Non-aqueous liquid detergent compositions containing bleaching agents and contained in plastic packages are stabilized against package bulging caused by oxygen release by means of transition metal macropolycyclic rigid ligand compounds.

The present invention relates to non-aqueous detergent compositions containing a bleach source.
Detergent products in the form of liquid are often considered to be more convenient to use than are dry powdered or particulate detergent products. Said detergents have therefore found substantial favor with consumers. Such detergent products are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting. They also usually occupy less storage space than granular products. Additionally, such detergents may have incorporated in their formulations materials which could not withstand drying operations without deterioration, which operations are often employed in the manufacture of particulate or granular detergent products.
Although said detergents have a number of advantages over granular detergent products, they also inherently possess several disadvantages. In particular, detergent composition components which may be compatible with each other in granular products may tend to interact or react with each other. Thus such components as enzymes, surfactants, perfumes, brighteners, solvents and especially bleaches and bleach activators can be especially difficult to incorporate into liquid detergent products which have an acceptable degree of chemical stability.
One approach for enhancing the chemical compatibility of detergent composition components in detergent products has been to formulate non-aqueous (or anhydrous) detergent compositions. In such non-aqueous products, at least some of the normally solid detergent composition components tend to remain insoluble in the liquid product and hence are less reactive with each other than if they had been dissolved in the liquid matrix. Non-aqueous liquid detergent compositions, including those which contain reactive materials such as peroxygen bleaching agents, have been disclosed for example, in Hepworth et al., U.S. Pat. No. 4,615,820, Issued Oct. 17, 1986; Schultz et al., U.S. Pat. No. 4,929,380, Issued May 29, 1990; Schultz et al., U.S. Pat. No. 5,008,031, Issued Apr. 16, 1991; Elder et al., EP-A-030,096, Published Jun. 10, 1981; Hall et al., WO 92109678, Published Jun. 11, 1992 and Sanderson et al., EP-A-565,017, Published Oct. 13, 1993.
A particular problem that has been observed with the incorporation of bleach precursors in non-aqueous detergents, includes the chemical stability of the bleach and bleach precursor. Bleach and bleach precursors should remain chemically stable in the concentrate, while rapidly reacting with each other upon dilution in the wash liquor. Unfortunately, the bleach and/or bleach precursor present in the concentrate show some degree of decomposition. This is usually accompanied by the evolution of oxygen, thereby creating internal pressure in the container which builds up with time.
Especially in the cases of plastic containers, the containers are progressively subjected to deformation due to the internal pressure build-up. This phenomenon is often referred to as xe2x80x9cbulgingxe2x80x9d. This phenomenon is especially acute in warm countries where the containers may be exposed to particularly elevated temperatures. In some instances, bulging can be so severe so as to induce a base deformation which is such that the container can no longer stay in upright position. For instance, in supermarkets, the containers may fall of the shelves.
The problem of bulging can to some extent be addressed by venting systems. However, venting systems are expensive to incorporate into the package design, and tend to fail when they are in contact with the liquid product (e.g., bottles lying or upside-down), or cause leakage of the product. Therefore, there is a continuing need to reduce the amount of packaging bulging for non-aqueous, bleach containing liquid detergents.
It has now been found that the bulging can be reduced by specific compounds which are capable of interacting with the oxygen evolving from the non-aqueous liquid detergents.
According to the present invention, non-aqueous liquid detergent compositions are provided, containing specific compounds capable of interacting with oxygen.
According to the present invention it has been found that the problem of package bulging is reduced by adding specific compounds into the non-aqueous liquid detergent compositions which serve to interact with the oxygen released by the decomposition of the bleaching source. By interacting is meant that these compounds either react or that the oxygen is adsorbed by this compound.
As a consequence, these specific compounds are effective to reduce or eliminate oxygen which would build-up in the package.
Preferred compounds that are able to react with the oxygen are oxygen scavengers. Preferred oxygen scavengers are compounds that contain a metal ion. Examples are iron, cobalt and manganese. According to a preferred embodiment, the compound is a catalyst containing the metal-ion.
Preferred catalysts are bleach catalysts which are transition metal complexes of a macropolycyclic rigid ligand. The phrase xe2x80x9cmacropolycyclic rigid ligandxe2x80x9d is sometimes abbreviated as xe2x80x9cMRLxe2x80x9d in discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein xe2x80x9cppbxe2x80x9d denotes parts per billion by weight and xe2x80x9cppmxe2x80x9d denotes parts per million by weight).
Suitable transition metals e.g., Mn are illustrated hereinafter. xe2x80x9cMacropolycyclicxe2x80x9d means a MRL is both a macrocycle and is polycyclic. xe2x80x9cPolycyclicxe2x80x9d means at least bicyclic. The term xe2x80x9crigidxe2x80x9d as used herein herein includes xe2x80x9chaving a superstructurexe2x80x9d and xe2x80x9ccross-bridgedxe2x80x9d. xe2x80x9cRigidxe2x80x9d has been defined as the constrained converse of flexibility: see D. H. Busch., Chemical Reviews., (1993), 93, 847-860, incorporated by reference. More particularly, xe2x80x9crigidxe2x80x9d as used herein means that the MRL must be determinably more rigid than a macrocycle (xe2x80x9cparent macrocyclexe2x80x9d) which is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacking a superstructure (especially linking moieties or, preferably cross-bridging moieties) found in the MRL""s. In determining the comparative rigidity of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bound form) of the macrocycles. Rigidity is well-known to be useful in comparing macrocycles; suitable tools for determining, measuring or comparing rigidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta, (1989), 164, 73-84. A determination of whether one macrocycle is more rigid than another can be often made by simply making a molecular model, thus it is not in general essential to know configurational energies in absolute terms or to precisely compute them. Excellent comparative determinations of rigidity of one macrocycle vs. another can be made using inexpensive personal computer-based computational tools, such as ALCHEMY III, commercially available from Tripos Associates. Tripos also has available more expensive software permitting not only comparative, but absolute determinations; alternately, SHAPES can be used (see Zimmer cited supra). One observation which is significant in the context of the present invention is that there is an optimum for the present purposes when the parent macrocycle is distinctly flexible as compared to the cross-bridged form. Thus, unexpectedly, it is preferred to use parent macrocycles containing at least four donor atoms, such as cyclam derivatives, and to cross-bridge them, rather than to start with a more rigid parent macrocycle. Another observation is that cross-bridged macrocycles are significantly preferred over macrocycles which are bridged in other manners.
Preferred MRL""s herein are a special type of ultra-rigid ligand which is cross-bridged. A xe2x80x9ccross-bridgexe2x80x9d is nonlimitingly illustrated in 1.11 hereinbelow. In 1.11, the cross-bridge is a xe2x80x94CH2CH2xe2x80x94 moiety. It bridges N1 and N8 in the illustrative structure. By comparison, a xe2x80x9csame-sidexe2x80x9d bridge, for example if one were to be introduced across N1 and N12 in 1.11, would not be sufficient to constitute a xe2x80x9ccross-bridgexe2x80x9d and accordingly would not be preferred.
Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(II), and Ru(IV). Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium. Preferred oxidation states include the (II) and (III) oxidation states. Manganese(II) in both the low-spin configuration and high spin complexes are included. It is to be noted that complexes such as low-spin Mn(II) complexes are rather rare in all of coordination chemistry. The designation (II) or (III) denotes a coordinated transition metal having the requisite oxidation state; the coordinated metal atom is not a free ion or one having only water as a ligand.
