Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom

Abstract

In some variations, this disclosure provides a surface-modified hydrophobic clay composition for an ink formulation, the composition comprising up to 99 wt % clay particles with a particle-size distribution characterized in that at least 10% are smaller than 0.2 microns, at least 25% are smaller than 0.5 microns, and at least 95% are less than 5 microns; and from about 1 wt % to about 10 wt % of one or more organic compounds selected from quaternary ammonium compounds, organic acids, fatty acids, organic silanes, or organic polysilanes. The surface-modified hydrophobic clay composition may be produced by various methods, including a slurry method or a dry-mixing method. Ink clay loadings in heatset ink formulations may be increased to 10-15% without losing ink gloss. Inks may be produced with lower solvent, resin, and/or pigment concentrations, thereby reducing cost.

Claims

1. A surface-modified hydrophobic clay composition for an ink formulation, said composition comprising: (i) from more than 0 to 99 wt % of clay particles with a particle-size distribution characterized in that 40% to 60% of said clay particles are smaller than 0.2 microns, 70% to 98% of said clay particles are smaller than 0.5 microns, and substantially all of said clay particles are less than 5 microns; and (ii) from about 1 wt % to about 5 wt % of one or more quaternary ammonium compounds given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup.], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X.sup. is a monovalent anion.

2. The composition of claim 1, wherein at least 50% of said clay particles are smaller than 0.2 microns.

3. The composition of claim 1, wherein said clay particles comprising one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al.sub.2Si.sub.2O.sub.5(OH).sub.4.

4. The composition of claim 3, wherein said clay particles are kaolin clay particles.

5. The composition of claim 1, wherein at least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.10-C.sub.24 chains.

6. The composition of claim 5, wherein at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from C.sub.10-C.sub.24 chains.

7. The composition of claim 1, wherein at least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.1-C.sub.9 chains.

8. The composition of claim 7, wherein at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from C.sub.1-C.sub.9 chains.

9. The composition of claim 1, wherein at least one of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is a methyl group.

10. The composition of claim 9, wherein at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are methyl groups.

11. The composition of claim 1, wherein two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are methyl groups and wherein the other two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from C.sub.16-C.sub.18 chains.

12. The composition of claim 1, wherein X.sup. is an organic anion.

13. The composition of claim 1, wherein X.sup. is an inorganic anion.

14. The composition of claim 13, wherein X.sup. is a halide anion.

15. An ink formulation containing a surface-modified hydrophobic clay composition, said composition comprising: (i) from more than 0 to 99 wt % of clay particles with a particle-size distribution characterized in that 40% to 60% of said clay particles are smaller than 0.2 microns, 70% to 98% of said clay particles are smaller than 0.5 microns, and substantially all of said clay particles are less than 5 microns; and (ii) from about 1 wt % to about 10 wt % of one or more organic compounds selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof, wherein said ink formulation has an ink gloss of least 90%.

16. The ink formulation of claim 15, wherein said composition comprises from about 2 wt % to about 8 wt % of said one or more organic compounds.

17. The ink formulation of claim 15, wherein at least 50% of said clay particles are smaller than 0.2 microns.

18. The ink formulation of claim 15, wherein said clay particles comprising one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al.sub.2Si.sub.2O.sub.5(OH).sub.4.

19. The ink formulation of claim 18, wherein said clay particles are kaolin clay particles.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a graph depicting the experimental influence of particle size on ink gloss development.

(2) FIG. 2 is a graph depicting the experimental influences of both particle size and treatment level of a quaternary ammonium compound on ink gloss development.

(3) FIG. 3A is an SEM micrograph (100) of a fine-particle kaolin clay that has not been treated with a quaternary ammonium compound.

(4) FIG. 3B is an SEM micrograph (100) of a fine-particle kaolin clay that has been treated with a quaternary ammonium compound, in some embodiments.

(5) FIG. 4A is an SEM micrograph (1000) of a fine-particle kaolin clay that has not been treated with a quaternary ammonium compound.

(6) FIG. 4B is an SEM micrograph (1000) of a fine-particle kaolin clay that has been treated with a quaternary ammonium compound, in some embodiments.

