WO1995014755A1

WO1995014755A1 - Cleaning composition

Info

Publication number: WO1995014755A1
Application number: PCT/US1994/013694
Authority: WO
Inventors: Phillip E. Figdore; Pierre Stewart
Original assignee: Penetone Corporation
Priority date: 1993-11-24
Filing date: 1994-11-21
Publication date: 1995-06-01
Also published as: AU1332195A

Abstract

There are provided low VOC content cleaning compositions comprising an admixture of (a) at least one high VOC content unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon solvent; (b) at least one low VOC content alkyl benzene or alkyl naphthalene; and (c) optionally, a surfactant. These admixtures are low VOC content cleaning compositions, which preferably have a VOC content of less than 60 %. Also contemplated are water-containing emulsions of these admixtures. Additionally within the scope of the invention is a method of removing ink from printing machines.

Description

CLEANING COMPOSITION FIELD OF THE INVENTION This invention relates to cleaning compositions which are admixtures of at least one working solvent which is a high VOC unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon; at least one low VOC Cι₂-C₂₆ alkyl benzene or naphthalene wherein the alkyl group is a C₈-C₂₀ alkyl group; and optionally, a surfactant. These cleaning compositions have a low volatile organic compound (VOC) content but retain the excellent cleaning properties of the relatively high VOC component.

BACKGROUND OF THE INVENTION

The Clean Air Act of 1990 imposed stringent restrictions on the amounts and types of materials that can be emitted into the atmosphere. One category of chemicals which was targeted for lower emissions is volatile organic compounds (VOCs) . Although not specifically considered hazardous air pollutants, this group of materials is thought to contribute to the overall lowering of air quality.

Many high VOC content materials are excellent solvents and possess excellent cleaning properties. Such materials include low to intermediate flash point mineral spirits, lower alkyl aromatic hydrocarbons, terpene hydrocarbons, low molecular weight alcohol glycol ethers, ether acetates, and ketones. However, because of environmental regulation and related concerns, less hazardous alternatives have been sought. For example, petroleum or vegetable oils have been mixed with high VOC solvents. However, the resultant products have proven unsuitable, due to the tendency of the petroleum or vegetable oil to impart high viscosity to the final product.

High viscosity adversely affects the application and removal of the cleaning product. Furthermore, odor can be a problem, particularly with vegetable oils, because they can become rancid due to oxidation. Finally, these products are unsuitable for the removal of certain types of soil, such as some printing inks.

Prigge, U.S. Patent No. 4,734,215, attempted to combine a major amount of a saturated hydrocarbon with a minor amount of at least one alkylated aromatic compound. The saturated hydrocarbon was an aliphatic and/or cyclo-aliphatic compound.

Saturated hydrocarbons were incorporated because these were considered non-toxic.

Woo et al., U.S. Patent No. 5,232,632, disclose a detergent composition utilizing a C₆-C₉ alkyl aromatic, and particularly an alkyl benzene, as a hydrophobic solvent in combination with a mixture of nonionic and zwitterionic detergent surfactants. The use of any other solvents is not disclosed.

It has now been discovered that particular alkyl benzenes or naphthalenes, when combined with unsaturated, substituted or unsubstituted interrupted or uninterrupted hydrocarbons, and optionally, a surfactant, provide an effective low VOC content cleaning composition, particularly for cleaning printing machines.

SUMMARY OF THE INVENTION

According to the present invention, there are provided low VOC content cleaning compositions comprising an admixture of (a) at least one unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon solvent; (b) (i) at least one low VOC Cι₂-C₂₆ alkyl benzene wherein the alkyl group is a C₆- C₂₀ alkyl group; (ii) at least one low VOC C₁₆-C₃₀ alkyl naphthalene wherein the alkyl group is a C₆-C₂₀ alkyl group; or (iii) any combination thereof; and (c) optionally, a surfactant. Also contemplated are emulsions of these admixtures. Additionally provided are methods for of removing ink and for cleaning printing presses. The ink or the machine are contacted with the cleaning compositions above.

