AU2343392A

AU2343392A - Paint detackifying and flocculating composition and process

Info

Publication number: AU2343392A
Application number: AU23433/92A
Authority: AU
Inventors: Wilbert J Roberts
Original assignee: Henkel Corp
Current assignee: Henkel Corp
Priority date: 1991-07-19
Filing date: 1992-07-15
Publication date: 1993-02-23
Also published as: NZ243547A; ZA925325B; CN1068839A; CA2110905A1; WO1993002147A1; JPH06509371A; BR9206277A; EP0595898A1; MX9204213A

Description

PAINT DETACKIFYING AND FLOCCULATING COMPOSITION AND PROCESS

FIELD OF THE INVENTION

This invention relates to compositions and processes for both detackifying and flocculating paint entrained in water, particularly circulating water in a conventional spray booth, to produce a flocculated sludge that floats on the circulating water from which it has been flocculated. "Paint" as used herein is to be understood as a generic term which encompasses all common varieties of water insoluble organic binder containing coatings commonly applied in spraying operations, including but not limited to oil based paints, enamels, lacquers, high solids solvent based automotive body base coat, high solids solvent based automotive body clear coat, water borne auto body base and clear coats, urethane polymer containing auto body top coats, and solvent and water borne primers. These paints may utilize asphaltic, acrylic, polyester, melamine-form- aldehyde, isocyanate, epoxy, alkyd, melamine alkyd, and blocked polyurethane resins among others, along with appropriate solvents, pigments, and ancillary additives. Paint "overspray", the portion of the sprayed paint which does not fall on the surface(s) it is intended to protect, if left untreated, readily adheres to the walls of spray booths and any other surfaces that it contacts, such as the surfaces of water distribution piping, spray nozzles, and the like. Use of a process according to this invention converts the paint overspray to a non-sticky sludge suitable for convenient disposal. STATEMENT OF RELATED ART

A very wide variety of compositions and processes for detackifying and/or flocculating paint are known in the prior art. In the older technology for spray booth manage¬ ment, it was normal to produce a detackified paint sludge that was denser than water and therefore accumulated at the bottom of a settling basin provided in the water circula¬ tion system used for the water that provides the "water curtain" that keeps oversprayed paint from accumulating on the walls of the booth. In this type of booth management, periodic cleaning of the settling basin bottoms while the operation of the spray booth is interrupted is required and is expensive, both in direct personnel cost and in lost time for profitable use of the spray booth.

Because of this disadvantage of the formation of dense sludge in detackifying, more up-to-date spray booth opera¬ tions generally are designed to produce paint sludge that, at least to a predominant extent and most preferably en- tirely, floats on the circulating water from which it is flocculated rather than sinks. The floating sludge can then be skimmed more or less continuously from the circulating water systems, so that at best no shutdowns for sludge pit cleaning are ever required, and at worst such shutdowns are needed much less often than with the type of spray booth management where most or all of the sludge formed is denser than water.

Normal current commercial spray booth management that produces floating sludge, especially in high volume output automotive spray booths, requires additions of at least three separately supplied chemical compositions: a detack- ifier; a flocculant that is chemically different from the detackifier; and a basic (usually caustic) material to adjust the pH of the circulating water used in the spray booth. The most widely used flocculants for such an opera¬ tion are normally supplied commercially as solvent con- taining polymer emulsions, which must be diluted with water before use to a concentration of only about 0.1 - 0.5 % of the concentration as supplied. The dilution process is time consuming and normally is repeated every day. If mixing is not adequately and correctly controlled during dilution, gelation or separation into two immiscible phases of the partially diluted flocculant composition can easily occur, and if it does often requires very expensive produc¬ tion shutdowns for cleaning the spray booth and/or its wat¬ er circulation system. One object of the present inven- tion is to provide a single chemical composition that can be effectively used to achieve both flocculation and de- tackification if needed, while avoiding the mixing diffi¬ culties described above and producing sludge that largely floats on water. Some of the specific items of related art considered most pertinent to the present invention are summarized be¬ low, without any representation that an exhaustive search has been made.

U. S. Patent 4,686,047 of Aug. 11, 1987 to Arots teaches detackifying paint with water soluble polymers of N-dialkyldiallyamine hydrohalides and epihalohydrins. Sim¬ ple metal salts such as aluminum chloride and sulfate are taught as acceptable, although not preferred, optional ingredients. ϋ. S. Patent 4,440,647 of Apr. 3, 1984 to Puchalski teaches a detackifying composition comprising a water- dispersible polyamide-epichlorohydrin resin, another polymer formed by reaction of hexamethylene diamine and ethylene dichloride, and an amphoteric metal salt. The latter component may be aluminum chloride, although zinc salts are preferred.