(7) FIG. 5 summarizes experimental ink-gloss data associated with Example 4 of this disclosure.

(8) FIG. 6 summarizes additional experimental data associated with Example 4 of this disclosure.

DETAILED DESCRIPTION OF SOME EMBODIMENTS

(9) This description will enable one skilled in the art to make and use the principles of the disclosure, and it describes several embodiments, adaptations, variations, alternatives, and uses of the disclosure.

(10) As used in this specification and the appended claims, the singular forms a, an, and the include plural referents unless the context clearly indicates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this invention belongs. As used herein, a composition, blend, compound, or mixture are all intended to be used interchangeably.

(11) As used herein, the phase consisting of excludes any element, step, or ingredient not specified in the claim. When the phrase consists of (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. As used herein, the phase consisting essentially of limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel characteristic(s) of the claimed subject matter.

(12) With respect to the terms comprising, consisting of, and consisting essentially of, where one of these three terms is used herein, the presently disclosed and claimed subject matter may include the use of either of the other two terms. Thus in some embodiments not otherwise explicitly recited, any instance of comprising may be replaced by consisting of or, alternatively, by consisting essentially of.

(13) Unless otherwise indicated, all numbers expressing parameters, conditions, concentrations, and so forth used in the specification and claims are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending at least upon a specific analytical technique.

(14) The examples described herein are examples of the disclosure, including examples of various embodiments as well as comparative examples. None of the examples should be construed as limiting the principles of the invention, or its application, in any way. All examples are exemplary only.

(15) Some embodiments are premised on the discovery that ink clay loadings in heatset ink formulations may be increased from 3-5% to 10-15% without losing ink gloss, by incorporating certain treatments to the clay particles. In particular, fine clay particles may be treated with organic compounds, such as (but not limited to) quaternary ammonium compounds. The organic compounds react with the clay, such as by electrostatic bonding. The clay particles transition from hydrophilic to hydrophobic. The result is to engender or enhance a glossing effect, extend the resin in the composition (allowing to reduce the amount of resin), and lower overall cost.

(16) In some embodiments, the invention provides a method of producing a surface-modified clay for an ink formulation, the method comprising:

(17) (a) providing clay particles with a particle-size distribution characterized in that at least 10% of the clay particles are smaller than 0.2 microns, at least 25% of the clay particles are smaller than 0.5 microns, and at least 95% of the clay particles are less than 5 microns;

(18) (b) forming a slurry comprising the clay particles in water;

(19) (c) introducing the slurry to a reactor, operated under effective treatment conditions and in the presence of an organic compound to modify a surface of the clay particles, to form a treated clay slurry; and

(20) (d) conveying the treated clay slurry to a dryer to produce a product comprising a surface-modified clay.

(21) The fine clay particles are treated with one or more organic compounds to modify the surface and make them hydrophobic. The organic compound may be selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof.

(22) Quaternary ammonium compounds may be given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup. ], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion. In some embodiments, it is believed (without being limited to any theories) that quaternary ammonium compounds are particularly effective owing to the anchoring effect of the N.sup.+ center onto the clay surface.

(23) In some embodiments employing quaternary ammonium compounds, at least one or at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.10-C.sub.24 chains. In some embodiments, at least one or at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.1-C.sub.9 chains. In some embodiments, at least one or at least two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is a methyl group. In certain embodiments, two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are methyl groups and the other two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from C.sub.16-C.sub.18 chains. Generally speaking, the R groups (R.sub.1, R.sub.2, R.sub.3, and R.sub.4) can be linear, branched, olefinic, cyclic, aromatic, or functionalized in any way. X may be an organic or inorganic anion. In some embodiments, X is a halide anion such as chlorine or bromine.

(24) Organic acids may include fatty acids, which generally are regarded as having at least four carbon atoms. Any known unsaturated fatty acid, such as oleic acid, or saturated fatty acid, such as stearic acid may be employed. In some embodiments, organic acid may be selected from short-chain acids such as lactic acid, acetic acid, formic acid, citric acid, and oligomers or polymers thereof.