DETAILED DESCRIPTION OF THE INVENTION

Low VOC content cleaning compositions are those cleaning compositions that have a VOC content of 60 percent or less, while high VOC solvents are those having a VOC content of greater than 60 percent. Preferably, the cleaning compositions of the present invention have a VOC content of 40 percent or less, and most preferably, they have a VOC content of 20 percent or less. VOC content is measured using the methods of determining volatile matter content as outlined in EPA Methods 24 or 24A (40 C.F.R. Ch. 1 (7-1-91 edition)). The high VOC unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbons suitable for use in the present invention typically are volatile organic compounds. They include, but are not limited to, alpha-olefins, terpenes, lower

(Cj-Qi) alkyl esters of low molecular weight (C₂-C₉) acids, and C₈- C₁₃ aromatics. Most preferred terpenes include, but are not limited to, d-limonene. Most preferred esters of low molecular weight (C₂-C₉) acids include, but are not limited to, lower (Cj-C alkyl or di-lower alkyl (C₂-C₈) esters of fatty acids or diacids, and particularly dibasic esters such as the dimethyl esters of C₂-C₈ di-acids such as the dimethyl esters of glutaric, adipic, and succinic acids such as those sold under the tradename DBE by DuPont-Wilmington, DE. Most preferred C₈-C₁₃ aromatics include, but are not limited to, benzene or naphthalene derivatives which have Ci-C₇ or C,-C₃ constituents respectively either singly or multiply substituted. These hydrocarbons can be substituted with other functional groups such as hydroxy or amine groups and can be interrupted such as with one or more oxygen atom, nitrogen atom, sulfur atom, or any combination thereof.

Typically, mixtures of more than one high VOC unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbons as described above will be used. An example of a mixture of C₈-C₁₃ aromatic hydrocarbon solvents is Aromatic 150 (Exxon Chemicals-Houston, TX) . This solvent is a blend of high VOC C₈-C₁₃ aromatic hydrocarbons, which are primarily isomers of benzene substituted with single or multiple C,-C₅ alkyl groups.

These high VOC unsaturated hydrocarbons may also be combined with other high VOC hydrocarbons such as aliphatics, cyclo-aliphatics, or saturated naphthalene-based (naphthalenic) hydrocarbons.

C₁₂-C₂₆ alkyl benzenes or C₁₆-C₃₀ naphthalenes suitable for use in the present invention may also be solvents and include alkyl benzenes wherein the alkyl group is a C₆-C₂₀ alkyl group, preferably a C₁₀-C_1S group, and most preferably a C or C₁₃ alkyl group. They are typically of lower VOC than the working solvent.

The alkyl chain in these materials is typically linear and is attached to the benzene ring of any carbon in the alkyl chain.

However, branched, cyclic, or depleted alkyl substituted materials, such as, for example, dodecylbenzene with low 2- dodecylbenzene content, are suitable as well. For example, material produced as dodecylbenzene, more commonly known as detergent alkylate, used in the manufacture of dodecylbenzene sulfonic acid, and which when neutralized is a common anionic detergent, has been found to be particularly effective. Mixtures of more than one alkyl benzene or alkyl naphthalene, including, but not limited to, isomeric mixtures, are useful herein.

The optional surfactant of the present invention can be any surfactant known in the art which is suitable for use in combination with hydrocarbon solvents. These surfactants include, but are not limited to, anionic, cationic, nonionic, a photeric, or zwitterionic surfactants. A preferred surfactant is Surfonic N60 (Texaco Petrochemical-Purchase, NY) which is nonylphenol (6 mole) ethoxylate.

The low VOC cleaning composition described herein comprises a cleaning effective amount of the high VOC unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon, and a VOC content lowering effective amount of the C₁₂-C₂₆ alkyl benzene, Cι₆-C₃₀ alkyl naphthalene, or combination thereof. However, the cleaning effective amount of the high VOC unsaturated hydrocarbon is that amount effective to clean, particularly ink on printing machines in the presence of or in conjunction with this alkyl benzene or alkyl naphthalene in the composition.

