US3382607A - Figure toy having fibers impregnated with indicator dye - Google Patents

Description

May 14, 1968 J. w. RYAN ETAL 3,382,607

FIGURE TOY HAVING FIBERS IMPREGNATED WITH INDICATOR DYE Filed Jan. 4, 1965 IND/CA TO? INVENTOPS Jmv W Am/v Ju/v FJ'a/vss MnrshnLL PenrLmun ATTORNEYS United States Patent 3,382,607 FIGURE TOY HAVING FIBERS IMPREGNATED WITH INDICATOR DYE John W. Ryan, Bel Aire, John F. Jones, Torrance,

and Marshall Pearlman, Beverly Hills, Calif., assignors to Mattel, Inc., Hawthorne, Califi, a corporation of California Filed Jan. 4, 1965, Ser. No. 423,382 6 Claims. (Cl. 46-156) ABSTRACT OF THE DISCLOSURE A toy, such as a doll, having a visible portion comprising fibers permanently impregnated with an indicator dye capable of repeated and reversible color change in response to contact with liquids of different pH concentrations.

The invention relates directly to a mode of dyeing fiber and has direct application in the toy field as related to chlidrens dolls. Specifically the disclosed invention relates to an article produced and a method of use which will enable a child at play to readily dye the dolls hair, thus enhancing the play value of the toy.

Coloring dyes per se have been classified or categorized in many ways. The chemist, from his vantage point, has often classified the myriad of available dyes from the standpoint of chemical or molecular similarity. The artisan on the other hand, being concerned with the application of color to various prodrfcts, has tended to classify dyes with respect to the properties that determine their use. In this area, the classifications have included acid dyes, azoic compositions, basic dyes, dispersed dyes, fiber-reactive dyes, mordant dyes to name only a few of the general classifications which will be familiar to those skilled in this art.

Another and practical classification of dye type materials has been developed, namely, materials known as indicators, and specifically indicator dyes. The broad grouping of materials that have been discovered and are currently being discovered which will function as indicators escape conventional chemical classification. They are commonly categorized by their functional ability to visually show, by a capacity for color change, the condition of a solution or product with respect to its relative acidity. An example of a classical use of an indicator is detecting the end point of a tit-ration.

The present invention specifically com-prehends the use of those products which historically have been classified as indicator dyes. More specifically, the present invention is concerned with specific indicator dyes that effectuate a color change in response to a variation in hydrogen-ion concentration which may be defined as pH variation or pH sensitivity. Secondarily, the present invention comprehends pH responsive indicator dyes which have the capacity to initially color or tinge a fiber, and thereafter, in response to pH change, induce a visible color variation of the fiber.

Considering one useful application of the invention, it will be understood that dolls traditionally have been fascinating playthings for chlidren, especially little girls. Recent years have seen a particular phenomenon become existent in the toy industry. The teenage fashion doll has captured the imagination of the collective childrens mind and has achieved a place therein virtually unequalled in doll history. The natural tendency of chlidren, especially little girls, to play grown up has been captured and directed towards the teenage fashion doll. As a result, the industry has seen develop a family of teenage dolls characterized by a virtual living personality group and which 3,382,607 Patented May 14, 1968 have, if any single indicia can be used to categorize same, the characteristic of an existence in an adult world the child anticipates will be his or her own upon personal entrance into that adult world. The personalities created in the teenage fashion doll field are de facto engaged in virtually every aspect of adult life that would be anticipated by a child of relative tender years. For example, dress, sport activity, family relationships, the boy-girl relationship incident to youthful development, as well as the myriad of day to day activities that characterize life in mid-20th century America are the natural habitat of the doll personalities. Though vicarious, their existence and activity are very real.

By the very mental intimacy of the association, the children, at play with their teenage dolls, experience a vista of human emotions normally associated with the childs entrance into an adult pattern of life. With typical childish enthusiasm and optimism, each child tends to live, through its teenage doll play activity, those desirable experiences which produce the maximum joy to the developing immature mind,

As noted above, the child at play with its teenage fashion doll in effect duplicates or vicariously lives adult activities. Logically, therefore, hair or wig dyeing of the doll could become an important aspect of play activity of the child.