U. S. Patent 4,566,986 of Jan. 28, 1986 to aldmann teaches flocculating agents that are inorganic polymers including divalent and trivalent metal atoms, optionally including aluminum. No reference to paint detackifying has been noted in this reference, but it does describe floccu- lating acrylic sizing latex waste water, an application that might be considered somewhat analogous. There appears to be no mention of cationic organic polymers in the teach¬ ings of this reference, and thus ipso facto no mention of any combination of such cationic organic polymers with aluminum containing polymers.

U. S. Patents 3,738,945 of June 12, 1973 and 3,894,946 of July 15, 1975, both to Panzer et al. (the latter being a continuation-in-part of a division of the application on which the former issued) teach flocculation with polyquat- ernary polymers obtained by interaction of a secondary amine, a difunctional epoxy compound, and a polyfunctional amine. Such flocculation is taught for use in treating river water, sewer water, oil in water emulsions, enzyme mash liquors, ilmenite digestion liquors, and iron ore slimes and in washing bituminous coal, but no reference to detackifying or flocculating paint appears in either of these patents.

U. S. Patent 4,401,574 of Aug. 30, 1983 to Farrington et al . teaches the use of polyaluminum chloride, optionally combined with acryla ide polymers that may include cationic acry a ide polymers, in flocculating aqueous waste process streams generated during the production of latex based paints. There is no teaching of using such materials for detackifying paint, however, U. S. Patent 4,792,364 of Dec. 20, 1988 to Huang teaches a paint spray booth detackifying composition com¬ prising a mixture of melamine-formaldehyde polymers and polyvinyl alcohol polymers, optionally also including styrene-acrylate polymers. U. S. Patent 4,759,855 of July 26, 1988 to Kaiser teaches the use of inorganic detackifying agents including alkaline zinc compounds. Quaternary polymers are taught as optional but not preferred ingredients, along with clays and other materials, including aluminum oxide. ϋ. S. Patent 4,629,572 of Dec. 16, 1986 to Leitz et al . teaches paint detackification with a composition in- eluding both a water dispersible polymer of urea or an a inotriazine with an aldehyde and a water swellable clay.

Many clays contain aluminum.

U. S. Patent 4,637,824 of Jan. 20, 1987 to Pominville teaches detackifying with a combination of an alkali metal silicate, an amphoteric metal salt, and a poly(diallyldi- alkylammoniu halide) . Aluminum chloride is listed as one of three preferred amphoteric metal salts. Because of the silicate content, it is expected that the sludge produced by such a composition would sink in water rather than float on it, and silicate is an objectionable content of sludges that are to be used as fuel, a growing practice, because of the danger of forming glassy materials that will impede the operation of the fuel using burners.

U. S. Patents 4,800,039 of Jan. 24, 1989 and 4,746,457 of May 24, 1988 to Hassick et al. teach clarifying turbid aqueous suspension such as river water with a combination of aluminum chlorohydrate and a water soluble cationic polymer, but do not teach detackifying any kind of paint. ϋ. S. Patent 4,765,867 of Aug. 23, 1988 to Dreisbach et al. teaches a process for controlling pitch deposition in paper making plants by adding to the paper pulp an ef¬ fective amount of water soluble quaternized polya ine ion- ene polymer.

DESCRIPTION OF THE INVENTION In this description, except in the claims and the op¬ erating examples or where explicitly otherwise indicated, all numbers describing amounts of ingredients or reaction conditions are to be understood as modified by the word "about" in describing the broadest embodiments of the in- vention. Operation within the exact numerical limits given is generally preferred.