In general, as used herein, a xe2x80x9cligandxe2x80x9d is any moiety capable of direct covalent bonding to a metal ion. Ligands can be charged or neutral and may range widely, including simple monovalent donors, such as chloride, or simple amines which form a single coordinate bond and a single point of attachment to a metal; to oxygen or ethylene, which can form a three-membered ring with a metal and thus can be said to have two potential points of attachment, to larger moieties such as ethylenediamine or aza macrocycles, which form up to the maximum number of single bonds to one or more metals that are allowed by the available sites on the metal and the number of lone pairs or alternate bonding sites of the free ligand. Numerous ligands can form bonds other than simple donor bonds, and can have multiple points of attachment.
Ligands useful herein can fall into several groups: the MRL, preferably a cross-bridged macropolycycle (preferably there will be one MRL in a useful transition-metal complex, but more, for example two, can be present, but not in preferred mononuclear transition-metal complexes); other, optional ligands, which in general are different from the MRL (generally there will be from 0 to 4, preferably from 1 to 3 such ligands); and ligands associated transiently with the metal as part of the catalytic cycle, these latter typically being related to water, hydroxide, oxygen or peroxides. Ligands of the third group are not essential for defining the metal bleach catalyst, which is a stable, isolable chemical compound that can be fully characterized. Ligands which bind to metals through donor atoms each having at least a single lone pair of electrons available for donation to a metal have a donor capability, or potential denticity, at least equal to the number of donor atoms. In general, that donor capability may be fully or only partially exercised.
Generally, the MRL""s herein can be viewed as the result of imposing additional structural rigidity on specifically selected xe2x80x9cparent macrocyclesxe2x80x9d.
More generally, the MRL""s (and the corresponding transition-metal catalysts) herein suitably comprise:
(a) at least one macrocycle main ring comprising four or more heteroatoms; and
(b) a covalently connected non-metal superstructure capable of increasing the rigidity of the macrocycle, preferably selected from
(i) a bridging superstructure, such as a linking moiety;
(ii) a cross-bridging superstructure, such as a cross-bridging linking moiety; and
(iii) combinations thereof.
The term xe2x80x9csuperstructurexe2x80x9d is used herein as defined in the literature by Busch et al., see, for example, articles by Busch in xe2x80x9cChemical Reviewsxe2x80x9d.
Preferred superstructures herein not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle so that it coordinates to a metal in a cleft. Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in 1.9 and 1.10 below, can be used.
wherein n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or
wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkyl-ammonium, halogen, nitro, sulfonate, or the like. The aromatic ring in 1.10 can be replaced by a saturated ring, in which the atom in Z connecting into the ring can contain N, O, S or C.
Without intending to be limited by theory, it is believed that the preorganization built into the MRL""s herein that leads to extra kinetic and/or thermodynamic stability of their metal complexes arises from either or both of topological constraints and enhanced rigidity (loss of flexibility) compared to the free parent macrocycle which has no superstructure. The MRL""s as defined herein and their preferred cross-bridged sub-family, which can be said to be xe2x80x9cultra-rigidxe2x80x9d, combine two sources of fixed preorganization. In preferred MRL""s herein, the linking moieties and parent macrocycle rings are combined to form ligands which have a significant extent of xe2x80x9cfoldxe2x80x9d, typically greater than in many known superstructured ligands in which a superstructure is attached to a largely planar, often unsaturated macrocycle. See, for example: D. H. Busch, Chemical Reviews, (1993), 93, 847-880. Further, the preferred MRL""s herein have a number of particular properties, including (1) they are characterized by very high proton affinities, as in so-called xe2x80x9cproton spongesxe2x80x9d; (2) they tend to react slowly with multivalent transition metals, which when combined with (1) above, renders synthesis of their complexes with certain hydrolyzable metal ions difficult in hydroxylic solvents; (3) when they are coordinated to transition metal atoms as identified herein, the MRL""s result in complexes that have exceptional kinetic stability such that the metal ions only dissociate extremely slowly under conditions that would destroy complexes with ordinary ligands; and (4) these complexes have exceptional thermodynamic stability; however, the unusual kinetics of MRL dissociation from the transition metal may defeat conventional equilibrium measurements that might quantitate this property.
In one aspect of the present invention, the MRL""s include those comprising:
(i) an organic macrocycle ring containing four or more donor atoms (preferably at least 3, more preferably at least 4, of these donor atoms are N) separated from each other by covalent linkages of at least one, preferably 2 or 3, non-donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms being coordinated to the same transition metal in the complex; and
(ii) a linking moiety, preferably a cross-bridging chain, which covalently connects at least 2 (preferably non-adjacent) donor atoms of the organic macrocycle ring, said covalently connected (preferably non-adjacent) donor atoms being bridgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein said linking moiety (preferably a cross-bridged chain) comprises from 2 to about 10 atoms (preferably the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donor atom).
Suitable MRL""s are further nonlimitingly illustrated by the following compound:
This is a MRL in accordance with the invention which is a highly preferred, cross-bridged, methyl-substituted (all nitrogen atoms tertiary) derivative of cyclam. Formally, this ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended von Baeyer system. See xe2x80x9cA Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993xe2x80x9d, R. Panico, W. H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-126.96.36.199. According to conventional terminology, N1 and N8 are xe2x80x9cbridgehead atomsxe2x80x9d; as defined herein, more particularly xe2x80x9cbridgehead donor atomsxe2x80x9d since they have lone pairs capable of donation to a metal. N1 is connected to two non-bridgehead donor atoms, N5 and N12, by distinct saturated carbon chains 2,3,4 and 14,13 and to bridgehead donor atom N8 by a xe2x80x9clinking moietyxe2x80x9d a,b which here is a saturated carbon chain of two carbon atoms. N8 is connected to two non-bridgehead donor atoms, N5 and N12, by distinct chains 6,7 and 9,10,11. Chain a,b is a xe2x80x9clinking moietyxe2x80x9d as defined herein, and is of the special, preferred type referred to as a xe2x80x9ccross-bridgingxe2x80x9d moiety. The xe2x80x9cmacrocyclic ringxe2x80x9d of the ligand supra, or xe2x80x9cmain ringxe2x80x9d (IUPAC), includes all four donor atoms and chains 2,3,4; 6,7; 9,10,11 and 13,14 but not a,b. This ligand is conventionally bicyclic. The short bridge or xe2x80x9clinking moietyxe2x80x9d a,b is a xe2x80x9ccross-bridgexe2x80x9d as defined herein, with a,b bisecting the macrocyclic ring.
The MRL""s herein are of course not limited to being synthesized from any preformed macrocycle plus preformed xe2x80x9crigidizingxe2x80x9d or xe2x80x9cconformation-modifyingxe2x80x9d element: rather, a wide variety of synthetic means, such as template syntheses, are useful. See for example Busch et al., reviewed in xe2x80x9cHeterocyclic compounds: Aza-crown macrocyclesxe2x80x9d, J. S. Bradshaw et. al.
