DE3831421C2 - A composition for treating waste water containing paint and varnish and process for their preparation - Google Patents

Description

The invention relates to a composition for detackification and clarifying acidic and alkaline paint and varnish-containing Wastewater and waste from paint spray booths as well a process for producing such compositions.

Industrial wastewater as well as waste water-based and Colors from industrial processes, such as the electrophoretic deposition of color and color Work in spray booths can pose serious problems cause pollution. Water-based paints and waste water, which is used as an aqueous carrier with paint or varnish Remains to be drained significantly increase the chemical Oxygen demand (COD). such Remains of paint and varnish are caused by aging or chemi modification and become sticky or hard. This has the consequence that pipes and equipment clogged. Such blockages are extremely difficult to remove.

In addition to the disclosed in US 49 02 779 Stand the Technique are the following patents of the prior art in connection with the subject of the present application dung.

US 40 67 806 discloses a method for detackifying waste water from paint and spray booths using amphoteric salts such as zinc chloride, etc., and a graft terpolymer based on diallyldimethyl ammonium halide / N-vinylpyrrolidone / acrylamide. The together However, they have the enormous disadvantage that they use amphoteric salts such as ZnCl₂, the zinc hydroxide form only at a high pH of 10 to 10.5. below half and above this pH range is the zinc hydroxide soluble again, if ever flakes bil the. On the other hand, the zinc hydroxide is very flaky and in stable and absorbs large amounts of water. This does the Products very unsafe for this type of application. The Ab Water and sludge are alkaline and can not live without it be drained further treatment. This makes such Procedures uneconomical. In addition, among the in the patent described the amphoteric salt (ZnCl₂) easily according to the subsequent reaction in inactive Anions, such as (ZnCl₃) are converted:

This lowers the efficiency of treatment procedures and / or removal of anodic or cathodic paints, lacquers, as in US 4,759,855, US 4,637,824 and in US 4,055,495.

From EP 0 293 129 a method for Treatment of wastewater is known at relatively low pH values (up to pH = 7.5) is working. There are Ca (CO₃) carbonates to Adjusting the pH value used, leading to a high water content of the resulting Sludge leads.

From JP 50150683 A it is known that quaternized polyamides have a positive effect on the Flocculation rate of with polyamides treated wastewater.

US 39 90 986 teaches as the above Patent US 40 67 806 the detackification of colors  and paints using amphoteric salts such as ZnCl₂ or a Mi Such salts with alkanolamines and / or aliphati amino alcohols. The procedure according to this Pa tent is subject to the same negative aspects as the steps described in the Mauceri patent. It is about it It should also be noted that the conditions of the Ent An insufficient amount for an honest test Insert paint (0.5 ml / 500 ml water). The selected Product, namely polyalkylene oxide of molecular weight (Mw) of 200 has a low glass transition temperature (glass transaction temperature, Tg). This makes the reaction hydrophilic, resulting in a very unsafe flocculation result Has. As a result, the dye can only partially harmless be made.

According to US 44 01 574 is in Ab water, based on the color such as a color a polyvinyl acetate latex or a paint on vinyl acrylic contains acidic base, polyaluminum chloride (PAC) used. The polyaluminum chloride (PAC) alone or in admixture with normal aluminum and / or iron salts (chlorides, Sul faten) is completely ineffective in the treatment of wastewater of airborne paints and varnishes. Even with waste water of normal colors, the water is not clear, but with 35 NTU still cloudy.

US 41 82 839 discloses a method for Her tion of a cationic, water-soluble resin Base melamine / formaldehyde / alkyl and / or alkanolamine / chlorine hydrogen acid. The resulting products are in The paper industry used to be paper resistant against moisture or in a moist environment ver lend.

US 36 45 841 discloses a Process for the preparation of cationic quaternized resins by reacting a mixture of melamine, formaldehyde and Dimethyl sulfate. The products are also used in the paper industry.

Electrophoretic colors consist of an organic sub strat on which ionic charges were applied. today On the market, colors become anodic electri separation or formulations for cathodic deposition offered. For more than 20 years, the Ver way in it, a chemical coagulant, näm either iron (III) salts or aluminum salts, under Control of the pH value to add and thereby in the water to form distributed oxide flakes to which the color particles ad can be sorbed. Anodic dyes become sticky, when they get into acidic solutions, and cathodic color Materials become sticky if they are in an alkaline environment guess. In the production of exterior paint coatings on Car bodies are made of primer from an im Electro-process applied solvent-based paint Formulated colors applied by spraying. It follows Curing step. The spraying of the paint is in one Chamber with a trigger system carried out to surpluses remove the paint applied with compressed air. The ge velvet peeled material passes a curtain of what circulated and paint and solvents tel absorbed. Paint and solvent must be from the Water should be removed before the wastewater returns to the Process cycle is introduced.

The most widely used colors come in two groups divided:

• a) applied in spray booths colors, such as thermosetting Acrylic-based clear topcoat, thermosetting one Acrylic based stain paints, thermoplastic acrylic paints and stoving alkyd resins,
• b) electrophoretically applied colors, such as anodic Acrylic based paints, epoxy based cathodic paints and anodic polybutadiene based paints.

Other paint systems that are also used can, are:

• 1. Epoxy-based systems, such as prepolymerized Epoxy resins and crosslinked copolymers on amide Epoxy-based;
• 2. styrene crosslinked alkyd resins;
• 3. drying oils;
• 4. phenolic resins;
• 5. Harnstoffalkydharze;
• 6. urea-melamine resins; and
• 7. silicone resins.

The commonly used treatment system is in a controlled manner, the coagulants below the same early control of the pH value. The coagulier The masses are then released by air flotation, electroflot tion or sedimentation, keeping the slurry in one Sedimentation tank and filter presses removed. In the case of the air flotation, it is still a goal, complete chemical Flocculation with good effectiveness produce. The conventional iron (III) - or aluminum sulfates are to a set to render the color harmless, even though it is in white scope in coagulation procedures. The problems the elimination of industrial wastewater and paint Water based with the inorganic-organic or organic alloy polymer adducts were treated, have a strong effect on coagulation processes. The Alloy polymer adducts mentioned serve as primary Coagulants, which under neutral process conditions, preferred when it comes to hydrophobic compositions act, flocculate and kill the color (kill). Good performances were achieved by operating at a pH Value from 6.0 to 9.0 for anodic and cathodic deposition achieves bare colors. There was a high degree of clarity of the Supernatant and high settling velocities or Ent wässerungsgeschwindigkeiten. For adjusting the pH can be any reagents or alkaline inorganic or organic compounds are used. before zugt are hydrophobic alkaline agents. For the production hydrophobic  Alkaline materials can be the following Substances are used:

• a) any inorganic or organic alkaline Substances, such as NaOH, KOH, Ca (OH) ₂, sodium aluminate, potassium aluminate, sodium zincate, sodium silicate or metasilicate, sodium borate, alkylamines, Alka nolamine or mixtures of these compounds in combi nation with hydrophobic materials;
• b) (co) polymers, surfactants (preferably nonionic and / or or anionic or mixtures of these surfactants with Proportions of the components in the range of 0.5% by weight 95.5% by weight - 0.5% by weight). The most preferred hydrophobic products are (co) polymers, for example Copolymers of ethylene alkyl or vinyl or Vinyl latex type as ethylenically unsaturated building blocks, Styrollatex, styrene-divinylbenzene latex, optionally modified styrene-butadiene latex, styrene-acrylates or acrylic latex, acrylates and / or copolymers natural polymers;
• c) hydroxyalkyl (poly) carboxylic acid salts or the ent speaking acids, such as sodium gluconate, Sodium heptanoate, salts of modified natural (Co) - Polymers, rosin acid sodium salts, sodium derivatives of Glucosides or other cation combinations, with organic or organic groups, including cationic group modifiers clay and bento nit;
• d) other products can be used in any ger form as inorganic or organic alkali some of the strip assets including those of the haloge type or in combination with the used under a), b) or c) products become.

For the procedures under Luftflotation or Elektroflota tion is widely used NaOH, and in some cases Both hydrophobic agents arise, as well as less dense and easily floatable flakes. To treat anodic of separable colors, it is possible, the aqueous phase alkali metered in before the coagulant is added. In this case, one approaches the final pH of the higher pH values ago.

The choice of polyelectrolytes is also very important. These must have very high molecular weights (Mw). in the Case of treatment of waste water the use of colors water-based improved the dosage of less than 1.0 ppm often the clarity of the supernatant and increased the Speed of the settling process. Higher concentrations can cause voluminous, open-structured Flakes arise.