(25) Organic silanes or polysilanes may include any suitable linear or branched silanes with at least one organic group having one to 20 carbon atoms. Silanes are chemical compounds of silicon and another atom such as carbon or hydrogen, which are analogues of alkane hydrocarbons. Silanes consist of a chain of silicon atoms covalently bonded to each other, to carbon, or to hydrogen atoms.

(26) Any suitable clay basic material may be used including kaolin, bentonite, montmorillonite, synthetic layered silicates such as laponites, hectorites, as well as analogous aluminosilicate compositions which would be functionally equivalent. Preferred clay particles comprise clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al.sub.2Si.sub.2O.sub.5(OH).sub.4. In certain embodiments, the clay particles are kaolinite.

(27) A preferred range of particle sizes of the base clay is as follows: 40-60% less than 0.2 microns; 70-98% less than 0.5 microns; and substantially all less than 5 microns. In some embodiments, coarser clay particles are utilized, although still less than 5 microns. For example, the range of particle sizes of the base clay may be 5-20% less than 0.2 microns; 10-40% less than 0.5 microns; and substantially all less than 5 microns. Substantially all means about 100%, but there can be a few particles present (in a given sample) that are larger than 5 microns, such as due to impurities or random clay particles.

(28) The amount of organic compound may vary. In some embodiments, the treatment includes a quaternary ammonium compound in a concentration of at least about 1 wt %, 2 wt %, 2.5 wt %, 3 wt %. 3.5 wt %, 4 wt %, 5 wt %, or more, of the mass of the clay particles.

(29) A variety of process approaches may be utilized to treat the fine clay particles. In some embodiments, the following process is employed: 1. Pump diluted fine particle clay with water to 20-25% slurry solid into treatment vessel. 2. Heat clay slurry to 65-72 C. and mix moderately continuously. 3. Pump diluted treatment chemical to the heated vessel and allow treatment for 20-40 minutes. 4. Pump treated clay slurry to spray dryer or to a flash dryer. 5. Finished product can be dry ground to produce low-density treated clay with a grinding mill.

(30) When a spray dryer is employed, it will typically contain a set of nozzles to spray treated slurry in micron-sized beads, which are then dried in a heated air chamber. When a flash dryer is employed, it will typically utilize mechanical drying and mixing simultaneously in a heated chamber. Hot air will push dried ground material upward to a cyclone.

(31) The above-described steps are exemplary, and the invention is not limited to these ranges of slurry solids content, or treatment time or temperature. Generally, a quantity of one or more organic compounds will be contacted with suitable fine clay particles, and allowed to react (chemically and/or physically) under effective conditions of time, temperature, pressure, and mixing so that the clay surface is modified to become more hydrophobic.

(32) In some embodiments, only a portion of the organic compounds that are added actually react and bind with the clay particles. In other embodiments, all or substantially all of the organic compounds bind with the clay particles and remain there (i.e., are not removed by any subsequent washing steps).

(33) Some embodiments thus provide a surface-modified hydrophobic clay composition for an ink formulation, comprising:

(34) (i) up to 99 wt % clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(35) (ii) from about 1 wt % to about 5 wt % of one or more quaternary ammonium compounds given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup.], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.

(36) There may be some amount of moisture present in the surface-modified hydrophobic clay composition. For example, the composition may include about 0.5 wt %, 1.0 wt %, 1.5 wt %, 2.0 wt %, or more water.

(37) The surface-modified hydrophobic clay composition may be characterized in a number of ways. In some embodiments, the Fineness of Grind (NPIRI Grinding, ASTM) shows a Scratches value of 0 and a Speckles value less than or equal to 9. The brightness by % Reflectance (TAPPI) may be 84 or higher. Preferably, there is 0.1 wt % or less crystalline silica present.

(38) The surface-modified hydrophobic clay composition may be incorporated into any known ink formulation, in various embodiments. In some embodiments, the surface-modified hydrophobic clay composition is combined with an organic solvent and a resin, along with a pigment and/or dye, to form a heatset ink formulation. It is theorized, without limitation, that the surface-treated clay causes the clay to become more hydrophobic and therefore more easily dispersible in the various ink formulations.