One embodiment of the present invention is a single water based liquid product composition suitable for both flocculating and detackifying paint entrained in water, to produce a sludge that will, to the extent of at least 60% of its total volume, or, with increasing preference, to the extent of 75%, 82 %, or 90% of its total volume, float on the entraining water from which it is flocculated. The water based liquid composition comprises, or preferably consists essentially of, water and an effective amount of a combination of: (A) a component of water soluble and/or dispersible inor¬ ganic polymers of aluminum compounds, optionally in¬ cluding other metal ions, said polymers being prefer¬ ably selected from the group consisting of poly{alumi- num chloride}, poly{aluminum hydroxychloride}, poly- {aluminum hydroxysulfate}, poly{aluminum magnesium hy- droxysulfate}, poly{aluminumhydroxysilicate sulfate}, poly{aluminumhydroxysilicate chloride}, poly{aluminum hydroxysilicate phosphate}, poly{aluminum hydroxy¬ chloride}, poly {aluminum ferric hydroxychloride}, poly{aluminum ferrous hydroxychloride}, poly{aluminum (mixed ferric and ferrous) hydroxychloride}, poly {aluminum hydroxy (mixed sulfate and phosphate)}, poly{aluminum hydroxy (mixed chloride and phosphate)} , poly{aluminum hydroxy (mixed sulfate, chloride, and phosphate)}, poly{aluminum zinc hydroxychloride}, poly{aluminum zinc hydroxy (mixed phosphate and chlor¬ ide}, and poly{aluminum magnesium hydroxychloride}; said polymers being more preferably selected from the group consisting of poly{aluminum hydroxychloride} and poly {aluminum hydroxysilicate sulfate}; said polymers having a molecular weight of at least 1250 and preferably a molecular weight of not more than 30,000; and (B) a component of organic polymers containing cationic quaternized nitrogen atoms that are separated from any atom that is part of the polymer backbone chain by a distancing moiety that contains at least three, or preferably at least four, carbon, nitrogen, and/or oxygen atoms connected in a chain of chemical bonds, one end of the distancing moiety being connected to the cationic nitrogen atom and the opposite end of the distancing moiety being connected to an atom that is part of the polymer backbone chain, said organic poly¬ mers preferably having a molecular weight of at least lxiO⁶, more preferably of at least 5x10 , still more preferably of at least 9xl0⁶; said organic polymers independently preferably having (i) a molecular weight of not more than 1.2X10⁷ and (ii) a polymer backbone chain structure that could be made by polymerizing or copolymerizing monomers selected from the group con¬ sisting of the esters and amides of acrylic and meth- acrylic acids.

As used in the description above, the term "effective amount" for each of components (A) and (B) means an amount such that when the combination is dissolved and/or dis¬ persed at some concentration level in water containing dis- persed entrained paint, detackification and flocculation of the paint to produce a sludge that floats on water to the extent of at least 60 % of its total volume will occur. The concentration of the detackifying and flocculating com¬ position that is needed to achieve this result varies sub- stantially with the conditions of painting, but normally an amount of the active detackifying and flocculating agent, i.e., of the combination of components (A) and (B) as described above (not including any water or other mater¬ ials that may be present in the sources used for the spec- ified ingredients), of between 0.2 grams per liter ("g/L") and 25 g/L of circulating water would be preferable in a typical circulating water scrub system as used in a paint spray booth, with from 1 to 5 g/L even more preferable. These values are for formulations of the detackifying and flocculating agent that contain, as is preferred, from 5 - 40 %, or more preferably from 10 - 20 %, by weight of the total of components (A) and (B) as described above. Preferably, the ratio by weight between component (A) and component (B) is in the range from 12:1 to 1:5, more preferably in the range from 8:1 to 1:1, still more pref¬ erably in the range from 5.8:1 to 3.5:1. All these ratios are based on the specific ingredients as described above, not including any water or other materials that may be present in the sources used for the specified ingredients.

With increasing preference, each of the three organic moieties, other than the distancing moiety, that is at¬ tached to the nitrogen atom in each quaternary nitrogen atom in the polymers used for component (B) as described above has no more than 4, 3, 2, or 1 carbon atoms.

Some suitable and preferred polymers for this inven¬ tion are those in which at least 25 % of the mass, more preferably at least 40 % of the mass, still more preferably at least 80 % of the mass, of the polymer is provided by repeating units conforming to the formula shown below:

In the formula immediately above, R represents a divalent moiety derived by removing two hydrogen atoms from methane, ethane, propane, methyl propane, or butane; or R represents a divalent moiety derived by removing two hydrogen atoms, including the hydrogen atom from the hydroxyl group or one of the hydrogen atoms from the amino group, from methanol or methyl amine, ethanol or ethylamine, 1-propanol or 1- aminopropane, 2-propanol or 2-aminopropane, 2-methyl-l- propanol or 2-methyl-l-aminopropane, 2-methyl-2-propanol or 2-methyl-2-aminopropane, 1-butanol or 1-aminobutane, or 2- butanol or 2-aminobutane; x is an integer from 0 to 10; and X represents an anion, preferably chloride or methylsul- fate. Most preferably, R is ethylene and x is 0. If the polymers contain other types of repeating units that do not contain quaternary nitrogen atoms, such repeating units are preferably those derived from acrylamide. Some polymers of these preferred types are commercially available, and oth¬ ers may be conveniently made by reacting polymers of acryl¬ amide, methacrylamide, and the like with formaldehyde and dialkyl or alkyl alkoxyl amines, then quaternizing by treatment with dimethyl sulfate or methyl chloride.

Preferably, the paint sludge formed by detackification and flocculation according to this invention should be cap¬ able of being easily handled, by a human hand inside a thin latex glove, without sticking. Even more preferably, the sludge should remain non-tacky after being squeezed, rolled, and rubbed between the fingertips while held in such a gloved hand. One reason for the superior perform¬ ance of compositions containing an inorganic aluminum con- taining polymer as required for this invention is that the sludge produced in a process using such a composition can resist more shear without becoming retackified.