Treatment of wastewater with selected inorganic organic alloy polymer adducts or organic Alloy polymer adducts in combination with hydrophobic alkaline substances or alkaline substances leads to De naturierung of the surface or the dispersed substances and for denaturing the semi-dispersed colored beads. These Treatment is sufficient to the color beads relatively unkleb to keep rig. It is also possible, the pebbles from the surface of the treatment solution into filter bags skim. The use of selected products resulting sludges have a low water content and can be dewatered much faster than sludges with Any known from the prior art combination erhal had been. The clarified procedure can then in the Spray booth be returned.

If necessary, the polyelectrolyte is in Einheitli way and at one or more distribution points added with gentle stirring. Because the water is high Contains electrolyte content, the flocculation runs process is not completely off most of the time. Therefore If several addition points should be selected. In many cases can be found that the flocculation only part wisely expires and the rest of the electrolyte in a ver Thick material converts, very rubbery and sticky produces flocks.

On the other hand, when using calcium or magnesium hydroxide, the materials of the resulting flocculation are more compact and the sludge settles more easily. NaOH is the compound of choice for producing less dense and more easily floated flakes. It has been found that when using Al ³⁺ or Fe ³⁺ , either as chloride or as sulfate or else as a mixture of the salts of both anions, a customary coagulant can in no case afford satisfactory results. The formed flocculation is sticky, not to eliminate, voluminous and leads to turbidity of the water. Most of the systems proposed to date use very high pH values, for example pH values in the range of 10 to 14. US 39 90 986 even proposes a dosage with amounts up to 100,000 ppm. Any system that results after treatment at such a high pH and with amphoteric salts leads to other problems requiring additional treatment of both the sludge and the effluent. The alkaline sludge can not be diffused or ignited. In addition, water containing large amounts of alkali and suspended matter can not be drained. In contrast to existing technologies, the selected organic-inorganic alloy polymer compositions or organic alloy polymer compositions require a much lower dose of the respective substances for the treatment, namely 5 to 7000 ppm, depending on the nature of the color. When treating a mixture of individual colors, the normal pH of 7 to 9 is sufficient for efficient treatment. The products are non-corrosive and the precipitated color flakes can easily be handled by other common industrial process steps. Of the products mentioned, the most valuable are the quaternary ammonium polymers which can be prepared by the following process steps:

• 1. Quaternization of a monomeric compound, for example example of a vinyl monomer or an epoxide and after following polymerization;
• 2. Quaternization of the tertiary amine with a haloge nated polymer;  
• 3. spontaneous one-step polymerization of the unsaturated tertiary amine (eg of vinylpyridine) with alkylating resources;
• 4. Quaternization of the polyamine with an alkyl halide;
• 5. Polymerization of the tertiary diamine with an alkylene dichloride to form polyions or polymerization a chloroalkyl-substituted tertiary amine below Formation of polyions;
• 6. after reaction of the suitably reactive functional groups containing polymers with quaternary ammonium compound fertilize.

The inorganic-organic polymer adducts are multianio NEN. In these, an ion with a single charge, for example, (Cl) ^- or 1/2 (SO₄) ^{2- be} replaced by an anion system with a polyvalent metal, with more active flocculation and / or coagulants are formed. For example, when an inorganic polymer adduct such as aluminum hydroxysulfate is added with polydiallyldimethylammonium chloride, the chloride anion (Cl) ^{- is} replaced by the complex anion. This happens according to the following reaction sequence:

In the preceding equation, the dissociation constant is (Kd) greater than the association constant (Ka):

In the above formula R₁ and R₂ is hydrogen, methyl and ethyl groups. R₃ and R₄ are each alkyl groups, alkoxyalkyl groups and hydroxyalkyl groups having 1 to 8 carbon atoms. Y ^- stands for an anion and an anion of two complexes. Examples of Y ^- are methosulfate, ethosulfate, chloride, bromide and iodide.

The synthesis can be carried out at temperatures in the Range from room temperature (RT) to 175 ° C and at pressures in the range of normal pressure to 0.02 to 2.5 MPa. Some one Details of the preparation of these complexes are described in US Re 34,486, filed March 21, 1986. The subject of this application is by reference to this Registered in the present application.

The products according to the invention are based on inorganic organic polymer alloy adducts, compositions from inorganic-organic polymer alloy adducts, Surfactants or humectants or compositions organic polymer alloy adducts, surfactants or Moisturizers and are highly effective, highly effective products for the treatment of any wastewater waterborne waste, including paints and varnishes Paints. The inorganic-organic polymer alloy adduct te can be produced in high yield and have a viscosity below 20 Pa.s (20,000 cps) as aqueous Solution with or without special humectants or Ten side, for example alcohols, hydroxy alcohols, glycols, Polyglycols, aprotic solvents, such as dimethyl sulfoxide, Ketones, lactones, alkyl and alkoxyalkyl phosphonates or polyphosphonates (called humectants), Salts, such as sodium hydrogen sulfate, ammonium and sodium citrate, the amount ranging from 0 to 45% by weight can be changed. The most useful Surfactants for the present application are:

I anionic surfactants II nonionic surfactants III cationic surfactants IV zwitterionic surfactants V N-Laurylsarcosid VI linear alkyl benzene sulfonate VII higher alkylbenzenesulfonate VIII linear sulfonate IX petroleum sulfonate X N-aryl-N-alkyllaurat XI Paraffin sulphonate (SAS) XII L-Olefinsulfonates (AOS) XIII alkylnaphthalene XV sulfated linear alkyl alcohols XVI sulfated polyethylene oxide-substituted straight-chain alcohols XVII Sulf (on) ized oils XVIII Phosphoric acid and polyphosphoric acid, their esters, polyoxyacids, disubstituted phosphonates in monomeric or polymeric form XIX quaternary ammonium salts XX amine oxides XXI polyethylene oxide-substituted long-chain amines and their quaternized derivatives XXII polyethylene oxide-substituted straight-chain alcohols, alcohol ethoxylate, XXIII Ethylene oxide derivatives of sulfated linear alkyl alcohols (having from 1 to 60 EO groups) XXIV sulfated polyethylene oxide substituted straight-chain alcohols XXV Sulf (on) iert oils and their mixtures XXVI Esters of phosphoric acid and polyphosphoric acid with phosphonic disubstituted polyalkyloxy acids in monomeric or polymeric form XXVII quaternary ammonium salts, N-alkyltrimethylammonium chloride, N, N-dialkyldimethylammonium chloride, benzylmonoalkylammonium chloride or dialkylammonium chloride or trialkylammonium chloride XXVIII Amine oxide copolymers XXIX polyethylene oxide-substituted long-chain amines and their quaternized derivatives XXX polyethylene oxide substituted polyoxypropylene glycol XXXI polyethylene oxide substituted mercaptans XXXII quaternary ammonium benzosulfamides XXXIII Ethoxylates of oligosaccharides XXXIV Mixtures of anionic and nonionic surfactants in the range of 0.5 to 95 wt .-% or of cationic and nonionic surfactants in the range of 0.505 to 95 wt .-% and / or anionic, cationic or nonionic surfactants in the range of 0.5 to 99.5 wt .-%.

The products are stable, can be produced at low cost and contribute to a large extent to the problems of Ver Pollution of the water and the air, by the color fabric, car, chemical and furniture industries are caused, to eliminate.

The chemical compositions according to the invention are inorganic-organic polymer alloys or together or organic alloy polymer adducts Compositions for the treatment of wastes on what serbasis and of paint colors. The compositions have the Formula according to the above description:

The components will be described in detail below.

Component A

The new (co) polymer alloy of inorganic polymers (A) is by one of the following general  Formulas I (a) to I (g) define:

[{(SiO₂ / Me ^I ₂O) _{u} s} Me Me _m ^II _n ^III (OH) _p (SO₄) _y (Aci) _{(2m + 3n) -p-2y] r} I (a)

In this formula, the ratio SiO₂ / Me ^I ₂O with u be distinguished and is in the range of 1.5 to 3.5. Me ^I is Na, K, Li or Cs;
SiO₂ represents sodium silicate, sodium metasilicate or mixtures thereof;
r indicates an amount of 0 to 98%. s indicates an amount of 0 to 10%;
Me ^II is a divalent cation from the group Mg ²⁺ , Zn ²⁺ , Ca ²⁺ and Fe ²⁺ , and m is a number in the range of 0 to 5;
Me ^III is a tri- or polyvalent metal ion, preferably Fe ³⁺ , Al ³⁺ or complexes of Al and Zr, and n is a number in the range of 1 to 20;
Aci is selected from monovalent anionic groups such as (a) Cl ^- , (b) Br ^- , (c) I ^- , (d) NO₃ ^- , (e) CH₃COO ^- , (f) H₂PO₄ ^- , or (g) a mixture of two or more of the above-mentioned anions. Preferably Aci is Cl.