Transition-metal bleach catalysts useful in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-limitingly illustrated by any of the following:
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate
Aquo-hydroxy-5,12-dimethyl-1,5,8,12tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate
Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Hexafluorophosphate
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate
Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Tetrafluoroborate
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II)
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II)
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Copper(II)
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Copper(II)
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Cobalt(II)
Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Cobalt(II)
Dichloro 5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-4,10-dimethyl-3-phenyl- 1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-4,10-dimethyl4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II)
Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II)
Aquo-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Aquo-chloro-10-(2-hydroxybenzyl)4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Chloro-2-(2-hydroxybenzyl)-5-methyl,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II)
Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Chloride
Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Chloride
Dichloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III)
Aquo-Chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Aquo-Chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5-(Trimethylammoniopropyl) dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Chloride
Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[8.5.2]heptadecane Manganese(II)
Dichloro-14,20-dimethyl-1,10,14,20-tetraazatriyclo[8.6.6]docosa-3(8),4,6-triene Manganese(II)
Dichloro4,11-dimethyl- 1,4,7,11-tetraazabicyclo[6.5.2]pentadecane Manganese(II)
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecane Manganese(II)
Dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo[7.7.2]heptadecane Manganese(II)
Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[220.127.116.11,7.111,15.]pentacosa-3,5,7(24), 11,13,15(25)-hexaene Manganese(II) Hexafluorophosphate
Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[18.104.22.168,7.111,15.]pentacosa-3,5,7(24), 11,13,15(25)-hexaene Manganese(II) Trifluoromethanesulfonate
Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo[22.214.171.124,7.111,15.]pentacosa-3,5,7(24), 11,13,15(25)-hexaene Iron(II) Trifluoromethanesulfonate
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II) Hexafluorophosphate
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II) Hexafluorophosphate
Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II) Chloride
Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II) Chloride.
The practitioner may further benefit if certain terms receive additional definition and illustration. As used herein, xe2x80x9cmacrocyclic ringsxe2x80x9d are covalently connected rings formed from four or more donor atoms (i.e., heteroatoms such as nitrogen or oxygen) with carbon chains connecting them, and any macrocycle ring as defined herein must contain a total of at least ten, preferably at least twelve, atoms in the macrocycle ring. A MRL herein may contain more than one ring of any sort per ligand, but at least one macrocycle ring must be identifiable. Moreover, in the preferred embodiments, no two hetero-atoms are directly connected. Preferred transition-metal bleach catalysts are those wherein the MRL comprises an organic macrocycle ring (main ring) containing at least 10-20 atoms, preferably 12-18 atoms, more preferably from about 12 to about 20 atoms, most preferably 12 to 16 atoms.
xe2x80x9cDonor atomsxe2x80x9d herein are heteroatoms such as nitrogen, oxygen, phosphorus or sulfur, which when incorporated into a ligand still have at least one lone pair of electrons available for forming a donor-acceptor bond with a metal. Preferred transition-metal bleach catalysts are those wherein the donor atoms in the organic macrocycle ring of the cross-bridged MRL are selected from the group consisting of N, O, S, and P, preferably N and O, and most preferably all N. Also preferred are cross-bridged MRL""s comprising 4 or 5 donor atoms, all of which are coordinated to the same transition metal. Most preferred transition-metal bleach catalysts are those wherein the cross-bridged MRL comprises 4 nitrogen donor atoms all coordinated to the same transition metal, and those wherein the cross-bridged MRL comprises 5 nitrogen atoms all coordinated to the same transition metal.
xe2x80x9cNon-donor atomsxe2x80x9d of the MRL herein are most commonly carbon, though a number of atom types can be included, especially in optional exocyclic substituents (such as xe2x80x9cpendantxe2x80x9d moieties, illustrated hereinafter) of the macrocycles, which are neither donor atoms for purposes essential to form the metal catalysts, nor are they carbon. Thus, in the broadest sense, the term xe2x80x9cnon-donor atomsxe2x80x9d can refer to any atom not essential to forming donor bonds with the metal of the catalyst. Examples of such atoms could include heteroatoms such as sulfur as incorporated in a non-coordinatable sulfonate group, phosphorus as incorporated into a phosphonium salt moiety, phosphorus as incorporated into a P(V) oxide, a non-transition metal, or the like. In certain preferred embodiments, all non-donor atoms are carbon.
Transition metal complexes of MRL""s can be prepared in any convenient manner. Two such preparations are illustrated as follows:

(a) Method I.
xe2x80x9cBcyclamxe2x80x9d (5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane) is prepared by a synthesis method described by G. R. Weisman, et al., J.Amer.Chem.Soc., (1990), 112, 8604. Bcyclam (1.00 g., 3.93 mmol) is dissolved in dry CH3CN (35 mL, distilled from CaH2). The solution is then evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. Mn(pyridine)2Cl2 (1.12 g., 3.93 mmol), synthesized according to the literature procedure of H. T. Witteveen et al., J. Inora. Nucl. Chem., (1974), 36, 1535, is added under Ar. The cloudy reaction solution slowly begins to darken. After stirring overnight at room temperature, the reaction solution becomes dark brown with suspended fine particulates. The reaction solution is filtered with a 0.2 xcexc filter. The filtrate is a light tan color. This filtrate is evaporated to dryness using a rotoevaporator. After drying overnight at 0.05 mm at room temperature, 1.35 g. off-white solid product is collected, 90% yield. Elemental Analysis: % Mn, 14.45; % C, 44.22; % H, 7.95; theoretical for [Mn(Bcyclam)Cl2], MnC14H30N4Cl2, MW =380.26. Found: % Mn, 14.98; % C, 44.48; % H, 7.86; Ion Spray Mass Spectroscopy shows one major peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]+.
(b) Method II.
Freshly distilled Bcyclam (25.00 g., 0.0984 mol), which is prepared by the same method as above, is dissolved in dry CH3CN (900 mL, distilled from CaH2). The solution is then evacuated at 15 mm until the CH3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. MnCl2 (11.25 g., 0.0894 mol) is added under Ar. The cloudy reaction solution immediately darkens. After stirring 4 hrs. under reflux, the reaction solution becomes dark brown with suspended fine particulates. The reaction solution is filtered through a 0.2 xcexc filter under dry conditions. The filtrate is a light tan color. This filtrate is evaporated to dryness using a rotoevaporator. The resulting tan solid is dried overnight at 0.05 mm at room temperature. The solid is suspended in toluene (100 mL) and heated to reflux. The toluene is decanted off and the procedure is repeated with another 100 mL of toluene. The balance of the toluene is removed using a rotoevaporator. After drying overnight at.05 mm at room temperature, 31.75 g. of a light blue solid product is collected, 93.5% yield. Elemental Analysis: % Mn, 14.45; % C, 44.22; % H, 7.95; % N, 14.73; % Cl, 18.65; theoretical for [Mn(Bcyclam)Cl2], MnC14H30N4Cl2, MW=380.26. Found: % Mn, 14.69; % C, 44.69; % H, 7.99; % N, 14.78; % Cl, 18.90 (Karl Fischer Water, 0.68%). Ion Spray Mass Spectroscopy shows one major peak at 354 mu corresponding to [Mn(Bcyclam)(formate)]+.
Bleach Source
An essential component of the invention is a bleach precursor and/or a bleaching agent.
Bleach precursors for inclusion in the composition in accordance with the invention typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, nitriles and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. The acylation products of sorbitol, glucose and all saccharides with benzoylating agents and acetylating agents are also suitable.
Specific O-acylated precursor compounds include 3,5,5-tri-methyl hexanoyl oxybenzene sulfonates, benzoyl oxybenzene sulfonates, cationic derivatives of the benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl oxybenzene sulfonates, monobenzoyltetraacetyl glucose and pentaacetyl glucose. Phthalic anhydride is a suitable anhydride type precursor. Useful N-acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.
Preferred precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas and the N,N-Nxe2x80x2Nxe2x80x2 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. A most preferred precursor compound is N,N-Nxe2x80x2,Nxe2x80x2 tetra acetyl ethylene diamine (TAED).
N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-955735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
Suitable caprolactam bleach precursors are of the formula:
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
Suitable valero lactams have the formula:
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred embodiments, R1 is selected from phenyl, heptyl, octyl; nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Other suitable materials are those which are normally solid at  less than 30xc2x0 C., particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino, nitro, alkyl, alkyl, aryl and alkyoxy derivatives.
