Water-Soluble Coloring Compositions Comprising Alcohol Alkoxylates with 40 to 160 Ethoxy Units Derived from Primary Alcohols Having a Chain Length Between 20 and 30 Carbon Atoms

Abstract

The invention relates to water-soluble marking compositions comprising alcohol alkoxylates having 40 to 160 ethoxy units and derived from a primary alcohol having a chain length between 20 and 30 carbon atoms.

Claims

1. A water-soluble coloring composition comprising at least one alcohol alkoxylate of the formula (I)
R—O—(C.sub.zH.sub.2zO).sub.x—H   (I) wherein R is a linear or branched alkyl having a total number of carbon atoms from 20 to 30; z has a value of 2 or 3; and x has a value of from 40 to 160; at least one filler; and at least one coloring substance.

2. The composition according to claim 1, wherein R is a linear or branched alkyl having a total number of carbon atoms from 22 to 30.

3. The composition according to claim 1, wherein z is 2.

4. The composition according to claim 1, wherein x has a value from 45 to 155.

5. The composition according to claim 3, wherein the alcohol ethoxylate has an average EO-content from 85 to 95 wt.%.

6. The composition according to claim 3, wherein the alcohol ethoxylate has a HLB-number from 17 to 20.

7. The composition according to claim 3, wherein the alcohol ethoxylate has a hydroxyl number from 5 to 25.

8. The composition according to claim 3, wherein the alcohol ethoxylate has at least one of the following characteristics: an average molecular weight of at least 2000 g/mol, a cloud point from 60 to 75° C., a melting (range) from 50 to 65° C., and a time to dissolve in water from 1200 to 4000 seconds.

9-11. (canceled)

12. The composition according to claim 3, wherein it comprises 10 to 90 wt.-% alcohol ethoxylate.

13. The composition according to claim 1, wherein it comprises 90 to 10 wt.-% filler.

14. The composition according to claim 1, wherein the coloring substance is active in the visual wavelength range of 400 nm to 800 nm of the electromagnetic spectrum of light.

15. The composition according to claim 14, wherein the coloring substance is a dye or pigment.

16. The composition according to claim 1, wherein the said coloring composition has a rod or stick format.

17. The composition according to claim 1, wherein it is a water-soluble coloring crayon.

18. The composition according to claim 15, wherein it comprises 1 to 5 wt.-% pigment or dye.

19. A method of producing a water-soluble coloring composition comprising the steps of providing an alcohol alkoxylate of the formula (I)
R—O—(C.sub.zH.sub.2zO).sub.x—H   (I) wherein R is a linear or branched alkyl having a total number of carbon atoms from 20 to 30; z has a value of 2 or 3; and x has a value from 40 to 160; providing a filler, providing a coloring substance; melt blending said alcohol alkoxylate, filler and coloring substance under stirring and heating to obtain a melt-blend; shaping the melt-blend in a selected form; and cooling down the melt-blend so that it solidifies.

20. The method according to claim 19, wherein the melt-blend is shaped in the form of a rod or a stick.

21. The method according to claim 19 wherein the melt-blending is conducted in an injection-molding apparatus and the water-soluble coloring composition is produced by injection molding.

22. The method according to claim 19, wherein the melt-blending is conducted in an extruder apparatus and the water-soluble coloring composition is produced by extrusion.

23. The method according to claim 19, wherein the shaping of the melt-blend comprises decanting or pouring the melt-blend into a heated mold; cooling down the melt-blend in the mold with rotating blades; and removing, as a casting, the solidified melt-blend from the mold.

24-25. (canceled)

Description

DESCRIPTION OF THE INVENTION

[0013] It is surprisingly found that water-soluble coloring compositions comprising [0014] at least one alcohol alkoxylate of the formula (I)

R—O—(C.sub.zH.sub.2zO).sub.x—H   (I) [0015] wherein R is a linear or branched alkyl having a total number of carbon atoms from 20 to 30; [0016] z has a value of 2 or 3; and [0017] x has a value from 40 to 160; [0018] at least one filler; and [0019] at least one coloring substance;

[0020] show superior stability, washability, and pigment dispersibility.