These products can be produced by a variety of methods as set forth in US patent application Ser No. 6 46 012, which was incorporated on 31 August 1984 was enough.

Al _m (OH) _n X _3m-n-2k (SO₄) _k (I (b))

wherein X is sodium or potassium aluminate and k, m and n are positive numbers.

Al _1-x Fe _x ^III Fe _y ^II (OH) _{3 + 2y-2} (Al) Hal _z (I (c))

wherein Hal represents chlorine, bromine, iodine or a mixture of these atoms.
(x + y) / (1-x) has a value of about 0.2 to 1.5,
z has the value 3 + 2y and
(3 + 2y-2) / (3 + 2y) has a value of about 0.24 to 0.67.

Al _m (OH) _x (SO 4) _y (H 2 PO 4) _z (I (d))

where the sum of x + 2y + 2 is 3,
m and x are positive integers,
y is 0 or a positive integer and
z is 0 or a positive integer.

Me _n (OH) _m X _3n-m (I (e))

where m and n are positive integers,
Me _{n is} a trivalent or polyvalent metal and
X is Cl ^- , CH₃COO ^- or NO₃ ^- means.

I (f): Normal salts of aluminum, iron, titanium, Vana dium, chromium or antimony, for example chlorides, Sulfates, phosphates, nitrates, acetates or their mixtures, Sodium or potassium silicate, magnesium or Calcium silicate, aluminum magnesium silicate, sodium meta silicate, bentonite and / or cationic modified bentonite Bentonite modified with organic cationic groups or mixtures thereof.

The term "inorganic polymer adducts" as used in the This description includes the following Compounds, without any limitation:

• 1. polyhydroxyaluminum; Al₄ (OH) ₉ (Cl) ₃ or Al₈ (OH) ₂ (Cl) ₃ or Al₁₁ (H) ₃₀ (Cl) ₃;
• 2. Hydroxyaluminium chloride: Al₂ (OH) ₅Cl as the products Chlorhydrol TR-50 and Astrigen TR-50;
• 3. polyhydroxyaluminum magnesium chloride: Al₃Mg (OH) ₉ (Cl) ₂;
• 4. Polyhydroxyaluminum calcium chloride: Al ₇ Ca _0.04 (OH) _17.01 (Cl) ₄ ;
• 5. polyhydroxyaluminum magnesium sulfate: Al ₄ Mg (OH) ₇ (SO ₄ ) _3.5 ;
• 6. hydroxyaluminum sulfate: Al₂ (OH) ₄ (SO₄);
• 7. oxyaluminum sulfate or polyaluminum oxide sulfate: Al _m O _n (SO 4) _p , wherein m is 2 to 4, n is 0.75 to 2.0, and p is 2.0 to 4.0;
• 8. Polyhydroxyaluminiumzinkoxidchlorid: Al₃ (OH) ₃ZnO (OH) (Cl) ₅;
• 9. Polyhydroxyaluminum and / or magnesium chlorosulphate: Al₄ (OH) ₆ (Cl) ₄ (SO₄) or Al₃Mg (OH) ₆ (Cl) ₃ (SO₄);
• 10. Polyaluminum iron (II) and / or iron (III) chloride: Al ₂ Fe ₂ (OH) _3,32 (Cl) _6,68 or AlFe _0,25 (II) Fe _0,25 (III) ( OH) _2,12 (Cl);
• 11. Polyaluminum chloride sulfate, and
• 12. Polyhydroxyaluminiumchlorsilikat;
• 13. Aluminum zirconium pentane or tetrachlorohydrate: Al₈Zr (OH) ₂₃Cl₅ or Al₄Zr (OH) ₁₂Cl₄ etc.

Component B⁺

The amount of component (B⁺) is between 0 and 98% by weight. the total amount of alloy compositions: the compo component (B⁺) of the composition consists of a resin with high nitrogen content and / or (co) polymer products the following components: guanidine, arylguanidine or cyanoguanidine, cyanoguanidine melamine, melamine formaldehyde hyd, melamine-glyoxal, melamine-urea-formaldehyde, Melamine-alkylamine-urea-formaldehyde, melamine-formaldehyde hyd-sulfide or bisulfide salt, amino-azines (which if applicable) including Aminotria zin, mixtures of carbamides or aminoacids (the can also be used) including melamine Melam, Ammelin; Thioamelin and substituted ammeline, Aminodiazines, mixtures of carbamides and / or amino azines, which may also be used For example, urea and melamine, melamine and Cynoguanidine, melamine and thioammelin, urea, melamine and 2,6- or 1,3-diazine and similar mixtures, cyanamide, Dicyandiamide, guanidine and allylalkyl and aralkyl substituents urea condensed with aldehydes such as glyoxal, but not limited to these.

Aldehydes used for the purposes mentioned may include, the following aldehydes: formaldehyde or p-formaldehyde, acetaldehyde, benzaldehyde, butyraldehyde, Furfuraldehyde, glyoxal and mixtures of two or more Aldehydes, for example formaldehyde and p-formaldehyde, Formaldehyde and acetaldehyde and benzaldehyde, acetaldehyde and Furfuraldehyde and formaldehyde, benzaldehyde and furfuryl aldehyde and the like. Other aminoplast resins and / or cationic Aminoplast resins which can also be used include resins on melamine-formaldehyde or p-formaldehyde-based resins on melamine-formaldehyde-glyoxal Base, resins based on melamine-urea or melamine Thiourea-formaldehyde base and resins from the following Components: melaminguanidine or melamine cyanoguanidine Formaldehyde, melamine-formaldehyde or melamine formal dehyd-glyoxal, melamine-urea-formaldehyde or Melaminguanidine or cyanoguanidine-formaldehyde, wherein the resins with mineral acids or organic acids like Hydrochloric acid, nitric acid, phosphoric acid, sw acid or organic acids, such as formic acid, Acetic acid, glycolic acid, lactic acid, citric acid, propion acid, butyric, oxalic, maleic, glutaric or Mixtures of these acids can be protonated. The resins from melamine, glyoxal and sulfuric acid or a Mixture of sulfuric acid and hydrochloric acid or a mixture of hydrochloric acid and formic acid are unknown resins.

The protonated resins used according to the invention can consist of components which in following mol quantities are mixed with each other:

melamine 0.0 to 1.2 moles cyanoguanidine 0.0 to 3.333 moles combined with formaldehyde 0.1 to 15.0 moles Polyamine or aliphatic amine or alkanolamines 0.0 to 5.0 moles glyoxal 0.0 to 5.0 moles Urea (purity for resins) 0.0 to 2.05 moles mineral acid 0.0 to 5.0 moles Quaternizing agents such as alkyl halides, dialkyl sulfates, halogenated benzyl or aryl sulfonic acids 0.0 to 1.0 mole organic acids 0.0 to 5.0 moles ammonium chloride 0.0-3.340 moles

An alternative composition of protonated resins, which can be used according to the invention include Kom components, which are combined in the following molar amounts become:

melamine 0.12 to 1.12 moles cyanoguanidine 0.0 to 2.16 moles formaldehyde 0.0 to 7.5 moles Polyamine or aliphatic amine or alkanolamines 0.0 to 5.0 moles glyoxal 2.5 to 5.0 moles mineral acids 0.098 to 3.33 moles Quaternizing agents such as alkyl halides, dialkyl sulfates, halogenated benzyl or aryl sulfonic acids 0.0 to 1.0 mole organic acids 0.0 to 5.0 moles

Another alternative composition of protonated Resins which can also be used according to the invention includes components in the following molar amounts be merged:

melamine 0.0 to 0.25 mole cyanoguanidine 1.0 to 2.20 moles formaldehyde 1.0 to 7.5 moles Polyamine or aliphatic amine or alkanolamines 0.0 to 5.0 moles glyoxal 0.0 to 0.25 mole Urea (purity for resins) 0.0 to 1.80 moles Quaternizing agents such as alkyl halides, dialkyl sulfates, halogenated benzyl or aryl sulfonic acids 0.0 to 1.0 mole organic acids 0.0 to 5.0 moles ammonium chloride 0.25 to 1.50 moles

Other aminoplast resins that can also be used are

• a) polyamine-modified urea-formaldehyde resins,
• b) melamine-formaldehyde resins and
• c) any suitable means of modifying the polymers Base polyamine or polyacrylamide can be used in the modifi grained urea-formaldehyde resins are used. Sol For example, these means are without being construed as limiting kung: cyanoguanidine-diethylenetriamine-melamine; Reaction product of about 1 mole of cyanoguanidine, about 3 moles Formaldehyde and about 0.5 to 1 mole of urea per mole of Cyanoguanidine and / or the reaction product of about 0.9 mol of cyanoguanidine, about 0.1 mol of melamine, about 3 moles Formaldehyde and about 0.5 mole to about 1 mole of urea per Moles of cyanoguanidine and melamine prepared as well as a Part of the mixture of said resins to about 9 parts of poly amine and / or polyacrylamine or one part by weight of the Polyacrylamins and about 2 to 9 parts by weight of said Aminoplast resin and / or cationic aminoplast resin.

