0%
by weiqht. For marker inks, the concentration of dye in the composition is desirably in the range of from about 0.5% to about 8 to 10% by weight and the concentration of the sulfonated phenol-formaldehyde condensation product is desirably in the range of from about 18% to about 40%
by weight.
It has been found that the addition of a sulfonated phenol-formaldehyde condensation product additive produces skin washability and may enhance fabric launderability when included in acid dye-containing composition~. In the practice of this invention, it is also preferable to select acid dyes which otherwise are known to have good launderability from fabrics in the absence of the additive. When used in the composition of the invention, such acid dyes not only have washability from skin, but enhanced launderability from fabric as well. By way of illustration, and not in limitation, 11 2 ~ ~! Q .~
acid dyes that have been found suitable for use in this invention are Acid Violet 17, Acid Blue 9, Acid Yellow 17, and Acid Red 388. Yellow F . D . & C #6 may also be used.
In addition to the acid dye, water and the sulfonated phenol-for~aldehyde condensation product, the compositions of the invention may, when in the ~orm of a tempera paint, also advantageously include defoamers, binders, extenders, thic~eners, freeze-thaw additives and preservatives~ These materials and their functions are well known, and their mention here is by way of illustration only.
For example, it is desirable to include a de~oamer in the tempera paint to reduce foaming of the composition during preparation. A small amount of defoamer may be used, for example, less then one percent.
A binder may also be included in the composition to promote adhesion o~ the paint to the substrate and to assist in the film forming character of the paint after the water evaporates. Suitable binders include starches, such as dextrin, for example. A generally useful concentration range for the binder is ~rom about 5% to about 20% by weight.
A thickener may be advantageously included in th~
composition in order to impart thic~ness and body to the paint. Suitable thickeners include, for example, water soluble cellulosics. Generally the concentration range 12 2 0 ~ O ~ ~ ~
for the thickeners is from about 0.5~ to about 5% by weight.
Extenders may also be included in the paint composition in order to impart body to the paint and to assist in the brushability of the paint. Illustrative of suitable extenders are magnesium silicate hydrate (talc), microcrystalline silica, sodium aluminosilicate, calcium carbonate, clays and mi~tures thereof. A generally useful concentration range for the extenders is from about 15% to about 40% by weight.
A freeze-thaw additive may be advantageously included in thc tempera paint composition in order to prevent coagulation of the paint after a freeze-thaw cycle. The preferred freeze-thaw additive i5 sodium acetate. The concentration of this additive in the composition may be from about 2% to about 5% by weight.
In addition to the acid dye, water, and the sulfonated phenol-formaldehyde condensation praduct, the compositions of the invention may, when in the form of a marker ink, also advantageously include a humectant, a surfactant, and a preservative. These materials and their functions are well known, and their mention here is by way of illustration only.
For example, it is desirable to include a humectant in a marker ink to retard the evaporation of water from the ink solution. This avoids unduly rapid drying of the ink in the marker nib which can cause clogging of the ni~
and impaix the function of the marker. Typical 13 2~ ;7 humectants include polyhydric alcohols such as glycerine, propylene glycol, ethylene glycol, and diethylene glycol, hydroxylated starches, low molecular weight (m.w. =
200-400) poly(ethylene glycols)~ and mixtures of these materials. A generally useful concentration range for these humectants is from about 5% up to about 30% by weight.
Small amounts of surfactant (up to about 0.1% by weight) are also useful in marker ink compositions for the purpose of adjusting such properties as viscosity (for proper dispensing of ink through thP nib), and surface tension (for good flow properties without creating "strike-through"~. Nonionic surfactants, such as poly (ethylene glycol) ether, alkylaryl polyether alcohol, fluorinated alkyl esters, and mixtures of such materials are preferred for use in marker inks.
Preservatives of conventional types are also advantageously employed in marker inks and tempera paints in order to extend the shelf life of the composition.
Some typical preservatives useful in the present invention include methyl p-hydroxybenzoate, glutaraldehyde, hydroxybenzoic acid esters, 3-iodo-2-propynyl butyl carbamate, bicyclic ox~zolidones, and a biocide comprising as the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and, 2-methyl-4-isothiazolin-3-one. Preservatives are usually effective when present in an amount of from about 0.1% up to about 0.8% by weight.
2 ~ ~ ~ t~ ",; jl ~E8? PROC~D~RB~
The washability from skin of the compositions of the invention was measured by the following test:
1. Wash hands with soap and warm water. The pre-stain cleansing re~oves excess oil and dirt from the skin and provides a more consistent skin surface for testing. Allow the skin to dry for 30 seconds.