(39) A surface-modified hydrophobic clay composition for an ink formulation comprises, in some embodiments:

(40) (i) up to 99 wt % clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(41) (ii) from about 1 wt % to about 10 wt %, such as from about 2 wt % to about 8 wt % pr about 2 wt % to about 5 wt %, of one or more organic compounds selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof.

(42) In some embodiments, a surface-modified hydrophobic clay composition for an ink formulation comprises:

(43) (i) up to 99 wt % clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(44) (ii) from about 1 wt % to about 5 wt % of one or more quaternary ammonium compounds given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup.], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.

(45) In some embodiments, the composition includes from about 2 wt % to about 4 wt % of the one or more quaternary ammonium compounds. Some water may also be present, such as up to about 2 wt % H.sub.2O.

(46) In some embodiments, at least 50% or at least 60% of the clay particles are smaller than 0.2 microns. In these or other embodiments, at least 80% or at least 95% of the clay particles are smaller than 0.5 microns. In these or still other embodiments, substantially all of the clay particles are less than 2 microns, 3 microns, or 4 microns.

(47) The clay particles preferably include one or more clays selected from the Kaolin group of minerals comprising kaolinite, dickite, halloysite, nacrite, montmorrilite, or any other polymorph of Al.sub.2Si.sub.2O.sub.5(OH).sub.4. The clay particles are kaolin clay particles, in certain embodiments.

(48) At least one (such as one, two, or three) of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.10-C.sub.24 chains, in some embodiments. At least one (such as one, two, or three) of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 is selected from C.sub.1-C.sub.9 chains, such as methyl (CH.sub.3), in some embodiments. In certain embodiments, two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are methyl groups and the other two of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are selected from C.sub.16-C.sub.18 chains. The monovalent anion X may be organic or inorganic, but is preferably inorganic such as Cl.sup. or Br.sup..

(49) Other variations provide a heatset ink formulation comprising:

(50) (i) a solvent;

(51) (ii) a pigment or dye;

(52) (iii) a resin;

(53) (iv) clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(54) (v) from about 1 wt % to about 5 wt % of one or more organic compounds selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof.

(55) The resin may be present at about 25-35 wt % or less in the heatset ink formulation. The clay particles may be present at about 5-15 wt % or more in the heatset ink formulation.

(56) Still other variations provide a heatset ink formulation comprising:

(57) (i) a solvent;

(58) (ii) a pigment or dye;

(59) (iii) a resin;

(60) (iv) clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(61) (v) from about 1 wt % to about 5 wt % of one or more quaternary ammonium compounds given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup.], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.

(62) In some embodiments, the resin is present at about 35 wt % or less in the heatset ink formulation, such as about 30 wt %, 25 wt %, or less in the heatset ink formulation.

(63) In some embodiments, the clay particles are present at about 5 wt % or more in the heatset ink formulation, such as about 10 wt %, about 15 wt %, or more in the heatset ink formulation.

(64) Many other variations are possible. For example, a UV-curable ink formulation is provided, comprising:

(65) (i) a solvent;

(66) (ii) a pigment or dye;

(67) (iii) a resin;

(68) (iv) clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(69) (v) from about 1 wt % to about 5 wt % of one or more quaternary ammonium compounds given by the formula [R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+][X.sup.], wherein each of R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected hydrocarbon groups or chains, and wherein X is a monovalent anion.

(70) A UV-curable ink formulation as disclosed may comprise:

(71) (i) a solvent;

(72) (ii) a pigment or dye;

(73) (iii) a resin;

(74) (iv) clay particles with a particle-size distribution characterized in that at least 40% of the clay particles are smaller than 0.2 microns, at least 70% of the clay particles are smaller than 0.5 microns, and substantially all of the clay particles are less than 5 microns; and

(75) (v) from about 1 wt % to about 5 wt % of one or more organic compounds selected from the group consisting of a quaternary ammonium compound, an organic acid, a fatty acid, an organic silane, an organic polysilane, and combinations thereof.

EXAMPLES

Example 1: Influence of Particle Size on Ink Gloss Development

(76) Various ink clay bases are tested for their ability to impart ink gloss in a heatset ink formulation, using the methods disclosed herein. As shown in FIG. 1, finer clay particles lead to better ink gloss. The sample labeled Lithosperse corresponds to the smallest particle size tested, while the sample labeled Hydrafine corresponds to the largest particle size tested.