[0021] Preferably, R is a linear or branched alkyl having a total number of carbon atoms from 22 to 30. More preferably, R is a linear or branched alkyl having a total number of carbon atoms from 23 or 24 to 30 and most preferably from 24 to 28. The alkyl moiety “R” may also be a mixture of such alkyl entities having an individual carbon count/molecule consisting essentially of from 20 to 30 and wherein the number average carbon count of the mixture is from 20 to 30 per molecule, preferably from 22 to 30 per molecule, and more preferably from 22 to 28 per molecule.

[0022] Preferably, z is 2, so that the alcohol alkoxylate of formula (I) is an alcohol ethoxylate.

[0023] Preferably, x has a value of from 45 to 155. More preferably, x has a value of from 100 to 150.

[0024] The alcohol ethoxylate may be produced by reaction of a corresponding alcohol with ethylene oxide (EO) over a suitable ethoxylation catalyst. Suitable catalysts are those derived from the Group IA and Group IIA metals including potassium, sodium, calcium, magnesium; typically, the metal is present as a base salt and notably its hydroxide. Certain catalyst species are recognized by their ability to produce narrow range ethoxylated alcohols. Catalysts derived from Group IIA metals, especially calcium or magnesium are typically recognized as being narrow range ethoxylation catalysts. In contrast catalysts derived from Group IA metals, such as potassium hydroxide are generally recognized as giving broad range ethoxylated alcohols.

[0025] For the presently disclosed invention; preferably, the alcohol ethoxylate is produced by reaction over a narrow range ethoxylation catalyst, more preferably over a calcium-containing ethoxylation catalyst providing for narrow range ethoxylated alcohols. Such catalysts and use thereof to produce ethoxylated alcohols are known to the person skilled in the art and exemplified by the teachings of, for example, U.S. Pat. No. 4,754,075. Exemplary of a suitable calcium-containing ethoxylation catalyst is the proprietary catalyst system developed by Sasol (USA) Corporation and as disclosed in U.S. Pat. Nos. 4,775,653; 4,835,321; 5,220,077; 5,626,121; 8,329,609 and 9,802,879, the disclosures of which are all incorporated herein by reference.

[0026] The alcohol alkoxylate of formula (I) may additionally have, independent of each other, one or more of the following properties: [0027] an average EO-content of from 85 to 95 wt.-%, preferably of from 88 to 95 wt.-%; [0028] a hydrophilic-lipophilic balance (HLB) number of from 17 to 20, preferably of from 17.5 to 19.5; [0029] a hydroxyl number of from 5 to 25, preferably of from 8 to 22; [0030] an average molecular weight of at least 2000 g/mol, preferably of at least 3000 g/mol; and more preferably of at least 5000 g/mol; [0031] a cloud point of from 60 to 75° C., preferably of from 65 to 73° C.; [0032] a melting (range) of from 50 to 65° C., preferably of from 54 to 62° C.; [0033] a time to dissolve in water of from 1200 to 4000 seconds, preferably of from 1300 to 3000 seconds, more preferably at maximum 2500 seconds.

[0034] The number and content of ethoxy-units is calculated based on molecular weight obtained by the gas chromatogram of the selected alcohol and the nuclear magnetic resonance spectrum of the ethoxylated alcohols from which the ratio of alcohol- to ethoxy-groups is obtained.

