IL27051A - White sulfur marking compositions - Google Patents

Description

7111111 |Ϊ13 Τ31Π1"! ·π PATENT ATTORNEYS · D'B IBS ' mi U OR. RBINHOLD COHN |Π3 ΤΙΙΠΙ'Ί 'Π OR. MICHAEL COHN ¾B ¾3BB mi* ISRAEL SHACHTER B.Sc. -D.a 1.3-1 unni' File CI 25693 PATENTS AND DESIGNS ORDINANCE SPECIFICATION WHITE SULFUR MARKING COMPOSITIONS 6TAUFFER CHEMICAL COMPANY, A CORPORATION ORGANIZED UNDER LAW8 OF THE STATE OF DELAWARE, OF 80 MAD I SON AVENUE, NEW 17, NEW YORK, U.S.A. do hereby declare the nature of this invention and in what manner the same is to be performed, to particularly described and ascertained in and by t following statement:- WHITE SULFUR MARKING COMPOGITIONS This invention is concerned with sulfur compositions and more particularly with white pigmented sulfur compositions suitable for use as marking materials and for other uses where color is an important consideration. Because of its natural yellow color, sulfur has for some time presented a problem in the preparation of white compositions. This difficulty is especially significant when the composition contains a high proportion or preponderance of sulfur, but is nevertheless significant for sulfur concentrations as low as about 2570 by weight .

Heretofore, where a different color was desired for sulfur compositions such as those used in building, jointing and insulating materials, the prior art suggested various clays and pigments. Such clays and pigments, however, did not successfully whiten or lighten to a high degree a composition comprising a major amount of sulfur so as to render it suitable for marking uses, specifically road marking.

It is accordingly a primary object of this invention to provide sulfur compositions having a white color.

Another object is to provide white sulfur containing compositions useful as road marking materials, coating compositions, bonding agents, and the like, which may be economically and easily prepared.

Other objects will be apparent from the detailed explanation which follows. therein both (1) an organic toner and (2) an inorganic pigment. Moreover, I have found the organic toner and inorganic pigment combination of this invention to be effective in increasing the brightness or amount of reflected light of the sulfur composition to the extent that the composition is competitive in coloration with white road marking paints without having the limited durability of said paints.

The sulfur compositions of the present invention may comprise between 35$ and 95$ by weight of sulfur, excluding any sulfur which may be added in the form of sulfur-containing organic or inorganic additives. Where the compositions of this invention have utility as road marking materials and the like, the preferred sulfur concentration is between 35$ and 3$ by weight. Hereinafter and in the appended claims, the sulfur content of the compositions of the invention is intended only to refer to the sulfur combined as elemental sulfur, excluding sulfur content of all organic and inorganic additives.

The organic toner (hereinafter alternatively referred to as the "masking agent") is a compound or mixture of compounds which, when incorporated with molten sulfur, in a minor amount, masks or neutralizes the primary yellow color of the sulfur-containing composition. Only a limited number of substances are effective. For example, I have found that various shades of violet and purple pigments, such as those exhibiting purplish pink, purplish red, reddish purple and red-purple colors [Kelly, Journal of Research of the National Bureau of Standards, 1, 2γ (i943)] are particularly satisfactory. Some acceptable organic toners by the present invention may be more specifically characterized as those organic pigments having a dominant wave length within the spectrum between about 92 c nyu and 560 c mji and preferably from between U92 c mu and 510 c mu. The preferred organic pigments include the red-violet shades of quinacridones, alizarines, and alizarine derivatives of quinacridones.

The toner need be present in only a minor amount from about 0.005$ to 5$ and preferably from about 0.01$ to 0.1$ by weight of the total sulfur-containing composition. Since the organic toners are pigments or dyes, excess quantities of them will color the sulfur composition, and in most instances this is undesirable.

The inorganic pigment (hereinafter alternatively referred to as a "whitening agent") may be present from about 5 to 30$ and preferably from 10 to 25$ by weight of the total sulfur composition. A number of materials may be used as whitening agents but one, titanium dioxide, is especially effective in road marking compositions where light reflectance is important. Good light reflecting compositions may also be obtained by combining lithopone (mixture of zinc sulfide and barium sulfate) and titanium dioxide in equal proportions; it is generally not desirable to have more than 50$ of the total amount of whitening agent as lithopone. Other whitening agents which may be used alone or in combination with titanium dioxide include the following: calcium carbonate, silica, calcium sulfate, zinc oxide, zinc sulfide, barium sulfate, and barium carbonate. The whitening agents for the purpose of this invention may be Other materials are often combined within the sulfur composition; the most important of these is a sulfur-containing plasticizer. The type and amount of other materials will depend upon the intended use for the composition. Representative classes of plasticizers include the organic mercaptans, sulfides, poly-sulfides or polymers thereof, for example: polyethylene sulfide, ethylene dimercaptan, /d"3,/<_?' dimercaptodiethyl ether, triethylene glycol dimercaptan, 1,3 propane dimercaptan, and the like.