The inorganic-organic (co) polymer alloy adducts, which can be used according to the invention, conclude sol These compounds are subject to the following general conditions Formula to be defined:

A-B-C-D or A-B⁺-C-D⁺

This includes those compounds that are in one in the US Re 34 486 be which was filed on 21 March 1986.

The inorganic-organic (co) polymer alloy adducts or organic (co) polymer alloy adducts which he can be used according to the invention and above or in the are described in the present application, are also suitable net for polyamines or polyacrylamides or katio niche, anionic or nonionic compounds. Your Ge can be in the range of 0 to 95 wt .-% move. you are commonly used in combination, for example with melamine-formaldehyde resins, melamine-formaldehyde-glyoxal Resins, melamine-formaldehyde resins, alkyl ether melamine Formaldehyde or alkyl ether-melamine-formaldehyde resins, which is protonated with inorganic or organic acids are melamine-urea-formaldehyde resins with anorga protonated with niche or organic acids, methylol Amino-epihalohyrin resin products and / or a mixture of these products. In this mixture is the molecular weight Mw 100,000, and R₁ is a divalent radical of the formula II-a, II-b, II-c, II-d, II-e, II-f or II-g. These radicals are cationic bridge residues with a charge and / or or ganic cationic multiply charged residues, such as wise

and

and, wherein the bridging molecule with the cationic charge and / or or the organic cationic molecule with the multiple charge, for example, the following structure, without this to be regarded as a limitation is:

or

N, N, N, N ', N', N'-hexamethyl-B-hydroxytrimethylendiammonium dibromide, N, N, N ', N'-tetramethyl-N, N'-dimethyl-B-hydroxy Dimethylendiammoniumdibromid or mixtures of the mentioned groups. The more detailed description can be found in US patent application Ser. 8 42 515, the 21st March Filed in 1986.

In the formulas given above, X is also cyano and / or hydrogen,
R₂ represents the following groups: hydrogen, a radical of the formula II-a to II-g, alkyl or dialkylphosphonic acid esters, ester amines, phosphonic acids and / or their amine derivatives, cationic phosphonium derivatives, tetrakis (hydromeethl-) phosphonium halide or hydroxide or oxalate or acetate or phosphate, tris (hydroxy methyl) phosphonium halides and / or halide derivatives or tetramethyl halides, lower alkyl halides and / or lower alkyl sulfates or derivatives thereof, wherein the halide group is chloride, bromide or iodide, the lower alkyl sulfate Methoxysulfate and / or ethoxysulfate, sulfonates and / or metal sulfates including the sodium, potassium or ammonium salts, substituted amides of the methylenephosphonic acid having the formula

N-CH₂PO₃H₂,

which have been prepared from urea (U), formaldehyde (F) and phosphorous acid and / or a mixture of phosphorous acid with hydrochloric acid, in which 0.25 to 0.5 mol of hydrogen chloride are used as the catalyst and the molar ratio (U): ( F): (H₃PO₃) 1: 3.5: 3.25
R₂ is hydrogen, hydroxyl or an optionally substituted organic aliphatic, cycloaliphatic, heterocyclic or aromatic group,
R₃, R₄: R₃ is hydrogen or as R₄ is an alkyl group having 1 to 4 carbon atoms, and R₁, R₂, R₃ and R₄ are present in amounts ranging from 0 to 80 wt .-%.

Component C

Component C is present in an amount of 0 to 95% by weight. based on the entire alloy composition. you consists in an aqueous solution of a cationic resin, mixed with a reagent from the following group is: polyalkylamines, polyetherpolyamines, polyethylenepoly amine (s), N-substituted ethyleneimines, polyquaternary Ver compounds, 1,3-biquaternary ammonium compounds, poly quaternary alkylamines, polydiaziridinyl compounds, Epi halohydrin with an aqueous mixture of a larger amount a secondary alkylamine and a minor amount of a primary alkylamines, polyenes (polyonenes), a polyamine, which is quaternized with an alkyl halide, and one tertiary amine reacted with a halogenated polymer qua is ternated. The polyamine can have a molecular weight in the Range from 200 to 500 000 have.

Component D⁺

The component D⁺ is in an amount of 0 to 95 wt .-%, based on the total alloy composition, before. The Component D is selected from compounds of the following Group: Aqueous solutions of the (co) polymeric acrylamide and / or acrylates of quaternary ammonium compounds and aq Rige and / or latex-like ethylenically unsaturated (co) poly merisable compounds, polydadmac amphoteric polydadmac (Co) polymers, polydadmac-melamine-formaldehyde alloys, Melamine-formaldehyde polyacrylamide (co) polymers and the ent cationic co (polymers), melamine-formaldehyde Colloids and corresponding resinous compounds, urine fabric-melamine-formaldehyde (co) polymers and their alloys with (co) polyacrylamide derivatives and cationic derivatives thereof, melamine-dicyan-diamide-formaldehyde-melamine-glyoxal and / or melamine-glyoxal-formaldehyde-melamine-dicyan-diamide Formaldehyde (co) polymers, acrylamide and its cationic and nonionic derivatives, dicyandiamide-formaldehyde alkyl amide and / or polyalkylamine and / or dialkylamine derivatives, (co) polymerized with polyacrylamide and its cationic and nonionic derivatives, emulsion (co) polymers on poly vinyl base and base of unsaturated compounds, melamine Formaldehyde and / or polyalkyl and / or aryl / aldehyde and / or their (co) polymers with unsaturated (co) polymeri Each compound of melamine can be made with about 1.75 compounds to about 6 moles of formaldehyde and / or polyalkylaldehydes and / or polyarylpolyaldehydes are condensed. Insbeson Alkali salts of sulfuric acid, which are in are used in the method selected so that about 0.25 to 2.5 moles of bisulfite (-HSO₃) or sulfite (-SO₃) on each Mol come melamine. Among the compounds that as a compo D⁺ can be used, fall out of the urine Substance-formaldehyde and urea-formaldehyde alkylamine and / or or polyalkylamine (co) polymers, modified urea Formaldehyde resins, the water-soluble products of a Reak tion of (1) dicyandiamide with (2) the product of a reaction formaldehyde and / or an amine selected from following group under acidic reaction conditions built, included. The above amines are selected from the group of primary aromatic monoamines and sec därer monoamines with at least one monovalent aromati remainder, d. H. at least one aryl radical attached to primary and secondary monoamines bound, wherein the aryl radical at least two of its ortho and para positions unsubsti has done. Also included are alkyleneamines and / or poly Alkyleneamines and / or polyimine, which kon kon with epichlorohydrin are densified, and / or their co (polymers) with cationic and / or nonionic compounds derived from polyacrylamide derived, terpolymers or polymers of diallyldi methyl and / or diethyl ammonium chloride and / or sulfate with N-vinyl-2-pyrrolidone- (co) polyacrylamide (co) polymers as Nonionic, anionic or cationic surfactants Type with a molecular weight in the range of a lower Limit from 1000 to a very high ceiling to 25 million and resin soap products.

It should be noted that the glyoxal solution is a glyoxal content (CHO-CHO) content, ranging between 65 and 85 wt .-% moves. The remaining part of the solution is Glyoxalhydrat with the formula

Certain complicated competition reactions take place but not negligible is the competitive reaction between glyoxal and glyoxal hydrate and formaldehyde with Melamine under acidic conditions. The water-soluble Melamine resin contains the following macromolecule, wherein the End of the reaction by the following reaction equation is reproduced:

In this reaction sequence, Y is ^- for the inorganic and / organic anionic acid residue, for example, Cl ^-, H₂PO₄, 1/2 (SO₄) ^-2, HCO₂, CH₃COO ^-, NO₃ ^-, the Lactatrest, the propionate, the Butyratrest, the Glykolatrest etc Under such acidic reaction conditions, the protonation of the triazine ring and an isomerization reaction is just as possible.