Caprolactam and valerolactam precursor materials wherein the R1 moiety contains at least 6, preferably from 6 to about 12, carbon atoms provide peroxyacids on perhydrolysis of a hydrophobic character which afford nucleophilic and body soil clean-up. Precursor compounds wherein R1 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains. Mixtures of xe2x80x98hydrophobicxe2x80x99 and xe2x80x98hydrophilicxe2x80x99 caprolactams and valero lactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
Another preferred class of bleach precursor materials include the cationic bleach activators, derived from the valerolactam and acyl caprolactam compounds, of formula:
wherein x is 0 or 1, substituents R, Rxe2x80x2 and Rxe2x80x3 are each C1-C10 alkyl or C2-C4 hydroxy alkyl groups, or [(CyH2y)O]nxe2x80x94Rxe2x80x2xe2x80x3 wherein y=2-4, n=1-20 and Rxe2x80x2xe2x80x3 is a C1-C4 alkyl group or hydrogen and X is an anion.
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing peroxyacid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Another preferred class of bleach activator compounds are the amide substituted compounds of the following general formulae:
R1N(R5)C(O)R2C(O)L
or
R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl, alkylene, aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 should preferably not contain more than 18 carbon atoms total. Preferred examples of bleach precursors of the above formulae include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-caproyl) oxybenzene-sulfonate, and mixtures thereof as described in EP-A-0170386.
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A482,807, particularly those having the formula:
including the substituted benzoxazins of the type
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, secondary or tertiary amines and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions.
A precursor of the benzoxazin-type is:
These bleach precursors can be partially replaced by preformed peracids such as N,N phthaloylaminoperoxy acid (PAP), nonyl amide of peroxyadipic acid (NAPAA), 1,2 diperoxydodecanedioic acid (DPDA) and trimethyl ammonium propenyl imidoperoxy mellitic acid (TAPIMA).
Most preferred among the above described bleach precursors are the amide substituted bleach precursor compounds. Most preferably, the bleach precursors are the amide substituted bleach precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.
The bleach precursor may be in any known suitable particulate form for incorporation in a detergent composition, such as agglomerate, granule, extrudate or spheronised extrudate. Preferably, the bleach precursor is in a form of a spheronised extrudate.
Preferred bleaching agents are solid sources of hydrogen peroxide.
Preferred sources of hydrogen peroxide include perhydrate bleaches. The perhydrate is typically an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is normally incorporated at a level of from 0.1% to 60%, preferably from 3% to 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.
The perhydrate may be any of the alkalimetal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate.
Sodium percarbonate, is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material. A variety of coatings can be used including borate, boric acid and citrate or sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate. However the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride.
The particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of approximately 500-1000 micrometers.
The non-aqueous detergent compositions of this invention may further comprise a surfactant- and low-polarity solvent-containing liquid phase having dispersed therein the bleach precursor composition. The components of the liquid and solid phases of the detergent compositions herein, as well as composition form, preparation and use, are described in greater detail as follows:
All concentrations and ratios are on a weight basis unless otherwise specified.
Surfactant
The amount of the surfactant mixture component of the non-aqueous liquid detergent compositions herein can vary depending upon the nature and amount of other composition components and depending upon the desired rheological properties of the ultimately formed composition. Generally, this surfactant mixture will be used in an amount comprising from about 10% to 90% by weight of the composition. More preferably, the surfactant mixture will comprise from about 15% to 50% by weight of the composition.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,664,961 issued to Norris on May 23, 1972.
Highly preferred anionic surfactants are the linear alkyl benzene sulfonate (LAS) materials. Such surfactants and their preparation are described for example in U.S. Pat. No. 2,220,099 and 2,477,383, incorporated herein by reference. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C11-C14, e.g., C12, LAS is especially preferred.
Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C18 alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C18 alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (C12-C15E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (C12-C15E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(4.0)M), wherein M is conveniently selected from sodium and potassium.
Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to xe2x80x9cThe Journal of the American Oil Chemists Societyxe2x80x9d, 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations. Preferably, R3 is C10-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C10-C16 alkyl.
Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kxe2x80x94CH2COOxe2x80x94M+ wherein R is a C8-C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in xe2x80x9cSurface Active Agents and Detergentsxe2x80x9d (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
xe2x80x83RO(CnH2nO)tZx
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0094 118.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
wherein R1 is H, or R1 is C14 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
Non-aqueous Liquid Diluent
To form the liquid phase of the detergent compositions, the hereinbefore described surfactant (mixture) may be combined with a non-aqueous liquid diluent such as a liquid alcohol alkoxylate material or a non-aqueous, low-polarity organic solvent.
Alcohol Alkoxylates
One component of the liquid diluent suitable to form the compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to the general formula:
R1(CmH2mO)nOH
wherein R1 is a C8- C16 alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R1 is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. Preferably also the alkoxylated fatty alcohols will be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol component of the liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
Examples of fatty alcohol alkoxylates useful as one of the essential components of the non-aqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12-C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9-C11 primary alcohol having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially marketed by Union Carbide Corporation. The former is a mixed ethoxylation product of C11 to C15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products have also been commercially marketed by Shell Chemical Company.
The alcohol alkoxylate component when utilized as part of the liquid diluent in the non-aqueous compositions herein will generally be present to the extent of from about 1% to 60% by weight of the composition. More preferably, the alcohol alkoxylate component will comprise about 5% to 40% by weight of the compositions herein. Most preferably, the alcohol alkoxylate component will comprise from about 10% to 25% by weight of the detergent compositions herein.
ps Non-aqueous Low-Polarity Organic Solvent
Another component of the liquid diluent which may form part of the detergent compositions herein comprises non-aqueous, low-polarity organic solvent(s). The term xe2x80x9csolventxe2x80x9d is used herein to connote the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the xe2x80x9csolventxe2x80x9d-containing phase, other components will be present as particulate material dispersed within the xe2x80x9csolventxe2x80x9d-containing phase. Thus the term xe2x80x9csolventxe2x80x9d is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
The non-aqueous organic materials which are employed as solvents herein are those which are liquids of low polarity. For purposes of this invention, xe2x80x9clow-polarityxe2x80x9d liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate. Thus relatively polar solvents such as ethanol should not be utilized. Suitable types of low-polarity solvents useful in the non-aqueous liquid detergent compositions herein do include alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
A preferred type of non-aqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra-C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.
Yet another preferred type of non-polar, non-aqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: R1xe2x80x94C(O)xe2x80x94OCH3 wherein R1 ranges from 1 to about 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
The non-aqueous, low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein. Such a solvent component will generally be utilized in an amount of from about 1% to 60% by weight of the composition. More preferably, the non-aqueous, low-polarity organic solvent will comprise from about 5% to 40% by weight of the composition, most preferably from about 10% to 25% by weight of the composition.
Liquid Diluent Concentration
As with the concentration of the surfactant mixture, the amount of total liquid diluent in the compositions herein will be determined by the type and amounts of other composition components and by the desired composition properties. Generally, the liquid diluent will comprise from about 20% to 95% by weight of the compositions herein. More preferably, the liquid diluent will comprise from about 50% to 70% by weight of the composition.
SOLID PHASE
The non-aqueous detergent compositions herein may further comprise a solid phase of particulate material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from about 0.1 to 1500 microns. More preferably such material will range in size from about 5 to 500 microns.
The particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the non-aqueous liquid phase of the composition. The types of particulate materials which can be utilized are described in detail as follows:
Surfactants
Another type of particulate material which can be suspended in the non-aqueous liquid detergent compositions herein includes ancillary anionic surfactants which are fully or partially insoluble in the non-aqueous liquid phase. The most common type of anionic surfactant with such solubility properties comprises primary or secondary alkyl sulfate anionic surfactants. Such surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROSO3xe2x80x94M+
wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. Preferably R is a C10-C14 alkyl, and M is alkali metal. Most preferably R is about C12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl xe2x80x9cbackbonexe2x80x9d of the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOSO3xe2x88x92M+)(CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m+n is typically about 9 to 15, and M is a water-solubilizing cation.
If utilized as all or part of the requisite particulate material, ancillary anionic surfactants such as alkyl sulfates will generally comprise from about 1% to 10% by weight of the composition, more preferably from about 1% to 5% by weight of the composition. Alkyl sulfate used as all or part of the particulate material is prepared and added to the compositions herein separately from the unalkoxylated alkyl sulfate material which may form part of the alkyl ether sulfate surfactant component essentially utilized as part of the liquid phase herein.
Organic Builder Material
Another possible type of particulate material which can be suspended in the non-aqueous liquid detergent compositions herein comprises an organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein. Examples of such materials include the alkali metal, citrates, succinates, malonates, fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples of organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts are highly preferred.
Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark.
Another suitable type of organic builder comprises the water-soluble salts of higher fatty acids, i.e., xe2x80x9csoapsxe2x80x9d. These include alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
If utilized as all or part of the requisite particulate material, insoluble organic detergent builders can generally comprise from about 1% to 20% by weight of the compositions herein. More preferably, such builder material can comprise from about 4% to 10% by weight of the composition.
Inorganic Alkalinity Sources
Another possible type of particulate material which can be suspended in the non-aqueous liquid detergent compositions herein can comprise a material which serves to render aqueous washing solutions formed from such compositions generally alkaline in nature. Such materials may or may not also act as detergent builders, i.e., as materials which counteract the adverse effect of water hardness on detergency performance.
Examples of suitable alkalinity sources include water-soluble alkali metal carbonates, bicarbonates, borates, silicates and metasilicates. Although not preferred for ecological reasons, water-soluble phosphate salts may also be utilized as alkalinity sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of all of these alkalinity sources, alkali metal carbonates such as sodium carbonate are the most preferred.
The alkalinity source, if in the form of a hydratable salt, may also serve as a desiccant in the non-aqueous liquid detergent compositions herein. The presence of an alkalinity source which is also a desiccant may provide benefits in terms of chemically stabilizing those composition components such as the peroxygen bleaching agent which may be susceptible to deactivation by water.
If utilized as all or part of the particulate material component, the alkalinity source will generally comprise from about 1% to 15% by weight of the compositions herein. More preferably, the alkalinity source can comprise from about 2% to 10% by weight of the composition. Such materials, while water-soluble, will generally be insoluble in the non-aqueous detergent compositions herein. Thus such materials will generally be dispersed in the non-aqueous liquid phase in the form of discrete particles.
OPTIONAL COMPOSITION COMPONENTS
In addition to the composition liquid and solid phase components as hereinbefore described, the detergent compositions herein can, and preferably will, contain various optional components. Such optional components may be in either liquid or solid form. The optional components may either dissolve in the liquid phase or may be dispersed within the liquid phase in the form of fine particles or droplets. Some of the materials which may optionally be utilized in the compositions herein are described in greater detail as follows:
Optional Organic Additives
The detergent compositions may contain an organic additive. A preferred organic additive is hydrogenated castor oil and its derivatives.
Hydrogenated castor oil is a commercially available commodity being sold, for example, in various grades under the trademark CASTORWAX.RTM. by NL Industries, Inc., Highstown, N.J. Other Suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST. Especially preferred hydrogenated castor oil is Thixatrol ST.
The castor oil can be added as a mixture with, for example stereamide.
The organic additive will be partially dissolved in the non-aqueous liquid diluent. To form the structured liquid phase required for suitable phase stability and acceptable rheology, the organic additive is generally present to the extent of from about 0.05% to 20% by weight of the liquid phase. More preferably, the organic additive will comprise from about 0.1% to 10% by weight of the non-aqueous liquid phase of the compositions herein. The organic additive is present in the total composition of from about 0.01% to 10% by weight, more preferably from about 0.05% to 2.5% by weight of the total detergent composition.
Optional Inorganic Detergent Builders
The detergent compositions herein may also optionally contain one or more types of inorganic detergent builders beyond those listed herein before that also function as alkalinity sources. Such optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are more fully discussed in Corkill et al., U.S. Pat. No. 4,605,509; Issued Aug. 12, 1986, the disclosure of which is incorporated herein by reference. Also crystalline layered silicates, such as those discussed in this ""509 U.S. patent, are also suitable for use in the detergent compositions herein. If utilized, optional inorganic detergent builders can comprise from about 2% to 15% by weight of the compositions herein.
Optional Enzymes
The detergent compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes can include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available. They may be incorporated into the non-aqueous liquid detergent compositions herein in the form of suspensions, xe2x80x9cmarumesxe2x80x9d or xe2x80x9cprillsxe2x80x9d. Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants. Enzymes in this form have been commercially marketed, for example, by Novo Nordisk under the tradename xe2x80x9cLDP.xe2x80x9d
Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
If employed, enzymes will normally be incorporated into the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, more typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. Stated otherwise, the non-aqueous liquid detergent compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Optional Chelating Agents
The detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous detergent compositions herein. Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent. Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylene-diaminetriacetates, nitrilotriacetates, ethylene-diamine tetrapropionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanoldiglycines. The alkali metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the compositions of this invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Preferred chelating agents include hydroxyethyl-diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The chelating agent may, of course, also act as a detergent builder during use of the compositions herein for fabric laundering/bleaching. The chelating agent, if employed, can comprise from about 0.1% to 4% by weight of the compositions herein. More preferably, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.
Optional Thickening, Viscosity Control and/or Dispersing Agents
The detergent compositions herein may also optionally contain a polymeric material which serves to enhance the ability of the composition to maintain its solid particulate components in suspension. Such materials may thus act as thickeners, viscosity control agents and/or dispersing agents. Such materials are frequently polymeric polycarboxylates but can include other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric amine derivatives such as quaternized, ethoxylated hexamethylene diamines.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. Such materials may also perform a builder function.
If utilized, the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from about 0.1% to 4% by weight. More preferably, such materials can comprise from about 0.5% to 2% by weight of the detergents compositions herein.
Optional Brighteners, Suds Suppressors and/or Perfumes
The detergent compositions herein may also optionally contain conventional brighteners, suds suppressors, silicone oils, and/or perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts, and perfumes must, of course, be compatible and non-reactive with the other composition components in a non-aqueous environment. If present, brighteners, suds suppressors and/or perfumes will typically comprise from about 0.01% to 4% by weight of the compositions herein.
COMPOSITION FORM
The particulate-containing liquid detergent compositions of this invention are substantially non-aqueous (or anhydrous) in character. While very small amounts of water may be incorporated into such compositions as an impurity in the essential or optional components, the amount of water should in no event exceed about 5% by weight of the compositions herein. More preferably, water content of the non-aqueous detergent compositions herein will comprise less than about 1% by weight.
The particulate-containing non-aqueous detergent compositions herein will be in the form of a liquid.
COMPOSITION PREPARATION AND USE
The non-aqueous liquid detergent compositions herein can be prepared by mixing non-aqueous liquid phase and by thereafter adding to this phase the additional particulate components in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the stable compositions herein. In a typical process for preparing such compositions, essential and certain preferred optional components will be combined in a particular order and under certain conditions.