2. In the case of a composition of the invention used in a marker, draw a stripe on the palm of the hand with the flat side of the nib. In the usual case, a 1/4 inch wide by 1 inch long stripe works well. Apply enough pressure and/or multiple passes to develop a stripe with good color intensity. If it is desired to make a comparison among two or more compositions, more than one stripe may be drawn. Let stripes dry for fifteen minutes.
3. In the case of a composition of the invention used in a tempera paint, apply a stripe of paint with a pain~ brush and allow to dry for fifteen minutes.
4. In the case of a marker, place hand under tap and briefly rinse off excess inX with warm water.
20~005~
5. In the case of tempera paint rinse with cold water and gPntly rub the stripe with a finger.
6. Wash hands with Ivory brand bar soap in the following manner: lather using a minimum amount of soap; replace soap in soap dish; rub hand~
together briskly with modest pressure for 30 seconds; rinse away soap.
together briskly with modest pressure for 30 seconds; rinse away soap.
7. Wipe hands dry with paper towels, and complete th~ drying with a relatively dry towel. A
dry towel will help to rub off residual traces of ink.
The launderability from fabric of the compositions of the invention was measured by the following test.
1. Pre-wash test fabrics with bleach, non-staining water softener and ordinary household phosphate d~tergent powder using 120F hot water as directed in ASTM D4265-83, and dry.
2. Cut test swatches of fabric to be tested.
3. Brush paint onto fabric swatches and allow to dry for 4 hours.
I
16 2~005'~
4. Staple a group of stained swatches to the edges of a bath towel.
5. Add a dummy load of unstained fabrics to provide a four psund wash load. Wash the load in a washing machine for 12 minutes with a hot (120F)/cold cycle.
6. Dry the load in a dryer.
7. Detach the test swatches from the carrier towel, iron, and observe degree of staining.
B~luation o~ Te~t D~ta Skin washability and fabric launderability data are based on a visual rating system as follows:
0 = no stain 1 = barely visible 2 = visible 3 = noticeable 4 = intense In the following examples, dye-containing compositions were made from a base mix composition for a tempera paint. The base mix did not contain either dye or sulfonated phenol-formaldehyde condensation product.
17 2~90~
The base mix, wherein the weight of ingredient is based on the total weight of the base mix, is as follows:
Inqredient Amount ~L~ %2 Water 51.86 Defoamer 0.51 Binder 8.65 Extenders 33.98 Thickener 1.25 Freeze/Thaw additive 3.12 Preservatives 0.63 Different color paints using different acid-dyes were made using the base mix composition described above.
To 95.96 grams of the base mix, water, the acid-dye(s) set forth in Table I, and the sulfonated phenol-formaldehyde condensation product, if any, were added in the amounts also set forth in Table I. The pH was adjusted with 70% acetic acid to pH of 6.5. Controls without sulfonated phenol-formaldehyde condensation product were also prepared from the base mix. In all examples, when the composition includes an additive, the additive is the sulfonated phenol-formaldehyde condensation product, Intratex N. The compositions are set forth in Table I.
TAB~ I
Washability Example Additive H,O Added Number Weiaht ~ Dve 1/Weiaht % Dve 2lWeiqht % (wt.%) 1 3.5~ RPd 388; 0.5 --- o 2 __ Red 388; 0.5 --- 3.5 3 -- Red 388; 0.24 Blue 9; 0.16 3.6 4 3.5~ Red 388; 0.24 Blue 9; 0.16 0.1 -- Violet 17; 0.125 Red 388; 0.375 3.5 6 3.5~ Violet 17; 0.125 Red 3B8; 0.375 0 20~.37 The skin washability and ~abric launderability o~ tempera paint compositions which include the sul~onated phenol-formaldehyde condensation product in accordance with this invention were tested and compared both to controls which do not include ~he condensation product and to tempera paints commercially available from Binney ~ Smith, Inc. identified as "stock," and having the same or comparable color to the color of the tempera paint in accordance with this invention. The data is set forth in Table II below. ~n Table II, the following abbreviations are used:
WR denotes water rinse C deno~es cotton 419 C/PE denotes cotton/polyester 9406 W denotes wool V denotes viscose SS denotes spun silk N denotes nylon A denotes acetate BC denotes bleached cotton ABL~ II
SKIN FABRICS _ _ Example W~ Soap C C/PE W V SS N A BC
Ex. No.3 4 3 0 1 2 - 3 - -Ex. No.4 3 0 0 o o - 2 - - -Stock 2 0 0 1 0 - 3 - -Ex. No.5 5 4 1 2.5 3 - 4 2 Ex. No.6 0 0 0 0.5 1 2 0 - 0 Stock 3 1.5 1 2 0 - 3 0 - -19 ~ 7 The data in Table II illustrate that an acid dye-containing coloring composition which includes a sulfonated phenol-formaldehyde condensation product in accordance with the invention is washable from skin and is launderable from fabric.