Accordingly, it is a general object of the invention to provide dolls hair which offers a child the opportunity to easily change the dolls hair color, thus simulating the actual hair dyeing operation of an adult.

It is a further object of the invention to provide a doll hair dyeing mode that is strikingly effective yet simple and easy to accomplish and thus Well within the child's personal capacity.

It is yet a further specific object of the invention to provide a method of manufacturing dolls hair that will be readily subject to play dyeing activity of the child.

It is yet a further specific object of the invention to provide doll hair of the type described that can be color changed by the child by employing readily available household materials.

It is also a further specific feature of the invention to provide an article of the type described that is safe from the standpoint of use as a childs plaything.

Another specific object of the invention is to provide an article of the type described that is relatively stable under all normal use conditions and which will provide the child with a desirable toy over an extended service life.

Specifically, the invention comprehends a mode of fiber dyeing utilizing pH sensitive coloring material as applied to dolls hair, which com prehends a reversible color variation in the dolls hair fiber in response to pH variation thereof.

These and other objects, advantages and features of the herein disclosed invention will become apparent in the course of the following description of certain example illustrations of the invention.

As noted above, many commercially available dyes illustrate a high degree of sensitivity to pH, that, is hydrogen-ion concentration. pH has been defined as the negative logarithm of the effective hydrogen-ion concentration or hydrogen-ion activity in gram equivalents per liter of fluid. It is characteristically used for expressing both acidity and alkalinity in a relative manner on an empirical scale of zero to 14, in which 7 represents neutrality: the pH value of pure water at 25 degrees centigrade. Values less than 7 represent increasing hydrogenion concentration and increasing acidity or the acid range. Values greater than 7 represent decreasing hydrogen-ion concentration and increasing alkalinity or the basic range. The indicator dyes here under consideration all exhibit a definite characteristic relative to the pH scale, namely,

to exhibit a first color at one level of hydrogen-ion concentration and to sharply change color at another level of hydrogen-ion concentration. The scale range through which the color change takes place is usually referred to as the shift range or shift point.

Considering a specific application of the disclosed invention, namely, as a toy, certain parameters are dictated by this ultimate use which have an effect of setting prac tical limits on the practice of the invention. With the thought in mind that the ultimate purpose of this application of the invention is to provide doll hair that can be readily play dyed by a child, it will be apparent that the mode of practice of the invention must meet a major requirement of safety. Clearly, the dyes utilized must have relatively non-toxic characteristics. To provide the child with a doll having an extended play life, the dyed hairproduct must exhibit sufficient stability in the presence of Water, light, ultra-violet rays and infra red rays all of which are found in the play environment. In other words, the hair colors created must be reasonably fast in extended service. It is further desirable that the dyes employed produce consistently repeatable variation to enable the child to anticipate the hair color to be produced.

While it will be understood that the invention comprehends the dyeing of any type of suitable fiber, the doll industry has characterically utilized as dolls hair certain specific materials including nylon, orlon, viscous rayons, and cellulose acetate products. In some instances human or animal hair products have been used to provide dolls hair. The most frequently utilized fibers however, are in the cellulose acetate group in that they offer many application advantages. For example, they are relatively strong and are capable of being produced in very fine diameters that may be easily Worked by the child from the standpoint of brushing and hair setting. Additionally, acetate fibers are economical. Their physical and molecular structure is such that they readily take commercially available dyes and, upon impregnation are found to be satisfactorily color fast. However, the invention as disclosed may be applied to any type of fiber and particularly any fiber that may be appropriate for use as a doll hair material.

The single figure of the drawing is illustrative of a portion of a doll embodying the present invention.

With the above in mind, a few examples of the disclosed invention will be given, which, in actual application have proved highly satisfactory both from the standpoint of initial application and subsequent color change as applied to dolls hair.