Another embodiment of the invention is a process for detackifying and flocculating paint by using a composition according to the invention as noted above, and still another embodiment is a concentrate, from which a composi¬ tion ready for direct use in a detackifying and flocculat¬ ing process as noted above, can be prepared by dilution with water. Optional and preferred additional components for compositions according to the invention include: (C) water soluble inorganic salts of amphoteric, prefer¬ ably polyvalent metals, for example the sulfates, ni¬ trates, and chlorides of aluminum, magnesium, zinc, calcium, and ferric iron, with aluminum and magnesium sulfates being most preferred; the weight ratio of this component to the sum of components (A) and (B) is, with increasing preference, less than 10:1, in the range from 5:1 to 1:2, and in the range from 2:1 to 1.2:1; and (D) water soluble acids or bases as needed to adjust the pH to a desirable value: from 2 to 6, or more prefer¬ ably from 3 to 5. (These pH values refer to the con¬ centrate only; the pH of the circulating water after the concentrate is added in a process according to the invention is preferably from 6.5 to 10, or more pref- erably from 7.5 to 8.5.)

A defoamer may also be used in the compositions according to this invention, but generally is not needed.

In order to increase the efficiency of the detackifi¬ cation and flocculation according to the invention, it is highly preferred to have the paint that is to be detacki¬ fied and flocculated dispersed into fine droplets before or during contact with the detackifying and flocculating com¬ position. It is therefore preferred either to contact the paint to be detackified with a dispersing agent before de- tackifying and flocculating the paint, or to include a dis¬ persing agent in the solution used for detackifying and flocculating. The most preferred dispersing agent for a process or composition according to this invention is an aqueous solution of one or more alkali metal hydroxide such as sodium hydroxide and/or potassium hydroxide; other suit¬ able dispersing agents include water soluble alkali metal and alkaline earth metal silicates, such as sodium sili¬ cate, and some polyacrylics.

The various embodiments of this invention produce sev- eral advantages in operation, compared with the previous¬ ly used methods. The use of polymeric aluminum compounds in combination with cationic polymers significantly in¬ creases the shear stability of the detackified and floccu¬ lated paint sludge, compared with use of cationic polymers alone or with mixtures of cationic polymers and simple aluminum salts. This is important because modern high speed painting requires relatively rapid water circulation in spray booths, and such rapid circulation can cause once detackified paint sludge particles to be sheared to expose fresh, tacky surfaces.

Compared with the use of conventional clay and/or talc based detackifiers, detackification according to this in¬ vention produces far less solid waste per unit volume of paint detackified. While exact values depend upon specific conditions such as the type of paint used, the "absorbent" clay and/or talc detackifiers normally produce detackified sludge volumes of at least five times the volume of the paint detackified. Operation according to this invention generally produces detackified sludge volumes that are no more than twice the volume of paint detackified, and often considerably less. Compared with the use as detackifying and flocculating agents of metal salt and/or metal salt polymers without cationic organic polymers, the practice of the present in¬ vention offers a smaller, but still significant, relative volume advantage even when measured at the stage of wet detackified sludge. This comparative advantage of the present invention can be further increased, because the organic part of the detackifying and flocculating composi¬ tions according to this invention can normally be disposed of by incineration, leaving only a relatively small amount of ash requiring conventional solid waste disposal.

Compared with the use of salts of most other metals, aluminum is regarded as less hazardous, substantially re¬ ducing the cost of waste disposal.

The sludge texture produced by the preferred embodi- ments of the present invention is as easily handled as that obtained now with conventional clay and/or talc based de¬ tackifiers or with conventional polymer salt detackifiers, in either case combined with conventional flocculating agents, which are generally regarded as the best products available for present commercial use with respect to ease of handling the sludge produced. As already noted above, however, compositions according to the present invention produce significantly less volume of both wet detackified sludge and dry solid waste derived from this sludge per unit volume of paint detackified.

Compositions according to the present invention can readily be formulated without requiring special care in diluting and/or mixing with any other materials that may be used and do not require any special storage conditions or mixing conditions, unlike most current commercial floccu- lants. The results achieved, however, are as good as those normally now achieved with a combination of the best of commercial flocculants and detackifiers now available sepa¬ rately.

In addition to all their other advantages, the pre¬ ferred components of a detackifying and flocculating agent according to this invention often are less expensive than other materials conventionally used for the purpose.

The practice of the invention can be further appre¬ ciated with the help of the following working examples and comparison example.