The Examples set forth in Table III illustrate the thermal stability of tempera paint compositions which include a sulfonated phenol-formaldehyde condensation product in accordance with this invention. The additive used is the commercially available Intratex N. The compositions of Examples 2 (with no sulfonated phenol-formaldehyde condensation product) and of Example 1 (with Intratex N) were tested for thermal stability over a temperature range of from room temperature to 140F for a period of one month. The results of the test are set forth in Table III.
TAB~
Composition of Temp. Fre~h 2 weeks 1 month ExamPle F ~H/vi~c* ~H/vlsc~ PH/vi3~
2 RT 6.8/2800 7.5/2900 7.5/lO00 1 RT 6.85/2900 7.2/2900 7.25/3300 2 105 7.3/2500 7.4/2900 1 105 7.2/3300 7.3/3500 2 1~0 7.25/2300 7.3/2500 1 120 7.20/2400 7.3/2800 2 140 7.10/1700 7.10/1700 1 140 7.10/2200 7.10/1700 * vi0c denotu~ vi~c05ity mea~ured on Brookf ield vi~cometer o~ a # 4 spindle at 20 rpm.
As can be seen from the viscosity and pH of the compositions' the thermal stability of acid dye-containing compositions are not impaired by the sulfonated phenol-formaldehyde condensation product. Additionally, at the elevated temperature of 140F, the additive containing 20 2~ 5~
compositions in accordance with this invention did not precipitate or phase separa~e. Accordingly, the long term stability of these compositions is not impaired by the use of the condensation product.
A tempera paint composition was made with the following formulation:
~8~ Yor~ulaParts Water 59.40 Defoamer0.75 F D ~ C Yellow 0.50 Violet 170.27 81ue 9 0.30 Yellow 170 12 Binder 8 30 Extender20.00 Thickener2.60 Fr~eze/Thaw Additive 3.00 Preservatives were added to the composition after neutralization with 70% acetic acid to pH 6.5. Different amounts of the sulfonated phenol-formaldehyde condensation product, Intratex N, were added to the composition. For Example 7, 2 wt.% Intratex N was added. For Example 8, 3 wt.%
Intratex N was added, and for Example 9, 4 wt.~ Intratex N was added. The compositions were adjusted with water to make a 100% fo~mulation. These compositions were then tested for skin washability and fabric launderability, without aging, and after aging for 14 days at 140F. The results are set forth in Table IV.
21 ~a~
TAB~ IV
SKIN _ FABRICS
ExamplQ WR Soap C C/PE W SS
Ex. No. 7 2-3 1 0 1 2 4 Ex. No.8 2-3 0 0 0.5 2 4 EX. No. 9 2 0 0 0 2 4 Ex. No.7~ 2 0 0 0 3 4 0 Ex . No . 8* 1 0 0 0 2 3 . 5 Ex. No . 9* 0 0 0 0 1 3 * After 14 days at 140P
The data in Table IV illustrates the skin washability and fabric launderability of acid dye-containing compositions in accordance with the present invention, at different concentrations of sulfonated phenol-formaldehyde condensation product.
From the foregoing description and examples, it can be seen that the addition of a sulfonated phenol-formaldehyde condensation product imparts washability to an acid dye-ccntaining coloring composition. Skin washability and/orfabric launderability are imparted to such washable acid dye-containing compositions as marker inks and tempera paints, and it is apparent that the objects of the present invention have been achieved. While only certain embodiments have been set forth, alternative embodiments and various modifications will be apparent to those s~illed in th~ art. These and other alternatives are considered equivalents and within the spirit and scope of the present invention.
dry towel will help to rub off residual traces of ink.
The launderability from fabric of the compositions of the invention was measured by the following test.
1. Pre-wash test fabrics with bleach, non-staining water softener and ordinary household phosphate d~tergent powder using 120F hot water as directed in ASTM D4265-83, and dry.