In the compositions of the present invention, preferably, (a) the high VOC hydrocarbon comprises from about 10 to about 55 parts by weight; (b) the Cι₂-C₂₆ alkyl benzene, C₁₆-C₃₀ alkyl naphthalene, or combination thereof, comprises from about 45 parts by weight to about 90 parts by weight; and (c) the surfactant comprises 0 to about 10 parts by weight based upon 100 parts by weight of (a) , (b) , and (c) combined. Most preferably, component (a) comprises from about 15 to about 45 parts by weight, component (b) comprises from about 55 parts by weight to about 85 parts by weight, and component (c) comprises from about 1 to about 5 parts by weight, on the same basis. Special mention is made of compositions wherein component (a) comprises about 40 parts by weight, component (b) comprises about 59 parts by weight, and component (c) comprises about 1 part by weight, on the same basis, and cleaning compositions wherein component (a) comprises about 20 parts by weight, component (b) comprises about 79 parts by weight, and component (c) comprises about 1 part by weight on the same basis.

The admixture can be combined with water, to form an emulsion and most preferably an oil-in-water emulsion, although a water-in-oil emulsion may also be used. When formulating such emulsions, the weight ratio of the (i) water to (ii) high VOC hydrocarbon; C₁₂-C₂₆ alkyl benzene, C₁₆-C₃₀ alkyl naphthalene, or combination thereof; and optional surfactant combined ranges from about 1:3 to about 20:1.

Water can also be used to dilute the composition or the emulsion to suitable strength. For example, in printing applications, such as the removal of inks, including, but not limited to, oil-based inks and UV curable inks, from printing rollers and blankets during the printing process, the composition can be diluted up to 1:3, depending on the weight of the printing paper, without causing web breakage (i.e., without the paper breaking) . The determination of a suitable dilution would be within the ordinary skill of those in the art. For other cleaning equipment, floors, etc., the composition may be diluted up to 20:1 with water and still be effective depending on the amount and type of soilant to be removed.

The cleaning compositions of the present invention are prepared by conventional methods known to those skilled in the art such as mixing or blending.

Any additional components well-known in the art to be included in cleaning compositions are within the scope of the present invention. Among these contemplated additives are colorants, fragrances, preservatives, antioxidants, biocides, thickeners, chelators, builders, acids, bases, or combinations thereof. These low VOC cleaning compositions are useful in cleaning and particularly in the cleaning of printing machines. Similarly, the low VOC C₁₂-C₂₆ alkyl benzene or naphthalene component of these cleaning compositions has been found useful in such applications. A cleaning effective amount of the composition or the component is contacted with the ink on the printing press in a manner known to those skilled in the art. Particularly, these compositions or components can be contacted with a printing press "on the fly" or when the press is running and paper is passing through the press, thereby avoiding shut down. Methods of applying the cleaner include, but are not limited to manual methods such as soaking a rag with the material and hand wiping it into the press (including the blankets or rollers) or spraying with equipment known to those skilled in the art, such as that designed by Baldwin, Oxy-Air, Printex, Heidelberg, and others, to clean automatically the blankets and rollers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate the invention without limitation. All parts are given by weight unless otherwise indicated.

Example 1 40 parts of a mixture of C₈-C₁₃ aromatic hydrocarbons

(Aromatic 150-Exxon-Houston, TX) were combined with 59 parts of a C₁₈ alkyl benzene solvent (the alkyl group is C,₂) and 1 part nonylphenol (6 mole) ethoxylate (Surfonic N60) by mechanical agitation until the mixture was homogeneous. The mixture of this example is effective in the removal of soil, particularly the removal of ink from printing rollers and blankets.