Examples 1 - 5 and Comparison Example

The following components were used to prepare the detackifying and flocculating compositions of these ex¬ amples, and/or as auxiliary materials for the process em¬ bodiments of the examples: PAC-10 M, CAS Registry No.1327-41-9, is an aqueous solution of basic poly{aluminum chloride}, with an average molecular weight of about 217, 32 - 34 w/o total solids and 5.3 - 5.8 w/o aluminum, with no more than 3 w/o sulfate. (This product is commercially available from Pine River Group, Detroit, Michigan.)

PASS is an acronym for a poly{aluminum silicate sulfate} solution in water containing about 33 w/o of polymer (8.3 w/o stoichiometric equivalent of alum¬ ina) . It is available commercially from Pine River Group, Detroit, Michigan. "50 % Liquid Alum" is an aqueous solution containing 48.5 % by weight of A1₂(S0₄)₃.

HYPERFLOC™ CP-708, CP-712, and CP-713 are all white, free-flowing, granular powdered solid materials prepared by quaternizing, by treatment with dimethyl sulfate, homopolymers of dimethylaminoethyl methacry¬ late or copolymers of dimethylaminoethyl methacrylate and acrylamide. The mole % of the dimethylaminoethyl methacrylate (out of the total of this monomer and acrylamide) in the polymers is from 40 - 50 % for CP- 708, 80 - 90 % for CP-712, and 100 % for CP-713, and their average molecular weights are about 10, 9, and 6 million respectively. These polymers are commerci¬ ally available from hychem incorporated, 10014 North Dale Mabry Highway, Tampa, Florida.

MAGNIFLOC 486 C is a generally similar materi- al to the HYPERFLOC polymers described immediately above, except that it is quaternized with methyl chloride instead of dimethyl sulfate. It has a con- centration of quaternary nitrogen atoms intermediate between that of CP-708 and CP-712 and a molecular weight of about 9 million. It was supplied by Amer¬ ican Cyanamid Co.

"Dispersant 1" is a basic aqueous solution con- taining about 13 w/o of sodium hydroxide and about 38 w/o of sodium aluminate.

"Dispersant 2" is an aqueous solution containing about 10 % by weight of sodium hydroxide and about

13.5 % by weight of potassium hydroxide.

The following concentrate compositions according e invention were prepared:

Composition 1

Ingredient Parts by weight

PAC-10™ 140 HYPERFLOC™ CP-713 10 Aluminum sulfate, technical powder 220 Sulfuric acid (66° Baume) 10 Zinc oxide 10 Water 610

Composition 2

Ingredient Parts bv weight

PAC-10™ 150

HYPERFLOC™ CP-712 10

Aluminum sulfate, technical powder 180

Sulfuric acid (66° Baume) 17

Magnesium oxide 11

Water 632

Composition 3 Ingredient Parts by weight

PAC-10™ 150

HYPERFLOC™ CP-708 10

50 % liquid alum 362

_Sulfuric acid (66° Baume) 17

Magnesium oxide 11

Water 450

Composition 5

Ingredient Parts by weight

PAC-10™ 150

HYPERFLOC™ CP-712 10 50 % liquid alum 362

Sulfuric acid (66° Baume) 17

Magnesium oxide 11

Water 450

The composition for the comparative example was as follows:

Composition CE1

Ingredient Parts by weight

Fine talc 396

Ethylene glycol 108 Non-ionic dispersant 2

Water 494

The composition for the comparison example was pre¬ pared by the methods known in the art. All the composi¬ tions according to the invention were mixed by adding the water first to a mechanically stirred vessel, then adding the remaining ingredients slowly with constant stirring, with sufficient intervals between ingredients to allow the mixture to become clear. Ingredients were added to the initial charge of water in the following order: acid, metal oxide(s), inorganic salt(s) , inorganic polymer(s), organic polymer(s) .

Acid is usually used in these compositions to control the pH of the product. Either acid or base, more often the latter, is usually also added to control the pH of the cir- culating water during prolonged operation of a detackify¬ ing and flocculating process according to this invention.

The compositions above were tested in a pilot scale spray booth apparatus. This uses 1041 liters of water in addition to all the other components shown below. The a- terials, other than paint, shown under the description of specific experiment numbers below are metered into the cir¬ culating water of this spray booth while paint is being sprayed into it in a consistent manner that approximates very closely the practical use of a full scale spray booth. The resulting solid sludge is collected and separated by means conventional for practical spray booths and is avail¬ able for conventional chemical analysis, with some results of such analysis shown in Table 1. Some characteristics of the composition of the treated circulating water are shown in Table 2. The experiment numbers in Table 2 refer to use of the same compositions as for the same experiment number in Table 1, and the abbreviation "nd" has the same meaning in Table 2 as in Table 1.