[0035] Molecular weight of alcohol=Average molecular weight from gas chromatogram

[0036] Average EO-content=Calculated from signal ratio of alcohol-chain to ethoxy groups in NMR-spectrum

[0037] Molecular weight of alcohol ethoxylate=Molecular weight of alcohol/(1−Average EO-content)

[0038] Number of EO-units (x in the alcohol alkoxylate of formula (I))=(MW of alcohol ethoxylate−MW of alcohol)/44 g/mol

[0039] The HLB-value is calculated according to the Griffin's method as follows:

HLB=20*M.sub.h/M [0040] M.sub.h=molecular weight of the hydrophilic portion of the molecule [0041] M=molecular weight of the whole molecule

[0042] The hydroxyl-number is determined according to European standard method DIN EN 13926 and the cloud point is determined according to ASTM D2024. The melting point/range is determined according to standard method ASTM D-127.

[0043] The solubility (time to dissolve) is determined by putting a defined amount of alcohol ethoxylate (1 g) in a beaker with 99 ml water at ambient temperature (20° C.) and stirring it with a magnetic stirrer at 300 rpm until the alcohol ethoxylate is completely dissolved.

[0044] In further preferred embodiments the water-soluble coloring compositions comprise [0045] 10 to 90 wt.-% alcohol ethoxylate, preferably 15 to 50 wt.-% alcohol ethoxylate, more preferably 17.5 to 35 wt.-% alcohol ethoxylate; [0046] 90 to 10 wt.-% filler, preferably 85 to 50 wt.-% filler, more preferably 82.5 to 65 wt.-% filler, whereas the filler preferably comprises calcium carbonate, talc, bentonite clay, kaolin clay, or mixtures thereof; and [0047] 1 to 5 wt.-% coloring substance in the form of pigment or dye, preferably 1.5 to 2.5 wt.-% pigment or dye, whereas the pigment or dye preferably comprises Violet 19, Green LX-11774, Orange LX 11360, ultramarine pink, titanium dioxide, methylene blue, iron blue, red aluminum lake dye, red calcium lake dye, or mixtures thereof.

[0048] In preferred embodiments, the coloring substance is active in the visual wavelength range of 400 nm to 800 nm of the electromagnetic spectrum of light.

[0049] In another embodiment of the invention, the water-soluble coloring compositions comprise [0050] 15 to 60 wt.-% alcohol ethoxylate, preferably 20 to 40 wt.-% alcohol ethoxylate; [0051] 85 to 40 wt.-% filler, preferably 80 to 60 wt.-% filler, whereas the filler preferably comprises calcium carbonate, talc, bentonite clay, kaolin clay, or mixtures thereof; and [0052] 1 to 5 wt.-% coloring substance in the form of pigment or dye, preferably 1.5 to 2.5 wt.-% pigment or dye, whereas the pigment or dye preferably comprises Violet 19, Green LX-11774, Orange LX 11360, ultramarine pink, titanium dioxide, methylene blue, iron blue, red aluminum lake dye, red calcium lake dye, or mixtures thereof.

[0053] The invention also includes a method of producing water-soluble coloring composition comprising the steps of [0054] providing an alcohol alkoxylate of formula the formula (I)

R—O—(C.sub.zH.sub.2zO).sub.x—H   (I) [0055] wherein R is a linear or branched alkyl having a total number of carbon atoms from 20 to 30; [0056] z has a value of 2 or 3; and [0057] x has a value from 40 to 160; [0058] providing a filler; [0059] providing a coloring substance; [0060] melt blending said alcohol alkoxylate, filler and coloring substance under stirring and heating to obtain a melt-blend; [0061] shaping the melt-blend in a selected form; and [0062] cooling down the melt-blend so that it solidifies.

[0063] In a preferred embodiment the melt-blend is shaped in the form of a rod or a stick.

[0064] Furthermore, the melt-blending is preferably conducted in an injection-molding apparatus and the water-soluble coloring composition is produced by injection molding or in an extruder apparatus and the water-soluble coloring composition is produced by extrusion.

[0065] Another alternative is the shaping of the melt-blend comprising [0066] decanting or pouring the melt-blend into a heated mold; [0067] cooling down the melt-blend in the mold with rotating blades so that it solidifies; and [0068] removing, as a casting, the solidified melt-blend from the mold.