Example 2 20 parts of a mixture of C₈-C₁₃ aromatic hydrocarbon solvents (Aromatic 150) were combined with 79 parts of a C₁₈ alkyl benzene solvent (the alkyl group is C₁₂) and 1 part nonylphenol (6 mole) ethoxylate (Surfonic N60) by mechanical agitation until the mixture was homogeneous. The mixture of this example is effective in removal of soil, particularly the removal of ink from printing rollers and blankets.

Example 3 40 parts of a mixture of C₈-C₁₃ aromatic hydrocarbons

(Aromatic 150-Exxon-Houston, TX) were combined with 60 parts of a mixture of C_n and C₁₂ alkyl benzene (Nalkylene 525-Vista Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous. The mixture of this example is effective in the removal of soil, particularly the removal of oil-based ink from printing rollers and blankets.

Example 4

40 parts of a d-limonene were combined with 60 parts of a mixture of C_n and C₁₂ alkyl benzene (Nalkylene 525-Vista Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous. The mixture of this example is effective in the removal of soil, particularly the removal of oil-based ink from printing rollers and blankets.

Example 5 40 parts of (4-hydroxy-4-methyl) -2-pentanone (Diacetone alcohol-Union Carbide-Danbury, CT) were combined with 60 parts of a mixture of C_n and C_n alkyl benzene (Nalkylene 525-Vista Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous. The mixture of this example is effective in the removal of soil, particularly the removal of oil-based ink from printing rollers and blankets.

Example 6 40 parts of 1-decene (Ethyl Corp.-Baton Rouge, LA) were combined with 60 parts of a mixture of C_π and C₁₂ alkyl benzene (Nalkylene 525-Vista Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous.

The mixture of this example is effective in the removal of soil, particularly the removal of oil-based ink from printing rollers and blankets.

Example 7 30 parts of a mixture the dibasic esters, dimethyl glutarate, dimethyl adipate, and dimethyl succinate (DBE^®-DuPont- Wilmington, DE) were combined with 70 parts of a mixture of C,₂ and C,₃ alkyl benzene (Nalkylene 575-Vista Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous.

The mixture of this example is effective in the removal of soil, particularly the removal of UV curable inks from printing rollers and blankets.

Example 8

40 parts of (4-hydroxy-4-methyl) -2-pentanone (Diacetone alcohol-Union Carbide-Danbury, CT) were combined with 70 parts of a mixture of C_π and C₁₃ alkyl benzene (Nalkylene 575-Vista

Chemical-Houston, TX) by mechanical agitation until the mixture was homogeneous.

All patents and test methods mentioned herein are hereby incorporated by reference.

Many variations of the present invention would suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the scope of the appended claims.

Claims

IN THE CLAIMS: 1. A low VOC content cleaning composition comprising an admixture of: (a) at least one high VOC content unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon solvent; (b) at least one ( i) low VOC C₁₂- C₂₆ alkyl benzene wherein said alkyl group is a C₆- C₂₀ alkyl group ; ( ii) low VOC C₁₆- C₃₀ alkyl naphthalene wherein said alkyl group is a C₆- C₂₀ alkyl group ; or (iii) any combination thereof; and (c) optionally, a surfactant.

2. A low VOC content cleaning composition as defined in claim 1, having a VOC content of less than 60%.

3. A low VOC content cleaning composition as defined in claim 2, having a VOC content of less than 40%.

4. A low VOC content cleaning composition as defined in claim 1, wherein said high VOC content unsaturated, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon solvent is selected from the group consisting of alpha-olefins, terpenes, lower (Cj-C,) alkyl esters of low molecular weight (C₂- C₉) acids, lower (C,-C₄) alkyl esters of low molecular weight (C₂-C₉) diacids, C₈-C₁₃ aromatics, or any combination thereof.

5. A low VOC content cleaning composition as defined in claim 4, wherein said terpene comprises d-limonene.

6. A low VOC content cleaning composition as defined in claim 4, wherein said lower (Cj-C alkyl ester of a low molecular weight (C₂-C₉) acid is selected from the group consisting of lower (C,-C₄) alkyl esters of C₂-C₈ fatty acids, di lower (Cj-Q,) alkyl esters of C₂-C₈ fatty acids, or any combination thereof.