Table 1

MATERIALS FOR EXPERIMENTS 1 - 5 AND COMPARATIVE EXPERIMENT 1

Notes for Table 1

A simple number in this column refers to the composi¬ tion number above. A number prefixed by "CE" refers to the comparison example composition.

2 This is short for "Dispersant 1 as described above. 3 This analysis was for zinc rather than aluminum.

4 nd ^*■^*** not determined Table 2

ANALYSIS OF WATER TREATED IN EXPERIMENTS 1 - 5 AND COMPARATIVE EXPERIMENT 1

Experiment Parts per Million by Weight in the Water of: Numbe ot Solids ϋndissolved Solid s luminum

12

68

25 50

10 700

The same apparatus and general operating conditions as for examples 1 - 5 were used. The pH of the circulating water was first adjusted to a value of 8 by addition of Dispersant 1 as described above. In the first part of this example, the paint used was JI Case Red Baking Enamel. Composition 2 as described above was fed into the header and the chemical port of the apparatus at approximately equal rates to yield a total of about one-third of the volume of the paint being sprayed simultaneously into the booth. This produced a condition known in the art as "overkill", meaning that the flocculated sludge that floated on the surface contained a considerable amount of entrained liquid, so that its texture was "muddy" rather than nearly dry as is most desirable. Accordingly, the feed of detackifying and flocculating composition was dis- continued at the header port but continued at the chemical port, to give a volume ratio of about 1:6 for the detack¬ ifying and flocculating composition according to this in¬ vention as compared to the paint sprayed. These operating conditions produced a slightly wet sludge which dried very well within 24 hours after forming, and the circulating water after treatment appeared entirely clear visually.

In a second part of the experiment, Fisher Scientific White Enamel was used as the paint, and for fifteen minutes of operation, no detackifying or flocculating chemical was added. After than time, addition of Composition 2 as de¬ scribed above began at a volume ratio of 1:5 for Composi¬ tion 2 to paint, with feeding only into the chemical port. Again, slightly wet sludge was produced, and other operat¬ ing conditions were excellent.

During the total example, about 2800 grams of both kinds of paint, 100 ml of Dispersant 1, and 520 ml of Composition 2 were used. Undesirable dispersion of paint in the booth circulating water was not observed at any time; it was impossible to sink the sludge floating in the booth, even after allowing it to sit undisturbed for 48 hours; after circulation of water was discontinued, any paint that had been entrained in the water immediately floated to the surface; and the sludge on the filter media in the circulating pipework dried completely after 24 hours. All of these are favorable operating characteris¬ tics in practical spray painting operations. Example 7 In this example, the same equipment as in the previous examples was used, but with a wider variety of paints and paint:detackifying and flocculating composition ratios. Also, Dispersant 2 rather than Dispersant 1 was used as the dispersing agent and also for pH control. The paints used were:

7.1 Armitage FZ-21200A, a high solids polyester paint from the Crown Division, Wooster, Ohio;

7.2 JI Case Red Baking Enamel (as in Example 6);

7.3 JI Case Red Epoxy Primer; and 7.4 Akzo Red Enamel.

With each paint, the feed ratios were varied until a satisfactory value was found as follows: For paint 7.1, a ratio of paint to Composition 2 of 5.3:1, with pH main¬ tained between 8.2 and 8.5 was best; for paint 7.2, a vol- ume ratio of paint to Composition 2 of 3.4:1 and a ratio of Composition 2 to 10 % aqueous sodium hydroxide solution of about 2:1.gave the best results obtained; for paint 7.3, amounts of 160 milliliters (hereinafter "mL") of Composi¬ tion 2 and 110 mL of 10 % aqueous sodium hydroxide solution for 1300 grams (hereinafter "g") of paint were best; and for paint 7.4, amounts of 270 mL of Composition 2, 340 mL of base, and 1555 g of paint gave satisfactory results, al¬ though slightly more of the detackifying and flocculating composition and less base than this would be expected to give even better results.

What is claimed is:

Claims

CLAIM?

1. A liquid composition of matter, consisting essentially of water and an effective amount of:

(A) a component selected from the group of water soluble and water dispersible inorganic polymers of aluminum compounds, having an average molecular weight of at least about 1250; and

(B) a component selected from the group of water soluble and water dispersible organic polymers containing cationic quaternized nitrogen atoms that are separat¬ ed from the polymer backbone chain by a distancing moiety, said organic polymers having an average molecular weight of at least about lxlO⁶; and, optionally (C) water soluble inorganic salts of amphoteric polyvalent metals; and, optionally, (D) water soluble acids and bases not part of components (A), (B), and (C).