Preferably, the road marking compositions of the instant invention will contain between 2$ and 30$ by weight of the total composition of sulfur-containing plasticizer.

In road marking compositions it is often desirable to incorporate other substances such as glass beads and other reflective materials as well as optical brighteners or the like. Hard materials such as silica and crushed marble may also be added as aggregate to improve the wearability of the composition.

To prepare the plasticized sulfur compositions, the sulfur may be first melted and then any fillers added together with any plasticizer. It is common but not essential to add, in addition, a minor amount of an alkaline material (i.e., about 0.5 to 1.5$ of the total composition)^ to aid the reaction between plasticizer and sulfur. A variety of alkaline materials may be used such as the alkali metal and alkaline earth metal carbonates and organic primary, secondary and tertiary amines. The masking and whitening agents may then be added while agitating the melt.

The resulting composition is then allowed to cool. The order of addition is not critical althou h we have found that dr mixin the materials prior to heating results in superior masking of the characteristic yellow sulfur color for a given weight of masking agent, reducing the quantity required by approximately 50$. The temperature of the reaction mixture should be maintained between about ll8° C. and 250° C. and preferably between about 1300 C. and 1800 C. during reaction between sulfur and plasticizer.

The following examples will serve to illustrate the invention. In said examples, all percentages are by weight.

EXAMPLE 1 To a 1200 ml. stainless steel beaker contained in a heating mantle was added 300 grams of molten sulfur at a temperature of 135° C. The sulfur was then heated to a temperature of 1500 C. after which 5 grams of calcium carbonate and 100 grams of a polysulfide of the formula HS- (C2H4-O-CH2-O-C2H4-S-S)6-CaH4-0-CH2-0-C2H4-SH were added while the mixture was agitated. To this plasticizer-sulfur mixture was added a blend of 100 mg. surface-treated Super Maroon pigment having a dominant wave length of 1+9T»1 c mu and 100 grams of titanium dioxide while maintaining the temperature at 135° C. As the melt was vigorously agitated for 5 minutes to disperse the components, the temperature rose to 155° C. Tfye resulting melt, was poured into 7" x ll" x 1/2" deep aluminum foil trays and allowed to cool at room temperature for 18 hours. The solidified material was tested with a Hunterlab D 25 Color Difference Meter (hereinafter "Hunter") which furnishes the following readings; +a = red, -a = green, +b = yellow, and -b .= blue. The L scale extends from 0 to 100, with 0 representing black and 100 pure white; the green-red and blue-yellow color scales extend from -100 to +100, with 0 representing white or neutral . The sulfur composition of this example had a reading of L = 89.}+, a = -1.0, b = +6.0, and appeared white to the naked eye. A non-pigmented control sample prepared by the above procedure and consisting of the reaction product of ^00 grams of sulfur, 100 grams of the sulfur plasticizer and 5 grams of calcium carbonate gave the following reading: L = 93.2, a = -8.3, b = +20.6, and appeared yellow to the naked eye. A composition containing the whitening agent but not the masking agent and consisting of the reaction product, of 300 grams of sulfur, 100 grams of sulfur plasticizer, 100 grams of titanium dioxide and 5 grams of calcium carbonate gave the following reading: L = 95 · 0, a '= -b . , b = +10.6, and appeared pale yellow to the naked eye.

EXAMPLE 2 In accordance with the procedure of EXAMPLE l, 50 mg. of Monastral Violet. R having a dominant wave length of kyh . c mu was substituted for the masking agent of EXAMPLE 1. The resulting solidified composition was found to have a Hunter reading of L = 89.2, a = -0.7, b = +h . 6 , and appeared white to the naked eye.

EXAMPLE 3 In accordance with the procedure of EXAMPLE 1, 250 mg. of Alizarine Maroon having a dominant wave length of ^92.3 c mu was substituted for the masking agent of EXAMPLE l. The composition was found to have a Hunter reading of L = 88.6, a = -1.7, b = +5· 8, and appeared white to the naked e e.

EXAMPLE h To a 1200 ml. stainless steel beaker was added 300 gnu of sulfur, 100 gm. of β,β dimercaptodiethyl ether, 5 gm. of calcium carbonate, 50 mg. of Monastral Violet R having a dominant wave length of ^9^.7 c mu and 100 gm. of titanium dioxide. The mixture was dry-blended at room temperature, heated to 1500 C, and maintained at that temperature for approximately five minutes while vigorously agitating. The composition was then cooled, tested according to the procedure of EXAMPLE l, and was found to have a Hunter reading of L ■= 89.5, a = -1.6 and b = +5·1· It appeared white to the naked eye.