The inorganic-organic alloy polymers and the or Ganic alloy (co) polymers can be formed by a reaction at a temperature of from room temperature (RT) to 175 ° C at normal pressure of 0.2 to 25 bar from the components A, B, C, D⁺ are produced. More details will be out directed in US Patent Application Serial Number 0 96 681, filed on September 15, 1987.

The invention will be in terms of products, process steps and their application together with the relevant Results are explained in more detail below in the examples. It is understood that these examples are not limiting of the invention, but only as examples of their behavior visualization and presentation of their feasibility are meant.

The coagulation performance in the examples is determined by the haze test described in ASTM D. 2035-68 is.

example 1

"MAXIFLOX-MD-1A" is an inorganic-organic alloy in an aqueous alkyl glycol system and has a pH of 2.56, a density of 1.308 g / ml and a viscosity of 2.25 Pa · s (2250 cps ) (spindle no. 4 at 60 min ^-1). The compound has the formula A · D⁺.

Example 2

The inorganic-organic alloy "MAXIFLOC-MD-1" is a semi-transparent polymer alloy adduct having a pH of 2.38, a density of 1.327 g / ml and a viscosity of 1.2 Pa · s (1200 cps). (spindle no. 4 at 60 min ^-1) 200 g of the product was 1 wt .-% of a very fine Pul vers of activated carbon was added and the mixture mixed well for 30 min.

The product "MAXIFLOC-MD-1AC" had a pH of 2.42, a density of 1.288 g / ml and a viscosity of 1.05 Pas (1050 cps). The product had the formula A · D⁺.

Example 3

The product "MAXIFLOC-MD-1B" is a semi-transparent polymer alloy adduct with a pH of 2.72, a density of 1.232 g / ml and a viscosity of 0.7 Pa · s (700 cps) (spindle no. 4 at 60 min ^-1 ). The product had the formula A · D⁺.

Example 4

The product "MAXIFLOC-MD-1C" is a semi-transparent polymer alloy adduct having a pH of 3.35, a density of 1.202 g / ml and a viscosity of 0.35 Pa.s (350 cps) (spindle no. 4 at 60 min ^-1 ). The product had the formula A · D⁺.

Example 5A

The product "MAXIFLOC-MD-1D" is a semi-impermeable Polymer alloy adduct with a pH of 2.96, one Density of 1.260 g / ml and a viscosity of 2.95 Pa · s (2950 cps). The product had the formula A · D⁺.

Example 5B

The product "MAXIFLOC-MD-1DAC" is an inorganic one Alloy mixture with activated carbon with a pH value of 2.80 a density of 1.240 g / ml and a viscosity of 2.9 Pa · s (2900 cps). The product had the formula A · D⁺

Example 6

MAXIFLOC-MD-MGH is a cationic resin with a pH Value of 2.12 to 2.25, a density of 1.075 to 1.100 g / ml and a solids content of 20 to 25% with the formula B⁺.

Example 6A

MAXIFLOC-MD-6A2 is a semi-transparent, complex Adduct with a pH of 1.85, a density of 1.246 g / ml and a viscosity of 0.5 Pa · s (500 cps). The product had the formula A · B⁺ · D⁺.

Example 7

MAXIFLOC-MD-MGS is a cationic resin with a pH Value of 0.90, a density of 1.078 g / ml and a solid substance content of 17 wt .-%. The product had the formula B⁺.

Example 7A

MAXIFLOC-MD-MGS-7A is a light brown, inorganic organic complex polymer adduct with a pH of 1.50, a density of 1.352 g / ml and the formula A · B⁺.

Example 7B

MAXIFLOC-MD-MGS-7B is a pale yellow inorganic organic complex polymer adduct with a pH of 1.50, a density of 1.2540 g / ml and the formula A · B⁺.

Example 8

MAXIFLOC-MD-MGHCS is a light blue colloidal cationi beautiful resin with a pH of 1.32, a density of 1.72 g / ml and a solids content of 14 wt .-% with the Formula B⁺.

Example 9

MAXIFLOC-MD-MGHP is a colloidal light yellow-blue resin with a pH of 2.73, a density of 1.080 g / ml and a solids content of 18 wt .-% with the formula B⁺.

Example 9A

MAXIFLOC-MD-MGHP-9A is a light blue organic complex alloy adduct with a pH of 2.68, a density of 1.027 g / ml and a viscosity of 0.375 Pa · s (375 cps). It had the formula B⁺ · D⁺.

Example 9B

MAXIFLOC-MD-MGHP-9B is an inorganic-organic complex polymer adduct with a light brown to chocolate creamy color with a pH of 1.65, a density of 1.340 g / ml and a viscosity of less than 0.015 Pa · s (less than 15 cps). It had the formula B⁺ · D⁺.

Example 10

MAXIFLOC-8200AP10 is a polyamine with a pH of 3.0, a density of 1.200 g / ml,  a viscosity of 0.139 Pa · s (139 cps), a solids content of 53% and a water clear appearance. It had the formula B. The Product was stable for more than a year. The sample of the Pro Ducts were even after dilution to a solids content of 50% and a viscosity of 0.1 Pa · s (100 cps) longer stable for 1.5 years.

Example 10A

MAXIFLOC-820AP10A is a deep blue, organic polymer adduct complex with a pH of 4.42, a density of 1.15 g / ml, a viscosity of 0.125 Pa · s (125 cps) and the Formula B · B⁺.

Example 11

MAXIFLOC-820AMFC is a resin of light blue color with a pH of 6.30, a density of 1.146 g / ml, a Viscosity of 0.07 Pa · s (70 cps), a solids content of 43% and the formula B⁺.

Example 11A

MAXIFLOC-820MFC11A is a deep blue colloidal organi beautiful complex polymer adduct with a pH of 2.34, a density of 1.087 g / ml, a viscosity of less as 0.03 Pa · s (less than 30 cps) and the formula B⁺.

Example 12

MAXIFLOC-MGHC is a polyamine with a pH of 3.56, a density of 1.042 g / ml, a solids content of 8 wt .-% and the formula B⁺.

Example 12A

MAXIFLOC-GFMGC-12A is an organic complex poly guanidine-based meraduct product with translucent blue color with a pH of 4.42, a density of 1.555 g / ml and the formula B⁺.

Example 12B

MAXIFLOC-GFMCG-12G is a complex polymer adduct with medium-high cationic polyacrylamide-based charge with a pH of 3.34, a viscosity of 1.5 Pa · s (1500 cps), a light yellow color and the formula B⁺ · D⁺.

For the preparation of the hydrophobic alkaline agent fol gender path suggested.

Example 13

In the described in Example 1 or another ge closed mechanical mixer against chemical is inert, the following components are filled in:

1. Sodium hydroxide (30 to 35% by weight) 81.43% by weight 2. anionic surfactant (such as, for example, a long-chain C₁₂-alkyl sulfate sodium salt) 7.14% by weight 3. (Co) polystyrene latex 11.43% by weight

The reactants were well for 15 to 30 minutes or so long mixed until a uniform product has formed. The half-white to creamy white product is the reactor Ent and it has a pH = 11.5 and a density of 1.283 g / ml.

Example 14

The procedure of Example 13 is repeated the following components were used:

1. 35% sodium hydroxide 87.6% by weight and 65.5%, respectively 2. anionic surfactant (as in Example 13) 5.88% by weight and 2.4%, respectively 3. (Co) polystyrene-acrylic latex 9.41% by weight and 9.2%, respectively 4. Aprotic solvents and / or mixtures of these solvents and / or water (preferably dimethyl sulfoxide) 17.65% by weight and 22.9%, respectively

The components were thoroughly mixed for 30 minutes, until they had become a white fluid latex. These was removed from the reactor and had a pH = 11.5 and a density of 1.269 g / ml.  

Example 15

Example 14 was repeated but replacing the surfactant by an anion type, for example the sodium salt an alkylaryl sulfonate, such as the sodium salt of dodecyl Phenoxybenzene-disulfonate. The composition was 30 min mixed very well, up to a fluid product had become of chocolate cream color. This was the Taken from the reactor and had a pH = 11.5 and a Density of 1.277 g / ml.