In a first step of a preferred preparation process, the anionic surfactant-containing liquid phase is prepared. This preparation step involves the formation of an aqueous slurry containing from about 30 to 60% of one or more alkali metal salts of linear C10-16 alkyl benzene sulfonic acid and from about 2-15% of one or more diluent non-surfactant salts. In a subsequent step, this slurry is dried to the extent necessary to form a solid material containing less than about 4% by weight of residual water.
After preparation of this solid anionic surfactant-containing material, this material can be combined with one or more of the non-aqueous organic diluents to form the surfactant-containing liquid phase of the detergent compositions herein. This is done by reducing the anionic surfactant-containing material formed in the previously described pre-preparation step to powdered form and by combining such powdered material with an agitated liquid medium comprising one or more of the non-aqueous organic diluents, either surfactant or non-surfactant or both as herein before described. This combination is carried out under agitation conditions which are sufficient to form a thoroughly mixed dispersion of particles of the insoluble fraction of the co-dried LAS/salt material throughout a non-aqueous organic liquid diluent.
In a subsequent processing step, particulate material to be used in the detergent compositions herein can be added. Such components which can be added under high shear agitation include any optional surfactant particles, particles of substantially all of an organic builder, e.g. citrate and/or fatty acid and/or alkalinity source, e.g. sodium carbonate, can be added while continuing to maintain this admixture of composition components under shear agitation. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.
The non-aqueous liquid dispersion so prepared can be subjected to milling or high shear agitation. Milling conditions will generally include maintenance of a temperature between about 10 and 90xc2x0 C., preferably between 20xc2x0 C. and 60xc2x0 C. Suitable equipment for this purpose includes: stirred ball mills, co-ball mills (Fryma), colloid mills, high pressure homogenizers, high shear mixers, and the like. The colloid mill and high shear mixers are preferred for their high throughput and low capital and maintenance costs. The small particles produced in such equipment will generally range in size from 0.4-150 microns.
Agitation is then continued, and if necessary, can be increased at this point to form a uniform dispersion of insoluble solid phase particles within the liquid phase.
In a second process step, the bleach precursor particles are mixed with the ground suspension from the first mixing step in a second mixing step. This mixture is then subjected to wet grinding so that the average particle size of the bleach precursor is less than 600 microns, preferably between 50 and 500 microns, most preferred between 100 and 400 microns.
After some or all of the foregoing solid materials have been added to this agitated mixture, the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation.
In a third processing step, the activation of the organic additive is obtained. The organic additives are subjected to wetting and dispersion forces to reach a dispersed state. It is well within the ability of a skilled person to activate the organic additive. The activation can be done according to that described by Rheox, in Rheology Handbook, A practical guide to rheological additives. There are basically three distinct stages. The first stage consists in adding the agglomerated powder in the solvent. This combination is carried out under agitation conditions (shear, heat, Stage 2) which are sufficient to lead to complete deagglomeration. With continued shear and heat development over a period of time, the solvent-swollen particles of the organic additive are reduced to their active state in stage 3.
In adding solid components to non-aqueous liquids in accordance with the foregoing procedure, it is advantageous to maintain the free, unbound moisture content of these solid materials below certain limits. Free moisture in such solid materials is frequently present at levels of 0.8% or greater (see method described below). By reducing free moisture content, e.g. by fluid bed drying, of solid particulate materials to a free moisture level of 0.5% or lower prior to their incorporation into the detergent composition matrix, significantly stability advantages for the resulting composition can be realized.
Free and Total Water Determinations:
For the purpose of this patent application, and without wanting to be bound by theory, we refer to xe2x80x9cfree waterxe2x80x9d as the amount of water that can be detected after removal of the solid, undissolved components of the product, whereas xe2x80x9ctotal waterxe2x80x9d is referred to as the amount of water that is present in the product as a whole, be it bound to solids (e.g. water of hydration), dissolved in the liquid phase, or in any other form. A preferred method of water determinations is the so-called xe2x80x9cKarl Fischer titrationxe2x80x9d. Other methods than Karl Fischer titration, e.g. NMR, microwave, or IR spectroscopy, may also be suited for the determination of water in the liquid part of the product and in the full product as described below.
The xe2x80x9cfree waterxe2x80x9d of a formulation is determined in the following way. At least one day after preparation of the formula (to allow for equilibration), a sample is centrifuged until a visually clear layer, free of solid components, is obtained. This clear layer is separated from the solids, and a weighed sample is directly introduced into a coulometric Karl Fischer titration vessel. The water level determined in this way (mg water/kg clear layer) is referred to as xe2x80x9cfree waterxe2x80x9d (in ppm).
The xe2x80x9ctotal waterxe2x80x9d is determined by first extracting a weighed amount of finished product with an anhydrous, polar extraction liquid. The extraction liquid is selected in such a way that interferences from dissolved solids are minimized. In most cases, dry methanol is a preferred extraction liquid. Usually, the extraction process reaches an equilibrium within a few hoursxe2x80x94this needs to be validated for different formulationsxe2x80x94and can be accelerated by sonification (ultrasonic bath). After that time, a sample of the extract is centrifuged or filtered to remove the solids, and a known aliqot then introduced into the (coulometric or volumetric) Karl Fischer titration cell. The value found in this way (mg water/kg product) is referred to as xe2x80x9ctotal waterxe2x80x9d of the formulation.
Preferably, the non-aqueous liquid detergent compositions of the present invention comprise less than 5%, preferably less than 3%, most preferred less than 1% of free water.
Viscosity and Yield Measurements:
The particulate-containing non-aqueous liquid detergent compositions herein will be relatively viscous and phase stable under conditions of commercial marketing and use of such compositions. Frequently, the viscosity of the compositions herein will range from about 300 to 5000 cps, more preferably from about 500 to 3000 cps. The physical stability of such formulations can also be determined by yield measurements. Frequently, the yield of the compositions herein will range from about 1 to 10 Pa, more preferably from about 1.5 to 7 Pa. For the purpose of this invention, viscosity and yield are measured with a Carri-Med CSL2100 rheometer according to the method described herein below.
Rheological properties were determined by means of a constant stress rheometer (Carri-Med CSL2100) at 25xc2x0 C. A parallel-plate configuration with a disk radius of 40 mm and a layer thickness of 2 mm was used. The shear stress was varied between 0.1 Pa and 125 Pa. The reported viscosity was the value measured at a shear rate of about 20 sxe2x88x921. Yield stress was defined as the stress above which motion of the disk was detected. This implies that the shear rate was below 3xc3x9710xe2x88x924 sxe2x88x921.
Gas evolution Rate Measurements:
Gas evolution rates (GERs) can be measured by placing a product sample (usually 1000-1200 g) in an Erlenmeyer which can be closed gas tight by means of an adapter and a valve. The product is then stored at a constant temperature (usually 35xc2x0 C.), and connected to a gas burette. After a certain time (usually 1-10 days), the valve is opened and the volume difference is measured. To minimize effects of ambient pressure changes, the values are referenced versus a sample that does not contain bleach. In general, the GER of the non-aqueous liquid detergent compositions containing Y % of a bleaching agent, said bleaching agent having a GER of Z mL/day/kg product at 35xc2x0 C., should be less than 0.008 Yxc3x97Z mL/day/kg product at 35xc2x0 C.
The compositions of this invention, prepared as herein before described, can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions. The aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.
An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 5,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.

Non-aqueous detergent compositions containing bleach


The object is to provide a simplified but highly efficient fuel cell system, permitting to perform the flame off detection and so on without supplying the burner with additional raw fuel, even if a flame rod system flame detection means is adopted as burner for reformer. The invention concerns a fuel cell system, comprising a reformer for reforming a hydrocarbon base fuel such as natural gas into hydrogen, a CO transformer, a CO eliminator, a fuel cell for generating electricity from hydrogen, and a burner for reformer for burning hydrogen gas discharged from the fuel cell and supply the reformer with heat necessary for reforming reaction, wherein the burner for reformer is provided with a flame rod system flame detection means and, at the same time, supplied with hydrogen gas containing a flame detectable amount of fuel gas.