EXAMPLE 5 In accordance with the procedure set forth in EXAMPLE l, a composition was prepared substituting 100 mg. of Monastral Violet R having a dominant wave length of 9U.7 c mu and 100 gm. of β ,β^ dimercaptodiethyl ether for the masking agent and plasticizer, respectively, of said Example. The composition was found to have a Hunter reading of L = 89.3, a = -1.8 and b .= +6.9, and appeared white to the naked eye. A non-pigmented composition comprising ¼00 gm. of sulfur and 100 gm. of the plasticizer was found to have a Hunter reading of L = 92.1, a = -9.1 and b = +20.1, and appeared yellow to the naked eye. A composition containing the whitening agent but not the masking agent and consisting of the reaction product of 300 gm. of sulfur, 100 gm. of β,β dimercaptodiethyl ether, 100 gm. of titanium dioxide and 5 gm. of calcium carbonate gave the following reading: L = 95 °0, a = - » i b = +12.2, and appeared pale yellow to the naked eye.

EXAMPLE 6 In accordance with the procedure of EXAMPLE 1, a composition was prepared substituting 100 mg. of surface-treated Super Maroon having a dominant wave length of U97.I c ιημ and 100 gm. oi /& dimercaptodiethyl ether for the toner and plasticizer, respectively, of said Example. The composition was found to have a Hunter reading of L = 88.6, a = -1.8 and b = +6Λ, and appeared white to the naked eye.

The following experiments were conducted in accordance with the general procedure and proportions set forth in EXAMPLE 1, substituting only the given masking and whitening agents: Masking Agent Whitening Agent Type. Amount Type Amount EXAMPLE m gm. Hunter Reading Monastral Ti02 100 L= 89.2, a= -0.7, b= +h.6 Violet R 50 8 Monastral Ti02 50) L= 88.6, a= -1.6, b= +6.0 Violet R 50 Litho- 50) pone Monastral Ti02 100 L= Q6.k, a- 0.0, b= +3.8 Violet R 100 Monastral Ti02 50) L= 81.7, +1.0, b= +2.8 Violet R 100 CaC03 50) 11 Monastral Ti02 50) L= 81.2, +1.1, b= +2.5 Violet R 100 Si02 50) 12 Monastral Ti02 50) L= 83.9, 0.0, b= +h . k Violet R 100 CaS04 50) 13 Monastral TiOi 50) L= 80.5, -1.1, b= +5.2 Violet R 100 BaC03 50) EXAMPLE lh A 100 mg. portion of Monastral Violet R is preblended with 100 gm. Ti02 and added to hoo gm. molten sulfur at 150° C.

Claims (2)

1. 27051/2 1· A volte sulfur <caposltioa ooaprialng between 35$ and 95¾ by weight of sulfur, a whitening aaouat of at least one o anio toner havinja dominant wawe length ef the speotrua between about 492 e an and 560 o an and at least one inorganic pigment having a refractive index of froa between abaat 1.5 to 2.7.
2. 2. A white sulfur eontaining composition assorting to Claia 1 and suitable for aarking roadway eurfaeea and the like, comprising the reaction product sfι (a) 5 to 93 sulfur; (b) 2 to 30 sul ur-oontaining plae iolser; (o) 0*005 to 5 organio toner baring a doalnant ware length of the speotrua between about 492 e an and 560 o aa, and (d) 5 to 305* inorganic plgaent having a refractive index of froa between about 1·5 to 2*7. 5· Te eonpoaltien of O aia 2 wherein the sulfur concentration Is froa about 50 to SOJt* 4· The ooaposltioa of Claia 2 wherein the eslfur-ooataitting plaetiolser ooaoontratioa is froa ateat 10 to 25#. 5· Te ooaposltioa of Claia 2 wherein the organio toner concentration is froa about «01 to 0.1^. 6» The ooaposltioa of Claia 2 wherein te inorg¾¾ic plgaent concentration is froa about 10 to 255*· 7· The composition of Claim 2 wherein the sulfur concentration is from about 50 to 80$, the sulfur containing plasti-cizer concentration is from about 10 to 2 $, the organic toner concentration is from about .01 to 0.1$, and the inorganic pigment concentration is from about 10 to 5$. 8. The composition of Claim 2 wherein said composition additionally comprises from about 0.5 to 1. $ alkaline material. 9. The composition of Claim 2 wherein said composition additionally comprises from about l to 10$ reflective material. 10. The composition of Claim 2 wherein said composition additionally comprises from about 10 to 30$ aggregate. 11. The composition of Claim 2 wherein said organic toner has a dominant wave length between ^ 2 c mu and 510 c mji. 12. A process for preparing plasticized sulfur compositions comprising; (a) dry blending sulfur, and a sulfur-containing plasticizer in a sulfu :plasticizer weight ratio of 99:1 to 3:1 with about .005 to $ of an organic toner having a dominant wave length within the spectrum from between ^92 c mu to 560 c mp, and about 10 to 25$ of an inorganic pigment having a refractive index of from between 1.5 to 2.7; (b) heating the resultant dry blend to a temperature between about 118 and 250° C. while agitating the mixture for a time sufficient to disperse the organic toner and inorganic pigment and sufficient to cause reaction between sulfur and the plasticizer, and (c) cooling and recovering the resultant plasticized sulfur composition. DATED TH I S 12ΤΗ DAY OF DEOEMBER , 1966