Example 16

The process steps of Example 15 were among the conditions specified therein repeated; it became, however the dimethyl sulfoxide by an organic alkaline Ab stripping agent based on an aprotic solvent replaced, for example, N-methylpyrrolidone, and a Solvent with a high boiling point. For comparison can also US patent application Ser. 42 209, Example 5 or US-PS 41 20 810, Example 1 are used. After 40 minutes of mixing, the reactor became a creamy taken from a fluid product having a pH = 10 and a Density of 1.267 g / ml.

Example 17

In the reactor described in Example 13, the following were Filled components:

1. water 54.35% by weight 2. Sodium gluconate 0.694% by weight 3. KOH 17.19% by weight 4. Alkyl glycoside ethoxylate (surfactant) 0.694% by weight 5. aluminate (salt and / or polymeric salt) 26.54% by weight 6. Silicone (defoamer) 0.514% by weight

The composition was mixed for 15 min. Until a Product of light brown color had formed. This was taken from the reactor and had a pH = 10.0, a Density of 1.295 g / ml and a solids content of 50%.

Example 17A

267 g of the product of Example 17 were used in the course of a Time of 10 minutes 27 g of a (co) polystyrene-acrylic acid latex added. The mixing was continued for another 15 min leads until a uniform emulsion had formed. The product was removed from the reactor and had a pH of Value = 10.50, a density of 1.313 g / ml and a solid substance content of 56 wt .-%.

Example 18

The following were described in the plant described in Example 13 Filled components:

1. water 73.0% by weight 2. Sodium hydroxide (30% by weight) 4% by weight 3. sodium metasilicate × 5 H₂O 1% by weight 4. trisodium silicate 0.2% by weight 5. Sodium salt of resin acids (soap) 2.0% by weight 6. (Co) polystyrene-acrylic acid latex 20.60% by weight 7. Silicone (defoamer) 0.2% by weight

The composition was mixed until clear or until after 15 min a light chocolate brown colored Product has formed. This was taken from the reactor and had a pH = 10.50, a density of 1.020 g / ml and a solids content of 17%.

In addition, the improved characteristics of the new flocculating material of this invention, for example to portray and demonstrate were countless Tests performed. These tests and their results are in illustrated in the table below. The water to the Wa paint and paint spray to remove paint Over-sprays in the paint spray booths will come with the following Decoating compositions in alkaline and acidic Media treated.

observations:
*) see US Re 34 486
**) Nalco Chemical Co. US 40 67 806

MAGNIFLOC is a trademark of American Cyanamid Co.
MAXIFLOC is a trademark of Maxichem. Inc.
PERCOL is a trademark of Allied Colloids Inc.
MDR = mean drainage rate
SDR = slow drainage speed
F. to VF. DR. = Fast to very fast drainage speed
K = color eliminated
MAXICHEM-IDTM = polymelamine-formaldehyde condensate
MAXICHEM-957 = Modified polymelamine condensate (Ureid type).
MAXIFLOC-509C = polymelamine-formaldehyde condensate.
(C) = cation type.
(A) = anion type.
(N) = nonionic type.

The degrees of detackification are arbitrarily defined as:
1 = very good (color removed)
2 = good
3 = satisfactory
4 = bad
5 = unacceptable

The water supernatant (clarity) is expressed in the Gardner color scale; the values are as follows:
0 = watercolors (clear)
1 = white
2 = light yellow
3 = yellow
4 = brown yellow
5 = brown
6 = dark brown
7 = dark black color

Claims (24)