1. Field of the Invention
The present invention concerns a fuel cell system.
2. Detailed Description of the Prior Art
Of latest years, a fuel cell system, comprising a reformer for reforming a hydrocarbon base fuel including natural gas, city gas, methanol, LPG, butane and so on as raw fuel into hydrogen, a CO transformer for transforming carbon monoxide, a CO eliminator for removing carbon monoxide, a fuel cell for generating electricity from hydrogen, and a burner for reformer for burning hydrogen gas discharged from the fuel cell and supply the reformer with heat necessary for reforming reaction, or a fuel cell system as small power supply comprising further a process gas burner burning hydrogen until each reactor stabilizes during the start or stop, have been proposed.
FIG. 5 is a system diagram showing a fuel cell system of the prior art.
A fuel cell system GS using a fuel cell 6 comprises a heat recovery unit RD in addition to the fuel cell 6.
The heat recovery unit RD is linked by a hot water circuit or the like comprising a hot water storage tank 50, heat exchangers 32, 46, 71 and pumps 33, 47, 72.
The fuel cell 6 is provided with a fuel gas supply unit comprising a desulfurizer 2, a reformer 3, a CO transformer 4, a CO eliminator 5 and so on, a reaction air supply unit comprising an air pump 11, a water pump 21 and so on, electrodes such as fuel electrode 6a, air electrode 6k and so on, and a refrigeration unit of the fuel cell 6 comprising a water tank 21, a pump 48, a refrigeration section 6c and so on.
Electricity generated by the fuel cell 6 is boosted by a DC/DC converter and connected to the main power through a distribution system link inverter (not shown). On the other hand, the power is supplied from here as power of other electric apparatus such as lighting, air conditioner, in a house, office, and so on.
The fuel cell system GS using such a fuel cell 6 intends to use efficiently the energy held by the fuel used for the fuel cell 6, for example, by producing hot water from the city water using heat generated during the power generation by the fuel cell 6 at the same time as the power generation, storing the hot water in a hot water storage tank 50 and supplying to the bath, kitchen and so on.
In the fuel gas supply unit of the aforementioned fuel cell system GS, natural gas, city gas, methanol, LPG, butane or other raw fuel 1 supplied to a desulfurizer 2, and here, sulfur component is removed form the raw fuel.
When the raw fuel having passed through the desulfurizer 2 is boosted up by a booster pump 10 and delivered to the reformer 3, hot water is sent from a water tank 21 through a water pump 22 and heated by the heat exchanger 17 to generate water vapor, and they meet before being supplied. A reformed gas containing hydrogen, carbon dioxide, and carbon monoxide is produced in the reformer 3. Gas having passed through the reformer 3 is supplied to the CO transformer 4, and here, carbon monoxide contained in the reformed gas is transformed into carbon dioxide. Gas having passed through the CO transformer 4 is supplied to the CO eliminator 5 and here, untransformed carbon monoxide in the gas having passed through the CO transformer 4 is reduced, for instance, equal or inferior to 10 ppm (volume) and aqueous gas (reformed gas) of high hydrogen concentration is supplied to a fuel electrode 6a of the fuel cell 6 through a pipe 64.
At this time, the moisture addition amount to the reformed gas is adjusted by regulating the amount of hot water supplied from the water tank 21 to the reformer 3.
The reaction air supply unit humidifies by supplying air from the air pump 11 to the water tank 21, and delivering to a gas phase 53 all the way frothing up reaction air in the hot water in the water tank 21.
Thus, the reaction air after humidification so as to maintain the reaction properly in the fuel cell 6 is supplied to the air electrode 6k of the fuel cell 6 from the water tank 21 through the pipe 25.
In the fuel cell 6, power is generated by electrochemical reaction of hydrogen in the reformed gas supplied to the fuel electrode 6a and oxygen in the air supplied to the air electrode 6k though the gas phase 53 of the air pump 11 and the water tank 21.
The refrigeration unit of the fuel cell 6 is a refrigeration unit placed side by side with the electrodes 6a, 6k of the fuel cell 6, in order to prevent the fuel cell 6 from overheating due to reaction heat or the like of the electrochemical reaction, and designed to circulate hot water of the water tank 21 in a refrigeration section 6c as cooling water by a pump 48, and controls to maintain the temperature in the fuel cell 6 to a temperature appropriate for power generation (for instance, to the order of 70 to 80° C.) by the cooling water.
The chemical reaction in the reformer 3 being endoergic, it has a burner for reformer 12 to sustain the chemical reaction by heating, which is supplied with raw fuel through the pipe 13, supplied with unreacted hydrogen passing through the fuel electrode 6a, through the pipe 15, and supplied with air through a fan 14. When the present fuel cell system GS starts, raw fuel is supplied to the burner for reformer 12 through the pipe 13 and burned, and when the temperature of the fuel cell 6 stabilizes, after the starting, the supply of raw fuel from the pipe 13 is reduced, and unreacted hydrogen (off-gas) discharged from the fuel electrode 6a is supplied through the pipe 15 to sustain the combustion.
On the other hand, the chemical reaction in the CO transformer 4 and the CO eliminator 5 is exothermic. The refrigeration control is performed, during the operation, so that the temperature does not exceed the reaction temperature by the heat of the exothermic reaction. Thus, these predominated chemical reaction and power generation are sustained in reformer 3, the CO transformer 4, the CO eliminator 5 and the fuel cell 6.
Heat exchangers 18, 19 are connected respectively between the aforementioned reformer 3 and the CO transformer 4, and, the CO transformer 4 and the CO eliminator 5.
And, how water of the water tank 21 circulates in respective heat exchangers 18, 19 through the pumps 23, 24, and these hot waters cool respectively the gas having passed through the reformer 3 and the CO transformer 4. Though not illustrated, it is also possible to connect a heat exchanger between the CO eliminator 5 and the fuel cell 6 for cooling gas having passed through the CO eliminator 5.
A heat exchanger 17 is connect to an exhaust system 31 of the aforementioned reformer 3 and, when hot water from the water tank 21 is supplied through the pump 22, it is vaporized by the heat exchanger 17, and the water vapor is mixed with the raw fuel and supplied to the reformer 3.
The present fuel cell system GS is provided with a process gas burner (PG burner) 34.
When the fuel cell system GS starts, the composition of the reformed gas having passed through the reformer 3, CO transformer 4 and CO eliminator 5 has not attained a stable specified value appropriate for operating the fuel cell 6, and it is impossible to supply the fuel cell 6 with the gas, until it stabilizes. There, until the stabilization of respective reactor, the gas whose gas composition has not attained the specific value is introduced in the PG burner 34 and burned.
37 is a fan for delivering combustion air to the PG burner 34.
Then, when respective reactor stabilizes and the CO concentration in the gas has attained the specific value (for instance, equal or inferior to 10 ppm (volume)), it is introduced in the fuel cell 6 for power generation. Unreacted gas that could not be used for power generation in the fuel cell 6 is introduced initially in the PG burner 34 and burned and, when the temperature of the fuel cell 6 stabilizes, off-gas from the fuel cell 6 is introduced in the burner 12 of the reformer 3 through the pipe 15 and burned.
In other words, after the start of the fuel cell system GS, an on-off valve 91 is closed until the temperature stabilization of respective reactor, and the reformed gas is supplied to the PG burner 34 through a pipe line 35 and an on-off valve 36.