2. Cut test swatches of fabric to be tested.
3. Brush paint onto fabric swatches and allow to dry for 4 hours.
I
16 2~005'~
4. Staple a group of stained swatches to the edges of a bath towel.
5. Add a dummy load of unstained fabrics to provide a four psund wash load. Wash the load in a washing machine for 12 minutes with a hot (120F)/cold cycle.
6. Dry the load in a dryer.
7. Detach the test swatches from the carrier towel, iron, and observe degree of staining.
B~luation o~ Te~t D~ta Skin washability and fabric launderability data are based on a visual rating system as follows:
0 = no stain 1 = barely visible 2 = visible 3 = noticeable 4 = intense In the following examples, dye-containing compositions were made from a base mix composition for a tempera paint. The base mix did not contain either dye or sulfonated phenol-formaldehyde condensation product.
17 2~90~
The base mix, wherein the weight of ingredient is based on the total weight of the base mix, is as follows:
Inqredient Amount ~L~ %2 Water 51.86 Defoamer 0.51 Binder 8.65 Extenders 33.98 Thickener 1.25 Freeze/Thaw additive 3.12 Preservatives 0.63 Different color paints using different acid-dyes were made using the base mix composition described above.
To 95.96 grams of the base mix, water, the acid-dye(s) set forth in Table I, and the sulfonated phenol-formaldehyde condensation product, if any, were added in the amounts also set forth in Table I. The pH was adjusted with 70% acetic acid to pH of 6.5. Controls without sulfonated phenol-formaldehyde condensation product were also prepared from the base mix. In all examples, when the composition includes an additive, the additive is the sulfonated phenol-formaldehyde condensation product, Intratex N. The compositions are set forth in Table I.
TAB~ I
Washability Example Additive H,O Added Number Weiaht ~ Dve 1/Weiaht % Dve 2lWeiqht % (wt.%) 1 3.5~ RPd 388; 0.5 --- o 2 __ Red 388; 0.5 --- 3.5 3 -- Red 388; 0.24 Blue 9; 0.16 3.6 4 3.5~ Red 388; 0.24 Blue 9; 0.16 0.1 -- Violet 17; 0.125 Red 388; 0.375 3.5 6 3.5~ Violet 17; 0.125 Red 3B8; 0.375 0 20~.37 The skin washability and ~abric launderability o~ tempera paint compositions which include the sul~onated phenol-formaldehyde condensation product in accordance with this invention were tested and compared both to controls which do not include ~he condensation product and to tempera paints commercially available from Binney ~ Smith, Inc. identified as "stock," and having the same or comparable color to the color of the tempera paint in accordance with this invention. The data is set forth in Table II below. ~n Table II, the following abbreviations are used:
WR denotes water rinse C deno~es cotton 419 C/PE denotes cotton/polyester 9406 W denotes wool V denotes viscose SS denotes spun silk N denotes nylon A denotes acetate BC denotes bleached cotton ABL~ II
SKIN FABRICS _ _ Example W~ Soap C C/PE W V SS N A BC
Ex. No.3 4 3 0 1 2 - 3 - -Ex. No.4 3 0 0 o o - 2 - - -Stock 2 0 0 1 0 - 3 - -Ex. No.5 5 4 1 2.5 3 - 4 2 Ex. No.6 0 0 0 0.5 1 2 0 - 0 Stock 3 1.5 1 2 0 - 3 0 - -19 ~ 7 The data in Table II illustrate that an acid dye-containing coloring composition which includes a sulfonated phenol-formaldehyde condensation product in accordance with the invention is washable from skin and is launderable from fabric.
The Examples set forth in Table III illustrate the thermal stability of tempera paint compositions which include a sulfonated phenol-formaldehyde condensation product in accordance with this invention. The additive used is the commercially available Intratex N. The compositions of Examples 2 (with no sulfonated phenol-formaldehyde condensation product) and of Example 1 (with Intratex N) were tested for thermal stability over a temperature range of from room temperature to 140F for a period of one month. The results of the test are set forth in Table III.
TAB~
Composition of Temp. Fre~h 2 weeks 1 month ExamPle F ~H/vi~c* ~H/vlsc~ PH/vi3~
2 RT 6.8/2800 7.5/2900 7.5/lO00 1 RT 6.85/2900 7.2/2900 7.25/3300 2 105 7.3/2500 7.4/2900 1 105 7.2/3300 7.3/3500 2 1~0 7.25/2300 7.3/2500 1 120 7.20/2400 7.3/2800 2 140 7.10/1700 7.10/1700 1 140 7.10/2200 7.10/1700 * vi0c denotu~ vi~c05ity mea~ured on Brookf ield vi~cometer o~ a # 4 spindle at 20 rpm.