2. A composition according to claim 1, wherein component (A) is selected from poly{aluminum chloride}, poly{alumi- num hydroxychloride}, poly{aluminum hydroxysulfate}, poly {aluminum magnesium hydroxysulfate}, poly{aluminum hydrox¬ ysilicate sulfate}, poly {aluminum hydroxysilicate chlor¬ ide}, poly{aluminum hydroxysilicate phosphate}, poly{alum- inu hydroxychloride}, poly{aluminum ferric hydroxychlor¬ ide}, poly{aluminum ferrous hydroxychloride}, poly{aluminum (mixed ferric and ferrous) hydroxychloride}, poly {aluminum hydroxy(mixed sulfate and phosphate)}, poly{aluminum hy¬ droxy (mixed chloride and phosphate)}, poly{aluminum hy- droxy (mixed sulfate, chloride, and phosphate) }, poly{alum- inum zinc hydroxychloride}, poly{aluminum zinc hydroxy (mixed phosphate and chloride}, and poly{aluminum magnesium hydroxychloride}; and wherein the ratio by weight between component (A) and component (B) is in the range from 12:1 to 1:5.

3. A composition according to claim 2, wherein component

(A) is selected from the group consisting of poly{aluminum hydroxychloride} and poly {aluminum hydroxysilicate sul- fate} and the ratio by weight between component (A) and component (B) is in the range from about 8:1 to 1:1.

4. A composition according to claim 3, wherein component

(B) is selected from the group consisting of polymers in which at least 50 % of the mass of the polymer is provided by repeating units conforming to the formula:

wherein R represents a divalent moiety derived by removing two hydrogen atoms from methane, ethane, propane, methyl propane, or butane; or R represents a divalent moiety de¬ rived by removing two hydrogen atoms, including the hydro¬ gen atom from the hydroxy1 group or one of the hydrogen atoms from the amino group, from methanol or methyl amine, ethanol or ethylamine, 1-propanol or 1-aminopropane, 2- propanol or 2-aminopropane, 2-methyl-l-propanol or 2- methyl-1-aminopropane, 2-methyl-2-propanol or 2-methyl-2- aminopropane, 1-butanol or 1-aminobutane, or 2-butanol or 2-aminobutane; x is an integer from 0 to 10; and X repre¬ sents an anion.

5. A composition according to claim 2, wherein component (B) is selected from the group consisting of polymers in which at least 25 % of the mass of the polymer is provided by repeating units conforming to the formula:

wherein R represents a divalent moiety derived by removing two hydrogen atoms from methane, ethane, propane, methyl propane, or butane; or R represents a divalent moiety de¬ rived by removing two hydrogen atoms, including the hydro¬ gen atom from the hydroxyl group or one of the hydrogen atoms from the amino group, from methanol or methyl amine, ethanol or ethylamine, 1-propanol or 1-aminopropane, 2- propanol or 2-aminopropane, 2-methyl-l-propanol or 2- methyl-1-aminopropane, 2-methyl-2-propanol or 2-methyl-2- a inopropane, 1-butanol or 1-aminobutane, or 2-butanol or 2-aminobutane; x is an integer from 0 to 10; and X repre¬ sents an anion.

6. A composition according to claim 1, wherein component (B) is selected from the group consisting of polymers in which at least 25 % of the mass of the polymer is provided by repeating units conforming to the formula:

7. A composition according to claim 6, wherein component (B) is selected from polymers having a structure that could be made by quaternizing with methyl chloride or dimethyl sulfate a homopolymer of dimethylaminoethyl methacrylate or a copolymer of dimethylaminoethyl methacrylate and acrylamide that contains at least 40 mole percent of di¬ methylaminoethyl methacrylate.

8. A composition according to claim 5, wherein component (B) is selected from polymers having a structure that could be made by quaternizing with methyl chloride or dimethyl sulfate a homopolymer of dimethylaminoethyl methacrylate or a copolymer of dimethylaminoethyl methacrylate and acrylamide that contains at least 40 mole percent of di¬ methylaminoethyl methacrylate.

9. A composition according to claim 4, wherein component (B) is selected from polymers having a structure that could be made by quaternizing with methyl chloride or dimethyl sulfate a homopolymer of dimethylaminoethyl methacrylate or a copolymer of dimethylaminoethyl methacrylate and acrylamide that contains at least 80 mole percent of di¬ methylaminoethyl methacrylate.

10. A composition according to claim 9, wherein the ratio by weight between component (A) and component (B) is in the range from 5.8:1 to 3.5:1 and the ratio by weight of com¬ ponent (C) to the total of components (A) and (B) is in the range from 2:1 to 1.2:1.

11. A composition according to claim 8, wherein the ratio by weight between component (A) and component (B) is in the range from 5.8:1 to 3.5:1 and the ratio by weight of com¬ ponent (C) to the total of components (A) and (B) is in the range from 2:1 to 1.2:1.