EXAMPLE 1 In a first illustration of the invention, clear acetate fiber as produced in its natural state and without any dye impregnation is obtained. Quality production control suggests that the fiber be first subjected to a clear water rinse to make it as clean as possible. Thereafter the fiber is preferably bathed in an appropriate alkaline solution to remove any residual acetic acid which may adhere to the fiber as an incident to fiber manufacture. A second clear water rinse may be used to clean the fiber of alkaline solution. A suggested alkali that may be employed is tetrasodium pyrophosphate.

A dye solution is then prepared. For example, methyl red, sometimes known as Acid Red No. 2, is dissolved in an appropriate solute which may comprise methyl alcohol and water in a 50% to 50% ratio, respectively. A satisfactory methyl red dye concentration may be obtained by using /2% by weight of methyl red based on weight of solute. The fiber is then thoroughly soaked in the dye solution for a period in excess of fifteen minutes and at a bath temperature of approximately 125 degrees F. When acetate fibers are used, it has been found that the fiber diameter swells considerably as a result of the solute used for the dye. Dye impregnation takes place during solution soaking and the fiber is thor ug y colored n impregnated. As an adjunct of fiber swelling it has been found that the dye actually molecularly enters the fiber to assure a good color set thereon.

As the dyeing application is completed, which may be visually judged, the fiber is then again rinsed in clear water to accomplish initial removal of loose dye material and any foreign matter that may be adhering to the fiber as a result of the prior process steps. To accomplish complete removal of loose dye material and provide a high quality dyed doll hair, it is suggested that a subsequent rinse employing a conventional detergent and adding a 1% by weight acetic acid solution in water. The loose methyl red dye material fragments are effectively removed from the fiber but the coloring of the fiber per se is not attacked. Thereafter a subsequent Wash in clear water is suggested until the rinse runs clear.

It is desirable that the dolls hair be of uniform color throughout. Accordingly, it is suggested that the fiber be bathed or soaked at room temperature in a mild acid solution. The effect is to set the pH sensitive dye at a concentration on the acid side of its shift range and uniformity of product color results. The fiber is then dried in any suitable manner and it is ready for subsequent processing and use as dolls hair.

In actual use as a toy, namely, dolls hair either as a wig or as hair mechanically fixed to the dolls head, the child at play merely need obtain an appropriate basic solution having a pH concentration on the basic side of the shift range of the particular dye applied to the doll hair. The child prepares a mild solution thereof in Water. Upon preparing the solution, the child rinses the dolls hair therein. The pH sensitive methyl red dye is driven in a basic direction by the reaction. On its acid side the methyl red dye exhibits a bright red color at approximately pH 5 or lower. With the addition of the basic solution, the hydrogen-ion concentration within the dye is changed and brought to pH 6 or higher, namely, in the basic direction. As the reaction is completed, the hair changes dramatically to a golden yellow. The golden yellow condition obtains regardless of any further change in hydrogen-ion concentration in the basic direction. If desired, the reaction may be reversed when the childs play inclination dictates. To achieve this result the child obtains a mild acid material and mixes a mild solution in water. The pH level of the solution must be below the pH shift range of the methyl red. When the child subsequently rinses the dolls hair in the mild solution, the pH concentration of the dye is again changed and is driven in an acid direction. As the pH concentration reaches approximately pH 5, the dolls hair resumes its previous bright red coloring.