[0069] The invention also includes the use of an alcohol alkoxylate of the formula (I)

R—O—(C.sub.zH.sub.2zO).sub.x—H   (I) [0070] wherein R is a linear or branched alkyl having a total number of carbon atoms from 20 to 30; [0071] z has a value of 2 or 3; and [0072] x has a value from 40 to 160,

[0073] in water-soluble coloring compositions.

[0074] This use preferably improves: the mechanical stability of the coloring compositions; the pigment dispersibility, and; the washability as well as the color development of the coloring compositions when applied to different surfaces and/or the ability to remove the coloring compositions with water from any surface to which it has been applied.

EXAMPLES

[0075] The alcohol ethoxylates from Table 1 have been used to prepare water-soluble crayon compositions according to Tables 2 and 3. The MAGNATHOX branded alcohol ethoxylates are new products available from Sasol and have not previously been available for crayon compositions. The alcohol ethoxylates sold under the trademark of UNITHOX are available from Baker-Hughes; and those under the trademark of ALFONIC available from Sasol.

TABLE-US-00001 TABLE 1 Properties of alcohol ethoxylates used to prepare crayon compositions. Invention Invention Invention Invention Comp. MAGNA- MAGNA- MAGNA- MAGNA- AL- Comp. Comp. THOX THOX THOX THOX FONIC Unithox Unithox Properties 20 + N-50 20 + N-75 20 + N-100 20 + N-150 1214-30 480 490 Average EO 88 90 93 95 87 80 90 content (wt %) .sup.1 Number of 45 75 100 150 30 42 95 EO-units .sup.2 Carbon atom C20+ C20+ C20+ C20+ C12/14 C32 C32 content (“R”) (av. 21.5) (av. 21.5) (av 21.5) (av. 21.5) (av.) (av.) Molecular weight 319 319 319 319 199 460  460  of alcohol (g/mol) .sup.3 HLB .sup.4 17.6 18.2 18.6 19.0 17.4 16 18 Hydroxyl number 20-22 16-18 12-14  8-10 36 22 12 DIN EN 13926 Cloud point (° C.) 69-73 69-70 68-69 65-67 75-75 n.a. n.a. ASTM D2204 due to due to high high melting melting Melting point/ 54-57 58-60 50-54 60-62 48.5 86 71 range (° C.) ASTM D-127 Molecular weight 2658 3606 4615 6380 1534 2300  4600  (g/mol) .sup.5 Time to dissolve 2068 2940 1920 1306 1180 / 4473  (sec) .sup.6 The number and content of ethoxy-units is calculated based on molecular weight of the used alcohol obtained by the gas chromatogram and the nuclear magnetic resonance spectrum of the alcohol ethoxylates from which the ratio of alcohol- to ethoxy-groups is obtained. .sup.1 Average EO-content = Calculated from signal ratio of alcohol-chain to ethoxy groups in NMR-spectrum .sup.2 Number of EO-units = (MW of alcohol ethoxylate − MW of alcohol)/44 g/mol .sup.3 Molecular weight of alcohol = Average molecular weight from gas chromatogram .sup.4 The HLB-value is calculated according to the Griffin's method as follows: HLB = 20*M.sub.h/M M.sub.h = molecular weight of the hydrophilic portion of the molecule M = molecular weight of the whole molecule .sup.5 Molecular weight of alcohol ethoxylate = Molecular weight of alcohol/(1 − Average EO-content) .sup.5 The solubility (time to dissolve) is determined by putting a defined amount of alcohol ethoxylate (1 g) in a beaker with 99 ml water at ambient temperature (20° C.) and stirring it with a magnetic stirrer at 300 rpm until the ethoxylated alcohol was completely dissolved.