Example 2: Comparison of Two Different Ink Bases and Three Treatment Levels

(77) In this example, treatments using a quaternary ammonium compound as disclosed herein at 2 wt % and 4 wt % loading are compared to a treatment without a quaternary ammonium compound. Also, two different kaolin clay particle types are tested: HG90 and HuberFine (HF90 in the legend). The particle size of HG90 is 40-60% less than 0.2 microns; 70-98% less than 0.5 microns; and substantially all less than 5 microns. The particle size of HF90 is 5-20% less than 0.2 microns; 10-40% less than 0.5 microns; and substantially all less than 5 microns.

(78) As shown in FIG. 2, ink gloss development of ink clay is primarily associated with its particle size, and secondarily with the concentration of the quaternary ammonium compound used in the treatment.

Example 3: Ink Gloss Development for Pilot-Plant Ink Clay Samples

(79) Jet-milled (dispersed) clay samples are compared against beads (undispersed), using a large spray dryer. It is found that there are no significant differences. The dispersed filter cake contains anionic dispersant which was added after dewatering. The undispersed filter cake contains no added anionic dispersant after dewatering.

Example 4: Surface Treatment for Maximum Ink Gloss and Resistance to Fountain Solution Bleed

(80) A fine-particle kaolin clay is subjected to the disclosed treatment with a quaternary ammonium compound. SEM micrographs of two different spray-dried beads are shown at 100 in FIGS. 3A and 3B. FIG. 3A is an SEM image showing regular spray-dried beads, without treatment. FIG. 3B is an SEM image showing soft-dried beads, with treatment. FIGS. 4A and 4B show the same materials, except at 1000. The soft spray-dried beads reveal better dispersion. Soft beads are formed due to the coating of fatty acid to the clay surface in the treatment process.

(81) A test procedure for conducting ink clay performance test is the following: 1. Weigh out 75 grams of heatset free flow varnish in a mixing cup. 2. Use lab disperser (cowls blade) to premix the varnish, at a temperature of 20-40 C., at less than 1000 rmp mixing speed. 3. Weigh out a proper amount of treated ink clay and add to varnish. 4. Adjust mixer speed to 4000 rpm; mix 10 minutes. 5. Add mineral solvent for viscosity adjustment. 6. Check for varnish dispersion with NIPRI fineness grind gauge (ASTM ink testing standard). 7. Check bleed with Duke emulsification test (ASTM ink testing standard).

(82) FIG. 5 shows that Lithosperse NextGen (Lsperse Nextgen in the legend) shows the highest gloss for a given % ink clay in extender. At 20% ink clay loading, Lithosperse NextGen is 25 points higher than ASP101. At 15% ink clay loading, Lithosperse NextGen is 19 points higher than ASP101. FIG. 6 shows other property data.

(83) This disclosure reveals utility and benefits in several areas, such as improved product performance, lower organic solvent emissions, and overall cost reduction.

(84) In this detailed description, reference has been made to multiple embodiments of the disclosure and non-limiting examples relating to how the disclosure can be understood and practiced. Other embodiments that do not provide all of the features and advantages set forth herein may be utilized, without departing from the spirit and scope of the present disclosure. This disclosure incorporates routine experimentation and optimization of the methods and systems described herein. Such modifications and variations are considered to be within the scope of the invention defined by the claims.

(85) All publications, patents, and patent applications cited in this specification are herein incorporated by reference in their entirety as if each publication, patent, or patent application were specifically and individually put forth herein.

(86) Where methods and steps described above indicate certain events occurring in certain order, those of ordinary skill in the art will recognize that the ordering of certain steps may be modified and that such modifications are in accordance with the variations of the disclosure. Additionally, certain of the steps may be performed concurrently in a parallel process when possible, as well as performed sequentially.

(87) Therefore, to the extent there are variations of the disclosure, which are within the spirit of the disclosure or equivalent to the inventions found in the appended claims, it is the intent that this patent will cover those variations as well. The present invention shall only be limited by what is claimed.