In case of temperature stabilization of respective reactor, now the on-off valve 91 is opened while the on-off valve 92 is closed, until the temperature of the fuel cell 6 stabilizes in a temperature range near the operation temperature (for instance 70 to 80° C.), and the reformed gas is supplied to the PG burner 34 through a pipe line 38 and an on-off valve 39, and burned there.
In case where the temperature of the fuel cell 6 stabilizes at the operation temperature, and power is generated continuously, the on-off valves 91, 92 are opened while the on-off valves 36, 39 are closed, and unreacted gas (off-gas) having passed through the fuel cell 6 is supplied to the burner for reformer 12 through a pipe line 15.
The hot water storage tank 50 is supplied with city water though a water pipe 61. The city water supplied to the hot water storage tank 50 is heated by exhaust heat generated from the fuel cell system GS, and the hot water risen in temperature is supplied outside through a hot water supply pipe 62.
For instance, another heat exchanger 32 is further connected to the exhaust system 31, in addition to the heat exchanger 17, and water of the hot water storage tank 50 circulates in the heat exchanger 32, through a pump 33, for exhaust heat recovery.
Also, a heat exchanger 46 is connected to an exhaust system 45 of the PG burner 34 and, water of the hot water storage tank 50 circulates in the heat exchanger 46, through a pump 47, for heat recovery.
Water returning through the heat exchangers 18, 19 by the pumps 23, 24, 48 and cooling water circulating in the refrigeration section 6c of the fuel cell 6 flow in the water tank 21 through a water pipe 73 and, on the other hand, a water supply unit 68 for supplying the water tank 21 with water is connected.
The water supply unit 68 is comprised of an electric motor operated valve 56, a supply tank 67, a pump 74 and so on. The supply tank 67 is a tank for storing temporarily through a pipe 70 water generated from a city water supply unit 69 and the fuel cell 6 for permitting to supply the water tank 21 with water.
Water generated from the fuel cell 6 includes, for instance, drain water obtained by conducting gas discharged from the air electrode 6k of the fuel cell 6 into the heat exchanger 71 and cooling the inside of the heat exchanger 71 with water circulating between the hot water storage tank 50 by the pump 72 or water contained in the gas discharged from the fuel electrode 6a.
The city water supply unit 69 is connected to a water source 78 through a water pipe 52 having an electric motor operated valve 76 and when a water level gauge 79 detects the lowering of water level due to the reduction of water quantity in the supply tank 67, a liquid level control unit 77 opens the electric motor operated valve 76, and replenishes the supply tank 67 with water through the water pipe 52 and a water treatment unit (ion exchange resin) 51 using the water pressure of the water source 78, in order to retain a water quantity that would not impede the supply of the water tank 21 with water.
The water tank 21 has a liquid level control unit LC for keeping the level of water so as to form an air portion (gas phase) 53 all the time in the upper part in the tank and a temperature control unit TC for keeping the water temperature in the water tank 21 within the set range.
The liquid level control unit LC comprises a water level gauge 54 and a control unit of an electric motor operated valve 56 for monitoring the water quantity in the water tank 21 all the time, stores water in the tank so that reaction air is humidified moderately when it passes in the water tank 21 and supplied to the fuel cell 6, and controls the water quantity so as to form the gas phase 53 in the upper part, operates the pump 74 in case of lowering of the water level, introduces treated water from the supply tank 67 through a pipe 84 by adjusting the opening of the electric motor operated valve 56, for keeping the water level in the water tank 21 within the set range.
55 is a wave-eliminating board for preventing the level detection by the water level gauge 54 from becoming unstable due to frothing and so on.
The temperature control unit TC is an unit for keeping the water temperature in a temperature range of, for instance, 60 to 80° C. (set temperature) so as to realize a moderate humidification in the water tank 21, when the air electrode 6k of the fuel cell 6 is supplied with reaction air. 63 is a perforated board for bubbling.

Fuel cell system having a burner with a flame detection rod therein


A multimode scan converter includes a delay element (33) for delaying one horizontal line of video signal and selectively re-displaying that line. A multiplexer (30) is arranged to selectively provide either luminance signal or chrominance signal to the delay element. Output signal from the delay element and output signal from the multiplexer are coupled to a proportioning circuit (34) which sums the two signals in complementary proportions (e.g. K and 1-K). A second multiplexer (35), which provides up-converted output luminance signal, is arranged to selectively pass the luminance signal or signal from the proportioning circuit. A third multiplexer (36), which provides up-converted output chrominance signal, is arranged to selectively pass the chrominance signal or signal from the proportioning circuit.

This invention relates to an interpolator for scan converting decompressed video signal occurring in a plurality of alternative formats.
With the advent of compressed video signal transmissions, it is anticipated that receiver apparatus, to be competitive, will be expected to display images in a standardized format regardless of the format of the transmitted video data. For example, video signal compressed according to the MPEG 2 format (Moving Pictures Expert Group of the International Standardization Organization) may represent images in 4:2:2 format; 4:2:0 format and various other formats. Regardless of the transmitted format, the receiver should display all images in, for example, the 4:2:2 format.
There are many known systems for performing scan conversion from one format to another. Nominally such systems are optimized to convert one specific signal format to a second specific signal format. However, in the environment of a television receiver it is not practical to include a plurality of optimized scan converters, one for each anticipated transmitted signal format. Rather a compromise approach must be taken to scan conversion, where a plurality of signal formats may be converted in a single converter apparatus with acceptable rather than optimized performance.
Consider the MPEG 2 standard which supports different compression processes as well as different resolution formats. The different compression processes include intra-frame and intra-field processing.
Raw data from an MPEG decoding process is frames of video signal. A full resolution frame (4:2:0) consists of 480 lines of luminance signal and 240 lines of chrominance signal. A half resolution (4:2:0) includes 240 lines of luminance signal and 120 lines of chrominance signal. In the full resolution mode the decoded lines may be numbered
Y1, Y2, Y3, Y4, Y5, Y6 . . . Y480
C1, C2, C3, C4, . . . C240
and in the half resolution mode the decoded lines may be numbered
Y1, Y2, Y3, Y4, Y5, Y6 . . . Y240
C1, C2, C3, C4, . . . C120.
The output of the MPEG decoder is always twice as many luminance lines as chrominance lines. However the desired output 4:2:2 display format may be represented
OY1, OY2, OY3, OY4, . . . OY480
OC1, OC2, OC3, OC4, . . . OC480.
Regardless of the original resolution, the number of chrominance lines is up-converted. In the half resolution mode, the number of luminance lines is also up-converted. The mode of up-conversion may be variable depending upon the preprocessing implemented prior to the compression process used in developing the compressed signal. Certain modes of up-conversion are more conducive to up-converting intra-fame preprocessed signal and other modes are more conducive to up-converting inter-field preprocessed signal. The present invention is an interpolator for performing just such multi-mode vertical up-conversion of video signal.
The present interpolator includes a delay element for delaying one horizontal line of video signal and selectively re-displaying that line. A multiplexer is arranged to selectively provide either decoded luminance signal or decoded chrominance signal to the delay element. Output signal from the delay element and output signal from the multiplexer are coupled to a proportioning circuit which sums the two signals in complementary proportions (e.g. K and 1-K). A second multiplexer, which provides up-converted output luminance signal, is arranged to selectively pass the decoded luminance signal or signal from the proportioning circuit. A third multiplexer, which provides up-converted output chrominance signal, is arranged to selectively pass the decoded chrominance signal or signal from the proportioning circuit.

Multimode interpolation filter as for a TV receiver