EXAMPLE 2 For this example, we will again assume a natural acetate fiber in a natural or undyed condition. A readily available hydrogen-ion sensitive dye known as alizarine or Mordant Red No. 11 has been found to produce excellent results. A dyeing solution of approximately /2% by weight in methanol is prepared and again a 50% to 50% methanolwater ratio is used. The sequential steps noted above in Example 1 are again followed except that the alizarine solution is substituted for the methyl red solution in the dyeing step of the process. Again, after complete dyeing, the dyed hair is preferably set in the acid range by soaking in a mild acid solution. Using the alizarine indicator dye, the hair fiber presents a uniformly bright yellow color on the acid side of its shift range. To obtain hair color change the child again prepares a solution having a pH level on the basic side of the alizarine shift range and rinses. The dolls hair dye is driven in a basic direction from its initial pH of approximately 5 or lower to approximately pH 8 or higher, whereat the color changes distinctively to an attractive purple. Altern-ately, the application of a mild acid rinse drives the dye in the acid direction and the bright yellow color is resumed as the pH concentration reaches approximatly pH 5.

EXAMPLE 3 Another feature of the disclosed invention introduces a desirable quality of flexibility in the production of a variety of doll hair color patterns even though one or a few pH sensitive dyes are used. In this aspect of the invention the acetate fiber is first fast dyed to a first color in any conventional manner with a dye that when set is not pH sensitive. Thereafter, the pH sensitive dye is super-imposed on or applied over the pre-colored fiber in the general manner as above described. This procedure multiplies the available hair color effects many times since combinations of fast dyes and indicator dyes are virtually limitless and the sequential application of an indicator dye of one color over a pre-colored hair fiber produces the visual appearance of a third color.

As an example, if the acetate fiber is obtained having a first fast dyed non-pH sensitive blue color and is subsequently subjected to the pH sensitive alizarine solution as noted in the prior example, the alizarine dye is superimposed on the base dye of the fiber, and, in the acid condition of the pH sensitive alizarine dye the hair coloring produced is a light brown, rather than the yellow of the prior example. Subsequent rinsing of the hair in a basic solution changes the hydrogen-ion concentration of the dye in the hair with a resulting color change to a startling black. Again, if the black hair is subjected to an acid bath as noted above, the original brown color returns. Clearly the multiplicity of hair color patterns that may be economically obtained by utilizing the fast dye precoloring procedure enhances the play value of the toy.

EXAMPLE 4 The disclosed invention may be subject to another variant as applied to dolls hair to easily produce even further hair color variations. As an illustrative example, the alizarine dye and the methyl red dye noted above may be combined in an appropriate dyeing solution. A solution is prepared of equal parts of methanol and water, and /2 by weight each of methyl red and alizarine is added. Neutral acetate fiber, without pre-coloring, is then processed and dyed as defined in Example 1. The fiber is then subsequently processed in the described manner and acid set until ready for use as dolls hair.

The doll hair thus produced is an attractive auburn color. Upon subjection of the auburn dyed hair to an appropriate basic rinse solution, as above noted, a rather remarkable color change to a pleasing brown ensues. The auburn color may again be obtained by an appropriate acid rinse.

It will be clearly understood that the above examples are by way of illustration both as to the indicator dyes utilized and the suggested mode of use. Many commercially available indicator dyes reasonably would fall within the application of the invention and may be employed on an empirical test basis to obtain hair coloring desired. Some other examples of indicator dyes that may be utilized are the following: methyl violet, crystal violet, ethyl violet,

malachite green oxalate, methyl green, cresol red, quinaldine red, para methyl red, metanil yellow, thymol blue, meta cresol purple, eyrthrosin disodium salt, benzopurpurin 4B, dinitrophenol, congo red, methyl orange-xylene cyanole solution, methyl orange, ethyl orange, methoxybenzenesulfonic acid, bromocresol green, resazurin, ethyl red laomoid, alizarin red, methyl red, propyl red, bromocresol purple, chlorophenol red, nitrophenol, bromothymol blue, dinitrobenzoylene urea, brilliant yellow, phenol red, neutral red, nitrophenol, curcumin, meta cresol purple, thymol blue, cresolphthalein, naphtholbenzein, phenolphthalein, thymalphthalein, alizarin yellow R, to mention only illustrative examples.