12. A composition according to claim 7, wherein the ratio by weight between component (A) and component (B) is in the range from 5.8:1 to 3.5:1 and the ratio by weight of com¬ ponent (C) to the total of components (A) and (B) is in the range from 2:1 to 1.2:1.

13. A process comprising steps of (I) detackifying and flocculating paint entrained in a circulating water based liquid to produce a flocculated sludge that will, to the extent of at least 60 % of its total volume, float on the surface of the water based liquid, (II) separating detack¬ ified and flocculated paint solids from residual water based liquid, and (III) using the residual water based liquid to entrain additional paint, wherein the improve¬ ment comprises adding to the circulating water based liquid containing entrained paint a liquid composition that con¬ sists essentially of water and:

(B) a component selected from the group of water soluble and water dispersible organic polymers containing cationic quaternized nitrogen atoms that are separat¬ ed from the polymer backbone chain by a distancing moiety, said organic polymers having an average molecular weight of at least about ixiO⁶; and, optionally

(C) water soluble inorganic salts of amphoteric polyvalent metals; and, optionally, (D) water soluble acids and bases not part of components (A), (B), and (C).

14. A process according to claim 13, wherein, in the li¬ quid composition, component (A) is selected from the group consisting of poly{aluminum hydroxychloride} and poly- {aluminum hydroxysilicate sulfate} and the ratio by weight between component (A) and component (B) is in the range from about 8:1 to 1:1.

15. A process according to claim 14, wherein, in the li¬ quid composition, component (B) is selected from the group consisting of polymers in which at least 50 % of the mass of the polymer is provided by repeating units conforming to the formula:

wherein R represents a divalent moiety derived by removing two hydrogen atoms from methane, ethane, propane, methyl propane, or butane; or R represents a divalent moiety de¬ rived by removing two hydrogen atoms, including the hydro¬ gen atom from the hydroxyl group or one of the hydrogen atoms from the a ino group, from methanol or methyl amine, ethanol or ethylamine, 1-propanol or 1-aminopropane, 2- propanol or 2-aminopropane, 2-methyl-1-propanol or 2- methyl-1-aminopropane, 2-methyl-2-propanol or 2-methyl-2- a inopropane, 1-butanol or l-aminobutane, or 2-butanol or 2-aminobutane; x is an integer from 0 to 10; and X repre¬ sents an anion.

16. A process according to claim 13, wherein, in the li¬ quid composition, component (B) is selected from the group consisting of polymers in which at least 50 % of the mass of the polymer is provided by repeating units conforming to the formula:

wherein R represents a divalent moiety derived by removing two hydrogen atoms from methane, ethane, propane, methyl propane, or butane; or R represents a divalent moiety de¬ rived by removing two hydrogen atoms, including the hydro¬ gen atom from the hydroxyl group or one of the hydrogen atoms from the amino group, from methanol or methyl amine, ethanol or ethylamine, 1-propanol or 1-aminopropane, 2- propanol or 2-aminopropane, 2-methyl-l-propanol or 2- methyl-1-aminopropane, 2-methyl-2-propanol or 2-methyl-2- aminopropane, 1-butanol or 1-aminobutane, or 2-butanol or 2-aminobutane; x is an integer from 0 to 10; and X repre¬ sents an anion.

17. A process according to claim 16, wherein, in the li¬ quid composition, component (B) is selected from polymers having a structure that could be made by quaternizing with methyl chloride or dimethyl sulfate a homopolymer of di¬ methylaminoethyl methacrylate or a copolymer of dimethyl¬ aminoethyl methacrylate and acrylamide that contains at least 80 mole percent of dimethylaminoethyl methacrylate.

18. A process according to claim 15, wherein, in the li¬ quid composition, component (B) is selected from polymers having a structure that could be made by quaternizing with methyl chloride or dimethyl sulfate a homopolymer of di- methylaminoethyl methacrylate or a copolymer of dimethyl¬ aminoethyl methacrylate and acrylamide that contains at least 80 mole percent of dimethylaminoethyl methacrylate.

19. A process according to claim 18, wherein, in the li¬ quid composition, the ratio by weight between component (A) and component (B) is in the range from 5.8:1 to 3.5:1, the ratio by weight of component (C) to the total of components

(A) and (B) is in the range from 2:1 to 1.2:1, and the pH of the circulating water based liquid is maintained during the process in the range from about 7.5 to about 8.5.

20. A process according to claim 17, wherein the ratio by weight between component (A) and component (B) is in the range from 5.8:1 to 3.5:1, the ratio by weight of compon¬ ent (C) to the total of components (A) and (B) is in the range from 2:1 to 1.2:1, and the pH of the circulating wat- er based liquid is maintained during the process in the range from about 7.5 to about 8.5.