A composition for detackifying and clarifying effluents of acidic and alkaline paints and lacquers and paint waste from spray booths, obtainable by a process comprising the following process steps:
Mixing dicyandiamide or guanidine production or melamine, formaldehyde or glyoxal or mixtures of formaldehyde-glyoxal, water, aliphatic amine or polyamine or alkanolamine or urea,
Adjusting the pH to a value in the range of 3 to 10,
Condensing the formaldehyde or glyoxal and dicyandiamide or melamine by heating to a temperature between room temperature (RT) to 95 ° C for an additional period of 10 min to 4 h at normal pressure or a pressure in the range of 0.02-2.5 MPa, according to which the resin or (co) polymer formed is protonated with a mineral acid or organic acid or quaternized with an alkyl halide or a dialkyl sulfate or with halobenzyl or aryl sulfonic acid, the components involved being present in molar amounts in the following range: melamine 0.0 to 1.2 moles cyanoguanidine 0.0 to 3.333 moles in combination with formaldehyde 0.0 to 15.0 moles aliphatic amine or polyamine or alkanolamines 0.0 to 5.0 moles glyoxal 0.0 to 5.0 moles Urea or thiourea type resin 0.0 to 2.05 moles Mineral acids or organic acids 0.0 to 5.0 moles ammonium chloride 0.0-3.334 Quaternizing agents such as alkyl halide or dialkyl sulfates and / or halobenzyl or aryl sulfonic acid 0.0 to 1.0 mol A composition according to claim 1, wherein the composition comprises an inorganic-organic or organic polymer alloy adduct composition of the formula: A · B⁺ · C · D⁺worin
A is [{(SiO₂ / Me ^I ₂O) _{u} s} Me Me _m ^II _n ^III (OH) _p (SO₄) _y (Aci) _{(2m + 3n) -p-2y] r}
with r = 0 to 98% by weight;
B⁺ for [N-R₁-N] _x · (R₂) ₄
with x = 0 to 98% by weight;
C for [(PAM) _z - (PAM-PAD)] _{z + t}
With
z = 0 to 95 wt .-% polyamines (PAM) and
t = 0 to 95% by weight of polyamides (PAD), and
D⁺ for (PQAM) _w
with w = 0 to 95% by weight polyquaternised polymer (PQAM),
M ^II _{m is} selected from the divalent cations of the group Mg ²⁺ , Zn ²⁺ , Ca ²⁺ and Fe ²⁺ , where m is 0 to 5,
Me ^III _{n is} a trivalent or polyvalent metal from the group Fe, Al and complexes of Al and Zn, where n is 1 to 20,
Aci is selected from monovalent anionic groups such as Cl ^- , Br ^- , I ^- , NO₃ ^- , H₂PO₄, CH₃COO ^- or a mixture of two or more of the foregoing groups, with Aci preferably Cl ^- , NO₃ ^- , CH₃COO ^- or H₂PO₄ ^- is,
in the formula {(SiO₂) / Me ^I ₂O)} _{u s} u stands for a ratio of 1.5 to 3.5, Me represents ^I, Na, K, Li, or Cs, and s is a value from 0 to 10% % stands,
SiO₂ preferably sodium silicates and / or sodium meta silicate and / or mixtures thereof, magnesium and / or calcium silicate, aluminum magnesium silicate, kaolin-type clays, bentonite and / or an organic and / or inorganic modified bentonite including cationic bentonite and / or a mixture of these components is
PAM for polyamines,
PAD for polyamides,
PQAM represents a polyquaternized polymer,
p is a number in the range of 0 to 75,
y is a number in the range of 0 to 15,
in which besides
x is 100,000,
R₁ is a cationic bridging radical or a multicompound organic cationic radical or a divalent radical selected from the groups represented by the following formula II-a, II-b, II-c, II-d, II-e, II-f and II-g is selected and a cationic bridging radical and / or an organic cationic radical with multiple charge, for example wherein n is a number from 1 to 10,
C₆H₁₅NOCl; C₆H₄NOCl; C₁₃H₃ON₂O₃Cl₄; C₁₂H₂₆N₂O₂Cl₂; C₁₆N₃₆N₂O₆Cl _2S ; C₁₆H₃₆N₂O₂Cl₄; C₁₁H₂₆N₄O₃Cl₄; C₁₁H₂₄N₄O₃Cl₂;
N, N, N, N ', N', N'-hexamethyl-B-hydroxytrimethylene diammonium dibromide, N, N, N ', N'-tetrabutyl-N, N'-dimethyl-B-hydroxytrimethylene diammonium dibromide and a mixture of said compounds .
in which besides
X is a cyano group and / or hydrogen,
R₂ has the following meanings: hydrogen, a radical of the formula II-a to II-g, alkyl or dialkylphosphonic acid esters, ester amines, phosphonic acids and / or their amine derivatives, cationic phosphonium derivatives, tetrakis (hydroxymethyl) phosphonium halide or hydroxide or oxalate or acetate or phosphate, tris (hydroxy methyl) phosphonium halides and / or halide derivatives or tetramethyl halides, lower alkyl halides and / or lower alkyl sulfates or derivatives thereof, wherein the halide group is chloride, bromide or iodide, the lower alkyl sulfate Methoxysulfate and / or ethoxysulfate, sulfonates and / or metal sulfates including the sodium, potassium or ammonium salts, substituted amides of methylenephosphonic acid having the formulaN-CH₂PO₃H₂ consisting of urea (U), formaldehyde (F) and phosphorous acid and / or a mixture of phosphoric acid have been prepared with hydrochloric acid, wherein as the catalyst 0.25 to 0.5 moles of hydrogen chloride were used and the molar ratio (U): (F): (H₃PO₃) 1: 3.5: 3.25,
R₂ is hydrogen, hydroxyl or an optionally substituted organic aliphatic, cycloaliphatic, heterocyclic or aromatic group,
R₃, R₄: R₃ is hydrogen and / or as R₄ is an alkyl group having 1 to 4 carbon atoms, and R₁, R₂, R₃ and R₄ are present in amounts ranging from 0 to 80 wt .-%. A composition according to claim 2, wherein A is selected from the following groups Al _m (OH) _n X _3m-n-2k (SO₄) _k ;
Al _1-x Fe _x ^II Fe _y ^III (OH) _{3 = 2y = 2} (Hal) _z
Al _m (OH) _x (SO 4) _z ;
Me _n (OH) _m S _3n-m ; normal chloride, sulfate, phosphate, nitrate or acetate salts of aluminum, iron, titanium, vanadium, zirconium, chromium, antimony or their mixture. 4. A composition according to claim 2, wherein A ranges from 0 to 98% by weight of the total alloy composition is and is selected in the following groups: Polyhydroxyaluminum chloride, hydroxyaluminum chloride, Polyhydroxyaluminum magnesium chloride, Polyhydroxyalu miniummagnesium sulfate, hydroxyaluminum sulfate, oxyalu minium sulfate, polyaluminum oxide sulfate, oxyaluminum chloride, polyhydroxyaluminum zinc oxide chloride, poly hydroxyaluminum chlorosulphate, polyhydroxymagnesiumchlor sulfate, polyaluminum iron (III) chloride, polyaluminum iron (II) chloride, polyaluminium chloride silicate, poly hydroxyaluminum sodium sulfophosphate, aluminum zirconium pentachlorohydrate and aluminum district tetrachlorohydrate. 5. The composition of claim 2, wherein B⁺ in an amount is present in the range of 0 to 98% and is selected from compositions S containing nitrogen, which are resinous and / or (co) polymer products finally, resins or copolymers of the building blocks Cyanoguanidine melamine, melamine-formaldehyde, melamine Glyoxal, melamine-formaldehyde glyoxal and / or a Mi Scheme of aliphatic (alkyl) and / or heterocycli aromatic and / or aromatic aldehydes, Melamine-urea-formaldehyde and / or glyoxal, Cyanoguanidine-urea-formaldehyde and / or glyoxal, Melamine alkylamine and / or alkanolamine formaldehyde and / or glyoxal, melamine formaldehyde sulfide and / or bisulfite salt, aminoazines and / or monoguanamines and / or diguanamine-formaldehyde and / or (co) polymers with melamine, cyanoguanidine-formaldehyde and / or Glyoxal, the compounds mentioned optionally protonated with mineral acid and / or organic Acids, such as sulfuric acid, Hydrochloric acid, phosphoric acid, nitric acid, Formic acid, acetic acid, glycolic acid, lactic acid, Citric acid, propionic acid, butyric acid, oxalic acid, Maleic acid, glutaric acid and / or mixtures of these Acids, alkylamines and / or polyamines and / or poly acrylamide modified with melamine-formaldehyde and / or Glyoxal resins, urea-formaldehyde and / or Glyoxal resins, thiourea-formaldehyde and / or Glyoxal resins, wherein the aldehydes used form aldehyde and / or p-formaldehyde, acetaldehyde, benzaldehyde hyd, butyraldehyde, furfuraldehyde, glyoxal and mixtures of two or more of said aldehydes include, for example, formaldehyde and p-formaldehyde hyd, formaldehyde and acetaldehyde and benzaldehyde, Acetaldehyde and furfuraldehyde-formaldehyde and Benz aldehyde and furfuraldehyde. 6. A composition according to claim 5, wherein B⁺ is a resin and / or (co) polymer selected from the following compounds: melamine 0.0 to 1.2 moles cyanoguanidine 0.0 to 3.333 moles in combination with formaldehyde 0.0 to 15.00 mol aliphatic amine or polyamine or alkanolamines 0.0 to 5.0 moles glyoxal 0.0 to 5.0 moles Urea or thiourea type resin 0.0 to 2.05 moles Mineral acids or organic acids 0.0 to 5.0 moles ammonium chloride 0.0-3.340 Quaternizing agents such as alkyl halides or dialkyl sulfate or halobenzyl or aryl sulfonic acid 0.0 to 1.0 mol 7. A composition according to claim 6, wherein B⁺ is a resin or (co) polymer according to the general formula [-R₁-N] _x · (R₂) ₄ wherein x is less than 100,000, and
R₁ is present in an amount in the range of 0 to 80% by weight of the composition and a cationic charge bridging group and / or a multiple cationic charge organic group or a divalent group of the formula and wherein n is a number in the range of 1 to 10,
C₁₂H₂₆N₂O₂Cl₂; C₁₆H₃₆N₂O₂Cl₂₅; C₁₆H₃₆N₂O₂Cl₄; C₁₁H₂₆N₄O₃Cl₄; C₁₁H₂₄N₄O₃Cl₂;
N, N, N, N ', N', N'-hexamethyl-B-hydroxytrimethylenediammonium dibromide, N, N, N ', N'-tetra-butyl-N, N'-dimethyl-B-hydroxytrimethylenediammonium di bromide or a mixture of these compounds .
X is a cyano group and / or hydrogen,
R₂ represents one of the following groups: hydrogen, radical of the formulas II-a, II-b, II-c, II-d, II-e, II-f, II-g, alkyl or dialkylphosphonic, ester amines, phosphonic acid and or their amine derivatives, cationic phosphonium derivatives, tetrakis (hydroxymethyl) phosphonium halides or hydroxides or oxalates or acetates or phosphates, tris (hydroxymethyl) phosphonium halides or their derivatives or tetramethyl halides, phosphonium halide derivatives, Lower alkyl halides, lower alkyl sulfates or their derivatives, wherein the halide group is chloride, bromide or iodide, the lower alkyl sulfate is methoxy and / or ethoxy sulfate, metal sulfonates and / or metal sulfates with cations, such as sodium, potassium or ammonium, with a group the formulaN-CH₂PO₃H₂substituted amide of methylenephosphonic acid, Herge provides from urea (U), formaldehyde (F), Phosphori gersäure and / or a mixture of Phosphorigersäure with hydrochloric acid, wherein as Kata lysator 0.25 to 0.5 mol of the HCl are used and the molar ratio (U): (F): (H₃PO₃) 1: 3.50: 3.25,