In the specific application of the disclosed invention as a toy, namely, as applied to dolls hair, the heretofore mentioned parameter of safety must be kept clearly in mind. The utilitarian play value of the toy requires that the child sequentially utilizes acid and basic solutions to achieve the desired color change. The toy may be vended as a unit, that is, as a complete doll having pH sensitive dyed hair, or, a group of doll wigs dyed in a similar manner, together with acid and basic solutions that will satisfactorily coact with the particular dyed hair to achieve the desired color change. Solution concentrations are such that will be non-toxic if accidentally swallowed. In short, the solution concentration would in fact be edible in nature.

As an alternative, the toy may be vended as dolls hair together with instructions that the child employ readily available household items in the preparation of the acid and basic solutions required to induce color change. In this connection, it will be recalled that the terms acid and basic solution have relative meaning only with respect to the pH shift range of the particular indicator dye employed. They are not of necessity within the acid scale range or basic scale range with respect to neutral point pH 7, though they very well may be and still achieve the desired result.

Employing indicator dyes in the practice of the disclosed invention whose shift point or range falls relatively close to the neutral point 7, as for example within the range 3 to 11, it has been found that conventionally available household items such as citric juices, vinegar or the like function satisfactorily to set the dolls hair at the color level on the acid side of its shift range. The mentioned methyl red and alizarine dyes noted are illustrative examples. Further, readily available household items such as sodium carbonate, namely, common washing soda, or sodium bicarbonate, frequently used as an antacid for human consumption, are satisfactory to accomplish the pH shift required for color change in the basic direction. The solutions necessary to achieve the desired result may be of relatively weak concentration within the range of one-half percent to 5% by weight. The functional ability of the invention to employ vinegar, citric juices, sodium carbonate, or sodium bicarbonate and in the mild concentrations suggested clearly meets the safety parameter. The availability, non-toxic characteristics, and essentially edible nature of such products permits use by the child without producing undesired physical harm.

From the above, it will be apparent that the invention as particularly applied to the toy art presents a novel and unique creation having great utilitarian and play function. The invention in this particular application is consistent with childrens play safety requirements and offers stability in the play environment consistent with a long toy service life.

The invention is disclosed by way of illustration and may be subject to various modifications without departing from the scope of the appended claims.

What is claimed is:

1. As an article of manufacture, a figure toy having a plurality of fibers defining a portion only of said figure toy, at least a part of said fibers defining a visible portion thereof arranged in predetermined physical configuration, the material of said fibers being permanently impregnated with a dye to a first color, by a pH sensitive indicator dye, whereby the color thereof may be selectively and repeatedly changed to and from said first color and a second color by contact with liquids of predetermined pH concentrations.

2. A toy article of manufacture according to claim 1, wherein said pre-determined physical toy configuration is dolls hair, said indicator dye having a pH shift range falling within conventional scale range of 3 to 11.

3. A toy article of manufacture according to claim 2, wherein said pH variation and reversible fiber color change is responsive to liquids having pH concentrations externally of said shift range.

4. A toy article of manufacture according to claim 3, wherein said liquids comprise edible household products in water solutions.

5. A toy article of manufacture according to claim 4, 2,108,838 2/1938 Whitehead 8-56 X wherein said dolls hair is arranged in the form of a wig 2,185,467 1/ 1940 Kritchevsky 810 X for demountable application to a dolls head. 2,464,155 3/1949 Russell.

6. A toy article of manufacture according to claim 4, 2,656,647 10/1953 Schepp 46156 wherein said dolls hair is permanently secured to a dolls 5 2,695,259 11/1954 Charle 8-10 X head. 2,953,421 9/1960 Hoeple 8-25 References Cited 2,960,443 11/ 1960 Rosemarin 856 X "F F Tm 1442 248 S$ z i 46 158 LOUIS G. MANCENE, Primary Examiner. 1:730:177 929 i X 10 F. B. SHAY, A. O. OECHSLE, Examiners. 1,814,344 7/1931 Smelling 8--25 S. NATTER, Assistant Examiner. 2,073,723 3/1937 Woolnough 46-158

Images