7. A low VOC content cleaning composition as defined in claim 5, wherein said lower

alkyl ester of a low molecular weight (C₂-C₈) acid comprises a dimethyl ester of a C₂-C₈ diacid.

8. A low VOC content cleaning composition as defined in claim 1, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises a C₁₀-C₁₅ alkyl group.

9. A low VOC content cleaning composition as defined in claim 8, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises an alkyl group selected from the group consisting of a C_π alkyl group, a C₁₂ alkyl group, and a C₁₃ alkyl group.

10. A low VOC content cleaning composition as defined in claim 9, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises a C₁₂ alkyl group.

11. A low VOC content cleaning composition as defined in claim 1, wherein said surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, or any combination thereof.

12. A low VOC content cleaning composition as defined in claim 1, comprising a cleaning effective amount of component (a) and a VOC content lowering effective amount of component (b) .

13. A low VOC content cleaning composition as defined in claim 1 further comprising: (d) water; (e) a fragrance; (f) a preservative; (g) an antioxidant; (h) a biocide; (i) a thickener; (j) a chelator; (k) a builder; or (1) any combination thereof.

14. A low VOC content cleaning composition as defined in claim 1 which is an emulsion.

15. A method of removing ink, said method comprising contacting said ink with a low VOC content cleaning composition as defined in claim 1.

16. A method of removing ink from a printing machine, said method comprising contacting said ink with a low VOC content cleaning composition as defined in claim 1.

17. A method as defined in claim 16, wherein said ink comprises an oil-based ink.

18. A method as defined in calim 16, wherein said ink comprises a UV curable ink.

19. A low VOC content cleaning composition comprising an admixture of: (a) at least one high VOC content C₈-C₁₃ aromatic, substituted or unsubstituted, interrupted or uninterrupted hydrocarbon; (b) at least one low VOC content C₁₂-C₂₆ alkyl benzene wherein said alkyl group is a C₆-C₂₀ alkyl group; and (c) optionally, a surfactant.

20. A low VOC content cleaning composition as defined in claim 19, having a VOC content of less than 60%.

21. A low VOC content cleaning composition as defined in claim 20, having a VOC content of less than 40%.

22. A low VOC content cleaning composition as defined in claim 21 wherein said C₈-C₁₃ aromatic hydrocarbon comprises a C₉-C_n aromatic solvent.

23. A low VOC content cleaning composition as defined in claim 20, wherein said C₈-C₁₃ aromatic hydrocarbon is substituted with at least one -OH group.

24. A low VOC content cleaning composition as defined in claim 20, wherein said C₈-C₁₃ aromatic hydrocarbon comprises a mixture of at least two C₈-C₁₃ aromatic hydrocarbons.

25. A low VOC content cleaning composition as defined in claim 20, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises a C₁₀-C₁₅ alkyl group.

26. A low VOC content cleaning composition as defined in claim 25, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises an alkyl group selected from the group consisting of a C_u alkyl group, C₁₂ alkyl group, and a C₁₃ alkyl group.

27. A low VOC content cleaning composition as defined in claim 26, wherein said alkyl group of said C₁₂-C₂₆ alkyl benzene comprises a C₁₂ alkyl group.

28. A low VOC content cleaning composition as defined in claim 20, said surfactant comprises a surfactant selected from the group consisting of anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants, zwitterionic surfactants, or any combination thereof.

29. A low VOC content cleaning composition as defined in claim 20, comprising a cleaning effective amount of said C₈-C₁₃ aromatic hydrocarbon and a VOC content lowering effective amount of said C₁₂-C₂₆ alkyl benzene.