R₂ is hydrogen or hydroxy-substituted aliphatic, cycloaliphatic, heterocyclic or aromatic group,
R₃, R₄: R₃ is hydrogen and / or as R₄ is an alkyl radical having 1 to 4 carbon atoms and the amounts of R₁, R₂, R₃ and R₄ are in the range of 0 to 80% and the amount of B⁺ in the range of 0th to 98% by weight, in combination with inorganic adduct polymers according to formula A and / or organic adduct polymers,
C-PAM is selected from polyalkylamines, poly ethylene polyamines, N-substituted ethylene amines, poly quaternary compounds, 1,3-Bisquaternärammonium-, Polyquaternärarylalkylaminen, polyether polyamines, polydiaziridinyl compounds, Epihalohydri nen with an aqueous mixture of larger amounts of a secondary alkylamine and lower Quantities of a primary alkylamine, polyols, a polyamine quaternized with an alkyl halide and a tertiary amine, quaternized with a halogenated polymer, wherein the poly amines may have a molecular weight below 500,000, C-PAD an aqueous solution of a cationic resin is prepared by reacting an aliphatic carboxylic acid having 3 to 11 C atoms with a polyalkylenepolyamine having at least one nitrogen atom which is in the form of a tertiary amino group, two primary amino radicals, wherein at least two alkylene groups have 2 to 4 carbon atoms and wherein the polyalky lenamin and the carboxylic acid in a molar ratio of about 0.8 to 1.0 to about 1.2: 1.0 and z and t is the indication (in wt .-%) of the amount of polyamine and / or polyamide-polyamine in the composition being in the range of 0 to 95% by weight, the guanidine polymers and / or high nitrogen resins and / or (co) polymers are present in an amount of 0 to 70% by weight in the presence of a polyamine, polyamide, a polyamine-polyamide blend, a polyquaternary ammonium compound to form the inorganic-organic and / or organic alloy (co) polymers. 8. The composition of claim 2, wherein D⁺ (PQAM) from is selected from the following components: aqueous Lösun quaternary ammonium compounds in which an ethy lenically unsaturated compound or one with one of like compound copolymerizable compound einbe are withdrawn. 9. A composition according to claim 8, wherein D⁺ in the Legie ration compositions in an amount of 0 to 95% by weight. is present and selected from the group following Compounds: polydiallyldimethylammonium halides and their derivatives, polydiallylamines, polyallyl trialkyl ammonium salts and their (co) polymers, poly-N, N, N-tri methylallylammonium salts, poly-N, N-dimethylacrylamide and its (co) polymers, polymethacrylamidepropyltrimethyl ammonium salts and their (co) polymers, poly-2-trimethyl ammonium methacrylic acid salts and their (co) polymers, poly N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethyl ammonium betaine and its (co) polymers, poly-7- (3-sulfo propyl) -2-vinylpyridinium betaine and its (co) poly pure, polydadmac-melamine-formaldehyde alloy (a finally, Manich-type compound), (co) polyacrylic amide melamine from aldehyde alloy polymers, urea Melamine formaldehyde  (Co) polymers and their alloys with (co) polyacrylamide derivatives and derivatives of katio niche type, glyoxal-formaldehyde-melamine and / or Glyoxal-melamine copolymers and their alloys Polyacrylamide and its cationic (co) polymers and nonionic derivatives, dicyaninamide-formaldehyde Alkylamine and / or urea and / or polyalkylamine and / or dialkylamine derivatives copolymerized with Polyacrylamide and its cationic and / or not ionic derivatives, polyvinyl emulsion polymers and the emulsion copolymers with unsaturated compounds, Dicyandiamide-formaldehyde-urea and / or alkylamine and / or polyalkylamine (co) polymers, melamine formaldehyde hyd-alkali metal salts of sulfuric acid, which in the Method is used in an amount of about 0.25 to 2.5 moles of bisulfite or sulfite per mole of melamine, poly acrylamide derivatives of the cationic, anionic and / or nonionic type, terpolymers or polymers of Diallyldimethyl chloride and / or diethylammonium chloride and / or sulfate with N-vinyl-2-pyrrolidone or -poly acrylamide polymers or copolymers of the nonionic rule, anionic or cationic type with a Molecular weight of 1000 to 25 000 000 and with a Resin soap based product. 10. A process for the preparation of inorganic-organic and / or organic (co) polymer alloy adducts, which comprises the following process steps:
Mixing dicyandiamide or guanidine products or melamine, formaldehyde or glyoxal or mixtures of formaldehyde-glyoxal, water, aliphatic amine and / or polyamine and / or alkanolamine or urea,
Adjust the pH to a value in the range of 3 to 10.
Condensation of the formaldehyde or glyoxal and dicyan diamide or melamine by heating to a temperature between room temperature (RT) to 95 ° C for an additional period of time of 10 minutes to 4 hours at atmospheric pressure or a pressure in the range of 0.02 to 2.5 MPa, after which the resin formed and / or (co) polymer is protonated with a mineral ralsäure and / or organic acid or quaternized with an alkyl halide and / or a dialkyl sulfate or with halobenzyl and / or -aryl-sulfonic acid qua, the participating Components are present in molar amounts in the following range: melamine 0.0 to 1.2 moles cyanoguanidine 0.0 to 3.333 moles in combination with formaldehyde 0.0 to 15.00 mol aliphatic amine or polyamine or alkanolamines 0.0 to 5.0 moles glyoxal 0.0 to 5.0 moles Urea or thiourea type resin 0.0 to 2.05 moles Mineral acids or organic acids 0.0 to 5.0 moles ammonium chloride 0.0-3.334 Quaternizing agents such as alkyl halides or dialkyl sulfate or halobenzyl or aryl sulfonic acid 0.0 to 1.0 mol 11. The method of claim 10, wherein 0 to 98 wt .-% of inorganic polymer adducts or organic (co) poly mer adducts at a temperature in the range of room temperature to 95 ° C to form a polymeric complex adduct molecule are reacted. 12. The method of claim 10, wherein the components Dicyandiamide, formaldehyde and ammonium chloride as well Hydrochloric acid in molar amounts of about 0.256 to 3.333 and about 0.490 to 6.68 and about 0.0 to 3.334, respectively or about 0.0 to 4.925 are present. 13. The method of claim 12, wherein the reaction in a Time of less than 5 hours to complete. 14. The method of claim 13, wherein 0 to 98 wt .-% Guani din resin and / or polymers with an inorganic and / or organic polymer alloy adduct to be implemented. 15. The method of claim 10, wherein the components Melamine, cyanoguanidine, formaldehyde, glyoxal, urea, Alkylamine and / or polyamine and / or alkanolamine, mine acids and / or organic acids and moistening in approximate molar amounts ranging from 0.0 to 1.2 or 0.0 to 2.16 and 0 to 7.365 and 0.0 to 5.0, respectively or 0.0 to 2.05 or 0.0 to 5.0 or 0.0 to 3.25 available. 16. The method of claim 15, wherein the reaction at a Pressure of less than 25 bar and at a temperature in the Range from room temperature to 95 ° C for a time from about 10 minutes to 120 minutes. 17. The method of claim 15, wherein the melamine, form aldehyde, glyoxyl, mineral acid or organic acids in approximate molar amounts in the range of 0.2 to 0.06 or 0.0 to 7.365 and 0.0 to 0.6 and 0.19 to 1.209, respectively lie. 18. The method of claim 15, wherein 0 to 95 wt .-% of Melamine resin and / or polymer with at least one inorganic or organic polymer alloy adduct at a temperature ranging from room temperature to 50 ° C to be implemented. 19. The method of claim 10, wherein 0 to 95 wt .-% of inorganic adduct polymers or organic adducts (Co) polymers at a temperature in the range of 45 to 53 ° C to 90 to 110 ° C to form a complex (Co) polymer adduct molecule are reacted. 20. The method of claim 10, wherein the color detackification is carried out in acidic and / or alkaline solution at a pH in the range of 2.0 to 13.5. 21. The method according to claim 20, wherein the adjustment of the pH is carried out using any inorganic and / or alkaline substances, such as NaOH, KOH, Ca (OH) ₂, Na₂CO₃, sodium and / or potassium aluminate, sodium zincate, Sodium silicate and / or metasilicate, sodium borate, alkylamines, alkanol amines or mixtures of these compounds in combination with hydrophobic materials which have been added before and / or after the addition of the inorganic-organic and / or organic alloy (co) polymers the formula 22. The method of claim 21, wherein the hydrophobic substances include the following substances: surfactants (preferably nonionic and / or anionic and / or a mixture the surfactants mentioned) with a number from 5 to 50 C Atoms in the structure in an amount of 0.5 to 95 wt .-% and 95.0 to 0.5 wt .-%, (co) polymers of ethylenic type and / or vinyl type and / or Vinyl latex type as ethylenically unsaturated copoly mers, styrene-latex, styrene-divinylbenzene-latex, gege optionally modified styrene-butadiene latex, styrene Acrylates and / or acrylic latex acrylates and / or verbin type of natural polymers, such as Sodium gluconate, sodium heptanoate, rosin acid Sodium salts, sodium glucoside, alkyl glucoside, alkylglu koside ethoxylate, clays and / or bentonites obtained with Grup inorganic and / or organic type modifi are ornamented, including with organic cationic Groups modified bentonites, solvents, before added aprotic solvents, inorganic and / or organic stripping agents, halogenated organic Abstreifmittel and / or mixtures thereof. 23. The method of claim 21, wherein the alkaline mate rial, the hydrophobic material, the surfactants, the anorga niche and / or organic stripping agents, the aproti and the natural polymer salts in Weight amounts in the range of 2.5 to 50% and 1.5 to 45% or 0.5 to 15% or 0 to 38% or 0 to 5% available. 24. The method according to claim 23, wherein the operation of the Ent Glueing is stopped at a pH in the range of 6 to 9 and no additional chemical treatment for the Mud and / or the drained water required is.