As can be seen from the viscosity and pH of the compositions' the thermal stability of acid dye-containing compositions are not impaired by the sulfonated phenol-formaldehyde condensation product. Additionally, at the elevated temperature of 140F, the additive containing 20 2~ 5~
compositions in accordance with this invention did not precipitate or phase separa~e. Accordingly, the long term stability of these compositions is not impaired by the use of the condensation product.
A tempera paint composition was made with the following formulation:
~8~ Yor~ulaParts Water 59.40 Defoamer0.75 F D ~ C Yellow 0.50 Violet 170.27 81ue 9 0.30 Yellow 170 12 Binder 8 30 Extender20.00 Thickener2.60 Fr~eze/Thaw Additive 3.00 Preservatives were added to the composition after neutralization with 70% acetic acid to pH 6.5. Different amounts of the sulfonated phenol-formaldehyde condensation product, Intratex N, were added to the composition. For Example 7, 2 wt.% Intratex N was added. For Example 8, 3 wt.%
Intratex N was added, and for Example 9, 4 wt.~ Intratex N was added. The compositions were adjusted with water to make a 100% fo~mulation. These compositions were then tested for skin washability and fabric launderability, without aging, and after aging for 14 days at 140F. The results are set forth in Table IV.
21 ~a~
TAB~ IV
SKIN _ FABRICS
ExamplQ WR Soap C C/PE W SS
Ex. No. 7 2-3 1 0 1 2 4 Ex. No.8 2-3 0 0 0.5 2 4 EX. No. 9 2 0 0 0 2 4 Ex. No.7~ 2 0 0 0 3 4 0 Ex . No . 8* 1 0 0 0 2 3 . 5 Ex. No . 9* 0 0 0 0 1 3 * After 14 days at 140P
The data in Table IV illustrates the skin washability and fabric launderability of acid dye-containing compositions in accordance with the present invention, at different concentrations of sulfonated phenol-formaldehyde condensation product.
From the foregoing description and examples, it can be seen that the addition of a sulfonated phenol-formaldehyde condensation product imparts washability to an acid dye-ccntaining coloring composition. Skin washability and/orfabric launderability are imparted to such washable acid dye-containing compositions as marker inks and tempera paints, and it is apparent that the objects of the present invention have been achieved. While only certain embodiments have been set forth, alternative embodiments and various modifications will be apparent to those s~illed in th~ art. These and other alternatives are considered equivalents and within the spirit and scope of the present invention.
Claims (20)
1. A washable dye-containing coloring composition for imparting color to a surface comprising:
(a) an acid dye, (b) a dye vehicle, and (c) a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition.
(a) an acid dye, (b) a dye vehicle, and (c) a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition.
2. A composition according to claim 1, wherein said dye vehicle is water.
3. A composition according to claim 1, further comprising a binder.
4. A composition according to claim 3, wherein said binder is dextrin.
5. A composition according to claim 3, wherein said binder is present in an amount of from about 5% to about 15 by weight.
6. A composition according to claim 1, further comprising an extender.
7. A composition according to claim 6, wherein said extender is selected from the group consisting of magnesium silicate hydrate, microcrystalline silica, sodium aluminosilicate, calcium carbonate and mixtures thereof.
8. A composition according to claim 6, wherein said extender is present in an amount of from about 15% to about 40% by weight.
9. A composition according to claim 1, further comprising a preservative.
10. A composition according to claim 9, wherein said preservative is selected from the group consisting of methyl p-hydroxybenzoate, glutaraldehyde, hydroxybenzoic acid esters, 3-iodo-2-propynyl butyl carbamate, bicyclic oxazolidones solution and a biocide comprising as the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, and mixtures thereof.
11. A composition according to claim 9, wherein said preservative is present in amount of from about 0.1% to about 0.8% by weight.
12. A composition according to claim 1, wherein said sulfonated phenol-formaldehyde condensation product is present in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about 20:1.
13. An ink comprising (a) an acid dye, (b) water, and (c) a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition.
14. A marking instrument containing an ink, said ink comprising:
(a) an acid dye, (b) water, and (c) a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition.
(a) an acid dye, (b) water, and (c) a sulfonated phenol-formaldehyde condensation product in an amount effective to impart washability to the composition.