[0076] The number and content of ethoxy-units is calculated based on molecular weight of the used alcohol obtained by the gas chromatogram and the nuclear magnetic resonance spectrum of the alcohol ethoxylates from which the ratio of alcohol- to ethoxy-groups is obtained.

[0077] From the values in Table 1 it can be seen that the inventive alcohol ethoxylates are dissolving quicker than the comparative prior art products derived from longer primary alcohols and slower than the one derived from shorter primary alcohols. But the inventive ethoxylates are preferred to the ones derived from shorter primary alcohols as they have a higher melting range, which indicates a higher temperature stability.

TABLE-US-00002 TABLE 2 Crayon compositions according to invention. Composition [wt.-%] 1 2 3 4 5 6 7* 8* 9* 10* 20 + N-50 35 84 20 + N-150 35 84 20+-100 35 20+-75 35 Altonic 1214-30 35 84 UNITHOX 490 35 Filler (CaCO.sub.3) 63 63 14 14 63 63 63 14 63 25.5 Stearic acid 38.8 Pigment (Violet 19)** 2 2 2 2 2 2 2 2 2 2.2 Sorbitan Monostearate 1 Paraffin wax 4 Polyoxyethylene nonyl 3 phenol ether PEG 4000 25.5 *Comparative examples according to U.S. Pat. No. 5,417,746, U.S. Pat. No. 5,380,357 and EP0434163. **Violet 19 is a Quinacridone-based pigment.

[0078] The crayon compositions 1 to 10 were drawn onto a linoleum tile and water was run at a constant force and pressure from the sink across each section of the tile for 15 seconds. Formulations 1-6 and 9 were completely washed away while formulation 10 was not removed at all and formulations 7 and 8 were only partially removed.

[0079] Furthermore, a scrub test was performed to see what influence mechanical force has on removing crayon from the linoleum tiles. A modification of the method according ASTM D-4828 (Practical Washability of Organic Coatings) was used for this. A Gardner Abrasion Tester II Scrubber was used with a scrub rate of 37 strokes per minute. Soiled tiles were scrubbed for 50 strokes with a tap-water soaked sponge. One gram of each crayon formulation was melted and applied to an individual tile and then allowed to solidify. The weight of the tile and formulation was measured before and after the scrub test once the water on the tile had dried.

[0080] The results of the scrub tests are set out in Table 3 and clearly show that the inventive crayon compositions can be more easily removed than the prior art crayon compositions.

[0081] Advantageously, the inventive compositions can accommodate a larger filler loading which is beneficial in terms of lowering the cost of the crayon composition, while providing superior removal attributes compared to the prior art compositions.

TABLE-US-00003 TABLE 3 Results of scrub test of the produced crayon compositions. Tile weight Tile weight Composition before scrub after scrub removed Composition [g] [g] [g] Removal % 1 84.71 84.13 0.58 56% 2 89.55 88.72 0.83 93% 3 87.78 87.29 0.49 49% 4 85.16 84.65 0.51 60% 5 85.21 84.49 0.72 75% 6 88.67 87.82 0.85 82%  7* 85.89 85.43 0.46 54%  8* 85.23 84.57 0.66 77%  9* 84.98 84.31 0.67 79% 10* 89.07 89.02 0.05 5.6% 

[0082] The inventive compositions could also be used as a watercolor.

[0083] While working with the various samples, it was observed that on a simple snapbreak test the materials of the invention broke and presented relatively few if any sharp edges or flakes. In contrast, the comparative materials in a similar test gave undesirable sharp edges and flakes. While not wishing to be bound by theory, it is believed that the compositions of the invention exhibit a different rate of solidification and crystallization due to being a narrow-range ethoxylated alcohol and of defined EO content, compared to the comparative materials, leading to fewer stress lines in the cooled product. The presence of stress lines is believed to encourage formation of sharp edges and flakes in a snap-break test.

[0084] In summary the inventive alcohol ethoxylates clearly overcome the disadvantages of the prior art and provide superior water-soluble coloring compositions.