30. A low VOC content cleaning composition as defined in claim 29, wherein said C₈-C₁₃ aromatic hydrocarbon comprises from about 10 to about 50 parts by weight, said C₁₂-C₂₆ alkyl benzene comprises from about 50 to about 90 parts by weight, and said surfactant comprises from 0 to about 10 parts by weight, based upon 100 parts by weight of C₈-C₁₃ aromatic hydrocarbon, C₁₂- C₂₆ alkyl benzene, and surfactant combined.

31. A low VOC content cleaning composition as defined in claim 30, wherein said C₈-C₁₃ aromatic hydrocarbon comprises from about 15 to about 45 parts by weight, said C₁₂-C₂₆ alkyl benzene comprises from about 55 to about 85 parts by weight, and said surfactant comprises from about 1 to about 5 parts by weight, based upon 100 parts by weight of C₈-C₁₃ aromatic hydrocarbon, C,₄-C₂₆ alkyl benzene, and surfactant combined.

32. A low VOC content cleaning composition as defined in claim 31, wherein said C₈-C₁₃ aromatic hydrocarbon comprises from about 40 to about 45 parts by weight, said C₁ -C₂₆ alkyl benzene comprises from about 59 to about 85 parts by weight, and said surfactant comprises from about 1 to about 5 parts by weight, based upon 100 parts by weight of C₈-C₁₃ aromatic hydrocarbon, C₁₂-C₂₆ alkyl benzene hydrocarbon, surfactant combined.

33. A low VOC content cleaning composition as defined in claim 31, wherein said C₈-C₁₃ aromatic hydrocarbon comprises from about 20 to about 45 parts by weight, said C - C₂₆ alkyl benzene comprises from about 79 to about 85 parts by weight, and said surfactant comprises from about 1 to about 5 parts by weight, based upon 100 parts by weight of C₈-C₁₃ aromatic hydrocarbon, C₁₂-C₂₆ alkyl benzene, and surfactant combined.

34. A low VOC content cleaning composition as defined in claim 20, further comprising: (d) a colorant; (e) a fragrance; (f) a preservative; (g) an antioxidant; (h) a biocide; (i) a thickener; (j) a non-aromatic hydrocarbon solvent; (k) a chelator; (1) a builder; or (m) any combination thereof.

35. A low VOC content cleaning composition as defined in claim 20, further comprising water.

36. A low VOC content cleaning composition as defined in claim 35, which is an emulsion.

37. A low VOC cleaning composition as defined in claim 36, which is an oil-in-water emulsion.

38. A low VOC content cleaning composition as defined in claim 37, wherein the weight ratio of (i) water to (ii) said C₈-C₁₃ aromatic hydrocarbon, C₁₂-C₂₆ alkyl benzene, and optional surfactant combined, ranges from about 1:3 to about 20:1.

39. A method of removing ink, said method comprising contacting said ink with a low VOC content cleaning composition as defined in claim 20.

40. A method of removing ink from a printing machine, said method comprising contacting said ink with a low VOC content cleaning composition as defined in claim 20.

41. A method as defined in claim 40, wherein said ink comprises an oil-based ink.

42. A method as defined in claim 40, wherein said ink comprises a UV curable ink.

43. A method of removing ink, said method comprising contacting said ink with a composition comprising at least one (i) low VOC C,₂-C₂₆ alkyl benzene wherein said alkyl group is a C₆-C₂₀ alkyl group; (ii) low VOC C₁₆-C₃₀ alkyl naphthalene wherein said alkyl group is a C₆- C₂ alkyl group; or (iii) any combination thereof.

44. A method of removing ink from a printing machine, said method comprising contacting said ink with a composition comprising at least one (i) low VOC Cι₂-C₂₆ alkyl benzene wherein said alkyl group is a C₆-C₂₀ alkyl group; (ii) low VOC C₁₆-C₃₀ alkyl naphthalene wherein said alkyl group is a C₆-C₀ alkyl group; or (iii) any combination thereof.

45. A method as defined in claim 44, wherein said ink comprises an oil-based ink.

46. A method as defined in claim 44, wherein said ink comprises a UV curable ink.