15. A method of imparting skin washability to a water-soluble composition containing an acid dye, comprising adding to said composition a sulfonated phenol-formaldehyde condensation product in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about 20:1.
16. An aqueous paint composition comprising an acid dye, a thickener, an opacifier, and a sulfonated phenol-formaldehyde condensation product, said sulfonated phenol-formaldehyde condensation product present in said composition in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about 20:1.
17. A method of imparting washability to an aqueous ink composition containing an acid dye, comprising the step of adding to said composition a sulfonated phenol-formaldehyde condensation product in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about 20:1.
18. A method of imparting washability to an aqueous paint composition containing an acid dye, comprising the step of adding to said composition a sulfonated phenol-formaldehyde condensation product in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about 20:1.
19. An aqueous ink composition suitable for use in a marking instrument, said composition comprising:
an acid dye, a humectant in an amount of from about 5% up to about 30%
by weight, a surfactant in an amount of from 0% up to about 0.1% by weight, a preservative in an amount of from about 0.1% up to about 0.6% by weight, and, a sulfonated phenol-formaldehyde condensation product in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about
an acid dye, a humectant in an amount of from about 5% up to about 30%
by weight, a surfactant in an amount of from 0% up to about 0.1% by weight, a preservative in an amount of from about 0.1% up to about 0.6% by weight, and, a sulfonated phenol-formaldehyde condensation product in a weight ratio of sulfonated phenol-formaldehyde condensation product to dye of from about 3:1 to about
20:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83910092A | 1992-02-20 | 1992-02-20 | |
| US07/839,100 | 1992-02-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2090057A1 true CA2090057A1 (en) | 1993-08-21 |
Family
ID=25278856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2090057 Abandoned CA2090057A1 (en) | 1992-02-20 | 1993-02-22 | Washable dye-containing composition |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0557115A1 (en) |
| AU (1) | AU3318293A (en) |
| CA (1) | CA2090057A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5486228A (en) * | 1992-07-31 | 1996-01-23 | Binney & Smith Inc. | Washable color changing compositions |
| US5900094A (en) * | 1997-02-14 | 1999-05-04 | Binney & Smith Inc. | Image transfer method for use with water based dry erase markers |
| ES2216270T3 (en) * | 1997-02-14 | 2004-10-16 | BINNEY & SMITH INC. | WASHABLE COLORING COMPOSITION. |
| US5981626A (en) * | 1997-02-14 | 1999-11-09 | Binney & Smith Inc. | Washable coloring composition suitable for use in dry erase markers |
| US6372031B1 (en) | 1999-08-03 | 2002-04-16 | Milliken & Company | Washable coloring compositions comprising low molecular-weight styrene-maleic anhydride copolymers |
| US6458193B1 (en) | 2000-05-16 | 2002-10-01 | Milliken & Company | Washable coloring compositions |
| DE102007051279A1 (en) | 2007-10-26 | 2009-04-30 | Clariant International Ltd. | Colorant preparation, useful for tinting a cleanser, preferably softener or detergents, inks, crayons and markers, comprises coloring agent from acid-, polymer-, reactive- or solvent-dye, and oligo- or polyester-compounds |
| AU2014223461B2 (en) * | 2013-02-27 | 2017-07-27 | Crayola Llc | Rinsable inks and methods of making the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6054438B2 (en) * | 1980-03-31 | 1985-11-29 | 住友化学工業株式会社 | Reactive dye liquid composition for dyeing cellulose fiber materials |
| DE3315741A1 (en) * | 1983-04-30 | 1984-10-31 | Fa. J.S. Staedtler, 8500 Nürnberg | PIGMENT-CONTAINING WRITING AND ITS PRODUCTION AND USE |
| ZA849084B (en) * | 1984-01-10 | 1986-06-25 | Minnesota Mining & Mfg | Inks for transparency films |
| ES2032223T3 (en) * | 1987-12-18 | 1993-01-16 | Ciba-Geigy Ag | AQUEOUS DISPERSION OF A METALLIZABLE DYE. |
| JP2668422B2 (en) * | 1988-11-15 | 1997-10-27 | 株式会社サクラクレパス | Aqueous pigment ink composition for core type writing implements |
-
1993
- 1993-02-19 EP EP93301225A patent/EP0557115A1/en not_active Withdrawn
- 1993-02-19 AU AU33182/93A patent/AU3318293A/en not_active Abandoned
- 1993-02-22 CA CA 2090057 patent/CA2090057A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0557115A1 (en) | 1993-08-25 |
| AU3318293A (en) | 1993-08-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19950822 |